Blood plasma clinical-chemical parameters as biomarker endpoints for organohalogen contaminant exposure in Norwegian raptor nestlings.

Raptors are exposed to biomagnifying and toxic organohalogenated compounds (OHCs) such as organochlorines, brominated flame retardants and perfluorinated compounds. To investigate how OHC exposure may affect biochemical pathways we collected blood plasma from Norwegian northern goshawk (n=56), golden eagle (n=12) and white-tailed eagle (n=36) nestlings during three consecutive breeding seasons. We found that blood plasma concentrations of calcium, sodium, creatinine, cholesterol, albumin, total protein, urea, inorganic phosphate, protein:creatinine, urea:creatinine and uric acid:creatinine ratios and liver enzymes ALKP and ALAT were positively correlated to PCBs, chlordanes, p,p'-DDE, HCB, PFCs and/or PBDEs. Total bilirubin and glucose were negatively correlated to PCBs while magnesium and potassium were negatively correlated to HCB and p,p'-DDE. In addition, protein:creatinine and ALAT were also negatively correlated to PCBs and PFCs, respectively. The most significant relationships were found for the highly contaminated northern goshawks and white-tailed eagles. The statistical relationships between OHCs and BCCPs indicate that biochemical pathways could be influenced while it is uncertain if such changes have any health effects. The OHC concentrations were below concentrations causing reproductive toxicity in adults of other raptor species but similar to those of concern for endocrine disruption of thyroid hormones in e.g., bald eagles.

Effects of chain length, chlorination degree, and structure on the octanol-water partition coefficients of polychlorinated n-alkanes.

Log octanol-water partition coefficients (log Kow) of 40 synthesized polychlorinated n-alkanes (PCAs) with different chlorination degrees were determined using reversed-phase high performance liquid chromatography (RP-HPLC). In addition, log Kow values of a technical mixture namely Cereclor 63L as well as 15 individual in house synthesized C10, C11, and C12 chloroalkanes with known chlorine positions were estimated. Based on these results, the effects of chain length, chlorination degree, and structure were explored. The estimated log Kow values ranged from 4.10 (polychlorinated n-decanes with 50.2% chlorine content) to 11.34 (polychlorinated n-octacosanes with 54.8% chlorine content) for PCAs and from 3.82 (1,2,5,6,9,10-hexachlorodecane) to 7.75 (1,1,1,3,9,11,11,11-octachlorododecane) for the individual chloroalkanes studied. The results showed that log Kow value was influenced linearly at a given chlorine content by chain length, while a polynominal effect was observed in dependence on the chlorination degree of an alkane chain. Chlorine substitution pattern influenced markedly the log Kow value of chloroalkanes.

Characterization of certified reference material for quantification of polychlorinated biphenyls and organochlorine pesticides in fish.

Fish certified reference material (CRM), NMIJ CRM 7404-a, for the analysis of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) was developed by the National Metrology Institute of Japan, part of the National Institute of Advanced Industrial Science and Technology. Fish samples (Japanese seabass) used for the preparation of the CRM were collected from Tokyo Bay, and the edible part was freeze-dried, pulverized, sieved, homogenized, and sterilized by gamma-irradiation. This sample is in the form of a powder comprising approximately 10 g stored in a brown glass bottle. The certification was carried out using multiple analytical methods such as pressurized liquid extraction, Soxhlet extraction, saponification, and homogenization to ensure the reliability of analytical results; the certified values of target PCBs (PCB 28, PCB 70, PCB 105, PCB 153, and PCB 170) and OCPs (trans-nonachlor, dieldrin, p,p'-DDE, p,p'-DDT, and p,p'-DDD) were 1.05-14.0 microg kg(-1) and 1.57-18.0 microg kg(-1) for PCBs and OCPs, respectively. This is the first fish powder CRM in which PCBs and OCPs were determined by isotope dilution mass spectrometry.

Development of an analytical method based on microwave-assisted extraction and solid phase extraction cleanup for the determination of organochlorine pesticides in animal feed.

