Interactions between zooplankton and crude oil: toxic effects and bioaccumulation of polycyclic aromatic hydrocarbons.

Directory of Open Access Journals (Sweden)

Rodrigo Almeda

Full Text Available We conducted ship-, shore- and laboratory-based crude oil exposure experiments to investigate (1 the effects of crude oil (Louisiana light sweet oil on survival and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs in mesozooplankton communities, (2 the lethal effects of dispersant (Corexit 9500A and dispersant-treated oil on mesozooplankton, (3 the influence of UVB radiation/sunlight exposure on the toxicity of dispersed crude oil to mesozooplankton, and (4 the role of marine protozoans on the sublethal effects of crude oil and in the bioaccumulation of PAHs in the copepod Acartia tonsa. Mortality of mesozooplankton increased with increasing oil concentration following a sigmoid model with a median lethal concentration of 32.4 µl L(-1 in 16 h. At the ratio of dispersant to oil commonly used in the treatment of oil spills (i.e. 1∶20, dispersant (0.25 µl L(-1 and dispersant-treated oil were 2.3 and 3.4 times more toxic, respectively, than crude oil alone (5 µl L(-1 to mesozooplankton. UVB radiation increased the lethal effects of dispersed crude oil in mesozooplankton communities by 35%. We observed selective bioaccumulation of five PAHs, fluoranthene, phenanthrene, pyrene, chrysene and benzo[b]fluoranthene in both mesozooplankton communities and in the copepod A. tonsa. The presence of the protozoan Oxyrrhis marina reduced sublethal effects of oil on A. tonsa and was related to lower accumulations of PAHs in tissues and fecal pellets, suggesting that protozoa may be important in mitigating the harmful effects of crude oil exposure in copepods and the transfer of PAHs to higher trophic levels. Overall, our results indicate that the negative impact of oil spills on mesozooplankton may be increased by the use of chemical dispersant and UV radiation, but attenuated by crude oil-microbial food webs interactions, and that both mesozooplankton and protozoans may play an important role in fate of PAHs in marine environments.

Interactions between Zooplankton and Crude Oil: Toxic Effects and Bioaccumulation of Polycyclic Aromatic Hydrocarbons

Science.gov (United States)

Almeda, Rodrigo; Wambaugh, Zoe; Wang, Zucheng; Hyatt, Cammie; Liu, Zhanfei; Buskey, Edward J.

2013-01-01

We conducted ship-, shore- and laboratory-based crude oil exposure experiments to investigate (1) the effects of crude oil (Louisiana light sweet oil) on survival and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in mesozooplankton communities, (2) the lethal effects of dispersant (Corexit 9500A) and dispersant-treated oil on mesozooplankton, (3) the influence of UVB radiation/sunlight exposure on the toxicity of dispersed crude oil to mesozooplankton, and (4) the role of marine protozoans on the sublethal effects of crude oil and in the bioaccumulation of PAHs in the copepod Acartia tonsa. Mortality of mesozooplankton increased with increasing oil concentration following a sigmoid model with a median lethal concentration of 32.4 µl L−1 in 16 h. At the ratio of dispersant to oil commonly used in the treatment of oil spills (i.e. 1∶20), dispersant (0.25 µl L−1) and dispersant- treated oil were 2.3 and 3.4 times more toxic, respectively, than crude oil alone (5 µl L−1) to mesozooplankton. UVB radiation increased the lethal effects of dispersed crude oil in mesozooplankton communities by 35%. We observed selective bioaccumulation of five PAHs, fluoranthene, phenanthrene, pyrene, chrysene and benzo[b]fluoranthene in both mesozooplankton communities and in the copepod A. tonsa. The presence of the protozoan Oxyrrhis marina reduced sublethal effects of oil on A. tonsa and was related to lower accumulations of PAHs in tissues and fecal pellets, suggesting that protozoa may be important in mitigating the harmful effects of crude oil exposure in copepods and the transfer of PAHs to higher trophic levels. Overall, our results indicate that the negative impact of oil spills on mesozooplankton may be increased by the use of chemical dispersant and UV radiation, but attenuated by crude oil-microbial food webs interactions, and that both mesozooplankton and protozoans may play an important role in fate of PAHs in marine environments. PMID:23840628

Precipitation and temperature drive seasonal variation in bioaccumulation of polycyclic aromatic hydrocarbons in the planktonic food webs of a subtropical shallow eutrophic lake in China.

Science.gov (United States)

Tao, Yuqiang; Yu, Jing; Xue, Bin; Yao, Shuchun; Wang, Sumin

2017-04-01

Hydrophobic organic contaminants (HOCs) are toxic and ubiquitous in aquatic environments and pose great risks to aquatic organisms. Bioaccumulation by plankton is the first step for HOCs to enter aquatic food webs. Trophic status is considered to dominate variations in bioaccumulation of HOCs in plankton in temperate and frigid deep oligotrophic waters. However, long-term driving factors for bioaccumulation of HOCs in planktonic food webs of subtropical shallow eutrophic waters have not been well investigated. China has the largest subtropical lake density in the Northern Hemisphere. Due to limited field data, long-term variations in the bioaccumulation of HOCs in these lakes are almost unknown. Here we take Lake Xuanwu as an example to investigate long-term variations in the bioaccumulation, and biomagnification of polycyclic aromatic hydrocarbon (PAHs) in planktonic food webs of subtropical shallow eutrophic lakes in China, and elucidate the driving factors. Our results indicate that temperature rather than nutrients dominates long-term dynamics of planktonic biomass in this lake. Precipitation significantly enhances the concentrations of the PAHs, and total suspended particles, and consequently affects the distribution of the PAHs in the water column. Biomass dilution induced by temperature dominates bioaccumulation of the PAHs by both phytoplankton and zooplankton (copepods and cladocerans). Biomagnification of the PAHs from phytoplankton to zooplankton is positively correlated with temperature. Our study suggests that temperature and precipitation drive long-term variations in the bioaccumulation of the PAHs in the planktonic food webs of this subtropical shallow eutrophic lake. Lake Xuanwu has a similar mean annual temperature, annual precipitation, sunshine duration, and nutrient levels as other subtropical shallow eutrophic lakes in China. This study may also help to understand the bioaccumulation of HOCs in planktonic food webs of other subtropical shallow

FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

Energy Technology Data Exchange (ETDEWEB)

John F. Schabron; Joseph F. Rovani Jr.; Theresa M. Bomstad

2002-06-01

Western Research Institute (WRI) initiated exploratory work towards the development of new field screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of carbon-halogen bonds. Commercially available heated diode and corona discharge leak detectors were procured and evaluated for halogenated VOC response. The units were modified to provide a digital readout of signal related to VOC concentration. Sensor response was evaluated with carbon tetrachloride and tetrachloroethylene (perchloroethylene, PCE), which represent halogenated VOCs with and without double bonds. The response characteristics were determined for the VOCs directly in headspace in Tedlar bag containers. Quantitation limits in air were estimated. Potential interferences from volatile hydrocarbons, such as toluene and heptane, were evaluated. The effect of humidity was studied also. The performance of the new devices was evaluated in the laboratory by spiking soil samples and monitoring headspace for halogenated VOCs. A draft concept of the steps for a new analytical method was outlined. The results of the first year effort show that both devices show potential utility for future analytical method development work towards the goal of developing a portable test kit for screening halogenated VOCs in the field.

Polycyclic’ Aromatic Hydrocarbon Induced Intracellular Signaling and Lymphocyte Apoptosis

DEFF Research Database (Denmark)

Schneider, Alexander M.

The aryl hydrocarbon (dioxin) receptor (AhR) is a transcription factor possessing high affinity to potent environmental pollutants, polycyclic aromatic hydrocarbons (PAH) and related halogenated hydrocarbons (e.g. dioxins). Numerous research attribute toxicity of these compounds to the receptor...

Limitations of the toxic equivalency factor (TEF) approach for risk assessment of halogenated aromatic hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Safe, S. [Texas A and M Univ., College Station, TX (United States). Dept. of Veterinary Physiology and Pharmacology

1995-12-31

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) and related halogenated aromatic hydrocarbons (HAHs) are present as complex mixtures of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and biphenyls (PCBs) in most environmental matrices. Risk management of these mixtures utilize the toxic equivalency factor (TEF) approach in which the TCDD (dioxin) or toxic equivalents of a mixture is a summation of the congener concentration (Ci) times TEF{sub i} (potency relative to TCDD) where. TEQ{sub mixture} = {Sigma}[Cil] {times} TEF{sub i}. TEQs are determined only for those HAHs which are aryl hydrocarbon (Ah) receptor agonists and this approach assumes that the toxic or biochemical effects of individual compounds in a mixture are additive. Several in vivo and in vitro laboratory and field studies with different HAH mixtures have been utilized to validate the TEF approach. For some responses, the calculated toxicities of PCDD/PCDF and PCB mixtures predict the observed toxic potencies. However, for fetal cleft palate and immunotoxicity in mice, nonadditive (antagonistic) responses are observed using complex PCB mixtures or binary mixtures containing an Ah receptor agonist with 2,2{prime},4,4{prime},5,5{prime}-hexachlorobiphenyl (PCB153). The potential interactive effects of PCBs and other dietary Ah receptor antagonist suggest that the TEF approach for risk management of HAHs requires further refinement and should be used selectively.

Clam bioaccumulation of Alkylphenols and Polyciclic aromatic hydrocarbons in the Venice lagoon under different pressures.

Science.gov (United States)

Ademollo, N; Patrolecco, L; Matozzo, V; Marin, M G; Valsecchi, S; Polesello, S

2017-11-15

Biota-Sediment Accumulation Factors (BSAFs) of nonylphenols (NPs) and polycyclic aromatic hydrocarbons (PAHs) in Ruditapes philippinarum from the Venice Lagoon (Italy) were determined with the aim to verify whether the routine biomonitoring studies are reliable in contaminated sites. Clams and sediments were collected in field campaigns (October 2003 to June 2004) in three sites of the Venice Lagoon. Results showed that Marghera and Campalto sediments were more contaminated by NPs and PAHs than Poveglia. Different trends were observed in the contamination of clams with the highest BSAFs found at Poveglia. BSAF trend appeared to be inversely related to the contaminant pressure on the sites. These results suggest that clam bioaccumulation is not always representative of the chemical pressure on aquatic biota. The direct correlation between sediment and biota concentrations in contaminated sites can be lost as a function of the site-specific conditions such as sediment toxicity and food availability. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isostructurality and non-isostructurality in the series of halogenated organic crystal substances. The structure of Hal-aggregates

International Nuclear Information System (INIS)

Grineva, O.V.; Zorkij, P.M.

2001-01-01

Local characteristics and the type of intermolecular Hal-aggregates (ensembles of contacting halogen atoms of adjacent molecules) present in chemically similar halogenated crystal substances, differing only in the nature of Hal atoms, are compared. 23 series of halogenated hydrocarbons, including 57 crystal structures were considered. A clearly pronounced specificity of Hal-aggregates for compounds with a low and intermediate content of halogen was revealed. It was found that, as a rule, coordination number of Hal atom by Hal adjacent atoms increases in the series F-Cl-Br-I [ru

Identification and Characterisation of Major Hydrocarbons in ...

African Journals Online (AJOL)

Identification and Characterisation of Major Hydrocarbons in Thermally Degraded Low Density Polyethylene Films. ... There were alkanes, alkenes, halogenated alkanes, and very few aromatics in the liquid product and, the hydrocarbons were observed to range between C10 - C27. The FTIR and GC-MS results show the ...

Biological regeneration of carrier material for the adsorption of halogen hydrocarbons in plants for cleaning up contaminated groundwater. Final report

International Nuclear Information System (INIS)

Ressel, K.

1993-06-01

Halogen hydrocarbons and above all chlorinated hydrocarbons are widespread harmful substances in soils and in groundwater. When cleaning up groundwater contamination, the contaminants are brought into the gas phase by strip processes. From the gas phase, the contaminants can be adsorbed on different carrier materials, mostly active carbon. One was searching for ways to regenerate this adsorption material. The mixed culture from a sea sediment most suitable for the decomposition of chlorinated hydrocarbons was optimized regarding its decomposition performance and was later used on the technical scale. In the decomposition experiments on the large technical scale, the cultures were lodged on filling bodies which has a much higher amount of gaps. In this case, an optimum supply of the micro-organisms with oxygen and methane is guaranteed, which is used as co-substrate. No intermediate product was found in a gas chromatography examination. The biologically occupied stage is situated between a desorption column and the active carbon filters, and reduces the load of harmful substances which can no longer be brought into the gas phase by stripping out. This has the advantage that it can be integrated in existing plants and can be adapted to any case of contamination by lodging adapted micro-organisms on it. The basis for each application must be separately researched. (orig.) [de

Bioaccumulation of organic micropollutants in different aquatic organisms. Sublethal toxic effects on fish

NARCIS (Netherlands)

van der Oost, Ron; Heida, Henk; Opperhuizen, Antoon; Vermeulen, Nico P E

1991-01-01

Bioaccumulation of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) was investigated in plankton, crustaceans, and fish from two relatively small Amsterdam lakes, with different levels of contamination. Ratios between contaminant

[Pollution of Halogenated Polycyclic Aromatic Hydrocarbons in Atmospheric Particulate Matters of Shenzhen].

Science.gov (United States)

Sun, Jian-lin; Chang, Wen-jing; Chen, Zheng-xia; Zeng, Hui

2015-05-01

Concentrations of halogenated polycyclic aromatic hydrocarbons ( HPAHs) in atmospheric PM10 and PM2.5 samples collected from Shenzhen were determined using GC-MS. Total concentrations of nine HPAHs in atmospheric PM10 and PM2.5 samples ranged from 118 to 1,476 pg · m(-3) and 89 to 407 pg · m(-3), respectively. In PM10 and PM(2.5) samples, the concentration of 9-BrAnt was the highest, followed by 7-BrBaA and 9, 10-Br2Ant. Seasonal levels of total HPAHs in atmospheric PM10 and PM2.5 samples in Shenzhen decreased in the following order: winter > autumn > spring > summer, whereas concentrations of individual HPAHs showed different seasonal levels. Meteorological conditions, including temperature, precipitation, and relative humidity, might be important factors affecting the seasonal levels of HPAHs in atmospheric PM10 and PM2.5 In addition, there were significant correlations between concentrations of HPAHs and parent PAHs. Finally, the toxic equivalency quotients (TEQs) of HPAHs were estimated. The TEQs of HPAHs in atmospheric PM10 and PM2.5 samples ranged from 17.6 to 86.2 pg · m(-3) and 14.6 to 70.4 pg · m(-3), respectively. Among individual HPAHs, 7-BrBaA contributed greatly to the total TEQs of HPAHs. Our results indicated that the total TEQs of HPAHs were lower than parent PAHs in atmospheric PM10 and PM2.5 samples in Shenzhen.

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15-December 31, 1984

International Nuclear Information System (INIS)

1985-01-01

Energetic halogen atoms or ions, activated by various nuclear transformations are studied in gas, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and liquid and solid aqueous solutions of biomolecular and organic solutes in order to understand better the mechanisms and dynamics of high energy monovalent species. The experimental program and its goals remain the same, consisting of four interrelated areas: (1) The stereochemistry of energetic 18 F, /sup 34m/Cl, and 38 Cl substitution reactions with chiral molecules in the gas and condensed phase is studied. (2) The gas to condensed state transition in halogen high energy chemistry, involving energetic chlorine, bromine, and iodine reactions in halomethanes, saturated and unsaturated hydrocarbons and aqueous solutions of biomolecules and alkyl halides is being investigated in more detail. Current attention is given to defining the nature of the enhancement yields in the condensed phase. Specifically, energetic halogen reactions in liquid and frozen aqueous solutions or organic and biomolecular solutes are studied. (3) Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular and organic solutes in liquid and frozen aqueous solutions are being studied in an attempt to learn more about the activation events in the condensed phase. (4) The applications of hot chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Current attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as site indicators in liquid and frozen aqueous solutions of halogenated bases and nucleosides are currently being developed. 14 references

Enhanced metabolism of halogenated hydrocarbons in transgenic plants containing mammalian cytochrome P450 2E1

Science.gov (United States)

Lafferty Doty, Sharon; Shang, Tanya Q.; Wilson, Angela M.; Tangen, Jeff; Westergreen, Aram D.; Newman, Lee A.; Strand, Stuart E.; Gordon, Milton P.

2000-06-01

Chlorinated solvents, especially trichloroethylene (TCE), are the most widespread groundwater contaminants in the United States. Existing methods of pumping and treating are expensive and laborious. Phytoremediation, the use of plants for remediation of soil and groundwater pollution, is less expensive and has low maintenance; however, it requires large land areas and there are a limited number of suitable plants that are known to combine adaptation to a particular environment with efficient metabolism of the contaminant. In this work, we have engineered plants with a profound increase in metabolism of the most common contaminant, TCE, by introducing the mammalian cytochrome P450 2E1. This enzyme oxidizes a wide range of important pollutants, including TCE, ethylene dibromide, carbon tetrachloride, chloroform, and vinyl chloride. The transgenic plants had a dramatic enhancement in metabolism of TCE of up to 640-fold as compared with null vector control plants. The transgenic plants also showed an increased uptake and debromination of ethylene dibromide. Therefore, transgenic plants with this enzyme could be used for more efficient remediation of many sites contaminated with halogenated hydrocarbons.

On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons

Science.gov (United States)

Mitropoulos, A. C.; Stefanopoulos, K. L.; Favvas, E. P.; Vansant, E.; Hankins, N. P.

2015-06-01

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of ‘ink-bottle’ pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary.

Catalyst for hydrocarbon conversion

International Nuclear Information System (INIS)

Duhaut, P.; Miquel, J.

1975-01-01

A description is given for a catalyst and process for hydrocarbon conversions, e.g., reforming. The catalyst contains an alumina carrier, platinum, iridium, at least one metal selected from uranium, vanadium, and gallium, and optionally halogen in the form of metal halide of one of the aforesaid components. (U.S.)

Process for separating liquid hydrocarbons from waxes

Energy Technology Data Exchange (ETDEWEB)

Sowa, F J

1948-03-08

A process is described for the separation of liquid hydrocarbons from waxes comprising adding to a mixture of liquid hydrocarbons and waxes a sufficient quantity of an organo-silicon compound to cause the separation of the hydrocarbon and wax. The organo-silicon compounds are selected from the class of organic silicanes and their hydrolysis products and polymers. The silicanes have the formula R/sub y/SiX/sub z/, in which R is a saturated or unsaturated hydrocarbon radical, X is a halogen or another hydrocarbon radical or an -OR group, y has a value 1, 2, or 3 and z has a value 1, 2, or 3.

Tropospheric Halogen Chemistry

Science.gov (United States)

von Glasow, R.; Crutzen, P. J.

2003-12-01

Halogens are very reactive chemicals that are known to play an important role in anthropogenic stratospheric ozone depletion chemistry, first recognized by Molina and Rowland (1974). However, they also affect the chemistry of the troposphere. They are of special interest because they are involved in many reaction cycles that can affect the oxidation power of the atmosphere indirectly by influencing the main oxidants O3 and its photolysis product OH and directly, e.g., by reactions of the Cl radical with hydrocarbons (e.g., CH4).Already by the middle of the nineteenth century, Marchand (1852) reported the presence of bromine and iodine in rain and other natural waters. He also mentions the benefits of iodine in drinking water through the prevention of goitres and cretinism. In a prophetic monograph "Air and Rain: The Beginnings of a Chemical Climatology," Smith (1872) describes measurements of chloride in rain water, which he states to originate partly from the oceans by a process that he compares with the bursting of "soap bubbles" which produces "small vehicles" that transfer small spray droplets of seawater to the air. From deviations of the sulfate-to-chloride ratio in coastal rain compared to seawater, Smith concluded that chemical processes occur once the particles are airborne.For almost a century thereafter, however, atmospheric halogens received little attention. One exception was the work by Cauer (1939), who reported that iodine pollution has been significant in Western and Central Europe due to the inefficient burning of seaweed, causing mean gas phase atmospheric concentrations as high as or greater than 0.5 μg m-3. In his classical textbook Air Chemistry and Radioactivity, Junge (1963) devoted less than three pages to halogen gas phase chemistry, discussing chlorine and iodine. As reviewed by Eriksson (1959a, b), the main atmospheric source of halogens is sea salt, derived from the bursting of bubbles of air which are produced by ocean waves and other

Chlorine dioxide as phenol and H2S scavenger - formation of halogenated phenols and subsequent environmental risk

Energy Technology Data Exchange (ETDEWEB)

Melbye, Alf G.; Faksness, Liv-Guri; Knudsen, Boerre Leif

2006-03-15

Formation of halogenated phenols as side products from treatment of produced water with aqueous chlorine dioxide has been investigated. The literature describes formation of halogenated hydrocarbons in effluent treatment using chlorine, hypochlorite and chlorine dioxide. A new chlorine dioxide product, originally intended as a H2S scavenger in the oil and gas industry, has been tested both as a phenol scavenger and H2S-scavenger for produced water applications. The concern about the possible formation of halogenated by-products initiated laboratory testing of chlorine dioxide as phenol and H2S scavenger for produced water applications. The tests also included synthetic matrixes containing phenols, and the tests show that halogenated phenols, mainly brominated species, are found in produced water after treatment with chlorine dioxide. Due to potential environmental risk from halogenated organic contaminants, the use of chlorine dioxide as phenol and H2S scavenger is not recommended. (Author)

Bioaccumulation and biomagnification of classical flame retardants, related halogenated natural compounds and alternative flame retardants in three delphinids from Southern European waters

International Nuclear Information System (INIS)

Barón, E.; Giménez, J.; Verborgh, P.; Gauffier, P.; De Stephanis, R.; Eljarrat, E.; 2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, 17003 Girona (Spain))" data-affiliation=" (Institute of Environmental Assessment and Water Research Studies (IDAEA), Spanish Council for Scientific Research (CSIC), Jordi Girona 18-26, 08034 Barcelona (Spain); Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park of the University of Girona, Emili Grahit 101, 17003 Girona (Spain))" >Barceló, D.

2015-01-01

Occurrence and behaviour of classical (PBDEs) and alternative (HNs, HBB, PBEB, DBDPE and HBCD) flame retardants, together with naturally produced MeO-PBDEs, were studied in short-beaked common dolphin (Delphinus delphis), bottlenose dolphin (Tursiops truncatus) and long-finned pilot whale (Globicephala melas) in two sampling locations from Southern European waters. PBDEs, Dec 602, Dec 603, DP, α-HBCD and two MeO-PBDEs were detected in all three species. ∑PBDEs were between 17 and 2680 ng/g lw; ∑HNs were between 1.1 and 59 ng/g lw; α-HBCD levels ranged between 3.2 and 641 ng/g lw; ∑MeO-PBDEs were between 34 and 1966 ng/g lw. Bottlenose dolphins were the most contaminated species and some individuals could present health risk for endocrine disruption since levels found were above the reported threshold (1500 ng/g lw). Stable isotope analysis was used to evaluate the biomagnification capacity of these compounds. PBDEs, MeO-PBDEs and Dec 602 showed a significant positive correlation with trophic position. - Highlights: • Several FRs were detected in three dolphin species from Southern European waters. • Concentrations of classical FRs were higher than concentrations of alternative FRs. • MeO-PBDE concentrations were generally similar to PBDE concentrations. • Evidence of biomagnification capacity of some FRs was observed. • Some individuals were above the threshold level associated to endocrine disruption. - Bioaccumulation and biomagnification of halogenated compounds in dolphins

Effects of Crude Oil Exposure on Bioaccumulation of Polycyclic Aromatic Hydrocarbons and Survival of Adult and Larval Stages of Gelatinous Zooplankton

Science.gov (United States)

Almeda, Rodrigo; Wambaugh, Zoe; Chai, Chao; Wang, Zucheng; Liu, Zhanfei; Buskey, Edward J.

2013-01-01

Gelatinous zooplankton play an important role in marine food webs both as major consumers of metazooplankton and as prey of apex predators (e.g., tuna, sunfish, sea turtles). However, little is known about the effects of crude oil spills on these important components of planktonic communities. We determined the effects of Louisiana light sweet crude oil exposure on survival and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in adult stages of the scyphozoans Pelagia noctiluca and Aurelia aurita and the ctenophore Mnemiopsis leidyi, and on survival of ephyra larvae of A. aurita and cydippid larvae of M. leidyi, in the laboratory. Adult P. noctiluca showed 100% mortality at oil concentration ≥20 µL L−1 after 16 h. In contrast, low or non-lethal effects were observed on adult stages of A. aurita and M. leidyi exposed at oil concentration ≤25 µL L−1 after 6 days. Survival of ephyra and cydippid larva decreased with increasing crude oil concentration and exposition time. The median lethal concentration (LC50) for ephyra larvae ranged from 14.41 to 0.15 µL L−1 after 1 and 3 days, respectively. LC50 for cydippid larvae ranged from 14.52 to 8.94 µL L−1 after 3 and 6 days, respectively. We observed selective bioaccumulation of chrysene, phenanthrene and pyrene in A. aurita and chrysene, pyrene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, and benzo[a]anthracene in M. leidyi. Overall, our results indicate that (1) A. aurita and M. leidyi adults had a high tolerance to crude oil exposure compared to other zooplankton, whereas P. noctiluca was highly sensitive to crude oil, (2) larval stages of gelatinous zooplankton were more sensitive to crude oil than adult stages, and (3) some of the most toxic PAHs of crude oil can be bioaccumulated in gelatinous zooplankton and potentially be transferred up the food web and contaminate apex predators. PMID:24116004

Flue gas corrosion through halogen compounds in fuel gas

Energy Technology Data Exchange (ETDEWEB)

Eisenmann, R

1987-04-01

The halogens of chlorine and fluorine greatly influence the corrosion speed of metal materials. If small quantities of chlorinated and/or fluorinated hydrocarbons are present in fuel gas like in landfill gas, they must not result in enhanced corrosion of gas appliances. Data from literature and the initial results of tests run by the author indicate that quantities at about 10 mg/cbm (in terms of chlorine) can be assumed not to cause any noticeable acceleration of corrosion speed.

Low molecular weight halogenated hydrocarbons (LMHHs) in Mediterranean sea water: Preliminary observations

International Nuclear Information System (INIS)

Elder, D.L.; Villeneuve, J.P.; Harvey, G.R.

1976-01-01

Halogenated organic compounds containing 1-3 carbon atoms are among the most extensively produced synthetic chemicals. Within this group of compounds are solvents such as chloroform, carbon tetrachloride, trichloroethane and the chlorofluoro carbons or freons which are used as refrigerants and aerosol sprays. Once produced many of these compounds are eventually released to the environment

Halogenated fatty acids

DEFF Research Database (Denmark)

Mu, Huiling; Sundin, Peter; Wesén, Clas

1997-01-01

Halogenated fatty acids are the major contributors to organohalogen compounds in lipids of marine mammals, fish, and bivalves. For the initial characterization of these recently noticed compounds, a determination of the halogen concentration has usually been combined with some lipid isolation......), atomic emission spectrometry, and mass spectrometry. For most environmental samples, chlorinated FAMEs must be enriched prior to GC. ELCD is a useful detection method for indicating halogenated FAMEs in the chromatograms, and tentative identification of the halogenated species can be obtained...

Bio-accumulation of Polycyclic Aromatic Hydrocarbons in the Grey Mangrove (Avicennia marina along Arabian Gulf, Saudi Coast

Directory of Open Access Journals (Sweden)

Orif Mohammed

2018-04-01

Full Text Available The Arabian Gulf is considered as one of the most important sources for the crude oil all over the world. Due to the vast oil exploration and exploitation, huge amounts of organic pollutants infiltrate to the gulf. An important class of organic pollutants is polycyclic aromatic hydrocarbons (PAHs. One of the marine habitats in Arabian Gulf area is the mangrove stands, that are undoubtedly impacted by all anthropogenic factors like oil industries and sewage discharge. In the monitoring framework for mangrove ecosystem along Saudi coasts, nine mangrove stands were examined for the accumulation of PAHs in the Arabian Gulf coast. PAHs were measured using Gas Chromatography-Mass Spectrometry. The mean values detected for total PAHs in mangrove sediments, roots and leaf were 105.39, 680.0 and 282.4 ng/g, respectively. The trend of total PAHs concentrations in all sites showed the descending order: roots > leaf > sediments. Despite the sandy nature and low organic carbon contents of the mangrove sediments, moderate values of PAHs were detected in the major sites. PAH bio-accumulation factors for roots are higher than that in leaf. The diagnostic ratios revealed that the sources of PAHs are mainly pyrogenic, except for Damam and Damam Port that were found to be petrogenic.

Volatile halogenated hydrocarbons over the western Pacific between 43° and 4°N

Science.gov (United States)

Quack, Birgit; Suess, Erwin

1999-01-01

A spectrum of halogenated hydrocarbon compounds in marine air masses were surveyed over an area in the western Pacific between 43°N, 150°E and 4°N, 113°E in September 1994. The ship's track between northern Japan and Singapore traversed three climatic zones of the northern hemisphere. Recently polluted air, clean marine air derived from the central Pacific Ocean from different latitudes, and marine air from the Indonesian archipelago were collected. Tetrachloroethene and trichloroethene of anthropogenic origin, brominated halocarbons as tribromomethane, dibromochloromethane and bromodichloromethane of anthropogenic and natural sources, and other trace gases were measured in the air samples. Very sparse data on the distribution of these compounds exist for the western Pacific atmosphere. The distribution patterns of the compounds were related to synoptic-scale meteorology, spatial conditions, and origin of the air masses. Anthropogenic and natural sources for both chlorinated and brominated substances were identified. Tetrachloroethene and trichloroethene concentrations and their ratios identify anthropogenic sources. Their mixing ratios were quite low compared to previously published data. They are in agreement with expected low concentrations of photochemically active substances during autumn, with an overall decrease in concentrations toward lower latitudes, and with a decrease of emissions during recent years. Strong evidence for a natural source of trichloroethene was discovered in the tropical region. The concentrations of naturally released brominated species were high compared to other measurements over the Pacific. Gradients toward the coasts and elevated concentrations in air masses influenced by coastal emissions point to significant coastal sources of these compounds. The trace gas composition of anthropogenic and natural compounds clearly identified the air masses which were traversed during the cruise.

Hydrocarbon conversion with an attenuated superactive multimetallic catalytic composite

International Nuclear Information System (INIS)

Antos, G.J.

1981-01-01

Hydrocarbons are converted by contacting them at hydrocarbon conversion conditions with a novel attenuated superactive multimetallic catalytic composite comprising a combination of a catalytically effective amount of a pyrolyzed rhenium carbonyl component with a porous carrier material containing a uniform dispersion of catalytically effective amounts of a platinum group component, which is maintained in the elemental metallic state during the incorporation and pyrolysis of the rhenium carbonyl component, and of an iron component. In a highly preferred embodiment, this novel catalytic composite also contains a catalytically effective amount of a halogen component. The platinum group component, pyrolyzed rhenium carbonyl component, iron component and optional halogen component are preferably present in the multimetallic catalytic composite in amounts, calculated on an elemental basis, corresponding to about 0.01 to about 2 wt. % platinum group metal, about 0.01 to about 5 wt. % rhenium, about 0.005 to about 4 wt. % iron and about 0.1 to about 5 wt. % halogen. A key feature associated with the preparation of the subject catalytic composite is reaction of a rhenium carbonyl complex with a porous carrier material containing a uniform dispersion of an iron component and of a platinum group component maintained in the elemental state, whereby the interaction of the rhenium moiety with the platinum group moiety is maximized due to the platinophilic (i.e., platinum-seeking) propensities of the carbon monoxide ligands associated with the rhenium reagent. A specific example of the type of hydrocarbon conversion process disclosed herein is a process for the catalytic reforming of a low octane gasoline fraction wherein the gasoline fraction and a hydrogen stream are contacted with the attenuated superactive multimetallic catalytic composite at reforming conditions

Apparatus for washing out halogens

Energy Technology Data Exchange (ETDEWEB)

Pier, M; Hahn, J; Kroenig, W

1941-03-26

An apparatus is described for washing out of halogens and the like or liquid halogen compounds from the products, which are formed on pressure hydrogenation or splitting of carbon-containing material in the presence of halogens or halogen compounds, consisting of a washing apparatus installed between the reaction vessel and the hot separator, which is inclined in relatively small space for steam regulation and contains, with the steam, arranged baffles, especially spirals.

Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment?

Science.gov (United States)

Hai, Faisal I; Tadkaew, Nichanan; McDonald, James A; Khan, Stuart J; Nghiem, Long D

2011-05-01

This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable. Copyright © 2011 Elsevier Ltd. All rights reserved.

C2-C10 hydrocarbon emissions from a boreal wetland and forest floor

Directory of Open Access Journals (Sweden)

H. Hellén

2006-01-01

Full Text Available Emissions of various C2-C10 hydrocarbons (VOCs and halogenated hydrocarbons (VHOCs from a boreal wetland and a Scots pine forest floor in south-western Finland were measured by the static chamber technique. Isoprene was the main non-methane hydrocarbon emitted by the wetland, but small emissions of ethene, propane, propene, 1-butene, 2-methylpropene, butane, pentane and hexane were also detected. The isoprene emission from the wetland was observed to follow the commonly-used isoprene emission algorithm. The mean emission potential of isoprene was 224 µg m-2 h-1 for the whole season. This is lower than the emission potentials published earlier; that is probably at least partly due to the cold and cloudy weather during the measurements. No emissions were detected of monoterpenes or halogenated hydrocarbons from the wetland. The highest hydrocarbon emissions from the Scots pine forest floor were measured in spring and autumn. However, only a few measurements were conducted during summer. The main compounds emitted were monoterpenes. Isoprene emissions were negligible. The total monoterpene emission rates varied from zero to 373 µg m-2 h-1. The results indicated that decaying plant litter may be the source for these emissions. Small emissions of chloroform (100-800 ng m-2 h-1, ethene, propane, propene, 2-methylpropene, cis-2-butene, pentane, hexane and heptane were detected. Comparison with Scots pine emissions showed that the forest floor may be an important monoterpene source, especially in spring.

Halogenated and parent polycyclic aromatic hydrocarbons in vegetables: Levels, dietary intakes, and health risk assessments.

Science.gov (United States)

Wang, Li; Li, Chunmei; Jiao, Bining; Li, Qiwan; Su, Hang; Wang, Jing; Jin, Fen

2018-03-01

Halogenated polycyclic aromatic hydrocarbons (HPAHs) are attracting increasing concern because of their greater toxicity than their corresponding parent PAHs. However, human exposure to HPAHs via food consumption is not fully understood. In this study, daily intake via vegetable ingestion of 11 HPAHs and 16 PAHs and subsequent cancer risk were assessed for population in Beijing. A total of 80 vegetable samples were purchased from markets, including five leafy vegetables and three root vegetables. The concentrations of total HPAHs (∑HPAHs) were 0.357-0.874ng/g in all vegetables, lower than that of total PAHs (∑PAHs, 10.6-47.4ng/g). ∑HPAHs and ∑PAHs concentrations in leafy vegetables were higher than those in root vegetables, suggesting that the atmospheric deposition might be the dominant source of PAHs and HPAHs in leafy vegetables. Among the HPAH congeners, 2-BrFle and 9-ClFle were the predominant compounds and frequently detected in the vegetable samples. HPAHs and PAHs were also found in certificated vegetables at the concentrations of 0.466-0.751ng/g and 10.6-38.9ng/g, respectively, which were lower than those in non-certificated vegetables except for spinach. For leafy vegetables from local farms, the ∑PAHs and ∑HPAHs levels in the rape and Chinese cabbage samples significantly decreased with increasing the distance away from the incineration plant. The incremental lifetime cancer risks of HPAHs were below the acceptable risk level (10 -6 ), suggesting that there might be little or no risk to consumers from these compounds in vegetables. For all population groups, children were the most sensitive population to PAHs and HPAHs, and their health issues should be paid more attention. Copyright © 2017 Elsevier B.V. All rights reserved.

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1978--February 14, 1979

International Nuclear Information System (INIS)

Rack, E.P.

1979-02-01

High energy reactions of halogen atoms or ions, activated by nuclear transformations, were studied in gaseous, high pressure and condensed phase saturated and unsaturated hydrocarbons, halomethanes and other organic systems in order to better understand the mechanisms and dynamics of high energy monovalent species. The experimental and theoretical program consists of six interrelated areas: (1) the reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure and liquid systems; (2) the gas to condensed state transition in halogen high chemistry, involving bromine activated by the (n,γ) and (I.T.) processes in ethane was investigated in more detail; (3) systematics of halogen hot atom reactions. The reactions of 80 Br/sup m/, 80 Br, 82 Br/sup m/ + 82 Br, 82 Br, 128 I, 130 I, and 130 I/sup m/ + 130 I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators; (4) kinetic theory applications of high energy reactions and mathematical development of caging mechanisms were developed; (5) the sterochemistry of 38 Cl substitution reactions involving diastereomeric 1,2-dichloro-1,2-difluorethane in liquid mixtures was completed, suggesting that the stereochemical course of the substitution process is controlled by the properties of the solvent molecules; and (6) the applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems was continued, especially involving aluminum and vanadium trace determinations

Halogenated arsenenes as Dirac materials

International Nuclear Information System (INIS)

Tang, Wencheng; Sun, Minglei; Ren, Qingqiang; Wang, Sake; Yu, Jin

2016-01-01

Highlights: • We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. • All fully-halogenated arsenene except As_2I_2 would spontaneously form and stable in defending the thermal fluctuation in room temperature. - Abstract: Arsenene is the graphene-like arsenic nanosheet, which has been predicted very recently [S. Zhang, Z. Yan, Y. Li, Z. Chen, and H. Zeng, Angewandte Chemie, 127 (2015) 3155–3158]. Using first-principles calculations, we systematically investigate the structures and electronic properties of fully-halogenated arsenenes. Formation energy analysis reveals that all the fully-halogenated arsenenes except iodinated arsenene are energetically favorable and could be synthesized. We have revealed the presence of Dirac cone in fully-halogenated arsenene compounds. They may have great potential applications in next generation of high-performance devices.

Dissociative Photoionization of 1-Halogenated Silacyclohexanes: Silicon Traps the Halogen.

Science.gov (United States)

Bodi, Andras; Sigurdardottir, Katrin Lilja; Kvaran, Ágúst; Bjornsson, Ragnar; Arnason, Ingvar

2016-11-23

The threshold photoelectron spectra and threshold photoionization mass spectra of 1-halogenated-1-silacyclohexanes, for the halogens X = F, Cl, Br, and I, have been obtained using synchrotron vacuum ultraviolet radiation and photoelectron photoion coincidence spectroscopy. As confirmed by a similar ionization onset and density functional theory molecular orbitals, the ionization to the ground state is dominated by electron removal from the silacyclohexane ring for X = F, Cl, and Br, and from the halogen lone pair for X = I. The breakdown diagrams show that the dissociative photoionization mechanism is also different for X = I. Whereas the parent ions decay by ethylene loss for X = F to Br in the low-energy regime, the iodine atom is lost for X = I. The first step is followed by a sequential ethylene loss at higher internal energies in each of the compounds. It is argued that the tendency of silicon to lower bond angles stabilizes the complex cation in which C 2 H 4 is η 2 -coordinated to it, and which precedes ethylene loss. Together with the relatively strong silicon-halogen bonds and the increased inductive effect of the silacyclohexane ring in stabilizing the cation, this explains the main differences observed in the fragmentation of the halogenated silacyclohexane and halogenated cyclohexane ions. The breakdown diagrams have been modeled taking into account slow dissociations at threshold and the resulting kinetic shift. The 0 K appearance energies have been obtained to within 0.08 eV for the ethylene loss for X = F to Br (10.56, 10.51, and 10.51 eV, respectively), the iodine atom loss for X = I (10.11 eV), the sequential ethylene loss for X = F to I (12.29, 12.01, 11.94, and 11.86 eV, respectively), and the minor channels of H loss for X = F (10.56 eV) and propylene loss in X = Cl (also at 10.56 eV). The appearance energies for the major channels likely correspond to the dissociative photoionization reaction energy.

Boiling points of halogenated ethanes: an explanatory model implicating weak intermolecular hydrogen-halogen bonding.

Science.gov (United States)

Beauchamp, Guy

2008-10-23

This study explores via structural clues the influence of weak intermolecular hydrogen-halogen bonds on the boiling point of halogenated ethanes. The plot of boiling points of 86 halogenated ethanes versus the molar refraction (linked to polarizability) reveals a series of straight lines, each corresponding to one of nine possible arrangements of hydrogen and halogen atoms on the two-carbon skeleton. A multiple linear regression model of the boiling points could be designed based on molar refraction and subgroup structure as independent variables (R(2) = 0.995, standard error of boiling point 4.2 degrees C). The model is discussed in view of the fact that molar refraction can account for approximately 83.0% of the observed variation in boiling point, while 16.5% could be ascribed to weak C-X...H-C intermolecular interactions. The difference in the observed boiling point of molecules having similar molar refraction values but differing in hydrogen-halogen intermolecular bonds can reach as much as 90 degrees C.

Hydrocarbon toxicity: an analysis of AAPCC TESS data.

Science.gov (United States)

Cobaugh, Daniel J; Seger, Donna L; Krenzelok, Edward P

2007-01-01

Human hydrocarbon exposures have the potential to cause significant morbidity and mortality. To determine which hydrocarbons were associated with the most severe adverse outcomes, human exposure data reported to American poison information centers were analyzed. Outcome data for single-substance, hydrocarbon exposures reported to the American Association of Poison Control Centers Toxic Exposure Surveillance System from 1994 through 2003 were analyzed. Only cases with definitive medical outcomes were included. Analyses were stratified by five age groups: 59 years. Hazard factors were determined by calculating the sum of the major effects and fatalities for each hydrocarbon category and dividing this by the total number of exposures for that category. To normalize the data, the overall rate of major effects and deaths for each age group was assigned hazard factor value of 1. Hydrocarbon categories with a HF of > or = 1.5 were included in the final analyses. Estimated rates of major effect and fatal outcomes (outcomes/1000 people) were also calculated. 318,939 exposures were analyzed. Exposures to benzene, toluene/xylene, halogenated hydrocarbons, kerosene and lamp oil resulted in the highest hazard factor values. These data demonstrate that hydrocarbons that are absorbed systemically and those with low viscosities are associated with higher hazard factors. The risks associated with hydrocarbons often implicated in abuse by older children and adolescents are also confirmed.

Evidence for Interfacial Halogen Bonding.

Science.gov (United States)

Swords, Wesley B; Simon, Sarah J C; Parlane, Fraser G L; Dean, Rebecca K; Kellett, Cameron W; Hu, Ke; Meyer, Gerald J; Berlinguette, Curtis P

2016-05-10

A homologous series of donor-π-acceptor dyes was synthesized, differing only in the identity of the halogen substituents about the triphenylamine (TPA; donor) portion of each molecule. Each Dye-X (X=F, Cl, Br, and I) was immobilized on a TiO2 surface to investigate how the halogen substituents affect the reaction between the light-induced charge-separated state, TiO2 (e(-) )/Dye-X(+) , with iodide in solution. Transient absorption spectroscopy showed progressively faster reactivity towards nucleophilic iodide with more polarizable halogen substituents: Dye-F < Dye-Cl < Dye-Br < Dye-I. Given that all other structural and electronic properties for the series are held at parity, with the exception of an increasingly larger electropositive σ-hole on the heavier halogens, the differences in dye regeneration kinetics for Dye-Cl, Dye-Br, and Dye-I are ascribed to the extent of halogen bonding with the nucleophilic solution species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrocarbons, PCBs and DDT in the NW Mediterranean deep-sea fish Mora moro

Science.gov (United States)

Solé, Montserrat; Porte, Cinta; Albaigés, Joan

2001-02-01

Data on aliphatic and polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and DDTs in the deep-sea fish Mora moro are reported in relation to the animal's weight/size and tissues (muscle, liver, digestive tube and gills). Fish samples were collected in the Gulf of Lions (NW Mediterranean) at an approximate depth of 1000 m. The concentrations of these organic pollutants followed the trend musclelipid content of the organs. No clear bioaccumulation dependence on fish weight/size was observed for gills, digestive tube and liver when the fat contents of these tissues were taken into account. However, the concentrations in muscle decreased with size, possibly implying a simple dilution effect by the increase of body weight. Hydrocarbons, and particularly PAHs, were strongly depleted in all tissues with respect to organochlorinated compounds if compared with the amounts present in bottom waters and sediment. Smaller specimens displayed for most pollutants qualitatively different patterns than larger fish, which could be attributed to their particular habitat/diet. The aliphatic hydrocarbon profiles suggested that Mora moro was exposed to a more predominant intake of biogenic rather than petrogenic hydrocarbons. The entrance and storage organs exhibited characteristic PAH and PCB distributions, reflecting different bioaccumulation and metabolic pathways. Compared with the profiles currently found in surface fish species, a relatively higher contribution of heavier components, namely hepta- and octochlorinated PCBs, and 4-6-ringed PAHs, was found in the deep-sea fish.

Halogen bond: a long overlooked interaction.

Science.gov (United States)

Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

2015-01-01

Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

International Nuclear Information System (INIS)

1981-02-01

The stereochemistry of high energy 18 F, /sup 34m/Cl, and 76 Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,γ) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1980-February 14, 1981

Energy Technology Data Exchange (ETDEWEB)

1981-02-01

The stereochemistry of high energy /sup 18/F, /sup 34m/Cl, and /sup 76/Br substitution reactions involving enantiomeric molecules in the gas and condensed phase is studied. The gas to condensed state transition in halogen high energy chemistry, involving chlorine, bromine, and iodine activated by the (n,..gamma..) and (I.T.) processes in halomethanes, saturated and unsaturated hydrocarbons is being investigated in more detail. Special attention is given to defining the nature of the enhancement yields in the condensed phase. High energy halogen reactions in liquid and frozen aqueous solutions of organic and biomolecular solutes are studied in an attempt to learn more about these reactions. The applications of high energy chemistry techniques and theory to neutron activation analysis of biological systems are being continued. Special attention is given to developing procedures for trace molecular determinations in biological systems. The applications of hot halogen atoms as indicators of solute-solute interactions in liquid and frozen aqueous solutions of halogenated bases and nucleosides are being developed. Experiments are designed to explain the mechanisms of the radioprotection offered biomolecular solutes trapped within the frozen ice lattice. Reactions of bromine and iodine activated by isomeric transition with halogenated biomolecular solutes in liquid and frozen aqueous solutions are studied. The high energy reactions of iodine with the isomers of pentene have been studied in low pressure gaseous systems employing additives and rare gas moderators and liquid systems. Reactivity of excited complex formation and structural effects of electrophilic iodine attack on the pi-bond systems are studied.

Oral frostbite injury from intentional abuse of a fluorinated hydrocarbon.

Science.gov (United States)

Kuspis, D A; Krenzelok, E P

1999-01-01

A serious but rarely reported complication of halogenated hydrocarbon inhalation abuse is severe mucosal frostbite. A 16-year-old male attempted to "get high" by inhaling airbrush propellant which contained 1,1-difluoroethane (CAS #75-376). The patient lost consciousness and upon awakening his lips and tongue were frozen. He suffered first- and second-degree burns of the larynx with vocal cord involvement and first-degree burns of the trachea, main stem bronchi, and esophagus. The oral cavity had second- and third-degree burns which required debridement. This case demonstrates the unusual but severe damage that can occur with the abuse of fluorinated hydrocarbons.

Bioaccumulation factors for radionuclides in freshwater biota

International Nuclear Information System (INIS)

Vanderploeg, H.A.; Parzyck, D.C.; Wilcox, W.H.; Kercher, J.R.; Kaye, S.V.

1975-11-01

This report analyzes over 200 carefully selected papers to provide concise data sets and methodology for estimation of bioaccumulation factors for tritium and isotopes of strontium, cesium, iodine, manganese, and cobalt in major biotic components of freshwater environments. Bioaccumulation factors of different tissues are distinguished where significant differences occur. Since conditions in the laboratory are often unnatural in terms of chemical and ecological relationships, this review was restricted as far as possible to bioaccumulation factors determined for natural systems. Because bioaccumulation factors were not available for some shorter-lived radionuclides, a methodology for converting bioaccumulation factors of stable isotopes to those of shorter-lived radionuclides was derived and utilized. The bioaccumulation factor for a radionuclide in a given organism or tissue may exhibit wide variations among bodies of water that are related to differences in ambient concentrations of stable-element and carrier-element analogues. To account for these variations, simple models are presented that relate bioaccumulation factors to stable-element and carrier-element concentrations in water. The effects of physicochemical form and other factors in causing deviations from these models are discussed. Bioaccumulation factor data are examined in the context of these models, and bioaccumulation factor relations for the selected radionuclides are presented

Halogen bonding in solution: thermodynamics and applications.

Science.gov (United States)

Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

2013-02-21

Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

Contribution to freshwater hydro systems multi pollution study: experimental study of metallic and organic micro-pollutants on radionuclides bioaccumulation by fish

International Nuclear Information System (INIS)

Ausseil, O.

2001-07-01

The influence of some metallic (cadmium, zinc) and organic (17 β-oestradiol, atrazine, polychlorinated biphenyls, polycyclic aromatic hydrocarbons) pollutants on artificial radionuclide ( 110m Ag, 134 Cs 57 Co) bioaccumulation characteristics by rainbow trout (Oncorhynchus mykiss) has been tested. The basic hypothesis of this work assume that the organisms' exposure to pollutants induces mechanisms of response which could modify radionuclides bioaccumulation characteristics. During the experiments, some biological and biochemical (bio-markers) analyses were performed in order to characterize the nature and the intensity of induced stress in the organisms. These experiments were performed in field and in laboratory. The results show that a cadmium and zinc exposure leads to the induction of systems against oxidative stress or systems implied in metal sequestration. It also leads to a strong reduction of 110m Ag (- 60 %) and 134 Cs (- 33 %) bioaccumulation. No effect has been observed on 57 Co bioaccumulation. For all tested organic compounds except for fluoranthene, exposure leads to an increase of radioactive caesium ( + 10 to 45 %) and cobalt (+ 30 to 60 %) quantities bio-accumulated by rainbow trout. Only 17 β-oestradiol exposure leads to an increase of 110m Ag uptake by rainbow trout. Some hypothesis concerning the involved mechanisms are proposed, and the main implications of this work in operational radioecology are discussed. (author)

Halogenation processes of secondary organic aerosol and implications on halogen release mechanisms

Directory of Open Access Journals (Sweden)

J. Ofner

2012-07-01

Full Text Available Reactive halogen species (RHS, such as X·, X₂ and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA and organic aerosol derived from biomass-burning (BBOA has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols.

Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy, changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.

Organic halogens in landfill leachates

DEFF Research Database (Denmark)

Grøn, C.; Christensen, J. B.; Jensen, Dorthe Lærke

2000-01-01

Using a group parameter, total organic halogens (TOX), high TOX concentrations were found in leachates and leachate contaminated groundwaters at two Danish mixed sanitary and hazardous waste sites. With commonly used screening procedures for organic contaminants, the individual halogenated organi...

A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

Directory of Open Access Journals (Sweden)

K. Toyota

2004-01-01

Full Text Available A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry to investigate photochemical interactions between volatile organic compounds (VOCs and reactive halogen species in the marine boundary layer (MBL. Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2 initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO and alkenes (especially C3H6 are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl

Studies on halogen quenching through the Stern-Volmer plot

International Nuclear Information System (INIS)

Takiue, Makoto; Ishikawa, Hiroaki.

1978-01-01

The quenching effect for halogenated benzenes, methanes and ethanes have been investigated. The halogen quenching was accurately measured using the internal conversion electrons emitted from 113 Sn-sup(113m)In. From the quenching constants determined by the Stern-Volmer plots with respect to various halogen quenchers, the following results have been obtained. (1) The quenching constants increase with the number of halogen substituents, so as linearly in halogenated benzenes and exponentially in halogenated methanes and ethanes. Even the isomers of halogenides have different quenching constants. (2) There is a linearity between logarithm of the quenching constant and a polarographic half-wave reduction potential. (3) Electron excitation provides larger quenching constants than UV excitation for halogenated methanes. Based on these results, the mechanism of halogen quenching have been discussed in connection with the exciplex formation. (auth.)

Independent Evolution of Six Families of Halogenating Enzymes.

Science.gov (United States)

Xu, Gangming; Wang, Bin-Gui

2016-01-01

Halogenated natural products are widespread in the environment, and the halogen atoms are typically vital to their bioactivities. Thus far, six families of halogenating enzymes have been identified: cofactor-free haloperoxidases (HPO), vanadium-dependent haloperoxidases (V-HPO), heme iron-dependent haloperoxidases (HI-HPO), non-heme iron-dependent halogenases (NI-HG), flavin-dependent halogenases (F-HG), and S-adenosyl-L-methionine (SAM)-dependent halogenases (S-HG). However, these halogenating enzymes with similar biological functions but distinct structures might have evolved independently. Phylogenetic and structural analyses suggest that the HPO, V-HPO, HI-HPO, NI-HG, F-HG, and S-HG enzyme families may have evolutionary relationships to the α/β hydrolases, acid phosphatases, peroxidases, chemotaxis phosphatases, oxidoreductases, and SAM hydroxide adenosyltransferases, respectively. These halogenating enzymes have established sequence homology, structural conservation, and mechanistic features within each family. Understanding the distinct evolutionary history of these halogenating enzymes will provide further insights into the study of their catalytic mechanisms and halogenation specificity.

Influence of dispersants on trophic transfer of petroleum hydrocarbons in a marine food chain

International Nuclear Information System (INIS)

Wolfe, M. F.; Schwartz, G. J. B.; Singaram, S.; Tjeerdema, R. S.

1997-01-01

Experiments were conducted to determine the impact of dispersing agents on petroleum hydrocarbons (PH) bioavailability and trophic transfer in primary levels of a marine food chain. Uptake, bioaccumulation and metabolic transformation of a model PH, ( 1 4C)naphthalene, were measured and compared with Prudhoe Bay Crude Oil (PBCO) dispersed with Corexit 9527, and undispersed preparations of PBCO. The model food chain consisted of a primary algae producer and a primary rotifer consumer. Results showed that uptake of naphthalene increased significantly in the presence of a dispersant in algae. A significant increase in uptake was also recorded in rotifers via trophic transfer. Trophic transfer played a significant, sometimes even dominant, role in uptake and bioaccumulation. 27 refs., 6 figs

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

Energy Technology Data Exchange (ETDEWEB)

Rack, E.P.

1980-02-01

The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, /sup 80/Br, /sup 82m/Br + /sup 82/Br, /sup 82/Br, /sup 82/Br, /sup 128/I, /sup 130/I, and /sup 130m/I + /sup 130/I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation to determine the role of hot atom kinetic energy, halogen atom, enantioner structure, steric effects and phase on the extent of substitution by retention of configuration or by Walden inversion. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace element determinations in biological systems was continued.

Biological regeneration of carrier material for the adsorption of halogen hydrocarbons in plants for cleaning up contaminated groundwater. Final report. Biologische Regeneration von Traegermaterial fuer die Adsorption von Halogenkohlenwasserstoffen in Anlagen zur Sanierung kontaminierten Grundwassers. Abschlussbericht

Energy Technology Data Exchange (ETDEWEB)

Ressel, K

1993-06-01

Halogen hydrocarbons and above all chlorinated hydrocarbons are widespread harmful substances in soils and in groundwater. When cleaning up groundwater contamination, the contaminants are brought into the gas phase by strip processes. From the gas phase, the contaminants can be adsorbed on different carrier materials, mostly active carbon. One was searching for ways to regenerate this adsorption material. The mixed culture from a sea sediment most suitable for the decomposition of chlorinated hydrocarbons was optimized regarding its decomposition performance and was later used on the technical scale. In the decomposition experiments on the large technical scale, the cultures were lodged on filling bodies which has a much higher amount of gaps. In this case, an optimum supply of the micro-organisms with oxygen and methane is guaranteed, which is used as co-substrate. No intermediate product was found in a gas chromatography examination. The biologically occupied stage is situated between a desorption column and the active carbon filters, and reduces the load of harmful substances which can no longer be brought into the gas phase by stripping out. This has the advantage that it can be integrated in existing plants and can be adapted to any case of contamination by lodging adapted micro-organisms on it. The basis for each application must be separately researched. (orig.)

Biochar reduces the bioaccumulation of PAHs from soil to carrot (Daucus carota L.) in the rhizosphere: A mechanism study.

Science.gov (United States)

Ni, Ni; Song, Yang; Shi, Renyong; Liu, Zongtang; Bian, Yongrong; Wang, Fang; Yang, Xinglun; Gu, Chenggang; Jiang, Xin

2017-12-01

The aim of this study was to reveal the mechanisms on how biochar reduces bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in tuberous vegetables. Corn straw-derived biochar pyrolyzed at 300°C (CB300) or bamboo-derived biochar pyrolyzed at 700°C (BB700) was amended into PAH-contaminated soil planted with carrot (Daucus carota L.). After 150days, 2% CB300 or 2% BB700 amendments significantly reduced the bioaccumulation of PAHs in carrot root (pbiochars both showed better effectiveness at reducing the bioavailability of high-molecular-weight PAHs than the low-molecular-weight PAHs in the rhizosphere. Therefore, the mechanisms on how biochar reduces the PAH uptake into carrot are dependent on the type of biochar (e.g., pyrolysis temperature and feedstock) and root presence. Copyright © 2017 Elsevier B.V. All rights reserved.

Passivation of quartz for halogen-containing light sources

Science.gov (United States)

Falkenstein, Zoran

1999-01-01

Lifetime of halogen containing VUV, UV, visible or IR light sources can be extended by passivating the quartz or glass gas containers with halogens prior to filling the quartz with the halogen and rare gas mixtures used to produce the light.

Bioaccumulation of gasoline in brackish green algae and popular clams

Directory of Open Access Journals (Sweden)

Gihan A. El-Shoubaky

2016-03-01

Full Text Available The green algae (Ulva lactuca and Enteromorpha clathrata and the clams (Tapes decussates and Venerupis aurea grow together in Timsah Lake, Suez Canal, Egypt. Our ultimate goal is to validate the bioaccumulation of gasoline in the marine organisms and their behavior after exposure to the pollutant, experimentally. These species were treated with a serial treatment of gasoline (1000, 4000, 16,000 and 64,000 μl in aquaria with brackish sea-water for 72 h. The tested green algae and clams were taken for an analysis of total hydrocarbon accumulation daily. The statistical analysis showed significant differences between the four species and also between the duration of exposure. The accumulation of gasoline in U. lactuca and E. clathrata reached their maximum after 48 h at 1000 and 4000 μl. The highest absorption was registered after 24 h only at 16,000 and at 64,000 μl. U. lactuca recorded complete mortality in 64,000 μl at 72 h whereas E. clathrata registered death at 48 h and 72 h in the same treatment. V. aurea was more sensitive than T. decussates. The accumulation of gasoline reached its maximum in V. aurea after only 24 h in the first treatment while it retarded to 48 h in T. decussates with a lesser accumulation. However, both clam species accumulated the highest amount of petroleum hydrocarbons during the first hour of exposure at the first treatment. In the third and fourth treatments, clams did not accumulate gasoline but began to dispose it from their tissues till it became less than that in the control. Mortality gradually increased with time in each treatment except the last one (64,000 μl in which 100% death of the specimens was observed. In general, the bioaccumulation of gasoline level was in a descending order as follows: U. lactuca > E. clathrata > V. aurea > T. decussates. Their behavior changed from accumulation to detoxification with time and with the increase in pollutant concentration. Generally, these

Petroleum hydrocarbon concentrations in eight mollusc species along Tamilnadu coast, Bay of Bengal, India.

Science.gov (United States)

Veerasingam, S; Venkatachalapathy, R; Sudhakar, S; Raja, P; Rajeswari, V

2011-01-01

Eight mollusc species and sediment samples collected from three different stations along Tamilnadu coast, Bay of Bengal, India were analysed for the levels of petroleum hydrocarbons to elucidate the status of the petroleum residues in mollusc meant for human consumption. The concentrations of petroleum hydrocarbons in sediments along Tamilnadu coast varied from 5.04-25.5 microg/g dw (dry weight). High concentration of petroleum hydrocarbons in the sediment of Uppanar estuary (25.5 +/- 1.45 microg/g dw) was perhaps land and marine based anthropogenic sources of this region. The petroleum hydrocarbon residues in eight mollusc species collected from Uppanar, Vellar and Coleroon estuaries varied between 2.44-6.04 microg/g ww (wet weight). Although the concentration of petroleum hydrocarbons in sediment of the Uppanar region was markedly higher than the background, the petroleum hydrocarbon residues in mollusc collected from Uppanar estuary did not suggest bioaccumulation. The results signified that industrial growth has affected the aquatic environments and regular monitoring will help to adopt stringent pollution control measures for better management of the aquatic region.

High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

International Nuclear Information System (INIS)

Rack, E.P.

1980-02-01

The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, 80 Br, /sup 82m/Br + 82 Br, 82 Br, 82 Br, 128 I, 130 I, and /sup 130m/I + 130 I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace elements and trace molecule determinations in biological systems was continued

METHOD FOR PRODUCING ISOTOPIC METHANES AND PARTIALLY HALOGENATED DERIVATIVES THEROF

Science.gov (United States)

Frazer, J.W.

1959-08-18

A method is given for producing isotopic methanes and/ or partially halogenated derivatives. Lithium hydride, deuteride, or tritide is reacted with a halogenated methane or with a halogenated methane in combination with free halogen. The process is conveniently carried out by passing a halogenated methane preferably at low pressures or in an admixture with an inert gas through a fixed bed of finely divided lithium hydride heated initially to temperatures of 100 to 200 deg C depending upon the halogenated methane used.

The effect of halogen hetero-atoms on the vapor pressures and thermodynamics of polycyclic aromatic compounds measured via the Knudsen effusion technique

International Nuclear Information System (INIS)

Goldfarb, Jillian L.; Suuberg, Eric M.

2008-01-01

Knowledge of vapor pressures of high molar mass organics is essential to predicting their behavior in combustion systems as well as their fate and transport within the environment. This study involved polycyclic aromatic compounds (PACs) containing halogen hetero-atoms, including bromine and chlorine. The vapor pressures of eight PACs, ranging in molar mass from (212 to 336) g . mol -1 , were measured using the isothermal Knudsen effusion technique over the temperature range of (296 to 408) K. These compounds included those with few or no data available in the literature, namely: 1,4-dibromonaphthalene, 5-bromoacenaphthene, 9-bromoanthracene, 1,5-dibromoanthracene, 9,10-dibromoanthracene, 2-chloroanthracene, 9,10-dichloroanthracene, and 1-bromopyrene. Enthalpies of sublimation of these compounds were determined via application of the Clausius-Clapeyron equation. An analysis is presented on the effects of the addition of halogen hetero-atoms to pure polycyclic aromatic hydrocarbons using these data as well as available literature data. As expected, the addition of halogens onto these PACs increases their enthalpies of sublimation and decreases their vapor pressures as compared to the parent compounds

Bioaccumulation of petroleum hydrocarbons in arctic amphipods in the oil development area of the Alaskan Beaufort Sea.

Science.gov (United States)

Neff, Jerry M; Durell, Gregory S

2012-04-01

An objective of a multiyear monitoring program, sponsored by the US Department of the Interior, Bureau of Ocean Energy Management was to examine temporal and spatial changes in chemical and biological characteristics of the Arctic marine environment resulting from offshore oil exploration and development activities in the development area of the Alaskan Beaufort Sea. To determine if petroleum hydrocarbons from offshore oil operations are entering the Beaufort Sea food web, we measured concentrations of hydrocarbons in tissues of amphipods, Anonyx nugax, sediments, Northstar crude oil, and coastal peat, collected between 1999 and 2006 throughout the development area. Mean concentrations of polycyclic aromatic hydrocarbons (PAH), saturated hydrocarbons (SHC), and sterane and triterpane petroleum biomarkers (StTr) were not significantly different in amphipods near the Northstar oil production facility, before and after it came on line in 2001, and in amphipods from elsewhere in the study area. Forensic analysis of the profiles (relative composition and concentrations) of the 3 hydrocarbon classes revealed that hydrocarbon compositions were different in amphipods, surface sediments where the amphipods were collected, Northstar crude oil, and peat from the deltas of 4 North Slope rivers. Amphipods and sediments contained a mixture of petrogenic, pyrogenic, and biogenic PAH. The SHC in amphipods were dominated by pristane derived from zooplankton, indicating that the SHC were primarily from the amphipod diet of zooplankton detritus. The petroleum biomarker StTr profiles did not resemble those in Northstar crude oil. The forensic analysis revealed that hydrocarbons in amphipod tissues were not from oil production at Northstar. Hydrocarbons in amphipod tissues were primarily from their diet and from river runoff and coastal erosion of natural diagenic and fossil terrestrial materials, including seep oils, kerogens, and peat. Offshore oil and gas exploration and development

Organic halogens in spruce forest throughfall

DEFF Research Database (Denmark)

Öberg, G.; Johansen, C.; Grøn, C.

1998-01-01

. No relationship between the position of the collectors and the forest edge or dominating wind-direction was found, suggesting that dry deposition was not a major source. The concentration of organic halogens was related to that of organic carbon and decreased from the tree-trunk and outwards. In addition......, the concentrations were higher during the growing season than during the dormant season. This indicates that the major part of the organic carbon and organic halogens in spruce forest throughfall originates from canopy leachates or other internal sources. (C) 1998 Elsevier Science Ltd.......Deposition of dissolved organic halogens by throughfall was determined in a small spruce forest site in Denmark (56 degrees 28'N, 8 degrees 24'E). The mean annual deposition of dissolved organic halogens was 377 g ha(-1)yr(-1), and larger than the general deposition by precipitation...

Arbuscular mycorrhizal wheat inoculation promotes alkane and polycyclic aromatic hydrocarbon biodegradation: Microcosm experiment on aged-contaminated soil

International Nuclear Information System (INIS)

Ingrid, Lenoir; Lounès-Hadj Sahraoui, Anissa; Frédéric, Laruelle; Yolande, Dalpé; Joël, Fontaine

2016-01-01

Very few studies reported the potential of arbuscular mycorrhizal symbiosis to dissipate hydrocarbons in aged polluted soils. The present work aims to study the efficiency of arbuscular mycorrhizal colonized wheat plants in the dissipation of alkanes and polycyclic aromatic hydrocarbons (PAHs). Our results demonstrated that the inoculation of wheat with Rhizophagus irregularis allowed a better dissipation of PAHs and alkanes after 16 weeks of culture by comparison to non-inoculated condition. These dissipations observed in the inoculated soil resulted from several processes: (i) a light adsorption on roots (0.5% for PAHs), (ii) a bioaccumulation in roots (5.7% for PAHs and 6.6% for alkanes), (iii) a transfer in shoots (0.4 for PAHs and 0.5% for alkanes) and mainly a biodegradation. Whereas PAHs and alkanes degradation rates were respectively estimated to 12 and 47% with non-inoculated wheat, their degradation rates reached 18 and 48% with inoculated wheat. The mycorrhizal inoculation induced an increase of Gram-positive and Gram-negative bacteria by 56 and 37% compared to the non-inoculated wheat. Moreover, an increase of peroxidase activity was assessed in mycorrhizal roots. Taken together, our findings suggested that mycorrhization led to a better hydrocarbon biodegradation in the aged-contaminated soil thanks to a stimulation of telluric bacteria and hydrocarbon metabolization in mycorrhizal roots. - Highlights: • Phytoremediation of aged-hydrocarbon polluted soils may be improved using arbuscular mycorrhizal fungi. • Inoculation of wheat with R. irregularis improved dissipation of PAH and alkanes. • Dissipation resulted from adsorption and bioaccumulation in wheat and mainly from biodegradation in soil. • Biodegradation was due to a stimulation of rhizosphere bacteria and an induction of root peroxidase. - Inoculation of wheat by an arbuscular mycorrhizal fungus improves biodegradation of alkanes and polycyclic aromatic hydrocarbons in an aged

Experimental and computational evidence of halogen bonds involving astatine

Science.gov (United States)

Guo, Ning; Maurice, Rémi; Teze, David; Graton, Jérôme; Champion, Julie; Montavon, Gilles; Galland, Nicolas

2018-03-01

The importance of halogen bonds—highly directional interactions between an electron-deficient σ-hole moiety in a halogenated compound and an acceptor such as a Lewis base—is being increasingly recognized in a wide variety of fields from biomedicinal chemistry to materials science. The heaviest halogens are known to form stronger halogen bonds, implying that if this trend continues down the periodic table, astatine should exhibit the highest halogen-bond donating ability. This may be mitigated, however, by the relativistic effects undergone by heavy elements, as illustrated by the metallic character of astatine. Here, the occurrence of halogen-bonding interactions involving astatine is experimentally evidenced. The complexation constants of astatine monoiodide with a series of organic ligands in cyclohexane solution were derived from distribution coefficient measurements and supported by relativistic quantum mechanical calculations. Taken together, the results show that astatine indeed behaves as a halogen-bond donor—a stronger one than iodine—owing to its much more electrophilic σ-hole.

Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

Science.gov (United States)

Oliveira, Vytor; Cremer, Dieter

2017-08-01

Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

Removal of Intermediate Aromatic Halogenated DBPs by Activated Carbon Adsorption: A New Approach to Controlling Halogenated DBPs in Chlorinated Drinking Water.

Science.gov (United States)

Jiang, Jingyi; Zhang, Xiangru; Zhu, Xiaohu; Li, Yu

2017-03-21

During chlorine disinfection of drinking water, chlorine may react with natural organic matter (NOM) and bromide ion in raw water to generate halogenated disinfection byproducts (DBPs). To mitigate adverse effects from DBP exposure, granular activated carbon (GAC) adsorption has been considered as one of the best available technologies for removing NOM (DBP precursor) in drinking water treatment. Recently, we have found that many aromatic halogenated DBPs form in chlorination, and they act as intermediate DBPs to decompose and form commonly known DBPs including trihalomethanes and haloacetic acids. In this work, we proposed a new approach to controlling drinking water halogenated DBPs by GAC adsorption of intermediate aromatic halogenated DBPs during chlorination, rather than by GAC adsorption of NOM prior to chlorination (i.e., traditional approach). Rapid small-scale column tests were used to simulate GAC adsorption in the new and traditional approaches. Significant reductions of aromatic halogenated DBPs were observed in the effluents with the new approach; the removals of total organic halogen, trihalomethanes, and haloacetic acids by the new approach always exceeded those by the traditional approach; and the effluents with the new approach were considerably less developmentally toxic than those with the traditional approach. Our findings indicate that the new approach is substantially more effective in controlling halogenated DBPs than the traditional approach.

The halogen bond: Nature and applications

Science.gov (United States)

Costa, Paulo J.

2017-10-01

The halogen bond, corresponding to an attractive interaction between an electrophilic region in a halogen (X) and a nucleophile (B) yielding a R-X⋯B contact, found applications in many fields such as supramolecular chemistry, crystal engineering, medicinal chemistry, and chemical biology. Their large range of applications also led to an increased interest in their study using computational methods aiming not only at understanding the phenomena at a fundamental level, but also to help in the interpretation of results and guide the experimental work. Herein, a succinct overview of the recent theoretical and experimental developments is given starting by discussing the nature of the halogen bond and the latest theoretical insights on this topic. Then, the effects of the surrounding environment on halogen bonds are presented followed by a presentation of the available method benchmarks. Finally, recent experimental applications where the contribution of computational chemistry was fundamental are discussed, thus highlighting the synergy between the lab and modeling techniques.

Bioaccumulation and subacute toxicity of mechanically and chemically dispersed heavy fuel oil in sea urchin (Glyptocidaris crenulari

Directory of Open Access Journals (Sweden)

Bailin Yang

2015-12-01

Full Text Available Oil spills have a disastrous ecological impact on ecosystems but few data are available for the effects of dispersed oil on benthic marine organisms. In order to provide information for assessment, we analysed the hydrocarbon compositions of the mechanically dispersed water accommodated fraction (MDWAF and the chemically dispersed water accommodated fraction (CDWAF of No. 120 fuel oil, their bioaccumulation, and DNA damage related to oil exposure, using the sea urchin as a sentinel organism. The results show that the concentration of polycyclic aromatic hydrocarbon in the tissues of sea urchin exposed to the CDWAF is higher than that of those exposed to the MDWAF. The single cell gel electrophoresis assay results also indicated higher DNA damage from exposure to the CDWAF of oil. Thus, dispersants should be applied with caution in oil spill accidents.

Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse.

Science.gov (United States)

Agarwal, Vinayak; Miles, Zachary D; Winter, Jaclyn M; Eustáquio, Alessandra S; El Gamal, Abrahim A; Moore, Bradley S

2017-04-26

Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C-H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature's halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

Molecular activation analysis for organo-halogen contaminants in yogurt

International Nuclear Information System (INIS)

Zhang Hong; Chai Zhifang

2004-01-01

The concentrations of total halogen (TX), extractable organo-halogen (EOX), extractable persistent organo-halogen (EPOX), organo-chlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in 18 different yogurt specimens of 14 brands from Beijing, Tianjin, Shanghai, Guangzhou and Shijiazhuang were determined by epithermal neutron activation analysis (ENAA), molecular activation analysis (MAA) and GC-Mass Spectrometry (GC-MS), respectively. The results indicated that the halogen in yogurt mainly existed as inorganic species and non-extractable organo-halogen compounds. About 1/3 to 1/4 of EOX was EPOX. Further, EOCl and EPOCl were the main organo-halogen species in yogurt. The average concentration of the unknown organo-chlorine was 96% of the EPOCl. HCHs and DDTs were still the main contaminants of OCPs in the yogurt of interest. Also, PCB202, PCB103 and PCB208 were the main contaminants of PCBs. (authors)

Halogens in chondritic meteorites and terrestrial accretion

Science.gov (United States)

Clay, Patricia L.; Burgess, Ray; Busemann, Henner; Ruzié-Hamilton, Lorraine; Joachim, Bastian; Day, James M. D.; Ballentine, Christopher J.

2017-11-01

Volatile element delivery and retention played a fundamental part in Earth’s formation and subsequent chemical differentiation. The heavy halogens—chlorine (Cl), bromine (Br) and iodine (I)—are key tracers of accretionary processes owing to their high volatility and incompatibility, but have low abundances in most geological and planetary materials. However, noble gas proxy isotopes produced during neutron irradiation provide a high-sensitivity tool for the determination of heavy halogen abundances. Using such isotopes, here we show that Cl, Br and I abundances in carbonaceous, enstatite, Rumuruti and primitive ordinary chondrites are about 6 times, 9 times and 15-37 times lower, respectively, than previously reported and usually accepted estimates. This is independent of the oxidation state or petrological type of the chondrites. The ratios Br/Cl and I/Cl in all studied chondrites show a limited range, indistinguishable from bulk silicate Earth estimates. Our results demonstrate that the halogen depletion of bulk silicate Earth relative to primitive meteorites is consistent with the depletion of lithophile elements of similar volatility. These results for carbonaceous chondrites reveal that late accretion, constrained to a maximum of 0.5 ± 0.2 per cent of Earth’s silicate mass, cannot solely account for present-day terrestrial halogen inventories. It is estimated that 80-90 per cent of heavy halogens are concentrated in Earth’s surface reservoirs and have not undergone the extreme early loss observed in atmosphere-forming elements. Therefore, in addition to late-stage terrestrial accretion of halogens and mantle degassing, which has removed less than half of Earth’s dissolved mantle gases, the efficient extraction of halogen-rich fluids from the solid Earth during the earliest stages of terrestrial differentiation is also required to explain the presence of these heavy halogens at the surface. The hydropilic nature of halogens, whereby they track

Organic halogen compounds in the environment

International Nuclear Information System (INIS)

1979-07-01

There are 20 research reports on selected problems concerning the analysis, the occurence, and the behaviour of a wide spectrum of organic halogen compounds. The work was carried out in the framework of the project 'Organic Halogen Compounds in the Environment', financed by the BMFT, between 1975 and 1978. (orig.) [de

Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

Science.gov (United States)

Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

2016-05-15

This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided. Copyright © 2016 Elsevier B.V. All rights reserved.

Process for removal of hydrogen halides or halogens from incinerator gas

Science.gov (United States)

Huang, H.S.; Sather, N.F.

1987-08-21

A process for reducing the amount of halogens and halogen acids in high temperature combustion gas and through their removal, the formation of halogenated organics at lower temperatures, with the reduction being carried out electrochemically by contacting the combustion gas with the negative electrode of an electrochemical cell and with the halogen and/or halogen acid being recovered at the positive electrode.

Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

Science.gov (United States)

Ford, Melissa Coates; Ho, P Shing

2016-03-10

The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

Ozone Depletion in Tropospheric Volcanic Plumes: From Halogen-Poor to Halogen-Rich Emissions

Directory of Open Access Journals (Sweden)

Tjarda J. Roberts

2018-02-01

Full Text Available Volcanic halogen emissions to the troposphere undergo a rapid plume chemistry that destroys ozone. Quantifying the impact of volcanic halogens on tropospheric ozone is challenging, only a few observations exist. This study presents measurements of ozone in volcanic plumes from Kīlauea (HI, USA, a low halogen emitter. The results are combined with published data from high halogen emitters (Mt Etna, Italy; Mt Redoubt, AK, USA to identify controls on plume processes. Ozone was measured during periods of relatively sustained Kīlauea plume exposure, using an Aeroqual instrument deployed alongside Multi-Gas SO2 and H2S sensors. Interferences were accounted for in data post-processing. The volcanic H2S/SO2 molar ratio was quantified as 0.03. At Halema‘uma‘u crater-rim, ozone was close to ambient in the emission plume (at 10 ppmv SO2. Measurements in grounding plume (at 5 ppmv SO2 about 10 km downwind of Pu‘u ‘Ō‘ō showed just slight ozone depletion. These Kīlauea observations contrast with substantial ozone depletion reported at Mt Etna and Mt Redoubt. Analysis of the combined data from these three volcanoes identifies the emitted Br/S as a strong but non-linear control on the rate of ozone depletion. Model simulations of the volcanic plume chemistry highlight that the proportion of HBr converted into reactive bromine is a key control on the efficiency of ozone depletion. This underlines the importance of chemistry in the very near-source plume on the fate and atmospheric impacts of volcanic emissions to the troposphere.

Trace Metals Bioaccumulation Potentials of Three Indigenous ...

African Journals Online (AJOL)

User

grasses as bioaccumulators of trace metals from polluted soils. Seeds of ... transfer factor (TF) showed that Zn was the most bioaccumulated trace metals by all the grasses followed by. Pb, Mn ... was used to de-contaminate copper (Cu) and.

Biotransformation and induction: implications for toxicity, bioaccumulation and monitoring of environmental xenobiotics in fish

International Nuclear Information System (INIS)

Kleinow, K.M.; Melancon, M.J.; Lech, J.J.

1987-01-01

Biotransformation of xenobiotics in fish occurs by many of the same reactions as in mammals. These reactions have been shown to affect the bioaccumulation, persistence, residue dynamics, and toxicity of select chemicals in fish. P-450-dependent monooxygenase activity of fish can be induced by polycyclic aromatic hydrocarbons, but phenobarbital-type agents induce poorly, if at all. Fish monooxygenase activity exhibits ideal temperature compensation and sex-related variation. Induction of monooxygenase activity by polycyclic aromatic hydrocarbons can result in qualitative as well as quantitative changes in the metabolic profile of a chemical. Induction can also alter toxicity. In addition, multiple P-450 isozymes have been described for several fish species. The biotransformation productions of certain chemicals have been related to specific P-450 isozymes, and the formation of these products can be influenced by induction. Exposure of fish to low levels of certain environmental contaminants has resulted in induction of specific monooxygenase activities and monitoring of such activities has been suggested as a means of identifying areas of pollutant exposure in the wild

Bioaccumulation of hydrocarbons derived from terrestrial and anthropogenic sources in the Asian clam, Potamocorbula amurensis, in San Francisco Bay estuary

Science.gov (United States)

Pereira, Wilfred E.; Hostettler, Frances D.; Rapp, John B.

1992-01-01

An assessment was made in Suisun Bay, California, of the distributions of hydrocarbons in estuarine bed and suspended sediments and in the recently introduced asian clam, Potamocorbula amurensis. Sediments and clams were contaminated with hydrocarbons derived from petrogenic and pyrogenic sources. Distributions of alkanes and of hopane and sterane biomarkers in sediments and clams were similar, indicating that petroleum hydrocarbons associated with sediments are bioavailable to Potamocorbula amurensis. Polycyclic aromatic hydrocarbons in the sediments and clams were derived mainly from combustion sources. Potamocorbula amurensis is therefore a useful bioindicator of hydrocarbon contamination, and may be used as a biomonitor of hydrocarbon pollution in San Francisco Bay.

Retention of Halogens in Waste Glass

Energy Technology Data Exchange (ETDEWEB)

Hrma, Pavel R.

2010-05-01

In spite of their potential roles as melting rate accelerators and foam breakers, halogens are generally viewed as troublesome components for glass processing. Of five halogens, F, Cl, Br, I, and At, all but At may occur in nuclear waste. A nuclear waste feed may contain up to 10 g of F, 4 g of Cl, and ≤100 mg of Br and I per kg of glass. The main concern is halogen volatility, producing hazardous fumes and particulates, and the radioactive iodine 129 isotope of 1.7x10^7-year half life. Because F and Cl are soluble in oxide glasses and tend to precipitate on cooling, they can be retained in the waste glass in the form of dissolved constituents or as dispersed crystalline inclusions. This report compiles known halogen-retention data in both high-level waste (HLW) and low-activity waste (LAW) glasses. Because of its radioactivity, the main focus is on I. Available data on F and Cl were compiled for comparison. Though Br is present in nuclear wastes, it is usually ignored; no data on Br retention were found.

Uptake of Total Petroleum Hydrocarbon (TPH) and Polycyclic Aromatic Hydrocarbons (PAHs) by Oryza sativa L. Grown in Soil Contaminated with Crude Oil.

Science.gov (United States)

Patowary, Rupshikha; Patowary, Kaustuvmani; Devi, Arundhuti; Kalita, Mohan Chandra; Deka, Suresh

2017-01-01

The purpose of this study was to determine whether total petroleum hydrocarbon (TPH) and polycyclic aromatic hydrocarbons (PAHs) present in crude oil contaminated sites are transferred to roots, shoots and finally the grains of rice crops (Oryza sativa L.) grown in those sites. Soil was artificially contaminated with crude oil at concentrations of 0, 1000, 5000, 10,000, and 15,000 mg/kg, followed by planting of rice seedlings. After harvest, TPH in plant samples were measured, and it was determined that the uptake of TPH by the plants gradually increased as the concentration of oil in soil increased. Further, from GC-MS analysis, it was observed that PAHs including naphthalene and phenanthrene bioaccumulated in rice plant parts. Vital physico-chemical properties of soil were also altered due to crude oil contamination. Our study revealed that rice plants grown in crude oil polluted sites can uptake TPH including PAHs, thus emphasising the importance of prior investigation of soil condition before cultivation of crops.

E. S. R. studies of halogenated pyrimidines in. gamma. -irradiated alkaline glasses. [Halogenated uracil bases; bromouridine; bromodeoxyuridine

Energy Technology Data Exchange (ETDEWEB)

Simpson, L D; Zimbrick, J D [Kansas Univ., Lawrence (USA)

1975-11-01

The reactions of mobile electrons (e/sup -//sub m/) and oxygen radical anions (O./sup -/) with halogenated bases and nucleosides have been studied in ..gamma..-irradiated alkaline glasses by e.s.r. and specific halogen-ion electrode techniques. It was shown that electrons react with halogenated uracil bases (XUr where X = Cl, Br, I but not F) by dissociative electron attachment to form uracil-5-yl radicals (U.) and halogen anions. The relative rates of reaction of e/sup -//sub m/ with XUr decreased in the sequence BrUr > ClUr > FUr > IUr. Thermal annealing studies carried out on U. in H/sub 2/O and D/sub 2/O matrices supported the hypothesis that U. in H/sub 2/O hydrates across the 5-6 double bond in the temperature region 135/sup 0/ to 155/sup 0/ K, and deuterates to a much smaller extent in D/sub 2/O at temperatures above 155/sup 0/ K. Studies on bromouridine and bromodeoxyuridine suggested that e/sup -/sub(m) reacts with the base moieties to form U. type radicals which abstract H. from the sugar moieties of adjacent nucleosides.

Determination of tetrachloroethylene and other volatile halogenated organic compounds in oil wastes by headspace SPME GC-MS

Energy Technology Data Exchange (ETDEWEB)

Fabbri, D.; Bezzi, R.; Torri, C.; Galletti, P.; Tagliavini, E. [Bologna Univ., Ravenna (Italy). Lab. of Chemistry, C.I.R.S.A

2007-09-15

Oil wastes and slops are complex mixtures of hydrocarbons, which may contain a variety of contaminants including tetrachloroethylene (perchloroethylene, PCE) and other volatile halogenated organic compounds (VHOCs). The analytical determination of PCE at trace levels in petroleum-derived matrices is difficult to carry out in the presence of large amounts of hydrocarbon matrix components. In the following study, we demonstrate that headspace solid-phase microextraction (HS-SPME) combined with GC-MS analysis can be applied for the rapid measurement of PCE concentration in oil samples. The HS-SPME method was developed using liquid paraffin as matrix matching reference material for external and internal calibration and optimisation of experimental parameters. The limit of quantitation was 0.05 mg kg{sup -1}, and linearity was established up to 25 mg kg{sup -1}. The HS-SPME method was extended to several VHOCs, including trichloroethylene (TCE) in different matrices and was applied to the quantitative analysis of PCE and TCE in real samples.

Studies concerning thermodynamics and kinetics of the absorption of halogenated hydrocarbons relevant to environment

International Nuclear Information System (INIS)

Weisweiler, W.; Eidam, K.; Winterbauer, H.

1993-07-01

In the context of the research project the scrubbing of air contaminated by peculiar volatile organic compounds was investigated using the absorption technique by means of high boiling organics as washing liquids. Eight chlorinated hydrocarbons well known from technical processes were chosen to be representative for the volatile organic compounds. Eleven absorption media were selected on the basis of their physical properties. For the determination of the solubility data of the absorption media due to chlorinated hydrocarbons, nitrogen as well as a mixture of nitrogen and oxygen were used as carrier gas. The influence of the dipole moment of the absorption media on the amount of solubility - expressed as enrichment factor - was studied, too. Concerning the technical application, the thermostability and the stability against diluted inorganic acids were studied as well. (orig.). 56 figs., 8 tabs., 63 refs [de

Comparative study of polycyclic aromatic hydrocarbons in coral tissues and the ambient sediments from Kenting National Park, Taiwan

International Nuclear Information System (INIS)

Ko, Fung-Chi; Chang, Chiung-Wen; Cheng, Jing-O.

2014-01-01

Surface sediments and corals (Acropora sp. and Montipora sp.) from the coastline of Kenting were analyzed in 2009 and 2010 for content levels of polycyclic aromatic hydrocarbons (PAHs) using gas chromatography-mass spectrometry. The total PAH concentrations (t-PAH) in corasls (143–1715 ng g −1 dw) were significantly higher than in the ambient sediments (2–59 ng g −1 dw) indicating the bioaccumulation of PAHs in corals. The spatial and seasonal variation in PAH levels suggested that land-loaded contaminants may be the main source of PAHs in the Kenting coral reefs. Based on molecular indices, PAHs were substantially of petroleum origin. The major PAH components were phenanthrene, pyrene and fluorine, but PAH congeners in corals and sediments still have characteristic composition patterns which would be altered by the bio/accumulation mechanisms. Further study is essential to assess and understand the impacts of these chemicals on coral reefs. Highlights: • PAH concentrations in Kenting coral reefs ranked minor in the worldwide comparison. • Isomeric ratios of PAHs suggested an important contribution of petrogenic sources. • PAHs have characteristic composition patterns which would be altered by the bio/accumulation mechanisms. • Higher levels of PAHs were found in coral tissues than in sediments (bioaccumulation). • Coral body burdens of PAHs were significantly correlated to adjacent sediments only at the areas with higher levels of PAHs. -- PAH levels in coral tissues were higher than in adjacent sediments (bioaccumulation)

Bioaccumulation in aquatic systems: methodological approaches, monitoring and assessment

DEFF Research Database (Denmark)

Schäfer, Sabine; Buchmeier, Georgia; Claus, Evelyn

2015-01-01

, various scientific and regulatory aspects of bioaccumulation in aquatic systems and the relevant critical issues are discussed. Monitoring chemical concentrations in biota can be used for compliance checking with regulatory directives, for identification of chemical sources or event-related environmental...... temporal and geographical range. Bioaccumulation is also assessed for regulation of chemicals of environmental concern whereby mainly data from laboratory studies on fish bioaccumulation are used. Field data can, however, provide additional important information for regulators. Strategies...... for bioaccumulation assessment still need to be harmonised for different regulations and groups of chemicals. To create awareness for critical issues and to mutually benefit from technical expertise and scientific findings, communication between risk assessment and monitoring communities needs to be improved...

Predicting the bioaccumulation of polyaromatic hydrocarbons and polychlorinated biphenyls in benthic animals in sediments

NARCIS (Netherlands)

Tuikka, A. I.; Leppänen, M. T.; Akkanen, J.; Sormunen, A. J.; Leonards, P. E.G.; van Hattum, B.; van Vliet, L. A.; Brack, W.; Smedes, F.; Kukkonen, J. V.K.

2016-01-01

There were two main objectives in this study. The first was to compare the accuracy of different prediction methods for the chemical concentrations of polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the organism, based on the measured chemical concentrations existing in

Occurrence, distribution and bioaccumulation behaviour of hydrophobic organic contaminants in a large-scale constructed wetland in Singapore.

Science.gov (United States)

Wang, Qian; Kelly, Barry C

2017-09-01

This study involved a field-based investigation to assess the occurrence, distribution and bioaccumulation behaviour of hydrophobic organic contaminants in a large-scale constructed wetland. Samples of raw leachate, water and wetland plants, Typha angustifolia, were collected for chemical analysis. Target contaminants included polychlorinated biphenyls (PCBs), organochlorine pesticides (OCP), as well as several halogenated flame retardants (HFRs) and personal care products (triclosan and synthetic musks). In addition to PCBs and OCPs, synthetic musks, triclosan (TCS) and dechlorane plus stereoisomers (syn- and anti-DPs) were frequently detected. Root concentration factors (log RCF L/kg wet weight) of the various contaminants ranged between 3.0 and 7.9. Leaf concentration factors (log LCF L/kg wet weight) ranged between 2.4 and 8.2. syn- and anti-DPs exhibited the greatest RCF and LCF values. A strong linear relationship was observed between log RCF and octanol-water partition coefficient (log K OW ). Translocation factors (log TFs) were negatively correlated with log K OW . The results demonstrate that more hydrophobic compounds exhibit higher degrees of partitioning into plant roots and are less effectively transported from roots to plant leaves. Methyl triclosan (MTCS) and 2,8-dichlorodibenzo-p-dioxin (DCDD), TCS degradation products, exhibited relatively high concentrations in roots and leaves., highlighting the importance of degradation/biotransformation. The results further suggest that Typha angustifolia in this constructed wetland can aid the removal of hydrophobic organic contaminants present in this landfill leachate. The findings will aid future investigations regarding the fate and bioaccumulation of hydrophobic organic contaminants in constructed wetlands. Copyright © 2017 Elsevier Ltd. All rights reserved.

Scientific conferences: A big hello to halogen bonding

Science.gov (United States)

Erdelyi, Mate

2014-09-01

Halogen bonding connects a wide range of subjects -- from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin.

Science.gov (United States)

Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T

2018-01-26

The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiochemical investigation of the bioaccumulation of urea by the alga Hydrodictyon reticulatum

International Nuclear Information System (INIS)

Havelka, M.; Stary, J.; Kratzer, K.

1987-01-01

It is found that the bioaccumulation of 14 C-urea in the light is connected with the increase of pH-value of the external medium, of the intracellular concentration of ammonium ions and with the decrease of the intracellular concentration of potassium ions. The uptake rate does not depend on the concentration of urea in the range from 0.1 to 2.0 mmol dm -3 and it has a broad maximum at pH 6.5-8.0. The uptake rate of urea is a little higher compared with nitrite or nitrate anions, however it is at least three times lower in comparison with that of ammonium or hydrocarbonate ions. The uptake of urea in the dark leads to the increase of the intracellular concentration of ammonium ions, however, carbon dioxide formed is released from the cell. (author) 7 refs

Influence of Halogen Substituents on the Catalytic Oxidation of 2,4,6-Halogenated Phenols by Fe(III-Tetrakis(p-hydroxyphenyl porphyrins and Potassium Monopersulfate

Directory of Open Access Journals (Sweden)

Seiya Nagao

2011-12-01

Full Text Available The influence of halogen substituents on the catalytic oxidation of 2,4,6-trihalogenated phenols (TrXPs by iron(III-porphyrin/KHSO5 catalytic systems was investigated. Iron(III-5,10,15,20-tetrakis(p-hydroxyphenylporphyrin (FeTHP and its supported variants were employed, where the supported catalysts were synthesized by introducing FeTHP into hydroquinone-derived humic acids via formaldehyde poly-condensation. F (TrFP, Cl (TrCP, Br (TrBP and I (TrIP were examined as halogen substituents for TrXPs. Although the supported catalysts significantly enhanced the degradation and dehalogenation of TrFP and TrCP, the oxidation of TrBP and TrIP was not enhanced, compared to the FeTHP catalytic system. These results indicate that the degree of oxidation of TrXPs is strongly dependent on the types of halogen substituent. The order of dehalogenation levels for halogen substituents in TrXPs was F > Cl > Br > I, consistent with their order of electronegativity. The electronegativity of a halogen substituent affects the nucleophilicity of the carbon to which it is attached. The levels of oxidation products in the reaction mixtures were analyzed by GC/MS after extraction with n-hexane. The most abundant dimer product from TrFP via 2,6-difluoroquinone is consistent with a scenario where TrXP, with a more electronegative halogen substituent, is readily oxidized, while less electronegative halogen substituents are oxidized less readily by iron(III-porphyrin/KHSO5 catalytic systems.

40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

Construction of Tungsten Halogen, Pulsed LED, and Combined Tungsten Halogen-LED Solar Simulators for Solar Cell I-V Characterization and Electrical Parameters Determination

Directory of Open Access Journals (Sweden)

Anon Namin

2012-01-01

Full Text Available I-V characterization of solar cells is generally done under natural sunlight or solar simulators operating in either a continuous mode or a pulse mode. Simulators are classified on three features of irradiance, namely, spectral match with respect to air mass 1.5, spatial uniformity, and temporal stability. Commercial solar simulators use Xenon lamps and halogen lamps, whereas LED-based solar simulators are being developed. In this work, we build and test seven simulators for solar cell characterization, namely, one tungsten halogen simulator, four monochromatic (red, green, blue, and white LED simulators, one multicolor LED simulator, and one tungsten halogen-blue LED simulator. The seven simulators provide testing at nonstandard test condition. High irradiance from simulators is obtained by employing elevated supply voltage to tungsten halogen lamps and high pulsing voltages to LEDs. This new approach leads to higher irradiance not previously obtained from tungsten halogen lamps and LEDs. From I-V curves, electrical parameters of solar cell are made and corrected based on methods recommended in the IEC 60891 Standards. Corrected values obtained from non-STC measurements are in good agreement with those obtained from Class AAA solar simulator.

SYNTHESIS AND CHARACTERIZATION OF NEW HALOGENATED CURCUMINOIDS

Directory of Open Access Journals (Sweden)

Eugenio Torres

2013-12-01

Full Text Available In this work a novel procedure of synthesis of compounds analogues to curcumin with halogens atoms in its structure is described, which can increase its solubility and biological activity. Four halogenated curcuminoids were obtained with great pharmacological interest, none of them reported in literature before. Synthesis was carried out by means of the aldol condensation assisted by microwaves of halogenated aromatic aldehydes and acetylacetona, using morpholine as basic catalyst, in absence of solvent, and the reaction just needed 1 min. The products were purified by treatment of the reaction mixture with methanol under ultrasound irradiation, followed by chromatographic column. All obtained compounds were characterized by infrared spectroscopy, nuclear magnetic resonance, quantitative elementary analysis and high resolution mass spectrometry. The RMN-1H data demonstrate in all structures of synthesized curcuminoids the enol form is the most favored.

Laboratory Studies of Hydrocarbon Oxidation Mechanisms

Science.gov (United States)

Orlando, J. J.; Tyndall, G. S.; Wallington, T. J.; Burkholder, J. B.; Bertman, S. B.; Chen, W.

2001-12-01

The oxidation of hydrocarbon species (alkanes, alkenes, halogenated species, and oxygenates of both natural and anthropogenic origin) in the troposphere leads to the generation of numerous potentially harmful secondary pollutants, such as ozone, organic nitrates and acids, and aerosols. These oxidations proceed via the formation of alkoxy radicals, whose complex chemistry controls the ultimate product distributions obtained. Studies of hydrocarbon oxidation mechanisms are ongoing at NCAR and Ford, using environmental chamber / FTIR absorption systems. The focus of these studies is often on the product distributions obtained at low temperature; these studies not only provide data of direct relevance to the free/upper troposphere, but also allow for a more fundamental understanding of the alkoxy radical chemistry (eg., from the determination of the Arrhenius parameters for unimolecular processes, and the quantification of the extent of the involvement of chemical activation in the alkoxy radical chemistry). In this paper, data will be presented on some or all of the following topics: kinetics/mechanisms for the reactions of OH with the unsaturated species MPAN, acrolein, and crotonaldehyde; the mechanism for the oxidation of ethyl chloride and ethyl bromide; and the mechanism for the reaction of OH with acetone and acetaldehyde at low temperature. The relevance of the data to various aspects of tropospheric chemistry will be discussed.

40 CFR 721.8900 - Substituted halogenated pyridinol, alkali salt.

Science.gov (United States)

2010-07-01

..., alkali salt. 721.8900 Section 721.8900 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.8900 Substituted halogenated pyridinol, alkali salt. (a) Chemical... as substituted halogenated pyridinols, alkali salts (PMNs P-88-1271 and P-88-1272) are subject to...

Molecular effects and bioaccumulation of levonorgestrel in the non-target organism Dreissena polymorpha

International Nuclear Information System (INIS)

Contardo-Jara, Valeska; Lorenz, Claudia; Pflugmacher, Stephan; Nuetzmann, Gunnar; Kloas, Werner; Wiegand, Claudia

2011-01-01

Bioaccumulation and effects of the contraceptive hormone levonorgestrel were examined in the non-target organism Dreissena polymorpha. Molecular biomarkers of biotransformation, elimination, antioxidant defence and protein damage were analyzed after exposure to increasing concentrations of levonorgestrel in a flow-through system. The lowest concentration (0.312 μg L -1 ) was 100-fold bioconcentrated within four days. A decrease of the bioconcentration factor was observed within one week for the highest test concentrations (3.12 and 6.24 μg L -1 ) suggesting enhanced excretory processes. The immediate mRNA up-regulation of pi class glutathione S-transferase proved that phase II biotransformation processes were induced. Disturbance of fundamental cell functions was assumed since the aryl hydrocarbon receptor has been permanently down-regulated. mRNA up-regulation of P-glycoprotein, superoxide dismutase and metallothioneine suggested enhanced elimination processes and ongoing oxidative stress. mRNA up-regulation of heat shock protein 70 in mussels exposed to the two highest concentrations clearly indicated impacts on protein damage. - Fundamental cell processes as biotransformation, elimination and prevention from oxidative stress are influenced by exposure of the contraceptive levonorgestrel in non-target organisms. - Research highlights: → Bioaccumulation of levonorgestrel in mussels is higher than expected based on its lipophilicity. → Exposure to levonorgestrel causes oxidative stress and enhanced elimination processes. → Glutathione S-transferase (pi class) mRNA induction after one day hint on phase II biotransformation. → mRNA induction of heat shock protein 70 after one week prove protein damage.

The unique role of halogen substituents in the design of modern agrochemicals.

Science.gov (United States)

Jeschke, Peter

2010-01-01

The past 30 years have witnessed a period of significant expansion in the use of halogenated compounds in the field of agrochemical research and development. The introduction of halogens into active ingredients has become an important concept in the quest for a modern agrochemical with optimal efficacy, environmental safety, user friendliness and economic viability. Outstanding progress has been made, especially in synthetic methods for particular halogen-substituted key intermediates that were previously prohibitively expensive. Interestingly, there has been a rise in the number of commercial products containing 'mixed' halogens, e.g. one or more fluorine, chlorine, bromine or iodine atoms in addition to one or more further halogen atoms. Extrapolation of the current trend indicates that a definite growth is to be expected in fluorine-substituted agrochemicals throughout the twenty-first century. A number of these recently developed agrochemical candidates containing halogen substituents represent novel classes of chemical compounds with new modes of action. However, the complex structure-activity relationships associated with biologically active molecules mean that the introduction of halogens can lead to either an increase or a decrease in the efficacy of a compound, depending on its changed mode of action, physicochemical properties, target interaction or metabolic susceptibility and transformation. In spite of modern design concepts, it is still difficult to predict the sites in a molecule at which halogen substitution will result in optimal desired effects. This review describes comprehensively the successful utilisation of halogens and their unique role in the design of modern agrochemicals, exemplified by various commercial products from Bayer CropScience coming from different agrochemical areas.

Special features of self-compensation of halogen donor action in lead telluride

International Nuclear Information System (INIS)

Kajdanov, V.I.; Nemov, S.A.; Ravich, Yu.I.; Dereza, A.Yu.

1985-01-01

Specific features of self-compensation of halogen donor action in lead telluride are investigasted. Lead telluride samples with chlorine additions (with tellurium excess) and, besides, with bromine- and iodine additions were studied in order to reveal general regularities in alloyind with all halogen donor impurities. Experimental dependences of the difference between the electron and hole concentrations (n-p) in PbTe as a function of an amount of introduced halogen impurities (Ni) are presented for samples with a maximum compensation at 295 K. General features of the n-p=f(Ni) dependence are presented for all halogens. The hypothesis on the kinetic mechanism of increasing the efficiency of self-compensation of halogen donor action in lead telluride is suggested

Spectrographic determination of traces of halogens; Dosage de traces d'halogenes par la methode spectrographique

Energy Technology Data Exchange (ETDEWEB)

Melamed, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

1961-07-01

Hollow cathode source is employed for determining traces of halogens (fluorine - chlorine) in the uranium oxide U{sub 3}O{sub 8} qualitatively, detection of at least 40 ppm of fluorine, as alkali fluoride and 125 ppm of chlorine, is possible. (author) [French] Un tube a decharge a cathode creuse a ete utilise pour la determination spectrographique des halogenes (fluor - chlore) presentes a l'etat de traces dans un oxyde d'uranium U{sub 3}O{sub 8}. On a pu deceler qualitativement des teneurs de 40 ppm de fluor sous forme de fluorures alcalins. En ce qui concerne le chlore, la plus faible teneur decelee a ete de 125 ppm. (auteur)

Treating distillable carbonaceous materials with hydrocarbon gases, etc

Energy Technology Data Exchange (ETDEWEB)

1935-12-04

A process is described for the treatment of distillable carbonaceous materials with hydrogen gases in the presence of hydrogen halides to recover valuable hydrocarbon products, characterized by the stable halide forming the treating medium for the hot-test gasesous product of this treatment with hydrogen gases in combination with an alkaline metal or alkaline earth, able to be decomposed by an inorganic acid soluble in water, capable of driving off hydrogen halide from their salts and also with salts of ammonia of the mentioned inorganic acids, the halide being converted into halide of ammonia and halogen, and the ammonia halide or hydrogen halide being returned to the process alone or together with the feed of carbonaceous materials with which it began.

Halogenated organic compounds in archived whale oil: A pre-industrial record

International Nuclear Information System (INIS)

Teuten, Emma L.; Reddy, Christopher M.

2007-01-01

To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s

Halogenated organic compounds in archived whale oil: A pre-industrial record

Energy Technology Data Exchange (ETDEWEB)

Teuten, Emma L. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: emma.teuten@plymouth.ac.uk; Reddy, Christopher M. [Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, 360 Woods Hole Road, Woods Hole, MA 02543 (United States)]. E-mail: creddy@whoi.edu

2007-02-15

To provide additional evidence that several halogenated organic compounds (HOCs) found in environmental samples are natural and not industrially produced, we analyzed an archived whale oil sample collected in 1921 from the last voyage of the whaling ship Charles W. Morgan. This sample, which pre-dates large-scale industrial manufacture of HOCs, contained two methoxylated polybrominated diphenyl ethers (MeO-PBDEs), five halogenated methyl bipyrroles (MBPs), one halogenated dimethyl bipyrrole (DMBP), and tentatively one dimethoxylated polybrominated biphenyl (diMeO-PBB). This result indicates, at least in part, a natural source of the latter compounds. - Nine halogenated organic compounds have been detected in archived whale oil from the early 1920s.

Halogens are key cofactors in building of collagen IV scaffolds outside the cell.

Science.gov (United States)

Brown, Kyle L; Hudson, Billy G; Voziyan, Paul A

2018-05-01

The purpose of this review is to highlight recent advances in understanding the molecular assembly of basement membranes, as exemplified by the glomerular basement membrane (GBM) of the kidney filtration apparatus. In particular, an essential role of halogens in the basement membrane formation has been discovered. Extracellular chloride triggers a molecular switch within non collagenous domains of collagen IV that induces protomer oligomerization and scaffold assembly outside the cell. Moreover, bromide is an essential cofactor in enzymatic cross-linking that reinforces the stability of scaffolds. Halogenation and halogen-induced oxidation of the collagen IV scaffold in disease states damage scaffold function. Halogens play an essential role in the formation of collagen IV scaffolds of basement membranes. Pathogenic damage of these scaffolds by halogenation and halogen-induced oxidation is a potential target for therapeutic interventions.

Halonium Ions as Halogen Bond Donors in the Solid State [XL2]Y Complexes.

Science.gov (United States)

Rissanen, Kari; Haukka, Matti

2015-01-01

The utilization of halogen bonding interactions is one of the most rapidly developing areas of supramolecular chemistry. While the other weak non-covalent interactions and their influence on the structure and chemistry of various molecules, complexes, and materials have been investigated extensively, the understanding, utilizations, and true nature of halogen bonding are still relatively unexplored. Thus its final impact in chemistry in general and in materials science has not yet been fully established. Because of the polarized nature of a Z-X bond (Z=electron-withdrawing atom or moiety and X=halogen atom), such a moiety can act as halogen bond donor when the halogen is polarized enough by the atom/moiety Z. The most studied and utilized halogen bond donor molecules are the perfluorohalocarbons, where Z is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. Complementing the contemporary halogen bonding research, this chapter reviews the solid state structural chemistry of the most extremely polarized halogen atoms, viz. halonium ions, X+, and discussed them as halogen bond donors in the solid state [XL2]Y complexes (X=halonium ion, Y=any anion).

Halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1975--February 14, 1976

International Nuclear Information System (INIS)

Rack, E.P.

1976-02-01

High energy reactions of halogen atoms or ions, activated by nuclear transformations, are being studied in gaseous, high pressure, and condensed phase saturated and unsaturated hydrocarbons, halomethanes, and other organic systems. Experimental and theoretical data are presented in the following areas: systematics of iodine hot atom reactions in halomethanes, reactions and systematics of iodine reactions with pentene and butene isomers, radiative neutron capture activated reactions of iodine with acetylene, gas to liquid to solid transition in hot atom chemistry, kinetic theory applications of hot atom reactions and the mathematical development of caging reactions, solvent dependence of the stereochemistry of the 38 Cl for Cl substitution following 37 Cl(n,γ) 38 Cl in liquid meso and dl-(CHFCl) 2 . A technique was also developed for the radioassay of Al in urine specimens

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

Science.gov (United States)

Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

2018-04-01

Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

Incidence of real-world automotive parent and halogenated PAH in urban atmosphere.

Science.gov (United States)

Gao, Pan-Pan; Zhao, Yi-Bo; Ni, Hong-Gang

2018-06-01

This study reports results from a tunnel experiment impact of real-world traffic-related particle and gas parent and halogenated polycyclic aromatic hydrocarbons (PAHs and HPAHs) on urban air. The traffic related emission characteristics and subsequent environmental behavior of these compounds were investigated. To understand the significance of real-world transport emissions to the urban air, traffic-related mass emissions of PAHs and HPAHs were estimated based on measured emission factors. According to our results, PAHs and HPAHs emissions via particulate phase were greater than those via gaseous phase; particles in 2.1-3.3 μm size fraction, have the major contribution to particulate PAHs and HPAHs emissions. Over all, contribution of traffic-related emission of PAHs (only ∼3% of the total PAHs emission in China) is an overstated source of PAHs pollution in China. Actually, exhaust pipe emission contributed much less than the total traffic-related emission of pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

Halogenated furanones inhibit quorum sensing through accelerated LuxR turnover

DEFF Research Database (Denmark)

Manefield, M.; Rasmussen, Thomas Bovbjerg; Henzter, M.

2002-01-01

fischeri overproduced in Escherichia coli. Whilst a stable interaction between the algal metabolite and the bacterial protein was not found, it was noted by Western analysis that the half-life of the protein is reduced up to 100-fold in the presence of halogenated furanones. This suggests that halogenated...... that the reduction in LuxR concentration is the mechanism by which furanones control expression of AHL-dependent phenotypes. The mode of action by which halogenated furanones reduce cellular concentrations of the LuxR protein remains to be characterized....

Thermal behavior of halogenated imidebismaleimide resins

International Nuclear Information System (INIS)

Mohammad, A.; Al-Halim, N.Z.

1995-01-01

Several new poly-halogenated malecimides, bismaleimides and therir copoly resins were synthessised thermally from their corresponding amic acids. The synthesis was accomplished by two way method (amic acid-polimide) instead of the well-known three way method (amic acid-imide-polyimide). Thermal characterization of monomers and their cured resins was achieved using differential thermal analysis (DTA), dynamic thermogravimetric analysis (TGA) and isothermal gravimetric analysis (IGA). The effect of halogen substituent, especially in the ortho postion, is clear in the imidization proces, while polymerization proceeds almost equally in all systems. Thermal properties of homo and copolymers were correlated with their chemical structures. (author). 15 refs., 4

Development of non-halogen cables for nuclear power stations

Energy Technology Data Exchange (ETDEWEB)

Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao (Hitachi Cable, Ltd., Tokyo (Japan))

1983-12-01

The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables.

Development of non-halogen cables for nuclear power stations

International Nuclear Information System (INIS)

Yagyu, Hideki; Yamamoto, Yasuaki; Onishi, Takao

1983-01-01

The non-halogen fire-resistant cables for nuclear power stations which never generate halogen gas, have been developed. The cables comprise the insulator of EP rubber and the sheath of polyolefine containing non-halogen inorganic fire-retardant. The results of the environmental test and fire-resistance test are described. In the environmental test, the cables were subjected to the heating, gamma-irradiation and steam exposure successively, according to IEEE specification 323,383, and subsequently the change in the appearance, tensile strength and electrical performance of the cables was measured. In the fire-resistance test, the vertical tray fire test according to the IEEE specification 383 was adopted, and other tests including the vertical fire test on insulator cores, oxygen index, the generation of corrosive gas, copper mirror corrosion test, gas toxicity test and optical smoke density test were carried out. It became clear that the cables did not generate halogen gas on burning, and brought about reduced toxicity, corrosion and smoke, and that the safety against fire is greatly improved by using the cables. (Yoshitake, I.)

Quantitative structure-activity relationships for toxicity and genotoxicity of halogenated aliphatic compounds: wing spot test of Drosophila melanogaster.

Science.gov (United States)

Chroust, Karel; Pavlová, Martina; Prokop, Zbynek; Mendel, Jan; Bozková, Katerina; Kubát, Zdenek; Zajícková, Veronika; Damborský, Jiri

2007-02-01

Halogenated aliphatic compounds were evaluated for toxic and genotoxic effects in the somatic mutation and recombination test employing Drosophila melanogaster. The tested chemicals included chlorinated, brominated and iodinated; mono-, di- and tri-substituted; saturated and unsaturated alkanes: 1,2-dibromoethane, 1-bromo-2-chloroethane, 1-iodopropane, 2,3-dichloropropene, 3-bromo-1-propene, epibromohydrin, 2-iodobutane, 3-chloro-2-methylpropene, 1,2,3-trichloropropane, 1,2-dichloroethane, 1,2-dichlorobutane, 1-chloro-2-methylpropane, 1,3-dichloropropane, 1,2-dichloropropane, 2-chloroethymethylether, 1-bromo-2-methylpropane and 1-chloropentane. N-methyl-N-nitrosourea served as the positive and distilled water as the negative control. The set of chemicals for the toxicological testing was selected by the use of statistical experiment design. Group of unsaturated aliphatic hydrocarbons were generally more toxic than saturated analogues. The genotoxic effect was observed with 14 compounds in the wing spot test, while 3 substances did not show any genotoxicity by using the wing spot test at 50% lethal concentration. The highest number of wing spots was observed in genotoxicity assay with 1-bromo-2-chloroethane, 1,2-dichloroethane, 1,2-dibromoethane and 1-iodopropane. Nucleophilic superdelocalizability calculated by quantum mechanics appears to be a good parameter for prediction of both toxicity and genotoxicity effects of halogenated aliphatic compounds.

Process for reducing halogen impurities in oil products

Energy Technology Data Exchange (ETDEWEB)

Basler, F.

1990-08-14

Oil products, in particular waste oils, may be efficiently reprocessed according to an economic and technically simple method for removing impurities, notably halogens. In this method, the oil product is treated at temperatures up to about 150{degree}C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof. The oil product obtained in this step is treated at increased temperatures with at least one halogen binding agent. The water and/or solids from the product so treated are separated out. The process of the invention can be carried out in a conventional stripping apparatus. The strong acid used in the first step is preferably selected from sulfurous acid, phosphoric acid, phosphorous acid, and phosphonic acid. The salt of the weak base and strong acid is preferably ammonium sulfate, ammonium bisulfate, ammonium sulfite, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphite, and ammonium phosphonic acid. The second step of the method is preferably a coagulation step in which organic halogen compounds break down into hydrogen halides which are neutralized by the added halogen binding agents. The preferred halogen binding agents are ammonia and/or an organic base. The coagulation is preferably carried out in heat exchangers so that the oil is heated in 3 stages and the oil from each stage is passed through a cascade tower. In the third step, additives may be used to enhance separation of the oil. Experiments are described to illustrate the method of the invention. 1 tab.

Participation of the Halogens in Photochemical Reactions in Natural and Treated Waters

Directory of Open Access Journals (Sweden)

Yi Yang

2017-10-01

Full Text Available Halide ions are ubiquitous in natural waters and wastewaters. Halogens play an important and complex role in environmental photochemical processes and in reactions taking place during photochemical water treatment. While inert to solar wavelengths, halides can be converted into radical and non-radical reactive halogen species (RHS by sensitized photolysis and by reactions with secondary reactive oxygen species (ROS produced through sunlight-initiated reactions in water and atmospheric aerosols, such as hydroxyl radical, ozone, and nitrate radical. In photochemical advanced oxidation processes for water treatment, RHS can be generated by UV photolysis and by reactions of halides with hydroxyl radicals, sulfate radicals, ozone, and other ROS. RHS are reactive toward organic compounds, and some reactions lead to incorporation of halogen into byproducts. Recent studies indicate that halides, or the RHS derived from them, affect the concentrations of photogenerated reactive oxygen species (ROS and other reactive species; influence the photobleaching of dissolved natural organic matter (DOM; alter the rates and products of pollutant transformations; lead to covalent incorporation of halogen into small natural molecules, DOM, and pollutants; and give rise to certain halogen oxides of concern as water contaminants. The complex and colorful chemistry of halogen in waters will be summarized in detail and the implications of this chemistry for global biogeochemical cycling of halogen, contaminant fate in natural waters, and water purification technologies will be discussed.

The potential accumulation of polycyclic aromatic hydrocarbons in phytoplankton and bivalves in Can Gio coastal wetland, Vietnam.

Science.gov (United States)

Thuy, Hoang Thi Thanh; Loan, Tu Thi Cam; Phuong, Trinh Hong

2018-05-12

Polycyclic aromatic hydrocarbons (PAHs) are one of the most important classes of anthropogenic persistent organic contaminants in the marine environment. This review discusses a whole range of findings that address various aspects of the bioaccumulation of PAHs in two common marine biota (phytoplankton and bivalves) globally and especially for Can Gio coastal wetland, Vietnam. The published information and collected data on the bioconcentration and accumulation mechanisms of PAHs as well as implications for Can Gio coastal wetland are compiled for phytoplankton and bivalves. PAHs are still released to Can Gio coastal environments from various sources and then transported to coastal environments through various physical processes; they may enter marine food chains and be highly accumulated in phytoplankton and bivalves. Thus, PAHs' bioaccumulation should be considered as one important criterion to assess the water's quality, directly linked to human health due to seafood consumption. Ecologically, Can Gio coastal wetland plays an important role to the South Vietnam key economic zone. However, it is also an area of potential PAHs inputs. With the abundant phytoplankton and bivalves in Can Gio coastal wetland, the PAHs bioaccumulation in these biota is inevitably detected. Thus, further study on the bioavailability of these contaminants is urgently needed in order to mitigate their negative effects and protect the ecosystems.

Fish bioaccumulation and biomarkers in environmental risk assessment : a review

NARCIS (Netherlands)

van der Oost, Ron; Beyer, Jonny; Vermeulen, Nico P E

In this review, a wide array of bioaccumulation markers and biomarkers, used to demonstrate exposure to and effects of environmental contaminants, has been discussed in relation to their feasibility in environmental risk assessment (ERA). Fish bioaccumulation markers may be applied in order to

Bioaccumulation factors in aquatic ecosystems. A critical review

Energy Technology Data Exchange (ETDEWEB)

Karlsson, Sara; Meili, Markus; Bergstroem, Ulla [Studsvik Eco and Safety AB, Nykoeping (Sweden)

2002-07-01

The calculated concentrations of radionuclides in organisms are often obtained by means of bioaccumulation factors (BAF) that describe the internal concentration relative to an external concentration e.g. in the abiotic environments at steady-state conditions. Such factors are often used when modelling the dose to man from radio-nuclides released to the biosphere. Values of bioaccumulation factors vary widely in magnitude among elements, organisms, and environmental conditions which is not always considered. In order to relate the bioaccumulation factors for some radionuclides to environmental conditions as well as to the trophic level of the organism of concern we have compiled an extensive database with bioaccumulation factors (about 5,500 values) together with information on some environmental conditions. The data for nine radionuclides has been extracted and examined. A comparison between the bioaccumulation factors found in this study and values given in literature by IAEA and NCRP shows that the ranges presented in this study are generally somewhat higher with the exception of BAF for molybdenum in freshwater fish which is of the same order of magnitude. This is startling and calls for a thorough research. The amount of readily accessible and reliable values of BAF is limited, often because basic information such as e.g. units and part of organism examined, is not reported. This is surprising and also unfortunate for those who need such data for use in generic or specific models. A major update of recommended values appears to be necessary for many elements to account for the development of analytical methods and experiences from case studies over the past two decades.

Bioaccumulation factors in aquatic ecosystems. A critical review

International Nuclear Information System (INIS)

Karlsson, Sara; Meili, Markus; Bergstroem, Ulla

2002-07-01

The calculated concentrations of radionuclides in organisms are often obtained by means of bioaccumulation factors (BAF) that describe the internal concentration relative to an external concentration e.g. in the abiotic environments at steady-state conditions. Such factors are often used when modelling the dose to man from radio-nuclides released to the biosphere. Values of bioaccumulation factors vary widely in magnitude among elements, organisms, and environmental conditions which is not always considered. In order to relate the bioaccumulation factors for some radionuclides to environmental conditions as well as to the trophic level of the organism of concern we have compiled an extensive database with bioaccumulation factors (about 5,500 values) together with information on some environmental conditions. The data for nine radionuclides has been extracted and examined. A comparison between the bioaccumulation factors found in this study and values given in literature by IAEA and NCRP shows that the ranges presented in this study are generally somewhat higher with the exception of BAF for molybdenum in freshwater fish which is of the same order of magnitude. This is startling and calls for a thorough research. The amount of readily accessible and reliable values of BAF is limited, often because basic information such as e.g. units and part of organism examined, is not reported. This is surprising and also unfortunate for those who need such data for use in generic or specific models. A major update of recommended values appears to be necessary for many elements to account for the development of analytical methods and experiences from case studies over the past two decades

First-principles studies on the effects of halogen adsorption on monolayer antimony.

Science.gov (United States)

Yeoh, Keat Hoe; Yoon, Tiem Leong; Ong, Duu Sheng; Lim, Thong Leng; Zuntu Abdullahi, Yusuf

2017-09-27

Using first-principles calculations, we carry out systematic studies on the electronic, magnetic and structural properties of halogenated β-phase antimonene. We consider two different levels of halogen adatom coverage i.e. Θ = 1/8 and Θ = 1/18. It is found that F, Cl and Br adatoms act as acceptors whereas the I adatom acts as a donor. For a high coverage of Θ = 1/8, halogenated β-phase antimonene exhibits metallic characteristics. With a lower coverage of Θ = 1/18, through the adsorption of F, Cl and Br the semiconducting unstrained antimonene becomes metallic. In contrast, I-adsorbed antimonene remains semiconducting but exhibits magnetic behavior. We further investigate the effects of bi-axial strain on the halogenated β-phase antimonene. It is found that bi-axial strain can only induce ferromagnetism on the halogenated antimonene at Θ = 1/18. However, the ferromagnetism is suppressed when the applied strain is high. We uncover that the emergence of strain-dependent magnetism is attributed to the presence of localized states in the bandgap resulting from collective effects of bi-axial strain and the adsorption of halogen atoms.

Phytotoxicity and bioavailablity of nickel: chemical speciation and bioaccumulation

NARCIS (Netherlands)

Weng, L.P.; Lexmond, T.M.; Wolthoorn, A.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

2003-01-01

The effect of pH on the bioaccumulation of nickel (Ni) by plants is opposite when using a nutrient solution or a soil as a growing medium. This paradox can be understood if the pH effect on the bioaccumulation, on the chemical speciation in the soil solution, and on the binding to the soil of Ni are

Selection of bioaccumulation criteria for environmental emergency (E2) planning

International Nuclear Information System (INIS)

Ketcheson, K.; Hradecky, K.; Gagne, M.; St-Amant-Verret, M.

2006-01-01

Environment Canada's Environmental Emergency regulations require the evaluation of a substance by a Risk Evaluation Framework (REF). Bioaccumulation criteria are used within the environmental hazard ratings section of the REF to determine the risk of a substance to organisms and are obtained from 3 types of measurements depending on data reliability: (1) bioaccumulation factors (BAF); (2) bioconcentration factors (BCF); and (3) an octanol-water partition coefficient (log K ow ). This paper presented details of a study of international and regional bioaccumulation criteria conducted to aid in determining appropriate criteria for E2 regulations and plans, with specific reference to substances toxic to aquatic organisms. An E2 plan is required if a substance has a bioconcentration factor of more than 500 in conjunction with aquatic toxicity. Bioaccumulation criteria from several sources for 745 substances were obtained to aid in choosing the most important parameters. Various international and regional criteria were examined and corresponding sources were summarized, and different source criteria was compared with empirical chemical data. The criteria chosen included both log K ow values and BCF values, although it was suggested that BCF and BAF are more realistic measures of bioaccumulation than log K ow , as they are derived from animal studies. The chosen values agreed with the virtual elimination criteria set out by the Canadian Environmental Protection Act (CEPA) 1999 as well as United States Environmental Protection Agency (EPA) criteria. It was concluded that the bioaccumulation criteria for E2 planning will help Environment Canada ensure the protection of the environment from hazardous substances. 11 refs., 3 tabs., 5 figs

Bioaccumulation and uptake routes of perfluoroalkyl acids in Daphnia magna.

Science.gov (United States)

Dai, Zhineng; Xia, Xinghui; Guo, Jia; Jiang, Xiaoman

2013-02-01

Perfluoroalkyl acids (PFAs), one kind of emerging contaminants, have attracted great attentions in recent years. However, the study about their bioaccumulation mechanism remains scarce. In this research, the bioaccumulation of six kinds of PFAs in water flea Daphnia magna was studied. The uptake rates of PFAs in D. magna ranged from 178 to 1338 L kg(-1) d(-1), and they increased with increasing perfluoroalkyl chain length; the elimination rates ranged from 0.98 to 2.82 d(-1). The bioaccumulation factors (BAFs) of PFAs ranged from 91 to 380 L kg(-1) in wet weight after 25 d exposure; they increased with increasing perfluoroalkyl chain length and had a significant positive correlation with the n-octanol/water partition coefficients (logK(ow)) of PFAs (pPFAs plays an important role in their bioaccumulation. The BAFs almost kept constant when the PFA concentrations in aqueous phase increased from 1 to 10 μg L(-1). Scenedesmus subspicatus, as the food of D. magna, did not significantly affect the bioaccumulation of PFAs by D. magna. Furthermore, the body burden of PFAs in the dead D. magna was 1.08-2.52 times higher than that in the living ones, inferring that the body surface sorption is a main uptake route of PFAs in D. magna. This study suggested that the bioaccumulation of PFAs in D. magna is mainly controlled by their partition between organisms and water; further research should be conducted to study the intrinsic mechanisms, especially the roles of protein and lipid in organisms. Copyright © 2012 Elsevier Ltd. All rights reserved.

Halogenation dictates the architecture of amyloid peptide nanostructures.

Science.gov (United States)

Pizzi, Andrea; Pigliacelli, Claudia; Gori, Alessandro; Nonappa; Ikkala, Olli; Demitri, Nicola; Terraneo, Giancarlo; Castelletto, Valeria; Hamley, Ian W; Baldelli Bombelli, Francesca; Metrangolo, Pierangelo

2017-07-20

Amyloid peptides yield a plethora of interesting nanostructures though difficult to control. Here we report that depending on the number, position, and nature of the halogen atoms introduced into either one or both phenylalanine benzene rings of the amyloid β peptide-derived core-sequence KLVFF, four different architectures were obtained in a controlled manner. Our findings demonstrate that halogenation may develop as a general strategy to engineer amyloidal peptide self-assembly and obtain new amyloidal nanostructures.

Joint use of laboratory bioassays and field-collected plants to evaluate toxicity and contaminant bioaccumulation

International Nuclear Information System (INIS)

Long, S.P.; Byron, E.R.; Ohlendorf, H.M.

1995-01-01

Soil toxicity tests using lettuce (Latuca saliva) were conducted using soil samples collected as part of ecological risk assessments at two facilities in California. At some sites, terrestrial plants were collected in the field for chemical analysis. Ecological concerns focused on exposures to plants, phytophagous insects, and their secondary consumers, such as birds and small mammals. The toxicity tests were used to assess potential exposures to a variety of site-specific contaminants including organochlorine pesticides, PCBs, PAHs, petroleum hydrocarbons, heavy metals, and other inorganic substances. Site soils were combined with clean control soils to produce toxicity test soil dilutions containing 100%, 75%, 50%, 25%, and 0% site soils. Observations of seed germination and growth were made at day 0, 7, 14, 21 and 28. Toxicity test results were combined with soil chemical analytical results and physical characteristics to establish NOAELs and LOAELs. Bioaccumulation in the lettuce and field-collected plants was evaluated by comparing plant contaminant to soil contaminant concentrations. Allometric equations and sublethal toxicity data were used to predict potential effects on birds and small mammals. Whole-body contaminant concentrations in insects collected on some of the plants in the field were also considered in evaluating the potential for toxicity to insectivorous birds. The study indicated that contaminant uptake was occurring in the field-collected and bioassay plants but not the insects. Site factors in addition to soil contaminant concentration influenced the potential for plant toxicity and bioaccumulation

Induction of bacterial antibiotic resistance by mutagenic halogenated nitrogenous disinfection byproducts

International Nuclear Information System (INIS)

Lv, Lu; Yu, Xin; Xu, Qian; Ye, Chengsong

2015-01-01

Halogenated nitrogenous disinfection byproducts (N-DBPs) raise concerns regarding their mutagenicity and carcinogenicity threatening public health. However, environmental consequence of their mutagenicity has received less attention. In this study, the effect of halogenated N-DBPs on bacterial antibiotic resistance (BAR) was investigated. After exposure to bromoacetamide (BAcAm), trichloroacetonitrile (TCAN) or tribromonitromethane (TBNM), the resistance of Pseudomonas aeruginosa PAO1 to both individual and multiple antibiotics (ciprofloxacin, gentamicin, polymyxin B, rifampin, tetracycline, ciprofloxacin + gentamicin and ciprofloxacin + tetracycline) was increased, which was predominantly ascribed to the overexpression of efflux pumps. The mechanism of this effect was demonstrated to be mutagenesis through sequencing and analyzing antibiotic resistance genes. The same induction phenomena also appeared in Escherichia coli, suggesting this effect may be universal to waterborne pathogens. Therefore, more attention should be given to halogenated N-DBPs, as they could increase not only genotoxicological risks but also epidemiological risks of drinking water. - Highlights: • The halogenated N-DBPs could induce bacterial antibiotic resistance. • Both individual and multiple resistances could be induced. • Efflux mechanism played an important role in the induced antibiotic resistance. • The halogenated N-DBPs induced bacterial antibiotic resistance via mutagenesis. • Effects of N-DBPs on antibiotic resistance may be universal to waterborne pathogens. - Halogenated N-DBPs could increase antibiotic resistance, even multidrug resistance via mutagenesis, contributing to the enrichment of antibiotic resistant bacteria in drinking water

Bioaccumulation of decamethylcyclopentasiloxane in perch in Swedish lakes.

Science.gov (United States)

Kierkegaard, Amelie; Bignert, Anders; McLachlan, Michael S

2013-10-01

Decamethylcyclopentasiloxane (D5), a high production volume chemical used in personal care products, enters the environment both via air and sewage treatment plant (STP) recipients. It has been found in fish, and there is concern that it may be a bioaccumulative substance. In this work D5 was analyzed in perch from six Swedish lakes that did not receive STP effluent, and in perch and sediment from six lakes that received STP effluent. In the lakes receiving the STP effluent, the D5 concentrations in sediment varied over three orders of magnitude and were correlated with the number of persons connected to the STP normalized to the surface area of the receiving body. In the lakes not receiving effluent, the D5 levels in perch were all below the LOQ, while D5 was above the LOQ in almost all perch from lakes that received effluent. The D5 concentrations in perch and sediment from the lakes receiving STP effluent were correlated. This shows that STP effluent is a much more important source of D5 to aquatic ecosystems than atmospheric deposition, and that the risk of adverse effects of D5 on aquatic life will be greatest in small recipients receiving large amounts of STP effluent. The bioaccumulation of D5 was compared to that of PCB 180 on the basis of multimedia bioaccumulation factors (mmBAFs), which describe the fraction of the contaminant present in the whole aquatic environment (i.e. water and surface sediment) that is transferred to the fish. In four of the six lakes the mmBAF of D5 was >0.3 of the mmBAF of PCB 180. Given that PCB 180 is a known highly bioaccumulative chemical, this indicates that the bioaccumulation of D5 in perch is considerable. Copyright © 2012 Elsevier Ltd. All rights reserved.

Final technical report for the Center for Catalytic Hydrocarbon Functionalization (an EFRC)

Energy Technology Data Exchange (ETDEWEB)

Gunnoe, Thomas Brent [Univ. of Virginia, Charlottesville, VA (United States)

2016-11-11

Greater than 95% of all materials produced by the chemical industry are derived from a small slate of simple hydrocarbons that are derived primarily from natural gas and petroleum, predominantly through oxygenation, C–C bond formation, halogenation or amination. Yet, current technologies for hydrocarbon conversion are typically high temperature, multi-step processes that are energy and capital intensive and result in excessive emissions (including carbon dioxide). The Center for Catalytic Hydrocarbon Functionalization (CCHF) brought together research teams with the broad coalition of skills and knowledge needed to make the fundamental advances in catalysis required for next-generation technologies to convert hydrocarbons (particularly light alkanes and methane) at high efficiency and low cost. Our new catalyst technologies offer many opportunities including enhanced utilization of natural gas in the transportation sector (via conversion to liquid fuels), more efficient generation of electricity from natural gas using direct methane fuel cells, reduced energy consumption and waste production for large petrochemical processes, and the preparation of high value molecules for use in biological/medical applications or the agricultural sector. The five year collaborative project accelerated fundamental understanding of catalyst design for the conversion of C–H bonds to functionalized products, essential to achieve the goals listed above, as evidenced by the publication of 134 manuscripts. Many of these fundamental advancements provide a foundation for potential commercialization, as evidenced by the submission of 11 patents from research support by the CCHF.

Uptake and bioaccumulation of Cry toxins by an aphidophagous predator

International Nuclear Information System (INIS)

Paula, Débora P.; Andow, David A.

2016-01-01

Uptake of Cry toxins by insect natural enemies has rarely been considered and bioaccumulation has not yet been demonstrated. Uptake can be demonstrated by the continued presence of Cry toxin after exposure has stopped and gut contents eliminated. Bioaccumulation can be demonstrated by showing uptake and that the concentration of Cry toxin in the natural enemy exceeds that in its food. We exposed larvae of the aphidophagous predator, Harmonia axyridis, to Cry1Ac and Cry1F through uniform and constant tritrophic exposure via an aphid, Myzus persicae, and looked for toxin presence in the pupae. We repeated the experiment using only Cry1F and tested newly emerged adults. Both Cry toxins were detected in pupae, and Cry1F was detected in recently emerged, unfed adults. Cry1Ac was present 2.05 times and Cry1F 3.09 times higher in predator pupae than in the aphid prey. Uptake and bioaccumulation in the third trophic level might increase the persistence of Cry toxins in the food web and mediate new exposure routes to natural enemies. - Highlights: • Uptake and bioaccumulation of two Cry toxins by a larval coccinellid was tested. • Uptake was demonstrated by presence of the toxins in pupae and adults. • Bioaccumulation was shown by higher toxin concentration in pupae than prey. • Cry1Ac was present 2.05× and Cry1F 3.09× higher in predator pupae than prey. • This might increase persistence of Cry toxins in food webs with new exposure routes. - Immatures of the predaceous coccinellid Harmonia axyridis can uptake and bioaccumulate Cry toxins delivered via their aphid prey.

Concentration-dependent multiple chirality transition in halogen-bond-driven 2D self-assembly process

Science.gov (United States)

Miao, Xinrui; Li, Jinxing; Zha, Bao; Miao, Kai; Dong, Meiqiu; Wu, Juntian; Deng, Wenli

2018-03-01

The concentration-dependent self-assembly of iodine substituted thienophenanthrene derivative (5,10-DITD) is investigated at the 1-octanic acid/graphite interface using scanning tunneling microscopy. Three kinds of chiral arrangement and transition of 2D molecular assembly mainly driven by halogen bonding is clearly revealed. At high concentration the molecules self-assembled into a honeycomb-like chiral network. Except for the interchain van der Waals forces, this pattern is stabilized by intermolecular continuous Cdbnd O⋯I⋯S halogen bonds in each zigzag line. At moderate concentration, a chiral kite-like nanoarchitecture are observed, in which the Cdbnd O⋯I⋯S and I⋯Odbnd C halogen bonds, along with the molecule-solvent Cdbnd O⋯I⋯H halogen bonds are the dominated forces to determine the structural formation. At low concentration, the molecules form a chiral cyclic network resulting from the solvent coadsorption mainly by molecule-molecule Cdbnd O⋯I⋯S halogen bonds and molecule-solvent Cdbnd O⋯I⋯H halogen bonds. The density of molecular packing becomes lower with the decreasing of the solution concentration. The solution-concentration dependent self-assembly of thienophenanthrene derivative with iodine and ester chain moieties reveals that the type of intermolecular halogen bond and the number of the co-adsorbing 1-octanic acids by molecule-solvent Cdbnd O⋯I⋯H halogen bonds determine the formation and transformation of chirality. This research emphasizes the role of different types of halogen (I) bonds in the controllable supramolecular structures and provides an approach for the fabrication of chirality.

Integrated use of biomarkers and bioaccumulation data in Zebra mussel (Dreissena polymorpha) for site-specific quality assessment.

Science.gov (United States)

Binelli, A; Ricciardi, F; Riva, C; Provini, A

2006-01-01

One of the useful biological tools for environmental management is the measurement of biomarkers whose changes are related to the exposure to chemicals or environmental stress. Since these responses might vary with different contaminants or depending on the pollutant concentration reached in the organism, the support of bioaccumulation data is needed to prevent false conclusions. In this study, several persistent organic pollutants -- 23 polychlorinated biphenyl (PCB) congeners, 11 polycyclic aromatic hydrocarbons (PAHs), six dichlorodiphenyltricholroethane (DDT) relatives, hexachlorobenzene (HCB), chlorpyrifos and its oxidized metabolite -- and some herbicides (lindane and the isomers alpha, beta, delta; terbutilazine; alachlor; metolachlor) were measured in the soft tissues of the freshwater mollusc Zebra mussel (Dreissena polymorpha) from 25 sampling sites in the Italian portions of the sub-alpine great lakes along with the measure of ethoxyresorufin dealkylation (EROD) and acetylcholinesterase (AChE) activity. The linkage between bioaccumulation and biomarker data allowed us to create site-specific environmental quality indexes towards man-made chemicals. This classification highlighted three different degrees of xenobiotic contamination of the Italian sub-alpine great lakes: a high water quality in Lake Lugano with negligible pollutant levels and no effects on enzyme activities, an homogeneous poor quality for Lakes Garda, Iseo and Como, and the presence of some xenobiotic point-sources in Lake Maggiore, whose ecological status could be jeopardized, also due to the heavy DDT contamination revealed since 1996.