A method to determine 21 organochlorine pesticides in animal feed samples using microwave assisted extraction and solid phase extraction cleanup was optimised regarding its main parameters. After extraction with hexane-acetone (50:50), three different sorbents (alumina/ENVI-Florisil, ENVI-Carb and ENVI-Carb II/PSA) were assayed for the cleanup step. Analytes were eluted with hexane-ethyl acetate (80:20) and determined by gas chromatography and electron capture detection followed by gas chromatography-mass spectrometry. ENVI-Carb and ENVI-Carb II/PSA provided colourless eluates but fewer interferent compounds were found in ENVI-Carb II/PSA chromatograms, so this system was selected to carry out the purification of the extracts. The analytical recoveries obtained with this method were close to 100% in most cases with relative standard deviations lower than 10%. These percentages were similar to those obtained with the Soxhlet extraction procedure, which shows the method suitable for the determination of organochlorine pesticides in animal feed material. The method was also validated with the analysis of a certified reference material (CRM-115 BCR), and the results obtained were in good accordance with the certified values.

Persistent organochlorine pesticides in aquatic environments and fishes in Taiwan and their risk assessment.

Organochlorine pesticides (OCPs) are ubiquitous contaminants with high bioaccumulation and persistence in the environment; they can have adverse effects in humans and animals. This study examined residual concentrations in water, sediments, and fishes as well as the association between the health risks of OCPs and fish consumption in the Taiwanese population. Various water and sediment samples from Taiwanese aquaculture and fish samples from different sources were collected and analyzed through gas chromatography tandem mass spectrometry to determine the concentrations of 20 OCPs, namely, aldrin; cis-chlordane; trans-chlordane; dieldrin; endrin; alpha-endosulfan; beta-endosulfan; heptachlor; hexachlorobenzene; alpha-hexachlorocyclohexane; beta-hexachlorocyclohexane; lindane; mirex; pentachlorobenzene; o,p'-dichlorodiphenyltrichloroethane (DDT); p,p'-DDT; and DDT metabolites (o,p'-dichlorodiphenyldichloroethane [DDD]; p,p'-DDD; o,p'-dichlorodiphenyldichloroethylene [DDE]; and p,p'-DDE). None of the analyzed samples was positive for OCP contamination, suggesting no new input pollution from the land through washing into Taiwanese aquaculture environments. However, OCP residues were detected in fishes caught along the coast, namely, skipjack tuna and bigeye barracuda, and in imported fishes, such as codfish and salmon. DDT was the predominant pesticide. The contamination pattern of persistent organic pollutants was as follows: dieldrin > cis-chlordane > hexachlorobenzene, with average concentrations ranging from 0.09 to 2.74 ng/g. The risk was assessed in terms of the estimated daily intake (EDI) for potential adverse indices; the EDI of OCP residues was lower than 1% of the acceptable daily intake established by the Food and Agriculture Organization of the United Nations and World Health Organization. The assessed risk was negligible and considered to be at a safe level, suggesting no association between fish consumption and risks to human health in Taiwan. However, a continuous monitoring program for OCP residues in fishes is necessary to further assess the possible effects on human health.

Organochlorine residues in fish and water samples from lake victoria, Uganda.

Nile tilapia and Nile perch samples from Lake Victoria were analyzed for lindane (gamma-1,2,3,4,5,6-hexachlorocyclohexane), aldrin (1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene), alpha-endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3- benzo(e) dioxathiepin-3-oxide), dieldrin (1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-1,4,5,8-dimethanonaphthalene), DDE (p,p'-1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene), and DDT (p,p'-1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane). No significant difference (alpha = 0.05) in the residue levels between fish types for lindane, alpha-endosulfan, p,p'-DDE, p,p'-DDT, and dieldrin was observed. The aldrin levels in Nile perch (Lates niloticus) were significantly higher than the levels in Nile tilapia (Oreochromis niloticus). No difference was observed in the distribution of residues in the different parts of Nile tilapia, although a difference for p,p'-DDE was observed in the Nile perch. No significant difference was observed in the average fat content of the tissue of Nile perch and Nile tilapia; however, the distribution of fat was significantly different in the different parts of the fish, with the abdominal portion having the highest amount of fat. There was no correlation observed in this study between fat content and organochlorine concentration. Lower p,p'-DDT residues levels compared with the p,p'-DDE levels observed in this study indicate that DDT is no longer in use. The levels of organochlorine pesticide residues found in fish samples in this study were below the FAO, U.S. FDA, Australian, and German extraneous residue limits and maximum residue limits. The concentration of organochlorine residues in surface water within the Napoleon Gulf of Lake Victoria was below detection limit (0.1 microg L(-1)).

Characterising the individual health risk in infants exposed to organochlorine pesticides via breast milk by applying appropriate margins of safety derived from estimated daily intakes.