Assessing element-specific patterns of bioaccumulation across New England lakes

Energy Technology Data Exchange (ETDEWEB)

Ward, Darren M.; Mayes, Brandon; Sturup, Stefan; Folt, Carol L.; Chen, Celia Y., E-mail: celia.chen@dartmouth.edu

2012-04-01

Little is known about differences among trace elements in patterns of bioaccumulation in freshwater food webs. Our goal was to identify patterns in bioaccumulation of different elements that are large and consistent enough to discern despite variation across lakes. We measured methylmercury (MeHg) and trace element (As, Cd, Hg, Pb, and Zn) concentrations in food web components of seven New England lakes on 3-5 dates per lake, and contrasted patterns of bioaccumulation across lakes, metals and seasons. In each lake, trace element concentrations were compared across trophic levels, including three size fractions of zooplankton, planktivorous fish, and piscivorous fish. The trophic position of each food web component was estimated from N isotope analysis. Trace element concentrations varied widely among taxa, lakes and sampling dates. Yet, we identified four consistent patterns of bioaccumulation that were consistent across lakes: (1) MeHg concentration increased (i.e., was biomagnified) and Pb concentration decreased (i.e., was biodiminished) with increased trophic position. (2) Zinc concentration (as with MeHg) was higher in fish than in zooplankton, but overall variation in Zn concentration (unlike MeHg) was low. (3) Arsenic and Cd concentrations (as with Pb) were lower in fish than in zooplankton, but (unlike Pb) were not significantly correlated with trophic position within zooplankton or fish groups. (4) Average summer concentrations of As, Pb, Hg, and MeHg in zooplankton significantly predicted their concentrations in either planktivorous or piscivorous fish. Our secondary goal was to review sampling approaches in forty-five published studies to determine the extent to which current sampling programs facilitate cross-lake and cross-study comparisons of bioaccumulation. We found that studies include different components of the food web and sample too infrequently to enable strong cross-lake and cross-study comparisons. We discuss sampling strategies that would

Assessing element-specific patterns of bioaccumulation across New England lakes

International Nuclear Information System (INIS)

Ward, Darren M.; Mayes, Brandon; Sturup, Stefan; Folt, Carol L.; Chen, Celia Y.

2012-01-01

Little is known about differences among trace elements in patterns of bioaccumulation in freshwater food webs. Our goal was to identify patterns in bioaccumulation of different elements that are large and consistent enough to discern despite variation across lakes. We measured methylmercury (MeHg) and trace element (As, Cd, Hg, Pb, and Zn) concentrations in food web components of seven New England lakes on 3–5 dates per lake, and contrasted patterns of bioaccumulation across lakes, metals and seasons. In each lake, trace element concentrations were compared across trophic levels, including three size fractions of zooplankton, planktivorous fish, and piscivorous fish. The trophic position of each food web component was estimated from N isotope analysis. Trace element concentrations varied widely among taxa, lakes and sampling dates. Yet, we identified four consistent patterns of bioaccumulation that were consistent across lakes: (1) MeHg concentration increased (i.e., was biomagnified) and Pb concentration decreased (i.e., was biodiminished) with increased trophic position. (2) Zinc concentration (as with MeHg) was higher in fish than in zooplankton, but overall variation in Zn concentration (unlike MeHg) was low. (3) Arsenic and Cd concentrations (as with Pb) were lower in fish than in zooplankton, but (unlike Pb) were not significantly correlated with trophic position within zooplankton or fish groups. (4) Average summer concentrations of As, Pb, Hg, and MeHg in zooplankton significantly predicted their concentrations in either planktivorous or piscivorous fish. Our secondary goal was to review sampling approaches in forty-five published studies to determine the extent to which current sampling programs facilitate cross-lake and cross-study comparisons of bioaccumulation. We found that studies include different components of the food web and sample too infrequently to enable strong cross-lake and cross-study comparisons. We discuss sampling strategies that would

Fish bioaccumulation and biomarkers in environmental risk assessment: a review.

Science.gov (United States)

van der Oost, Ron; Beyer, Jonny; Vermeulen, Nico P E

2003-02-01

In this review, a wide array of bioaccumulation markers and biomarkers, used to demonstrate exposure to and effects of environmental contaminants, has been discussed in relation to their feasibility in environmental risk assessment (ERA). Fish bioaccumulation markers may be applied in order to elucidate the aquatic behavior of environmental contaminants, as bioconcentrators to identify certain substances with low water levels and to assess exposure of aquatic organisms. Since it is virtually impossible to predict the fate of xenobiotic substances with simple partitioning models, the complexity of bioaccumulation should be considered, including toxicokinetics, metabolism, biota-sediment accumulation factors (BSAFs), organ-specific bioaccumulation and bound residues. Since it remains hard to accurately predict bioaccumulation in fish, even with highly sophisticated models, analyses of tissue levels are required. The most promising fish bioaccumulation markers are body burdens of persistent organic pollutants, like PCBs and DDTs. Since PCDD and PCDF levels in fish tissues are very low as compared with the sediment levels, their value as bioaccumulation markers remains questionable. Easily biodegradable compounds, such as PAHs and chlorinated phenols, do not tend to accumulate in fish tissues in quantities that reflect the exposure. Semipermeable membrane devices (SPMDs) have been successfully used to mimic bioaccumulation of hydrophobic organic substances in aquatic organisms. In order to assess exposure to or effects of environmental pollutants on aquatic ecosystems, the following suite of fish biomarkers may be examined: biotransformation enzymes (phase I and II), oxidative stress parameters, biotransformation products, stress proteins, metallothioneins (MTs), MXR proteins, hematological parameters, immunological parameters, reproductive and endocrine parameters, genotoxic parameters, neuromuscular parameters, physiological, histological and morphological parameters

Comparing trace metal bioaccumulation characteristics of three freshwater decapods of the genus Macrobrachium

Energy Technology Data Exchange (ETDEWEB)

Cresswell, Tom, E-mail: tom.cresswell@ansto.gov.au [Centre for Environmental Contaminants Research, CSIRO Land and Water, New Illawarra Rd, Lucas Heights, 2234, NSW (Australia); School of Applied Sciences, RMIT University, Plenty Road, Bundoora 3083, VIC (Australia); Smith, Ross E.W. [Hydrobiology, Lang Parade, Auchenflower 4066, QLD (Australia); Nugegoda, Dayanthi [School of Applied Sciences, RMIT University, Plenty Road, Bundoora 3083, VIC (Australia); Simpson, Stuart L. [Centre for Environmental Contaminants Research, CSIRO Land and Water, New Illawarra Rd, Lucas Heights, 2234, NSW (Australia)

2014-07-01

Highlights: • Exposed three species of prawns of same genus to solid- and dissolved-phase metals. • Cd bioaccumulated from dissolved phase was significantly different between species. • All three species retained >95% of bioaccumulated Cd during the depuration phase. • Bioaccumulation of As, Pb and Zn from solid phase was different between species. • Results highlight variability among species, even under controlled conditions. - Abstract: Potential sources and kinetics of metal bioaccumulation by the three Macrobrachium prawn species M. australiense, M. rosenbergii and M. latidactylus were assessed in laboratory experiments. The prawns were exposed to two scenarios: cadmium in water only; and exposure to metal-rich mine tailings in the same water. The cadmium accumulation from the dissolved exposure during 7 days, followed by depuration in cadmium-free water for 7 days, was compared with predictions from a biokinetic model that had previously been developed for M. australiense. M. australiense and M. latidactylus accumulated significant tissue cadmium during the exposure phase, albeit with different uptake rates. All three species retained >95% of the bioaccumulated cadmium during the depuration phase, indicating very slow efflux rates. Following exposure to tailings, there were significant (p < 0.05) differences in tissue arsenic, cadmium, lead and zinc concentrations among species. Cadmium and zinc concentrations were increased relative to controls for all three species but were not different between treatments (direct/indirect contact with tailings), suggesting these metals were primarily accumulated via the dissolved phase. All species bioaccumulated significantly greater arsenic and lead when in direct contact with mine tailings, demonstrating the importance of an ingestion pathway for these metals. Copper was not bioaccumulated above control concentrations for any species. The differences between the metal accumulation of the three prawns indicated

Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

Directory of Open Access Journals (Sweden)

Naoya Usuki

2017-12-01

Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

Halogen bonding: A new retention mechanism for the solid phase extraction of perfluorinated iodoalkanes

International Nuclear Information System (INIS)

Yan Xiaoqing; Shen Qianjin; Zhao Xiaoran; Gao Haiyue; Pang Xue; Jin Weijun

2012-01-01

Highlights: ► Halogen bonding (XB) is firstly utilised in solid phase extraction. ► The perfluorinated iodine alkanes can be extracted by C-I⋯Cl − halogen bonding. ► The C-I⋯Cl − halogen bond is well characterised by spectroscopy methods. ► The analytes with strong halogen-bonding abilities can be selectively extracted. - Abstract: For the first time, halogen-bonding interaction is utilised in the solid phase extraction of perfluorinated iodoalkane (PFI). Nine PFIs, as model analytes, were tested, and analyses by UV, 19 F NMR and Raman spectroscopies demonstrate that the PFIs are extracted by a strong anion exchange (SAX) sorbent from n-hexane due to the C-I⋯Cl − halogen-bonding interactions. The results also show that the adsorptivities of SAX for the diiodoperfluoro-alkanes (diiodo-PFIs) were much stronger than those for the perfluoroalkyl iodides (monoiodo-PFIs). Specifically, the recoveries for 1,6-diiodoperfluorohexane and 1,8-diiodoperfluorooctane were higher than 80% when 100 mL of sample spiked with a 5 ng mL −1 analyte mixture was extracted. Interestingly, SAX had no adsorption for hexafluorobenzene at all, which is known to be unable to form a halogen bond with Cl − . The analytical performance of the halogen bond-based SPE-GC–MS method for the diiodo-PFIs was also examined in soil samples. The sorbent SAX enabled the selective extraction of four diiodo-PFIs successfully from soil samples. The recoveries of the diiodo-PFIs extracted from 5 g soil sample at the 100 ng g −1 spike level were in the range of 73.2–93.8% except 26.8% for 1,2-diiodoperfluoroethane. The limit of detection varied from 0.02 to 0.04 ng g −1 in soil samples. Overall, this work reveals the great application potential of halogen bonding in the field of solid phase extraction to selectively extract compounds with strong halogen-bonding abilities.

Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

CERN Document Server

MacKinlay, Alistair F; Whillock, M J

1989-01-01

This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard.

Ultraviolet radiation and blue-light emissions from spotlights incorporating tungsten halogen lamps

International Nuclear Information System (INIS)

McKinlay, A.F.; Whillock, M.J.; Meulemans, C.C.E.

1989-07-01

This report summarises measurements of the ultraviolet radiation and blue-light emissions from eleven 'desk-top' tungsten halogen (quartz) lamps and one 'floor-standing' tungsten halogen (quartz) lamp available in the UK. Values of occupational hazard weighted and erythemally weighted ultraviolet radiation irradiance and measurements and relevant calculations of blue-light hazards are presented. It is concluded that the safety design of some desk-top tungsten halogen lamps is inadequate to prevent unnecessary exposure of the skin to potentially harmful ultraviolet radiation. It is recommended that all tungsten halogen lamps should have sufficient filtration to reduce their ultraviolet emissions to an acceptably low level. As long as the comfort aversion responses of the eye are respected, direct viewing of the lamps examined should not constitute a retinal hazard. (author)

Role of metal mixtures (Ca, Cu and Pb) on Cd bioaccumulation and phytochelatin production by Chlamydomonas reinhardtii

International Nuclear Information System (INIS)

Abboud, Pauline; Wilkinson, Kevin J.

2013-01-01

The goal of the study was to determine whether metal uptake and biological effects could be predicted by free ion concentrations when organisms were exposed to Cd and a second metal. Bioaccumulation and algal phytochelatin (PC) concentrations were determined for Chlamydomonas reinhardtii following a 6-h exposure. Bioaccumulation results, after six hours of exposure, showed that Cd uptake decreased in the presence of relatively high concentrations of Ca, Cu and Pb, however, Cd bioaccumulation increased in the presence of ca. equimolar concentrations of Cu. A good correlation was observed between the production of PCs and the amount of metals bioaccumulated for the binary mixtures of Cd–Pb and Cd–Cu, but not the Cd–Ca mixture. Overall, the results suggested that, in the case of mixtures, bioaccumulated metal rather than free ion concentrations would be a better predictor of biological effect. -- Highlights: •Cd bioaccumulation and phytochelatin production were evaluated for metal mixtures. •Bioaccumulated metal rather than free ion was a better predictor of biological effect. •Calcium additions decreased Cd bioaccumulation but increased phytochelatin production. •Copper additions increased Cd bioaccumulation and phytochelatin production. •Lead additions had little effect on either Cd bioaccumulation or phytochelatin production. -- In metal mixtures containing Cd and Ca, Pb or Cu, bioaccumulated metal rather than free ion was a better predictor of biological effect

Uranium bioaccumulation in a freshwater ecosystem: Impact of feeding ecology

Energy Technology Data Exchange (ETDEWEB)

Kraemer, Lisa D., E-mail: lisakraemer@trentu.ca [Trent University, 1600 West Bank Drive, Peterborough, ON, K9J 7B8 (Canada); Evans, Douglas [Trent University, 1600 West Bank Drive, Peterborough, ON, K9J 7B8 (Canada)

2012-11-15

Uranium bioaccumulation in a lake that had been historically affected by a U mine and (2) to use a combined approach of gut content examination and stable nitrogen and carbon isotope analysis to determine if U bioaccumulation in fish was linked to foodweb ecology. We collected three species of fish: smallmouth bass (Micropterus dolomieu), yellow perch (Perca flavescens) and bluegill (Lepomis macrochirus), in addition to several invertebrate species including freshwater bivalves (family: Sphaeriidae), dragonfly nymphs (order: Odonata), snails (class: Gastropoda) and zooplankton (family: Daphniidae). Results showed significant U bioaccumulation in the lake impacted by historical mining activities. Uranium accumulation was 2-3 orders of magnitude higher in invertebrates than in the fish species. Within fish, U was measured in operculum (bone), liver and muscle tissue and accumulation followed the order: operculum > liver > muscle. There was a negative relationship between stable nitrogen ratios ({sup 15}N/{sup 14}N) and U bioaccumulation, suggesting U biodilution in the foodweb. Uranium bioaccumulation in all three tissues (bone, liver, muscle) varied among fish species in a consistent manner and followed the order: bluegill > yellow perch > smallmouth bass. Collectively, gut content and stable isotope analysis suggests that invertebrate-consuming fish species (i.e. bluegill) have the highest U levels, while fish species that were mainly piscivores (i.e. smallmouth bass) have the lowest U levels. Our study highlights the importance of understanding the feeding ecology of fish when trying to predict U accumulation.

Determination of halogens by flame emission of metal halogenides

International Nuclear Information System (INIS)

Henrion, G.; Marquardt, D.; Stoecker, B.

1979-01-01

The A-B systems InF, InCl, InBr, and InI have been excited by laminar H 2 -N 2 flames in order to dermine individual halogens or their mixtures qualitatively or quantitatively. In optimizing the fuel gas composition two different behavior patterns have been found for band intensities, which are correlated with binding energies of InX (X = halogen). The low temperature of the flame leads to complicated matrix effects which first of all result from effects on excitation and from competitive reactions. In general, cations cause a decreased intensity. Therefore, salts have to be converted into hydrohalide acids by ion exchange. Qualitative determinations of individual halogens are possible at a 500 to 50,000fold excess of the others, whereas quantitative determinations can be performed at a 100 to 5,000fold excess in 10 -4 molar solutions with errors of 2 to 10 per cent. (author)

The Dessau workshop on bioaccumulation: state of the art, challenges and regulatory implications.

Science.gov (United States)

Treu, Gabriele; Drost, Wiebke; Jöhncke, Ulrich; Rauert, Caren; Schlechtriem, Christian

2015-01-01

Bioaccumulation plays a vital role in understanding the fate of a substance in the environment and is key to the regulation of chemicals in several jurisdictions. The current assessment approaches commonly use the octanol-water partition coefficient (log K OW ) as an indicator for bioaccumulation and the bioconcentration factor (BCF) as a standard criterion to identify bioaccumulative substances show limitations. The log K OW does not take into account active transport phenomena or special structural properties (e.g., amphiphilic substances or dissociating substances) and therefore additional screening criteria are required. Regulatory BCF studies are so far restricted to fish and uptake through the gills. Studies on (terrestrial) air-breathing organisms are missing. Though there are alternative tests such as the dietary exposure bioaccumulation fish test described in the recently revised OECD test guideline 305, it still remains unclear how to deal with results of alternative tests in regulatory decision-making processes. A substantial number of bioaccumulation fish tests are required in regulation. The development of improved test systems following the 3R principles, namely to replace, reduce and refine animal testing, is thus required. All these aspects stress the importance to further develop the assessment of bioaccumulation. The Dessau Workshop on Bioaccumulation which was held from June 26th to 27th 2014, in Dessau, Germany, provided a comprehensive overview of the state of the art of bioaccumulation assessment, provided insights into the problems and challenges addressed by the regulatory authorities and described new research concepts and their regulatory implications. The event was organised by UBA (Dessau, Germany) and Fraunhofer IME (Schmallenberg, Germany). About 50 participants from industry, regulatory bodies and academia listened to 14 lectures on selected topics and joined the plenary discussions.

High-temperature peaks of thermostimulated luminescence in the ammonium halogens

International Nuclear Information System (INIS)

Kim, L.M.; Musenova, Eh.K.; Mukhamedrakhimov, K.U.

2003-01-01

The ammonium halogen crystals (AHC) are the close analogs of the alkali halogen crystals by the type of chemical bonds and crystal lattice structure. The ammonium halogen after irradiation by X-rays within 80-300 K range have two peaks of thermo-stimulation luminescence. Its maximums in dependence of anions type are in the 110-120 K and 170-180 K ranges. The first range is related with activation of auto-localized holes migration, and the second one - with the NH 3 + defects decay. Experimentally is established, that the pure ammonium halogens have memory about the previous irradiation at heating up to 300 K. After repeat irradiation the recombination luminescence high-temperature peak's shoulder is appearing. The second luminescence peak's shoulder revealing does not depend on the impurity center nature. It is known, that in the AHC there is the next thermo-stimulation luminescence peak within 340-360 K. The thermal annealing of this peak leads to the memory effect disappearance. So, the observing phenomenon is related with own defect of the matrix in the cation sublattice. Experimentally is established, that at a room temperature the AHC memorizing about previous irradiation during 20 h

Biosorption and bioaccumulation of thallium by thallium-tolerant fungal isolates.

Science.gov (United States)

Sun, Jialong; Zou, Xiao; Xiao, Tangfu; Jia, Yanlong; Ning, Zengping; Sun, Min; Liu, Yizhang; Jiang, Tao

2015-11-01

Little is known about the biosorption and bioaccumulation capacity of thallium (Tl) by microorganisms that occur in Tl-polluted soil. The present study focused on characterizing the biosorption and bioaccumulation of Tl by Tl-tolerant fungi isolated from Tl-polluted soils. Preliminary data showed a positive correlation between the biomass and the biosorbed Tl content. The Tl-tolerant strains were capable of bioaccumulating Tl, up to 7189 mg kg(-1) dry weight. The subcellular distribution of Tl showed obvious compartmentalization: cytoplasm ≫ cell wall > organelle. The majority of Tl (up to 79%) was found in the cytoplasm, suggesting that intracellular compartmentalization appeared to be responsible for detoxification. These findings further suggest the applicability of the fungal isolates for cleanup of Tl in Tl-polluted water and soil.

Dietary taurine supplementation ameliorates the lethal effect of phenanthrene but not the bioaccumulation in a marine teleost, red sea bream, Pagrus major.

Science.gov (United States)

Hano, Takeshi; Ito, Mana; Ito, Katsutoshi; Kono, Kumiko; Ohkubo, Nobuyuki

2017-03-01

The present study was performed to evaluate the effect of dietary taurine on the hepatic metabolic profiles of red sea bream (Pagrus major) and on phenanthrene (a polyaromatic hydrocarbon) toxicity and bioaccumulation. The fish were fed a diet supplemented with 0% (TAU0%), 0.5% (TAU0.5%), or 5% (TAU5%) taurine for 40-55d and subjected to phenanthrene acute toxicity and bioaccumulation tests. Taurine deficiency in feed severely affected the hepatic metabolic profiles of fish, which indicated a complementary physiological response to taurine deficiency. For the acute toxicity test, fish were fed the test diets for 55d and were then exposed to 0-893µg/L phenanthrene for 96h. Tolerance to phenanthrene was significantly improved by 0.5% of taurine inclusion in feed relative to TAU0%, but not by 5.0% inclusion. Reduced glutathione in the liver, which acts as an oxygen-free radical scavenger, was associated with a reduction in the toxicity of phenanthrene. For the bioaccumulation test, fish were fed the test diets for 40d and were thereafter chronically exposed to 20µg/L phenanthrene for 13d followed by depuration for 3d. The activity of hepatic biomarker, ethoxyresorufin-O-deethylase, was increased by phenanthrene exposure in the taurine inclusion groups. However, phenanthrene concentrations in the liver and muscle of fish fed TAU5.0% tended to be higher than those of fish fed TAU0% and TAU0.5% during the exposure period. These results indicate that 0.5% of taurine inclusion in feed plays an important role in the alleviation of phenanthrene toxicity but not bioaccumulation. Furthermore, larger amount of taurine inclusion (TAU5%) did not show marked beneficial effects against phenanthrene exposure. This study provides insight about a major concern of environmental contaminants into aquatic environment and can be effectively used for improvement of aquaculture. Copyright © 2016 Elsevier Inc. All rights reserved.

Bioaccumulation versus adsorption of reactive dye by immobilized growing Aspergillus fumigatus beads

International Nuclear Information System (INIS)

Wang, B.-E.; Hu Yongyou

2008-01-01

The removal of reactive brilliant blue KN-R using growing Aspergillus fumigatus (abbr. A. fumigatus) immobilized on carboxymethylcellulose (CMC) beads with respect to initial dye concentration was investigated. Bioaccumulation was the dominant mechanism of the dye removal. According to the UV-vis spectra and the results of three sets of experiments, it could be concluded that the bioaccumulation using immobilized growing A. fumigatus beads was achieved by metabolism-dependent accumulation and metabolism-independent adsorption (15-23% proportion of overall dye removal), which included biosorption by mycelia entrapped in them and adsorption on immobilization matrix. The transmission electron microscope (TEM) images showed the intracellular structures of mycelia and the toxicity of dye. It was found that the fungus had a considerable tolerance to reactive brilliant blue KN-R at initial dye concentrations of <114.7 mg/l. Though at high initial dye concentrations the growth of mycelia was inhibited significantly by the dye molecules in the growth medium, the bioaccumulation capacity was not markedly affected and the maximum bioaccumulation capacity was 190.5 ± 2.0 mg/g at an initial dye concentration of 374.4 mg/l. The bioaccumulation rates were not constant over the contact time

Trait-based modelling of bioaccumulation by freshwater benthic invertebrates.

Science.gov (United States)

Sidney, Livia Alvarenga; Diepens, Noël J; Guo, Xiaoying; Koelmans, Albert A

2016-07-01

Understanding the role of species traits in chemical exposure is crucial for bioaccumulation and toxicity assessment of chemicals. We measured and modelled bioaccumulation of polychlorinated biphenyls (PCBs) in Chironomus riparius, Hyalella azteca, Lumbriculus variegatus and Sphaerium corneum. We used a battery test procedure with multiple enclosures in one aquarium, which maximized uniformity of exposure for the different species, such that the remaining variability was due mostly to species traits. The relative importance of uptake from either pore water or sediment ingestion was manipulated by using 28 d aged standard OECD sediment with low (1%) and medium (5%) OM content and 13 months aged sediment with medium OM (5%) content. Survival was ≥76% and wet weight increased for all species. Reproduction of H. azteca and weight gain of H. azteca and S. corneum were significantly higher in the medium OM aged sediments than in other sediments, perhaps due to a more developed microbial community (i.e., increase in food resources). Biota-sediment accumulation factors (BSAF) ranged from 3 to 114, depending on species and PCB congener, with C. riparius (3-10)bioaccumulation model with species-specific bioaccumulation parameters fitted well to the experimental data and showed that bioaccumulation parameters were depended on species traits. Enclosure-based battery tests and mechanistic BSAF models are expected to improve the quality of the exposure assessment in whole sediment toxicity tests. Copyright © 2016 Elsevier B.V. All rights reserved.

Halogens determination in vegetable NBS standard reference materials

International Nuclear Information System (INIS)

Stella, R.; Genova, N.; Di Casa, M.

1977-01-01

Levels of all four halogens in Orchard Leaves, Pine Needles and Tomato Leaves NBS reference standards were determined. For fluorine a spiking isotope dilution method was used followed by HF absorption on glass beads. Instrumental nuclear activation analysis was adopted for chlorine and bromine determination. Radiochemical separation by a distillation procedure was necessary for iodine nuclear activation analysis after irradiation. Activation parameters of Cl, Br and I are reported. Results of five determinations for each halogen in Orchard Leaves, Pine Needles and Tomato Leaves NBS Standard Materials and Standard deviations of the mean are reported. (T.I.)

Heavy metal distribution and bioaccumulation in Chihuahuan Desert Rough Harvester ant (Pogonomyrmex rugosus) populations

International Nuclear Information System (INIS)

Del Toro, I.; Floyd, K.; Gardea-Torresdey, J.; Borrok, D.

2010-01-01

Heavy metal contamination can negatively impact arid ecosystems; however a thorough examination of bioaccumulation patterns has not been completed. We analyzed the distribution of As, Cd, Cu, Pb and Zn in soils, seeds and ant (Pogonomyrmex rugosus) populations of the Chihuahuan Desert near El Paso, TX, USA. Concentrations of As, Cd, Cu, and Pb in soils, seeds and ants declined as a function of distance from a now inactive Cu and Pb smelter and all five metals bioaccumulated in the granivorous ants. The average bioaccumulation factors for the metals from seeds to ants ranged from 1.04x (As) to 8.12x (Cd). The findings show bioaccumulation trends in linked trophic levels in an arid ecosystem and further investigation should focus on the impacts of heavy metal contamination at the community level. - Heavy metals bioaccumulate in desert ants.

Monitoring of polycyclic aromatic hydrocarbons in a produced water disposal area in the Potiguar Basin, Brazilian equatorial margin.

Science.gov (United States)

Lourenço, Rafael André; de Oliveira, Fábio Francisco; de Souza, João Maximino; Nudi, Adriana Haddad; de Luca Rebello Wagener, Ângela; de Fátima Guadalupe Meniconi, Maria; Francioni, Eleine

2016-09-01

The Potiguar Basin has oil and gas production fields offshore and onshore. All treated produced water (PW) from these fields is discharged through submarine outfalls. Although polycyclic aromatic hydrocarbons (PAHs) are minor constituents of PW, their input into the marine ecosystem is environmentally critical due to potential ecological hazards. A 2-year monitoring program was conducted in the vicinity of the outfalls to evaluate PAH bioaccumulation in marine life from PW discharges. The study was performed using transplanted bivalves Crassostrea brasiliana and semipermeable membrane devices (SPMDs) to measure PAH concentrations via bioaccumulation and in seawater. The bioaccumulation of PAH in transplanted bivalves reached up to 1105 ng g(-1) in the vicinity of the monitored outfall. Significantly lower PAH concentrations were found in the reference area in comparison to the studied area around the outfalls. Time-integrated PAH concentrations in seawater ranged from 38 to 0.3 ng L(-1) near the outfalls and from 10 ng L(-1) to not detected in the reference area. Both measurement techniques were found to be effective for determining a gradient of descending PAH concentrations from the outfalls. In addition, this study also evaluated the bioavailability of PAH for local marine biota and provided information about the influence of PW discharges on the water quality of marine ecosystems.

Importance of growth rate on Hg and PCB bioaccumulation in fish

Science.gov (United States)

Li, Jiajia; Haffner, G. Douglas; Patterson, Gordon; Walters, David M.; Burtnyk, Michael D.; Drouillard, Ken G.

2018-01-01

To evaluate the effect of fish growth on mercury (Hg) and polychlorinated biphenyls (PCBs) bioaccumulation, a non‐steady state toxicokinetic model, combined with a Wisconsin bioenergetics model, was developed to simulate Hg and PCB bioaccumulation in Bluegill (Lepomis macrochirus). The model was validated by comparing observed versus predicted Hg and PCB 180 concentrations across 5 age classes from five different waterbodies across North America. The non‐steady state model generated accurate predictions for Hg and PCB bioaccumulation in three of five waterbodies: Apsey, Sharbot and Stonelick Lake. The poor performance of the model for the Detroit River and Lake Hartwell, which were two well‐known contaminated sites with possibly high heterogeneity in spatial contamination, was attributed to changes in the feeding behavior and/ or change in prey contamination. Model simulations indicate that growth dilution is a major component of contaminant bioaccumulation patterns in fish especially during early life stages and was predicted to be more important for hydrophobic PCBs compared to Hg. Simulations which considered tissue specific growth provided some improvement in model performance particularly for PCBs in fish populations which exhibited changes in their whole body lipid content with age. Higher variation in lipid growth compared with that of lean dry protein was also observed between different bluegill populations which partially explains the greater variation in PCB bioaccumulation slopes compared with Hg across sampling sites.

Halogen Bonding Involving CO and CS with Carbon as the Electron Donor

Directory of Open Access Journals (Sweden)

Janet E. Del Bene

2017-11-01

Full Text Available MP2/aug’-cc-pVTZ calculations have been carried out to investigate the halogen-bonded complexes formed when CO and CS act as electron-pair donors through C to ClF, ClNC, ClCl, ClOH, ClCN, ClCCH, and ClNH2. CO forms only complexes stabilized by traditional halogen bonds, and all ClY molecules form traditional halogen-bonded complexes with SC, except ClF which forms only an ion-pair complex. Ion-pair complexes are also found on the SC:ClNC and SC:ClCl surfaces. SC:ClY complexes stabilized by traditional halogen bonds have greater binding energies than the corresponding OC:ClY complexes. The largest binding energies are found for the ion-pair SC–Cl+:−Y complexes. The transition structures which connect the complex and the ion pair on SC:ClNC and SC:ClCl potential surfaces provide the barriers for inter-converting these structures. Charge-transfer from the lone pair on C to the σ-hole on Cl is the primary charge-transfer interaction stabilizing OC:ClY and SC:ClY complexes with traditional halogen bonds. A secondary charge-transfer occurs from the lone pairs on Cl to the in-plane and out-of-plane π antibonding orbitals of ClY. This secondary interaction assumes increased importance in the SC:ClNH2 complex, and is a factor leading to its unusual structure. C–O and C–S stretching frequencies and 13C chemical shieldings increase upon complex formation with ClY molecules. These two spectroscopic properties clearly differentiate between SC:ClY complexes and SC–Cl+:−Y ion pairs. Spin–spin coupling constants 1xJ(C–Cl for OC:ClY complexes increase with decreasing distance. As a function of the C–Cl distance, 1xJ(C–Cl and 1J(C–Cl provide a fingerprint of the evolution of the halogen bond from a traditional halogen bond in the complexes, to a chlorine-shared halogen bond in the transition structures, to a covalent bond in the ion pairs.

Bioaccumulation and chemical modification of Tc by soil bacteria

International Nuclear Information System (INIS)

Henrot, J.

1989-01-01

Bioaccumulation and chemical modification of pertechnetate (TcO 4 -) by aerobically and anaerobically grown soil bacteria and by pure cultures of sulfate-reducing bacteria (Desulfovibrio sp.) were studied to gain insight on the possible mechanisms by which bacteria can affect the solubility of Tc in soil. Aerobically grown bacteria had no apparent effect on TcO 4 -; they did not accumulate Tc nor modify its chemical form. Anaerobically grown bacteria exhibited high bioaccumulation and reduced TcO 4 -, enabling its association with organics of the growth medium. Reduction was a metabolic process and not merely the result of reducing conditions in the growth medium. Association of Tc with bacterial polysaccharides was observed only in cultures of anaerobic bacteria. Sulfate-reducing bacteria efficiently removed Tc from solution and promoted its association with organics. Up to 70% of the total Tc in the growth medium was bioaccumulated and/or precipitated. The remaining Tc in soluble form was entirely associated with organics. Pertechnetate was not reduced by the same mechanism as dissimilatory sulfate reduction, but rather by some reducing agent released in the growth medium. A calculation of the amount of Tc that could be associated with the bacterial biomass present in soil demonstrates that high concentration ratios in cultures do not necessarily imply that bioaccumulation is an important mechanism for long-term retention of Tc in soil

A Survey of Electron Impact Cross-Sections for Halogens and Halogen Compounds of Interest to Plasma Processing

Science.gov (United States)

Sharma, S. P.; Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)

1998-01-01

Published electron impact cross section data on halogens Cl2, F2, and halogen containing compounds such as Cx Fy, HCl, Cx Cly Fz are reviewed and critically evaluated based on the information provided by various researchers. The present work reports data on electron impact excitation, ionization, dissociation, electron attachment, electron detachment, and photo detachment. Elastic scattering cross sections and data on bulk properties such as diffusion coefficients in various background gases are also evaluated. Since some of the cross sectional data is derived from indirect measurements such as drift velocity, care has been taken to reconcile the differences among the reported data with due attention to the measurement technique. In conclusion, the processes with no or very limited amount of data and questionable set of data are identified and recommendation for further research direction is made.

Estrogenicity of halogenated bisphenol A: in vitro and in silico investigations.

Science.gov (United States)

Zhang, Jie; Li, Tiezhu; Wang, Tuoyi; Yuan, Cuiping; Zhong, Shuning; Guan, Tianzhu; Li, Zhuolin; Wang, Yongzhi; Yu, Hansong; Luo, Quan; Wang, Yongjun; Zhang, Tiehua

2018-03-01

The binding interactions of bisphenol A (BPA) and its halogenated derivatives (halogenated BPAs) to human estrogen receptor α ligand binding domain (hERα-LBD) was investigated using a combined in vitro and in silico approach. First, the recombinant hERα-LBD was prepared as a soluble protein in Escherichia coli BL21(DE3)pLysS. A native fluorescent phytoestrogen, coumestrol, was employed as tracer for the fluorescence polarization assay. The results of the in vitro binding assay showed that bisphenol compounds could bind to hERα-LBD as the affinity ligands. All the tested halogenated BPAs exhibited weaker receptor binding than BPA, which might be explained by the steric effect of substituents. Molecular docking studies elucidated that the halogenated BPAs adopted different conformations in the flexible hydrophobic ligand binding pocket (LBP), which is mainly dependent on their distinct halogenation patterns. The compounds with halogen substituents on the phenolic rings and on the bridging alkyl moiety acted as agonists and antagonists for hERα, respectively. Interestingly, all the compounds in the agonist conformation of hERα formed a hydrogen bond with His524, while the compounds in the antagonist conformation formed a hydrogen bond with Thr347. These docking results suggested a pivotal role of His524/Thr347 in maintaining the hERα structure in the biologically active agonist/antagonist conformation. Comparison of the calculated binding energies vs. experimental binding affinities yielded a good correlation, which might be applicable for the structure-based design of novel bisphenol compounds with reduced toxicities and for environmental risk assessment. In addition, based on hERα-LBD as a recognition element, the proposed fluorescence polarization assay may offer an alternative to chromatographic techniques for the multi-residue determination of bisphenol compounds.

Halogen degassing during ascent and eruption of water-poor basaltic magma

Science.gov (United States)

Edmonds, M.; Gerlach, T.M.; Herd, Richard A.

2009-01-01

A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of < 1??MPa, equivalent to < ~ 35??m in the conduit. Fluid-melt partition coefficients for Cl and F are low (< 1.5); F only degasses appreciably at < 0.1??MPa above atmospheric pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

Emission of Volatile OrganoHalogens by Southern African Solar Salt Works

Science.gov (United States)

Kotte, Karsten; Weissflog, Ludwig; Lange, Christian Albert; Huber, Stefan; Pienaar, Jacobus J.

2010-05-01

hyper-saline environments, rich in chloride, bromide and partly iodide. They can be seen as semi natural reactors for hypersaline microorganisms like bacteria, algae and archaea as they can be found in natural hypersaline environments as well. To assess possible VOX emission of solar salt works the Walfishbay Salt Refiners (PTY) LTD (Namibia) were investigated and sediments of several crystallizer pans where collected. Only affected by natural temperature and radiation regime the VOX production inside the tightly closed incubation vials were determined regularly for several months by using headspace GC combined with an electron capture detector. Besides a number of non halogenated volatile hydrocarbons, detected by a self modified purge and trap GC/MS system the following VOX have been identified: CHCl3, CH3J, CH3Br, CCl4, C2HCl3, C2Cl4. According to earlier experiments on natural salt sediments of Southern Russia a biosynthesis process involving halophilic archaea is highly probable. Although the metabolic routes entailed are not yet identified. Obtained long term emission data are presented by focussing on possible meteorological propulsion as solar and UV radiation as well as temperature. Discussing the incubation experiments Southern African solar salt works reveal to represent interesting sources of chemically active VOX.

Bioaccumulation of 14C-hexachlorobenzene in eggs and fry of Japanese medaka (Oryzias latipes)

International Nuclear Information System (INIS)

Huang, Y.; Biddinger, G.R.; Gloss, S.P.

1986-01-01

Hexachlorobenzene (HCB) is a widespread pollutant that is persistent once it enters the ecosphere. It bioaccumulates in both terrestrial and aquatic animals and is not readily metabolized. Although HCB bioaccumulation in fresh water fish has been reported, few data are available on bioaccumulation of this or other chemicals during early developmental stages of fish. The authors used the Japanese medaka (Oryzias latipes) to examine the rates of HCB bioaccumulation during early life stages subjected to both short term (24 h) and long term (14 day) aqueous exposure. The relatively rapid development and ease of laboratory maintenance made the medaka an ideal organism for this purpose

Explaining differences between Bioaccumulation Measurements in laboratory and field data through use of probabilistic modeling approach

NARCIS (Netherlands)

Selck, H.; Drouillard, K.; Eisenreich, K.; Koelmans, A.A.; Palmqvist, A.; Ruus, A.; Salvito, D.; Schultz, I.; Stewart, R.; Weisbrod, A.; Brink, van den N.W.; Heuvel-Greve, van den M.J.

2012-01-01

In the regulatory context, bioaccumulation assessment is often hampered by substantial data uncertainty as well as by the poorly understood differences often observed between results from laboratory and field bioaccumulation studies. Bioaccumulation is a complex, multifaceted process, which calls

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

Science.gov (United States)

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1983-09-20

A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

Bioaccumulation Studies Associated with the Kingston Fly Ash Spill, Spring 2009 - Fall 2010

Energy Technology Data Exchange (ETDEWEB)

Adams, Marshall [ORNL; Brandt, Craig C [ORNL; Fortner, Allison M [ORNL

2012-05-01

In December 2008, an ash dike at the Tennessee Valley Authority (TVA) Kingston Fossil Plant ruptured, releasing over one billion gallons of coal fly ash into the Emory and Clinch Rivers. Coal fly ash may contain several contaminants of concern, but of these selenium (Se) and arsenic (As) have been highlighted because of their toxicity and tendency to bioaccumulate in aquatic food chains. To assess the potential impact of the spilled fly ash on humans and the environment, a comprehensive biological and environmental monitoring program was established, for which resident aquatic organisms (among other sample media) are collected to determine contaminant exposure and evaluate the risk to humans and wildlife. Studies on bioaccumulation and fish health are major components of the TVA Biological Monitoring Program for the Kingston fly ash project. These studies were initiated in early Spring 2009 for the purposes of: (1) documenting the levels of fly ash-associated metals in various tissues of representative sentinel fish species in the area of the fly ash spill, (2) determining if exposure to fly ash-associated metals causes short, intermediate, or long-term health effects on these sentinel fish species, (3) assessing if there are causal relationships between exposure (to metals) and effects on fish, (4) evaluating, along with information regarding other ecological and physicochemical studies, the nature and route of contaminant transfer though food chains into higher level consumers, (5) providing important information for the Ecological Risk Assessment (ERA) for the Kingston fly ash project, and (6) serving as an important technology transfer or model study focused on how to best evaluate the environmental effects of fly ash, not only at the Kingston site, but also at sites on other aquatic systems where coal-fired generating stations are located. This report summarizes the bioaccumulation results from the first two years of study after the fly ash spill, including

Risk assessment for halogenated solvents

International Nuclear Information System (INIS)

Travis, C.C.

1988-01-01

A recent development in the cancer risk area is the advent of biologically based pharmacokinetic and pharmacodynamic models. These models allow for the incorporation of biological and mechanistic data into the risk assessment process. These advances will not only improve the risk assessment process for halogenated solvents but will stimulate and guide basic research in the biological area

Great Lakes water quality initiative technical support document for the procedure to determine bioaccumulation factors. Draft report

International Nuclear Information System (INIS)

1993-03-01

The purpose of the document is to provide the technical information and rationale in support of the proposed procedures to determine bioaccumulation factors. Bioaccumulation factors, together with the quantity of aquatic organisms eaten, determine the extent to which people and wildlife are exposed to chemicals through the consumption of aquatic organisms. The more bioaccumulative a pollutant is, the more important the consumption of aquatic organisms becomes as a potential source of contaminants to humans and wildlife. Bioaccumulation factors are needed to determine both human health and wildlife tier I water quality criteria and tier II values. Also, they are used to define Bioaccumulative Chemicals of Concern among the Great Lakes Initiative universe of pollutants. Bioaccumulation factors range from less than one to several million

Development of halogen-free cables for nuclear power plants

International Nuclear Information System (INIS)

Yamamoto, Mitsuo; Ito, Kazumi; Yaji, Takeo; Yoshida, Shin; Sakurai, Takako; Matsushita, Shigetoshi.

1990-01-01

On the occasion where serious fire accidents were experienced in the past, the need for making flame-retardant wire and cable incombustible took place and has since been generalizing. Various sorts of flame-retardant cables have already been developed and been actually used. From the viewpoint of avoiding the interference with the evacuation and fire-fighting activity in case of fire or the secondary accidents such as corrosion of the distributing panel, etc., the demand for non-halogen flame-retardant cable has rapidly been increasing in recent years in some fields of general industries, because this specific cable would generate the least amount of toxic smoke or corrosive gas even when it should burn. Similar demand has been increasing also for the cable used for nuclear power plants. In this field, earnest desire has been made for the development of non-halogen flame-retardant cable having specific environmental resistance specially required at nuclear power plants in addition to the properties and capacities required in general industries. The authors have continued examinations on the anti-environmental properties of the materials for cable such as long heat resistance, radiation resistance, steam resistance and succeeded in completing various sorts of non-halogen flame-retardant cable for nuclear power plants. In this report, we will introduce various features of the cable we have developed this time as well as the long-term reliability of non-halogen flame-retardant materials. (author)

Mercury in mercury(II)-spiked soils is highly susceptible to plant bioaccumulation.

Science.gov (United States)

Hlodák, Michal; Urík, Martin; Matúš, Peter; Kořenková, Lucia

2016-01-01

Heavy metal phytotoxicity assessments usually use soluble metal compounds in spiked soils to evaluate metal bioaccumulation, growth inhibition and adverse effects on physiological parameters. However, exampling mercury phytotoxicity for barley (Hordeum vulgare) this paper highlights unsuitability of this experimental approach. Mercury(II) in spiked soils is extremely bioavailable, and there experimentally determined bioaccumulation is significantly higher compared to reported mercury bioaccumulation efficiency from soils collected from mercury-polluted areas. Our results indicate this is not affected by soil sorption capacity, thus soil ageing and formation of more stable mercuric complexes with soil fractions is necessary for reasonable metal phytotoxicity assessments.

Cyclic volatile methylsiloxane bioaccumulation in flounder and ragworm in the Humber Estuary.

Science.gov (United States)

Kierkegaard, Amelie; van Egmond, Roger; McLachlan, Michael S

2011-07-15

Cyclic volatile methylsiloxanes are being subjected to regulatory scrutiny as possible PBT chemicals. The investigation of bioaccumulation has yielded apparently contradictory results, with high laboratory fish bioconcentration factors on the one hand and low field trophic magnification factors on the other. In this study, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were studied along with polychlorinated biphenyls (PCBs) in sediments, ragworm, and flounder from six sites in the Humber Estuary. Bioaccumulation was evaluated using multimedia bioaccumulation factors (mmBAFs) which quantified the fraction of the contaminant present in the aquatic environment that is transferred to the biota. PCB 180, a known strongly bioaccumulative chemical, was used as a benchmark. The mean mmBAF of D5 was about twice that of PCB 180 in both polycheates and flounder, while for D4 it was 6 and 14 times higher, respectively. The mmBAF of D6 was a factor 5-10 lower than that of PCB180. The comparatively strong multimedia bioaccumulation of D4 and D5, even in the absence of biomagnification, was explained by both compounds having a >100 times stronger tendency to partition into lipid rather than into organic carbon, while PCB 180 partitions to a similar extent into both matrices.

Mercury bioaccumulation and elimination by Xenomelanires brasiliensis - radioactive tracers technique

International Nuclear Information System (INIS)

Malagrino, Waldir; Mesquita, Carlos Henrique de; Sousa, Eduinetty Ceci P.M. de

2002-01-01

The present work has as main objective to emphasized the importance of using radioactive tracers as well as to establish a methodology for the utilization of 203 Hg in the bioaccumulation study of mercury by X enomelanires brasiliensis. The exposure time was 168 hours. The bioaccumulation of mercury from the water as well as the elimination of the metal previously absorbed were determined by measuring the activity of 203 Hg, which was added to the water in the beginning of the experiments. The technique chosen is suitable to study the behavior of the stable mercury since the radioisotope used is an isotope of the same element and therefore presents the same chemical properties. The results obtained show that the absorption and elimination of mercury by Xenomelanires brasiliensis is slow, 168 hours being necessary for the elimination of 38 % of the previously absorbed mercury. The results are of main concern if it is considered that the literature about bioaccumulation of mercury by the Brazilian ichthyofauna is scarce. Furthermore the species Xenomelanires brasiliensis is part of the food chain and the results can be used in the evaluation of the potential risk of the mercury bioaccumulation by fishes of higher trophic levels and by men who are the final link of the food chain. (author)

Assessment of the bioavailability and phytotoxicity of sediment spiked with polycyclic aromatic hydrocarbons.

Science.gov (United States)

Rončević, Srđan; Spasojević, Jelena; Maletić, Snežana; Jazić, Jelena Molnar; Isakovski, Marijana Kragulj; Agbaba, Jasmina; Grgić, Marko; Dalmacija, Božo

2016-02-01

Large amounts of sediment are dredged globally every year. This sediment is often contaminated with low concentrations of metals, polycyclic aromatic hydrocarbons, pesticides and other organic pollutants. Some of this sediment is disposed of on land, creating a need for risk assessment of the sediment disposal method, to minimize the degradation of environmental quality and prevent risks to human health. Evaluating the available fractions of certain polycyclic aromatic hydrocarbons is very important, as in the presence of various organisms, they are believed to be easily subject to the processes of bioaccumulation, biosorption and transformation. In order to determine the applicability of applying these methods for the evaluation of pollutant bioavailability in sediments, the desorption kinetics from the sediment of various polycyclic aromatic hydrocarbons in the presence of Tenax and XAD4 were examined over the course of 216 h. Changes in the PAH concentrations in dredged sediments using five different seed plants during a short time of period (10 days) were also followed. Using chemical extraction techniques with Tenax and XAD4, a time of around 24 h is enough to achieve equilibrium for all four PAHs. Results showed good agreement between the seed accumulation and PAH extraction methods with both agents. If we compare the two extraction techniques, XAD4 gave better results for phenanthrene, pyrene and benzo(a)pyrene, and Tenax gave better results for chrysene.

FIELD SCREENING FOR HALOGENATED VOLATILE ORGANIC COMPOUNDS

Energy Technology Data Exchange (ETDEWEB)

John F. Schabron; Joseph F. Rovani, Jr.; Theresa M. Bomstad

2003-07-01

Western Research Institute (WRI) is continuing work toward the development of new screening methodology and a test kit to measure halogenated volatile organic compounds (VOCs) in the field. Heated diode and corona discharge sensors are commonly used to detect leaks of refrigerants from air conditioners, freezers, and refrigerators. They are both selective to the presence of halogens. In prior work, the devices were tested for response to carbon tetrachloride, heptane, toluene, and water vapors. In the current work, sensor response was evaluated with sixteen halogenated VOCs relative to carbon tetrachloride. The results show that the response of the various chlorinated VOCs is within an order of magnitude of the response to carbon tetrachloride for each of the sensors. Thus, for field screening a single response factor can be used. Both types of leak detectors are being further modified to provide an on-board LCD signal readout, which is related to VOC concentration. The units will be fully portable and will operate with 115-V line or battery power. Signal background, noise level, and response data on the Bacharach heated diode detector and the TIF corona discharge detector show that when the response curves are plotted against the log of concentration, the plot is linear to the upper limit for the particular unit, with some curvature at lower levels. When response is plotted directly against concentration, the response is linear at the low end and is curved at the high end. The dynamic ranges for carbon tetrachloride of the two devices from the lower detection limit (S/N=2) to signal saturation are 4-850 vapor parts per million (vppm) for the corona discharge unit and 0.01-70 vppm for the heated diode unit. Additional circuit modifications are being made to lower the detection limit and increase the dynamic response range of the corona discharge unit. The results indicate that both devices show potential utility for future analytical method development work toward

Halogenation of Hydraulic Fracturing Additives in the Shale Well Parameter Space

Science.gov (United States)

Sumner, A. J.; Plata, D.

2017-12-01

Horizontal Drilling and Hydraulic fracturing (HDHF) involves the deep-well injection of a `fracking fluid' composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. The potential impacts of HDHF operations on water resources and ecosystems are numerous, and analyses of flowback samples revealed organic compounds from both geogenic and anthropogenic sources. Furthermore, halogenated chemicals were also detected, and these compounds are rarely disclosed, suggesting the in situ halogenation of reactive additives. To test this transformation hypothesis, we designed and operated a novel high pressure and temperature reactor system to simulate the shale well parameter space and investigate the chemical reactivity of twelve commonly disclosed and functionally diverse HDHF additives. Early results revealed an unanticipated halogenation pathway of α-β unsaturated aldehyde, Cinnamaldehyde, in the presence of oxidant and concentrated brine. Ongoing experiments over a range of parameters informed a proposed mechanism, demonstrating the role of various shale-well specific parameters in enabling the demonstrated halogenation pathway. Ultimately, these results will inform a host of potentially unintended interactions of HDHF additives during the extreme conditions down-bore of a shale well during HDHF activities.

Arbuscular mycorrhizal wheat inoculation promotes alkane and polycyclic aromatic hydrocarbon biodegradation: Microcosm experiment on aged-contaminated soil.

Science.gov (United States)

Ingrid, Lenoir; Lounès-Hadj Sahraoui, Anissa; Frédéric, Laruelle; Yolande, Dalpé; Joël, Fontaine

2016-06-01

Very few studies reported the potential of arbuscular mycorrhizal symbiosis to dissipate hydrocarbons in aged polluted soils. The present work aims to study the efficiency of arbuscular mycorrhizal colonized wheat plants in the dissipation of alkanes and polycyclic aromatic hydrocarbons (PAHs). Our results demonstrated that the inoculation of wheat with Rhizophagus irregularis allowed a better dissipation of PAHs and alkanes after 16 weeks of culture by comparison to non-inoculated condition. These dissipations observed in the inoculated soil resulted from several processes: (i) a light adsorption on roots (0.5% for PAHs), (ii) a bioaccumulation in roots (5.7% for PAHs and 6.6% for alkanes), (iii) a transfer in shoots (0.4 for PAHs and 0.5% for alkanes) and mainly a biodegradation. Whereas PAHs and alkanes degradation rates were respectively estimated to 12 and 47% with non-inoculated wheat, their degradation rates reached 18 and 48% with inoculated wheat. The mycorrhizal inoculation induced an increase of Gram-positive and Gram-negative bacteria by 56 and 37% compared to the non-inoculated wheat. Moreover, an increase of peroxidase activity was assessed in mycorrhizal roots. Taken together, our findings suggested that mycorrhization led to a better hydrocarbon biodegradation in the aged-contaminated soil thanks to a stimulation of telluric bacteria and hydrocarbon metabolization in mycorrhizal roots. Copyright © 2016 Elsevier Ltd. All rights reserved.

An investigation into ciguatoxin bioaccumulation in sharks.

Science.gov (United States)

Meyer, Lauren; Capper, Angela; Carter, Steve; Simpfendorfer, Colin

2016-09-01

Ciguatoxins (CTXs) produced by benthic Gambierdiscus dinoflagellates, readily biotransform and bioaccumulate in food chains ultimately bioconcentrating in high-order, carnivorous marine species. Certain shark species, often feeding at, or near the top of the food-chain have the ability to bioaccumulate a suite of toxins, from both anthropogenic and algal sources. As such, these apex predators are likely sinks for CTXs. This assumption, in conjunction with anecdotal knowledge of poisoning incidents, several non-specific feeding trials whereby various terrestrial animals were fed suspect fish flesh, and a single incident in Madagascar in 1994, have resulted in the widespread acceptance that sharks may accumulate CTXs. This prompted a study to investigate original claims within the literature, as well as investigate CTX bioaccumulation in the muscle and liver of 22 individual sharks from nine species, across four locations along the east coast of Australia. Utilizing an updated ciguatoxin extraction method with HPLC-MS/MS, we were unable to detect P-CTX-1, P-CTX-2 or P-CTX-3, the three primary CTX congeners, in muscle or liver samples. We propose four theories to address this finding: (1) to date, methods have been optimized for teleost species and may not be appropriate for elasmobranchs, or the CTXs may be below the limit of detection; (2) CTX may be biotransformed into elasmobranch-specific congeners as a result of unique metabolic properties; (3) 22 individuals may be an inadequate sample size given the rare occurrence of high-order ciguatoxic organisms and potential for CTX depuration; and (4) the ephemeral nature and inconsistent toxin profiles of Gambierdiscus blooms may have undermined our classifications of certain areas as CTX hotspots. These results, in combination with the lack of clarity within the literature, suggest that ciguatoxin bioaccumulation in sharks remains elusive, and warrants further investigation to determine the dynamics of toxin production

Pollution by polycyclic aromatic hydrocarbons (PAH's) in sediments and organisms from Salina Cruz Port, Oaxaca, Mexico

International Nuclear Information System (INIS)

Botello, A.V.; Villanueva, S.; Diaz, G.; Pica, Y.

1995-01-01

The presence and levels of polycyclic aromatic hydrocarbons (PAH's) in [sediments and biota from the Port of Salina Cruz, Oaxaca; were evaluated by means of gas capillary chromatography using columns of high resolution. The results show a seasonal variability of the PAH's concentrations in sediments being higher in the port area and lower in oceanic sediments. The increase of the PAH's levels in Crassostrea iridiscens and Penaeus stylirostris is important and related to the bioaccumulation process. The presence of PAH's conformed by 4 y 5 benzene rings in these species must be noted specially because they have carcinogenic properties and their effects on the local fisheries should be considered. (Author)

Bioaccumulation of zinc in foodstuffs by nuclear and related techniques

International Nuclear Information System (INIS)

Diaz Rizo, O.; Olivares Reumont, S.; Lima Cazorla, L.; Gelen Rudnikas, A.; D'Alessandro Rodriguez, K.; Arado Lopez, J. O.; Denis Alpizar, O.; Diaz Arado, O.; Viguri Fuente, J.

2011-01-01

The bioaccumulation of zinc in regular consumption foodstuff (sugar, rice, some vegetables, roots and shellfishes) in Cuba is reported. Zinc content in food samples and its corresponding soils or sediments are determined by Instrumental Neutron Activation analysis (INAA), X-Ray Fluorescence analysis (XRF), inductively coupled plasma emission spectrometry (ICP-AES) and Atomic Absorption spectrometry (AES). The obtained results show rice as the major Zn bioaccumulator of the studied products and the main Zn source in Cuban human diet. (Author)

Evaluating the Relationship between Equilibrium Passive Sampler Uptake and Aquatic Organism Bioaccumulation (IPSW)

Science.gov (United States)

This review evaluates passive sampler uptake of hydrophobic organic contaminants (HOCs) as it relates to organism bioaccumulation in the water column and interstitial water. Fifty-five studies were found where both passive samplers and organism bioaccumulation were used to measur...

BIOACCUMULATION AND AQUATIC SYSTEM SIMULATOR (BASS) USER'S MANUAL BETA TEST VERSION 2.1

Science.gov (United States)

BASS (Bioaccumulation and Aquatic System Simulator) is a Fortran 95 simulation program that predicts the population and bioaccumulation dynamics of age-structured fish assemblages that are exposed to hydrophobic organic pollutants and class B and borderline metals that complex wi...

Evaluation of remaining behavior of halogen on the fabrication of MOX pellet containing Am

International Nuclear Information System (INIS)

Ozaki, Yoko; Osaka, Masahiko; Obayashi, Hiroshi; Tanaka, Kenya

2004-11-01

It is important to limit the content of halogen elements, namely fluorine and chlorine that are sources of making cladding material corrode, in nuclear fuel from the viewpoint of quality assurance. The halogen content should be more carefully limited in the MOX fuel containing Americium (Am-MOX), which is fabricated in the Alpha-Gamma Facility (AGF) for irradiation testing to be conducted in the experimental fast reactor JOYO, because fluorine may remain in the sintered pellets owing to a formation of AmF 3 known to have a low vapor pressure and may exceeds the limit of 25 ppm. In this study, a series of experimental determination of halogen element in Am-MOX were performed by a combination method of pyrolysis and ion-chromatography for the purpose of an evaluation of behavior of remaining halogen through the sintering process. Oxygen potential, temperature and time were changed as experimental parameters and their effects on the remaining behavior of halogen were examined. It was confirmed that good pellets, which contained small amount of halogen, could be obtained by the sintering for 3 hour at 1700degC in the oxygen potential range from -520 to -390 kJ/mol. In order to analysis of fluorine chemical form in green pellet, thermal analysis was performed. AmF 3 and PuF 3 have been confirmed to remain in the green pellet. (author)

Development of Halogen-free flame-retardant cable for nuclear power plant

International Nuclear Information System (INIS)

Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

1992-01-01

Conventional flame-retardant cables release a large volume of corrosive and toxic gases as well as smoke while combusted. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and have already been used in telecommunication service, subway and shipboard applications. However, for cables for nuclear power plant, covering materials should also have radiation resistance and other properties, including long-term physical stability. We have developed halogen-free flame-retardant cables for BWR nuclear power plant with sufficient flame retardancy radiation resistance and environmental resistance including steam-exposure resistance all of which are in accordance with Japanese specifications for BWR nuclear cables and have such characteristics as low corrosiveness, low toxicity and low smoke emission. (author)

Development of halogen-free flame-retardant cable for nuclear power plant

International Nuclear Information System (INIS)

Ishii, Nobuhisa; Morii, Akira; Fujimura, Shunichi

1991-01-01

Conventional flame-retardant cables release a large amount of corrosive and toxic gases and also smoke during combustion on fire. Cables covered with halogen-free flame-retardant material, containing no halogen in it, have been developed to reduce generation of such gases and smoke, and already used in telecommunication plant, subway and shipboard applications. In the case of nuclear power plant application, cable covering materials should also have radiation resistance and other properties including long-term physical stability. We have developed halogen-free flame-retardant cables for nuclear power plant with sufficient flame retardancy, radiation resistance, and environmental resistance including steam-exposure resistance, all of which are in accordance with Japanese specifications for nuclear cables, and with characteristics as low corrosiveness, low toxicity, and low smoke evolution. (author)

Halogen Bonding from Dispersion-Corrected Density-Functional Theory: The Role of Delocalization Error.

Science.gov (United States)

Otero-de-la-Roza, A; Johnson, Erin R; DiLabio, Gino A

2014-12-09

Halogen bonds are formed when a Lewis base interacts with a halogen atom in a different molecule, which acts as an electron acceptor. Due to its charge transfer component, halogen bonding is difficult to model using many common density-functional approximations because they spuriously overstabilize halogen-bonded dimers. It has been suggested that dispersion-corrected density functionals are inadequate to describe halogen bonding. In this work, we show that the exchange-hole dipole moment (XDM) dispersion correction coupled with functionals that minimize delocalization error (for instance, BH&HLYP, but also other half-and-half functionals) accurately model halogen-bonded interactions, with average errors similar to other noncovalent dimers with less charge-transfer effects. The performance of XDM is evaluated for three previously proposed benchmarks (XB18 and XB51 by Kozuch and Martin, and the set proposed by Bauzá et al.) spanning a range of binding energies up to ∼50 kcal/mol. The good performance of BH&HLYP-XDM is comparable to M06-2X, and extends to the "extreme" cases in the Bauzá set. This set contains anionic electron donors where charge transfer occurs even at infinite separation, as well as other charge transfer dimers belonging to the pnictogen and chalcogen bonding classes. We also show that functional delocalization error results in an overly delocalized electron density and exact-exchange hole. We propose intermolecular Bader delocalization indices as an indicator of both the donor-acceptor character of an intermolecular interaction and the delocalization error coming from the underlying functional.

Symmetric and asymmetric halogen-containing metallocarboranylporphyrins and uses thereof

Science.gov (United States)

Miura, Michiko; Wu, Haitao

2013-05-21

The present invention is directed to low toxicity boronated compounds and methods for their use in the treatment, visualization, and diagnosis of tumors. More specifically, the present invention is directed to low toxicity halogenated, carborane-containing 5,10,15,20-tetraphenylporphyrin compounds and methods for their use particularly in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for the treatment of tumors of the brain, head and neck, and surrounding tissue. The invention is also directed to using these halogenated, carborane-containing tetraphenylporphyrin compounds in methods of tumor imaging and/or diagnosis such as MRI, SPECT, or PET.

Structure-Energy Relationships of Halogen Bonds in Proteins.

Science.gov (United States)

Scholfield, Matthew R; Ford, Melissa Coates; Carlsson, Anna-Carin C; Butta, Hawera; Mehl, Ryan A; Ho, P Shing

2017-06-06

The structures and stabilities of proteins are defined by a series of weak noncovalent electrostatic, van der Waals, and hydrogen bond (HB) interactions. In this study, we have designed and engineered halogen bonds (XBs) site-specifically to study their structure-energy relationship in a model protein, T4 lysozyme. The evidence for XBs is the displacement of the aromatic side chain toward an oxygen acceptor, at distances that are equal to or less than the sums of their respective van der Waals radii, when the hydroxyl substituent of the wild-type tyrosine is replaced by a halogen. In addition, thermal melting studies show that the iodine XB rescues the stabilization energy from an otherwise destabilizing substitution (at an equivalent noninteracting site), indicating that the interaction is also present in solution. Quantum chemical calculations show that the XB complements an HB at this site and that solvent structure must also be considered in trying to design molecular interactions such as XBs into biological systems. A bromine substitution also shows displacement of the side chain, but the distances and geometries do not indicate formation of an XB. Thus, we have dissected the contributions from various noncovalent interactions of halogens introduced into proteins, to drive the application of XBs, particularly in biomolecular design.

Biocide by-products in aquatic environments. Annual report, October 1, 1977--September 30, 1978

International Nuclear Information System (INIS)

Anderson, D.R.; Bean, R.M.; Gibson, C.I.

1979-01-01

The Biocide By-Products in Aquatic Environments Program is composed of analytical chemistry and biological phases with freshwater and marine biological subdivisions. The objectives of the analytical studies are: to identify those chloroorganic chemical compounds that result from the addition of chlorine to fresh or saltwater; to develop methods for detecting chlorinated organics in the effluents discharged to receiving water bodies from nuclear stations; and to verify laboratory findings through analysis for chlorination by-products in water and biota samples from cooling water bodies of nuclear power stations. The objectives of the biological studies are: to investigate the immediate toxicity of specific chlorination by-products (chloroform in freshwater and bromoform in marine waters); to evaluate the chronic toxicity of chlorination by-products; to follow their pathways of action; and to analyze for bioaccumulation or biomagnification of halogenated hydrocarbons on selected aquatic or marine biota

Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

KAUST Repository

Ward, Jeremy W.; Li, Ruipeng; Obaid, Abdulmalik; Payne, Marcia M.; Smilgies, Detlef Matthias; Anthony, John Edward; Amassian, Aram; Jurchescu, Oana D.

2014-01-01

new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting

Improving plant bioaccumulation science through consistent reporting of experimental data.

Science.gov (United States)

Fantke, Peter; Arnot, Jon A; Doucette, William J

2016-10-01

Experimental data and models for plant bioaccumulation of organic contaminants play a crucial role for assessing the potential human and ecological risks associated with chemical use. Plants are receptor organisms and direct or indirect vectors for chemical exposures to all other organisms. As new experimental data are generated they are used to improve our understanding of plant-chemical interactions that in turn allows for the development of better scientific knowledge and conceptual and predictive models. The interrelationship between experimental data and model development is an ongoing, never-ending process needed to advance our ability to provide reliable quality information that can be used in various contexts including regulatory risk assessment. However, relatively few standard experimental protocols for generating plant bioaccumulation data are currently available and because of inconsistent data collection and reporting requirements, the information generated is often less useful than it could be for direct applications in chemical assessments and for model development and refinement. We review existing testing guidelines, common data reporting practices, and provide recommendations for revising testing guidelines and reporting requirements to improve bioaccumulation knowledge and models. This analysis provides a list of experimental parameters that will help to develop high quality datasets and support modeling tools for assessing bioaccumulation of organic chemicals in plants and ultimately addressing uncertainty in ecological and human health risk assessments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal Bioaccumulation by Estuarine Food Webs in New England, USA

Directory of Open Access Journals (Sweden)

Celia Y. Chen

2016-06-01

Full Text Available Evaluating the degree of metal exposure and bioaccumulation in estuarine organisms is important for understanding the fate of metals in estuarine food webs. We investigated the bioaccumulation of Hg, methylmercury (MeHg, Cd, Se, Pb, and As in common intertidal organisms across a watershed urbanization gradient of coastal marsh sites in New England to relate metal exposure and bioaccumulation in fauna to both chemical and ecological factors. In sediments, we measured metal and metalloid concentrations, total organic carbon (TOC and SEM-AVS (Simultaneously extracted metal-acid volatile sulfides. In five different functional feeding groups of biota, we measured metal concentrations and delta 15N and delta 13C signatures. Concentrations of Hg and Se in biota for all sites were always greater than sediment concentrations whereas Pb in biota was always lower. There were positive relationships between biota Hg concentrations and sediment concentrations, and between biota MeHg concentrations and both pelagic feeding mode and trophic level. Bioavailability of all metals measured as SEM-AVS or Benthic-Sediment Accumulation Factor was lower in more contaminated sites, likely due to biogeochemical factors related to higher levels of sulfides and organic carbon in the sediments. Our study demonstrates that for most metals and metalloids, bioaccumulation is metal specific and not directly related to sediment concentrations or measures of bioavailability such as AVS-SEM.

Modelling PCB bioaccumulation in a Baltic food web

International Nuclear Information System (INIS)

Nfon, Erick; Cousins, Ian T.

2007-01-01

A steady state model is developed to describe the bioaccumulation of organic contaminants by 14 species in a Baltic food web including pelagic and benthic aquatic organisms. The model is used to study the bioaccumulation of five PCB congeners of different chlorination levels. The model predictions are evaluated against monitoring data for five of the species in the food web. Predicted concentrations are on average within a factor of two of measured concentrations. The model shows that all PCB congeners were biomagnified in the food web, which is consistent with observations. Sensitivity analysis reveals that the single most sensitive parameter is log K OW . The most sensitive environmental parameter is the annual average temperature. Although not identified amongst the most sensitive input parameters, the dissolved concentration in water is believed to be important because of the uncertainty in its determination. The most sensitive organism-specific input parameters are the fractional respiration of species from the water column and sediment pore water, which are also difficult to determine. Parameters such as feeding rate, growth rate and lipid content of organism are only important at higher trophic levels. - The bioaccumulation behaviour of PCB congeners in a Baltic food web is studied using a novel mechanistic model

Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

Science.gov (United States)

Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

2016-09-05

The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Singlet oxygen production by combining erythrosine and halogen light for photodynamic inactivation of Streptococcus mutans.

Science.gov (United States)

Fracalossi, Camila; Nagata, Juliana Yuri; Pellosi, Diogo Silva; Terada, Raquel Sano Suga; Hioka, Noboru; Baesso, Mauro Luciano; Sato, Francielle; Rosalen, Pedro Luiz; Caetano, Wilker; Fujimaki, Mitsue

2016-09-01

Photodynamic inactivation of microorganisms is based on a photosensitizing substance which, in the presence of light and molecular oxygen, produces singlet oxygen, a toxic agent to microorganisms and tumor cells. This study aimed to evaluate singlet oxygen quantum yield of erythrosine solutions illuminated with a halogen light source in comparison to a LED array (control), and the photodynamic effect of erythrosine dye in association with the halogen light source on Streptococcus mutans. Singlet oxygen quantum yield of erythrosine solutions was quantified using uric acid as a chemical-probe in an aqueous solution. The in vitro effect of the photodynamic antimicrobial activity of erythrosine in association with the halogen photopolimerizing light on Streptococcus mutans (UA 159) was assessed during one minute. Bacterial cultures treated with erythrosine alone served as negative control. Singlet oxygen with 24% and 2.8% degradation of uric acid in one minute and a quantum yield of 0.59 and 0.63 was obtained for the erythrosine samples illuminated with the halogen light and the LED array, respectively. The bacterial cultures with erythrosine illuminated with the halogen light presented a decreased number of CFU mL(-1) in comparison with the negative control, with minimal inhibitory concentrations between 0.312 and 0.156mgmL(-1). The photodynamic response of erythrosine induced by the halogen light was capable of killing S. mutans. Clinical trials should be conducted to better ascertain the use of erythrosine in association with halogen light source for the treatment of dental caries. Copyright © 2016 Elsevier B.V. All rights reserved.

Bioaccumulation of 137Cs by culture collection strains of bacteria and fungi

International Nuclear Information System (INIS)

Pipiska, M.; Rozloznik, M.; Augustin, J.

2003-01-01

Soil decontamination of soil contaminated by low-level activities of radionuclides, mainly by caesium-137, which come from accidental releases by maintenance of nuclear devices and by liquid wastes reprocessing, is long-term and expensive technology. Knowledge of the causations, which control the processes of bioaccumulation of radionuclides, is a necessary condition for critical assessment and successful utilization of processes of bioremediation in situ in practise. The authors present the experimentally gained quantitative values of bioaccumulation of caesium-137 from water solutions by micro organism cultures of Rhodotorula aurantiaca CCY 20-9-1, Sacharomyces cerevisiae, Rhodococcus rhodochrous ATCC 15906, Streptomyces sp. DX-IX, Coriolus versicolor CCWDF-14 and Rhizopus sp. R-18. Intensively growing cultures reach the highest values of bioaccumulation; the cultures in non-growing phase reach several orders lower values. From researched micro organisms the highest values of bioaccumulation of Cs + 5.1 pmol/g (wet weight) at initial concentration of Cs + in solution co = 1 nmol/l (without carrier) and 29.2 μmol/g (wet weight) at co = 6 mmol/l Cs + (adding of carrier CsCl) were found out at growing culture S. cerevisiae as model of eukaryotic cell after an achievement of maximal stationary grow phase. Acquired information refer to the possible role of soil micro organisms at bioaccumulation of 137 Cs in contaminated soils and their potential utilization in lowering of radioactive contamination of environment (authors)

Importance of growth rate on mercury and polychlorinated biphenyl bioaccumulation in fish

Science.gov (United States)

Li, Jiajia; Haffner, G. Douglas; Patterson, Gordon; Walters, David M.; Burtnyk, Michael D.; Drouillard, Ken G.

2018-01-01

To evaluate the effect of fish growth on mercury (Hg) and polychlorinated biphenyl (PCB) bioaccumulation, a non–steady‐state toxicokinetic model, combined with a Wisconsin bioenergetics model, was developed to simulate Hg and PCB bioaccumulation in bluegill (Lepomis macrochirus). The model was validated by comparing observed with predicted Hg and PCB 180 concentrations across 5 age classes from 5 different waterbodies across North America. The non–steady‐state model generated accurate predictions for Hg and PCB bioaccumulation in 3 of 5 waterbodies: Apsey Lake (ON, Canada), Sharbot Lake (ON, Canada), and Stonelick Lake (OH, USA). The poor performance of the model for the Detroit River (MI, USA/ON, Canada) and Lake Hartwell (GA/SC, USA), which are 2 well‐known contaminated sites with possibly high heterogeneity in spatial contamination, was attributed to changes in feeding behavior and/or prey contamination. Model simulations indicate that growth dilution is a major component of contaminant bioaccumulation patterns in fish, especially during early life stages, and was predicted to be more important for hydrophobic PCBs than for Hg. Simulations that considered tissue‐specific growth provided some improvement in model performance particularly for PCBs in fish populations that exhibited changes in their whole‐body lipid content with age. Higher variation in lipid growth compared with that of lean dry protein was also observed between different bluegill populations, which partially explains the greater variation in PCB bioaccumulation slopes compared with Hg across sampling sites.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

International Nuclear Information System (INIS)

Chandra, Sankhabrata; Bhattacharya, Atanu; Periyasamy, Ganga

2015-01-01

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH 2 , CF 3 , and COOH substituents) molecules paired with NH 3 (referred as ACl:NH 3 complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH 3 complex, the hole is predicted to migrate from the NH 3 -end to the ClCN-end of the NCCl⋯NH 3 complex in approximately 0.5 fs on the D 0 cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H 2 NCl:NH 3 , F 3 CCl:NH 3 , and HOOCCl:NH 3 , exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH 3 and HOCl:NH 3 complexes do not exhibit any charge migration following vertical ionization to the D 0 cation state, pointing to interesting halogen bond strength-dependent charge migration

First principles study of halogens adsorption on intermetallic surfaces

International Nuclear Information System (INIS)

Zhu, Quanxi; Wang, Shao-qing

2016-01-01

Graphical abstract: - Highlights: • The linear relation between adsorbates induced work function change and dipole moment change also exists for intermetallic surfaces. • It is just a common linear relationship rather than a directly proportion. • A new weight parameter β is proposed to describe different factors effect on work function shift. - Abstract: Halides are often present at electrochemical environment, they can directly influence the electrode potential or zero charge potential through the induced work-function change. In this work, we focused in particular on the halogen-induced work function change as a function of the coverage of fluorine, chlorine, bromine and iodine on Al_2Au and Al_2Pt (110) surfaces. Results show that the real relation between work function change and dipole moment change for halogens adsorption on intermetallic surfaces is just a common linear relationship rather than a directly proportion. Besides, the different slopes between fitted lines and the theoretical slope employed in pure metal surfaces demonstrating that the halogens adsorption on intermetallic surfaces are more complicated. We also present a weight parameter β to describe different factors effect on work function shift and finally qualify which factor dominates the shift direction.

A biodynamic model predicting waterborne lead bioaccumulation in Gammarus pulex: Influence of water chemistry and in situ validation

International Nuclear Information System (INIS)

Urien, N.; Uher, E.; Billoir, E.; Geffard, O.; Fechner, L.C.; Lebrun, J.D.

2015-01-01

Metals bioaccumulated in aquatic organisms are considered to be a good indicator of bioavailable metal contamination levels in freshwaters. However, bioaccumulation depends on the metal, the species, and the water chemistry that influences metal bioavailability. In the laboratory, a kinetic model was used to describe waterborne Pb bioaccumulated in Gammarus pulex. Uptake and elimination rate constants were successfully determined and the effect of Ca 2+ on Pb uptake was integrated into the model. Thereafter, accumulated Pb concentrations in organisms were predicted with the model and compared with those measured in native populations from the Seine watershed (France). The predictions had a good agreement with the bioaccumulation levels observed in native gammarids and particularly when the effect of calcium was considered. To conclude, kinetic parameters experimentally derived for Pb in G. pulex are applicable in environmental conditions. Moreover, the consideration of the water's chemistry is crucial for a reliable interpretation of bioaccumulation. - Highlights: • Kinetic model was used to describe waterborne Pb bioaccumulation in G. pulex. • Ca 2+ inhibits Pb uptake by G. pulex in the laboratory. • Model predictions were compared to bioaccumulated Pb in native G. pulex. • Model accurately predicts waterborne bioaccumulated Pb in gammarids. • Considering the influence of Ca 2+ improves the model predictions in the field. - An experimentally-derived kinetic model considering the effect of calcium was relevant to predict the waterborne Pb bioaccumulation in native Gammarus pulex

Bioaccumulation of short chain chlorinated paraffins in a typical freshwater food web contaminated by e-waste in south china: Bioaccumulation factors, tissue distribution, and trophic transfer.

Science.gov (United States)

Sun, Runxia; Luo, Xiaojun; Tang, Bin; Chen, Laiguo; Liu, Yu; Mai, Bixian

2017-03-01

Short chain chlorinated paraffins (SCCPs) are under review for inclusion into the Stockholm Convention on Persistent Organic Pollutants. However, limited information is available on their bioaccumulation and biomagnification in ecosystems, which is hindering evaluation of their ecological and health risks. In the present study, wild aquatic organisms (fish and invertebrates), water, and sediment collected from an enclosed freshwater pond contaminated by electronic waste (e-waste) were analyzed to investigate the bioaccumulation, distribution, and trophic transfer of SCCPs in the aquatic ecosystem. SCCPs were detected in all of the investigated aquatic species at concentrations of 1700-95,000 ng/g lipid weight. The calculated bioaccumulation factors (BAFs) varied from 2.46 to 3.49. The relationship between log BAF and the octanol/water partition coefficient (log K OW ) for benthopelagic omnivorous fish species followed the empirical model of bioconcentration, indicating that bioconcentration plays an important role in accumulation of SCCPs. In contrast, the relationship for the benthic carnivorous fish and invertebrates was not consistent with the empirical model of bioconcentration, implying that the bioaccumulation of SCCPs in these species could be more influenced by other complex factors (e.g., habitat and feeding habit). Preferential distribution in the liver rather than in other tissues (e.g., muscle, gills, skin, and kidneys) was noted for the SCCP congeners with higher log K OW , and bioaccumulation pathway (i.e. water or sediment) can affect the tissue distribution of SCCP congeners. SCCPs underwent trophic dilution in the aquatic food web, and the trophic magnification factor (TMF) values of SCCP congener groups significantly correlated with their corresponding log K OW values (p < 0.0001). The present study results improved our understanding on the environmental behavior and fate of SCCPs in aquatic ecosystem. Copyright © 2016 Elsevier Ltd. All rights

Process for the preparation of lubricants

Energy Technology Data Exchange (ETDEWEB)

Pier, M

1927-06-04

A process is described for preparation of lubricants from mixtures of hydrocarbons or hydrocarbon derivatives of mean molecular weight and nonaromatic nature, which is characterized by halogenating the raw oil by the action of halogens or halogen-exchanging compounds and submitting the obtained product to a condensation in presence of aluminum chloride, tin chloride, iron chloride, or other condensing metal chloride or boron fluoride or activated metals, such as activated aluminum, whereby it is worked up in two steps at a temperature below 150 and preferably below 100/sup 0/C.

Halogens in pore water of peat bogs – the role of peat decomposition and dissolved organic matter

Directory of Open Access Journals (Sweden)

H. Biester

2006-01-01

Full Text Available Halogens are strongly enriched in peat and peatlands and such they are one of their largest active terrestrial reservoir. The enrichment of halogens in peat is mainly attributed to the formation of organohalogens and climatically controlled humification processes. However, little is known about release of halogens from the peat substrate and the distribution of halogens in the peat pore water. In this study we have investigated the distribution of chlorine, bromine and iodine in pore water of three pristine peat bogs located in the Magellanic Moorlands, southern Chile. Peat pore waters were collected using a sipping technique, which allows in situ sampling down to a depth greater than 6m. Halogens and halogen species in pore water were determined by ion-chromatography (IC (chlorine and IC-ICP-MS (bromine and iodine. Results show that halogen concentrations in pore water are 15–30 times higher than in rainwater. Mean concentrations of chlorine, bromine and iodine in pore water were 7–15 mg l−1, 56–123 μg l−1, and 10–20 μg l−1, which correspond to mean proportions of 10–15%, 1–2.3% and 0.5–2.2% of total concentrations in peat, respectively. Organobromine and organoiodine were the predominant species in pore waters, whereas chlorine in pore water was mostly chloride. Advection and diffusion of halogens were found to be generally low and halogen concentrations appear to reflect release from the peat substrate. Release of bromine and iodine from peat depend on the degree of peat degradation, whereas this relationship is weak for chlorine. Relatively higher release of bromine and iodine was observed in less degraded peat sections, where the release of dissolved organic carbon (DOC was also the most intensive. It has been concluded that the release of halogenated dissolved organic matter (DOM is the predominant mechanism of iodine and bromine release from peat.

Methylmercury bioaccumulation in an urban estuary: Delaware River USA.

Science.gov (United States)

Buckman, Kate; Taylor, Vivien; Broadley, Hannah; Hocking, Daniel; Balcom, Prentiss; Mason, Rob; Nislow, Keith; Chen, Celia

2017-09-01

Spatial variation in mercury (Hg) and methylmercury (MeHg) bioaccumulation in urban coastal watersheds reflects complex interactions between Hg sources, land use, and environmental gradients. We examined MeHg concentrations in fauna from the Delaware River estuary, and related these measurements to environmental parameters and human impacts on the waterway. The sampling sites followed a north to south gradient of increasing salinity, decreasing urban influence, and increasing marsh cover. Although mean total Hg in surface sediments (top 4cm) peaked in the urban estuarine turbidity maximum and generally decreased downstream, surface sediment MeHg concentrations showed no spatial patterns consistent with the examined environmental gradients, indicating urban influence on Hg loading to the sediment but not subsequent methylation. Surface water particulate MeHg concentration showed a positive correlation with marsh cover whereas dissolved MeHg concentrations were slightly elevated in the estuarine turbidity maximum region. Spatial patterns of MeHg bioaccumulation in resident fauna varied across taxa. Small fish showed increased MeHg concentrations in the more urban/industrial sites upstream, with concentrations generally decreasing farther downstream. Invertebrates either showed no clear spatial patterns in MeHg concentrations (blue crabs, fiddler crabs) or increasing concentrations further downstream (grass shrimp). Best-supported linear mixed models relating tissue concentration to environmental variables reflected these complex patterns, with species specific model results dominated by random site effects with a combination of particulate MeHg and landscape variables influencing bioaccumulation in some species. The data strengthen accumulating evidence that bioaccumulation in estuaries can be decoupled from sediment MeHg concentration, and that drivers of MeHg production and fate may vary within a small region.

Halogen poisoning effect of Pt-TiO{sub 2} for formaldehyde catalytic oxidation performance at room temperature

Energy Technology Data Exchange (ETDEWEB)

Zhu, Xiaofeng; Cheng, Bei [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Yu, Jiaguo, E-mail: jiaguoyu@yahoo.com [State Key Laboratory of Advanced Technology for Material Synthesis and Processing, Wuhan University of Technology, Luoshi Road 122#, Wuhan 430070 (China); Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia); Ho, Wingkei, E-mail: keithho@ied.edu.hk [Department of Science and Environmental Studies and Centre for Education in Environmental Sustainability, The Hong Kong Institute of Education, Tai Po, N.T. Hong Kong (China)

2016-02-28

Graphical abstract: - Highlights: • The Pt-TiO{sub 2} catalyst is deactivated by adsorption of halogen ions. • The halogen poison is mainly attributed to the active site blocking of the Pt surface. • Halogen ions and Pt form Pt−X coordination bonds. • Large halogen diameter exhibits severe poisoning effect. - Abstract: Catalytic decomposition of formaldehyde (HCHO) at room temperature is an important method for HCHO removal. Pt-based catalysts are the optimal catalyst for HCHO decomposition at room temperature. However, the stability of this catalyst remains unexplored. In this study, Pt-TiO{sub 2} (Pt-P25) catalysts with and without adsorbed halogen ions (including F{sup −}, Cl{sup −}, Br{sup −}, and I{sup −}) were prepared through impregnation and ion modification. Pt-TiO{sub 2} samples with adsorbed halogen ions exhibited reduced catalytic activity for formaldehyde decomposition at room temperature compared with the Pt-TiO{sub 2} sample; the catalytic activity followed the order of F-Pt-P25, Cl-Pt-P25, Br-Pt-P25, and I-Pt-P25. Characterization results (including XRD, TEM, HRTEM, BET, XPS, and metal dispersion) showed that the adsorbed halogen ions can poison Pt nanoparticles (NPs), thereby reducing the HCHO oxidation activity of Pt-TiO{sub 2}. The poison mechanism is due to the strong adsorption of halogen ions on the surface of Pt NPs. The adsorbed ions form coordination bonds with surface Pt atoms by transferring surplus electrons into the unoccupied 5d orbit of the Pt atom, thereby inhibiting oxygen adsorption and activation of the Pt NP surface. Moreover, deactivation rate increases with increasing diameter of halogen ions. This study provides new insights into the fabrication of high-performance Pt-based catalysts for indoor air purification.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

Energy Technology Data Exchange (ETDEWEB)

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in [Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore (India); Periyasamy, Ganga [Department of Chemistry, Central College Campus, Bangalore University, Bangalore (India)

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this is the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.

Reconciliation of Halogen-Induced Ozone Loss with the Total-Column Ozone Record

Science.gov (United States)

Shepherd, T. G.; Plummer, D. A.; Scinocca, J. F.; Hegglin, M. I.; Fioletov, V. E.; Reader, M. C.; Remsberg, E.; von Clarmann, T.; Wang, H. J.

2014-01-01

The observed depletion of the ozone layer from the 1980s onwards is attributed to halogen source gases emitted by human activities. However, the precision of this attribution is complicated by year-to-year variations in meteorology, that is, dynamical variability, and by changes in tropospheric ozone concentrations. As such, key aspects of the total-column ozone record, which combines changes in both tropospheric and stratospheric ozone, remain unexplained, such as the apparent absence of a decline in total-column ozone levels before 1980, and of any long-term decline in total-column ozone levels in the tropics. Here we use a chemistry-climate model to estimate changes in halogen-induced ozone loss between 1960 and 2010; the model is constrained by observed meteorology to remove the eects of dynamical variability, and driven by emissions of tropospheric ozone precursors to separate out changes in tropospheric ozone. We show that halogen-induced ozone loss closely followed stratospheric halogen loading over the studied period. Pronounced enhancements in ozone loss were apparent in both hemispheres following the volcanic eruptions of El Chichon and, in particular, Mount Pinatubo, which significantly enhanced stratospheric aerosol loads. We further show that approximately 40% of the long-term non-volcanic ozone loss occurred before 1980, and that long-term ozone loss also occurred in the tropical stratosphere. Finally, we show that halogeninduced ozone loss has declined by over 10% since stratospheric halogen loading peaked in the late 1990s, indicating that the recovery of the ozone layer is well underway.

Bioaccumulation factor of 137Cs in some marine biotas from West Bangka Indonesia

Science.gov (United States)

Suseno, Heny

2014-03-01

Radionuclides may be released from nuclear facilities to the marine environment. Concentrations of radionuclides within marine biotic systems can be influenced by a number of factors, including the type of biota, its source, the radionuclide, and specific characteristics of the sampled specimens and the marine environment (salinity, etc.). The bioconcentration factor for a marine organism is the ratio of the concentration of a radionuclide in that organism to the concentration found in its marine water environment - under conditions of equilibrium. Information on the bioaccumulation of Cs-137 in marine organisms is required to risk assessment evaluates the potential risks to human health. Bioaccumulation of Cs was investigated in marine biota from west Bangka such as Marine cat fish (Arius thalassinus), Baramundi (Lates calcarifer), Mackerel (Scomberomorus commerson), Striped eel catfish (Plotosus lineatus), eel tailed fish (Euristhmus microceps), Yellowtail fusilier (Caesio erythrogaster), Coastal crab (Scylla sp), White shrimp (Penaeus merguiensis) and marine bivalve mollusk (Anadara granosa). Muscle of these marine biota, sediments and water were assayed for Cs-137 by HPGe gamma spectrometer. The bioaccumulation factor for fishes were calculated by ratio of concentration Cs-137 in muscle biota to the its concentration in water. The bioaccumulation factor for mollusks were calculates by ratio of concentration Cs-137 in muscle biota to the its concentration in sediments. The bioaccumulation factor were range 4.99 to 136.34.

Bioaccumulation factor of 137Cs in some marine biotas from West Bangka Indonesia

International Nuclear Information System (INIS)

Suseno, Heny

2014-01-01

Radionuclides may be released from nuclear facilities to the marine environment. Concentrations of radionuclides within marine biotic systems can be influenced by a number of factors, including the type of biota, its source, the radionuclide, and specific characteristics of the sampled specimens and the marine environment (salinity, etc.). The bioconcentration factor for a marine organism is the ratio of the concentration of a radionuclide in that organism to the concentration found in its marine water environment - under conditions of equilibrium. Information on the bioaccumulation of Cs-137 in marine organisms is required to risk assessment evaluates the potential risks to human health. Bioaccumulation of Cs was investigated in marine biota from west Bangka such as Marine cat fish (Arius thalassinus), Baramundi (Lates calcarifer), Mackerel (Scomberomorus commerson), Striped eel catfish (Plotosus lineatus), eel tailed fish (Euristhmus microceps), Yellowtail fusilier (Caesio erythrogaster), Coastal crab (Scylla sp), White shrimp (Penaeus merguiensis) and marine bivalve mollusk (Anadara granosa). Muscle of these marine biota, sediments and water were assayed for Cs-137 by HPGe gamma spectrometer. The bioaccumulation factor for fishes were calculated by ratio of concentration Cs-137 in muscle biota to the its concentration in water. The bioaccumulation factor for mollusks were calculates by ratio of concentration Cs-137 in muscle biota to the its concentration in sediments. The bioaccumulation factor were range 4.99 to 136.34

The bioaccumulation factor for phosphorus-32 in edible fish tissue. Final report 1 Aug 77-15 Oct 79

International Nuclear Information System (INIS)

Kaho, B.; Turgeon, K.

1980-03-01

Information used to derive the bioaccumulation factor for P-32 in edible portions of fish from water was reviewed to evaluate the currently recommended values of 100,000 in fresh water and 29,000 in sea water that are applied in generic calculations of radiation doses to persons from nuclear power reactor effluents. A phosphorus bioaccumulation factor of 70,000 was calculated for larger rivers and estuarine waters on the basis of geometric mean phosphorus concentrations of 2 mg/g wet weight in fish muscle and 0.03 mg/1 dissolved in water. A bioaccumulation factor for P-32 of 3,000 was computed by multiplying the phosphorus bioaccumulation factor by the ratio of the biological to the effective turnover rate in fish muscle. A biological turnover rate in muscle of 0.2 percent per day was estimated from phosphorus balances as a long-term average for large fish, although more rapid turnovers have been observed for brief periods. Large deviations from these selected generic bioaccumulation factors occur because of differences in phosphorus concentrations and turnover rates. Bioaccumulation of this magnitude is due to P-32 concentration at lowest trophic levels in the food web, not by concentration in fish, hence the availability of concentrating organisms determines whether this bioaccumulation factor is reached. Several other conditions that affect the P-32 bioaccumulation factor have not been quantified but are suggested for study. Measurement programs are recommended to determine site-specific P-32 bioaccumulation factors and enlarge the data base for the generic values

Iron Mineral Catalyzed C-H Activation As a Potential Pathway for Halogenation Processes

Science.gov (United States)

Tubbesing, C.; Schoeler, H. F.; Benzing, K.; Krause, T.; Lippe, S.; Rudloff, M.

2014-12-01

Due to increasing drinking water demand of mankind and an expected climate change the impact of salt lakes and salt deserts will increase within the next decades. Furthermore, a rising sea level influences coastal areas like salt marshes and abets processes which will lead to elevated organohalogen formation. An additional increase of the global warming potential, of particle formation and stratospheric ozone depletion is expected. Understanding these multifaceted processes is essential for mankind to be prepared for these alterations of the atmosphere. For example, Keppler et al. (2000) described the production of volatile halogenated organic compounds via oxidation of organic matter driven by ferric iron. However, the formation of long-chained alkyl halides in salt lakes is yet undisclosed. Despite the relative "inertness" of alkanes a direct halogenation of these compounds might be envisaged. In 2005 Vaillancourt et al. discovered a nonheme iron enzyme which is able to halogenate organic compounds via generating the high valent ferryl cation as reaction center. Based on various publications about C-H activation (Bergman, 2007) we postulate a halogenation process in which an iron containing minerals catalyse the C-H bond cleavage of organic compounds in soils. The generated organic radicals are highly reactive towards halides connected to the iron complex. We suggest that next to diagenetically altered iron containing enzymes, minerals such as oxides, hydroxides and sulfides are involved in abiotic halogenation processes. We applied the amino acid methionine as organic model compound and soluble iron species as reactants. All samples were incubated in aqueous phases containing various NaCl concentrations. As a result various halogenated ethanes and ethenes were identified as reaction products. References Bergman, R. G. (2007) Nature, 446(7134) 391-393 Keppler, F., et al. (2000) Nature, 403(6767) 298-301 Vaillancourt, F. H., et al. (2005) Nature, 436(7054) 1191-1194

Development of halogen-free, heat-resistant, low-voltage wire for automotive use

International Nuclear Information System (INIS)

Ueno, Keiji; Suzuki, Sizuo; Takahagi, Masatoshi; Uda, Ikujiro

1995-01-01

The environmental load of our motorized society is of major concern, and includes considerations of recycling of automotive parts as the industrial wastes. The total average length of AV, AVX (electrical wire insulated with PVC, cross-linked PVC), and AEX (electrical wire insulated with cross-linked polyolefin) wires required for the harnesses in modern automobiles is approximately 2,000-3,000 meters per unit. However these electrical wires contain a large amount of halogen, which can generate the smoke and corrosive gas. In response to this problem the authors have developed the electron beam irradiated halogen-free, heat-resistant, low-voltage electrical wire which does not contain any halogen based polymer or flame retardants. The developed wire features the reliability equivalent to AEX wire with minimum environmental load. (Author)

Drug: D06055 [KEGG MEDICUS

Lifescience Database Archive (English)

Full Text Available D06055 Drug Teflurane (USAN/INN) ... C2HBrF4 D06055.gif ... Neuropsychiatric agent ... DG02030 ... Anesthetic...s ... DG02027 ... General anesthetics ... DG02028 ... Inhalational anaesthetics ... DG01994 ... Halogen...ated hydrocarbons ... DG02027 ... General anesthetics ... DG02028 ... Inhalational anaesthetics ... DG01994 ... Halogenated

Drug: D05208 [KEGG MEDICUS

Lifescience Database Archive (English)

Full Text Available D05208 Drug Norflurane (USAN/INN) ... C2H2F4 D05208.gif ... Neuropsychiatric agent ... DG02030 ... Anesthetics... ... DG02027 ... General anesthetics ... DG02028 ... Inhalational anaesthetics ... DG01994 ... Halogen...ated hydrocarbons ... DG02027 ... General anesthetics ... DG02028 ... Inhalational anaesthetics ... DG01994 ... Halogenated

Mercury bioaccumulation in the Mediterranean

Directory of Open Access Journals (Sweden)

Cinnirella S.

2013-04-01

Full Text Available This study details mercury pollution within the food chain of the Mediterranean by analysing the most comprehensive mercury dataset available for biota and water measurements. In this study we computed a bioaccumulation factor (BAF for datasets in the existing mercury-related scientific literature, in on-going programs, and in past measurement campaigns. Preliminary results indicate a major lack of information, making the outcome of any assessment very uncertain. Importantly, not all marine eco-regions are (or have ever been covered by measurement campaigns. Most lacking is information associated with the South-Eastern part of the Mediterranean, and in several eco-regions it is still impossible to reconstruct a trophic net, as the required species were not accounted for when mercury measurements were taken. The datasets also have additional temporal sampling problems, as species were often not sampled systematically (but only sporadically during any given sampling period. Moreover, datasets composed of mercury concentrations in water also suffer from similar geographic limitations, as they are concentrated in the North-Western Mediterranean. Despite these concerns, we found a very clear bioaccumulation trend in 1999, the only year where comprehensive information on both methylmercury concentrations in water and biota was available.

Bioaccumulation and food chain transfer of corrosion products from radioactive stainless steel

International Nuclear Information System (INIS)

Young, J.S.

1986-07-01

Two sets of experiments were conducted to determine if corrosion products from radioactive Type 347 stainless steel could be biologically transferred from sediment through a marine food chain, and whether corrosion products dissolved in seawater could be bioaccumulated and then eliminated. Corrosion products containing 60 Co and 63 Ni from the radioactive stainless steel were introduced into marine sediments. Infaunal polychaete worms exposed to these sediments bioaccumulated the radionuclides. The feeding of these worms to shrimp and fish resulted in a trophic transfer of the radioactive products across a one-step food chain. The magnitude of the transfers are described in terms of transfer factors. Dissolved corrosion products as measured by the radionuclides were also bioaccumulated by shrimp and fish concentrating more than fish. Concentration factors were calculated

Toxicity and bioaccumulation of chlorophenols in earthworms, in relation to bioavailability in soil

Energy Technology Data Exchange (ETDEWEB)

van Gestel, C.A.; Ma, W.C.

1988-06-01

The acute toxicity of five chlorophenols for two earthworm species was determined in two sandy soils differing in organic matter content and the results were compared with adsorption data. Adsorption increased with increasing organic matter content of the soils, but for tetra- and pentachlorophenol was also influenced by soil pH. Earthworm toxicity was significantly higher in the soil with a low level of organic matter. This difference disappeared when LC50 values were recalculated to concentrations in soil solution using adsorption data. Eisenia fetida andrei showed LC50 values lower than those of Lumbricus rubellus although bioaccumulation was generally higher in the latter species. Toxicity and bioaccumulation based on soil solution concentrations increased with increasing lipophilicity of the chlorophenols. The present results indicate that the toxicity and bioaccumulation and therefore the bioavailability of chlorophenols in soil to earthworms are dependent on the concentration in soil solution and can be predicted on the basis of adsorption data. Both the toxicity of and bioaccumulation data on chlorophenols in earthworms demonstrated surprisingly good agreement with those on chlorophenols in fish.

Recoil halogen reactions in liquid and frozen aqueous solutions of biomolecules

International Nuclear Information System (INIS)

Arsenault, L.J.; Blotcky, A.J.; Firouzbakht, M.L.; Rack, E.P.; Nebraska Univ., Omaha

1982-01-01

Reactions of recoil 38 Cl, 80 Br and 128 I have been studied in crystalline systems of 5-halouracil, 5-halo-2'-deoxyuridine and 5-halouridine as well as liquid and frozen aqueous solutions of these halogenated biomolecules. In all systems expect crystalline 5-iuodouracil the major product was the radio-labelled halide ion. There was no evidence for other halogen inorganic species. The major labelled organic product was the parent molecule. A recoil atom tracer technique was developed to acquire site information of the biomolecule solutes in the liquid and frozen aqueous systems. For all liquid and frozen aqueous systems, the halogenated biomolecules tended to aggregate. For liquid systems, the tendency for aggregation diminished as the solute concentration approached zero, where the probable state of the solute approached a monomolecular dispersion. Unlike the liquid state, the frozen ice lattice demonstated a ''caging effect'' for the solute aggregates which resulted in constant product yields over the whole concentration range. (orig.)

Environmental levels and toxicological potencies of a novel mixed halogenated carbazole

Directory of Open Access Journals (Sweden)

Miren Pena-Abaurrea

2016-09-01

Full Text Available The present work involves an extensive analytical and toxicological description of a recently identified mixed halogenated carbazole found in sediment samples, 1,8-dibromo-3,6-dichloro-9H-carbazole (BCCZ. Concentrations and the relative effect potency (REP were calculated for the target BCCZ in a set of stream sediments collected in 2008 in Ontario, Canada. The levels calculated for BCCZ as compared to those previously assessed for legacy persistent organic pollutants (POPs in the same samples revealed a significant contribution of BCCZ to the total organic chemical contamination (<1%–95%; average 37%. The corresponding dioxin toxic equivalencies (TEQs of BCCZ in the sediment extracts were estimated from experimental REP data. The experimental data presented supports the classification of this emerging halogenated chemical as a contaminant of emerging environmental concern. Although potential emission sources could not be identified, this study highlights the importance of on-going research for complete characterization of halogenated carbazoles and related compounds.

Development of no halogen incombustible cables for atomic energy

International Nuclear Information System (INIS)

Ishii, Nobumasa; Kimura, Hitoshi; Fujimura, Shun-ichi

1990-01-01

In upgrading light water reactor technology, it is important to improve the reliability of machinery and equipment, to make regular inspection efficient, to extend the period of continuous operation, to optimize operation cycle and to improve the maintainability of plant facilities. For the cables for nuclear power stations, high incombustibility is required, and at present halogen system incombustible materials are used. Recently the development of no halogen incombustible cables has been advanced, with which the generation of corrosive gas and smoke at the time of fires is slight. In this study, the application of such no halogen incombustible cables to nuclear power stations and the improvement of reliability of the cables were investigated. The cables to be developed are those for electric power, control and instrumentation in BWR plants and insulated electric wires. The required characteristics are incombustibility, no generation of smoke and corrosive gas at the time of fires, radiation resistance and steam resistance in LOCA. The selection of base polymers, metal hydrates and radiation protectors, the evaluation of radiation resistance and steam resistance, the examination of the corrosive and poisonous properties of generated gas and smoke generation and so on are reported. The development was successful. (K.I.)

Determination of N-containing halogenated natural products using gas chromatography in combination of a nitrogen-phosphorus-detector

Energy Technology Data Exchange (ETDEWEB)

Melcher, J.; Vetter, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie

2004-09-15

In the last few years several nonpolar halogenated natural products (HNPs) such as Q1, MHC-1, BC-2, BC-3, BC-10 were detected at elevated concentrations in marine biota samples. In addition, there are still some abundant peaks of halogenated compounds frequently found in the gas chromatograms of many marine samples which have not yet been identified. Some of the known halogenated natural products (Q1, HDBPs including BC-10, bromoindoles) contain N-heterocyclic backbones. Since nitrogen is scarcely found in anthropogenic halogenated compounds, the detection of N-containing halogenated substances may be used as a first indicator for the presence of HNPs in a sample extract. In the presented method we studied the suitability of a nitrogen phosphorous detector (NPD) for quantification of Q1 and the detection of Ncontaining compounds in marine biota. Analyses were accompanied with GC/ECD analyses.

Heavy metal bioaccumulation in Callinectes amnicola and ...

African Journals Online (AJOL)

The bioaccumulation of heavy metals in organisms is as a result of pollutants discharge generated by anthropogenic and natural activities which has become a tremendous concern in developing nations. The levels of cadmium, copper, chromium, lead, zinc and nickel in the tissue of Callinectes amnicola and ...

Bioaccumulation and distribution of organochlorine residues across ...

African Journals Online (AJOL)

Eighteen organochlorine pesticide (OCP) residues were measured in the water, sediment, plankton, benthic invertebrates and fish in various sections of the Lagos Lagoon in 2014 to investigate their bioaccumulation and distribution in the food web. The analysis was done using gas chromatography with an electron capture ...

A 19F NMR study of C-I....pi- halogen bonding

DEFF Research Database (Denmark)

Hauchecorne, Dieter; vand er Veken, Benjamin J.; Herrebout, Wouter A.

2011-01-01

The formation of halogen bonded complexes between toluene-d8 and the perfluoroiodopropanes 1-C3F7I and 2-C3F7I has been investigated using 19F NMR spectroscopy. For both Lewis acids, evidence was found for the formation of a C–I⋯π halogen bonded complex. The complex formed is a 1:1 type. Using sp...... results are supported by ab initio calculations at the B3LYP-PCM/6-311++G(d,p) + LanL2DZ∗ level....

Discriminative stimulus effects of inhaled 1,1,1-trichloroethane in mice: comparison to other hydrocarbon vapors and volatile anesthetics.

Science.gov (United States)

Shelton, Keith L

2009-04-01

Because the toxicity of many inhalants precludes evaluation in humans, drug discrimination, an animal model of subjective effects, can be used to gain insights on their poorly understood abuse-related effects. The purpose of the present study was to train a prototypic inhalant that has known abuse liability, 1,1,1-trichloroethane (TCE), as a discriminative stimulus in mice, and compare it to other classes of inhalants. Eight B6SJLF1/J mice were trained to discriminate 10 min of exposure to 12,000 ppm inhaled TCE vapor from air and seven mice were trained to discriminate 4,000 ppm TCE from air. Tests were then conducted to characterize the discriminative stimulus of TCE and to compare it to representative aromatic and chlorinated hydrocarbon vapors, volatile halogenated anesthetics as well as an odorant compound. Only the 12,000 ppm TCE versus the air discrimination group exhibited sufficient discrimination accuracy for substitution testing. TCE vapor concentration- and exposure time-dependently substituted for the 12,000 ppm TCE vapor training stimulus. Full substitution was produced by trichloroethylene, toluene, enflurane, and sevoflurane. Varying degrees of partial substitution were produced by the other volatile test compounds. The odorant, 2-butanol, did not produce any substitution for TCE. The discriminative stimulus effects of TCE are shared fully or partially by chlorinated and aromatic hydrocarbons as well as by halogenated volatile anesthetics. However, these compounds can be differentiated from TCE both quantitatively and qualitatively. It appears that the degree of similarity is not solely a function of chemical classification but may also be dependent upon the neurochemical effects of the individual compounds.

Enantiomerization and stereoselectivity in bioaccumulation of furalaxyl in Tenebrio molitor larvae.

Science.gov (United States)

Yin, Jing; Gao, Yongxin; Zhu, Feilong; Hao, Weiyu; Xu, Qi; Wang, Huili; Guo, Baoyuan

2017-11-01

Furalaxyl is a chiral pesticide and widely used in modern agriculture as racemate mixture. The enantiomerization and enantioselecive bioaccumulation by a single dose of furalaxyl to Tenebrio molitor larvae under laboratory conditions were studied using a high-performance liquid chromatography tandem mass spectroscopy method based on a ChiralPAK IC column. Our results showed that a significant enantiomerization (interconversion between R-enantiomer and S-enantiomer) was observed in Tenebrio molitor larvae under R- or S-furalaxyl exposure. Though the two furalaxyl enantiomers exhibited low-capacity of bioaccumulation in Tenebrio molitor larvae, bioaccumulation of rac-furalaxyl was enantioselective with a preferential accumulation of S-furalaxyl at 10mg/kg dosage exposure. In addition, enantiomerization and enantioselective degradation of the two enantiomers was not observed in wheat bran. These results showed that enantioselectivtiy of furalaxyl enantiomers was an important process combined with degradation, metabolism and enatiomerization in organisms. Copyright © 2017 Elsevier Inc. All rights reserved.

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

Science.gov (United States)

Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

2015-06-01

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

Apparent bioaccumulation of cylindrospermopsin and paralytic shellfish toxins by finfish in Lake Catemaco (Veracruz, Mexico).

Science.gov (United States)

Berry, J P; Jaja-Chimedza, A; Dávalos-Lind, L; Lind, O

2012-01-01

Compared to the well-characterized health threats associated with contamination of fish and shellfish by algal toxins in marine fisheries, the toxicological relevance of the bioaccumulation of toxins from cyanobacteria (blue-green algae), as the primary toxigenic algae in freshwater systems, remains relatively unknown. Lake Catemaco (Veracruz, Mexico) is a small, tropical lake system specifically characterized by a year-round dominance of the known toxigenic cyanobacterial genus, Cylindrospermopsis, and by low, but detectable, levels of both a cyanobacterial hepatotoxin, cylindrospermopsin (CYN), and paralytic shellfish toxins (PSTs). In the present study, we evaluated, using enzyme-linked immunoassay (ELISA), levels of both toxins in several species of finfish caught and consumed locally in the region to investigate the bioaccumulation of, and possible health threats associated with, these toxins as potential foodborne contaminants. ELISA detected levels of both CYN and PSTs in fish tissues from the lake. Levels were generally low (≤ 1 ng g(-1) tissue); however, calculated bioaccumulation factors (BAFs) indicate that toxin levels exceed the rather low levels in the water column and, consequently, indicated bioaccumulation (BAF >1). A reasonable correlation was observed between measured bioaccumulation of CYN and PSTs, possibly indicating a mutual source of both toxins, and most likely cells of Cylindrospermopsis, the dominant cyanobacteria in the lake, and a known producer of both metabolites. The potential roles of trophic transport in the system, as well as possible implications for human health with regards to bioaccumulation, are discussed.

Halogen bond tunability II: the varying roles of electrostatic and dispersion contributions to attraction in halogen bonds

Czech Academy of Sciences Publication Activity Database

Riley, Kevin Eugene; Murray, J. S.; Fanfrlík, Jindřich; Řezáč, Jan; Solá, R. J.; Concha, M. C.; Ramos, F. M.; Politzer, P.

2013-01-01

Roč. 19, č. 11 (2013), s. 4651-4659 ISSN 1610-2940 R&D Projects: GA ČR GBP208/12/G016 Grant - others:Operational Program Research and Development for Innovations(XE) CZ.1.05/2.1.00/03.0058 Institutional support: RVO:61388963 Keywords : dispersion * electrostatics * halogen bonding * noncovalent interactions Subject RIV: CE - Biochemistry Impact factor: 1.867, year: 2013

Role of metal mixtures (Ca, Cu and Pb) on Cd bioaccumulation and phytochelatin production by Chlamydomonas reinhardtii.

Science.gov (United States)

Abboud, Pauline; Wilkinson, Kevin J

2013-08-01

The goal of the study was to determine whether metal uptake and biological effects could be predicted by free ion concentrations when organisms were exposed to Cd and a second metal. Bioaccumulation and algal phytochelatin (PC) concentrations were determined for Chlamydomonas reinhardtii following a 6-h exposure. Bioaccumulation results, after six hours of exposure, showed that Cd uptake decreased in the presence of relatively high concentrations of Ca, Cu and Pb, however, Cd bioaccumulation increased in the presence of ca. equimolar concentrations of Cu. A good correlation was observed between the production of PCs and the amount of metals bioaccumulated for the binary mixtures of Cd-Pb and Cd-Cu, but not the Cd-Ca mixture. Overall, the results suggested that, in the case of mixtures, bioaccumulated metal rather than free ion concentrations would be a better predictor of biological effect. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biochemical basis of mercury remediation and bioaccumulation by Enterobacter sp. EMB21.

Science.gov (United States)

Sinha, Arvind; Kumar, Sumit; Khare, Sunil Kumar

2013-01-01

The aims of this study were to isolate metal bioaccumulating bacterial strains and to study their applications in removal of environmental problematic heavy metals like mercury. Five bacterial strains belonging to genera Enterobacter, Bacillus, and Pseudomonas were isolated from oil-spilled soil. Among these, one of the strains Enterobacter sp. EMB21 showed mercury bioaccumulation inside the cells simultaneous to its bioremediation. The bioaccumulation of remediated mercury was confirmed by transmission electron microscopy and energy dispersive X-ray. The mercury-resistant loci in the Enterobacter sp. EMB21 cells were plasmid-mediated as confirmed by transformation of mercury-sensitive Escherichia coli DH5α by Enterobacter sp. EMB21 plasmid. Effect of different culture parameters viz-a-viz inoculum size, pH, carbon, and nitrogen source revealed that alkaline pH and presence of dextrose and yeast extract favored better remediation. The results indicated the usefulness of Enterobacter sp. EMB21 for the effective remediation of mercury in bioaccumulated form. The Enterobacter sp. EMB21 seems promising for heavy metal remediation wherein the remediated metal can be trapped inside the cells. The process can further be developed for the synthesis of valuable high-end functional alloy, nanoparticles, or metal conjugates from the metal being remediated.

Evidence of the aryl hydrocarbon receptor in chemosynthetic mussels from the Gulf of Mexico

International Nuclear Information System (INIS)

Willett, K.; Thomsen, J.; Wilson, C.; McDonald, S.; Safe, S.

1995-01-01

The aryl hydrocarbon receptor (AhR) is a ligand-activated transcription factor that controls expression of various genes including cytochrome P450. Polynuclear aromatic and halogenated aromatic hydrocarbons are agonists for the AhR in fish and mammalian species. Previously, a homologous AhR has not been identified in marine invertebrate species. Chemosynthetic mussels were collected from gas and petroleum seeps in the Gulf of Mexico to investigate the presence of the AhR and the induction of the cytochrome P450 system. Aryl hydrocarbon hydroxylase and glutathione S-transferase activities in the gill and hepatopancreas were elevated in the petroleum seep mussels relative to those from the gas seep. A nuclear AhR in the hepatopancreas was detected in both mussel populations after treatment with [ 3 H]-tetrachlorodibenzo-p-dioxin (tcdd) followed by sucrose density gradient analysis. Gel mobility shift assays using a labeled dioxin responsive element (DRE) oligonucleotide and tcdd-transformed mussel cytosol showed a retarded band which could be competed with excess unlabeled DRE. Results from gel shifts indicated specific binding of the tcdd-mussel AhR complex to its responsible element. Finally, PCR primers designed to amplify a 700 base pair region of the human AhR detected AhR mRNA in both mussel populations. The sequence of this PCR product is being determined. The presence of the AhR in marine invertebrates has important implications in the evolutionary age of the AhR

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms.

Science.gov (United States)

Carter, Korey P; Kalaj, Mark; Surbella, Robert G; Ducati, Lucas C; Autschbach, Jochen; Cahill, Christopher L

2017-11-02

Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Medium-chain chlorinated paraffins (MCCPs): a review of bioaccumulation potential in the aquatic environment.

Science.gov (United States)

Thompson, Roy; Vaughan, Martin

2014-01-01

Chlorinated paraffins (CPs) are high molecular weight organochlorine compounds that have been used in a variety of industrial applications for many years. Medium-chain chlorinated paraffins (MCCPs) (CAS 85535-85-9; Alkanes, C14-17 , chloro) are currently under investigation as potential persistent bioaccumulative toxic (PBT) compounds. In this article, the bioaccumulation potential of MCCPs is assessed using a tiered framework proposed after a recent Society of Environmental Toxicology and Chemistry (SETAC) Pellston Workshop in 2008. The framework proposes the use of physicochemical properties and modeling assessment, bioconcentration/bioaccumulation (BCF/BAF) assessment, biomagnification (BMF) assessment, and trophic magnification factor (TMF) assessment. It is hoped that use of this framework could harmonize and improve the efficiency and effectiveness of the chemical substance evaluation screening process for PBT properties. When applied to MCCPs, the following conclusions were made: empirical physiochemical data is available negating the use of models; laboratory BCFs range from 1000 to 15 000 (growth-corrected lipid normalized values) for 2 MCCP structures; field BAFs were an order of magnitude higher than the trigger criterion for "B status possible"; although results may not meet acceptance criteria for field studies, laboratory-derived BMFs for a number of C14-17 chlorinated alkanes were less than the trigger value of 1 (based on whole-body concentrations) whereas field-derived BMFs were less than 1 (based on lipid corrected values [generally used for field data] excluding one measure for sculpin, [Cottus cognatus]-Diporeia that was based on only one detectable sample); and finally, TMFs were less than the trigger criterion value of 1, which are considered the most convincing evidence for bioaccumulative properties of a compound and the "Gold Standard" measure of bioaccumulation. This article also discusses the uncertainties surrounding the published data

Tuning the viscosity of halogen free bulk heterojunction inks for inkjet printed organic solar cells

NARCIS (Netherlands)

Lamont, C.A.; Eggenhuisen, T.M.; Coenen, M.J.J.; Slaats, T.W.L.; Andriessen, R.; Groen, P.

2015-01-01

For the solution processing of organic photovoltaics on an industrial scale, the exclusion of halogenated solvents is a necessity. However, the limited solubility of most semiconducting polymer/fullerene blends in non-halogenated solvents results in ink formulations with low viscosities which poses

Impact of enhanced ozone deposition and halogen chemistry on tropospheric ozone over the Northern Hemisphere

Science.gov (United States)

Fate of ozone in marine environments has been receiving increased attention due to the tightening of ambient air quality standards. The role of deposition and halogen chemistry is examined through incorporation of an enhanced ozone deposition algorithm and inclusion of halogen ch...

Review of laboratory-based terrestrial bioaccumulation assessment approaches for organic chemicals: Current status and future possibilities.

Science.gov (United States)

Hoke, Robert; Huggett, Duane; Brasfield, Sandra; Brown, Becky; Embry, Michelle; Fairbrother, Anne; Kivi, Michelle; Paumen, Miriam Leon; Prosser, Ryan; Salvito, Dan; Scroggins, Rick

2016-01-01

In the last decade, interest has been renewed in approaches for the assessment of the bioaccumulation potential of chemicals, principally driven by the need to evaluate large numbers of chemicals as part of new chemical legislation, while reducing vertebrate test organism use called for in animal welfare legislation. This renewed interest has inspired research activities and advances in bioaccumulation science for neutral organic chemicals in aquatic environments. In January 2013, ILSI Health and Environmental Sciences Institute convened experts to identify the state of the science and existing shortcomings in terrestrial bioaccumulation assessment of neutral organic chemicals. Potential modifications to existing laboratory methods were identified, including areas in which new laboratory approaches or test methods could be developed to address terrestrial bioaccumulation. The utility of "non-ecotoxicity" data (e.g., mammalian laboratory data) was also discussed. The highlights of the workshop discussions are presented along with potential modifications in laboratory approaches and new test guidelines that could be used for assessing the bioaccumulation of chemicals in terrestrial organisms. © 2015 SETAC.

Bioaccumulation factor of {sup 137}Cs in some marine biotas from West Bangka Indonesia

Energy Technology Data Exchange (ETDEWEB)

Suseno, Heny, E-mail: henis@batan.go.id [Radioactive Waste Technology Center - The Indonesia Nuclear Energy Agency (BATAN) (Indonesia)

2014-03-24

Radionuclides may be released from nuclear facilities to the marine environment. Concentrations of radionuclides within marine biotic systems can be influenced by a number of factors, including the type of biota, its source, the radionuclide, and specific characteristics of the sampled specimens and the marine environment (salinity, etc.). The bioconcentration factor for a marine organism is the ratio of the concentration of a radionuclide in that organism to the concentration found in its marine water environment - under conditions of equilibrium. Information on the bioaccumulation of Cs-137 in marine organisms is required to risk assessment evaluates the potential risks to human health. Bioaccumulation of Cs was investigated in marine biota from west Bangka such as Marine cat fish (Arius thalassinus), Baramundi (Lates calcarifer), Mackerel (Scomberomorus commerson), Striped eel catfish (Plotosus lineatus), eel tailed fish (Euristhmus microceps), Yellowtail fusilier (Caesio erythrogaster), Coastal crab (Scylla sp), White shrimp (Penaeus merguiensis) and marine bivalve mollusk (Anadara granosa). Muscle of these marine biota, sediments and water were assayed for Cs-137 by HPGe gamma spectrometer. The bioaccumulation factor for fishes were calculated by ratio of concentration Cs-137 in muscle biota to the its concentration in water. The bioaccumulation factor for mollusks were calculates by ratio of concentration Cs-137 in muscle biota to the its concentration in sediments. The bioaccumulation factor were range 4.99 to 136.34.

Organochlorine pollution in tropical rivers (Guadeloupe): Role of ecological factors in food web bioaccumulation

Energy Technology Data Exchange (ETDEWEB)

Coat, Sophie, E-mail: coatsophie@gmail.com [EA 926 DYNECAR, Laboratoire de Biologie Marine, UFR Sciences, Universite des Antilles et de la Guyane, BP592, 97159 Pointe-a-Pitre Cedex (France); Monti, Dominique, E-mail: dominique.monti@univ-ag.fr [EA 926 DYNECAR, Laboratoire de Biologie Marine, UFR Sciences, Universite des Antilles et de la Guyane, BP592, 97159 Pointe-a-Pitre Cedex (France); Legendre, Pierre, E-mail: pierre.legendre@umontreal.ca [Departement de Sciences Biologique, Universite de Montreal, C.P. 6128, succursale A, Montreal, Quebec H3C 3J7 (Canada); Bouchon, Claude, E-mail: claude.bouchon@univ-ag.fr [EA 926 DYNECAR, Laboratoire de Biologie Marine, UFR Sciences, Universite des Antilles et de la Guyane, BP592, 97159 Pointe-a-Pitre Cedex (France); Massat, Felix, E-mail: fmassat@ladrome.fr [LDA26, laboratoire Departemental d' Analyses de la Drome, 27 avenue Lautagne, 26000 Valence (France); Lepoint, Gilles, E-mail: g.lepoint@ulg.ac.be [MARE Centre, Laboratoire d' Oceanologie, Universite de Liege, Bat. B6, 4000 Sart Tilman, Belgique (Belgium)

2011-06-15

Concentrations of organochlorine pesticides and stable isotope ratios of nitrogen and carbon were measured in a tropical freshwater ecosystem to evaluate the contamination level of biota and examine the bioaccumulation patterns of pollutants through the food web. Chemical analyses showed a general and heavy contamination of the entire food web. They revealed the strong accumulation of pollutants by juveniles of diadromous fishes and shrimps, as they re-enter the river. The role of ecological factors in the bioaccumulation of pesticides was evaluated. Whereas the most persistent pollutants (chlordecone and monohydro-chlordecone) were related to the organisms diet and habitat, bioaccumulation of {beta}-HCH was only influenced by animal lipid content. The biomagnification potential of chlordecone through the food chain has been demonstrated. It highlighted the importance of trophic transfer in this compound bioaccumulation process. In contrast, bioconcentration by passive diffusion from water seemed to be the main exposure route of biota to {beta}-HCH. - Highlights: > We measured OC pesticides and stable isotope ratios in a tropical stream. > Results showed a strong and ubiquitous contamination of the entire food web. > Diadromous juveniles strongly accumulated pollutants when they re-enter the river. > The most persistent pollutant (chlordecone) was related to species diet and habitat. > {beta}-HCH was only influenced by animal lipid content. - This paper determines the bioaccumulation and transfer processes of organochlorine pesticides within the stream food web in Guadeloupe (Caribbean).

Model study of multiphase DMS oxidation with a focus on halogens

Directory of Open Access Journals (Sweden)

R. von Glasow

2004-01-01

Full Text Available We studied the oxidation of dimethylsulfide (DMS in the marine boundary layer (MBL with a one-dimensional numerical model and focused on the influence of halogens. Our model runs show that there is still significant uncertainty about the end products of the DMS addition pathway, which is especially caused by uncertainty in the product yield of the reaction of the intermediate product methyl sulfinic acid (MSIA with OH. BrO strongly increases the importance of the addition branch in the oxidation of DMS even when present at mixing ratios smaller than 0.5pmol mol-1. The inclusion of halogen chemistry leads to higher DMS oxidation rates and smaller DMS to SO2 conversion efficiencies. The DMS to SO2 conversion efficiency is also drastically reduced under cloudy conditions. In cloud-free model runs between 5 and 15% of the oxidized DMS reacts further to particulate sulfur, in cloudy runs this fraction is almost 100%. Sulfate production by HOClaq and HOBraq is important in cloud droplets even for small Br- deficits and related small gas phase halogen concentrations. In general, more particulate sulfur is formed when halogen chemistry is included. A possible enrichment of HCO3- in fresh sea salt aerosol would increase pH values enough to make the reaction of S(IV* (=SO2,aq+HSO3-+SO32- with O3 dominant for sulfate production. It leads to a shift from methyl sulfonic acid (MSA to non-sea salt sulfate (nss-SO42- production but increases the total nss-SO42- only somewhat because almost all available sulfur is already oxidized to particulate sulfur in the base scenario. We discuss how realistic this is for the MBL. We found the reaction MSAaq+OH to contribute about 10% to the production of nss-SO42- in clouds. It is unimportant for cloud-free model runs. Overall we find that the presence of halogens leads to processes that decrease the albedo of stratiform clouds in the MBL.

Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

Science.gov (United States)

Mo, Lixin; Zeng, Yanli; Li, Xiaoyan; Zhang, Xueying; Meng, Lingpeng

2016-07-01

The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.

Rational design of organic semiconductors for texture control and self-patterning on halogenated surfaces

KAUST Repository

Ward, Jeremy W.

2014-05-15

Understanding the interactions at interfaces between the materials constituting consecutive layers within organic thin-film transistors (OTFTs) is vital for optimizing charge injection and transport, tuning thin-film microstructure, and designing new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self-assembled monolayer on the formation of the crystalline texture directly affecting the performance of OTFTs is explored. By correlating the results from microbeam grazing incidence wide angle X-ray scattering (μGIWAXS) measurements of structure and texture with OTFT characteristics, two or more interaction paths between the terminating atoms of the semiconductor and the halogenated surface are found to be vital to templating a highly ordered morphology in the first layer. These interactions are effective when the separating distance is lower than 2.5 dw, where dw represents the van der Waals distance. The ability to modulate charge carrier transport by several orders of magnitude by promoting "edge-on" versus "face-on" molecular orientation and crystallographic textures in OSCs is demonstrated. It is found that the "edge-on" self-assembly of molecules forms uniform, (001) lamellar-textured crystallites which promote high charge carrier mobility, and that charge transport suffers as the fraction of the "face-on" oriented crystallites increases. The role of interfacial halogenation in mediating texture formation and the self-patterning of organic semiconductor films, as well as the resulting effects on charge transport in organic thin-film transistors, are explored. The presence of two or more anchoring sites between a halogenated semiconductor and a halogenated self-assembled monolayer, closer than about twice the corresponding van der Waals distance, alter the microstructure and improve electrical properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereoselectivity in bioaccumulation and excretion of epoxiconazole by mealworm beetle (Tenebrio molitor) larvae.

Science.gov (United States)

Lv, Xiaotian; Liu, Chen; Li, Yaobin; Gao, Yongxin; Wang, Huili; Li, Jianzhong; Guo, Baoyuan

2014-09-01

Stereoselectivity in bioaccumulation and excretion of stereoisomers of epoxiconazole by mealworm beetle (Tenebrio molitor) larvae through dietary exposure was investigated. Liquid chromatography tandem mass spectrometry (HPLC-MS/MS) method that use a ChiralcelOD-3R[cellulosetris-Tris-(3, 5-dichlorophenyl-carbamate)] chromatography column was applied to carry out chiral separation of the stereoisomers. Wheat bran was spiked with racemic epoxiconazole at two dose levels of 20mg/kg and 2mg/kg (dry weight) to feed T. molitor larvae. The results showed that both the doses of epoxiconazole were taken up by Tenebrio molitor larvae rapidly at the initial stages. There was a significant trend of stereoselective bioaccumulation in the larvae with a preferential accumulation of (-)-epoxiconazole in the 20mg/kg dose. The stereoselectivity in bioaccumulation in the 2mg/kg dosage was not obvious compared to the 20mg/kg group. Results of excretion indicated an active excretion is an important pathway for the larvae to eliminate epoxiconazole which was a passive transport process with non stereoselectivity. The faster elimination might be the reason for the low accumulation of epoxiconazole, as measured by bioaccumulation factor (BAF). Copyright © 2014 Elsevier Inc. All rights reserved.

Bioaccumulation of radiocesium by fish: the influence of physicochemical factors and trophic structure

International Nuclear Information System (INIS)

Rowan, D.J.; Rasmussen, J.B.

1994-01-01

Although many measurements have been made on radiocesium levels in water and aquatic biota, no agreement has been reached regarding the factors affecting bioaccumulation of these radionuclides. With monitoring data from countries that operate nuclear facilities and data from the primary literature, we explored the chemical and ecological factors that determine the bioaccumulation of radiocesium. Using log-linear regression we found that the bioaccumulation of 137 CS by fish was a negative function of both dissolved potassium and suspended sediment concentration, and a positive function of temperature. Important ecological factors were the trophic level of the fish (piscivores bioaccumulate more than planktivores and benthivores), and the length of the food chain as reflected by the ratio of piscivore yield relative to net primary production. Fish from softwater drainages, which make up a large portion of northern Europe and Canada, are more vulnerable to radiocesium contamination than fish from hardwater sedimentary drainages, because these waters are extremely low in potassium and suspended sediment, and their watersheds are less efficient in retaining radiocesium. High dissolved potassium, short food chains, and the much greater volume and mixing potential of the ocean make marine fish less vulnerable to releases of radiocesium. (author)

Bioaccumulation of 137Cs and 60Co by Helianthus annuus

International Nuclear Information System (INIS)

Hornik, M.; Pipiska, M.; Vrtoch, L.; Augustin, J.; Lesny, J.

2005-01-01

The 60 Co and 137 Cs bioaccumulation by Helianthus annuus L. was measured during 9 day cultivation at 20 ± 2 o C in hydroponic Hoagland medium. Previous starvation for K + and for NH 4 + 2.2 and 2.7 times, respectively, enhanced 137 Cs uptake rate. Previous cultivation in surplus of K + ions 50 mmol·l -1 has no effect on 137 Cs bioaccumulation rate. Both 137 Cs and 60 Co bioaccumulation significantly increase with dilution of basic Hoagland medium up to 1:7 for caesium and up to 1:3 for cobalt followed by mild decrease at higher dilutions. Root to shoot specific 137 Cs radioactivity ratio (Bq.g -1 /Bq·g -1 , fresh wt.) increased with dilution from 1.46 to 9.6-9.8. The values root to shoot specific radioactivity ratio for 60 Co were less dependent on the nutrient concentrations and were within the range 5.7 to 8.5. 137 Cs was localized mainly in young leaves (30%) and roots (39%) and 60 Co mainly in roots (67%) and leaves (20%). Obtained data showed less sensitivity of 60 Co uptake by sunflower on nutrient concentration in hydroponic media. (author)

Bioaccumulation of microcystins in two freshwater gastropods from a cyanobacteria-bloom plateau lake, Lake Dianchi

International Nuclear Information System (INIS)

Zhang Junqian; Wang Zhi; Song Zhuoyan; Xie Zhicai; Li Lin; Song, Lirong

2012-01-01

To investigate the bioaccumulation patterns of microcystins (MCs) in organs of two gastropods, samples were collected in Lake Dianchi monthly from May to October, 2008, when cyanobacteria typically bloom. The average MCs concentrations for Radix swinhoei (pulmonate) and Margarya melanioides (prosobranch) tended to be similar for the different organs: the highest values in the hepatopancreas (9.33 by 3.74 μg/g DW), followed by digestive tracts (1.66 by 3.03 μg/g DW), gonads (0.45 by 1.34 μg/g DW) and muscles (0.22 by 0.40 μg/g DW). Pulmonate had higher value than prosobranch because of the stronger bioaccumulation ability in hepatopancreas. The levels in organs of R. swinhoei were correlated with environmentally dissolved MCs, but influenced by intracellular MCs for M. melanioides. The estimated MCs concentrations in edible parts of M. melanioides were beyond the WHO’s provisional tolerable daily intake (0.04 μg/kg), suggesting the risk of consumption of M. melanioides from the lake. Highlights: ► We probe bioaccumulated patterns of microcystins in organs of pulmonate and prosobranch. ► The highest microcystins in hepatopancreas for both snails. ► The higher microcystins for pulmonate results from the stronger bioaccumulation ability in hepatopancreas. ► Environmentally dissolved microcystins are the main sources for pulmonate, but intracellular for prosobranch. ► Suggesting the risk of consumption snails in the studying regions. - Higher bioaccumulation MCs level for pulmonate mainly contributed to the stronger bioaccumulation ability in its hepatopancreas.

Flame retardant synergism between molybdenum and halogen-containing compounds in unsaturated polyesters. [Smoke suppression

Energy Technology Data Exchange (ETDEWEB)

Skinner, G.A.; Parker, L.E.; Marshall, P.J.

1978-01-01

Oxygen index results for a series of unsaturated polyesters, containing molybdenum oxide and various halogenated compounds, have provided definite evidence for some form of flame retardant synergistic effect between molybdenum and halogen. With the halogenated compounds used, the magnitude of the effect was greater in the presence of bromine but was dependent on the type of compound. When dibromoneopentyl glycol was used as the bromine source, the synergistic effect exhibited by molybdenum oxide was comparable to that shown by antimony oxide. Since molybdenum oxide also acts as a smoke suppressant, it could offer a useful alternative to antimony oxide particularly in the light of probable changes in standards and regulatory control regarding smoke emission. 4 figures, 2 tables.

BIOACCUMULATION AND DEPURATION STUDIES OF LEAD NITRATE ON ECONOMICALLY IMPORTANT SHRIMP PENAEOUS MONODON

OpenAIRE

S.Palani Kumar; A.S.Sharadhamma

2013-01-01

Current study of Bioaccumulation and Depuration of Lead nitrate on marine shrimp Penaeous monodon shows Lead nitrate accumulation more in hepatopancreas compared to muscle and the depuration level of heavy metal Lead nitrate was more through hepatopancreas comparing to muscle tissues, when comparing to the control animals.This shows the major role of Hepatopacreas in Bioaccumulation and depuration in this study on muscle tissues and hepatopancreas tissues

Study of the halogenation of EuBa[sub 2]Cu[sub 3]O[sub 6]. Etude de l'halogenation de EuBa[sub 2]Cu[sub 3]O[sub 6

Energy Technology Data Exchange (ETDEWEB)

Kabeya, D.T. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Mokhtari, M. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Perrin, C. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Sergent, M. (Rennes-1 Univ., 35 (France). Lab. de Chimie du Solide et Inorganique Moleculaire); Grushko, Yu. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.); Kokovina, L. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.); Rozhniakova, N. (Russian Academy of Sciences, Gatchina (Russian Federation). Nuclear Physics Inst.)

1994-11-01

Sintered samples of EuBa[sub 2]Cu[sub 3]O[sub 6] have been halogenated at low temperature (t<300 C) by treatments under NF[sub 3] or CCl[sub 4] flow diluted in nitrogen, or by reaction with iodine in sealed tubes. Such mild conditions of synthesis allowed to avoid the decomposition of the material during the reactions. The incorporation of the halogen in the sample has been evidenced by the weight gain, by the evolution of the unit-cell parameters and by SEM and EDS analyses. After fluorination and chlorination, the samples become superconducting, but no superconducting behaviour is observed after iodination. These results are compared to the ones previously obtained during the halogenation of YBa[sub 2]Cu[sub 3]O[sub 6]. (orig.).

UARS Halogen Occultation Experiment (HALOE) Level 2 V001

Data.gov (United States)

National Aeronautics and Space Administration — The HALOE home page on the WWW is http://haloe.gats-inc.com/home/index.php The Halogen Occultation Experiment (HALOE) on NASA's Upper Atmosphere Research Satellite...

Biogas from MSW landfill: Composition and determination of chlorine content with the AOX (adsorbable organically bound halogens) technique

International Nuclear Information System (INIS)

Rey, M.D.; Font, R.; Aracil, I.

2013-01-01

An exhaustive characterization of the biogas from some waste disposal facilities has been carried out. The analysis includes the main components (methane, carbon dioxide, nitrogen and oxygen) as well as trace components such as hydrogen sulphide, ammonia and VOCs (volatile organic compounds) including siloxanes and halogenated compounds. VOCs were measured by GC/MS (Gas Chromatography/Mass Spectrometry) using two different procedures: thermal desorption of the Tenax TA and Carbotrap 349 tubes and SPME (Solid Phase Micro-Extraction). A method has been established to measure the total halogen content of the biogas with the AOX (adsorbable organically bound halogens) technique. The equipment used to analyze the samples was a Total Organic Halogen Analyzer (TOX-100). Similar results were obtained when comparing the TOX (Total Organic Halogen) values with those obtained by GC/MS. The halogen content in all the samples was under 22 mg Cl/Nm 3 which is below the limit of 150 mg/Nm 3 proposed in the Spanish Regulations for any use of the biogas. The low chlorine content in the biogas studied, as well as the low content of other trace compounds, makes it suitable for use as a fuel for electricity generating engines

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

International Nuclear Information System (INIS)

Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing; Bai, Hongcun

2015-01-01

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M 2 (CN) 5 ] −1 (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca 2 (CN) 5 ] −1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

Energy Technology Data Exchange (ETDEWEB)

Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao; Li, Jian-Li; Yin, Bing, E-mail: rayinyin@nwu.edu.cn [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Bai, Hongcun [Key Laboratory of Energy Source and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021 (China)

2015-06-15

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

Bioaccumulation dynamics of polychlorinated biphenyls (PCBs) and organochlorine pesticides

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — Bioaccumulation dynamics of polychlorinated biphenyls (PCBs) and organochlorine pesticides was examined in young-of-the-year bluefish from seven sub-estuaries of New...

Nanoparticle interactions with co-existing contaminants: joint toxicity, bioaccumulation and risk.