Milk secretion being an important way of elimination of organochlorine pesticides (OCPs) poses a concern due to potential risk for breastfed infants. This study aims to provide a tool for assessing such risks to infants exposed to OCPs (through accumulation in the mother's body), using calculated individual margins of safety (MoS). Selected OCPs included; p,p'-DDT, p,p'-DDD, p,p'-DDE, ß-HCH, γ-HCH and HCB which were analysed in 28 samples of maternal milk. The highest intakes were recorded for p,p'-DDE (at 2.90 µg kg(-1)bw d(-1)) whilst the lowest was for γ-HCH, (at 0.019 µg kg(-1)bwd(-1)). For the risk characterisation purposes MoSs were calculated for the compounds for which toxicological reference values (e.g. ADI, TDI) were adopted. The MoS for average ∑DDT concentrations was found to be relatively low (2.82) somewhat similar to that for HCB at 7.08, and for γ-HCH, the MoS was substantially higher at 263.1. This, however does not take into account the extremely high individual concentrations. Thus, it was decided to calculate estimated daily intake (EDI) values based on OCP levels in individual milk samples. MoS levels of <1 (meaning unacceptable risk) were noted both for HCB in one sample as well as for ∑DDT in 3 samples indicating likely threats to infant's health. The lowest MoS noted for γ-HCH equalled to 60.6, indicating that this compound was not a threat to the health of any of the breastfed infants from the study group.

A novel abbreviation standard for organobromine, organochlorine and organophosphorus flame retardants and some characteristics of the chemicals.

Ever since the interest in organic environmental contaminants first emerged 50years ago, there has been a need to present discussion of such chemicals and their transformation products using simple abbreviations so as to avoid the repetitive use of long chemical names. As the number of chemicals of concern has increased, the number of abbreviations has also increased dramatically, sometimes resulting in the use of different abbreviations for the same chemical. In this article, we propose abbreviations for flame retardants (FRs) substituted with bromine or chlorine atoms or including a functional group containing phosphorus, i.e. BFRs, CFRs and PFRs, respectively. Due to the large number of halogenated and organophosphorus FRs, it has become increasingly important to develop a strategy for abbreviating the chemical names of FRs. In this paper, a two step procedure is proposed for deriving practical abbreviations (PRABs) for the chemicals discussed. In the first step, structural abbreviations (STABs) are developed using specific STAB criteria based on the FR structure. However, since several of the derived STABs are complicated and long, we propose instead the use of PRABs. These are, commonly, an extract of the most essential part of the STAB, while also considering abbreviations previously used in the literature. We indicate how these can be used to develop an abbreviation that can be generally accepted by scientists and other professionals involved in FR related work. Tables with PRABs and STABs for BFRs, CFRs and PFRs are presented, including CAS (Chemical Abstract Service) numbers, notes of abbreviations that have been used previously, CA (Chemical Abstract) name, common names and trade names, as well as some fundamental physico-chemical constants.

Persistent organic pollutants in sediments from Sai Gon-Dong Nai River basin, Vietnam: levels and temporal trends.

Surficial sediment samples were collected from Hochiminh City canals, the Sai Gon-Dong Nai River, and its estuary, one of the most predominant industrial areas in Hochiminh City, southern Vietnam, for determination of selected persistent organic pollutants (POPs). Contamination pattern was as follows: PCBs > or = DDTs > HCB > CHLs > HCHs. Concentrations of PCBs and DDTs ranged from 0.50-150 ng/g and 0.15-72 ng/g dry wt, respectively. On the other hand, concentrations of CHLs, HCHs, and HCB were mostly <2 ng/g dry wt. Levels of the all organochlorines (OCs) in Hochiminh City canals were significantly higher than those in the other areas, indicating the urban areas as major pollution sources to the aquatic environment. The contamination pattern was PCBs > DDTs in the city canals but PCBs < DDTs in the downstream and the estuary, suggesting particularly high contamination by PCBs in the city. Examination of DDTs composition and their ratios demonstrated continuous input of this pesticide to the city canals. However, the combination of our data and those from available literature implies a decreasing trend of PCBs and DDTs in the environment. DDTs concentrations have been reduced 50% after approximately 5 years. Composition of CHLs in the sediment from Hochiminh City canals was comparable to those of common technical mixtures, suggesting continuous input of CHLs to the environment. CHLs might be in use for purposes like termite control, wood preservation, and protection of underground cables. Hazard assessment implies high toxic potential of DDTs for sediments from Hochiminh City canals and suggests the need for better management of municipal discharges.