Science.gov (United States)

Deng, Rui; Lin, Daohui; Zhu, Lizhong; Majumdar, Sanghamitra; White, Jason C; Gardea-Torresdey, Jorge L; Xing, Baoshan

2017-06-01

With their growing production and application, engineered nanoparticles (NPs) are increasingly discharged into the environment. The released NPs can potentially interact with pre-existing contaminants, leading to biological effects (bioaccumulation and/or toxicity) that are poorly understood. Most studies on NPs focus on single analyte exposure; the existing literature on joint toxicity of NPs and co-existing contaminants is rather limited but beginning to develop rapidly. This is the first review paper evaluating the current state of knowledge regarding the joint effects of NPs and co-contaminants. Here, we review: (1) methods for investigating and evaluating joint effects of NPs and co-contaminants; (2) simultaneous toxicities from NPs co-exposed with organic contaminants, metal/metalloid ions, dissolved organic matter (DOM), inorganic ligands and additional NPs; and (3) the influence of NPs co-exposure on the bioaccumulation of organic contaminants and heavy metal ions, as well as the influence of contaminants on NPs bioaccumulation. In addition, future research needs are discussed so as to better understand risk associated with NPs-contaminant co-exposure.

Self-assembly of iodine in superfluid helium droplets. Halogen bonds and nanocrystals

Energy Technology Data Exchange (ETDEWEB)

He, Yunteng; Zhang, Jie; Lei, Lei; Kong, Wei [Department of Chemistry, Oregon State University, Corvallis, OR (United States)

2017-03-20

We present evidence of halogen bond in iodine clusters formed in superfluid helium droplets based on results from electron diffraction. Iodine crystals are known to form layered structures with intralayer halogen bonds, with interatomic distances shorter than the sum of the van der Waals radii of the two neighboring atoms. The diffraction profile of dimer dominated clusters embedded in helium droplets reveals an interatomic distance of 3.65 Aa, much closer to the value of 3.5 Aa in iodine crystals than to the van der Waals distance of 4.3 Aa. The profile from larger iodine clusters deviates from a single layer structure; instead, a bi-layer structure qualitatively fits the experimental data. This work highlights the possibility of small halogen bonded iodine clusters, albeit in a perhaps limited environment of superfluid helium droplets. The role of superfluid helium in guiding the trapped molecules into local potential minima awaits further investigation. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

Science.gov (United States)

Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

2008-10-30

A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes.

Ab Initio Calculations on Halogen Bond Between N-Br and Electron-donating Groups

Institute of Scientific and Technical Information of China (English)

WANG Yan-hua; CHEN Xue-song; ZOU Jian-wei; YU Qing-sen

2007-01-01

Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ* to gain a deeper insight into the nature of the N-Br halogen stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N＞O＞S; O(sp3)＞O(sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.

Selenium-Mediated Dehalogenation of Halogenated Nucleosides and its Relevance to the DNA Repair Pathway.

Science.gov (United States)

Mondal, Santanu; Manna, Debasish; Mugesh, Govindasamy

2015-08-03

Halogenated nucleosides can be incorporated into the newly synthesized DNA of replicating cells and therefore are commonly used in the detection of proliferating cells in living tissues. Dehalogenation of these modified nucleosides is one of the key pathways involved in DNA repair mediated by the uracil-DNA glycosylase. Herein, we report the first example of a selenium-mediated dehalogenation of halogenated nucleosides. We also show that the mechanism for the debromination is remarkably different from that of deiodination and that the presence of a ribose or deoxyribose moiety in the nucleosides facilitates the deiodination. The results described herein should help in understanding the metabolism of halogenated nucleosides in DNA and RNA. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling the role of microplastics in Bioaccumulation of organic chemicals to marine aquatic organisms. Critical Review

NARCIS (Netherlands)

Koelmans, A.A.

2015-01-01

It has been shown that ingestion of microplastics may increase bioaccumulation of organic chemicals by aquatic organisms. This paper critically reviews the literature on the effects of plastic ingestion on the bioaccumulation of organic chemicals, emphasizing quantitative approaches and mechanistic

Benchmark Calculations of Noncovalent Interactions of Halogenated Molecules

Czech Academy of Sciences Publication Activity Database

Řezáč, Jan; Riley, Kevin Eugene; Hobza, Pavel

2012-01-01

Roč. 8, č. 11 (2012), s. 4285-4292 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : halogenated molecules * noncovalent interactions * benchmark calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.389, year: 2012

Polar Flattening and the Strength of Halogen Bonding

Czech Academy of Sciences Publication Activity Database

Sedlák, Robert; Kolář, Michal H.; Hobza, Pavel

2015-01-01

Roč. 11, č. 10 (2015), s. 4727-4732 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : density functional theory * interaction energies * halogen bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.301, year: 2015

Contrasting PCB bioaccumulation patterns among Lake Huron lake trout reflect basin-specific ecology.

Science.gov (United States)

Paterson, Gordon; Ryder, Mark; Drouillard, Ken G; Haffner, G Douglas

2016-01-01

This study collected multiple age classes of lake trout from Lake Huron's Main Basin, Georgian Bay, and North Channel regions to compare and contrast top predator polychlorinated biphenyl (PCB) bioaccumulation patterns in separate compartments of the same ecosystem. Sum PCB concentrations were highest for Main Basin (260 ± 24.9 ng g(-1) wet wt) fish, followed by Georgian Bay (74.6 ± 16.2 ng g(-1) ) and North Channel (42.0 ± 3.3 ng g(-1)) fish. Discriminant functions analysis of lake trout PCB profiles and stable carbon (δ(13)C) and nitrogen (δ(15)N) isotope values clearly distinguished fish by location, indicating high degrees of basin fidelity throughout their lifetimes in addition to highly contrasting PCB bioaccumulation profiles. These unique profiles were not attributable to significant differences in lake trout lipid contents (p = 0.856) or trophic position (δ(15)N; p = 0.334), with rainbow smelt representing the primary prey across the basins. Furthermore, significant differences were observed among the basins for the relationships between PCB biomagnification factors and hydrophobicity. An empirical model for predicting PCB biomagnification in Lake Huron lake trout indicated that basin-specific population growth rates and prey abundances were significant for explaining these contrasting patterns of PCB bioaccumulation. The results of the present study are fundamental for understanding the role of ecology in legacy persistent organic pollutant (POP) bioaccumulation. Specifically, ecosystem characteristics such as prey abundances, foraging ecology, and ultimately consumer growth can regulate the variability of legacy POP bioaccumulation as observed within and among a wide range of freshwater ecosystems. © 2015 SETAC.

The Effect of Intermolecular Halogen Bond on 19F DNP Enhancement in 1, 4-Diiodotetrafluorobenzene/4-OH-TEMPO Supramolecular Assembly

Directory of Open Access Journals (Sweden)

GAO Shan

2017-12-01

Full Text Available Halogen bond, as hydrogen bond, is a non-covalent bond. Dynamic nuclear polarization (DNP technique has been used previously to study hydrogen bonds-mediated intermolecular interactions. However, no study has been carried out so far to study the halogen bond-mediated intermolecular interactions with DNP. In this work, 19F DNP polarization efficiency of the halogen bonds existing in supramolecular assembling by 4-OH-TEMPO and 1,4-diiodotetrafluorobenzene (DITFB was studied on a home-made DNP system. The formation of intermolecular halogen bonds appeared to increase 19F DNP polarization efficiency, suggesting that the spin-spin interactions among electrons were weakened by the halogen bonds, resulting in an increased T2e and a larger saturation factor.

Bioaccumulation of heavy metals in two wet retention ponds

DEFF Research Database (Denmark)

Søberg, Laila C.; Vollertsen, Jes; Blecken, Godecke-Tobias

2016-01-01

Metal accumulation in stormwater ponds may contaminate the inhabiting fauna, thus jeopardizing their ecosystem servicing function. We evaluated bioaccumulation of metals in natural fauna and caged mussel indicator organisms in two wet retention ponds. Mussel cages were distributed throughout...... the ponds to detect bioaccumulation gradients and obtain a time-integrated measure of metal bioavailability. We further investigated if sediment metal concentrations correlate with those in the fauna and mussels. Metal concentrations in the fauna tended to be higher in the ponds than in a reference lake......, but statistical significance was only shown for Cu. Positive correlations were found for some metals in fauna and sediment. Sediment metal concentrations in one pond decreased from inlet to outlet while no gradients were observed in the mussels in either pond. These findings indicate that metal accumulation...

Isomorphism of 2-methylnaphthalene and 2-halonaphthalenes as a revealer of a special interaction between methyl and halogen

Science.gov (United States)

Calvet, T.; Cuevas-Diarte, M. A.; Haget, Y.; Mondieig, D.; Kok, I. C.; Verdonk, M. L.; Van Miltenburg, J. C.; Oonk, H. A. J.

1999-03-01

The systems 2-methylnaphthalene+2-chloronaphthalene and 2-methylnaphthalene+2-bromonaphthalene belong to the exceptional group of binary systems where the formation of mixed crystals goes together with a solid-liquid phase diagram with a maximum. For these systems a thermodynamic analysis is presented which is based on new phase diagram and thermochemical data. The excess Gibbs energies, excess enthalpies, and excess entropies of the mixed crystalline state all are negative. These properties correspond to a net attraction between methyl and substituted halogen. Additional evidence of such an attraction is given by the outcome of a statistical search on intermolecular contacts, in the crystalline state of pure substances, among methyl+halogen, halogen+halogen, and methyl+methyl.

A systematic structural study of halogen bonding versus hydrogen bonding within competitive supramolecular systems

Directory of Open Access Journals (Sweden)

Christer B. Aakeröy

2015-09-01

Full Text Available As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. As hydrogen and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. To address this challenge, a series of molecules containing both hydrogen- and halogen-bond donors were co-crystallized with various monotopic, ditopic symmetric and ditopic asymmetric acceptor molecules. The outcome of each reaction was examined using IR spectroscopy and, whenever possible, single-crystal X-ray diffraction. 24 crystal structures were obtained and subsequently analyzed, and the synthon preferences of the competing hydrogen- and halogen-bond donors were rationalized against a background of calculated molecular electrostatic potential values. It has been shown that readily accessible electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in these co-crystals as long as the potential differences are weighted appropriately.

Temporal trends 1987-2002 of regulated POPs in beluga whales from the St. Lawrence Estuary, Canada

Energy Technology Data Exchange (ETDEWEB)

Lebeuf, M; Noel, M; Trottier, S.; Measures, L. [Fisheries and Oceans, Ottawa, ON (Canada)

2005-07-01

Beluga populations in the St. Lawrence Estuary (SLE) are now threatened. The decline of the beluga population has been attributed to the presence of high concentrations of persistent organic pollutants (POPs). This study assessed the temporal trends of POPs in beluga, including polychlorinated biphenyls (PCBs), DDT, chlordanes, halogenated cyclic hydrocarbon (HCH) isomers, halogenated cyclic hydrocarbons (HCB), and mirex in SLE populations between 1987 and 2002. Blubber concentrations of individual POP or POP groups in both male and female belugas were fitted to simple natural algorithms using linear regression analyses. Only animals older than 10 years were examined. POPs, PCBs, and organochlorine pesticides (OCPs) were determined in blubber samples. Temporal trends of biological parameters such as age, lipid content, and length of the animals were assessed separately for both female and male belugas. POP concentrations were expressed on a lipid weight basis for the statistical analyses. Temporal trends of biological parameters, individual POP or POP group concentrations in both females and males were assessed using simple in-linear regression analysis from which half-life time was calculated for each statistically significant time trend. Results showed that approximately half of the POPs showed significant decreasing levels in female beluga between 1987 and 2002 and in males between 1988 and 2002. Temporal trends of PCBs, DDTs, and HCH were significant in both males and females, while chlordanes, and mirex levels were not significant in either sex. HCB exhibited a significant time trend in males. Time trends were in agreement with expected declines for regulated POPs. It was concluded that bioaccumulative POPs must be rapidly regulated before they reach high levels, as POP compounds are very slowly eliminated by belugas. 9 refs., 1 tab.

Influence of salinity on uptake rate and bioaccumulation of /sup 137/Cs in the oyster crassostrea glomerata

International Nuclear Information System (INIS)

Mashiatullah, A.; Qureshi, R.M.; Khan, S.; Chaghtai, F.; Akhter, P.; Jabbar, A.

2008-01-01

This paper describes results of experiment on bioaccumulation and uptake rate of radiocesium /sup 137/Cs from dissolved phase in the flesh of the Oysters (Crassostrea glomerata) collected off Karachi coast. A radiotracer experiment was conducted under laboratory conditions to determine the uptake rate and bioaccumulation of /sup 137/Cs from dissolved phase in the flesh of the Oyster. Oysters (size: 6-7 cm) were subjected to radiocesium activity of 24 Kilobecquerel per liter (kBq L/sup -1/) under three salinity Ievels (25, 30 and 35 ppt). The uptake of /sup 137/Cs was monitored for a period of seven days. The results showed that bioaccumulation and uptake of /sup 137/Cs in oysters were considerably dependent of salinity levels. Higher bioaccumulation factors and uptake rates were found at low salinity levels. (author)

Influence of dispersants on trophic transfer of petroleum hydrocarbons in a marine food chain

Energy Technology Data Exchange (ETDEWEB)

Wolfe, M.; Tjeerdema, R. [Univ. of California, Santa Cruz, CA (United States). Dept. of Chemistry and Biochemistry; Sowby, M. [California Dept. of Fish and Game, Sacramento, CA (United States)

1995-12-31

When crude oil is accidentally released into the ocean, it threatens many levels of marine life. Intervention, in the form of chemical dispersing agents, alters the normal behavior of petroleum hydrocarbons (PH) by increasing their functional water solubility and the extent of their exposure to sub-surface organisms. Dispersing agents may modify bioavailability as a result of altered interactions between dispersed PH droplets and organismal cell membranes.The objective of this research was to determine the impact of dispersing agents on PH bioavailability and trophic transfer in primary levels of a marine food chain. Uptake, bioaccumulation, depuration, and metabolic transformation of a model PH, {sup 14}C-naphthalene, were measured and compared for Prudhoe Bay Crude Oil (PBCO) dispersed with Corexit 9527 and undispersed preparations of the water-accommodated fractions (WAF) of PBCO at two salinities and temperatures. The model food chain consisted of Isochrysis galbana and Brachionus plicatilis. Direct aqueous exposure was compared with combined aqueous and dietary exposure. Fractionation and identification of metabolites was done by HPLC co-chromatography with analytical standards, and quantitation was done by liquid scintillation counting. GC-FID characterization of WAF and dispersed oil (DO) preparations shows higher concentrations of petroleum hydrocarbons and a greater number of individual constituents in the dispersed oil preparations.

Influence of dispersants on trophic transfer of petroleum hydrocarbons in a marine food chain

International Nuclear Information System (INIS)

Wolfe, M.; Tjeerdema, R.

1995-01-01

When crude oil is accidentally released into the ocean, it threatens many levels of marine life. Intervention, in the form of chemical dispersing agents, alters the normal behavior of petroleum hydrocarbons (PH) by increasing their functional water solubility and the extent of their exposure to sub-surface organisms. Dispersing agents may modify bioavailability as a result of altered interactions between dispersed PH droplets and organismal cell membranes.The objective of this research was to determine the impact of dispersing agents on PH bioavailability and trophic transfer in primary levels of a marine food chain. Uptake, bioaccumulation, depuration, and metabolic transformation of a model PH, 14 C-naphthalene, were measured and compared for Prudhoe Bay Crude Oil (PBCO) dispersed with Corexit 9527 and undispersed preparations of the water-accommodated fractions (WAF) of PBCO at two salinities and temperatures. The model food chain consisted of Isochrysis galbana and Brachionus plicatilis. Direct aqueous exposure was compared with combined aqueous and dietary exposure. Fractionation and identification of metabolites was done by HPLC co-chromatography with analytical standards, and quantitation was done by liquid scintillation counting. GC-FID characterization of WAF and dispersed oil (DO) preparations shows higher concentrations of petroleum hydrocarbons and a greater number of individual constituents in the dispersed oil preparations

Global impacts of tropospheric halogens (Cl, Br, I on oxidants and composition in GEOS-Chem

Directory of Open Access Journals (Sweden)

T. Sherwen

2016-09-01

Full Text Available We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I. Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016 we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O3 concentrations, except in polar regions where the model now underestimates O3 concentrations. Halogen chemistry reduces the global tropospheric O3 burden by 18.6 %, with the O3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28  ×  106 molecules cm−3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH4 lifetime (10.8 % due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH4 by Cl is small (∼  2 % but Cl oxidation of other VOCs (ethane, acetone, and propane can be significant (∼  15–27 %. Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.

Thermodynamics parameters for binding of halogenated benzotriazole inhibitors of human protein kinase CK2α.

Science.gov (United States)

Winiewska, Maria; Kucińska, Katarzyna; Makowska, Małgorzata; Poznański, Jarosław; Shugar, David

2015-10-01

The interaction of human CK2α (hCK2α) with nine halogenated benzotriazoles, TBBt and its analogues representing all possible patterns of halogenation on the benzene ring of benzotriazole, was studied by biophysical methods. Thermal stability of protein-ligand complexes, monitored by calorimetric (DSC) and optical (DSF) methods, showed that the increase in the mid-point temperature for unfolding of protein-ligand complexes (i.e. potency of ligand binding to hCK2α) follow the inhibitory activities determined by biochemical assays. The dissociation constant for the ATP-hCK2α complex was estimated with the aid of microscale thermophoresis (MST) as 4.3±1.8 μM, and MST-derived dissociation constants determined for halogenated benzotriazoles, when converted according to known ATP concentrations, perfectly reconstruct IC50 values determined by the biochemical assays. Ligand-dependent quenching of tyrosine fluorescence, together with molecular modeling and DSC-derived heats of unfolding, support the hypothesis that halogenated benzotriazoles bind in at least two alternative orientations, and those that are efficient hCK2α inhibitors bind in the orientation which TBBt adopts in its complex with maize CK2α. DSC-derived apparent heat for ligand binding (ΔΔHbind) is driven by intermolecular electrostatic interactions between Lys68 and the triazole ring of the ligand, as indicated by a good correlation between ΔΔHbind and ligand pKa. Overall results, additionally supported by molecular modeling, confirm that a balance of hydrophobic and electrostatic interactions contribute predominantly (~40 kJ/mol), relative to possible intermolecular halogen/hydrogen bonding (less than 10 kJ/mol), in binding of halogenated benzotriazoles to the ATP-binding site of hCK2α. This article is part of a Special Issue entitled: Inhibitors of Protein Kinases. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong.

Science.gov (United States)

Guo, H; Lee, S C; Louie, P K K; Ho, K F

2004-12-01

Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas

Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

Energy Technology Data Exchange (ETDEWEB)

Hissung, A; Isildar, M; von Sonntag, C [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenforschung; Witzel, H [Biochemisches Institut der Westfaelischen Wilhelms-Universitaet, Muenster, West Germany

1981-02-01

The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N/sub 2/O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10/sup 5/s/sup -1/) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10/sup 3/ M/sup -1/s/sup -1/ was estimated. Compound 4 has also been investigated by product analysis after 60-Co-..gamma..-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O/sub 2/ to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA.

Radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety

International Nuclear Information System (INIS)

Hissung, A.; Isildar, M.; Sonntag, C. von; Witzel, H.

1981-01-01

The pulse radiolysis of aqueous solutions of nucleosides halogenated at the sugar moiety (2'-bromo-2'-deoxyuridine 4, 3'-deoxy-3'-iodothymidine 5, 5'-deoxy-5'-iodouridine 6) has been studied. G(Hal) were determined by conductometry varying the experimental conditions (pH, saturation with Ar, N 2 O or air, addition of t-butanol). The results indicate that solvated electrons both add to the nucleobases and eliminate halogen ions from the halogenated sugar moiety. In the case of 4(and possibly of 5) the radical anion of the base transfers (k approximately 10 5 s -1 ) an electron to the sugar-bound halogen atom thus cleaving the C-Hal bond. In competition with this reaction there is a protonation of the radical anion of the base by protons and by water. For the latter reaction constant of k = 5 x 10 3 M -1 s -1 was estimated. Compound 4 has also been investigated by product analysis after 60-Co-γ-irradiation. In aerated solutions erythrose is formed with a G-value of 0.12. Its precursor radical is the 2'-radical generated from 4 by dissociative electron capture which reacts with O 2 to the corresponding peroxyl radical. Erythrose is formed after a sequence of reactions, one of which involves the scission of the C-1'-C-2'bond. Under this condition G(HBr) as measured by pulse radiolysis is 0.8. Thus erythrose is formed in 15 per cent yield with respect to its precursor radical. This result is of importance in assessing the precursor radical of a similar product observed in irradiated DNA. (author)

Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom

Science.gov (United States)

Ding, Xin; Tuikka, Matti; Hirva, Pipsa; Haukka, Matti

2017-09-01

Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2'-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]ṡI2 with only one NCSṡṡṡI2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCSṡṡṡI2 and SCNṡṡṡI2 bonding modes. The reason for the observed NCSṡṡṡI2 mode lies most probably in the more favourable packing effects rather than energetic preferences between NCSṡṡṡI2 and SCNṡṡṡI2 contacts.

Organohalide respiration in pristine environments: implications for the natural halogen cycle.

Science.gov (United States)

Atashgahi, Siavash; Häggblom, Max M; Smidt, Hauke

2018-03-01

Halogenated organic compounds, also termed organohalogens, were initially considered to be of almost exclusively anthropogenic origin. However, over 5000 naturally synthesized organohalogens are known today. This has also fuelled the hypothesis that the natural and ancient origin of organohalogens could have primed development of metabolic machineries for their degradation, especially in microorganisms. Among these, a special group of anaerobic microorganisms was discovered that could conserve energy by reducing organohalogens as terminal electron acceptor in a process termed organohalide respiration. Originally discovered in a quest for biodegradation of anthropogenic organohalogens, these organohalide-respiring bacteria (OHRB) were soon found to reside in pristine environments, such as the deep subseafloor and Arctic tundra soil with limited/no connections to anthropogenic activities. As such, accumulating evidence suggests an important role of OHRB in local natural halogen cycles, presumably taking advantage of natural organohalogens. In this minireview, we integrate current knowledge regarding the natural origin and occurrence of industrially important organohalogens and the evolution and spread of OHRB, and describe potential implications for natural halogen and carbon cycles. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

Photofragmentation spectra of halogenated methanes in the VUV photon energy range

Energy Technology Data Exchange (ETDEWEB)

Cartoni, Antonella, E-mail: antonella.cartoni@uniroma1.it [Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza Università di Roma, P.le Aldo Moro 5, Roma 00185 (Italy); Bolognesi, Paola; Fainelli, Ettore; Avaldi, Lorenzo [CNR-IMIP, Area della Ricerca di Roma 1, Monterotondo Scalo (Rm) 00015 (Italy)

2014-05-14

In this paper an investigation of the photofragmentation of dihalomethanes CH{sub 2}X{sub 2} (X = F, Cl, Br, I) and chlorinated methanes (CH{sub n}Cl{sub 4−n} with n = 0–3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH{sub 2}F{sub 2} as a source of both fluorine and hydrogen atoms and the characteristic formation of I{sub 2}{sup +} and CH{sub 2}{sup +} ions from the photofragmentation of the CH{sub 2}I{sub 2} molecule.

Mutagenic activity of halogenated propanes and propenes: effect of bromine and chlorine positioning.

Science.gov (United States)

Låg, M; Omichinski, J G; Dybing, E; Nelson, S D; Søderlund, E J

1994-10-01

A series of halogenated propanes and propenes were studied for mutagenic effects in Salmonella typhimurium TA100 in the absence or presence of NADPH plus liver microsomes from phenobarbital-induced rats as an exogenous metabolism system. The cytotoxic and mutagenic effects of the halogenated propane 1,2-dibromo-3-chloropropane (DBCP) has previously been studied in our laboratories. These studies showed that metabolic activation of DBCP was required to exert its detrimental effects. All of the trihalogenated propane analogues were mutagenic when the microsomal activation system was included. The highest mutagenic activity was obtained with 1,2,3-tribromopropane, with approximately 50-fold higher activity than the least mutagenic trihalogenated propane, 1,2,3-trichloropropane. The order of mutagenicity was as follows: 1,2,3-tribromopropane > or = 1,2-dibromo- 3-chloropropane > 1,3-dibromo-2-chloropropane > or = 1,3-dichloro-2-bromopropane > 1-bromo-2,3-dichloropropane > 1,2,3-trichloropropane. Compared to DBCP, the dihalogenated propanes were substantially less mutagenic. Only 1,2-dibromopropane was mutagenic and its mutagenic potential was approximately 1/30 of that of DBCP. In contrast to DBCP, 1,2-dibromopropane showed similar mutagenic activity with and without the addition of an activation system. The halogenated propenes 2,3-dibromopropene and 2-bromo-3-chloropropene were mutagenic to the bacteria both in the absence and presence of the activation system, whereas 2,3-dichloropropene did not show any mutagenic effect. The large differences in mutagenic potential between the various halogenated propanes and propenes are proposed to be due to the formation of different possible proximate and ultimate mutagenic metabolites resulting from the microsomal metabolism of the various halogenated propanes and propenes, and to differences in the rate of formation of the metabolites. Pathways are proposed for the formation of genotoxic metabolites of di- and trihalogenated

Extending Halogen-based Medicinal Chemistry to Proteins: IODO-INSULIN AS A CASE STUDY.

Science.gov (United States)

El Hage, Krystel; Pandyarajan, Vijay; Phillips, Nelson B; Smith, Brian J; Menting, John G; Whittaker, Jonathan; Lawrence, Michael C; Meuwly, Markus; Weiss, Michael A

2016-12-30

Insulin, a protein critical for metabolic homeostasis, provides a classical model for protein design with application to human health. Recent efforts to improve its pharmaceutical formulation demonstrated that iodination of a conserved tyrosine (Tyr B26 ) enhances key properties of a rapid-acting clinical analog. Moreover, the broad utility of halogens in medicinal chemistry has motivated the use of hybrid quantum- and molecular-mechanical methods to study proteins. Here, we (i) undertook quantitative atomistic simulations of 3-[iodo-Tyr B26 ]insulin to predict its structural features, and (ii) tested these predictions by X-ray crystallography. Using an electrostatic model of the modified aromatic ring based on quantum chemistry, the calculations suggested that the analog, as a dimer and hexamer, exhibits subtle differences in aromatic-aromatic interactions at the dimer interface. Aromatic rings (Tyr B16 , Phe B24 , Phe B25 , 3-I-Tyr B26 , and their symmetry-related mates) at this interface adjust to enable packing of the hydrophobic iodine atoms within the core of each monomer. Strikingly, these features were observed in the crystal structure of a 3-[iodo-Tyr B26 ]insulin analog (determined as an R 6 zinc hexamer). Given that residues B24-B30 detach from the core on receptor binding, the environment of 3-I-Tyr B26 in a receptor complex must differ from that in the free hormone. Based on the recent structure of a "micro-receptor" complex, we predict that 3-I-Tyr B26 engages the receptor via directional halogen bonding and halogen-directed hydrogen bonding as follows: favorable electrostatic interactions exploiting, respectively, the halogen's electron-deficient σ-hole and electronegative equatorial band. Inspired by quantum chemistry and molecular dynamics, such "halogen engineering" promises to extend principles of medicinal chemistry to proteins. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Chiral halogenated Schiff base compounds: green synthesis, anticancer activity and DNA-binding study

Science.gov (United States)

Ariyaeifar, Mahnaz; Amiri Rudbari, Hadi; Sahihi, Mehdi; Kazemi, Zahra; Kajani, Abolghasem Abbasi; Zali-Boeini, Hassan; Kordestani, Nazanin; Bruno, Giuseppe; Gharaghani, Sajjad

2018-06-01

Eight enantiomerically pure halogenated Schiff base compounds were synthesized by reaction of halogenated salicylaldehydes with 3-Amino-1,2-propanediol (R or S) in water as green solvent at ambient temperature. All compounds were characterized by elemental analyses, NMR (1H and 13C), circular dichroism (CD) and FT-IR spectroscopy. FS-DNA binding studies of these compounds carried out by fluorescence quenching and UV-vis spectroscopy. The obtained results revealed that the ligands bind to DNA as: (Rsbnd ClBr) > (Rsbnd Cl2) > (Rsbnd Br2) > (Rsbnd I2) and (Ssbnd ClBr) > (Ssbnd Cl2) > (Ssbnd Br2) > (Ssbnd I2), indicating the effect of halogen on binding constant. In addition, DNA-binding constant of the Ssbnd and R-enantiomers are different from each other. The ligands can form halogen bonds with DNA that were confirmed by molecular docking. This method was also measured the bond distances and bond angles. The study of obtained data can have concluded that binding affinity of the ligands to DNA depends on strength of halogen bonds. The potential anticancer activity of ligands were also evaluated on MCF-7 and HeLa cancer cell lines by using MTT assay. The results showed that the anticancer activity and FS-DNA interaction is significantly dependent on the stereoisomers of Schiff base compounds as R-enantiomers displayed significantly higher activity than S-enantiomers. The molecular docking was also used to illustrate the specific DNA-binding of synthesized compounds and groove binding mode of DNA interaction was proposed for them. In addition, molecular docking results indicated that there are three types of bonds (Hsbnd and X-bond and hX-bond) between synthesized compounds and base pairs of DNA.

Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

International Nuclear Information System (INIS)

Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D.; DeYoung, Paul A.; Blum, Arlene; Stapleton, Heather M.; Peaslee, Graham F.

2015-01-01

A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography–Mass Spectrometry (GC–MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC–MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams

Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

Energy Technology Data Exchange (ETDEWEB)

Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D. [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States); DeYoung, Paul A. [Department of Physics, Hope College, 27 Graves Place, Holland, MI 49423 (United States); Blum, Arlene [Green Science Policy Institute, Box 5455, Berkeley, CA 94705 (United States); Stapleton, Heather M. [Nicholas School of the Environment, Duke University, LSRC Box 90328, Durham, NC 27708 (United States); Peaslee, Graham F., E-mail: peaslee@hope.edu [Department of Chemistry, Hope College, 35 E. 12th Street, Holland, MI 49423 (United States)

2015-09-01

A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography–Mass Spectrometry (GC–MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC–MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams.

Zinc bioaccumulation in a terrestrial invertebrate fed a diet treated with particulate ZnO or ZnCl2 solution.

Science.gov (United States)

Pipan-Tkalec, Ziva; Drobne, Damjana; Jemec, Anita; Romih, Tea; Zidar, Primoz; Bele, Marjan

2010-03-10

A number of reports on potential toxicity of nanoparticles are available, but there is still a lack of knowledge concerning bioaccumulation. The aim of this work was to investigate how different sources of zinc, such as uncoated and unmodified ZnO nanoparticles, ZnCl(2) in solution, and macropowder ZnO influence the bioaccumulation of this metal in the terrestrial isopod Porcellio scaber. After exposure to different sources of Zn in the diet, the amount of assimilated Zn in whole body, the efficiency of zinc assimilation, and bioaccumulation factors (BAFs) were assessed. The bioaccumulation potential of Zn was found to be the same regardless of Zn source. The amount of assimilated Zn and BAF were dose-dependent, and Zn assimilation efficiency was independent of exposure concentrations. The Zn assimilation capacity was found to be up to 16% of ingested Zn. It is known that as much as approximately 20% of Zn can be accreted from ZnO particles by dissolution. We conclude that bioaccumulation of Zn in isopods exposed to particulate ZnO depends most probably on Zn dissolution from ZnO particles and not on bioaccumulation of particulate ZnO.

Can Halogen Enrichment in Reduced Enstatite Chondrites Provide Clues to Volatile Accretion in the Early Earth?

Science.gov (United States)

Clay, P. L.; Burgess, R.; Busemann, H.; Ruzié, L.; Joachim, B.; Ballentine, C.

2013-12-01

Understanding how the Earth obtained and ultimately retained its volatiles is important for our overall understanding of large scale planetary evolution. Numerous models exist for the heterogeneous accretion of volatiles to early Earth, but accounting for all elements through accretion of typical planetary building blocks (e.g., CI chondrites) is difficult. Proto-planetary collisions resulting in the accretion of volatile-poor material under reducing conditions followed by accretion of volatile-rich material under oxidizing conditions has been suggested in such models [e.g., 1]. The heavy halogens (Cl, Br and I), a group of moderately volatile elements, are excellent tracers of planetary processing due to their low abundance and incompatible nature. Therefore characterizing halogen abundance and distribution in materials that accreted to form the planets, e.g., primitive meteorites, is crucial. One group of primitive meteorites, the enstatite chondrites (EC's), are amongst the most reduced materials in the solar system as evidenced by their unique mineral assemblage. Yet despite forming under ultra-reducing conditions, they are enriched in the moderately volatile elements, such as the halogens. The ECs are of particular interest owing to their oxygen isotopic composition which plots along the terrestrial fractionation line, linking them isotopically to the Earth-Moon system. These samples can thus potentially provide clues on the accretion of moderately volatile element rich material under reducing conditions, such as it may have existed during the early stages of Earth's accretion. Chlorine, Br and I concentrations in ECs were determined through step-heating small neutron-irradiated samples (0.3 to 3.3 mg) and measured by mass spectrometry using the noble gas proxy isotopes 38ArCl/Cl, 80KrBr/Br and 128XeI/I. The EH chondrites are consistently enriched in the heavy halogens (up to 330 ppm Cl, 2290 ppb Br and 180 ppb I), compared to other ordinary and carbonaceous

Habitat-specific bioaccumulation of methylmercury in invertebrates of small mid-latitude lakes in North America

Energy Technology Data Exchange (ETDEWEB)

Chetelat, John, E-mail: john.chetelat@ec.gc.c [Groupe de recherche interuniversitaire en limnologie, Departement de sciences biologiques, Universite de Montreal, Montreal, Quebec H3C 3J7 (Canada); Amyot, Marc; Garcia, Edenise [Groupe de recherche interuniversitaire en limnologie, Departement de sciences biologiques, Universite de Montreal, Montreal, Quebec H3C 3J7 (Canada)

2011-01-15

We examined habitat-specific bioaccumulation of methylmercury (MeHg) in aquatic food webs by comparing concentrations in pelagic zooplankton to those in littoral macroinvertebrates from 52 mid-latitude lakes in North America. Invertebrate MeHg concentrations were primarily correlated with water pH, and after controlling for this influence, pelagic zooplankton had significantly higher MeHg concentrations than littoral primary consumers but lower MeHg than littoral secondary consumers. Littoral primary consumers and pelagic zooplankton are two dominant prey for fish, and greater MeHg in zooplankton is likely sufficient to increase bioaccumulation in pelagic feeders. Intensive sampling of 8 lakes indicated that habitat-specific bioaccumulation in invertebrates (of similar trophic level) may result from spatial variation in aqueous MeHg concentration or from more efficient uptake of aqueous MeHg into the pelagic food web. Our findings demonstrate that littoral-pelagic differences in MeHg bioaccumulation are widespread in small mid-latitude lakes. - Methylmercury levels in dominant invertebrate prey for fish differ between littoral and pelagic habitats within a lake.

Habitat-specific bioaccumulation of methylmercury in invertebrates of small mid-latitude lakes in North America

International Nuclear Information System (INIS)

Chetelat, John; Amyot, Marc; Garcia, Edenise

2011-01-01

We examined habitat-specific bioaccumulation of methylmercury (MeHg) in aquatic food webs by comparing concentrations in pelagic zooplankton to those in littoral macroinvertebrates from 52 mid-latitude lakes in North America. Invertebrate MeHg concentrations were primarily correlated with water pH, and after controlling for this influence, pelagic zooplankton had significantly higher MeHg concentrations than littoral primary consumers but lower MeHg than littoral secondary consumers. Littoral primary consumers and pelagic zooplankton are two dominant prey for fish, and greater MeHg in zooplankton is likely sufficient to increase bioaccumulation in pelagic feeders. Intensive sampling of 8 lakes indicated that habitat-specific bioaccumulation in invertebrates (of similar trophic level) may result from spatial variation in aqueous MeHg concentration or from more efficient uptake of aqueous MeHg into the pelagic food web. Our findings demonstrate that littoral-pelagic differences in MeHg bioaccumulation are widespread in small mid-latitude lakes. - Methylmercury levels in dominant invertebrate prey for fish differ between littoral and pelagic habitats within a lake.

Evaluation of bio-accumulation stress in chicken by arsenite: haematological case study

International Nuclear Information System (INIS)

Rasul, L.; Tufail, S.; Rasool, H.

2016-01-01

Water. This bio-accumulation disturbs the eco-physiological and blood parameters. Haematological studies of anti-coagulated and serum blood samples core parameters reveals that As (III) contamination in drinking water is the significant source of adverse disturbance of blood parameters of red blood cell, white blood cell, hemoglobin, packed cell volume, sodium, calcium, potassium ions, albumin, urea, creatinine and cholesterol, with a highly significant p value of less than 0.01 after 14th brooding day with bio-accumulation of 25.8 micro g/L of As (III) in blood samples. (author)

Speciation of bioaccumulated uranium(VI) by Euglena mutabilis cells obtained by laser fluorescence spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Brockmann, Sina; Bernhard, Gert [Technical Univ. Dresden (Germany). Radiochemistry; Helmholtz-Zentrum Dresden-Rossendorf (HZDR) e.V., Dresden (Germany). Inst. of Resource Ecology; Arnold, Thuro [Helmholtz-Zentrum Dresden-Rossendorf (HZDR) e.V., Dresden (Germany). Inst. of Resource Ecology

2014-07-01

The ability of Euglena mutabilis cells - a unicellular protozoan with a flexible pellicle, which is typically found in acid mine drainage (AMD) environments - to bioaccumulate uranium under acid conditions was studied in batch sorption experiments at pH 3 and 4 using Na{sub 2}SO{sub 4} and NaClO{sub 4} as background media. It was found that axenic cultures of Euglena mutabilis Schmitz were able to bioaccumulate in 5 days 94.9 to 99.2% of uranium from a 1 x 10{sup -5} mol/L uranium solution in perchlorate medium and 95.1 to 95.9% in sodium sulfate medium, respectively. The speciation of uranium in solution and uranium bioaccumulated by Euglena mutabilis cells, were studied by laser induced fluorescence spectroscopy (LIFS). The LIFS investigations showed that the uranium speciation in the NaClO{sub 4} systems was dominated by free uranyl(VI) species and that the UO{sub 2}SO{sub 4} species was dominating in the Na{sub 2}SO{sub 4} medium. Fluorescence spectra of the bioaccumulated uranium revealed that aqueous uranium binds to carboxylic and/or (organo)phosphate groups located on the euglenid pellicle or inside the Euglena mutabilis cells. Reduced uranium immobilization rates of 0.93-1.43 mg uranium per g Euglena mutabilis biomass were observed in similar experiments, using sterile filtrated AMD waters containing, 4.4 x 10{sup -5} mol/L uranium. These lower rates were attributed to competition with other cations for available sorption sites. Additional LIFS measurements, however, showed that the speciation of the bioaccumulated uranium by the Euglena mutabilis cells was found to be identical with the uranium speciation found in the bioaccumulation experiments carried out in Na{sub 2}SO{sub 4} and NaClO{sub 4} media. The results indicate that Euglena mutabilis has the potential to immobilize aqueous uranium under acid condition and thus may be used in future as promising agent for immobilizing uranium in low pH waste water environments. (orig.)

Speciation of bioaccumulated uranium(VI) by Euglena mutabilis cells obtained by laser fluorescence spectroscopy

International Nuclear Information System (INIS)

Brockmann, Sina; Bernhard, Gert; Helmholtz-Zentrum Dresden-Rossendorf; Arnold, Thuro

2014-01-01

The ability of Euglena mutabilis cells - a unicellular protozoan with a flexible pellicle, which is typically found in acid mine drainage (AMD) environments - to bioaccumulate uranium under acid conditions was studied in batch sorption experiments at pH 3 and 4 using Na 2 SO 4 and NaClO 4 as background media. It was found that axenic cultures of Euglena mutabilis Schmitz were able to bioaccumulate in 5 days 94.9 to 99.2% of uranium from a 1 x 10 -5 mol/L uranium solution in perchlorate medium and 95.1 to 95.9% in sodium sulfate medium, respectively. The speciation of uranium in solution and uranium bioaccumulated by Euglena mutabilis cells, were studied by laser induced fluorescence spectroscopy (LIFS). The LIFS investigations showed that the uranium speciation in the NaClO 4 systems was dominated by free uranyl(VI) species and that the UO 2 SO 4 species was dominating in the Na 2 SO 4 medium. Fluorescence spectra of the bioaccumulated uranium revealed that aqueous uranium binds to carboxylic and/or (organo)phosphate groups located on the euglenid pellicle or inside the Euglena mutabilis cells. Reduced uranium immobilization rates of 0.93-1.43 mg uranium per g Euglena mutabilis biomass were observed in similar experiments, using sterile filtrated AMD waters containing, 4.4 x 10 -5 mol/L uranium. These lower rates were attributed to competition with other cations for available sorption sites. Additional LIFS measurements, however, showed that the speciation of the bioaccumulated uranium by the Euglena mutabilis cells was found to be identical with the uranium speciation found in the bioaccumulation experiments carried out in Na 2 SO 4 and NaClO 4 media. The results indicate that Euglena mutabilis has the potential to immobilize aqueous uranium under acid condition and thus may be used in future as promising agent for immobilizing uranium in low pH waste water environments. (orig.)

Feeding reduces waterborne Cu bioaccumulation in a marine rabbitfish Siganus oramin

International Nuclear Information System (INIS)

Guo, Zhiqiang; Zhang, Wei; Du, Sen; Zhou, Yanyan; Gao, Na; Zhang, Li; Green, Iain

2016-01-01

Waterborne metal uptake has been extensively studied and dietary metal assimilation is increasingly recognized in fish, whilst the interaction between the two uptake routes is largely overlooked. This study compared the waterborne Cu bioaccumulation ("6"5Cu as tracer) in a juvenile rabbitfish at different feeding regimes (starvation (SG), feeding normal diet (NDG) or diet supplemented with extra Cu (DCG)) to test the hypothesis that feeding can influence waterborne metal uptake in marine fish. NDG and DCG diet was fed as a single meal and then all fish were exposed to waterborne "6"5Cu for 48 h, during which the time course sampling was conducted to determine "6"5Cu bioaccumulation, chyme flow and dietary Cu assimilation. The results revealed that SG fish accumulated the highest "6"5Cu, followed by NDG (61% of SG), whilst DCG fish accumulated the lowest "6"5Cu (34% of SG). These results suggested a protective effect of feeding against waterborne Cu bioaccumulation. This effect was most notable between 10 min and 16 h when there was chyme in gastrointestinal tract (GT). Dietary Cu assimilation mainly occurred before 16 h after feeding. Waterborne "6"5Cu influx rate in the GT was positively correlated with "6"5Cu contents of chyme in NDG, whereas it was largely negatively correlated with "6"5Cu contents of chyme in DCG. The waterborne Cu uptake in the GT was mainly influenced by the chyme flow and dietary Cu assimilation. Overall, our findings suggested that feeding has an important effect on waterborne metal uptake and that both the feeding status of the fish and the relative metal exposure through water and food should be considered in prediction of the metal bioaccumulation and biomonitoring programs. - Highlights: • Feeding shows a protective effect against waterborne Cu uptake in fish. • The elevated dietary Cu can greatly suppress the waterborne Cu uptake. • The presence of chyme reduces Cu uptake in the gastrointestinal tract. • Feeding status has

Bioaccumulation of Fe2O3(magnetic) nanoparticles in Ceriodaphnia dubia

International Nuclear Information System (INIS)

Hu Ji; Wang Demin; Wang Jiangtao; Wang Jianmin

2012-01-01

While nano-Fe 2 O 3 (magnetic) is generally considered non-toxic, it could serve as a carrier of other toxic chemicals such as As(V) and enhance their toxicity. The bioaccumulation of nano-Fe 2 O 3 (m) with different exposure times, NP concentrations, and pH conditions was investigated using Ceriodaphnia dubia (C. dubia) as the model organism. Under natural pH conditions, C. dubia significantly accumulated nano-Fe 2 O 3 (m) in the gut, with the maximum accumulation being achieved after 6 h of exposure. The concentration of nano-Fe 2 O 3 also impacted its accumulation, with the maximum uptake occurring at 20 mg/L or more. In addition, the highest bioaccumulation occurred in a pH range of 7–8 where the highest feeding rate was reported, confirming that the ingestion of NPs is the main route of nano-Fe 2 O 3 (m) bioaccumulation. In a clean environment without NPs, depuration of nano-Fe 2 O 3 (m) occurred, and food addition accelerated the depuration process. - Highlights: ► Nano-Fe 2 O 3 (m) enhances the toxicity of As(V). ► C. dubia significantly accumulate nano-Fe 2 O 3 (m) through ingestion. ► The bioaccumulation of nano-Fe 2 O 3 (m) is affected by time, NP concentration, and pH. ► Food addition accelerates the depuration process of accumulated nano-Fe 2 O 3 (m). - Nano-Fe 2 O 3 (m) could enhance the toxicity of As(V) due to the significant accumulation of nano-Fe 2 O 3 (m) along with sorbed As(V) by C. dubia through ingestion.

Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration.

Science.gov (United States)

Grigg, R David; Van Hoveln, Ryan; Schomaker, Jennifer M

2012-10-03

A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

[Near infrared light irradiator using halogen lamp].

Science.gov (United States)

Ide, Yasuo

2012-07-01

The practical electric light bulb was invented by Thomas Alva Edison in 1879. Halogen lamp is the toughest and brightest electric light bulb. With light filter, it is used as a source of near infrared light. Super Lizer and Alphabeam are made as near infrared light irradiator using halogen lamp. The light emmited by Super Lizer is linear polarized near infrared light. The wave length is from 600 to 1,600 nm and strongest at about 1,000 nm. Concerning Super Lizer, there is evidence of analgesic effects and normalization of the sympathetic nervous system. Super Lizer has four types of probes. SG type is used for stellate ganglion irradiation. B type is used for narrow area irradiation. C and D types are for broad area irradiation. The output of Alphabeam is not polarized. The wave length is from 700 to 1,600 nm and the strongest length is about 1,000nm. Standard attachment is used for spot irradiation. Small attachment is used for stellate ganglion irradiation. Wide attachment is used for broad area irradiation. The effects of Alphabeam are thought to be similar to that of Super Lizer.

Relationship between the lability of sediment-bound Cd and its bioaccumulation in edible oyster.

Science.gov (United States)

Chakraborty, Parthasarathi; Ramteke, Darwin; Chakraborty, Sucharita; Chennuri, Kartheek; Bardhan, Pratirupa

2015-11-15

A linkage between Cd speciation in sediments and its bioaccumulation in edible oyster (Crassostrea sp.) from a tropical estuarine system was established. Bioaccumulation of Cd in edible oyster increased with the increasing lability and dissociation rate constants of Cd-sediment complexes in the bottom sediments. Total Cd concentration in sediment was not a good indicator of Cd-bioavailability. Increasing trace metal competition in sediments increased lability and bioavailability of Cd in the tropical estuarine sediment. Low thermodynamic stability and high bioavailability of Cd in the estuarine sediment were responsible for high bioaccumulation of Cd in edible oysters (3.2-12.2mgkg(-1)) even though the total concentration of Cd in the bottom sediment was low (0.17-0.49mgkg(-1)). Copyright © 2015 Elsevier Ltd. All rights reserved.

Enantioselective bioaccumulation of diniconazole in Tenebrio molitor larvae.

Science.gov (United States)

Liu, Chen; LV, Xiao Tian; Zhu, Wen Xue; QU, Hao Yang; Gao, Yong Xin; Guo, Bao Yuan; Wang, Hui Li

2013-12-01

The enantioselective bioaccumulation of diniconazole in Tenebrio molitor Linne larva was investigated with liquid chromatography tandem mass spectrometry based on the ChiralcelOD-3R[cellulose tri-(3,5-dimethylphenyl carbamate)] column. In this study we documented the effects of dietary supplementation with wheat bran contaminated by racemic diniconazole at two dose levels of 20 mg kg(-1) and 2 mg kg(-1) (dry weight) in Tenebrio molitor. The results showed that both doses of diniconazole were taken up by Tenebrio molitor rapidly in the first few days, the concentrations of R-enantiomer and S-enantiomer at high doses reached the highest level of 0.55 mg kg(-1) and 0.48 mg kg(-1) , respectively, on the 1(st) d, and the concentrations of them obtained a maxima of 0.129 mg kg(-1) and 0.128 mg kg(-1) at low dose, respectively, on the 3(rd) d, which means that the concentration of diniconazole was proportional to the time of achieving the highest accumulated level. It afterwards attained equilibrium after a sharp decline at both 20 mg kg(-1) and 2 mg kg(-1) of diniconazole. The determination results from the feces of Tenebrio molitor demonstrated that the extraction recovery (ER) values of the high dose group were higher than that of the low dose group and the values were all above 1; therefore, it could be inferred that enantiomerization existed in Tenebrio molitor. Additionally, the biota accumulation factor was used to evaluate the bioaccumulation of diniconazole enantiomers, showing that the bioaccumulation of diniconazole in Tenebrio molitor was enantioselective with preferential accumulation of S-enantiomer. © 2013 Wiley Periodicals, Inc.

Tissue-specific bioaccumulation of human and veterinary antibiotics in bile, plasma, liver and muscle tissues of wild fish from a highly urbanized region

International Nuclear Information System (INIS)

Zhao, Jian-Liang; Liu, You-Sheng; Liu, Wang-Rong; Jiang, Yu-Xia; Su, Hao-Chang; Zhang, Qian-Qian; Chen, Xiao-Wen; Yang, Yuan-Yuan; Chen, Jun; Liu, Shuang-Shuang; Pan, Chang-Gui; Huang, Guo-Yong; Ying, Guang-Guo

2015-01-01

We investigated the bioaccumulation of antibiotics in bile, plasma, liver and muscle tissues of wild fish from four rivers in the Pearl River Delta region. In total, 12 antibiotics were present in at least one type of fish tissues from nine wild fish species in the four rivers. The mean values of log bioaccumulation factors (log BAFs) for the detected antibiotics in fish bile, plasma, liver, and muscle tissues were at the range of 2.06–4.08, 1.85–3.47, 1.41–3.51, and 0.48–2.70, respectively. As the digestion tissues, fish bile, plasma, and liver showed strong bioaccumulation ability for some antibiotics, indicating a different bioaccumulation pattern from hydrophobic organic contaminants. Human health risk assessment based on potential fish consumption indicates that these antibiotics do not appear to pose an appreciable risk to human health. To the best of our knowledge, this is first report of bioaccumulation patterns of antibiotics in wild fish bile and plasma. - Highlights: • We investigated the bioaccumulation of antibiotics in wild fish from the Pearl River Delta region. • Twelve antibiotics were found in fish bile, plasma, liver and muscle tissues. • High log bioaccumulation factors suggested strong bioaccumulation ability for some antibiotics in wild fish tissues. • The presence of antibiotics in fish bile and plasma tissues indicates a novel bioaccumulation pattern. • Potential adverse effects are possibly caused by the high internal antibiotic concentrations in tissues. - Fish bile and plasma displayed strong bioaccumulation ability for some antibiotics, indicating a novel bioaccumulation pattern for antibiotics in the contaminated environment

PCDD/F and dioxin-like PCB bioaccumulation by Manila clam from polluted areas of Venice lagoon (Italy)

International Nuclear Information System (INIS)

Sfriso, Adriano; Facca, Chiara; Raccanelli, Stefano

2014-01-01

POP bioaccumulation pathways in the clam Tapes philippinarum were examined for two years from juveniles to adult size. Two polluted sites, one with sandy sediment, the other muddy were compared with a reference site characterized by low contamination levels. Juvenile clams coming from a hatchery were reared both on the sediment and in nets suspended at 30 cm from the bottom. POP changes in clam tissue were related to the concentrations recorded in sediments and in the particulate matter during the entire fattening period. Results provided interesting data on the relationships between environmental contamination and bioaccumulation. Contrary to studies on the decontamination times of the clams collected in polluted areas, this work investigates the preferential clam bioaccumulation pathways during growth under different environmental conditions. In general POP bioaccumulation resulted to be correlated to concentrations in SPM rather than in sediments and was higher in S-clams rather than in B-clams. -- Highlights: • PCDD/Fs and dioxin-like PCB accumulation in clam tissues during growth. • Muddy and sandy polluted areas. • How sediment and suspended matter contamination affect clam toxicity. • Clam toxicity and law limits. -- Clam bioaccumulation pathways in polluted areas

Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

Science.gov (United States)

Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

2018-04-01

The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.

The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates.

Science.gov (United States)

Dureckova, Hana; Woo, Tom K; Udachin, Konstantin A; Ripmeester, John A; Alavi, Saman

2017-10-13

Clathrate hydrate phases of Cl 2 and Br 2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen-halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen-halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme-substrate compounds. The nature of the halogen-water interactions for the Cl 2 and Br 2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl 2 and Br 2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

Molecular Engineering of Non-Halogenated Solution-Processable Bithiazole based Electron Transport Polymeric Semiconductors

KAUST Repository

Fu, Boyi

2015-04-01

The electron deficiency and trans planar conformation of bithiazole is potentially beneficial for the electron transport performance of organic semiconductors. However, the incorporation of bithiazole into polymers through a facile synthetic strategy remains a challenge. Herein, 2,2’-bithiazole was synthesized in one step and copolymerized with dithienyldiketopyrrolopyrrole to afford poly(dithienyldiketopyrrolopyrrole-bithiazole), PDBTz. PDBTz exhibited electron mobility reaching 0.3 cm2V-1s-1 in organic field-effect transistor (OFET) configuration; this contrasts with a recently discussed isoelectronic conjugated polymer comprising an electron rich bithiophene and dithienyldiketopyrrolopyrrole, which displays merely hole transport characteristics. This inversion of charge carrier transport characteristics confirms the significant potential for bithiazole in the development of electron transport semiconducting materials. Branched 5-decylheptacyl side chains were incorporated into PDBTz to enhance polymer solubility, particularly in non-halogenated, more environmentally compatible solvents. PDBTz cast from a range of non-halogenated solvents exhibited film morphologies and field-effect electron mobility similar to those cast from halogenated solvents.

Molecular Engineering of Non-Halogenated Solution-Processable Bithiazole based Electron Transport Polymeric Semiconductors

KAUST Repository

Fu, Boyi; Wang, Cheng-Yin; Rose, Bradley Daniel; Jiang, Yundi; Chang, Mincheol; Chu, Ping-Hsun; Yuan, Zhibo; Fuentes-Hernandez, Canek; Bernard, Kippelen; Bredas, Jean-Luc; Collard, David M.; Reichmanis, Elsa

2015-01-01

The electron deficiency and trans planar conformation of bithiazole is potentially beneficial for the electron transport performance of organic semiconductors. However, the incorporation of bithiazole into polymers through a facile synthetic strategy remains a challenge. Herein, 2,2’-bithiazole was synthesized in one step and copolymerized with dithienyldiketopyrrolopyrrole to afford poly(dithienyldiketopyrrolopyrrole-bithiazole), PDBTz. PDBTz exhibited electron mobility reaching 0.3 cm2V-1s-1 in organic field-effect transistor (OFET) configuration; this contrasts with a recently discussed isoelectronic conjugated polymer comprising an electron rich bithiophene and dithienyldiketopyrrolopyrrole, which displays merely hole transport characteristics. This inversion of charge carrier transport characteristics confirms the significant potential for bithiazole in the development of electron transport semiconducting materials. Branched 5-decylheptacyl side chains were incorporated into PDBTz to enhance polymer solubility, particularly in non-halogenated, more environmentally compatible solvents. PDBTz cast from a range of non-halogenated solvents exhibited film morphologies and field-effect electron mobility similar to those cast from halogenated solvents.

Mercury and halogens in coal: Chapter 2

Science.gov (United States)

Kolker, Allan; Quick, Jeffrey C.; Granite, Evan J.; Pennline, Henry W.; Senior, Constance L.

2014-01-01

Apart from mercury itself, coal rank and halogen content are among the most important factors inherent in coal that determine the proportion of mercury captured by conventional controls during coal combustion. This chapter reviews how mercury in coal occurs, gives available concentration data for mercury in U.S. and international commercial coals, and provides an overview of the natural variation in halogens that influence mercury capture. Three databases, the U.S. Geological Survey coal quality (USGS COALQUAL) database for in-ground coals, and the 1999 and 2010 U.S. Environmental Protection Agency (EPA) Information Collection Request (ICR) databases for coals delivered to power stations, provide extensive results for mercury and other parameters that are compared in this chapter. In addition to the United States, detailed characterization of mercury is available on a nationwide basis for China, whose mean values in recent compilations are very similar to the United States in-ground mean of 0.17 ppm mercury. Available data for the next five largest producers (India, Australia, South Africa, the Russian Federation, and Indonesia) are more limited and with the possible exceptions of Australia and the Russian Federation, do not allow nationwide means for mercury in coal to be calculated. Chlorine in coal varies as a function of rank and correspondingly, depth of burial. As discussed elsewhere in this volume, on a proportional basis, bromine is more effective than chlorine in promoting mercury oxidation in flue gas and capture by conventional controls. The ratio of bromine to chlorine in coal is indicative of the proportion of halogens present in formation waters within a coal basin. This ratio is relatively constant except in coals that have interacted with deep-basin brines that have reached halite saturation, enriching residual fluids in bromine. Results presented here help optimize mercury capture by conventional controls and provide a starting point for

Zinc bioaccumulation by microbial consortium isolated from nickel smelter sludge disposal site

Directory of Open Access Journals (Sweden)

Kvasnová Simona

2017-06-01

Full Text Available Heavy metal pollution is one of the most important environmental issues of today. Bioremediation by microorganisms is one of technologies extensively used for pollution treatment. In this study, we investigated the heavy metal resistance and zinc bioaccumulation by microbial consortium isolated from nickel sludge disposal site near Sereď (Slovakia. The composition of consortium was analyzed based on MALDI-TOF MS of cultivable bacteria and we have shown that the consortium was dominated by bacteria of genus Arthrobacter. While consortium showed very good growth in the zinc presence, it was able to remove only 15 % of zinc from liquid media. Selected members of consortia have shown lower growth rates in the zinc presence but selected isolates have shown much higher bioaccumulation abilities compared to whole consortium (up to 90 % of zinc removal for NH1 strain. Bioremediation is frequently accelerated through injection of native microbiota into a contaminated area. Based on data obtained in this study, we can conclude that careful selection of native microbiota could lead to the identification of bacteria with increased bioaccumulation abilities.

Cyanotoxins: Bioaccumulation and Effects on Aquatic Animals

Directory of Open Access Journals (Sweden)

Betina Kozlowsky-Suzuki

2011-12-01

Full Text Available Cyanobacteria are photosynthetic prokaryotes with wide geographic distribution that can produce secondary metabolites named cyanotoxins. These toxins can be classified into three main types according to their mechanism of action in vertebrates: hepatotoxins, dermatotoxins and neurotoxins. Many studies on the effects of cyanobacteria and their toxins over a wide range of aquatic organisms, including invertebrates and vertebrates, have reported acute effects (e.g., reduction in survivorship, feeding inhibition, paralysis, chronic effects (e.g., reduction in growth and fecundity, biochemical alterations (e.g., activity of phosphatases, GST, AChE, proteases, and behavioral alterations. Research has also focused on the potential for bioaccumulation and transferring of these toxins through the food chain. Although the herbivorous zooplankton is hypothesized as the main target of cyanotoxins, there is not unquestionable evidence of the deleterious effects of cyanobacteria and their toxins on these organisms. Also, the low toxin burden in secondary consumers points towards biodilution of microcystins in the food web as the predominant process. In this broad review we discuss important issues on bioaccumulation and the effects of cyanotoxins, with emphasis on microcystins, as well as drawbacks and future needs in this field of research.

Cyanotoxins: bioaccumulation and effects on aquatic animals.

Science.gov (United States)

Ferrão-Filho, Aloysio da S; Kozlowsky-Suzuki, Betina

2011-12-01

Cyanobacteria are photosynthetic prokaryotes with wide geographic distribution that can produce secondary metabolites named cyanotoxins. These toxins can be classified into three main types according to their mechanism of action in vertebrates: hepatotoxins, dermatotoxins and neurotoxins. Many studies on the effects of cyanobacteria and their toxins over a wide range of aquatic organisms, including invertebrates and vertebrates, have reported acute effects (e.g., reduction in survivorship, feeding inhibition, paralysis), chronic effects (e.g., reduction in growth and fecundity), biochemical alterations (e.g., activity of phosphatases, GST, AChE, proteases), and behavioral alterations. Research has also focused on the potential for bioaccumulation and transferring of these toxins through the food chain. Although the herbivorous zooplankton is hypothesized as the main target of cyanotoxins, there is not unquestionable evidence of the deleterious effects of cyanobacteria and their toxins on these organisms. Also, the low toxin burden in secondary consumers points towards biodilution of microcystins in the food web as the predominant process. In this broad review we discuss important issues on bioaccumulation and the effects of cyanotoxins, with emphasis on microcystins, as well as drawbacks and future needs in this field of research.

Aromatic hydrocarbons

International Nuclear Information System (INIS)

Roder, M.

1985-01-01

Papers dealing with radiolysis of aromatic hydrocarbons of different composition (from benzene to terphenyls and hydrocarbons with condensed rings) as well as their mixtures (with alkanes, alkenes, other aromatic hydrocarbons) are reviewed. High radiation stability of aromatic hydrocarbons in condensed phases associated with peculiarities of molecular structure of compounds is underlined. Mechanisms of radiolytic processes, vaues of product yields are considered

Comparing humic substance and protein compound effects on the bioaccumulation of perfluoroalkyl substances by Daphnia magna in water.

Science.gov (United States)

Xia, Xinghui; Dai, Zhineng; Rabearisoa, Andry Harinaina; Zhao, Pujun; Jiang, Xiaoman

2015-01-01

The influence of humic substances and protein compounds on the bioaccumulation of six types of perfluoroalkyl substances (PFASs) in Daphnia magna was compared. The humic substances included humic acid (HA) and fulvic acid (FA), the protein compounds included chicken egg albumin (albumin) and peptone, and the PFASs included perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid. Four concentrations (0, 1, 10, and 20 mg L(-1)) of the four dissolved organic matter (DOM) types were investigated. At the 1 mg L(-1) level, HA and albumin enhanced all tested PFAS bioaccumulation, whereas FA and peptone only enhanced the bioaccumulation of shorter-chain PFASs (PFOS, PFOA, and PFNA). However, all four DOM types decreased all tested PFAS bioaccumulation at the 20 mg L(-1) level, and the decreasing ratios of bioaccumulation factors caused by FA, HA, albumin, and peptone were 1-49%, 23-77%, 17-58%, and 8-56%, respectively compared with those without DOM. This is because DOM not only reduced the bioavailable concentrations and uptake rates of PFASs but also lowered the elimination rates of PFASs in D. magna, and these opposite effects would change with different DOM types and concentrations. Although the partition coefficients (L kg(-1)) of PFASs between HA and water (10(4.21)-10(4.98)) were much lower than those between albumin and water (10(4.92)-10(5.86)), their effects on PFAS bioaccumulation were comparable. This study suggests that although PFASs are a type of proteinophilic compounds, humic substances also have important effects on their bioavailability and bioaccumulation in aquatic organisms. Copyright © 2014 Elsevier Ltd. All rights reserved.

Bioaccumulation and effects of perfluorinated compounds (PFCs) in zebra mussels (Dreissena polymorpha).

Science.gov (United States)

Fernández-Sanjuan, María; Faria, Melissa; Lacorte, Silvia; Barata, Carlos

2013-04-01

Perfluorinated chemicals (PFCs) have been used for many years in numerous industrial products and are known to accumulate in organisms. A recent survey showed that tissue levels of PFCs in aquatic organisms varied among compounds and species being undetected in freshwater zebra mussels Dreissena polymorpha. Here we studied the bioaccumulation kinetics and effects of two major PFCs, perfluorooctane sulfonic acid compound (PFOS) and perfluorooctanoic acid (PFOA), in multixenobiotic transporter activity (MXR) and filtration and oxygen consumption rates in zebra mussel exposed to a range of concentrations of a PCF mixture (1-1,000 μg/L) during 10 days. Results indicate a low potential of the studied PFCs to bioaccumulate in zebra mussel tissues. PFCs altered mussel MXR transporter activity being inhibited at day 1 but not at day 10. Bioaccumulation kinetics of PFCs were inversely related with MXR transporter activity above 9 ng/g wet weight and unrelated at tissue concentration lower than 2 ng/g wet weight suggesting that at high tissue concentrations, these type of compounds may be effluxed out by MXR transporters and as a result have a low potential to be bioaccumulated in zebra mussels. Oxygen consumption rates but not filtering rates were increased in all exposure levels and periods indicating that at environmental relevant concentrations of 1 μg/L, the studied PFCs enhanced oxidative metabolism of mussels. Overall, the results obtained in this study confirm previous findings in the field indicating that an important fraction of PFC accumulated in mussel tissues is eliminated actively by MXR transporters or other processes that are metabolically costly.

Characterization of halogenated DBPs and identification of new DBPs trihalomethanols in chlorine dioxide treated drinking water with multiple extractions.

Science.gov (United States)

Han, Jiarui; Zhang, Xiangru; Liu, Jiaqi; Zhu, Xiaohu; Gong, Tingting

2017-08-01

Chlorine dioxide (ClO 2 ) is a widely used alternative disinfectant due to its high biocidal efficiency and low-level formation of trihalomethanes and haloacetic acids. A major portion of total organic halogen (TOX), a collective parameter for all halogenated DBPs, formed in ClO 2 -treated drinking water is still unknown. A commonly used pretreatment method for analyzing halogenated DBPs in drinking water is one-time liquid-liquid extraction (LLE), which may lead to a substantial loss of DBPs prior to analysis. In this study, characterization and identification of polar halogenated DBPs in a ClO 2 -treated drinking water sample were conducted by pretreating the sample with multiple extractions. Compared to one-time LLE, the combined four-time LLEs improved the recovery of TOX by 2.3 times. The developmental toxicity of the drinking water sample pretreated with the combined four-time LLEs was 1.67 times higher than that pretreated with one-time LLE. With the aid of ultra-performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry, a new group of polar halogenated DBPs, trihalomethanols, were detected in the drinking water sample pretreated with multiple extractions; two of them, trichloromethanol and bromodichloromethanol, were identified with synthesized standard compounds. Moreover, these trihalomethanols were found to be the transformation products of trihalomethanes formed during ClO 2 disinfection. The results indicate that multiple LLEs can significantly improve extraction efficiencies of polar halogenated DBPs and is a better pretreatment method for characterizing and identifying new polar halogenated DBPs in drinking water. Copyright © 2017. Published by Elsevier B.V.

Bioaccumulation of sediment-bound Cr-51, Ni-63 and C-14 by benthic invertebrates

International Nuclear Information System (INIS)

Kumblad, L.; Bradshaw, C.; Giled, M.

2004-01-01

Sediments in many areas of the Baltic Sea are highly contaminated with particle-reactive trace metals and/or radionuclides. These may be re-mobilised into aquatic food chains by bioaccumulation into benthic organisms. In this study, we examined and compared assimilation efficiencies and bioaccumulation kinetics (rates of uptake and elimination) of sediment-associated Cr-51, Ni-63 and organic-associated C- 14 in three common benthic invertebrates from the Baltic Sea (the bivalve Macoma balthica, the amphipod Monoporeia affinis and the priapulid worm Halicryptus spinulosus). There were differences between animals and radionuclides in both the rate of uptake and elimination and the maximum amount accumulated. Understanding how and to what degree different deposit-feeding benthic invertebrates are exposed to and bio-accumulate sediment-associated metals are important for both ecological risk assessment and management decisions in coastal ecosystems. (author)

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Science.gov (United States)

2010-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this subpart that... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

Polycyclic aromatic hydrocarbons in Northwest Atlantic finfish : available and needed knowledge for monitoring

International Nuclear Information System (INIS)

Hellou, J.; Leonard, J.; Collier, T.K.; Ariese, F.

2004-01-01

This study addressed some of the human health risk factors associated with polycyclic aromatic hydrocarbons (PAHs). These toxic chemicals degrade with time, depending on their source and structure. However, they can also persist long enough and exist at elevated levels to have a possible toxic risk associated with exposure. Most studies on invertebrates have examined bioaccumulation rather than biotransformation. Biotransformation occurs more readily in vertebrates because they have active mixed function oxygenase enzymes. The fate of the oxidation products is of particular interest because they are associated with the formation of DNA-adducts that have carcinogenic effects. Exposed organisms can be monitored for chemical, biochemical or biological endpoints. This study examined PAH concentrations in small finfish such as capelin, sand lance, American plaice, yellowtail flounder and herring collected from the district of the Northwest Atlantic Fisheries Organization. Variables included pool size, size differences within species, lipid content and location. The exposure routes for bioaccumulation were respiration and feeding. The two sources were combustion and fossil fuels. All samples showed signs of alkylated naphthalene which would have been take up by respiration. They were likely derived from petroleum seeps in the water column. Smaller fish had higher concentrations of 3 alkylated naphthalenes. This paper described the relative concentrations in whole fish and internal organs. Measurements carried out prior to development of the Hibernia oil fields revealed baseline levels. Biotransformation products must yet be measured in order to assess future exposure and effects, particularly with long term exposure to waste water. 7 refs., 1 fig

Bioaccumulation studies with Eisenia fetida using an established degradation test system

Energy Technology Data Exchange (ETDEWEB)

Norr, C.; Riepert, F. [Biological Research Centre for Agriculture and Forestry, Inst. for Ecotoxicology and Ecochemistry in Plant Protection, Berlin (Germany)

2007-12-15

Background. Earthworms are considered as an appropriate test system to assess the bioaccumulation potential of substances in the terrestrial environment. For regulatory purposes test methods were developed and incorporated in the validation process. A test design that is particularly suited for testing {sup 14}C-labelled substances will be described here. This design was adapted from an established degradation test system for bioaccumulation tests with earthworms in soil. The antibiotic sulfadiazine was used as test substance in this study. Due to the biological activity and the widespread entering into soil by manure application, veterinary medicines have become the target of ecotoxicological risk assessment. A German research group provided the soil samples mixed with liquid pig manure, which contained the {sup 14}C-labelled test substance after having passed through the gut of animals. This exposure pathway reflects the real environmental conditions. Therefore, sulfadiazine was tested even though a significant bioaccumulation potential was not expected to be detected owing to its chemical properties. Methods. Two adult earthworms of the species Eisenia fetida were inserted in a 500 ml glass container filled with 100 g soil. The test substrate consisted of soil mixed with liquid manure containing {sup 14}C-sulfadiazine. The glass containers were fitted with a soda-lime trap, which is permeable for oxygen but absorbs produced CO{sub 2} and other volatile metabolites. As food source for the earthworms, 5 g of mashed potato powder was applied per test container at the beginning of the test. The levels of radioactivity in soil samples and earthworms were determined by combustion in an oxidizer over a four-week exposure phase. The test design follows the instructions described by the OECD draft guideline for testing the bioaccumulation behaviour of chemicals with oligochaetes in soil. (orig.)

Evaluating mercury bioaccumulation rates in fish using mark-recapture techniques

Science.gov (United States)

Mathews, T.; Surendran Nair, S.; McManamay, R.

2017-12-01

Mercury (Hg) bioaccumulation can be described by models of varying complexity, from the simplified bioconcentration factor which describes the partitioning of contaminants between water and the organism, to more sophisticated models which take into consideration speciation, complexation, and/or bioavailability. At contaminated sites, especially those that are undergoing remediation, it is helpful to have a dynamic framework to identify critical Hg sources and processes, and to predict time scales to recovery. However, understanding the relationship between changes in exposure concentrations and bioaccumulation rates remains a challenge. East Fork Poplar Creek (EFPC) is a Hg-contaminated stream located in East Tennessee. Over the past 30 years, various remediation actions have succeeded in significantly reducing Hg inputs to this stream. One of the major goals of remediation is to reduce Hg bioaccumulation in resident sunfish in order to meet human health guidelines. Mercury is measured in sunfish fillets bi-annually at various sites along the stream. Because Hg analysis requires only 100 mg of tissue, fish can be sampled non-lethally and released at the site of capture. Since 2008, passive induced transponder (PIT) tags have been used to identify individual fish that are collected from EFPC for Hg analysis. Approximately 10% of PIT tagged fish were recaptured, allowing for the measurement of growth rates and Hg bioaccumulation rates in individual fish. While traditional biomonitoring studies conducted in EFPC have found that the average Hg concentrations in sacrificed fish have not responded to changes in aqueous Hg concentrations over the past 10 years, data from the mark-recapture study show that individual fish may respond to changes in aqueous inorganic Hg concentrations on shorter time scales. Rapid changes in aqueous Hg concentrations over a four year period resulted in measurable increases and decreases in Hg concentrations in individual fish that could not

Improving plant bioaccumulation science through consistent reporting of experimental data

DEFF Research Database (Denmark)

Fantke, Peter; Arnot, Jon A.; Doucette, William J.

2016-01-01

Experimental data and models for plant bioaccumulation of organic contaminants play a crucial role for assessing the potential human and ecological risks associated with chemical use. Plants are receptor organisms and direct or indirect vectors for chemical exposures to all other organisms. As new...... experimental data are generated they are used to improve our understanding of plant-chemical interactions that in turn allows for the development of better scientific knowledge and conceptual and predictive models. The interrelationship between experimental data and model development is an ongoing, never......-ending process needed to advance our ability to provide reliable quality information that can be used in various contexts including regulatory risk assessment. However, relatively few standard experimental protocols for generating plant bioaccumulation data are currently available and because of inconsistent...

Bioaccumulation of Cs-137 and Co-57 by marine phytoplankton

International Nuclear Information System (INIS)

Heldal, H.E.; Stupakoff, I.; Fisher, N.S.

1999-01-01

Under controlled laboratory conditions we have examined the bioaccumulation of Cs-137 and Co-57 in three prymnesiophytes, the coccolithophorid Emiliania huxleyi and the non-calcareous species Isochrysis galbana and Phaeocystis globosa, and two diatoms Skeletonema costatum and Thalassiosira pseudonana. We measured uptake in growing and non-growing cells, and determined concentration factors on both volume and dry weight basis. For Co-57 uptake in non-growing cells, volume concentration factors (VCF) at equilibrium ranged from 0.2 * 10 3 for Emiliana huxleyi to 4 * 10 3 for the diatom Thalassiosira pseudonana. For Cs-137 uptake in non-growing cells the VCFs were close to zero. The results suggest that, in contrast to Co, the cycling and bioaccumulation in animals of Cs in marine systems is unlikely to be affected by primary producers. (au)

Platinum bioaccumulation by mustard plants (Sinapis alba L.)

International Nuclear Information System (INIS)

Hawienczyk, M.; Bystrzejewska-Piotrowska, G.; Kowalska, J.; Asztemborska, M.

2005-01-01

The ability of hydroponically cultivated Indian mustard plants (Sinapis alba L.) to accumulate platinum was investigated. The Pt-bioaccumulation in leaves, stem and shoots of plants growing for 2 and 4 weeks at Pt-concentration of 50 and 500 μg/L was compared. The relation between dry and fresh weight was also estimated. Adsorptive stripping voltammetry (AdSV) and mass spectrometry with inductively coupled plasma (ICP-MS) were applied for determination of Pt. Increasing Pt-concentration from 50 to 500 μg/L in the medium causes: (1) reduction of the root tissue hydration level at unchanged modification in aboveground parts of the plants and (2) decrease of the Pt transfer factor (TF) for roots and increase for leaves and stem. Duration of the culture influenced on Pt-accumulation in roots and in aboveground organs of mustard plants. Transfer factor for Pt between 560 and 1600 makes Indian mustard plants one at Pt-hyperaccumulators. Distribution of Pt-bioaccumulation in the plant organs may be useful for biomonitoring of platinum in the environment. (author)

Bioaccumulation of animal adenoviruses in the pink shrimp

Directory of Open Access Journals (Sweden)

Roger B. Luz

2015-09-01

Full Text Available Adenoviruses are among the most promising viral markers of fecal contamination. They are frequently found in the water, sediment and soil of regions impacted by human activity. Studies of the bioaccumulation of enteric viruses in shrimp are scarce. The cities located in the northern coast of the lake systems in Southern Brazil have high urbanization and intensive farming rates, and poor sewage collection and treatment. One hundred (n = 100 Farfantepenaeus paulensis pink-shrimp specimens and 48 water samples were collected from coastal lagoons between June 2012 and May 2013. Water samples were concentrated and the shrimp, mashed. After DNA extraction, samples were analyzed by real time polymerase chain reaction (qPCR in order to detect and quantify viral genomes. Thirty-five percent of shrimp samples were positive for contamination, predominantly by avian adenoviruses. A total of 91.7% of water samples contained adenoviruses DNA, with the human form being the most frequent. Our results provided evidence of significant bioaccumulation of adenoviruses in shrimp, showing the extent of the impact of fecal pollution on aquatic ecosystems.

Organophosphorus and Organochlorine Pesticides Bioaccumulation by Eichhornia crassipes in Irrigation Canals in an Urban Agricultural System.

Science.gov (United States)

Mercado-Borrayo, B M; Cram Heydrich, Silke; Pérez, Irma Rosas; Hernández Quiroz, Manuel; De León Hill, Claudia Ponce

2015-01-01

A natural wetland in Mexico City Metropolitan Area is one of the main suppliers of crops and flowers, and in consequence its canals hold a high concentration of organochlorine (OC) and organophosphorus (OP) pesticides. There is also an extensive population of water hyacinth (Eichhornia crassipes), which is considered a plague; but literature suggests water hyacinth may be used as a phytoremediator. This study demonstrates bioaccumulation difference for the OC in vivo suggesting their bioaccumulation is ruled by their log K(ow), while all the OP showed bioaccumulation regardless of their log K(ow). The higher bioaccumulation factors (BAF) of the accumulated OC pesticides cannot be explained by their log K(ow), suggesting that the OC pesticides may also be transported passively into the plant. Translocation ratios showed that water hyacinth is an accumulating plant with phytoremediation potential for all organophosphorus pesticides studied and some organochlorine pesticides. An equation for free water surface wetlands with floating macrophytes, commonly used for the construction of water-cleaning wetlands, showed removal of the pesticides by the wetland with room for improvement with appropriate management.

Reductive dehalogenation by anaerobic bacteria

NARCIS (Netherlands)

Holliger, H.C.

1992-01-01

The understanding of the fate of synthetic halogenated hydrocarbons became a matter of major interest over the last two decades. Halogenated compounds may threaten ecosystems due to their biocide properties. The degradability of halocompounds determines whether they will accumulate in a

In vitro to in vivo extrapolation of biotransformation rates for assessing bioaccumulation of hydrophobic organic chemicals in mammals.

Science.gov (United States)

Lee, Yung-Shan; Lo, Justin C; Otton, S Victoria; Moore, Margo M; Kennedy, Chris J; Gobas, Frank A P C

2017-07-01

Incorporating biotransformation in bioaccumulation assessments of hydrophobic chemicals in both aquatic and terrestrial organisms in a simple, rapid, and cost-effective manner is urgently needed to improve bioaccumulation assessments of potentially bioaccumulative substances. One approach to estimate whole-animal biotransformation rate constants is to combine in vitro measurements of hepatic biotransformation kinetics with in vitro to in vivo extrapolation (IVIVE) and bioaccumulation modeling. An established IVIVE modeling approach exists for pharmaceuticals (referred to in the present study as IVIVE-Ph) and has recently been adapted for chemical bioaccumulation assessments in fish. The present study proposes and tests an alternative IVIVE-B technique to support bioaccumulation assessment of hydrophobic chemicals with a log octanol-water partition coefficient (K OW ) ≥ 4 in mammals. The IVIVE-B approach requires fewer physiological and physiochemical parameters than the IVIVE-Ph approach and does not involve interconversions between clearance and rate constants in the extrapolation. Using in vitro depletion rates, the results show that the IVIVE-B and IVIVE-Ph models yield similar estimates of rat whole-organism biotransformation rate constants for hypothetical chemicals with log K OW  ≥ 4. The IVIVE-B approach generated in vivo biotransformation rate constants and biomagnification factors (BMFs) for benzo[a]pyrene that are within the range of empirical observations. The proposed IVIVE-B technique may be a useful tool for assessing BMFs of hydrophobic organic chemicals in mammals. Environ Toxicol Chem 2017;36:1934-1946. © 2016 SETAC. © 2016 SETAC.

Compound deterioration properties of non-halogen flame-resisting cables

International Nuclear Information System (INIS)

Yamamoto, Yasuaki; Yagyu, Hideki; Onishi, Takao; Kamiharako, Shinji

1984-01-01

Conventional flame-resisting cables release harmful gas such as hydrogen chloride and smoke on burning. To improve this disadvantage, the cables for nuclear power plants using new non-halogen flame-resisting insulating material have been developed. In this experiment, the non-halogen flame-resisting cables were subjected to the environmental test with varying test conditions. The test conditions included the order of exposure (heat treatment, γ-ray irradiation and steam exposure) and dose rate. After the environmental test, the mechanical and electrical properties of the samples were measured. In all test conditions, the samples did not crack in bending, and withstood the bending and withstand-voltage in-water test. The tensile strength and a.c. breakdown voltage did not change, and were stable. The elongation decreased greatly, but maintained the value of about 100 %, and the volumetric resistivity decreased by only one figure. It was confirmed that these cables were able to withstand various environmental tests. (Yoshitake, I.)

Determination of halogen content in glass for assessment of melter decontamination factors

International Nuclear Information System (INIS)

Goles, R.W.

1996-03-01

Melter decontamination factor (DF) values for the halogens (fluorine, chlorine, and iodine) are important to the Hanford Waste Vitrification Plant (HWVP) process because of the potential influence of DF on secondary-waste recycle strategies (fluorine and chlorine) as well as its impact on off-gas emissions (iodine). This study directly establishes the concentrations of halides-in HWVP simulated reference glasses rather than relying on indirect off-gas data. For fluorine and chlorine, pyrohydrolysis coupled with halide (ion chromatographic) detection has proven to be a useful analytical approach suitable for glass matrices, sensitive enough for the range of halogens encountered, and compatible with remote process support applications. Results obtained from pyrohydrolytic analysis of pilot-scale ceramic melter (PSCM) -22 and -23 glasses indicate that the processing behavior of fluorine and chlorine is quite variable even under similar processing conditions. Specifically, PSCM-23 glass exhibited a ∼90% halogen (F and Cl) retention efficiency, while only 20% was incorporated in PSCM-22 glass. These two sets of very dissimilar test results clearly do not form a sufficient basis for establishing design DF values for fluorine and chlorine. Because the present data do not provide any new halogen volatility information, but instead reconfirm the validity of previously obtained offgas derived values, melter DF values of 4, 2, and 1 for fluorine, chlorine, and iodine, respectively, are recommended for adoption; these values were conservatively established by a team of responsible engineers at Westinghouse Hanford Company (WHC) and Pacific Northwest Laboratory (PNL) on the basis of average behavior for many comparable melter tests. In the absence of further HWVP process data, these average melter DFs are the best values currently available

PCDD/F and dioxin-like PCB bioaccumulation by Manila clam from polluted areas of Venice lagoon (Italy).

Science.gov (United States)

Sfriso, Adriano; Facca, Chiara; Raccanelli, Stefano

2014-01-01

POP bioaccumulation pathways in the clam Tapes philippinarum were examined for two years from juveniles to adult size. Two polluted sites, one with sandy sediment, the other muddy were compared with a reference site characterized by low contamination levels. Juvenile clams coming from a hatchery were reared both on the sediment and in nets suspended at 30 cm from the bottom. POP changes in clam tissue were related to the concentrations recorded in sediments and in the particulate matter during the entire fattening period. Results provided interesting data on the relationships between environmental contamination and bioaccumulation. Contrary to studies on the decontamination times of the clams collected in polluted areas, this work investigates the preferential clam bioaccumulation pathways during growth under different environmental conditions. In general POP bioaccumulation resulted to be correlated to concentrations in SPM rather than in sediments and was higher in S-clams rather than in B-clams. Copyright © 2013 Elsevier Ltd. All rights reserved.

Composes inter-halogenes sous pression: etude des transformations structurales dans le monobromure d'iode sous forme dense

Science.gov (United States)

Bouchard, Alexandre

La famille des composes halogenes et inter-halogenes representent des solides moleculaires adoptant des phases denses communes avec des solides moleculaires diatomiques comme l'azote et l'hydrogene. Parmi les transformations structurales et electroniques induites sous haute pression et observees dans ces solides, on note, entre autres, la dissociation moleculaire et la metallisation. De plus, l'etude des phases denses de l'iode a permis recemment l'observation d'une structure cristalline possedant une modulation dite incommensurable, c'est-a-dire une modulation possedant une periodicite differente de celle de la structure cristalline, jetant ainsi une lumiere nouvelle sur le processus de dissociation moleculaire dans les solides halogenes. Dans ce memoire, on propose d'etudier les changements structuraux dans monobromure d'iode (IBr), un compose inter-halogene possedant des proprietes structurales semblables a celles de deux composes halogenes, soit l'iode (I 2) et le brome (Br2) sous leur forme solide. Des experiences de diffraction des rayons X de poudres en utilisant un rayonnement synchrotron ont ete realisees a temperature ambiante sur l'IBr en variant la pression jusqu'aux environs de 60 GPa. La nature chimique particuliere du compose IBr a necessite la mise au point de techniques de chargement d'echantillon destinees a preserver l'integrite chimique de la substance utilisee. On rapporte egalement l'observation d'une phase de l'IBr presentant une modulation incommensurable. Les phases observees dans l'IBr permettent d'etablir des paralleles avec les phases denses rapportees dans I2 et Br2 par le biais d'un modele phenomenologique decrivant la sequence structurale des solides halogenes sous forme condensee.

Development of halogen-free flame-retardant cable for nuclear power plant. 2

International Nuclear Information System (INIS)

Matsumoto, Tetsuo; Kimura, Hitoshi; Ishii, Nobuhisa

1997-01-01

Halogen-free flame-retardant cables were developed for PWR nuclear power stations. It was confirmed that the developed cables possess flame retardant property, corrosion resistance, low toxicity and low smoke generation, and withstand the normal operation in the environment in PWR containment vessels for 60 years and loss of coolant accident. In the advancement of LWR technology, it is important to improve the reliability of machinery and equipment, to extend the period of continuous operation, to optimize the operation cycle and to improve the maintenance of plants. By improving halogen-free flame-retardant material and applying it to the cables for nuclear power stations, it can contribute to the above purposes. The required characteristics of these cables are explained, and the targets of development are power cables, control cables, instrumentation cables and insulated wires which do not contain halogen. The basic material is polyolefin, in which flame retardant magnesium hydroxide and the agent for improving radiation resistance are mixed. The corrosive property and toxicity of gases, smoke generation and the prevention of spread of flame when the cables burn and the durability in environment were evaluated. (K.I.)

Bioaccumulation of heavy metals in fauna from wet detention ponds for stormwater runoff

DEFF Research Database (Denmark)

Stephansen, Diana; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild

2012-01-01

Stormwater detention ponds remove pollutants e.g. heavy metals and nutrients from stormwater runoff. These pollutants accumulate in the pond sediment and thereby become available for bioaccumulation in fauna living in the ponds. In this study the bioaccumulation was investigated by fauna samples...... from 5 wet detention ponds for analyses of heavy metal contents. Five rural shallow lakes were included in the study to survey the natural occurrence of heavy metals in water-dwelling fauna. Heavy metal concentrations in water-dwelling fauna were generally found higher in wet detention ponds compared...

Influence of body size on Cu bioaccumulation in zebra mussels Dreissena polymorpha exposed to different sources of particle-associated Cu

Energy Technology Data Exchange (ETDEWEB)

Zhong, Huan, E-mail: huanzhong1982@hotmail.com [Environmental and Resource Studies Program, Trent University, Peterborough, Ontario (Canada); Nanjing University, School of Environment, State Key Laboratory of Pollution Control and Resource Reuse, Nanjing, Jiangsu Province (China); Kraemer, Lisa; Evans, Douglas [Environmental and Resource Studies Program, Trent University, Peterborough, Ontario (Canada)

2013-10-15

Highlights: • Mussels exposed to algal/sediment-Cu have different size-related Cu accumulation. • Size-related Cu accumulation in mussels could be more dependant on algal-Cu uptake. • Importance of algal/sediment-Cu to Cu bioaccumulation varies with mussel body size. • Cu sources (algae and sediments) should be considered in “mussel watch” programs. • Cu stable isotope offers many advantages in Cu bioaccumulation studies. -- Abstract: Size of organisms is critical in controlling metal bioavailability and bioaccumulation, while mechanisms of size-related metal bioaccumulation are not fully understood. To investigate the influences of different sources of particle-associated Cu on body size-related Cu bioavailability and bioaccumulation, zebra mussels (Dreissena polymorpha) of different sizes were exposed to stable Cu isotope ({sup 65}Cu) spiked algae (Chlorella vulgaris) or sediments in the laboratory and the Cu tissue concentration-size relationships were compared with that in unexposed mussels. Copper tissue concentrations decreased with mussel size (tissue or shell dry weight) in both unexposed and algal-exposed mussels with similar decreasing patterns, but were independent of size in sediment-exposed mussels. Furthermore, the relative contribution of Cu uptake from algae (65–91%) to Cu bioaccumulation is always higher than that from sediments (9–35%), possibly due to the higher bioavailability of algal-Cu. Therefore, the size-related ingestion of algae could be more important in influencing the size-related variations in Cu bioaccumulation. However, the relative contribution of sediment-Cu to Cu bioaccumulation increased with body size and thus sediment ingestion may also affect the size-related Cu variations in larger mussels (tissue weight >7.5 mg). This study highlights the importance of considering exposure pathways in normalization of metal concentration variation when using bivalves as biomonitors.

Towards a proportionality assessment of risk reduction measures aimed at restricting the use of persistent and bioaccumulative substances.

NARCIS (Netherlands)

Oosterhuis, Frans; Brouwer, Roy; Janssen, Martien; Verhoeven, Julia; Luttikhuizen, Cees

2017-01-01

International chemicals legislation aims at adequately controlling persistent organic pollutants (POPs) and substances of very high concern (SVHCs), such as persistent, bioaccumulative, and toxic (PBT) and very persistent and very bioaccumulative (vPvB) substances, with a view to progressively

Bioaccumulation of Heavy Metals by Moringa Oleifera in Automobile ...

African Journals Online (AJOL)

Plants accumulate minerals essential for their growth from the environment alongside with heavy metals from contaminated areas.This study investigated bioaccumulation of heavy metals by Moringa oleifera in automobile workshops in three selected local government areas in Ibadan. This was done with a view to ...

Bioaccumulation and toxic effects of some heavy metals in ...

African Journals Online (AJOL)

The contamination of the aquatic systems with heavy metals from natural anthropogenic sources has become a global problem which poses threats to ecosystems and natural communities. Hence this study reviews the effects of heavy metals in freshwater fishes. Fishes bioaccumulate heavy metals (including cadmium, zinc ...

Quantum Chemical Examination of the Sequential Halogen Incorporation Scheme for the Modeling of Speciation of I/Br/Cl-Containing Trihalomethanes.

Science.gov (United States)

Zhang, Chenyang; Li, Maodong; Han, Xuze; Yan, Mingquan

2018-02-20

The recently developed three-step ternary halogenation model interprets the incorporation of chlorine, bromine, and iodine ions into natural organic matter (NOM) and formation of iodine-, bromine-, and chlorine-containing trihalomethanes (THMs) based on the competition of iodine, bromine, and chlorine species at each node of the halogenation sequence. This competition is accounted for using the dimensionless ratios (denoted as γ) of kinetic rates of reactions of the initial attack sites or halogenated intermediates with chlorine, bromine, and iodine ions. However, correlations between the model predictions made and mechanistic aspects of the incorporation of halogen species need to be ascertained in more detail. In this study, quantum chemistry calculations were first used to probe the formation mechanism of 10 species of Cl-/Br-/I- THMs. The HOMO energy (E HOMO ) of each mono-, bi-, or trihalomethanes were calculated by B3LYP method in Gaussian 09 software. Linear correlations were found to exist between the logarithms of experimentally determined kinetic preference coefficients γ reported in prior research and, on the other hand, differences of E HOMO values between brominated/iodinated and chlorinated halomethanes. One notable exception from this trend was that observed for the incorporation of iodine into mono- and di-iodinated intermediates. These observations confirm the three-step halogen incorporation sequence and the factor γ in the statistical model. The combined use of quantum chemistry calculations and the ternary sequential halogenation model provides a new insight into the microscopic nature of NOM-halogen interactions and the trends seen in the behavior of γ factors incorporated in the THM speciation models.

Performance analysis of photoresistor and phototransistor for automotive’s halogen and xenon bulbs light output

Science.gov (United States)

Rammohan, A.; Kumar, C. Ramesh

2017-11-01

Illumination of any light is measured using a different kind of calibrated equipment’s available in the market such as a goniometer, spectral radiometer, photometer, Lux meter and camera based systems which directly display the illumination of automotive headlights light distribution in the unit of lux, foot-candles, lumens/sq. ft. and Lambert etc., In this research, we dealt with evaluating the photo resistor or Light Dependent Resistor (LDR) and phototransistor whether it is useful for sensing light patterns of Automotive Halogen and Xenon bulbs. The experiments are conducted during night hours under complete dark space. We have used the headlamp setup available in TATA SUMO VICTA vehicle in the Indian market and conducted the experiments separately for Halogen and Xenon bulbs under low and high beam operations at various degrees and test points within ten meters of distance. Also, we have compared the light intensity of halogen and xenon bulbs to prove the highest light intensity between halogen and Xenon bulbs. After doing a rigorous test with these two sensors it is understood both are good to sensing beam pattern of automotive bulbs and even it is good if we use an array of sensors or a mixed combination of sensors for measuring illumination purposes under perfect calibrations.

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Science.gov (United States)

2010-07-01

... Halogen HAP Emissions or HAP Metals Emissions From Process Vents 3 Table 3 to Subpart FFFF of Part 63... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

Bioaccumulation of organic pollutants in Indo-Pacific humpback dolphin: A review on current knowledge and future prospects.

Science.gov (United States)

Sanganyado, Edmond; Rajput, Imran Rashid; Liu, Wenhua

2018-06-01

Indo-Pacific humpback dolphin (Sousa chinensis) are chronically exposed to organic pollutants since they inhabit shallow coastal waters that are often impacted by anthropogenic activities. The aim of this review was to evaluate existing knowledge on the occurrence of organic pollutants in Indo-Pacific humpback dolphins, identify knowledge gaps, and offer recommendations for future research directions. We discussed the trends in the bioaccumulation of organic pollutants in Indo-Pacific humpback dolphins focusing on sources, physicochemical properties, and usage patterns. Furthermore, we examined factors that influence bioaccumulation such as gender, age, dietary intake and tissue-specific distribution. Studies on bioaccumulation in Indo-Pacific humpback dolphin remain scarce, despite high concentrations above 13,000 ng/g lw we previously detected for PFOS, ∑PBDE and chlorinated paraffins. The maximum concentration of organochlorines detected was 157,000 ng/g wt. Furthermore, variations in bioaccumulation were shown to be caused by factors such as usage patterns and physicochemical properties of the pollutant. However, restrictions in sampling inhibit investigations on exposure pathway and toxicity of organic pollutants in Indo-Pacific humpback dolphin. We proposed the use of biopsy sampling, predictive bioaccumulation and toxicity modeling, and monitoring other emerging contaminants such as microplastics and pharmaceuticals for future health risk assessment on this critically endangered marine mammal species. Copyright © 2018 Elsevier Ltd. All rights reserved.

Antibiotics in typical marine aquaculture farms surrounding Hailing Island, South China: Occurrence, bioaccumulation and human dietary exposure

International Nuclear Information System (INIS)

Chen, Hui; Liu, Shan; Xu, Xiang-Rong; Liu, Shuang-Shuang; Zhou, Guang-Jie; Sun, Kai-Feng; Zhao, Jian-Liang; Ying, Guang-Guo

2015-01-01

Highlights: • Thirty-seven antibiotics were systematically investigated in typical marine aquaculture farms. • Enrofloxacin was widely detected in the feed samples (16.6–31.8 ng/g). • ETM-H 2 O in the adult shrimp samples may pose a potential risk to human safety. • TMP was bioaccumulative in fish muscles. • Antibiotics were weakly bioaccumulated in mollusks. - Abstract: The occurrence, bioaccumulation, and human dietary exposure via seafood consumption of 37 antibiotics in six typical marine aquaculture farms surrounding Hailing Island, South China were investigated in this study. Sulfamethoxazole, salinomycin and trimethoprim were widely detected in the water samples (0.4–36.9 ng/L), while oxytetracycline was the predominant antibiotic in the water samples of shrimp larvae pond. Enrofloxacin was widely detected in the feed samples (16.6–31.8 ng/g) and erythromycin–H 2 O was the most frequently detected antibiotic in the sediment samples (0.8–4.8 ng/g). Erythromycin–H 2 O was the dominant antibiotic in the adult Fenneropenaeus penicillatus with concentrations ranging from 2498 to 15,090 ng/g. In addition, trimethoprim was found to be bioaccumulative in young Lutjanus russelli with a median bioaccumulation factor of 6488 L/kg. Based on daily intake estimation, the erythromycin–H 2 O in adult F. penicillatus presented a potential risk to human safety

Protection of halogenated DNA from strand breakage and sister-chromatid exchange induced by the topoisomerase I inhibitor camptothecin

International Nuclear Information System (INIS)

Orta, Manuel Luis; Mateos, Santiago; Cantero, Gloria; Wolff, Lisa J.; Cortes, Felipe

2008-01-01

The fundamental nuclear enzyme DNA topoisomerase I (topo I), cleaves the double-stranded DNA molecule at preferred sequences within its recognition/binding sites. We have recently reported that when cells incorporate halogenated nucleosides analogues of thymidine into DNA, it interferes with normal chromosome segregation, as shown by an extraordinarily high yield of endoreduplication, and results in a protection against DNA breakage induced by the topo II poison m-AMSA [F. Cortes, N. Pastor, S. Mateos, I. Dominguez, The nature of DNA plays a role in chromosome segregation: endoreduplication in halogen-substituted chromosomes, DNA Repair 2 (2003) 719-726; G. Cantero, S. Mateos, N. Pastor; F. Cortes, Halogen substitution of DNA protects from poisoning of topoisomerase II that results in DNA double-strand breaks (DSBs), DNA Repair 5 (2006) 667-674]. In the present investigation, we have assessed whether the presence of halogenated nucleosides in DNA diminishes the frequency of interaction of topo I with DNA and thus the frequency with which the stabilisation of cleavage complexes by the topo I poison camptothecin (CPT) takes place, in such a way that it protects from chromosome breakage and sister-chromatid exchange. This protective effect is shown to parallel a loss in halogen-substituted cells of the otherwise CPT-increased catalytic activity bound to DNA

Bioaccumulation of heavy metals by Dyera costulata cultivated in ...

African Journals Online (AJOL)

High concentrations of heavy metals are harmful to plants, animals and humans and their potential accumulation in human tissues and bio-magnification through the food chain cause serious health hazards. An experiment was conducted in the glasshouse to evaluate the potential of Dyera costulata as a bioaccumulator to ...

Pharmacological evaluation of halogenated and non-halogenated arylpiperazin-1-yl-ethyl-benzimidazoles as D(2) and 5-HT(2A) receptor ligands.

Science.gov (United States)

Tomić, Mirko; Vasković, Djurdjica; Tovilović, Gordana; Andrić, Deana; Penjišević, Jelena; Kostić-Rajačić, Sladjana

2011-05-01

Five groups of previously synthesized and initially screened non-substituted and 4-halogenated arylpiperazin-1-yl-ethyl-benzimidazoles were estimated for their in-vitro binding affinities at the rat D(2) , 5-HT(2A) , and α(1) -adrenergic receptors. Among all these compounds, 2-methoxyphenyl and 2-chlorophenyl piperazines demonstrate the highest affinities for the tested receptors. The effects of 4-halogenation of benzimidazoles reveal that substitution with bromine may greatly increase the affinity of the compounds for the studied receptors, while the effect of substitution with chlorine is less remarkable. Most of the tested components show 5-HT(2A)/D(2) pK(i) binding ratios slightly above or less than 1, while only 4-chloro-6-(2-{4-[3-(trifluoromethyl)phenyl]piperazin-1-yl}ethyl)-1H-benzimidazole expresses an appropriate higher binding ratio (1.14), which was indicated for atypical neuroleptics. This compound exhibits a non-cataleptic action in rats and prevents d-amphetamine-induced hyperlocomotion in mice, which suggest its atypical antipsychotic potency. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Joint use of laboratory bioassays and field-collected invertebrates to evaluate toxicity and contaminant bioaccumulation

International Nuclear Information System (INIS)

Long, S.P.; Byron, E.R.; Ohlendorf, H.M.

1995-01-01

Soil toxicity tests using earthworms (Eisenia andrei) were conducted using soil samples collected as part of ecological risk assessments for several sites at two facilities in California. At some sites, earthworms or other terrestrial invertebrates were collected in the field for chemical analysis. Ecological concerns focused on exposures to soil invertebrates and their secondary consumers, such as birds and small mammals. The toxicity tests were used to assess potential exposures to a variety of site-specific contaminants including organochlorine pesticides, PCBs, PAHs, petroleum hydrocarbons, heavy metals, and other inorganic substances. Site soils were combined with clean control soils to produce toxicity test soil dilutions containing 100%, 75%, 50%, 25%, and 0% site soils. Earthworm mortality and other observations were made at day 0, 7, 14, 21 and 28. Toxicity test results were combined with soil chemical analytical results and physical characteristics to establish NOAELs and LOAELs. Bioaccumulation in the laboratory earthworms and field-collected invertebrates was evaluated by comparing whole-body contaminant to soil contaminant concentrations. Allometric equations and sublethal toxicity data were used to predict potential effects on birds and small mammals. Earthworm toxicity tests indicated a wide range of sensitivity to on-site contaminants and showed the importance of considering potential confounding influences due to soil parameters other than contaminant concentration

Determination of volatile organic hydrocarbons in water samples by solid-phase dynamic extraction

Energy Technology Data Exchange (ETDEWEB)

Jochmann, Maik A.; Schmidt, Torsten C. [Eberhard-Karls-Universitaet Tuebingen, Center for Applied Geoscience (ZAG), Tuebingen (Germany); Chair of Instrumental Analysis, University Duisburg-Essen, Duisburg (Germany); Yuan, Xue [Eberhard-Karls-Universitaet Tuebingen, Center for Applied Geoscience (ZAG), Tuebingen (Germany)

2007-03-15

In the present study a headspace solid-phase dynamic extraction method coupled to gas chromatography-mass spectrometry (HS-SPDE-GC/MS) for the trace determination of volatile halogenated hydrocarbons and benzene from groundwater samples was developed and evaluated. As target compounds, benzene as well as 11 chlorinated and brominated hydrocarbons (vinyl chloride, dichloromethane, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, carbon tetrachloride, chloroform, trichloroethylene, tetrachloroethylene, bromoform) of environmental and toxicological concern were included in this study. The analytes were extracted using a SPDE needle device, coated with a poly(dimethylsiloxane) with 10% embedded activated carbon phase (50-{mu}m film thickness and 56-mm film length) and were analyzed by GC/MS in full-scan mode. Parameters that affect the extraction yield such as extraction and desorption temperature, salting-out, extraction and desorption flow rate, extraction volume and desorption volume, the number of extraction cycles, and the pre-desorption time have been evaluated and optimized. The linearity of the HS-SPDE-GC/MS method was established over several orders of magnitude. Method detection limits (MDLs) for the compounds investigated ranged between 12 ng/L for cis-dichloroethylene and trans-dichloroethylene and 870 ng/L for vinyl chloride. The method was thoroughly validated, and the precision at two concentration levels (0.1 mg/L and a concentration 5 times above the MDL) was between 3.1 and 16% for the analytes investigated. SPDE provides high sensitivity, short sample preparation and extraction times and a high sample throughput because of full automation. Finally, the applicability to real environmental samples is shown exemplarily for various groundwater samples from a former waste-oil recycling facility. Groundwater from the site showed a complex contamination with chlorinated volatile organic compounds and aromatic hydrocarbons. (orig.)

Determination of volatile organic hydrocarbons in water samples by solid-phase dynamic extraction.

Science.gov (United States)

Jochmann, Maik A; Yuan, Xue; Schmidt, Torsten C

2007-03-01

In the present study a headspace solid-phase dynamic extraction method coupled to gas chromatography-mass spectrometry (HS-SPDE-GC/MS) for the trace determination of volatile halogenated hydrocarbons and benzene from groundwater samples was developed and evaluated. As target compounds, benzene as well as 11 chlorinated and brominated hydrocarbons (vinyl chloride, dichloromethane, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, carbon tetrachloride, chloroform, trichloroethylene, tetrachloroethylene, bromoform) of environmental and toxicological concern were included in this study. The analytes were extracted using a SPDE needle device, coated with a poly(dimethylsiloxane) with 10% embedded activated carbon phase (50-microm film thickness and 56-mm film length) and were analyzed by GC/MS in full-scan mode. Parameters that affect the extraction yield such as extraction and desorption temperature, salting-out, extraction and desorption flow rate, extraction volume and desorption volume, the number of extraction cycles, and the pre-desorption time have been evaluated and optimized. The linearity of the HS-SPDE-GC/MS method was established over several orders of magnitude. Method detection limits (MDLs) for the compounds investigated ranged between 12 ng/L for cis-dichloroethylene and trans-dichloroethylene and 870 ng/L for vinyl chloride. The method was thoroughly validated, and the precision at two concentration levels (0.1 mg/L and a concentration 5 times above the MDL) was between 3.1 and 16% for the analytes investigated. SPDE provides high sensitivity, short sample preparation and extraction times and a high sample throughput because of full automation. Finally, the applicability to real environmental samples is shown exemplarily for various groundwater samples from a former waste-oil recycling facility. Groundwater from the site showed a complex contamination with chlorinated volatile organic compounds and aromatic hydrocarbons.

Chromatographic resolution of closely related species in pharmaceutical chemistry: dehalogenation impurities and mixtures of halogen isomers.

Science.gov (United States)

Regalado, Erik L; Zhuang, Ping; Chen, Yadan; Makarov, Alexey A; Schafer, Wes A; McGachy, Neil; Welch, Christopher J

2014-01-07

In recent years, the use of halogen-containing molecules has proliferated in the pharmaceutical industry, where the incorporation of halogens, especially fluorine, has become vitally important for blocking metabolism and enhancing the biological activity of pharmaceuticals. The chromatographic separation of halogen-containing pharmaceuticals from associated isomers or dehalogenation impurities can sometimes be quite difficult. In an attempt to identify the best current tools available for addressing this important problem, a survey of the suitability of four chromatographic method development platforms (ultra high-performance liquid chromatography (UHPLC), core shell HPLC, achiral supercritical fluid chromatography (SFC) and chiral SFC) for separating closely related mixtures of halogen-containing pharmaceuticals and their dehalogenated isosteres is described. Of the 132 column and mobile phase combinations examined for each mixture, a small subset of conditions were found to afford the best overall performance, with a single UHPLC method (2.1 × 50 mm, 1.9 μm Hypersil Gold PFP, acetonitrile/methanol based aqueous eluents containing either phosphoric or perchloric acid with 150 mM sodium perchlorate) affording excellent separation for all samples. Similarly, a survey of several families of closely related halogen-containing small molecules representing the diversity of impurities that can sometimes be found in purchased starting materials for synthesis revealed chiral SFC (Chiralcel OJ-3 and Chiralpak IB, isopropanol or ethanol with 25 mM isobutylamine/carbon dioxide) as well as the UHPLC (2.1 × 50 mm, 1.8 μm ZORBAX RRHD Eclipse Plus C18 and the Gold PFP, acetonitrile/methanol based aqueous eluents containing phosphoric acid) as preferred methods.

Toxicity and bioaccumulation of sediment-associated contaminants using freshwater invertebrates: A review of methods and applications

Science.gov (United States)

Ingersoll, C.G.; Ankley, G.T.; Benoit, D.A.; Brunson, E.L.; Burton, G.A.; Dwyer, F.J.; Hoke, R.A.; Landrum, P.F.; Norberg-King, T. J.; Winger, P.V.

1995-01-01

This paper reviews recent developments in methods for evaluating the toxicity and bioaccumulation of contaminants associated with freshwater sediments and summarizes example case studies demonstrating the application of these methods. Over the past decade, research has emphasized development of more specific testing procedures for conducting 10-d toxicity tests with the amphipod Hyalella azteca and the midge Chironomus tentans. Toxicity endpoints measured in these tests are survival for H. azteca and survival and growth for C. tentans. Guidance has also been developed for conducting 28-d bioaccumulation tests with the oligochaete Lumbriculus variegatus, including determination of bioaccumulation kinetics for different compound classes. These methods have been applied to a variety of sediments to address issues ranging from site assessments to bioavailability of organic and inorganic contaminants using field-collected and laboratory-spiked samples. Survival and growth of controls routinely meet or exceed test acceptability criteria. Results of laboratory bioaccumulation studies with L. variegatus have been confirmed with comparisons to residues (PCBs, PAHs, DDT) present from synoptically collected field populations of oligochaetes. Additional method development is currently underway to develop chronic toxicity tests and to provide additional data-confirming responses observed in laboratory sediment tests with natural benthic populations.

Four groups of new aromatic halogenated disinfection byproducts: effect of bromide concentration on their formation and speciation in chlorinated drinking water.

Science.gov (United States)

Pan, Yang; Zhang, Xiangru

2013-02-05

Bromide is naturally present in source waters worldwide. Chlorination of drinking water can generate a variety of chlorinated and brominated disinfection byproducts (DBPs). Although substantial efforts have been made to examine the effect of bromide concentration on the formation and speciation of halogenated DBPs, almost all previous studies have focused on trihalomethanes and haloacetic acids. Given that about 50% of total organic halogen formed in chlorination remains unknown, it is still unclear how bromide concentration affects the formation and speciation of the new/unknown halogenated DBPs. In this study, chlorinated drinking water samples with different bromide concentrations were prepared, and a novel approach-precursor ion scan using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry-was adopted for the detection and identification of polar halogenated DBPs in these water samples. With this approach, 11 new putative aromatic halogenated DBPs were identified, and they were classified into four groups: dihalo-4-hydroxybenzaldehydes, dihalo-4-hydroxybenzoic acids, dihalo-salicylic acids, and trihalo-phenols. A mechanism for the formation of the four groups of new aromatic halogenated DBPs was proposed. It was found that increasing the bromide concentration shifted the entire polar halogenated DBPs as well as the four groups of new DBPs from being less brominated to being more brominated; these new aromatic halogenated DBPs might be important intermediate DBPs formed in drinking water chlorination. Moreover, the speciation of the four groups of new DBPs was modeled: the speciation patterns of the four groups of new DBPs well matched those determined from the model equations, and the reactivity differences between HOBr and HOCl in reactions forming the four groups of new DBPs were larger than those in reactions forming trihalomethanes and haloacetic acids.

A Protein Data Bank survey reveals shortening of intermolecular hydrogen bonds in ligand-protein complexes when a halogenated ligand is an H-bond donor.

Science.gov (United States)

Poznański, Jarosław; Poznańska, Anna; Shugar, David

2014-01-01

Halogen bonding in ligand-protein complexes is currently widely exploited, e.g. in drug design or supramolecular chemistry. But little attention has been directed to other effects that may result from replacement of a hydrogen by a strongly electronegative halogen. Analysis of almost 30000 hydrogen bonds between protein and ligand demonstrates that the length of a hydrogen bond depends on the type of donor-acceptor pair. Interestingly, lengths of hydrogen bonds between a protein and a halogenated ligand are visibly shorter than those estimated for the same family of proteins in complexes with non-halogenated ligands. Taking into account the effect of halogenation on hydrogen bonding is thus important when evaluating structural and/or energetic parameters of ligand-protein complexes. All these observations are consistent with the concept that halogenation increases the acidity of the proximal amino/imino/hydroxyl groups and thus makes them better, i.e. stronger, H-bond donors.

UV-visible and resonance Raman spectroscopy of halogen molecules in clathrate hydrates

Energy Technology Data Exchange (ETDEWEB)

Janda, K.C.; Kerenskaya, G.; Goldsheleger, I.U.; Apkarian, V.A.; Fleischer, E.B. [California Univ., Irvine, CA (United States). Dept. of Chemistry

2008-07-01

Resonance Raman spectroscopy was used to study halogen clathrate hydrate solids. In particular, this paper presented an ultraviolet-visible spectra for a polycrystalline sample of chlorine clathrate hydrate and two single crystal samples of bromine clathrate hydrate. UV-visible spectroscopy was used to study the interactions between the halogen guest molecule and the host water lattice. The spectrum for chlorine hydrate had a strong temperature dependence, while the spectra for bromine clathrate hydrate single crystals had a stable cubic type 2 structure as well as a tetragonal structure. A metastable cubic type 1 structure was also observed. Resonance Raman spectroscopy showed how the molecules fit into the host cages. 25 refs., 2 tabs., 7 figs.

Bioaccumulation of metals in constructed wetlands used to treat acid drainage

International Nuclear Information System (INIS)

Edwards, G.S.; Mays, P.A.

1994-01-01

Constructed wetlands are being used extensively as a potential mitigation for acid drainage. However, removal of metals to meet compliance requirements has varied among wetlands, ranging from partial to total success. In addition, wetlands are sinks for contaminants found in acid drainage, and bioaccumulation of these contaminants to levels that would adversely affect the food web is of growing concern. The primary objective of this project was to determine whether bioaccumulation of metals occurs in wetlands constructed for treatment of acid drainage. Water, sediment, plant and benthos samples were collected from two wetlands constructed by the Tennessee Valley Authority and a natural wetland in the spring and fall of 1992, and metal concentrations were determined. One of the constructed wetlands, Impoundment 1, has generally been in compliance for NPDES; the other, Widow's Creek, has never been in compliance. Preliminary results indicate similarities in sediment and plant metal concentrations between Impoundment 1 and the natural wetland and greater metal concentrations in the sediment and plants at Widow's Creek. Data also indicate that Mn, Zn, Cu, Ni, and Cr are being accumulated in the plants at each wetland. However, accumulation of metals by these plants probably accounts for only a small percentage of the removal of the annual metal load supplied to each wetland. Bioaccumulation of metals in the benthic organisms at each wetland is currently being investigated

Habitat type-based bioaccumulation and risk assessment of metal and As contamination in earthworms, beetles and woodlice

International Nuclear Information System (INIS)

Vermeulen, Frouke; Van den Brink, Nico W.; D'Have, Helga; Mubiana, Valentine K.; Blust, Ronny; Bervoets, Lieven; De Coen, Wim

2009-01-01

The present study investigated the contribution of environmental factors to the accumulation of As, Cd, Cu, Pb and Zn in earthworms, beetles and woodlice, and framed within an exposure assessment of the European hedgehog. Soil and invertebrate samples were collected in three distinct habitat types. Results showed habitat-specific differences in soil and invertebrate metal concentrations and bioaccumulation factors when normalized to soil metal concentration. Further multiple regression analysis showed residual variability (habitat differences) in bioaccumulation that could not be fully explained by differences in soil metal contamination, pH or organic carbon (OC). Therefore, the study demonstrated that in bioaccumulation studies involving terrestrial invertebrates or in risk assessment of metals, it is not sufficient to differentiate habitat types on general soil characteristics such as pH and/or OC alone. Furthermore, simple generic soil risk assessments for Cd and Cu showed that risk characterization was more accurate when performed in a habitat-specific way. - Our study provided essential insights into habitat-specific accumulation patterns with respect to factors influencing metal bioaccumulation, BAFs, and site-specific risk assessment.

Habitat type-based bioaccumulation and risk assessment of metal and As contamination in earthworms, beetles and woodlice

Energy Technology Data Exchange (ETDEWEB)

Vermeulen, Frouke, E-mail: frouke.vermeulen@ua.ac.b [Ecophysiology, Biochemistry and Toxicology Group (U7), University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Van den Brink, Nico W., E-mail: nico.vandenbrink@wur.n [Alterra, Wageningen UR, Box 47, NL6700AA Wageningen (Netherlands); D' Have, Helga [Ecophysiology, Biochemistry and Toxicology Group (U7), University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Mubiana, Valentine K., E-mail: kayawe.mubiana@ua.ac.b [Ecophysiology, Biochemistry and Toxicology Group (U7), University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Blust, Ronny, E-mail: ronny.blust@ua.ac.b [Ecophysiology, Biochemistry and Toxicology Group (U7), University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); Bervoets, Lieven, E-mail: lieven.bervoets@ua.ac.b [Ecophysiology, Biochemistry and Toxicology Group (U7), University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp (Belgium); De Coen, Wim, E-mail: wim.decoen@ua.ac.b [Ecophysiology, Biochemistry and Toxicology Group (U7), University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp (Belgium)

2009-11-15

The present study investigated the contribution of environmental factors to the accumulation of As, Cd, Cu, Pb and Zn in earthworms, beetles and woodlice, and framed within an exposure assessment of the European hedgehog. Soil and invertebrate samples were collected in three distinct habitat types. Results showed habitat-specific differences in soil and invertebrate metal concentrations and bioaccumulation factors when normalized to soil metal concentration. Further multiple regression analysis showed residual variability (habitat differences) in bioaccumulation that could not be fully explained by differences in soil metal contamination, pH or organic carbon (OC). Therefore, the study demonstrated that in bioaccumulation studies involving terrestrial invertebrates or in risk assessment of metals, it is not sufficient to differentiate habitat types on general soil characteristics such as pH and/or OC alone. Furthermore, simple generic soil risk assessments for Cd and Cu showed that risk characterization was more accurate when performed in a habitat-specific way. - Our study provided essential insights into habitat-specific accumulation patterns with respect to factors influencing metal bioaccumulation, BAFs, and site-specific risk assessment.

Sterilization affects soil organic matter chemistry and bioaccumulation of spiked p,p'-DDE and anthracene by earthworms

Energy Technology Data Exchange (ETDEWEB)

Kelsey, Jason W., E-mail: kelsey@muhlenberg.ed [Program in Environmental Science and Department of Chemistry, Muhlenberg College, 2400 Chew Street, Allentown, PA 18104 (United States); Slizovskiy, Ilya B.; Peters, Richard D.; Melnick, Adam M. [Program in Environmental Science and Department of Chemistry, Muhlenberg College, 2400 Chew Street, Allentown, PA 18104 (United States)

2010-06-15

Laboratory experiments were conducted to assess the effects of soil sterilization on the bioavailability of spiked p,p'-DDE and anthracene to the earthworms Eisenia fetida and Lumbricus terrestris. Physical and chemical changes to soil organic matter (SOM) induced by sterilization were also studied. Uptake of both compounds added after soil was autoclaved or gamma irradiated increased for E. fetida. Sterilization had no effect on bioaccumulation of p,p'-DDE by L. terrestris, and anthracene uptake increased only in gamma-irradiated soils. Analyses by FT-IR and DSC indicate sterilization alters SOM chemistry and may reduce pollutant sorption. Chemical changes to SOM were tentatively linked to changes in bioaccumulation, although the effects were compound and species specific. Artifacts produced by sterilization could lead to inaccurate risk assessments of contaminated sites if assumptions derived from studies carried out in sterilized soil are used. Ultimately, knowledge of SOM chemistry could aid predictions of bioaccumulation of organic pollutants. - Soil sterilization affects soil organic matter chemistry and pollutant bioaccumulation.

Methylmercury bioaccumulation in invertebrates of boreal streams in Norway: Effects of aqueous methylmercury and diet retention

International Nuclear Information System (INIS)

Wit, Heleen A. de; Kainz, Martin J.; Lindholm, Markus

2012-01-01

Transfer of aqueous methylmercury (MeHg) to primary consumers in aquatic foodwebs is poorly understood despite its importance for bioaccumulation of MeHg. We studied bioaccumulation of MeHg in simple aquatic food chains of two humic boreal streams in relation to streamwater chemistry, food web characteristics and dietary fatty acid (FA) biomarkers. Transfer of aqueous MeHg into primary consumers was similar in both streams, resulting in higher MeHg in consumers in the MeHg-rich stream. Trophic enrichment of MeHg and dietary retention of FA biomarkers was the same in both streams, suggesting that exposure to aqueous MeHg at the base of the food chain determined levels of MeHg in biota. In addition, contents of dietary biomarkers suggested that ingestion of algae reduced MeHg bioaccumulation, while ingestion of bacteria stimulated MeHg uptake. Dietary uptake of bacteria could thus be an important pathway for MeHg-transfer at the bottom of food chains in humic streams. - Highlights: ► We examined MeHg bioaccumulation in simple food chains in two boreal streams. ► Higher MeHg in invertebrates was associated with higher aqueous MeHg. ► Dietary biomarkers showed that consumers in both streams accessed similar food sources. ► We concluded at exposure to aqueous MeHg determined bioaccumulation of MeHg. ► Seasonal variation in MeHg in biota could be related to diet using dietary biomarkers. - Exposure to aqueous methylmercury at the base of the food chain in boreal streams determines mercury in aquatic biota at higher trophic levels.

Attosecond Time Delay in Photoionization of Noble-Gas and Halogen Atoms

Directory of Open Access Journals (Sweden)

Liang-Wen Pi

2018-02-01

Full Text Available Ultrafast processes are now accessible on the attosecond time scale due to the availability of ultrashort XUV laser pulses. Noble-gas and halogen atoms remain important targets due to their giant dipole resonance and Cooper minimum. Here, we calculate photoionization cross section, asymmetry parameter and Wigner time delay using the time-dependent local-density approximation (TDLDA, which includes the electron correlation effects. Our results are consistent with experimental data and other theoretical calculations. The asymmetry parameter provides an extra layer of access to the phase information of the photoionization processes. We find that halogen atoms bear a strong resemblance on cross section, asymmetry parameter and time delay to their noble-gas neighbors. Our predicted time delay should provide a guidance for future experiments on those atoms and related molecules.

SYNTHESIS AND STUDY OF HALOGENATED BENZYLAMIDES OF SOME ISOCYCLIC AND HETEROCYCLIC ACIDS AS POTENTIAL ANTICONVULSANTS.

Science.gov (United States)

Strupińska, Marzanna; Rostafińska-Suchar, Grażyna; Pirianowicz-Chaber, Elżbieta; Grabczuk, Mateusz; Józwenko, Magdalena; Kowalczyk, Hubert; Szuba, Joanna; Wójcicka, Monika; Chen, Tracy; Mazurek, Aleksander P

2015-01-01

A series of potential anticonvulsants have been synthesized. There are eight fluorobenzylamides and three chlorobenzylamides of isocyclic or heterocyclic acids. Two not halogenated benzylamides were also synthesized to compare the effect of halogenation. The aim of the research performed was to evaluate whether halogenation of the mother structure is able to improve its anticonvulsant activity. The compounds were tested in Anticonvulsant Screening Project (ASP) of Antiepileptic Drug Development Program (ADDP) of NIH. Compound 1 showed MES ED50 = 80.32 mg/kg, PI = 3.16. Compound 7 showed CKM ED50 = 56.72 mg/kg. Compound 8 showed MES ED50 = 34.23 mg/kg and scPTZ ED50 > 300 mg/kg, PI = 8.53.Compound 13 showed 6Hz ED50 = 78.96, PI = 3.37. The results indicate that fluorination does not improve activity, whereas chlorination in our experiment even reduces it.

Bioaccumulation and retention kinetics of cadmium in the freshwater decapod Macrobrachium australiense

Energy Technology Data Exchange (ETDEWEB)

Cresswell, Tom, E-mail: tom.cresswell@ansto.gov.au [Centre for Environmental Contaminants Research, CSIRO Land and Water, Locked Bag 2007, Kirrawee, NSW 2232 (Australia); School of Applied Sciences, RMIT University, Plenty Road, Bundoora, VIC 3083 (Australia); Simpson, Stuart L. [School of Applied Sciences, RMIT University, Plenty Road, Bundoora, VIC 3083 (Australia); Smith, Ross E.W. [Hydrobiology, Lang Parade, Auchenflower, QLD 4066 (Australia); Nugegoda, Dayanthi [School of Applied Sciences, RMIT University, Plenty Road, Bundoora, VIC 3083 (Australia); Mazumder, Debashish [Institute for Environmental Research, ANSTO, Locked Bag 2001, Kirrawee, NSW 2232 (Australia); Twining, John [Austral Radioecology, Oyster Bay, NSW, 2225 (Australia)

2014-03-01

Highlights: • Sources and mechanisms of Cd bioaccumulation were examined using radiotracers. • Macrobrachium australiense readily accumulated cadmium from the dissolved phase. • Assimilation efficiencies were comparable for sediment and algae. • A biokinetic model predicted ingestion accounted for majority of bioaccumulated Cd. - Abstract: The potential sources and mechanisms of cadmium bioaccumulation by the native freshwater decapods Macrobrachium species in the waters of the highly turbid Strickland River in Papua New Guinea were examined using {sup 109}Cd-labelled water and food sources and the Australian species Macrobrachium australiense as a surrogate. Synthetic river water was spiked with environmentally relevant concentrations of cadmium and animals were exposed for 7 days with daily renewal of test solutions. Dietary assimilation of cadmium was assessed through pulse-chase experiments where prawns were fed separately {sup 109}Cd-labelled fine sediment, filamentous algae and carrion (represented by cephalothorax tissue of water-exposed prawns). M. australiense readily accumulated cadmium from the dissolved phase and the uptake rate increased linearly with increasing exposure concentration. A cadmium uptake rate constant of 0.10 ± 0.05 L/g/d was determined in synthetic river water. During depuration following exposure to dissolved cadmium, efflux rates were low (0.9 ± 5%/d) and were not dependent on exposure concentration. Assimilation efficiencies of dietary sources were comparable for sediment and algae (48–51%), but lower for carrion (28 ± 5%) and efflux rates were low (0.2–2.6%/d) demonstrating that cadmium was well retained by M. australiense. A biokinetic model of cadmium accumulation by M. australiense predicted that for exposures to environmentally relevant cadmium concentrations in the Strickland River, uptake from ingestion of fine sediment and carrion would be the predominant sources of cadmium to the organism. The model predicted

Computational insights into the photocyclization of diclofenac in solution: effects of halogen and hydrogen bonding.

Science.gov (United States)

Bani-Yaseen, Abdulilah Dawoud

2016-08-21

The effects of noncovalent interactions, namely halogen and hydrogen bonding, on the photochemical conversion of the photosensitizing drug diclofenac (DCF) in solution were investigated computationally. Both explicit and implicit solvent effects were qualitatively and quantitatively assessed employing the DFT/6-31+G(d) and SQM(PM7) levels of theory. Full geometry optimizations were performed in solution for the reactant DCF, hypothesized radical-based intermediates, and the main product at both levels of theories. Notably, in good agreement with previous experimental results concerning the intermolecular halogen bonding of DCF, the SQM(PM7) method revealed different values for d(ClO, Å) and ∠(C-ClO, °) for the two chlorine-substituents of DCF, with values of 2.63 Å/162° and 3.13 Å/142° for the trans and cis orientations, respectively. Employing the DFT/6-31+G(d) method with implicit solvent effects was not conclusive; however, explicit solvent effects confirmed the key contribution of hydrogen and halogen bonding in stabilizing/destabilizing the reactant and hypothesized intermediates. Interestingly, the obtained results revealed that a protic solvent such as water can increase the rate of photocyclization of DCF not only through hydrogen bonding effects, but also through halogen bonding. Furthermore, the atomic charges of atoms majorly involved in the photocyclization of DCF were calculated using different methods, namely Mulliken, Hirshfeld, and natural bond orbital (NBO). The obtained results revealed that in all cases there is a notable nonequivalency in the noncovalent intermolecular interactions of the two chlorine substituents of DCF and the radical intermediates with the solvent, which in turn may account for the discrepancy of their reactivity in different media. These computational results provide insight into the importance of halogen and hydrogen bonding throughout the progression of the photochemical conversion of DCF in solution.

Influence of body size on Cu bioaccumulation in zebra mussels Dreissena polymorpha exposed to different sources of particle-associated Cu.

Science.gov (United States)

Zhong, Huan; Kraemer, Lisa; Evans, Douglas

2013-10-15

Size of organisms is critical in controlling metal bioavailability and bioaccumulation, while mechanisms of size-related metal bioaccumulation are not fully understood. To investigate the influences of different sources of particle-associated Cu on body size-related Cu bioavailability and bioaccumulation, zebra mussels (Dreissena polymorpha) of different sizes were exposed to stable Cu isotope ((65)Cu) spiked algae (Chlorella vulgaris) or sediments in the laboratory and the Cu tissue concentration-size relationships were compared with that in unexposed mussels. Copper tissue concentrations decreased with mussel size (tissue or shell dry weight) in both unexposed and algal-exposed mussels with similar decreasing patterns, but were independent of size in sediment-exposed mussels. Furthermore, the relative contribution of Cu uptake from algae (65-91%) to Cu bioaccumulation is always higher than that from sediments (9-35%), possibly due to the higher bioavailability of algal-Cu. Therefore, the size-related ingestion of algae could be more important in influencing the size-related variations in Cu bioaccumulation. However, the relative contribution of sediment-Cu to Cu bioaccumulation increased with body size and thus sediment ingestion may also affect the size-related Cu variations in larger mussels (tissue weight >7.5mg). This study highlights the importance of considering exposure pathways in normalization of metal concentration variation when using bivalves as biomonitors. Copyright © 2013 Elsevier B.V. All rights reserved.

Toxicity, Bioaccumulation and Biotransformation of Silver Nanoparticles in Marine Organisms

Science.gov (United States)

The toxicity, bioaccumulation and biotransformation of citrate and polyvinylpyrrolidone (PVP) capped silver nanoparticles (NPs) (AgNP-citrate and AgNP-PVP) and titanium dioxide (TiO2) NPs in marine organisms via marine sediment exposure were investigated. Results from 7-d sedimen...

Identification of cinnabarinic acid as a novel endogenous aryl hydrocarbon receptor ligand that drives IL-22 production.

Science.gov (United States)

Lowe, Margaret M; Mold, Jeff E; Kanwar, Bittoo; Huang, Yong; Louie, Alexander; Pollastri, Michael P; Wang, Cuihua; Patel, Gautam; Franks, Diana G; Schlezinger, Jennifer; Sherr, David H; Silverstone, Allen E; Hahn, Mark E; McCune, Joseph M

2014-01-01

The aryl hydrocarbon receptor (AHR) binds to environmental toxicants including synthetic halogenated aromatic hydrocarbons and is involved in a diverse array of biological processes. Recently, the AHR was shown to control host immunity by affecting the balance between inflammatory T cells that produce IL-17 (Th17) and IL-22 versus regulatory T cells (Treg) involved in tolerance. While environmental AHR ligands can mediate this effect, endogenous ligands are likely to be more relevant in host immune responses. We investigated downstream metabolites of tryptophan as potential AHR ligands because (1) tryptophan metabolites have been implicated in regulating the balance between Th17 and Treg cells and (2) many of the AHR ligands identified thus far are derivatives of tryptophan. We characterized the ability of tryptophan metabolites to bind and activate the AHR and to increase IL-22 production in human T cells. We report that the tryptophan metabolite, cinnabarinic acid (CA), is an AHR ligand that stimulates the differentiation of human and mouse T cells producing IL-22. We compare the IL-22-stimulating activity of CA to that of other tryptophan metabolites and define stimulation conditions that lead to CA production from immune cells. Our findings link tryptophan metabolism to AHR activation and define a novel endogenous AHR agonist with potentially broad biological functions.

Is there theoretical evidence for mutual influence between halogen

Indian Academy of Sciences (India)

Based on many-body analysis, two and three-body terms of interaction energies have a positive contribution to the total interaction energy. It was found that the amount of charge transfer in the triads is higher than that in the corresponding dyads. AIM analyses showed that the halogen and pnicogen-hydride bonds in the ...

Study of heavy metals bioaccumulation in the process of ...

African Journals Online (AJOL)

Jane

2011-07-18

Jul 18, 2011 ... The bioaccumulation of heavy metals (Cd, Zn, Ni, Pb and Cr) and the relationship between them was investigated on ... this elements in 14 days) exposure, the metal accumulation was measured using atomic absorption spectroscopy. ... sed to the point that it endangers human life in some areas, and the ...

Structural changes in response to bioaccumulation of iron and mercury in Chromolaena odorata (L.) King & Robins.

Science.gov (United States)

Swapna, K S; Salim, Nabeesa; Chandra, Ratheesh; Puthur, Jos T

2015-09-01

A comparative study was designed to elucidate the effect of iron and mercury on the morphological and anatomical changes as well as bioaccumulation potential in Chromolaena odorata. Plants were grown in half-strength Hoagland nutrient medium artificially contaminated with known quantities of HgCl2 (15 μM) and FeCl3 (1000 μM). Bioaccumulation of Hg and Fe was maximum in the root, and comparatively reduced bioaccumulation was recorded in the stem and leaves. Microscopic studies on morphology and anatomy revealed development of trichomes and lenticels on the stem and modified trichomes on leaves. Localized deposits of stained masses in various internal parts of the root, stem and leaf also were observed. Differential adaptation/strategy of C. odorata to attain tolerance towards Hg and Fe and phytoremediation potential of the plant is discussed.

A Protein Data Bank survey reveals shortening of intermolecular hydrogen bonds in ligand-protein complexes when a halogenated ligand is an H-bond donor.

Directory of Open Access Journals (Sweden)

Jarosław Poznański

Full Text Available Halogen bonding in ligand-protein complexes is currently widely exploited, e.g. in drug design or supramolecular chemistry. But little attention has been directed to other effects that may result from replacement of a hydrogen by a strongly electronegative halogen. Analysis of almost 30000 hydrogen bonds between protein and ligand demonstrates that the length of a hydrogen bond depends on the type of donor-acceptor pair. Interestingly, lengths of hydrogen bonds between a protein and a halogenated ligand are visibly shorter than those estimated for the same family of proteins in complexes with non-halogenated ligands. Taking into account the effect of halogenation on hydrogen bonding is thus important when evaluating structural and/or energetic parameters of ligand-protein complexes. All these observations are consistent with the concept that halogenation increases the acidity of the proximal amino/imino/hydroxyl groups and thus makes them better, i.e. stronger, H-bond donors.

A comparison of PCB bioaccumulation factors between an arctic and a temperate marine food web.

Science.gov (United States)

Sobek, Anna; McLachlan, Michael S; Borgå, Katrine; Asplund, Lillemor; Lundstedt-Enkel, Katrin; Polder, Anuschka; Gustafsson, Orjan

2010-06-01

To test how environmental conditions in the Arctic and the resulting ecological adaptations affect accumulation of persistent organic pollutants (POPs) in the marine food web, bioaccumulation of four polychlorinated biphenyls (PCBs) in an arctic (Barents Sea 77 degrees N-82 degrees N) and a temperate marine (Baltic Sea 54 degrees N-62 degrees N) food web were compared. Three different trophic levels were studied (zooplankton, fish, and seal), representing the span from first-level consumer to top predator. Previously published high-quality data on PCB water concentrations in the two areas were used for calculation of bioaccumulation factors (BAF). BAF was calculated as the ratio of the PCB concentration in the organism ([PCB](org); pg/kg lipid) to the dissolved water concentration (C(w); pg/L). The BAF(Arctic):BAF(Temperate) ratios were above 1 for all four PCB congeners in zooplankton (6.4-13.8) and planktivorous fish (2.9-5.0)), whereas the ratios were below 1 in seal. The mean ratio between arctic and temperate BAFs for all trophic levels and congeners (BAF(Arcti):BAF(Temperate)) was 4.8. When the data were corrected for the seawater temperature difference between the two ecosystems, the ratio was 2.0. We conclude that bioaccumulation differences caused by ecological or physiological adaptations of organisms between the two ecosystems were well within a water concentration variability of 50%. Further, our data support the hypothesis that lower seawater temperature lead to a thermodynamically favoured passive partitioning to organic matrices and thus elevated ambient BAFs in the Arctic compared to the Baltic Sea. This would imply that bioaccumulation in the Arctic may be described in the same way as bioaccumulation in temperate regions, e.g. by the use of mechanistic models parameterised for the Arctic. Copyright (c) 2010. Published by Elsevier B.V.

A comparison of PCB bioaccumulation factors between an arctic and a temperate marine food web

International Nuclear Information System (INIS)

Sobek, Anna; McLachlan, Michael S.; Borga, Katrine; Asplund, Lillemor; Lundstedt-Enkel, Katrin; Polder, Anuschka; Gustafsson, Orjan

2010-01-01

To test how environmental conditions in the Arctic and the resulting ecological adaptations affect accumulation of persistent organic pollutants (POPs) in the marine food web, bioaccumulation of four polychlorinated biphenyls (PCBs) in an arctic (Barents Sea 77 o N-82 o N) and a temperate marine (Baltic Sea 54 o N-62 o N) food web were compared. Three different trophic levels were studied (zooplankton, fish, and seal), representing the span from first-level consumer to top predator. Previously published high-quality data on PCB water concentrations in the two areas were used for calculation of bioaccumulation factors (BAF). BAF was calculated as the ratio of the PCB concentration in the organism ([PCB] org ; pg/kg lipid) to the dissolved water concentration (C w ; pg/L). The BAF Arctic :BAF Temperate ratios were above 1 for all four PCB congeners in zooplankton (6.4-13.8) and planktivorous fish (2.9-5.0)), whereas the ratios were below 1 in seal. The mean ratio between arctic and temperate BAFs for all trophic levels and congeners (BAF Arcti :BAF Temperate ) was 4.8. When the data were corrected for the seawater temperature difference between the two ecosystems, the ratio was 2.0. We conclude that bioaccumulation differences caused by ecological or physiological adaptations of organisms between the two ecosystems were well within a water concentration variability of 50%. Further, our data support the hypothesis that lower seawater temperature lead to a thermodynamically favoured passive partitioning to organic matrices and thus elevated ambient BAFs in the Arctic compared to the Baltic Sea. This would imply that bioaccumulation in the Arctic may be described in the same way as bioaccumulation in temperate regions, e.g. by the use of mechanistic models parameterised for the Arctic.

Hydrocarbon-degrading sulfate-reducing bacteria in marine hydrocarbon seep sediments

OpenAIRE

Kleindienst, Sara

2012-01-01

Microorganisms are key players in our biosphere because of their ability to degrade various organic compounds including a wide range of hydrocarbons. At marine hydrocarbon seeps, more than 90% of sulfate reduction (SR) is potentially coupled to non-methane hydrocarbon oxidation. Several hydrocarbon-degrading sulfate-reducing bacteria (SRB) were enriched or isolated from marine sediments. However, in situ active SRB remained largely unknown. In the present thesis, the global distribution and a...

Polymorphism of the aryl-hydrocarbon receptor gene in intron 10 of human cancers

Directory of Open Access Journals (Sweden)

M. Rocas

2011-11-01

Full Text Available Polychlorinated dibenzo-p-dioxins (PCDDs and related halogenated aromatic hydrocarbons (e.g., PCDFs, often called "dioxins", are ubiquitously present environmental contaminants. Some of them, notably 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD, are among the most toxic synthetic compounds known. The biological effects of dioxins are mediated via the aryl hydrocarbon receptor (AhR. Mutations in the AhR transactivation domain are linked to sensitivity to the acute lethality of TCDD. We present here a study of AhR gene polymorphism in normal and cancer human tissues affecting pre-mRNA splicing in the AhR gene-coding transactivation domain region (exon 10, intron 10, exon 11 region, previously shown to be associated with AhR dysfunction. We tested 126 pairs of normal and cancer tissue samples from liver, lung, stomach, kidney, mucous, breast, and pancreas of 49 males and 77 females (45-70 years of age. We used in vitro splicing assay, RT-PCR and sequencing methods. Our results showed that in an in vitro system it is possible to reconstitute cellular pre-mRNA splicing events. Tested cancer tissues did not contain mutations in the AhR transactivation domain region when the DNA sequences were compared with those from normal tissues. There were also no differences in AhR mRNA splice variants between normal and malignant breast tissues and no polymorphisms in the studied regions or cDNA.

Evaluation of PCB bioaccumulation by Lumbriculus variegatus in field-collected sediments

Science.gov (United States)

Sediment bioaccumulation tests with Lumbriculus variegatus were performed on polychlorinated biphenyl (PCBs) contaminated sediment samples from the Hudson, Grasse, and Fox Rivers Superfund sites with concurrent measurement of PCB concentrations in sediment interstitial water. Th...

Arsenic bioaccumulation in a marine juvenile fish Terapon jarbua

International Nuclear Information System (INIS)

Zhang Wei; Huang Liangmin; Wang Wenxiong

2011-01-01

Highlights: Radiotracer technique was used to quantify the biokinetics of As(V) in a marine fish. As(V) had a low bioavailability to Terapon jarbua. Dietary assimilation of As was only 3.1–7.4% for fish fed with different preys. Dietary uptake could be the primary route for As bioaccumulation in fish. - Abstract: Arsenic (As) is a ubiquitous toxic metalloid that is causing widespread public concern. Recent measurements have indicated that some marine fish in China might be seriously contaminated with As. Yet the biokinetics and bioaccumulation pathway of As in fish remain little understood. In this study, we employed a radiotracer technique to quantify the dissolved uptake, dietary assimilation and subsequent efflux of As(V) in a marine predatory fish, Terapon jarbua. The dissolved uptake of As showed a linear pattern over a range of dissolved concentrations from 0.5 to 50 μg L −1 , with a corresponding uptake rate constant of 0.0015 L g −1 d −1 . The assimilation efficiencies (AEs) of dietary As were only 3.1–7.4% for fish fed with copepods, clams, prey fish, or artificial diets, and were much lower than the As that entered the trophically available metal fraction in the prey. The dietary AEs were independent of the As(V) concentrations in the artificial diets. The efflux rate constant of As in fish following the dietary exposure was 0.03 d −1 . Modeling calculations showed that dietary uptake could be the primary route for As bioaccumulation in fish, and the corresponding contributions of waterborne and dietary uptakes were related to the bioconcentration factor (BCF) of the prey and the ingestion rate of fish. This study demonstrates that As(V) has a low bioavailability to T. jarbua.

Laboratory Investigations of Stratospheric Halogen Chemistry

Science.gov (United States)

Wine, Paul H.; Nicovich, J. Michael; Stickel, Robert E.; Hynes, Anthony J.

1997-01-01

A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

Equilibrium sampling to determine the thermodynamic potential for bioaccumulation of persistent organic pollutants from sediment.

Science.gov (United States)

Jahnke, Annika; MacLeod, Matthew; Wickström, Håkan; Mayer, Philipp

2014-10-07

Equilibrium partitioning (EqP) theory is currently the most widely used approach for linking sediment pollution by persistent hydrophobic organic chemicals to bioaccumulation. Most applications of the EqP approach assume (I) a generic relationship between organic carbon-normalized chemical concentrations in sediments and lipid-normalized concentrations in biota and (II) that bioaccumulation does not induce levels exceeding those expected from equilibrium partitioning. Here, we demonstrate that assumption I can be obviated by equilibrating a silicone sampler with chemicals in sediment, measuring chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic pollutants (polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB)) to lipid-normalized concentrations for a range of biota from a Swedish background lake. PCBs in duck mussels, roach, eel, pikeperch, perch and pike were mostly below the equilibrium partitioning level relative to the sediment, i.e., lipid-normalized concentrations were ≤CLip⇌Sed, whereas HCB was near equilibrium between biota and sediment. Equilibrium sampling allows straightforward, sensitive and precise measurement of CLip⇌Sed. We propose CLip⇌Sed as a metric of the thermodynamic potential for bioaccumulation of persistent organic chemicals from sediment useful to prioritize management actions to remediate contaminated sites.

The Halogenated Metabolism of Brown Algae (Phaeophyta, Its Biological Importance and Its Environmental Significance

Directory of Open Access Journals (Sweden)

Stéphane La Barre

2010-03-01

Full Text Available Brown algae represent a major component of littoral and sublittoral zones in temperate and subtropical ecosystems. An essential adaptive feature of this independent eukaryotic lineage is the ability to couple oxidative reactions resulting from exposure to sunlight and air with the halogenations of various substrates, thereby addressing various biotic and abiotic stresses i.e., defense against predators, tissue repair, holdfast adhesion, and protection against reactive species generated by oxidative processes. Whereas marine organisms mainly make use of bromine to increase the biological activity of secondary metabolites, some orders of brown algae such as Laminariales have also developed a striking capability to accumulate and to use iodine in physiological adaptations to stress. We review selected aspects of the halogenated metabolism of macrophytic brown algae in the light of the most recent results, which point toward novel functions for iodide accumulation in kelps and the importance of bromination in cell wall modifications and adhesion properties of brown algal propagules. The importance of halogen speciation processes ranges from microbiology to biogeochemistry, through enzymology, cellular biology and ecotoxicology.

The Galeta oil spill: Pt. 4

International Nuclear Information System (INIS)

Burns, K.A.; Yelle-Simmons, L.

1994-01-01

This paper gives the detailed compositions of oil residues in sediments and encrusting bivalves, and the changes over time. Initial weathering processes removed most of the volatile hydrocarbons and all market alkanes in oil adsorbed to surface sediments within 6 months after the spill. This initially fast rate of biodegradation was not maintained in the rate of disappearance of the aromatic hydrocarbons over time. Oil leaching out of heavily contaminated sediments was bioaccumulated in bivalves for at least 5 years. The organisms accumulated the whole range of alkylated polynuclear aromatic hydrocarbons (PAHs) in the naphthalene through the benzoperylene elution range, seemingly in proportion to what was leached from sediments. A change in the composition of the aromatics bioaccumulated at most sites in year 5 indicated depletion of the most soluble and most acutely toxic hydrocarbons in the readily leachable reservoirs. (author)

Alkane and polycyclic aromatic hydrocarbons in sediments and benthic invertebrates of the northern Chukchi Sea

Science.gov (United States)

Harvey, H. Rodger; Taylor, Karen A.

2017-10-01

The Hanna Shoal region represents an important northern gateway for transport and deposition in the Chukchi Sea. This study determined the concentration and distribution of organic contaminants (aliphatic hydrocarbon and polycyclic aromatic hydrocarbons, PAHs) in surface sediments from 34 sites across Hanna Shoal. Up to 31 total PAHs, including parent and alkyl homologues were detected with total concentrations ranging from a low of 168 ng g-1 the western flank of Hanna Shoal (station H34) to 1147 ng g-1 at station in Barrow Canyon (station BarC5). Alkyl PAHs were more abundant than parent structures and accounted for 53-64% of the summed concentrations suggesting overall at background levels (< 1600 ng g-1) in sediments. Alkane (C15-C33) hydrocarbons ranged from 4.3 μg g-1 on the southern flank of Hanna shoal to 31 μg g-1 at a northern station. Sediments were often dominated by short chain (C15-C22) alkanes with overall terrestrial aquatic ratios (TAR) for the region averaging 0.20. Based on the ratio of Fl/(Fl+ Py) and BaF/(Baf+BeP) verses (BA/BA+Ch) in sediments, PAHs are largely derived from petrogenic sources with minor amounts of mixed combustion sources. A diversity of PAHs were detected in the northern whelk Neptunea heros foot muscle with total concentrations ranging from 0.14 to 1.5 μg g-1 dry tissue wt. Larger (and presumably older) animals showed higher levels of PAH per unit muscle tissue, suggesting that animals may bioaccumulate PAHs over time, with low but increasing concentrations also present in internal and external eggs. Alkane hydrocarbons were also higher in whelks with distributions similar to that seen in sediments. The mussel Muscularus discors collected in Barrow Canyon showed constrained distributions and substantially lower concentrations of both PAHs and alkanes than the surrounding surface sediments.

Persistence, bioaccumulation and toxicity of halogen-free flame retardants.

NARCIS (Netherlands)

Waaijers, S.L.; Kong, D; Hendriks, H.S.; de Wit, C.A.; Cousins, I.T.; Westerink, R.H.S.; Leonards, P.E.G.; Kraak, M.H.S.; Admiraal, W.; de Voogt, P.; Parsons, J.R.

2013-01-01

Polymers are synthetic organic materials that have a high carbon and hydrogen content, which renders them readily combustible. When used in buildings, electrical appliances, furniture, textiles, transportation, mining, and in many other applications, polymers have to fulfill flame retardancy

A method for improving predictive modeling by taking into account lag time: Example of selenium bioaccumulation in a flowing system

Energy Technology Data Exchange (ETDEWEB)

Beckon, William N., E-mail: William_Beckon@fws.gov

2016-07-15

Highlights: • A method for estimating response time in cause-effect relationships is demonstrated. • Predictive modeling is appreciably improved by taking into account this lag time. • Bioaccumulation lag is greater for organisms at higher trophic levels. • This methodology may be widely applicable in disparate disciplines. - Abstract: For bioaccumulative substances, efforts to predict concentrations in organisms at upper trophic levels, based on measurements of environmental exposure, have been confounded by the appreciable but hitherto unknown amount of time it may take for bioaccumulation to occur through various pathways and across several trophic transfers. The study summarized here demonstrates an objective method of estimating this lag time by testing a large array of potential lag times for selenium bioaccumulation, selecting the lag that provides the best regression between environmental exposure (concentration in ambient water) and concentration in the tissue of the target organism. Bioaccumulation lag is generally greater for organisms at higher trophic levels, reaching times of more than a year in piscivorous fish. Predictive modeling of bioaccumulation is improved appreciably by taking into account this lag. More generally, the method demonstrated here may improve the accuracy of predictive modeling in a wide variety of other cause-effect relationships in which lag time is substantial but inadequately known, in disciplines as diverse as climatology (e.g., the effect of greenhouse gases on sea levels) and economics (e.g., the effects of fiscal stimulus on employment).

A method for improving predictive modeling by taking into account lag time: Example of selenium bioaccumulation in a flowing system

International Nuclear Information System (INIS)

Beckon, William N.

2016-01-01

Highlights: • A method for estimating response time in cause-effect relationships is demonstrated. • Predictive modeling is appreciably improved by taking into account this lag time. • Bioaccumulation lag is greater for organisms at higher trophic levels. • This methodology may be widely applicable in disparate disciplines. - Abstract: For bioaccumulative substances, efforts to predict concentrations in organisms at upper trophic levels, based on measurements of environmental exposure, have been confounded by the appreciable but hitherto unknown amount of time it may take for bioaccumulation to occur through various pathways and across several trophic transfers. The study summarized here demonstrates an objective method of estimating this lag time by testing a large array of potential lag times for selenium bioaccumulation, selecting the lag that provides the best regression between environmental exposure (concentration in ambient water) and concentration in the tissue of the target organism. Bioaccumulation lag is generally greater for organisms at higher trophic levels, reaching times of more than a year in piscivorous fish. Predictive modeling of bioaccumulation is improved appreciably by taking into account this lag. More generally, the method demonstrated here may improve the accuracy of predictive modeling in a wide variety of other cause-effect relationships in which lag time is substantial but inadequately known, in disciplines as diverse as climatology (e.g., the effect of greenhouse gases on sea levels) and economics (e.g., the effects of fiscal stimulus on employment).

Capability of pentavalent arsenic bioaccumulation and biovolatilization of three fungal strains under laboratory conditions

Energy Technology Data Exchange (ETDEWEB)

Su, Shiming; Li, Lianfang; Bai, Lingyu; Zhang, Yanrong [Key Laboratory of Agro-Environment and Climate Change, Chinese Academy of Agricultural Sciences, Beijing (China); Jiang, Xiliang [Key Laboratory for Biological Control, Chinese Academy of Agricultural Sciences, Beijing (China); Zeng, Xibai

2010-03-15

In order to control and remediate arsenic (As) contaminated soil, sediment or water, fungi are used to investigate their potential accumulation and volatilization of As. In this study, after cultivation for 2 days, the dry weights of mycelia for Trichoderma asperellum, Fusarium oxysporum and Penicillium janthinellum all show an increased trend when the As(V) concentration ranges from 0-50, 0-50, 0-80 mg/L, respectively. When the culture system is loaded with 2500 {mu}g As(V), which represents 50 mg/L As, and cultivated for 5 days, P. janthinellum presents the highest efficiency of 87.0 {mu}g/g for As bioaccumulation, and the order of the efficiency for As bioaccumulation is P. janthinellum > T. asperellum > F. oxysporum. However, the order of the amount of volatilized As is F. oxysporum > P. janthinellum > T. asperellum, and the highest amount of volatilized As is observed for F. oxysporum at 181.0 {mu}g. Thus, the ability of As bioaccumulation and biovolatilization for T. asperellum and P. janthinellum is reported for the first time in this study. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

The bioaccumulation and toxicity induced by gold nanoparticles in ...

African Journals Online (AJOL)

It is essential to characterize the bioaccumulation and toxicity of gold nanoparticles (GNPs) in blood prior to using them in drug delivery, diagnostics, and treatment. The aim of the present study was to evaluate the blood absorbance spectra after intraperitoneal administration of 50 μl of 10, 20, and 50 nm GNPs in rat for ...

Role of the Ah locus in suppression of cytotoxic T lymphocyte activity by halogenated aromatic hydrocarbons (PCBs and TCDD): Structure-activity relationships and effects in C57Bl/6 mice congenic at the Ah locus

International Nuclear Information System (INIS)

Kerkvliet, N.I.; Baecher-Steppan, L.; Smith, B.B.; Youngberg, J.A.; Henderson, M.C.; Buhler, D.R.

1990-01-01

Previous studies have shown that the generation of cytotoxic T lymphocytes (CTL) following allogeneic tumor challenge is suppressed in Ah-responsive C57Bl/6 mice treated with a single oral dose of the toxic, Ah receptor-binding 3,4,5,3',4',5'-hexachlorobiphenyl (HxCB). The present studies have examined the specific role of the Ah receptor in this immunotoxic response by utilizing HxCB isomers of known, varied affinity for the Ah receptor as well as by comparing effects of high-affinity Ah receptor ligands (3,4,5,3',4',5'-HxCB and 2,3,7,8-tetrachlorodibenzo-p-dioxin [TCDD]) on the CTL response of mice that differ only at the Ah locus, that is, Ah-responsive (Ahbb) and Ah-nonresponsive (Ahdd) congenic C57Bl/6 mice. Correlative changes in thymic weight, serum corticosterone (CS) levels, and spleen cellularity were also measured. The potency of HxCB congeners (3,4,5,3',4',5'-; 2,3,4,5,3',4'-; 2,4,5,2',4',5'-) and 2,3,7,8-TCDD to suppress the CTL response, to reduce spleen cellularity, to cause thymic atrophy, and to elevate serum CS levels was directly correlated with the binding affinity of the congener for the Ah receptor. Furthermore, these parameters of immunotoxicity in Ahdd C57Bl/6 mice were significantly more resistant to alterations induced by either 3,4,5,3',4',5'-HxCB or 2,3,7,8-TCDD as compared to Ahbb C57Bl/6 mice. These results strongly support an Ah receptor-dependent immunotoxic mechanism in suppression of the CTL response following acute exposure to halogenated aromatic hydrocarbons

Reviewing the serotonin reuptake inhibitors (SSRIs) footprint in the aquatic biota: Uptake, bioaccumulation and ecotoxicology

International Nuclear Information System (INIS)

a Comba, 3000-548 Coimbra (Portugal))" data-affiliation=" (REQUIMTE, Group of Bromatology, Pharmacognosy and Analytical Sciences, Faculty of Pharmacy, University of Coimbra, Polo III, Azinhaga de Sta Comba, 3000-548 Coimbra (Portugal))" >Silva, Liliana J.G.; a Comba, 3000-548 Coimbra (Portugal))" data-affiliation=" (REQUIMTE, Group of Bromatology, Pharmacognosy and Analytical Sciences, Faculty of Pharmacy, University of Coimbra, Polo III, Azinhaga de Sta Comba, 3000-548 Coimbra (Portugal))" >Pereira, André a Comba, 3000-548 Coimbra (Portugal))" data-affiliation=" (REQUIMTE, Group of Bromatology, Pharmacognosy and Analytical Sciences, Faculty of Pharmacy, University of Coimbra, Polo III, Azinhaga de Sta Comba, 3000-548 Coimbra (Portugal))" >M.P.T.; Meisel, Leonor M.; a Comba, 3000-548 Coimbra (Portugal))" data-affiliation=" (REQUIMTE, Group of Bromatology, Pharmacognosy and Analytical Sciences, Faculty of Pharmacy, University of Coimbra, Polo III, Azinhaga de Sta Comba, 3000-548 Coimbra (Portugal))" >Lino, Celeste M.; a Comba, 3000-548 Coimbra (Portugal))" data-affiliation=" (REQUIMTE, Group of Bromatology, Pharmacognosy and Analytical Sciences, Faculty of Pharmacy, University of Coimbra, Polo III, Azinhaga de Sta Comba, 3000-548 Coimbra (Portugal))" >Pena, Angelina

2015-01-01

Selective serotonin re-uptake inhibitors (SSRIs) antidepressants are amongst the most prescribed pharmaceutical active substances throughout the world. Their presence, already described in different environmental compartments such as wastewaters, surface, ground and drinking waters, and sediments, and their remarkable effects on non-target organisms justify the growing concern about these emerging environmental pollutants. A comprehensive review of the literature data with focus on their footprint in the aquatic biota, namely their uptake, bioaccumulation and both acute and chronic ecotoxicology is presented. Long-term multigenerational exposure studies, at environmental relevant concentrations and in mixtures of related compounds, such as oestrogenic endocrine disruptors, continue to be sparse and are imperative to better know their environmental impact. - Highlights: • Current knowledge of uptake and bioaccumulation of SSRIs. • Ecotoxicology and effects of SSRIs in the aquatic biota. • Identification of existing knowledge gaps. - A comprehensive review focussing SSRIs antidepressants footprint in the aquatic biota, namely their uptake, bioaccumulation, and both acute and chronic ecotoxicology is presented

Enantiomerization and enantioselective bioaccumulation of metalaxyl in Tenebrio molitor larvae.

Science.gov (United States)

Gao, Yongxin; Wang, Huili; Qin, Fang; Xu, Peng; Lv, Xiaotian; Li, Jianzhong; Guo, Baoyuan

2014-02-01

The enantiomerization and enantioselective bioaccumulation of metalaxyl by a single dose of exposure to Tenebrio molitor larvae under laboratory condition were studied by high-performance liquid chromatography tandem mass spectroscopy (HPLC-MS/MS) based on a ChiralcelOD-3R [cellulosetris-tris-(3, 5-dichlorophenyl-carbamate)] column. Exposure of enantiopure R-metalaxyl and S-metalaxyl in Tenebrio molitor larvae exhibited significant enantiomerization, with formation of the R enantiomers from the S enantiomers, and vice versa, which might be attributed to the chiral pesticide catalyzed by a certain enzyme in Tenebrio molitor larvae. Enantiomerization was not observed in wheat bran during the period of 21 d. In addition, bioaccumulation of rac-metalaxyl in Tenebrio molitor larvae was enantioselective with a preferential accumulation of S-metalaxyl. These results showed that enantioselectivity was caused not only by actual degradation and metabolism but also by enantiomerization, which was an important process in the environmental fate and behavior of metalaxyl enantiomers. Copyright © 2013 Wiley Periodicals, Inc.

Neutron activation analysis for study of distribution patterns of organo-halogen pollutants in apple

International Nuclear Information System (INIS)

Zhang Hong; Luo Jialing; Sun Huibin; Chai Zhifang; Chinese Academy of Sciences, Beijing

2007-01-01

The distribution characteristics of organo-halogens in apple and their sources were studied by neutron activation analysis combined with statistical analysis. The results indicated that concentrations of organo-halogens in apple were in the order of organo-chlorine >> organo-bromine > organo-iodine, and concentrations of the organo-chlorine in four parts of apple were in the order of seed >> peel >> endocarp ≥ pulp. Also, the organo-chlorine, -bromine and-iodine in apple were found to have different sources. The latter two were mainly from naturally synthetic products by plant itself, while the former was mainly from anthropogenic pollutants. (authors)

Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

Science.gov (United States)

Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

2017-06-01

The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

Variation in bioaccumulation of persistent organic pollutants based on octanol-air partitioning: Influence of respiratory elimination in marine species.

Science.gov (United States)

Moses, Sara K; Harley, John R; Lieske, Camilla L; Muir, Derek C G; Whiting, Alex V; O'Hara, Todd M

2015-11-15

Risk assessments of persistent organic pollutants (POPs) are often based on octanol-water (KOW) partitioning dynamics and may not adequately reflect bioaccumulation in air-breathing organisms. It has been suggested that compounds with low KOW and high octanol-air partitioning (KOA) coefficients have the potential to bioaccumulate in air-breathing organisms, including marine mammals. Here we evaluate differences in concentrations of POPs for two trophically matched Arctic species, spotted seal (Phoca largha) and sheefish (Stenodus leucichthys). We compared concentrations of 108 POPs in matched tissues (liver and muscle) across three ranges of KOW. We found a significant positive correlation between POP concentration and log KOA in spotted seal tissues for low log KOW compounds (log KOW <5.5, p<0.05). This provides further evidence for empirical models and observed bioaccumulation patterns in air-breathing organisms, and highlights the potential for bioaccumulation of these compounds in Arctic marine mammals. Copyright © 2015 Elsevier Ltd. All rights reserved.

The mismatch between bioaccumulation in field and laboratory environments: Interpreting the differences for metals in benthic bivalves

International Nuclear Information System (INIS)

Belzunce-Segarra, Maria J.; Simpson, Stuart L.; Amato, Elvio D.; Spadaro, David A.; Hamilton, Ian L.; Jarolimek, Chad V.; Jolley, Dianne F.

2015-01-01

Laboratory-based bioaccumulation and toxicity bioassays are frequently used to predict the ecological risk of contaminated sediments in the field. This study investigates the bioassay conditions most relevant to achieving environmentally relevant field exposures. An identical series of metal-contaminated marine sediments were deployed in the field and laboratory over 31 days. Changes in metal concentrations and partitioning in both sediments and waters were used to interpret differences in metal exposure and bioaccumulation to the benthic bivalve Tellina deltoidalis. Loss of resuspended sediments and deposition of suspended particulate matter from the overlying water resulted in the concentrations of Cu, Pb and Zn (major contaminants) becoming lower in the 1-cm surface layer of field-deployed sediments. Lower exchange rates of overlying waters in the laboratory resulted in higher dissolved metal exposures. The prediction of metal bioaccumulation by the bivalves in field and laboratory was improved by considering the metal partitioning within the surface sediments. - Highlights: • Particulate metals are the dominant metal exposure route in laboratory and field tests (87). • There is an over-representation of the dissolved metal exposure in the laboratory (81). • Laboratory bioassays result in higher bioaccumulation of major metals, Cu, Pb, Zn (82). • Differences in exposure must be considered for a proper sediment quality evaluation (83). • Traditional measurements are not sufficient to explain bioaccumulation results (79). - To improve the value of field- and laboratory-based sediment bioassays in ecological risk assessments, it is necessary to create exposure conditions that resemble those in the field

Gas-liquid partitioning of halogenated volatile organic compounds in aqueous cyclodextrin solutions

Energy Technology Data Exchange (ETDEWEB)

Ondo, Daniel; Barankova, Eva [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Dohnal, Vladimir, E-mail: dohnalv@vscht.cz [Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic)

2011-08-15

Highlights: > Binding of halogenated VOCs with cyclodextrins examined through g-l partitioning. > Complex stabilities reflect host-guest size matching and hydrophobic interaction. > Presence of halogens in the guest molecule stabilizes the binding. > Thermodynamic origin of the binding varies greatly among the systems studied. > Results obey the guest-CD global enthalpy-entropy compensation relationship. - Abstract: Gas-liquid partitioning coefficients (K{sub GL}) were measured for halogenated volatile organic compounds (VOCs), namely 1-chlorobutane, methoxyflurane, pentafluoropropan-1-ol, heptafluorobutan-1-ol, {alpha},{alpha},{alpha}-trifluorotoluene, and toluene in aqueous solutions of natural {alpha}-, {beta}-, and {gamma}-cyclodextrins (CDs) at temperatures from (273.35 to 326.35) K employing the techniques of headspace gas chromatography and inert gas stripping. The binding constants of the 1:1 inclusion complex formation between the VOCs and CDs were evaluated from the depression of the VOCs volatility as a function of CD concentration. The host-guest size matching and the hydrophobic interaction concept were used to rationalize the observed widely different affinity of the VOC-CD pairs to form the inclusion complex. The enthalpic and entropic component of the standard Gibbs free energy of complex formation as derived from the temperature dependence of the binding constant indicate the thermodynamic origin of the binding to vary greatly among the systems studied, but follow the global enthalpy-entropy compensation relationships reported previously in the literature.

Hydration of the Atlantis Massif: Halogen, Noble Gas and In-Situ δ18O Constraints

Science.gov (United States)

Williams, M. J.; Kendrick, M. A.; Rubatto, D.

2017-12-01

A combination of halogen (Cl, Br, I), noble gases (He, Ne, Ar, Kr and Xe) and in situ oxygen isotope analysis have been utilized to investigate the fluid-mobile element record of hydration and alteration processes at the Atlantis Massif (30°N on the Mid-Atlantic Ridge). The sample suite investigated includes serpentinite, talc-amphibole ± chlorite schist and hydrated gabbro recovered by seafloor drilling undertaken at sites on a transect across the Atlantis Massif during IODP Expedition 357. Serpentine mesh and veins analysed in-situ by SHRIMP SI exhibit δ18O from 6‰ down to ≈0‰, suggesting serpentinization temperatures of 150 to >280°C and water/rock ratios >5. Differences of 1.5-2.5‰ are observed between adjacent generations of serpentine, but the δ18O range is similar at each investigated drilling site. Halogen and noble gas abundances in serpentinites, talc-amphibole schist and hydrated gabbro have been measured by noble gas mass spectrometry of both irradiated and non-irradiated samples. Serpentinites contain low abundances of halogens and noble gases (e.g. 70-430 ppm Cl, 4.7-12.2 x 10-14 mol/g 36Ar) relative to other seafloor serpentinites. The samples have systematically different Br/Cl and I/Cl ratios related to their mineralogy. Serpentinites retain mantle-like Br/Cl with a wide variation in I/Cl that stretches toward seawater values. Talc-amphibole schists exhibit depletion of Br and I relative to Cl with increasing Cl abundances, suggesting tremolite exerts strong control on halogen abundance ratios. Serpentinites show no evidence of interaction with halogen-rich sedimentary pore fluids. Iodine abundances are variable across serpentinites, and are decoupled from Br and Cl; iodine enrichment (up to 530 ppb) is observed within relatively oxidised and clay-bearing samples. Serpentinized harzburgites exhibit distinct depletion of Kr and Xe relative to atmospheric 36Ar in seawater. Oxygen isotope compositions and low abundances of both halogens

Mid-latitude Ozone Depletion Events Caused by Halogens from the Great Salt Lake in Utah

Science.gov (United States)

Fibiger, D. L.; Goldberger, L.; Womack, C.; McDuffie, E. E.; Dube, W. P.; Franchin, A.; Middlebrook, A. M.; Thornton, J. A.; Brown, S. S.

2017-12-01

Halogens are highly reactive chemicals and play an important role in atmospheric chemistry. They can be involved in many cycles which influence the oxidizing capacity of the atmosphere, including through destruction of ozone (O3). While the influence of halogens on O3 is well documented in the arctic, there are very few observations of O3 depletion driven by halogens in the mid-latitudes. To date, the most comprehensive study observed co-occurring plumes of BrO and depleted O3 near the Dead Sea in 1997. During the Utah Wintertime Fine Particulate Study (UWFPS) in winter 2017, simultaneous measurements of a comprehensive suite of halogen measurements by I- chemical ionization mass spectrometry and O3 from cavity ring-down spectroscopy, both at 1-second time resolution, were taken on a NOAA Twin Otter Aircraft over the Great Salt Lake and in the surrounding valleys. Many O3 depletion events were observed over the lake with O3 values sometimes below the instrument detection limit of 0.5 ppbv. Corresponding increases in BrO and/or ClO were observed. Many of these events were caused by extremely high levels of halogens (up to 1 ppmv Cl2) emitted from the U.S. Magnesium plant on the edge of the lake. The O3 depletion caused by U.S. Magnesium was usually isolated to a distinct vertical layer, but in other cases O3 depletion was vertically mixed and the origin of halogen activation was not immediately clear. The most complete O3 depletion was observed over the lake, but there were smaller events of a few ppbv observed in the adjacent valleys, including the highly populated Salt Lake Valley, with corresponding plumes of BrO and ClO, due to transport from the lake. Additionally, meteorology played a role in the observed O3 depletion. The strongest O3 depletion was observed during inversion events, when there is a low boundary layer and little mixing out of the air above the lake. During non-inversion conditions, only small depletions were observed, covering a much smaller

Origin of the X-Hal (Hal = Cl, Br) bond-length change in the halogen-bonded complexes.

Science.gov (United States)

Wang, Weizhou; Hobza, Pavel

2008-05-01

The origin of the X-Hal bond-length change in the halogen bond of the X-Hal...Y type has been investigated at the MP2(full)/6-311++G(d,p) level of theory using a natural bond orbital analysis, atoms in molecules procedure, and electrostatic potential fitting methods. Our results have clearly shown that various theories explaining the nature of the hydrogen bond cannot be applied to explain the origin of the X-Hal bond-length change in the halogen bond. We provide a new explanation for this change. The elongation of the X-Hal bond length is caused by the electron-density transfer to the X-Hal sigma* antibonding orbital. For the blue-shifting halogen bond, the electron-density transfer to the X-Hal sigma* antibonding orbital is only of minor importance; it is the electrostatic attractive interaction that causes the X-Hal bond contraction.

A facile approach towards increasing the nitrogen-content in nitrogen-doped carbon nanotubes via halogenated catalysts

International Nuclear Information System (INIS)

Ombaka, L.M.; Ndungu, P.G.; Omondi, B.; McGettrick, J.D.; Davies, M.L.; Nyamori, V.O.

2016-01-01

Nitrogen-doped carbon nanotubes (N-CNTs) have been synthesized at 850 °C via a CVD deposition technique by use of three ferrocenyl derivative catalysts, i.e. para-CN, -CF_3 and -Cl substituted-phenyl rings. The synthesized catalysts have been characterized by NMR, IR, HR-MS and XRD. The XRD analysis of the para-CF_3 catalyst indicates that steric factors influence the X-ray structure of 1,1′-ferrocenylphenyldiacrylonitriles. Acetonitrile or pyridine was used as carbon and nitrogen sources to yield mixtures of N-CNTs and carbon spheres (CS). The N-CNTs obtained from the para-CF_3 catalysts, in pyridine, have the highest nitrogen-doping level, show a helical morphology and are less thermally stable compared with those synthesized by use of the para-CN and -Cl as catalyst. This suggests that fluorine heteroatoms enhance nitrogen-doping in N-CNTs and formation of helical-N-CNTs (H-N-CNTs). The para-CF_3 and para-Cl catalysts in acetonitrile yielded iron-filled N-CNTs, indicating that halogens promote encapsulation of iron into the cavity of N-CNT. The use of acetonitrile, as carbon and nitrogen source, with the para-CN and -Cl as catalysts also yielded a mixture of N-CNTs and carbon nanofibres (CNFs), with less abundance of CNFs in the products obtained using para-Cl catalysts. However, para-CF_3 catalyst in acetonitrile gave N-CNTs as the only shaped carbon nanomaterials. - Graphical abstract: Graphical abstract showing the synthesis of N-CNTs using halogenated-ferrocenyl derivatives as catalyst with pyridine or acetonitrile as nitrogen and carbon sources via the chemical vapour deposition technique. - Highlights: • N-CNTs were synthesized from halogenated ferrocenyl catalysts. • Halogenated catalysts promote nitrogen-doping and pyridinic nitrogen in N-CNTs. • Halogenated catalysts facilitate iron filling of N-CNTs.

Long-term Studies of Marine Halogen Release

Science.gov (United States)

Tschritter, J.; Holla, R.; Frieß, U.; Platt, U.

2009-04-01

Institute of Enviromental Physics, Heidelberg, Germany. Long term measurements of atmospheric trace gases using multi-axis DOAS instruments are pursued at the new SOLAS observatory on the island of Sao Vicente, (Cape Verde). This research is part of the SOPRAN (Surface Ocean Processes in the ANthropocene) project (Fördernummer:03F0462F). Reactive halogen species (RHS) such as bromine- and iodine- containing species play major roles in the chemistry of ozone in both the troposphere and lower stratosphere and thus possibly influence the ozone budget on a global scale. In addition iodine-species emitted from the ocean surface have been shown to be responsible for the production of new atmospheric particles in the marine boundary layer. This may have an effect on cloud formation and radiation transfer on local and global scales. Long term measurements of RHS abundances will help to identify their key regions and processes for formation. A new long term Multi-MAX-DOAS instrument has been installed at the SOLAS observatory on the island of Sao Vicente, (Cape Verde). The main focus of these unique measurements is the investigation of reactive halogen chemistry in the subtropical marine boundary layer based on measurements of BrO, IO, and possibly OIO. Because of its wide spectral range also the use for O4-retrievals to gain aerosol profiles is possible. IO has been detected with mixing ratios up to 1.3 ppt. For BrO an upper limit of 2 ppt could be determined.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

Science.gov (United States)

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1982-03-31

A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

Impact of enhanced ozone deposition and halogen chemistry on model performance

Science.gov (United States)

In this study, an enhanced ozone deposition scheme due to the interaction of iodide in sea-water and atmospheric ozone and the detailed chemical reactions of organic and inorganic halogen species are incorporated into the hemispheric Community Multiscale Air Quality model. Prelim...

Tumour radiosensitization with the halogenated pyrimidines 5'-bromo-and 5'-iododeoxyuridine

International Nuclear Information System (INIS)

Epstein, A.H.; Cook, J.A.; Goffman, T.; Glatstein, E.

1993-01-01

The authors review studies of the use of iododeoxyuridine (IdUrd) and bromodeoxyuridine as radiosensitizers and attempt to correlate the clinical outcome for patients treated with radiation and IdUrd with the extent of halogenated pyrimidine cellular uptake and incorporation. (U.K.)

Agricultural wetlands as potential hotspots for mercury bioaccumulation: Experimental evidence using caged fish

Science.gov (United States)

Ackerman, Joshua T.; Eagles-Smith, Collin A.

2010-01-01

Wetlands provide numerous ecosystem services, but also can be sources of methylmercury (MeHg) production and export. Rice agricultural wetlands in particular may be important sites for MeHg bioaccumulation due to their worldwide ubiquity, periodic flooding schedules, and high use by wildlife. We assessed MeHg bioaccumulation within agricultural and perennial wetlands common to California's Central Valley during summer, when the majority of wetland habitats are shallowly flooded rice fields. We introduced caged western mosquitofish (Gambusia affinis) within white rice (Oryza sativa), wild rice (Zizania palustris), and permanent wetlands at water inlets, centers, and outlets. Total mercury (THg) concentrations and body burdens in caged mosquitofish increased rapidly, exceeding baseline values at introduction by 135% to 1197% and 29% to 1566% among sites, respectively, after only 60 days. Mercury bioaccumulation in caged mosquitofish was greater in rice fields than in permanent wetlands, with THg concentrations at wetland outlets increasing by 12.1, 5.8, and 2.9 times over initial concentrations in white rice, wild rice, and permanent wetlands, respectively. In fact, mosquitofish caged at white rice outlets accumulated 721 ng Hg/fish in just 60 days. Mercury in wild mosquito fish and Mississippi silversides (Menidia audens) concurrently sampled at wetland outlets also were greater in white rice and wild rice than permanent wetlands. Within wetlands, THg concentrations and body burdens of both caged and wild fish increased from water inlets to outlets in white rice fields, and tended to not vary among sites in permanent wetlands. Fish THg concentrations in agricultural wetlands were high, exceeding 0.2 ??g/g ww in 82% of caged fish and 59% of wild fish. Our results indicate that shallowly flooded rice fields are potential hotspots for MeHg bioaccumulation and, due to their global prevalence, suggest that agricultural wetlands may be important contributors to Me

Assessment of Mercury Bioaccumulation in Zebra Cichlid (Cichlasoma Nigrofasciatum Exposed to Sublethal Concentrations of Permethrin

Directory of Open Access Journals (Sweden)

Mahdi Banaee

2014-12-01

Full Text Available Background: Aquatic ecosystems are frequently subjected to contamination by toxic heavy metals and pesticides, yet very little is known about the influence of pesticides on bioaccumulation of heavy metals in aquatic organisms. Mercury is a toxic metal with no known biological benefit to organisms. Bioavailability of mercury in aquatic environments depends on biological and non-biological parameters including other pollutants. Therefore, the objectives of this research were to determine the effects of permethrin on bioaccumulation of mercury in zebra cichlid. Methods: Acute toxicity (LC50 of permethrin and mercury chloride was evaluated by estimating mortality in Probit Model in SPSS (version 19.0 IBM. In sub-lethal toxicity, zebra cichlid (Cichlasoma nigrofasciatum was exposed to various concentrations of permethrin (0.0, 0.40, 0.80, 1.20 and 1.60 µg.L-1 combined with 20 µg.L-1 mercury chloride for 15 days. At the end of the experiment, mercury concentrations were measured using ICP-OES-Perkin elmer (optima 7300-DV. Results: 96 h LC50 values of permethrin and mercury for C. nigrofasciatum were calculated to be 17.55 µg.L-1 and 140.38 µg.L-1, respectively. Our results clearly showed that the bioaccumulation of mercury in the specimens increased with increasing concentrations of permethrin to 1.20 and 1.60 µg.L-1. Conclusion: Increasing the concentration of permethrin had synergistic effects on the bioaccumulation of mercury in fish.

Different modes of TiO2 uptake by Ceriodaphnia dubia: relevance to toxicity and bioaccumulation.

Science.gov (United States)

Dalai, Swayamprava; Iswarya, V; Bhuvaneshwari, M; Pakrashi, Sunandan; Chandrasekaran, N; Mukherjee, Amitava

2014-07-01

The extensive environmental exposure of engineered metal oxide nanoparticles (NPs) may result in their bioaccumulation in aquatic organisms leading to their biotransfer in a food chain through various routes in a freshwater ecosystem. The present study focuses on the possible modes of TiO2 NP trophic transfer to Ceriodaphnia dubia, in presence and/absence of its diet, Scenedesmus obliquus (primary producer). The acute exposure studies (48h) were designed to have daphnids exposed to (i) the free NPs, (ii) both the free and the algae-borne NPs; and (iii) only the algae-borne NPs in separate tests to understand the possible routes of NP transfer. The dietary uptake of TiO2 NPs (algae-borne) was found to be the primary route for NP biotransfer with ∼70% of total NP uptake. Interestingly, in a separate study it was noticed that the NPs coated with algal exudates were easily taken up by daphnids as compared to pristine NPs of same concentrations, leading to their higher bioaccumulation. A chronic toxicity study, where daphnids were exposed to both free and algae-borne NPs for 21 days was undertaken to comprehend the TiO2 NP effect on daphnia growth and reproduction upon chronic exposure and also the bioaccumulation potential. Both acute and chronic exposure studies suggested higher bioaccumulation of TiO2 in daphnids when the particles were less toxic to the diet (algae). Copyright © 2014 Elsevier B.V. All rights reserved.

Ecological and human health sediment risk assessment for a hydrocarbon-impacted site in Lake Athabasca

International Nuclear Information System (INIS)

Mcdonald, B.; Wagenaar, A.; LaPorte, J.; Misfeldt, G.; Chatwell, I.

2009-01-01

The operation of a public port facility near Uranium City, Saskatchewan has resulted in elevated levels of hydrocarbons in soil, groundwater and sediment. Remedial action in the uplands portion of the site was successful and a risk management approach was initiated for the aquatic portion of the site in order to resolve human health and ecological issues. Ecological risks were assessed using a sediment weight-of-evidence approach involving chemistry, toxicity, bioaccumulation and benthic community structure. Human health risks were assessed via fish consumption, water ingestion and direct contact according to Health Canada guidance. This presentation included an overview of the general risk assessment approach as well as site-specific data and findings. The primary focus was on the challenges confronted during the risk assessment process, such as the need to include alkylated PAHs as a COPC in the human health risk assessment and to evaluate ongoing propeller wash and sediment resuspension for sediment risk management, even though the facility is no longer operational.

Acute toxicity and bio-accumulation of mercury and copper in ...

African Journals Online (AJOL)

The acute toxicity of Mercury and Copper on C. africanus and T. fuscatus and the bio-accumulation potentials of the metals were investigated in laboratory experiments employing standard bio–assay techniques. On the basis of LC50 values, both metals had similar magnitudes of toxicity against C. africanus. However ...

Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering

DEFF Research Database (Denmark)

Wegeberg, Christina; Donald, William A.; McKenzie, Christine

2017-01-01

in the crystalline phases of PhIO2 and its derivatives serve as models for the structures of larger gas-phase clusters, and calculations on simple model gas-phase dimer and trimer clusters result in similar motifs. This is the first account of halogen bonding playing an extensive role in gas-phase associations....

Equilibrium Sampling to Determine the Thermodynamic Potential for Bioaccumulation of Persistent Organic Pollutants from Sediment

DEFF Research Database (Denmark)

Jahnke, Annika; MacLeod, Matthew; Wickström, Håkan

2014-01-01

Equilibrium partitioning (EqP) theory is currently the most widely used approach for linking sediment pollution by persistent hydrophobic organic chemicals to bioaccumulation. Most applications of the EqP approach assume (I) a generic relationship between organic carbon-normalized chemical...... chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic...... organic chemicals from sediment useful to prioritize management actions to remediate contaminated sites....

Radiation-induced DNA damage in halogenated pyrimidine incorporated cells and its correlation with radiosensitivity

International Nuclear Information System (INIS)

Watanabe, R.; Nikjoo, H.

2003-01-01

Cells with DNA containing 5-halogenated pyrimidines in place of thymidine show significant reductions of slope (Do) and shoulder (Dq) of their radiation survival curves. Similar radiosensitization has also been observed in the yield of DNA strand breaks. The purpose of this study is to obtain an insight into the mechanism of cell lethality by examining the relationship between the spectrum of DNA damage and the cell survival. In this study we estimated the enhancement of strand breaks due to incorporation of halogenated pyrimidine, the complexity of DNA damage and the probability of the initial DNA damage leading to cell inactivation. Monte Carlo track structure methods were used to model and simulate the induction of strand breakage by X-rays. The increase of DNA strand break was estimated by assuming the excess strand break was caused by the highly reactive uracil radicals at the halouracil substituted sites. The assumption of the enhancement mechanism of strand breaks was examined and verified by comparison with experimental data for induction of SSB and DSB. The calculated DNA damage spectrum shows the increase in complexity of strand breaks is due to incorporation of halogenated pyrimidines. The increase in the yield of DSB and cell lethality show similar trend at various degrees of halogenated pyrimidine substitution. We asked the question whether this agreement supports the hypothesis that DSB is responsible for cell lethality? The estimated number of lethal damage from the cell survival using a linear-quadratic model is much less than the initial yield of DSB. This work examines the correlation of cell lethality as a function of frequencies of complex form of double strand breaks

Assessing indoor air quality of school environments: transplanted lichen Pseudovernia furfuracea as a new tool for biomonitoring and bioaccumulation.

Science.gov (United States)

Protano, Carmela; Owczarek, Malgorzata; Antonucci, Arianna; Guidotti, Maurizio; Vitali, Matteo

2017-07-01

The aim of this research is to evaluate the ability of transplanted lichen Pseudovernia (P). furfuracea to biomonitor and bioaccumulate in urban indoor environments. The elements As, Cd, Cr, Cu, Hg, Ni and Pb and 12 selected polycyclic aromatic hydrocarbons (PAHs) were used to assess P. furfuracea as a biomonitoring tool for the indoor air quality of school environments. To achieve this purpose, lichen samples were exposed for 2 months in the outdoor and indoor environments of five school settings located in urban and rural areas. The results demonstrated that transplanted lichen P. furfuracea is a suitable biomonitoring tool for metals and PAHs in indoor settings and can discriminate between different levels of air pollution related to urbanisation and indoor conditions, such as those characterised by school environments. A transplanted lichen biomonitoring strategy is cost-effective, "green", educational for attending children and less "invasive" than traditional air sampling methods. The feasibility of indoor monitoring by P. furfuracea is a relevant finding and could be a key tool to improve air quality monitoring programmes in school scenarios and thus focus on health prevention interventions for children, who are one of the most susceptible groups in the population.

Bioaccumulation of heavy metals by freshwater algal species of Bhavnagar, Gujarat, India.

Science.gov (United States)

Jaiswar, Santial; Kazi, Mudassar Anisoddin; Mehta, Shailesh

2015-11-01

The present study investigated copper, cadmium, lead and zinc accumulation in algal species Oedogonium, Cladophora, Oscillatoria and Spirogyra from freshwater habitats of Bhavnagar, India. Eight different locations were periodically sampled during August 2009 to March 2011. The general trend of heavy metal concentrations in all the algal species in present study (except at few stations), were found to be in the following order: Zn > Cu > Pb > Cd. Highest accumulation of Cu was recorded in Oedogonium, while Cladophora showed highest accumulation of Pb signifying a good bioaccumulator. Oscillatoria and Oedogonium were highest Zn accumulating algae which showed significant difference between the means at P Cu > Pb > Cd. The present study showed that Oedogonium, Cladophora, Oscillatoria and Spirogyra were excellent bioaccumulator and could be utilized as biomonitoring agents in water bodies receiving waste contaminated by metals.

Bioaccumulation Pattern of Mercury in Bacopa monnieri (L. Pennell

Directory of Open Access Journals (Sweden)

Hussain K

2012-05-01

Full Text Available Bioaccumulation pattern of mercury was studied in Bacopa monnieri plants cultivated in Hoagland nutrient medium artificially contaminated with 5 and 10μM HgCl2. Mercury content of roots, stem and leaves were analysed using Atomic Absorption Spectrophotometry (AAS. During a period 12 days of growth, more accumulation was noticed in roots followed by stem and leaves. Repeated addition of HgCl2 and enhanced growth period up to 50 days showed only negligible increase in accumulation maintaining a threshold level of mercury in the root. When a comparison was done between the quantities of HgCl2 added to the growth medium and the sum of total accumulation of the plant and content present in the residual medium, a significant quantity of mercury is found to be lost presumably through the process of phytovolatilization from the plant. Studies on the effect of pH on bioaccumulation of mercury showed that acidic pH enhanced accumulation rate and hence for phytoremediation technology ‘chlorination’ is recommended whereas for medicinal purpose, Bacopa monnieri plants can be harvested after ‘liming’ to increase the pH and thereby reducing accumulation rate of mercury.

A GIS-based tool for bioaccumulation risk analysis and its application to study polychlorinated biphenyls in the Great Lakes

Directory of Open Access Journals (Sweden)

Fernanda P. Maciel

2018-01-01

Full Text Available This paper presents a GIS-based tool named Arc-BEST (Bioaccumulation Evaluation Screening Tool to perform spatially distributed bioaccumulation risk analyses. Estimating bioaccumulation risk is important to help predict potentially adverse effects from contaminants on ecosystems and human health, which are key factors in the development of sound public policy. Arc-BEST is based on the BEST model in the U.S. Army Corps of Engineers BRAMS (Bioaccumulation Risk Assessment Modeling System software, released in 2012. It predicts concentration of concern contaminants in predators’ tissues from concentrations in organisms at the bottom of the food chain, and corresponding bioaccumulation factors. Additionally, it estimates carcinogenic and non-carcinogenic risks for humans that consume those species. The greatest contribution of Arc-BEST is that it enables the automated use of digital spatial data sets, which improves model creation speed, analysis and visualization of results, and comparison and cross-referencing with other geographic datasets. Furthermore, the model was improved to consider up to four trophic levels. The code is written in Python and is open-source. In this work Arc-BEST is used as part of a screening-level risk assessment process in order to identify hot spots where further studies and monitoring should be performed to ensure humans and ecosystems health. The tool is successfully applied to a case study in the Laurentian Great Lakes, where long-term effects of polychlorinated biphenyls (PCBs is performed, based on measured concentrations in zebra mussels (Dreissena polymorpha, and local bioaccumulation factors from previous studies. Zebra mussels have a great filtration capacity and high bioconcentration rates, increasing the bioavailability of contaminants for predator species. PCBs concentrations in different-level predators are predicted. Furthermore, health risks for humans that consume sport fish are estimated for various

Cooperativity of halogen, chalcogen, and pnictogen bonds in infinite molecular chains by electronic structure theory.

Science.gov (United States)

George, Janine; Deringer, Volker L; Dronskowski, Richard

2014-05-01

Halogen bonds (XBs) are intriguing noncovalent interactions that are frequently being exploited for crystal engineering. Recently, similar bonding mechanisms have been proposed for adjacent main-group elements, and noncovalent "chalcogen bonds" and "pnictogen bonds" have been identified in crystal structures. A fundamental question, largely unresolved thus far, is how XBs and related contacts interact with each other in crystals; similar to hydrogen bonding, one might expect "cooperativity" (bonds amplifying each other), but evidence has been sparse. Here, we explore the crucial step from gas-phase oligomers to truly infinite chains by means of quantum chemical computations. A periodic density functional theory (DFT) framework allows us to address polymeric chains of molecules avoiding the dreaded "cluster effects" as well as the arbitrariness of defining a "large enough" cluster. We focus on three types of molecular chains that we cut from crystal structures; furthermore, we explore reasonable substitutional variants in silico. We find evidence of cooperativity in chains of halogen cyanides and also in similar chalcogen- and pnictogen-bonded systems; the bonds, in the most extreme cases, are amplified through cooperative effects by 79% (I···N), 90% (Te···N), and 103% (Sb···N). Two experimentally known organic crystals, albeit with similar atomic connectivity and XB characteristics, show signs of cooperativity in one case but not in another. Finally, no cooperativity is observed in alternating halogen/acetone and halogen/1,4-dioxane chains; in fact, these XBs weaken each other by up to 26% compared to the respective gas-phase dimers.

METHOD EVALUATION TO MEASURE PERSISTENT BIOACCUMULATIVE TOXIC POLLUTANTS IN COW MILK

Science.gov (United States)

It is important to understand the persistent and bioaccumulative toxic (PBT) levels in milk, as milk fat may be one of the highest dietary sources of PBT exposure. Analysis of milk also allows the opportunity to investigate geographic variability, as milk is produced and distrib...

Distribution of hydrocarbon-utilizing microorganisms and hydrocarbon biodegradation potentials in Alaskan continental shelf areas

International Nuclear Information System (INIS)

Roubal, G.; Atlas, R.M.

1978-01-01

Hydrocarbon-utilizing microogranisms were enumerated from Alaskan continental shelf areas by using plate counts and a new most-probable-number procedure based on mineralization of 14 C-labeled hydrocarbons. Hydrocarbon utilizers were ubiquitously distributed, with no significant overall concentration differences between sampling regions or between surface water and sediment samples. There were, however, significant seasonal differences in numbers of hydrocarbon utilizers. Distribution of hydrocarbon utilizers within Cook Inlet was positively correlated with occurrence of hydrocarbons in the environment. Hydrocarbon biodegradation potentials were measured by using 14 C-radiolabeled hydrocarbon-spiked crude oil. There was no significant correlation between numbers of hydrocarbon utilizers and hydrocarbon biodegradation potentials. The biodegradation potentials showed large seasonal variations in the Beaufort Sea, probably due to seasonal depletion of available nutrients. Non-nutrient-limited biodegradation potentials followed the order hexadecane > naphthalene >> pristane > benzanthracene. In Cook Inlet, biodegradation potentials for hexadecane and naphthalene were dependent on availability of inorganic nutrients. Biodegradation potentials for pristane and benzanthracene were restricted, probably by resistance to attack by available enzymes in the indigenous population

Study of metal bioaccumulation by nuclear microprobe analysis of algae fossils and living algae cells

International Nuclear Information System (INIS)

Guo, P.; Wang, J.; Li, X.; Zhu, J.; Reinert, T.; Heitmann, J.; Spemann, D.; Vogt, J.; Flagmeyer, R.-H.; Butz, T.

2000-01-01

Microscopic ion-beam analysis of palaeo-algae fossils and living green algae cells have been performed to study the metal bioaccumulation processes. The algae fossils, both single cellular and multicellular, are from the late Neoproterozonic (570 million years ago) ocean and perfectly preserved within a phosphorite formation. The biosorption of the rare earth element ions Nd 3+ by the green algae species euglena gracilis was investigated with a comparison between the normal cells and immobilized ones. The new Leipzig Nanoprobe, LIPSION, was used to produce a proton beam with 2 μm size and 0.5 nA beam current for this study. PIXE and RBS techniques were used for analysis and imaging. The observation of small metal rich spores (<10 μm) surrounding both of the fossils and the living cells proved the existence of some specific receptor sites which bind metal carrier ligands at the microbic surface. The bioaccumulation efficiency of neodymium by the algae cells was 10 times higher for immobilized algae cells. It confirms the fact that the algae immobilization is an useful technique to improve its metal bioaccumulation

Understanding differences in the body burden-age relationships of bioaccumulating contaminants based on population cross sections versus individuals.

Science.gov (United States)

Quinn, Cristina L; Wania, Frank

2012-04-01

Body burdens of persistent bioaccumulative contaminants estimated from the cross-sectional biomonitoring of human populations are often plotted against age. Such relationships have previously been assumed to reflect the role of age in bioaccumulation. We used a mechanistic modeling approach to reproduce concentration-versus-age relationships and investigate factors that influence them. CoZMoMAN is an environmental fate and human food chain bioaccumulation model that estimates time trends in human body burdens in response to time-variant environmental emissions. Trends of polychlorinated biphenyl (PCB) congener 153 concentrations versus age for population cross sections were estimated using simulated longitudinal data for individual women born at different times. The model was also used to probe the influence of partitioning and degradation properties, length of emissions, and model assumptions regarding lipid content and liver metabolism on concentration-age trends of bioaccumulative and persistent contaminants. Body burden-age relationships for population cross sections and individuals over time are not equivalent. The time lapse between the peak in emissions and sample collection for biomonitoring is the most influential factor controlling the shape of concentration-age trends for chemicals with human metabolic half-lives longer than 1 year. Differences in observed concentration-age trends for PCBs and polybrominated diphenyl ethers are consistent with differences in emission time trends and human metabolic half-lives. Bioaccumulation does not monotonically increase with age. Our model suggests that the main predictors of cross-sectional body burden trends with age are the amount of time elapsed after peak emissions and the human metabolic and environmental degradation rates.

High-energy-density hydrogen-halogen fuel cells for advanced military applications

International Nuclear Information System (INIS)

Balko, E.N.; McElroy, J.F.

1981-01-01

It is pointed out that hydrogen-halogen fuel cell systems are particularly suited for an employment as ground power sources for military applications. The large cell potential and reversible characteristics of the H 2 Cl 2 and H 2 Br 2 couples permit high energy storage density and efficient energy conversion. When used as flow batteries, the fluid nature of the reactants in the hydrogen-halogen systems has several advantages over power sources which involve solid phases. Very deep discharge is possible without degradation of subsequent performance, and energy storage capacity is limited only by the external reactant storage volume. Very rapid chemical recharging is possible through replenishment of the reactant supply. A number of H 2 Cl 2 and H 2 Br 2 fuel cell systems have been studied. These systems use the same solid polymer electrolyte (SPE) cell technology originally developed for H2/O2 fuel cells. The results of the investigation are illustrated with the aid of a number of graphs

Plasma devices for hydrocarbon reformation

KAUST Repository

Cha, Min Suk

2017-02-16

Plasma devices for hydrocarbon reformation are provided. Methods of using the devices for hydrocarbon reformation are also provided. The devices can include a liquid container to receive a hydrocarbon source, and a plasma torch configured to be submerged in the liquid. The plasma plume from the plasma torch can cause reformation of the hydrocarbon. The device can use a variety of plasma torches that can be arranged in a variety of positions in the liquid container. The devices can be used for the reformation of gaseous hydrocarbons and/or liquid hydrocarbons. The reformation can produce methane, lower hydrocarbons, higher hydrocarbons, hydrogen gas, water, carbon dioxide, carbon monoxide, or a combination thereof.

Organic halogen compounds and surface water pollution; Composti organoalogenati alifatici e contaminazione delle acque superficiali

Energy Technology Data Exchange (ETDEWEB)

Cocchioni, M.; Pellegrini, M. G.; Grappasonni, I.; Nacciarriti, L.; Bernacchia, G. [Camerino, Univ. (Italy). Dipt. di Scienze Igienistiche e Sanitarie-Ambientali

1997-03-01

A brief review of the effects of halogenated organic compounds on the fluvial ecosystem is followed by results from a detailed monitoring of these substances in all the Marches Region rivers. The results show generally modest concentrations, except for sporadic peaks for chloroform. Sites revealing significant concentrations of halogenated organic compounds also manifested a worsening of the biological quality of the waters with lessening of E.B.I. Attention is drawn to the negative effects of indiscriminate chlorination of purification plant outputs, as this practice often fails to resolve infective problems and in itself adds toxicity to the watercourse.

Identification of cinnabarinic acid as a novel endogenous aryl hydrocarbon receptor ligand that drives IL-22 production.

Directory of Open Access Journals (Sweden)

Margaret M Lowe

Full Text Available The aryl hydrocarbon receptor (AHR binds to environmental toxicants including synthetic halogenated aromatic hydrocarbons and is involved in a diverse array of biological processes. Recently, the AHR was shown to control host immunity by affecting the balance between inflammatory T cells that produce IL-17 (Th17 and IL-22 versus regulatory T cells (Treg involved in tolerance. While environmental AHR ligands can mediate this effect, endogenous ligands are likely to be more relevant in host immune responses. We investigated downstream metabolites of tryptophan as potential AHR ligands because (1 tryptophan metabolites have been implicated in regulating the balance between Th17 and Treg cells and (2 many of the AHR ligands identified thus far are derivatives of tryptophan. We characterized the ability of tryptophan metabolites to bind and activate the AHR and to increase IL-22 production in human T cells. We report that the tryptophan metabolite, cinnabarinic acid (CA, is an AHR ligand that stimulates the differentiation of human and mouse T cells producing IL-22. We compare the IL-22-stimulating activity of CA to that of other tryptophan metabolites and define stimulation conditions that lead to CA production from immune cells. Our findings link tryptophan metabolism to AHR activation and define a novel endogenous AHR agonist with potentially broad biological functions.

Evaluating the Relationship between Equilibrium Passive Sampler Uptake and Aquatic Organism Bioaccumulation,

Science.gov (United States)

Objectives. This review evaluates passive sampler uptake of hydrophobic organic contaminants (HOCs) in water column and interstitial water exposures as a surrogate for organism bioaccumulation. Approach/Activities. Fifty-five studies were found where both passive sampler uptake...

Impact of bromide on halogen incorporation into organic moieties in chlorinated drinking water treatment and distribution systems.

Science.gov (United States)

Tan, J; Allard, S; Gruchlik, Y; McDonald, S; Joll, C A; Heitz, A

2016-01-15

The impact of elevated bromide concentrations (399 to 750 μg/L) on the formation of halogenated disinfection by-products (DBPs), namely trihalomethanes, haloacetic acids, haloacetonitriles, and adsorbable organic halogen (AOX), in two drinking water systems was investigated. Bromine was the main halogen incorporated into all of the DBP classes and into organic carbon, even though chlorine was present in large excess to maintain a disinfectant residual. Due to the higher reactivity of bromine compared to chlorine, brominated DBPs were rapidly formed, followed by a slower increase in chlorinated DBPs. Higher bromine substitution and incorporation factors for individual DBP classes were observed for the chlorinated water from the groundwater source (lower concentration of dissolved organic carbon (DOC)), which contained a higher concentration of bromide, than for the surface water source (higher DOC). The molar distribution of adsorbable organic bromine to chlorine (AOBr/AOCl) for AOX in the groundwater distribution system was 1.5:1 and almost 1:1 for the surface water system. The measured (regulated) DBPs only accounted for 16 to 33% of the total organic halogen, demonstrating that AOX measurements are essential to provide a full understanding of the formation of halogenated DBPs in drinking waters. In addition, the study demonstrated that a significant proportion (up to 94%) of the bromide in source waters can be converted AOBr. An evaluation of AOBr and AOCl through a second groundwater treatment plant that uses conventional treatment processes for DOC removal produced 70% of AOX as AOBr, with 69% of the initial source water bromide converted to AOBr. Exposure to organobromine compounds is suspected to result in greater adverse health consequences than their chlorinated analogues. Therefore, this study highlights the need for improved methods to selectively reduce the bromide content in source waters. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds using a modified QSAR model.

Science.gov (United States)

Lim, Seung Joo; Fox, Peter

2014-02-01

The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics. © 2013.

Petroleum hydrocarbons

International Nuclear Information System (INIS)

Farrington, J.W.; Teal, J.M.; Parker, P.L.

1976-01-01

Methods for analysis of petroleum hydrocarbons in marine samples are presented. Types of hydrocarbons present and their origins are discussed. Principles and methods of analysis are outlined. Infrared spectrometry, uv spectrometry, gas chromatography, mass spectroscopy, and carbon 14 measurements are described

Cellular effects of halogen blue light from dental curing unit

International Nuclear Information System (INIS)

Trosic, I.; Pavicic, I.; Jukic, S.

2008-01-01

Full text: Halogen curing lights are the most frequently used polymerization source in dental offices. Light-cured bonding systems have become increasingly popular among clinicians because they offer a number of advantages over self-cured adhesives. The effort to increase polymerization quality releases the commercially available high power light density dental curing units. Emitted visible blue light belongs to the range of nonionizing radiation. Common concern in both, patients and dentist grows with regard to the unfavorable effects on the pulp tissue. The aim of study was to evaluate the time and dose dependence effect of halogen light curing unit (Elipar TriLight, ESPE Dental AG, Germany) at the disposed condition modes in vitro. A quartz-tungsten-halogen light source emits radiation of the wavelengths between 400 and 515 nm. This halogen blue light source operates in the three illumination modes, medium (M), exponential (E) and standard (S), and five illumination times. The total irradiance or the light intensity was measured by the light intensity control area on the control panel of device and mean light intensity given by manufacturer was 800 m W/cm 2 . Continuous culture of V79 cells was illuminated in triplicate. The influence of medium mode (M), exponential (E) and standard (S) illumination during 20, 40 and 80 sec on the cell viability, colony forming ability and proliferation of V79 cell culture was investigated. Trypan blue exclusion test was used to determine cell viability, both, in the treated and control cell samples. Colony forming ability was assessed for each exposure time and mode by colony count on post-exposure day 7. Cell proliferation was determined by cell counts for each time and mode of exposure during five post-exposure days. Statistical difference were determined at p<0.05 (Statistica 7.0, StatSoft Inc., USA). Viability of cells was not affected by blue light in view of exposure time and modes. Regardless to exposure or illumination

Structural study of some halogen oxyfluorides

International Nuclear Information System (INIS)

Tantot, Georges.

1976-12-01

Some halogen oxyfluorides are studied from a structural point of view by vibrational spectroscopy and nuclear magnetic resonance. Force constant and molecular orbital calculations are added to the experimental data. The pyramidal shape of ClO 2 F under its three physical states is confirmed. In the gas and liquid phases an intermolecular association is observed. A similar interaction takes place in ClOF 3 . ClO 3 F has only a solid state transition above 10K. The structures of ClO 2 F and KBrO 2 F 2 are partly determined. The theoretical calculations are well correlated with the experimental data. They suggest a major influence of the ligands [fr

Analysis of Halogen-Mercury Reactions in Flue Gas

Energy Technology Data Exchange (ETDEWEB)

Paula Buitrago; Geoffrey Silcox; Constance Senior; Brydger Van Otten

2010-01-01

was observed at SO{sub 2} concentrations of 400 ppmv and higher. In contrast, SO{sub 2} concentrations as low as 50 ppmv significantly reduced mercury oxidation by bromine, this reduction could be due to both gas and liquid phase interactions between SO{sub 2} and oxidized mercury species. The simultaneous presence of chlorine and bromine in the flue gas resulted in a slight increase in mercury oxidation above that obtained with bromine alone, the extent of the observed increase is proportional to the chlorine concentration. The results of this study can be used to understand the relative importance of gas-phase mercury oxidation by bromine and chlorine in combustion systems. Two temperature profiles were tested: a low quench (210 K/s) and a high quench (440 K/s). For chlorine the effects of quench rate were slight and hard to characterize with confidence. Oxidation with bromine proved sensitive to quench rate with significantly more oxidation at the lower rate. The data generated in this program are the first homogeneous laboratory-scale data on bromine-induced oxidation of mercury in a combustion system. Five Hg-Cl and three Hg-Br mechanisms, some published and others under development, were evaluated and compared to the new data. The Hg-halogen mechanisms were combined with submechanisms from Reaction Engineering International for NO{sub x}, SO{sub x}, and hydrocarbons. The homogeneous kinetics under-predicted the levels of mercury oxidation observed in full-scale systems. This shortcoming can be corrected by including heterogeneous kinetics in the model calculations.

Induction and prevention of micronuclei and chromosomal aberrations in cultured human lymphocytes exposed to the light of halogen tungsten lamps.

Science.gov (United States)

D'Agostini, F; Caimo, A; De Filippi, S; De Flora, S

1999-07-01

Previous studies have shown that the light emitted by halogen tungsten lamps contains UV radiation in the UV-A, UV-B and UV-C regions, induces mutations and irreparable DNA damage in bacteria, enhances the frequency of micronuclei in cultured human lymphocytes and is potently carcinogenic to the skin of hairless mice. The present study showed that the light emitted by an uncovered, traditional halogen lamp induces a significant, dose-related and time-related increase not only in micronuclei but also in chromosome-type aberrations, such as breaks, and even more in chromatid-type aberrations, such as isochromatid breaks, exchanges and isochromatid/chromatid interchanges, all including gaps or not, in cultured human lymphocytes. All these genotoxic effects were completely prevented by shielding the same lamp with a silica glass cover, blocking UV radiation. A new model of halogen lamp, having the quartz bulb treated in order to reduce the output of UV radiation, was considerably less genotoxic than the uncovered halogen lamp, yet induction of chromosomal alterations was observed at high illuminance levels.

NATIONAL COW MILK SURVEY FOR PERSISTENT, BIOACCUMULATIVE AND TOXIC (PBT) POLLUTANTS

Science.gov (United States)

This is a survey for persistent, bioaccumulative, and toxic (PBT) pollutants in the U.S. milk supply. The EPA Environmental Radiation Ambient Monitoring System (ERAMS) was used to collect two sets of milk samples, one set in July 2000 and the second in January 2001. ERAMS has abo...

Converting high boiling hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Terrisse, H; DuFour, L

1929-02-12

A process is given for converting high boiling hydrocarbons into low boiling hydrocarbons, characterized in that the high boiling hydrocarbons are heated to 200 to 500/sup 0/C in the presence of ferrous chloride and of such gases as hydrogen, water gas, and the like gases under a pressure of from 5 to 40 kilograms per square centimeter. The desulfurization of the hydrocarbons occurs simultaneously.

High power light emitting diode (LED) arrays versus halogen light polymerization of oral biomaterials: Barcol hardness, compressive strength and radiometric properties.

Science.gov (United States)

Mills, Robin W; Uhl, Alexander; Blackwell, Gordon B; Jandt, Klaus D

2002-07-01

The clinical performance of light polymerized dental composites is greatly influenced by the quality of the light curing unit (LCU) used. Commonly used halogen LCUs have some specific drawbacks such as decreasing light output with time. This may result in a low degree of monomer conversion of the composites with negative clinical implications. Previous studies have shown that blue light emitting diode (LED) LCUs have the potential to polymerize dental composites without having the drawbacks of halogen LCUs. Since these studies were carried out LED technology has advanced significantly and commercial LED LCUs are now becoming available. This study investigates the Barcol hardness as a function of depth, and the compressive strength of dental composites that had been polymerized for 40 or 20s with two high power LED LCU prototypes, a commercial LED LCU, and a commercial halogen LCU. In addition the radiometric properties of the LCUs were characterized. The two high power prototype LED LCUs and the halogen LCU showed a satisfactory and similar hardness-depth performance whereas the hardness of the materials polymerized with the commercial LED LCU rapidly decreased with sample depth and reduced polymerization time (20 s). There were statistically significant differences in the overall compressive strengths of composites polymerized with different LCUs at the 95% significance level (p = 0.0016) with the two high power LED LCU prototypes and the halogen LCU forming a statistically homogenous group. In conclusion, LED LCU polymerization technology can reach the performance level of halogen LCUs. One of the first commercial LED LCUs however lacked the power reserves of the high power LED LCU prototypes.

Modelling 2,4-dichlorophenol bioavailability and bioaccumulation by the freshwater fingernail clam Sphaerium corneum using artificial particles and humic acids

International Nuclear Information System (INIS)

Verrengia Guerrero, N.R.; Taylor, M.G.; Simkiss, K.

2007-01-01

The complex and variable composition of natural sediments makes it very difficult to predict the bioavailability and bioaccumulation of sediment-bound contaminants. Several approaches have been proposed to overcome this problem, including an experimental model using artificial particles with or without humic acids as a source of organic matter. For this work, we have applied this experimental model, and also a sample of a natural sediment, to investigate the uptake and bioaccumulation of 2,4-dichlorophenol (2,4-DCP) by Sphaerium corneum. Additionally, the particle-water partition coefficients (K d ) were calculated. The results showed that the bioaccumulation of 2,4-DCP by clams did not depend solely on the levels of chemical dissolved, but also on the amount sorbed onto the particles and the characteristics and the strength of that binding. This study confirms the value of using artificial particles as a suitable experimental model for assessing the fate of sediment-bound contaminants. - An experimental model is proposed to better understand the bioavailability and bioaccumulation of sediment-bound 2,4-dichlorophenol

Quadrupole coupling constants and isomeric Moessbauer shifts for halogen-containing gold, platinum, niobium, tantalum and antimony compounds

International Nuclear Information System (INIS)

Poleshchuk, O. K.; Branchadell, V.; Ritter, R. A.; Fateev, A. V.

2008-01-01

We have analyzed by means of Density functional theory calculations the nuclear quadrupole coupling constants of a range of gold, antimony, platinum, niobium and tantalum compounds. The geometrical parameters and halogen nuclear quadrupole coupling constants obtained by these calculations substantially corresponded to the data of microwave and nuclear quadrupole resonance spectroscopy. An analysis of the quality of the calculations that employ pseudo-potentials and all-electron basis sets for the halogen compounds was carried out. The zero order regular approximation (ZORA) method is shown to be a viable alternative for the calculation of halogen coupling constants in molecules. In addition, the ZORA model, in contrast to the pseudo-potential model, leads to realistic values of all metal nuclear quadrupole coupling constants. From Klopman's approach, it follows that the relationship between the electrostatic bonding and covalent depends on the nature of the central atom. The results on Moessbauer chemical shifts are also in a good agreement with the coordination number of the central atom.

Quadrupole coupling constants and isomeric Moessbauer shifts for halogen-containing gold, platinum, niobium, tantalum and antimony compounds

Energy Technology Data Exchange (ETDEWEB)

Poleshchuk, O. K., E-mail: poleshch@tspu.edu.ru [Tomsk State Pedagogical University (Russian Federation); Branchadell, V. [Universitat Autonoma de Barcelona, Departament de Quimica (Spain); Ritter, R. A.; Fateev, A. V. [Tomsk State Pedagogical University (Russian Federation)

2008-01-15

We have analyzed by means of Density functional theory calculations the nuclear quadrupole coupling constants of a range of gold, antimony, platinum, niobium and tantalum compounds. The geometrical parameters and halogen nuclear quadrupole coupling constants obtained by these calculations substantially corresponded to the data of microwave and nuclear quadrupole resonance spectroscopy. An analysis of the quality of the calculations that employ pseudo-potentials and all-electron basis sets for the halogen compounds was carried out. The zero order regular approximation (ZORA) method is shown to be a viable alternative for the calculation of halogen coupling constants in molecules. In addition, the ZORA model, in contrast to the pseudo-potential model, leads to realistic values of all metal nuclear quadrupole coupling constants. From Klopman's approach, it follows that the relationship between the electrostatic bonding and covalent depends on the nature of the central atom. The results on Moessbauer chemical shifts are also in a good agreement with the coordination number of the central atom.

Distribution, bioaccumulation and trophic transfer of chlorinated polyfluoroalkyl ether sulfonic acids in the marine food web of Bohai, China.

Science.gov (United States)

Chen, Hong; Han, Jianbo; Cheng, Jiayi; Sun, Ruijun; Wang, Xiaomeng; Han, Gengchen; Yang, Wenchao; He, Xin

2018-06-04

Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) caused great concerns recently as novel fluorinated alternatives. However, information on their bioconcentration, bioaccumulation and biomagnification in marine ecosystems is limited. In this study, 152 biological samples including invertebrates, fishes, seabirds and mammals collected from Bohai Sea of China were analyzed to investigate the residual level, spatial distribution, bioaccumulation and biomagnification of Cl-PFESAs. 6:2 Cl-PFESA was found in concentrations ranging from bioaccumulation factors (BAFs) for 6:2 Cl-PFESA ranged from 2.23 to 4.21, implying the bioaccumulation of this compound. The trophic magnification factor (BMF) for 6:2 Cl-PFESA was determined to be 3.37 in the marine food web, indicating biomagnification potential along the marine food chain. Copyright © 2018 Elsevier Ltd. All rights reserved.

Assessment of soil stabilization by chemical extraction and bioaccumulation using earthworm, Eisenia fetida

Science.gov (United States)

Lee, Byung-Tae; Abd Aziz, Azilah; Han, Heop Jo; Kim, Kyoung-Woong

2014-05-01

Soil stabilization does not remove heavy metals from contaminated soil, but lowers their exposures to ecosystem. Thus, it should be evaluated by measuring the fractions of heavy metals which are mobile and/or bioavailable in soils. The study compared several chemical extractions which intended to quantify the mobile or bioaccessible fractions with uptake and bioaccumulation by earthworm, Eisenia fetida. Soil samples were taken from the abandoned mine area contaminated with As, Cd, Cu, Pb and/or Zn. To stabilize heavy metals, the soils were amended with limestone and steel slag at 5% and 2% (w/w), respectively. All chemical extractions and earthworm tests were applied to both the contaminated and the stabilized soils with triplicates. The chemical extractions consisted of six single extractions which were 0.01M CaCl2 (unbufferred), EDTA or DTPA (chelating), TCLP (acidic), Mehlich 3 (mixture), and aqua regia (peudo-total). Sequential extractions were also applied to fractionate heavy metals in soils. In earthworm tests, worms were exposed to the soils for uptake of heavy metals. After 28 days of exposure to soils, worms were transferred to clean soils for elimination. During the tests, three worms were randomly collected at proper sampling events. Worms were rinsed with DI water and placed on moist filter paper for 48 h for depuration. Filter paper was renewed at 24 h to prevent coprophagy. The worms were killed with liquid nitrogen, dried in the oven, and digested with aqua regia for ICP-MS analysis. In addition to the bioaccumulation, several toxicity endpoints were observed such as burrowing time, mortality, cocoon production, and body weight changes. Toxicokinetics was applied to determine the uptake and elimination heavy metals by the earthworms. Bioaccumulation factor (BAF) was estimated using total metal concentrations and body burdens. Pearson correlation and simple linear regression were applied to evaluate the relationship between metal fractions by single

Allergic contact dermatitis due to highly reactive halogenated compounds

Energy Technology Data Exchange (ETDEWEB)

Pickering, F C; Ive, F A

1983-11-01

Ten cases of dermatitis in a fine organic chemicals plant are reported. These cases were all due to exposure to chemical compounds with reactive bromine or chlorine atoms. This type of chemical is always extremely irritant, but evidence is put forward to suggest that these cases were the result of allergic sensitization. Chemicals with reactive halogen atoms should always be handled with extreme care and patch testing should be approached with caution.

Bioaccumulation of microcystins in invasive bivalves: A case study from the boreal lagoon ecosystem

Directory of Open Access Journals (Sweden)

Aistė Paldavičienė

2015-01-01

Full Text Available In the current study we present the first report on the bioaccumulation of microcystins (MC in zebra mussel Dreissena polymorpha from the eutrophic brackish water Curonian Lagoon. The bioaccumulation capacity was related to age structure of mussels and ambient environmental conditions. We also discuss the relevant implications of these findings for biomonitoring of toxic cyanobacteria blooms in the Curonian Lagoon and potential consequences for D. polymorpha cultivation activities considered for the futures as remediation measure. Samples for the analysis were collected twice per year, in June and September, in 2006, 2007 and 2008, from two sites within the littoral zone of the lagoon. The highest microcystin concentrations were measured in mussels larger than 30 mm length and sampled in 2006 (when a severe toxic cyanobacteria bloom occurred. In the following years, a consistent reduction in bioaccumulated MC concentration was noticed. However, certain amount of microcystin was recorded in mussel tissues in 2007 and 2008, when no cyanotoxins were reported in the phytoplankton. Considering high depuration rates and presence of cyanotoxins in the bottom sediments well after the recorded toxic blooms, we assume mechanism of secondary contamination when microcystin residuals could be uptaken by mussels with resuspended sediment particles.

Biosynthesis of polybrominated aromatic organic compounds by marine bacteria

Science.gov (United States)

Agarwal, Vinayak; El Gamal, Abrahim A.; Yamanaka, Kazuya; Poth, Dennis; Kersten, Roland D.; Schorn, Michelle; Allen, Eric E.; Moore, Bradley S.

2014-01-01

Polybrominated diphenyl ethers (PBDEs) and polybrominated bipyrroles are natural products that bioaccumulate in the marine food chain. PBDEs have attracted widespread attention due to their persistence in the environment and potential toxicity to humans. However, the natural origins of PBDE biosynthesis are not known. Here we report marine bacteria as producers of PBDEs and establish a genetic and molecular foundation for their production that unifies paradigms for the elaboration of bromophenols and bromopyrroles abundant in marine biota. We provide biochemical evidence of marine brominase enzymes revealing decarboxylative-halogenation enzymology previously unknown among halogenating enzymes. Biosynthetic motifs discovered in our study were used to mine sequence databases to discover unrealized marine bacterial producers of organobromine compounds. PMID:24974229

Influences on Mercury Bioaccumulation Factors for the Savannah River

International Nuclear Information System (INIS)

Paller, M.H.

2003-01-01

Mercury TMDLs (Total Maximum Daily Loads) are a regulatory instrument designed to reduce the amount of mercury entering a water body and ultimately to control the bioaccumulation of mercury in fish. TMDLs are based on a BAF (bioaccumulation factor), which is the ratio of methyl mercury in fish to dissolved methyl mercury in water. Analysis of fish tissue and aqueous methyl mercury samples collected at a number of locations and over several seasons in a 118 km reach of the Savannah River demonstrated that species specific BAFs varied by factors of three to eight. Factors contributing to BAF variability were location, habitat and season related differences in fish muscle tissue mercury levels and seasonal differences in dissolved methyl mercury levels. Overall (all locations, habitats, and seasons) average BAFs were 3.7 x 106 for largemouth bass, 1.4 x 106 for sunfishes, and 2.5 x 106 for white catfish. Inaccurate and imprecise BAFs can result in unnecessary economic impact or insufficient protection of human health. Determination of representative and precise BAFs for mercury in fish FR-om large rivers necessitates collecting large and approximately equal numbers of fish and aqueous methyl mercury samples over a seasonal cycle FR-om the entire area and all habitats to be represented by the TMDL

Modeling the effect of water chemistry on the bioaccumulation of waterborne cadmium in zebra mussels.

Science.gov (United States)

Bourgeault, Adeline; Gourlay-Francé, Catherine; Tusseau-Vuillemin, Marie-Hélène

2010-10-01

The present study aims at investigating the effects of Zn, Ca, and dissolved organic carbon (DOC) on the waterborne Cd bioaccumulation of a freshwater bivalve (Dreissena polymorpha). Mussels were exposed for 48 h at 3 µg/L of Cd in different media. Their physiological activities were assessed by separately measuring the filtration rate in the same exposure water. Increased Zn (from 3 to 89 µg/L) and Ca (from 37 to 131 mg/L) concentrations in water led to a threefold and sevenfold reduction of Cd bioaccumulation, whereas the effect of DOC varied greatly depending on its concentration. At low DOC concentrations (from 0.2 to 1.1 mg/L), the uptake of Cd increased, whereas at higher concentrations (from 1.1 to 17.1 mg/L), the uptake decreased. The filtration activity was not strongly influenced by either Zn or Ca concentration, whereas it was modified in enriched DOC media in the same manner as Cd uptake. A competitive model was built to predict the waterborne uptake rate constant of Cd (k (u)) as a function of Zn and Ca concentrations in the water. Over the range of DOC concentrations we tested, organic matter was shown to influence Cd bioaccumulation in two ways: by modifying Cd speciation and thus its bioavailability and its interaction with the biological membrane, and by affecting the mussel's physiology and therefore its sensitivity to metal. The present study provides a useful means of adjusting the toxicokinetic constant to the water's physicochemical characteristics and proposes a unifying model that takes into account the different geochemical and biological influences on bioaccumulation. Environ. Toxicol. Chem. 2010;29:2182-2189. © 2010 SETAC.

BIOACCUMULATION AND BIOTRANSFORMATION OF CHIRAL TRIAZOLE FUNGICIDES IN RAINBOW TROUT (ONCORHYNCHUS MYKISS)

Science.gov (United States)

There are very little data on the bioaccumulation and biotransformation of current-use pesticides (CUPs) despite the fact that such data are critical in assessing their fate and potential toxic effects in aquatic organisms. To help address this issue, juvenile rainbow trout (Onco...

Production of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Day, D T; Day, R E

1920-04-27

A process is disclosed of converting hydro-carbon oils having high boiling points to hydro-carbon oils having low boiling points, which process comprises adding the oil to be treated to a mass of hydro-carbon oil bearing shale, passing the shale with the oil through a conveyor retort and subjecting the material while in the retort to a heat treatment involving a temperature of at least 500/sup 0/F.

Distribution of total and methylmercury in different ecosystem compartments in the Everglades: Implications for mercury bioaccumulation

International Nuclear Information System (INIS)

Liu Guangliang; Cai Yong; Philippi, Thomas; Kalla, Peter; Scheidt, Daniel; Richards, Jennifer; Scinto, Leonard; Appleby, Charlie

2008-01-01

We analyzed Hg species distribution patterns among ecosystem compartments in the Everglades at the landscape level in order to explore the implications of Hg distribution for Hg bioaccumulation and to investigate major biogeochemical processes that are pertinent to the observed Hg distribution patterns. At an Everglade-wide scale, THg concentrations were significantly increased in the following order: periphyton < flocculent material (floc) < soil, while relatively high MeHg concentrations were observed in floc and periphyton. Differences in the methylation potential, THg concentration, and MeHg retention capacity could explain the relatively high MeHg concentrations in floc and periphyton. The MeHg/THg ratio was higher for water than for soil, floc, or periphyton probably due to high dissolved organic carbon (DOC) concentrations present in the Everglades. Mosquitofish THg positively correlated with periphyton MeHg and DOC-normalized water MeHg. The relative THg and MeHg distribution patterns among ecosystem compartments favor Hg bioaccumulation in the Everglades. - Mercury bioaccumulation in Florida Everglades is related to the distribution patterns of mercury species among ecosystem compartments

Distribution of total and methylmercury in different ecosystem compartments in the Everglades: Implications for mercury bioaccumulation

Energy Technology Data Exchange (ETDEWEB)

Liu Guangliang [Department of Chemistry and Biochemistry, Florida International University, 11200 SW 8th Street, Miami, FL 33199 (United States); Southeast Environmental Research Center, Florida International University, Miami, FL 33199 (United States); Cai Yong [Department of Chemistry and Biochemistry, Florida International University, 11200 SW 8th Street, Miami, FL 33199 (United States); Southeast Environmental Research Center, Florida International University, Miami, FL 33199 (United States)], E-mail: cai@fiu.edu; Philippi, Thomas [Department of Biological Sciences, Florida International University, Miami, FL 33199 (United States); Kalla, Peter; Scheidt, Daniel [US Environmental Protection Agency, Region 4, Science and Ecosystem Support Division, Athens, GA 30605 (United States); Richards, Jennifer [Department of Biological Sciences, Florida International University, Miami, FL 33199 (United States); Scinto, Leonard [Southeast Environmental Research Center, Florida International University, Miami, FL 33199 (United States); Appleby, Charlie [US Environmental Protection Agency, Region 4, Science and Ecosystem Support Division, Athens, GA 30605 (United States)

2008-05-15

We analyzed Hg species distribution patterns among ecosystem compartments in the Everglades at the landscape level in order to explore the implications of Hg distribution for Hg bioaccumulation and to investigate major biogeochemical processes that are pertinent to the observed Hg distribution patterns. At an Everglade-wide scale, THg concentrations were significantly increased in the following order: periphyton < flocculent material (floc) < soil, while relatively high MeHg concentrations were observed in floc and periphyton. Differences in the methylation potential, THg concentration, and MeHg retention capacity could explain the relatively high MeHg concentrations in floc and periphyton. The MeHg/THg ratio was higher for water than for soil, floc, or periphyton probably due to high dissolved organic carbon (DOC) concentrations present in the Everglades. Mosquitofish THg positively correlated with periphyton MeHg and DOC-normalized water MeHg. The relative THg and MeHg distribution patterns among ecosystem compartments favor Hg bioaccumulation in the Everglades. - Mercury bioaccumulation in Florida Everglades is related to the distribution patterns of mercury species among ecosystem compartments.

Bioaccumulation of 137Cs and 57Co by five marine phytoplankton species

International Nuclear Information System (INIS)

Heldal, H.E.; Stupakoff, I.; Fisher, N.S.

2001-01-01

Under controlled laboratory conditions, we have examined the bioaccumulation of 137 Cs and 57 Co in three prymnesiophytes, the coccolithophorid Emiliania huxleyi and the non-calcareous species Isochrysis galbana and Phaeocystis globosa, and two diatoms Skeletonema costatum and Thalassiosira pseudonana. We measured the uptake in growing and non-growing cells and determined concentration factors on both volume and dry weight bases. For uptake of 57 Co in non-growing cells, volume concentration factors (VCF) at equilibrium ranged from 0.2x10 3 for E. huxleyi to 4x10 3 for T. pseudonana. For uptake of 137 Cs in non-growing cells, the VCFs were low for all species and the uptake pattern seemed unsystematic. The results suggest that, in contrast to Co, the cycling and bioaccumulation of Cs in marine animals are unlikely to be affected by Cs accumulation in primary producers

Bioaccumulation of trace elements in pelagic fish from the Western Indian Ocean

International Nuclear Information System (INIS)

Kojadinovic, Jessica; Potier, Michel; Le Corre, Matthieu; Cosson, Richard P.; Bustamante, Paco

2007-01-01

Trace elements were analyzed in fish of commercial interest to determine their importance in marine systems of the Western Indian Ocean and their bioaccumulation patterns. The results are equivalent or lower than levels reported in ichthyofauna worldwide. Certain values of muscular Cd, Hg, Pb and Zn were, however, above thresholds for human consumption. Levels varied among tissues, species and fish length, but were seldom influenced by the nutritional condition of the fish, its gender and its reproductive status. Correlations between hepatic Hg and Se levels in Swordfish (r 2 = 0.747) and Yellowfin Tunas (r 2 = 0.226), and among metallothionein linking metals imply the existence of detoxification processes in these species. Level differences between fish from the Mozambique Channel and Reunion Island reflect differences of diets rather than differences of elemental availability in both environments. - Metal bioaccumulation was quantified in four species of pelagic fish

Sewage sludge biochar influence upon rice (Oryza sativa L) yield, metal bioaccumulation and greenhouse gas emissions from acidic paddy soil.

Science.gov (United States)

Khan, Sardar; Chao, Cai; Waqas, Muhammad; Arp, Hans Peter H; Zhu, Yong-Guan

2013-08-06

Biochar addition to soil has been proposed to improve plant growth by increasing soil fertility, minimizing bioaccumulation of toxic metal(liod)s and mitigating climate change. Sewage sludge (SS) is an attractive, though potentially problematic, feedstock of biochar. It is attractive because of its large abundance; however, it contains elevated concentrations of metal(loid)s and other contaminants. The pyrolysis of SS to biochar (SSBC) may be a way to reduce the availability of these contaminants to the soil and plants. Using rice plant pot experiments, we investigated the influence of SSBC upon biomass yield, bioaccumulation of nutrients, and metal(loid)s, and green housegas (GHG) emissions. SSBC amendments increased soil pH, total nitrogen, soil organic carbon and available nutrients and decreased bioavailable As, Cr, Co, Ni, and Pb (but not Cd, Cu, and Zn). Regarding rice plant properties, SSBC amendments significantly (P ≤ 0.01) increased shoot biomass (71.3-92.2%), grain yield (148.8-175.1%), and the bioaccumulation of phosphorus and sodium, though decreased the bioaccumulation of nitrogen (except in grain) and potassium. Amendments of SSBC significantly (P ≤ 0.05) reduced the bioaccumulation of As, Cr, Co, Cu, Ni, and Pb, but increased that of Cd and Zn, though not above limits set by Chinese regulations. Finally regarding GHG emissions, SSBC significantly (P rice paddy soil but the actual associated benefits will depend on site-specific conditions and source of SS; long-term effects remain a further unknown.

Bioaccumulation factor of tritium in oyster and tilapia

International Nuclear Information System (INIS)

Garcia, T.Y.; Juan, N.B.

1984-01-01

This paper reports on the bioaccumulation factor as well as the residence time of tritium in marine organisms such as tilapia fish (Tilapia mossambica) and oyster (Crassostrea iredalei) reared under laboratory conditions. The organisms were submerged in aquarium water containing tritium with specific activity of 1.0 nCi/ml. The samples were analyzed for tissue-free water tritium (TFWT) by freeze drying and for tissue-bound tritium (TBT) by combustion methods. Tritiated water collected was assayed using the liquid scintillation counting technique. (author)

Modeling bioaccumulation in humans using poly-parameter linear free energy relationships (PPLFERS)

Energy Technology Data Exchange (ETDEWEB)

Undeman, Emma, E-mail: emma.undeman@itm.su.se; Czub, Gertje; McLachlan, Michael S.

2011-04-01

Chemical partition coefficients between environmental media and biological tissues are a key component of bioaccumulation models. The single-parameter linear free energy relationships (spLFERs) commonly used for predicting partitioning are often derived using apolar chemicals and may not accurately capture polar chemicals. In this study, a poly-parameter LFER (ppLFER) based model of organic chemical bioaccumulation in humans is presented. Chemical partitioning was described by an air-body partition coefficient that was a volume weighted average of ppLFER based partition coefficients for the major organs and tissues constituting the human body. This model was compared to a spLFER model treating the body as a mixture of lipid ({approx} octanol) and water. Although model agreement was good for hydrophobic chemicals (average difference 15% for log K{sub OW} > 4 and log K{sub OA} > 8), the ppLFER model predicted {approx} 90% lower body burdens for hydrophilic chemicals (log K{sub OW} < 0). This was mainly due to lower predictions of muscle and adipose tissue sorption capacity for these chemicals. A comparison of the predicted muscle and adipose tissue sorption capacities of hydrophilic chemicals with measurements indicated that the ppLFER and spLFER models' uncertainties were similar. Consequently, little benefit from the implementation of ppLFERs in this model was identified. - Research Highlights: {yields}Implementation of ppLFERs resulted in on average 90% lower predicted body burdens. {yields}Uncertainties in spLFER and ppLFER predictions were similar. {yields}The benefit from implementation of ppLFERs in bioaccumulation models was limited.

Selenium bioaccumulation in fish exposed to coal ash at the Tennessee Valley Authority Kingston spill site.

Science.gov (United States)

Mathews, Teresa J; Fortner, Allison M; Jett, R Trent; Morris, Jesse; Gable, Jennifer; Peterson, Mark J; Carriker, Neil

2014-10-01

In December 2008, 4.1 million cubic meters of coal ash were released into the Emory and Clinch Rivers by the Tennessee Valley Authority Kingston Fossil Plant. Coal ash contains several contaminants, including the bioaccumulative metalloid selenium (Se). Because Se is predominantly accumulated in aquatic organisms through dietary rather than aqueous exposure, tissue-based toxicity thresholds for Se are currently being considered. The proposed threshold concentrations range between 4 μg/g and 9 μg/g Se (dry wt.) in whole body fish, with a proposed fillet threshold of 11.8 μg/g. In the present study, the authors examined the spatial and temporal trends in Se bioaccumulation and examined the relationship between the Se content in fillets and in whole bodies of fish collected around the Kingston spill site to determine whether Se bioaccumulation was a significant concern at the ash spill site. Whereas Se concentrations in fish (whole bodies and fillets) were elevated at sampling locations affected by the Kingston ash spill relative to reference locations, concentrations do not appear to be above risk thresholds and have not been increasing over the 5-yr period since the spill. These findings are not only relevant to guiding the human health and ecological risk assessments at the Kingston ash spill site, but because of current national discussions on appropriate guidelines for Se in fish as well for the disposal of coal combustion wastes, the results are also relevant to the general understanding of Se bioaccumulation in contaminated water bodies. © 2014 SETAC.

Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes

Czech Academy of Sciences Publication Activity Database

Fanfrlík, Jindřich; Holub, Josef; Růžičková, Z.; Řezáč, Jan; Lane, P. D.; Wann, D. A.; Hnyk, Drahomír; Růžička, A.; Hobza, Pavel

2016-01-01

Roč. 17, č. 21 (2016), s. 3373-3376 ISSN 1439-4235 R&D Projects: GA ČR(CZ) GBP208/12/G016; GA ČR(CZ) GA15-05677S Institutional support: RVO:61388963 ; RVO:61388980 Keywords : bromine * carboranes * halogen bonds * sigma holes * X-ray crystal structure Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T) Impact factor: 3.075, year: 2016

Strength and Character of Halogen Bonds in Protein-Ligand Complexes

Czech Academy of Sciences Publication Activity Database

Riley, Kevin Eugene; Hobza, Pavel

2011-01-01

Roč. 11, č. 10 (2011), s. 4272-4278 ISSN 1528-7483 R&D Projects: GA MŠk LC512 Grant - others:Research and Development for Innovations of European Social Fund(XE) CZ.1.05/2.1.00/03.0058 Institutional research plan: CEZ:AV0Z40550506 Keywords : halogen bond * protein-ligand complexes * calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.720, year: 2011

Risk Assessment of Bioaccumulation Substances. Part II: Description of a Model Framework

NARCIS (Netherlands)

Tamis, J.E.; Vries, de P.; Karman, C.C.

2009-01-01

This report provides a proposal for a framework for risk assessment of bioaccumulative substances, either from produced water discharges or present as background contamination. The proposed framework is such that it is compatible to the current EIF risk assessment models that are used in the

A halogen-free synthesis of gold nanoparticles using gold(III) oxide

International Nuclear Information System (INIS)

Sashuk, Volodymyr; Rogaczewski, Konrad

2016-01-01

Gold nanoparticles are one of the most used nanomaterials. They are usually synthesized by the reduction of gold(III) chloride. However, the presence of halide ions in the reaction mixture is not always welcome. In some cases, these ions have detrimental influence on the morphology and structure of resulting nanoparticles. Here, we present a simple and halogen-free procedure to prepare gold nanoparticles by reduction of gold(III) oxide in neat oleylamine. The method provides the particles with an average size below 10 nm and dispersity of tens of percent. The process of nanoparticle formation was monitored using UV–Vis spectroscopy. The structure and chemical composition of the nanoparticles was determined by SEM, XPS and EDX. We also proposed the mechanism of reduction of gold(III) oxide based on MS, IR and NMR data. Importantly, the synthetic protocol is general and applicable for the preparation of other coinage metal nanoparticles from the corresponding metal oxides. For instance, we demonstrated that the absence of halogen enables efficient alloying of metals when preparing gold–silver bimetallic nanoparticles.

Halogen doping of II-VI semiconductors during molecular beam epitaxy

Energy Technology Data Exchange (ETDEWEB)

Waag, A.; Litz, Th.; Fischer, F.; Heinke, H.; Scholl, S.; Hommel, D.; Landwehr, G. (Physikalisches Inst. der Univ. Wuerzburg (Germany)); Bilger, G. (Zentrum fuer Sonnenenergie und Wasserstoff-Forschung, Stuttgart (Germany))

1994-04-14

Results on the halogen doping of CdTe, (CdMn)Te as well as (CdMg)Te thin films and quantum well structures are reported. The structures were grown by molecular beam epitaxy. The samples have been investigated by Van der Pauw, photoconductivity, X-ray diffraction, XPS and SIMS measurements. ZnCl[sub 2] and ZnBr[sub 2] have been used as dopant sources. Free carrier concentrations at room temperature above 10[sup 18] cm[sup -3] can easily be achieved for CdTe for a wide range of Cd/Te flux ratios and substrate temperatures. In the ternary alloys, the free carrier concentration decreases drastically with increasing x-values, despite a constant incorporation of the dopant species. In addition, persistent photoconductivity has been observed in n-type doped ternary thin films at low temperatures. The decrease of the free carrier concentration with x-value is common to other wide-gap ternary alloys, and the reason for it is discussed in the frame of DX-like deep donor impurities in ternary II-VI compounds. In first experiments on planar halogen doping of CdTe, a doping level of 5x10[sup 18] cm[sup -3] could be reached in the doped regions, the highest value ever reported for CdTe. A clear influence of dopant incorporation on the structural quality of CdTe thin films has been seen even for dopant concentrations of as low as 10[sup 18] cm[sup -3]. The FWHM of the rocking curves decreased by a factor of 2 with increasing dopant incorporation. SIMS as well as XPS measurements demonstrate that the Cl/Zn and Br/Zn ratio in the doped films is 2/1, but no chemical shift corresponding to Zn-Cl or Zn-Br bonds could be detected. A model for the incorporation of the halogens is proposed on the basis of these results

Environmental and economic implications of a shift to halogen-free printed wiring boards

Energy Technology Data Exchange (ETDEWEB)

Bergendahl, C.G.; Johansson, G.; Zackrisson, M. [IVF Industrial Research and Development Corp., Moelndal (Sweden); Lichtenvort, K. [Technical Univ. of Berlin (Germany); Nyyssoenen, J. [Aspocomp Oy, Salo (Finland)

2004-07-01

The 'Restriction of Hazardous Substances Directive' (RoHS) and the 'Waste from Electrical and Electronic Equipment Directive' (WEEE) enforced by the European Commission require new materials and processes to be implemented in the production of electrical and electronic equipment (EEE). In response to this, the project grEEEn (Cost Management System for greening Electrical and Electronic Equipment) was defined and carried out within the 5th framework programme of the EU. This paper presents the grEEEn method and the outcome of applying the method on a case study. The study addressed the material shift in printed wiring boards (PWBs), from the traditional FR4 material containing halogenated flame retardants to halogen-free FR4 materials. The paper presents the product, process and scenario modelling and the results from analysing costs, environmental profile and legal compliance. (orig.)

Mercury Speciation and Bioaccumulation In Riparian and Upland Food Webs of the White Mountains Region, New Hampshire, USA

Science.gov (United States)

Rodenhouse, N.; Gebauer, R.; Lowe, W.; McFarland, K.; Bank, M. S.

2015-12-01

The soils and foods webs associated with mid to high elevation, forested, headwater streams are potential hotspots for mercury methylation and bioaccumulation but are not well studied. We tested the hypothesis that spatial variation in mercury bioaccumulation in upland taxa associated with headwater streams can be explained by variation in soil conditions promoting Hg methylation such as soil moisture, pH, and sulfur and organic matter content. We sampled at high (c. 700m) and mid elevation (c. 500m) in northern hardwood forest adjacent to and away from (75m) replicate headwater streams in the Hubbard Brook and Jeffers Brook watersheds of the White Mountains region, New Hampshire, USA. These forested watersheds differed primarily in soil calcium content and pH. We measured and assessed spatial variation in total Hg (THg) and methyl Hg (MeHg) concentrations in soils, insects, spiders, salamanders and birds. We also tested whether trophic position, as determined by nitrogen stable isotopes, was a major predictor of Hg bioaccumulation across these riparian and upland forest taxa. We found elevated levels of THg in all measured components of the food web, and conditions for methylation were better in the upland forest sites compared to the riparian sites located adjacent to headwater streams. Both THg and MeHg in biota were positively correlated with trophic position as indicated by 15N enrichment. In fact, trophic position was a better predictor of THg and MeHg content than spatial location, but the spatial patterning of bioaccumulation differed among taxa. Our data show that that significant Hg bioaccumulation and biomagnification can occur in soils and food webs of mid to high elevation temperate deciduous forests of the Northeast. They also suggest that mercury methylation in forested watersheds is a widespread phenomenon and not limited to areas with high soil moisture, such as lotic environments.

Optical modulation in nematic phase of halogen substituted hydrogen bonded liquid crystals

Science.gov (United States)

Vijayakumar, V. N.; Madhu Mohan, M. L. N.

2012-01-01

A series of halogen-substituted hydrogen-bonded liquid crystalline complexes have been designed and synthesised. A successful attempt has been made to form complementary hydrogen bonding between the dodecyloxy benzoic acid (12BAO) and halogen-substituted benzoic acids and the physical properties exhibited by the individual complexes are studied. The complexes obtained are analysed by polarising optical microscope (POM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and dielectric studies. The formation of complementary hydrogen bond is confirmed through FTIR spectra. An interesting feature of this series is the observation of a field-induced transition (FiT) in nematic phase. Another interesting phenomenon is the observation of a new smectic X phase (worm-like texture) in all the synthesised complexes. Dielectric relaxation studies in the smectic C phase of these hydrogen bonded complexes along with the Arrhenius and the Cole-Cole plots are discussed. Optical tilt angle in smectic C phase and the corresponding fitted data analysis concur with the Mean field theory prediction.

Hydrogenated and halogenated blue phosphorene as Dirac materials: A first principles study

International Nuclear Information System (INIS)

Sun, Minglei; Wang, Sake; Yu, Jin; Tang, Wencheng

2017-01-01

Highlights: • The fully hydrogenated and halogenated blue phosphorenes are 2D Dirac materials. • The Dirac cone in fluorinated and iodinated blue phosphorenes lies exactly at the Fermi level. • The mass density of hydrogenated and fluorinated blue phosphorenes is rather small. - Abstract: Using first-principles calculations, we systematically investigate the structures and electronic properties of fully hydrogenated and halogenated blue phosphorene (P_2X_2). All these systems possess Dirac cone at high-symmetry K point, which are mainly contributed by P s p_x p_y orbitals. The Dirac cone in P_2F_2 and P_2I_2 systems lies exactly at the Fermi level. Formation energy analysis denotes that all the systems are energetically stable except P_2I_2. The mass density for P_2H_2 and P_2F_2 systems is rather small. Our calculations proposed that these systems, especially P_2F_2 system, have great potential applications in future nanoelectronics.

Negative atomic halogens incident on argon and molecular nitrogen: electron detachment studies

International Nuclear Information System (INIS)

Jalbert, G; Medina, A; Magalhaes, S D; Wolff, W; Barros, A L F de; Carrilho, P; Rocha, A B; Faria, N V de Castro

2007-01-01

During the last years we have measured total detachment cross sections of atomic and cluster anions colliding with gases in the velocity range of 0.2 to 1.8 a.u. In particular, we measured negative atomic halogens incident on argon and molecular nitrogen. These last data are for the first time analyzed using the simple semi-classical model that we have developed. For that purpose, the values of elastic plus inelastic cross sections for impact of free electrons on Ar and N 2 , the latter showing a shape resonance, convoluted with the anion's outermost electron momentum distribution yielded the overall shape of the anion cross sections. Inclusion of a velocity independent additive term, interpreted as an effective area of the collision region, led to accurate absolute cross section values. The high affinity of the halogens and the existence of a not well described resonance in the e-N 2 collision, are characteristics that may be used to delimit the scope and validity of the model

Impact of humic substances on the aqueous solubility, uptake and bioaccumulation of platinum, palladium and rhodium in exposure studies with Dreissena polymorpha

International Nuclear Information System (INIS)

Sures, Bernd; Zimmermann, Sonja

2007-01-01

Zebra mussels (Dreissena polymorpha) were exposed to different types of water containing PGE salts (PtCl 4 , PdSO 4 , RhCl 3 ) to investigate the influence of humic substances on the aqueous solubility, uptake and bioaccumulation of noble metals. The results showed a time dependent decrease of the aqueous PGE concentrations in tank water for all groups. This could mainly be related to non-biological processes. The aqueous solubility of Pd and Rh was higher in humic water compared with non-chlorinated tap water, whereas Pt showed opposing results. Highest metal uptake rates and highest bioaccumulation plateaus were found for Pd, followed by Pt and Rh. Pd uptake and bioaccumulation was significantly hampered by humic substances, whose presence appear to increase Pt uptake and bioaccumulation. No clear trend emerged for Rh. Differences in effects of humic matter among the PGE may be explained by formation of metal complexes with different fractions of humic substances. - Precious metal accumulation in Dreissena polymorpha is affected by humic substances

A simple and automated sample preparation system for subsequent halogens determination: Combustion followed by pyrohydrolysis.

Science.gov (United States)

Pereira, L S F; Pedrotti, M F; Vecchia, P Dalla; Pereira, J S F; Flores, E M M

2018-06-20

A simple and automated system based on combustion followed by a pyrohydrolysis reaction was proposed for further halogens determination. This system was applied for digestion of soils containing high (90%) and also low (10%) organic matter content for further halogens determination. The following parameters were evaluated: sample mass, use of microcrystalline cellulose and heating time. For analytes absorption, a diluted alkaline solution (6 mL of 25 mmol L -1  NH 4 OH) was used in all experiments. Up to 400 mg of soil with high organic matter content and 100 mg of soil with low organic matter content (mixed with 400 mg of cellulose) could be completely digested using the proposed system. Quantitative results for all halogens were obtained using less than 12 min of sample preparation step (about 1.8 min for sample combustion and 10 min for pyrohydrolysis). The accuracy was evaluated using a certified reference material of coal and spiked samples. No statistical difference was observed between the certified values and results obtained by the proposed method. Additionally, the recoveries obtained using spiked samples were in the range of 98-103% with relative standard deviation values lower than 5%. The limits of quantification obtained for F, Cl, Br and I for soil with high (400 mg of soil) and low (100 mg of soil) organic matter were in the range of 0.01-2 μg g -1 and 0.07-59 μg g -1 , respectively. The proposed system was considered as a simple and suitable alternative for soils digestion for further halogens determination by ion chromatography and inductively coupled plasma mass spectrometry techniques. Copyright © 2018 Elsevier B.V. All rights reserved.

Modeling 137Cs bioaccumulation in the salmon–resident killer whale food web of the Northeastern Pacific following the Fukushima Nuclear Accident

International Nuclear Information System (INIS)

Alava, Juan José; Gobas, Frank A.P.C.

2016-01-01

To track the long term bioaccumulation of 137 Cs in marine organisms off the Pacific Northwest coast of Canada, we developed a time dependent bioaccumulation model for 137 Cs in a marine mammalian food web that included fish-eating resident killer whales. The model outcomes show that 137 Cs can be expected to gradually bioaccumulate in the food web over time as demonstrated by the increase of the apparent trophic magnification factor of 137 Cs, ranging from 0.76 after 1 month of exposure to 2.0 following 30 years of exposure. 137 Cs bioaccumulation is driven by relatively rapid dietary uptake rates, moderate depuration rates in lower trophic level organisms and slow elimination rates in high trophic level organisms. Model estimates of the 137 Cs activity in species of the food web, based on current measurements and forecasts of 137 Cs activities in oceanic waters and sediments off the Canadian Pacific Northwest, indicate that the long term 137 Cs activities in fish species including Pacific herring, wild Pacific salmon, sablefish and halibut will remain well below the current 137 Cs-Canada Action Level for consumption (1000 Bq/kg) following a nuclear emergency. Killer whales and Pacific salmon are expected to exhibit the largest long term 137 Cs activities and may be good sentinels for monitoring 137 Cs in the region. Assessment of the long term consequences of 137 Cs releases from the Fukushima aftermath should consider the extent of ecological magnification in addition to ocean dilution. - Highlights: • A food web bioaccumulation model to assess the biomagnification of 137 Cs is developed. • Cesium 137 exhibits bioaccumulation over time as simulated by the model. • Predicted activities in marine biota are below 137 Cs-food consumption benchmarks. • Long-term monitoring of 137 Cs in the ocean will improve the model predictions.

Mercury cycling in stream ecosystems. 3. Trophic dynamics and methylmercury bioaccumulation

Science.gov (United States)

Chasar, L.C.; Scudder, B.C.; Stewart, A.R.; Bell, A.H.; Aiken, G.R.

2009-01-01

Trophic dynamics (community composition and feeding relationships) have been identified as important drivers of methylmercury (MeHg) bioaccumulation in lakes, reservoirs, and marine ecosystems. The relative importance of trophic dynamics and geochemical controls on MeHg bioaccumulation in streams, however, remains poorly characterized. MeHg bioaccumulation was evaluated in eight stream ecosystems across the United States (Oregon, Wisconsin, and Florida) spanning large ranges in climate, landscape characteristics, atmospheric Hg deposition, and stream chemistry. Across all geographic regions and all streams, concentrations of total Hg (THg) in top predator fish and forage fish, and MeHg in invertebrates, were strongly positively correlated to concentrations of filtered THg (FTHg), filtered MeHg (FMeHg), and dissolved organic carbon (DOC); to DOC complexity (as measured by specific ultraviolet absorbance); and to percent wetland in the stream basins. Correlations were strongest for nonurban streams. Although regressions of log[Hg] versus ??15N indicate that Hg in biota increased significantly with increasing trophic position within seven of eight individual streams, Hg concentrations in top predator fish (including cutthroat, rainbow, and brown trout; green sunfish; and largemouth bass) were not strongly influenced by differences in relative trophic position. Slopes of log[Hg] versus ??15N, an indicator of the efficiency of trophic enrichment, ranged from 0.14 to 0.27 for all streams. These data suggest that, across the large ranges in FTHg (0.14-14.2 ng L-1), FMeHg (0.023-1.03 ng L-1), and DOC (0.50-61.0 mg L-1) found in this study, Hg contamination in top predator fish in streams likely is dominated by the amount of MeHg available for uptake at the base of the food web rather than by differences in the trophic position of top predator fish. ?? 2009 American Chemical Society.

Performance of a Throttle Cycle Refrigerator with Nitrogen-Hydrocarbon and Argon-Hydrocarbon Mixtures

Science.gov (United States)

Venkatarathnam, G.; Senthil Kumar, P.; Srinivasa Murthy, S.

2004-06-01

Throttle cycle refrigerators are a class of vapor compression refrigerators that can provide refrigeration at cryogenic temperatures and operate with refrigerant mixtures. The performance of our prototype refrigerators with nitrogen-hydrocarbon, nitrogen-hydrocarbon-helium and argon-hydrocarbon refrigerant mixtures is presented in this paper.

Petroleum hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in Hong Kong marine sediments

International Nuclear Information System (INIS)

Zheng, G.J.; Richardson, B.J.

1999-01-01

A total of 20 surficial sediment samples, obtained from Hong Kong coastal waters, were analysed for petroleum hydrocarbons (PHCs) and a suite of 15 polycyclic aromatic hydrocarbons (PAHs). The results indicate that Hong Kong coastal sediments are often seriously polluted with petroleum related hydrocarbons. This is especially so in heavily urbanised or industrialized localities, such as Kowloon Bay (Victoria Harbour), Tsing Yi North and Tolo Harbour. Petroleum hydrocarbon pollutants in marine sediments are believed to be mainly derived from the transportation of oil, shipping activities, spillages, and industrial, stormwater and waste wastewater discharge. The ratio of unresolved complex mixture (UCM) to n-alkanes, carbon preference index (CPI), and n-C 16 values indicate that the main contribution to petroleum hydrocarbon contamination is via oil and its products. Pollutant sources appear to be stable and continuing when compared with previous data. (author)

Purifying hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Demoulins, H D; Garner, F H

1923-02-07

Hydrocarbon distillates, including natural gases and vapors produced by cracking hydrocarbon oils, are desulfurized etc. by treating the vapor with an aqueous alkaline solution of an oxidizing agent. The hydrocarbons may be previously purified by sulfuric acid. In examples aqueous solutions of sodium or calcium hydrochlorite containing 1.5 to 5.0 grams per liter of available chlorine and sufficient alkali to give an excess of 0.1 percent in the spent reagent are preheated to the temperature of the vapor, and either sprayed or atomized into the vapors near the outlet of the dephlegmator or fractionating tower, or passed in countercurrent to the vapors through one or a series of scrubbers.

Influence of eutrophication on metal bioaccumulation and oral bioavailability in oysters, Crassostrea angulata.

Science.gov (United States)

Li, Shun-Xing; Chen, Li-Hui; Zheng, Feng-Ying; Huang, Xu-Guang

2014-07-23

Oysters (Crassostrea angulata) are often exposed to eutrophication. However, how these exposures influence metal bioaccumulation and oral bioavailability (OBA) in oysters is unknown. After a four month field experimental cultivation, bioaccumulation factors (BAF) of metals (Fe, Cu, As, Cd, and Pb) from seawater to oysters and metal oral bioavailability in oysters by bionic gastrointestinal tract were determined. A positive effect of macronutrient (nitrate N and total P) concentration in seawater on BAF of Cd in oysters was observed, but such an effect was not significant for Fe, Cu, Pb, and As. Only OBA of As was significantly positively correlated to N and P contents. For Fe, OBA was negatively correlated with N. The regular variation of the OBA of Fe and As may be due to the effect of eutrophication on the synthesis of metal granules and heat-stable protein in oysters, respectively.

Bioaccumulation of lead nitrate in freshwater crayfish (Astacus leptodactylus) tissues under aquaculture conditions.

Science.gov (United States)

Naghshbandi, N; Zare, S; Heidari, R; Soleimani Palcheglu, S

2007-09-15

The aim of this research was to evaluate the amount of lead in the tissue of Astacus leptodactylus especially in their muscle which the consumed part of their body. In this study the crayfish was exposed to intermediate concentration of lead nitrate (500 microg L(-1)) for periods up to 3 weeks. In the first, second and third weeks bioaccumulation in various tissues was under investigation. The data of toxicological analysis obtained by the method of atomic absorption revealed that the levels of bioaccumulation of metal are different in various tissues of this crayfish. The accumulation of the lead in gills was the highest and in muscles was lowest degree. The amount of heavy metals in the tissues of crayfish was as follow. Gills>exoskeleton>hepatopancreas (digestive glands)>digestive tract>green gland>testis and ovary>muscles.

Biosorption of Strontium from Simulated Nuclear Wastewater by Scenedesmus spinosus under Culture Conditions: Adsorption and Bioaccumulation Processes and Models

Science.gov (United States)

Liu, Mingxue; Dong, Faqin; Kang, Wu; Sun, Shiyong; Wei, Hongfu; Zhang, Wei; Nie, Xiaoqin; Guo, Yuting; Huang, Ting; Liu, Yuanyuan

2014-01-01

Algae biosorption is an ideal wastewater treatment method when coupled with algae growth and biosorption. The adsorption and bioaccumulation of strontium from simulated nuclear wastewater by Scenedesmus spinosus were investigated in this research. One hundred mL of cultured S. spinosus cells with a dry weight of 1.0 mg in simulated nuclear wastewater were used to analyze the effects on S. spinosus cell growth as well as the adsorption and bioaccumulation characters under conditions of 25 ± 1 °C with approximately 3,000 lux illumination. The results showed that S. spinosus had a highly selective biosorption capacity for strontium, with a maximum bioremoval ratio of 76%. The adsorbed strontium ion on cell walls was approximately 90% of the total adsorbed amount; the bioaccumulation in the cytoplasm varied by approximately10%. The adsorption quantity could be described with an equilibrium isotherm. The pseudo-second-order kinetic model suggested that adsorption was the rate-limiting step of the biosorption process. A new bioaccumulation model with three parameters was proposed and could give a good fit with the experiment data. The results suggested that S. spinosus may be a potential biosorbent for the treatment of nuclear wastewater in culture conditions. PMID:24919131

Biosorption of Strontium from Simulated Nuclear Wastewater by Scenedesmus spinosus under Culture Conditions: Adsorption and Bioaccumulation Processes and Models

Directory of Open Access Journals (Sweden)

Mingxue Liu

2014-06-01

Full Text Available Algae biosorption is an ideal wastewater treatment method when coupled with algae growth and biosorption. The adsorption and bioaccumulation of strontium from simulated nuclear wastewater by Scenedesmus spinosus were investigated in this research. One hundred mL of cultured S. spinosus cells with a dry weight of 1.0 mg in simulated nuclear wastewater were used to analyze the effects on S. spinosus cell growth as well as the adsorption and bioaccumulation characters under conditions of 25 ± 1 °C with approximately 3,000 lux illumination. The results showed that S. spinosus had a highly selective biosorption capacity for strontium, with a maximum bioremoval ratio of 76%. The adsorbed strontium ion on cell walls was approximately 90% of the total adsorbed amount; the bioaccumulation in the cytoplasm varied by approximately10%. The adsorption quantity could be described with an equilibrium isotherm. The pseudo-second-order kinetic model suggested that adsorption was the rate-limiting step of the biosorption process. A new bioaccumulation model with three parameters was proposed and could give a good fit with the experiment data. The results suggested that S. spinosus may be a potential biosorbent for the treatment of nuclear wastewater in culture conditions.

Phosphorylated lignin as a halogen-free flame retardant additive for epoxy composites

Science.gov (United States)

Gamini P. Mendis; Sydney G. Weiss; Matthew Korey; Charles R. Boardman; Mark Dietenberger; Jeffrey P. Youngblood; John A. Howarter

2016-01-01

Sustainable, non-halogenated flame retardants are desired for a variety of industry applications. Lignin, as an industrially processed wood derivative, has been examined as a potential sustainable flame retardant additive to polymer systems. Here, the lignin is phosphorylated using a pyridine-catalysed esterification reaction with diphenyl phosphoryl chloride to...

Role of environmental factors and microorganisms in determining the fate of polycyclic aromatic hydrocarbons in the marine environment

Science.gov (United States)

Duran, Robert; Cravo-Laureau, Cristiana

2016-01-01

Polycyclic aromatic hydrocarbons (PAHs) are widespread in marine ecosystems and originate from natural sources and anthropogenic activities. PAHs enter the marine environment in two main ways, corresponding to chronic pollution or acute pollution by oil spills. The global PAH fluxes in marine environments are controlled by the microbial degradation and the biological pump, which plays a role in particle settling and in sequestration through bioaccumulation. Due to their low water solubility and hydrophobic nature, PAHs tightly adhere to sediments leading to accumulation in coastal and deep sediments. Microbial assemblages play an important role in determining the fate of PAHs in water and sediments, supporting the functioning of biogeochemical cycles and the microbial loop. This review summarises the knowledge recently acquired in terms of both chronic and acute PAH pollution. The importance of the microbial ecology in PAH-polluted marine ecosystems is highlighted as well as the importance of gaining further in-depth knowledge of the environmental services provided by microorganisms. PMID:28201512

Bioaccumulation and excretion of enantiomers of myclobutanil in Tenebrio molitor larvae through dietary exposure.

Science.gov (United States)

Lv, Xiaotian; Liu, Chen; Li, Yaobin; Gao, Yongxin; Guo, Baoyuan; Wang, Huili; Li, Jianzhong

2013-12-01

The bioaccumulation and excretion of enantiomers of myclobutanil in Tenebrio molitor larvae through dietary exposure under laboratory conditions were investigated using high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) based on a ChiralcelOD-3R [cellulosetris-tris-(3, 5-dichlorophenyl-carbamate)] column. The wheat bran fed to Tenebrio molitor larvae was spiked with racemic myclobutanil at two dose levels of 20 mg/kg and 2 mg/kg (dry weight). The results showed that there was a significant trend of enantioselective bioaccumulation in the larvae with a preferential accumulation of (-)-myclobutanil in 20 mg/kg dose exposure, but it was not obviously observed in the 2 mg/kg dose group. A kinetic model considering enantiomerization between the two enantiomers based on first-order reactions was built and the rate constants were estimated to discuss the kinetic reason for the different concentrations of individual enantiomers in the larvae. The approximations implied an inversion between the two enantiomers with a relatively higher rate of the inversion from (-)-myclobutanil to (+)-myclobutanil. Meanwhile, analysis of data of excretion samples suggested the active excretion is probably an important pathway for the insect to eliminate myclobutanil rapidly with nonenantioselectivity as a passive transport process, which was consistent with the low accumulation efficiency of myclobutanil measured by BAF (bioaccumulation factor). © 2013 Wiley Periodicals, Inc.

Diversity of band gap and photoluminescence properties of lead halide perovskite: A halogen-dependent spectroscopic study

Science.gov (United States)

Yu, Wenlei; Jiang, Yunfeng; Zhu, Xiuwei; Luo, Chunhua; Jiang, Kai; Chen, Liangliang; Zhang, Juan

2018-05-01

The effects of halogen substitution on microstructure, optical absorption, and phonon modes for perovskite CH3NH3PbX3 (MAPbX3, X = I/Br/Cl) films grown on FTO substrates have been investigated. The X-ray diffraction analysis exhibited good crystallization, and the strong diffraction peak assigned to (1 0 0) c for X = Br/Cl shifted toward a higher angle compared to (1 1 0) t of MAPbI3. Band-gap tuning from 1.63 to 2.37 to 3.11 eV in the I-Br-Cl series can be found due to the halogen effects. These energy values closely match the positions of peak determined from photoluminescence experiments. The remarkable absorption dip and emission peak appear for the MAPbBr3, suggesting higher crystallinity under the same preparation conditions. The wavenumbers of main IR-vibrations slightly decrease with ionic radius of the halogen increasing (in the order of Cl-Br-I), which related to the increasing polarizability. These results provide important progress towards the understanding of the halide role in the realization of high performance MAPbX3-based solar cells.

Methylmercury cycling, bioaccumulation, and export from agricultural and non-agricultural wetlands in the Yolo Bypass

Science.gov (United States)

Windham-Myers, Lisamarie; Marvin-DiPasquale, Mark; Fleck, Jacob; Alpers, Charles N.; Ackerman, Joshua T.; Eagles-Smith, Collin A.; Stricker, Craig; Stephenson, Mark; Feliz, David; Gill, Gary; Bachand, Philip; Brice, Ann; Kulakow, Robin

2010-01-01

This 18-month field study addresses the seasonal and spatial patterns and processes controlling methylmercury (MeHg) production, bioaccumulation, and export from natural and agricultural wetlands of the Yolo Bypass Wildlife Area (YBWA). The data were collected in conjuntion with a Proposition 40 grant from the State Water Resources Control Board in support of the development of Best Management Practices (BMP's) for reducing MeHg loading from agricultural lands in the wetland-dominated Yolo Bypass to the Sacramento-San Joaquin River Delta. The four managemenr-based questions addressed in this study were: 1. Is there a different among agricultural and managfed wetland types in terms of Me Hg dynamic (production, degradation, bioaccumulation, or export)?

Linking precious metal enrichment and halogen cycling in mafic magmatic systems: insights from the Rum layered intrusion, NW Scotland

Science.gov (United States)

Kelly, A. P.; O'Driscoll, B.; Clay, P. L.; Burgess, R.

2017-12-01

Layered intrusions host the world's largest known concentrations of the platinum-group elements (PGE). Emphasis has been attached to the role of halogen-bearing fluids in concentrating the precious metals, but whether this occurs at the magmatic stage, or via subsequent metasomatism, is actively debated. One obstacle to progress has been the analytical difficulty of measuring low abundances of the halogens in the cumulate products of layered intrusions. To elucidate the importance of the halogens in facilitating PGE-mineralisation, as well as fingerprint halogen provenance and assess the importance of halogen cycling in mafic magma systems more generally, a suite of samples encompassing different stages of activity of the Palaeogene Rum layered intrusion was investigated. Halogen abundances were measured by neutron irradiation noble gas mass spectrometric analysis, permitting the detection of relatively low (ppm-ppb) abundances of Cl, Br and I in mg-sized samples. The samples include PGE-enriched chromite seams, various cumulates (e.g., peridotites), picrites (approximating the Rum parental magma), and pegmatites representing volatile-rich melts that circulated the intrusion at a late-stage in its solidification history. The new data reveal that PGE-bearing chromite seams contain relatively low Cl concentrations (2-3 ppm), with high molar ratios of Br/Cl and I/Cl (0.005 and 0.009, respectively). The picrites and cumulates have Br/Cl and I/Cl ratios close to sub-continental lithospheric mantle values of approximately 0.0013 and 0.00002, respectively, and thus likely reflect the Rum magma source region. A positive correlation between Cl and Br signifies comparable partitioning behaviour in all samples. However, I is more variable, displaying a positive correlation with Cl for more primitive samples (e.g. picrite and peridotite), and seemingly decoupling from Br and Cl in chromite seams and pegmatites. The relative enrichment of I over Cl in the chromite seams points

Tumour radiosensitization with the halogenated pyrimidines 5'-bromo-and 5'-iododeoxyuridine

Energy Technology Data Exchange (ETDEWEB)

Epstein, A.H.; Cook, J.A.; Goffman, T. (National Cancer Inst., Bethesda, MD (United States)); Glatstein, E. (Texas Univ., Dallas, TX (United States). Southwestern Medical Center)

1993-02-01

The authors review studies of the use of iododeoxyuridine (IdUrd) and bromodeoxyuridine as radiosensitizers and attempt to correlate the clinical outcome for patients treated with radiation and IdUrd with the extent of halogenated pyrimidine cellular uptake and incorporation. (U.K.).

Molecular recognition of halogen-tagged aromatic VOCs at the air-silicon interface.

Science.gov (United States)

Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Gurrieri, Ettore; Betti, Paolo; Dalcanale, Enrico

2010-01-14

Selective and reversible complexation of halogen-tagged aromatic VOCs by a quinoxaline cavitand-decorated Si surface is demonstrated. The specific host-guest interactions of the Si-bonded receptors are proved to be responsible of the surface recognition properties, while extracavity non specific adsorptions are totally suppressed compared to the bulk material.

Lettuce irrigated with contaminated water: Photosynthetic effects, antioxidative response and bioaccumulation of microcystin congeners.

Science.gov (United States)

Bittencourt-Oliveira, Maria do Carmo; Cordeiro-Araújo, Micheline Kézia; Chia, Mathias Ahii; Arruda-Neto, João Dias de Toledo; de Oliveira, Ênio Tiago; dos Santos, Flávio

2016-06-01

The use of microcystins (MCs) contaminated water to irrigate crop plants represents a human health risk due to their bioaccumulation potential. In addition, MCs cause oxidative stress and negatively influence photosynthetic activities in plants. The present study was aimed at investigating the effect of MCs on photosynthetic parameters and antioxidative response of lettuce. Furthermore, the bioaccumulation factor (BAF) of total MCs, MC-LR and MC-RR in the vegetable after irrigation with contaminated water was determined. Lettuce crops were irrigated for 15 days with water containing cyanobacterial crude extracts (Microcystis aeruginosa) with MC-LR (0.0, 0.5, 2.0, 5.0 and 10.0 µg L(-1)), MC-RR (0.0, 0.15, 0.5, 1.5 and 3.0 µg L(-1)) and total MCs (0.0, 0.65, 2.5, 6.5 and 13.0 µg L(-1)). Increased net photosynthetic rate, stomatal conductance, leaf tissue transpiration and intercellular CO2 concentration were recorded in lettuce exposed to different MCs concentrations. Antioxidant response showed that glutathione S-transferase activity was down-regulated in the presence of MCs. On the other hand, superoxide dismutase, catalase and peroxidase activities were upregulated with increasing MCs concentrations. The bioaccumulation factor (BAF) of total MCs and MC-LR was highest at 6.50 and 5.00 µg L(-1), respectively, while for MC-RR, the highest BAF was recorded at 1.50 µg L(-1) concentration. The amount of total MCs, MC-LR and MC-RR bioacumulated in lettuce was highest at the highest exposure concentrations. However, at the lowest exposure concentration, there were no detectable levels of MC-LR, MC-RR and total MCs in lettuce. Thus, the bioaccumulation of MCs in lettuce varies according to the exposure concentration. In addition, the extent of physiological response of lettuce to the toxins relies on exposure concentrations. Copyright © 2016 Elsevier Inc. All rights reserved.

Monitoring of environmental exposure to polycyclic aromatic hydrocarbons: a review.

Science.gov (United States)

Srogi, K

2007-01-01

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds with two or more fused aromatic rings. They have a relatively low solubility in water, but are highly lipophilic. Most of the PAHs with low vapour pressure in the air are adsorbed on particles. When dissolved in water or adsorbed on particulate matter, PAHs can undergo photodecomposition when exposed to ultraviolet light from solar radiation. In the atmosphere, PAHs can react with pollutants such as ozone, nitrogen oxides and sulfur dioxide, yielding diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively. PAHs may also be degraded by some microorganisms in the soil. PAHs are widespread environmental contaminants resulting from incomplete combustion of organic materials. The occurrence is largely a result of anthropogenic emissions such as fossil fuel-burning, motor vehicle, waste incinerator, oil refining, coke and asphalt production, and aluminum production, etc. PAHs have received increased attention in recent years in air pollution studies because some of these compounds are highly carcinogenic or mutagenic. Eight PAHs (Car-PAHs) typically considered as possible carcinogens are: benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene (B(a)P), dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene and benzo(g,h,i)perylene. In particular, benzo(a)pyrene has been identified as being highly carcinogenic. The US Environmental Protection Agency (EPA) has promulgated 16 unsubstituted PAHs (EPA-PAH) as priority pollutants. Thus, exposure assessments of PAHs in the developing world are important. The scope of this review will be to give an overview of PAH concentrations in various environmental samples and to discuss the advantages and limitations of applying these parameters in the assessment of environmental risks in ecosystems and human health. As it well known, there is an increasing trend to use the behavior of pollutants (i.e. bioaccumulation) as well

Bioremediation of polyaromatic hydrocarbons (PAHs using rhizosphere technology

Directory of Open Access Journals (Sweden)

Sandeep Bisht

2015-03-01

Full Text Available The remediation of polluted sites has become a priority for society because of increase in quality of life standards and the awareness of environmental issues. Over the past few decades there has been avid interest in developing in situ strategies for remediation of environmental contaminants, because of the high economic cost of physicochemical strategies, the biological tools for remediation of these persistent pollutants is the better option. Major foci have been considered on persistent organic chemicals i.e.polyaromatic hydrocarbons (PAHs due to their ubiquitous occurrence, recalcitrance, bioaccumulation potential and carcinogenic activity. Rhizoremediation, a specific type of phytoremediation that involves both plants and their associated rhizospheric microbes is the creative biotechnological approach that has been explored in this review. Moreover, in this review we showed the significance of rhizoremediation of PAHs from other bioremediation strategies i.e. natural attenuation, bioaugmentation and phytoremediation and also analyze certain environmental factor that may influence the rhizoremediation technique. Numerous bacterial species were reported to degrade variety of PAHs and most of them are isolated from contaminated soil, however few reports are available from non contaminated soil. Pseudomonas aeruginosa, Pseudomons fluoresens, Mycobacterium spp., Haemophilus spp., Rhodococcus spp., Paenibacillus spp. are some of the commonly studied PAH-degrading bacteria. Finally, exploring the molecular communication between plants and microbes, and exploiting this communication to achieve better results in the elimination of contaminants, is a fascinating area of research for future perspective.

Bioremediation of polyaromatic hydrocarbons (PAHs) using rhizosphere technology

Science.gov (United States)

Bisht, Sandeep; Pandey, Piyush; Bhargava, Bhavya; Sharma, Shivesh; Kumar, Vivek; Sharma, Krishan D.

2015-01-01

The remediation of polluted sites has become a priority for society because of increase in quality of life standards and the awareness of environmental issues. Over the past few decades there has been avid interest in developing in situ strategies for remediation of environmental contaminants, because of the high economic cost of physicochemical strategies, the biological tools for remediation of these persistent pollutants is the better option. Major foci have been considered on persistent organic chemicals i.e. polyaromatic hydrocarbons (PAHs) due to their ubiquitous occurrence, recalcitrance, bioaccumulation potential and carcinogenic activity. Rhizoremediation, a specific type of phytoremediation that involves both plants and their associated rhizospheric microbes is the creative biotechnological approach that has been explored in this review. Moreover, in this review we showed the significance of rhizoremediation of PAHs from other bioremediation strategies i.e. natural attenuation, bioaugmentation and phytoremediation and also analyze certain environmental factor that may influence the rhizoremediation technique. Numerous bacterial species were reported to degrade variety of PAHs and most of them are isolated from contaminated soil, however few reports are available from non contaminated soil. Pseudomonas aeruginosa , Pseudomons fluoresens , Mycobacterium spp., Haemophilus spp., Rhodococcus spp., Paenibacillus spp. are some of the commonly studied PAH-degrading bacteria. Finally, exploring the molecular communication between plants and microbes, and exploiting this communication to achieve better results in the elimination of contaminants, is a fascinating area of research for future perspective. PMID:26221084

Effects of microplastic on fitness and PCB bioaccumulation by the lugworm Arenicola marina

NARCIS (Netherlands)

Besseling, E.; Wegner, A.; Foekema, E.M.; Heuvel_Greve, van den M.J.; Koelmans, A.A.

2013-01-01

It has been speculated that marine microplastics may cause negative effects on benthic marine organisms and increase bioaccumulation of persistent organic pollutants (POPs). Here, we provide the first controlled study of plastic effects on benthic organisms including transfer of POPs. The effects of

Heavy metal bioaccumulation by the important food plant, olea europaea L., in an ancient metalliferous polluted area of Cyprus

OpenAIRE

Wilson, B; Pyatt, FB

2007-01-01

Aspects of the bioaccumulation of heavy metals are reviewed and possible evidence of homeostasis is highlighted. Examination and analysis of olive (Olea europaea L.) trees growing in close proximity to a copper dominated spoil tip dating from at least 2000 years BP, on the island of Cyprus, revealed both bioaccumulation and partitioning of copper, lead and zinc in various parts of the tree. A factor to quantify the degree of accumulation is illustrated and a possible seed protective mechanism...