Contaminant exposure of barn swallows nesting on Bayou d'Inde, Calcasieu Estuary, Louisiana, USA.

Current and historical point source discharges, storm water runoff, and accidental spills have contaminated the water, sediment, and biota within the Calcasieu Estuary in southwestern Louisiana. In 2003, barn swallow (Hirundo rustica) eggs and nestlings were collected beneath two bridges that cross Bayou d'Inde, the most contaminated waterway within the Calcasieu Estuary. Samples were also collected from a bridge over Bayou Teche, a reference site in south central Louisiana. Polychlorinated biphenyl (PCB) concentrations in barn swallow eggs and nestlings were significantly higher at the downstream site on Bayou d'Inde (2.8 micro g/g PCBs in eggs and 1.5 micro g/g PCBs in nestlings) than at the other two sites (< 0.2 micro g/g PCBs in eggs and nestlings at both sites). Ethoxyresorufin-O-dealkylase activity in nestling livers was significantly higher at the downstream site on Bayou d'Inde (50 pmol/min/mg) compared to the other two locations (24 pmol/min/mg, each), probably because of exposure to PCBs. Polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran concentrations in eggs and polycyclic aromatic hydrocarbons in nestlings were at background concentrations at all sites. Trace element concentrations in barn swallow eggs and nestling livers were at background levels and did not differ among the three sites. A biomarker of DNA damage did not differ among sites.

Persistent organochlorine compounds in human breast milk from mothers living in Penang and Kedah, Malaysia.

This study determined the concentrations of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides, and tris(4-chlorophenyl) methane (TCPMe) in human breast milk samples collected in 2003 from primipara mothers living in Penang, Malaysia. OCs were detected in all the samples analyzed with DDTs, hexachlorocyclohexane isomers (HCHs), and PCBs as the major contaminants followed by chlordane compounds (CHLs), hexachlorobenzene (HCB), and TCPMe. The residue levels of DDTs, HCHs, and CHLs were comparable to or higher than those in general populations of other countries, whereas PCBs and HCB were relatively low. In addition, dioxins and related compounds were also detected with a range of dioxin equivalent concentrations from 3.4 to 24 pg-TEQs/g lipid wt. Levels of toxic equivalents (TEQs) were slightly higher than those in other developing countries but still much lower than those of industrialized nations. One donor mother contained a high TEQs level, equal to the mean value in human breast milk from Japan, implying that some of the residents in Malaysia may be exposed to specific pollution sources of dioxins and related compounds. No association was observed between OCs concentrations and maternal characteristics, which might be related to a limited number of samples, narrow range of age of the donor mothers, and/or other external factors. The recently identified endocrine disrupter, TCPMe, was also detected in all human breast milk samples of this study. A significant positive correlation was observed between TCPMe and DDTs, suggesting that technical DDT might be a source of TCPMe in Malaysia. The present study provides a useful baseline for future studies on the accumulations of OCs in the general population of Malaysia.

Use of an internal standard in monitoring the bacterial degradation of crude oil.

Hexachloroethane is nonvolatile, insoluble in water, and apparently not toxic to or metabolized by bacteria. Its addition to cultures growing at the expense of crude oil thus provides an internal standard against which the rate of degradation of individual crude oil components can be conveniently and reproducibly measured.

River sediment (S-37)--a new analytical quality control material ensuring comparability of chlorinated hydrocarbon analysis during an international environmental study in China.

A sediment reference material (S-37) was prepared as analytical quality control material to be used within an international project on polychlorinated hydrocarbon analysis in two Chinese rivers. The raw material was sampled during a cruise on Yangtse River and transported afterwards to the JRC Ispra for further processing. The material was treated according to the general principles applicable for candidate reference material production. After a thorough homogeneity study of the bulk the material was bottled. A total of 1,080 bottles each containing 50 g of dry sediment powder was obtained. Final homogeneity and stability testing proved the material to be fit for the purpose. Isotope dilution GC/MS was used to establish target values for pentachlorobenzene (1.17 +/- 0.08 ng/g), hexachlorobenzene (3.60 +/- 0.17 ng/g), octachlorostyrene (0.19 +/- 0.01 ng/g), pentachloroanisole (0.52 +/- 0.02 ng/g), alpha-HCH (0.70 +/- 0.05 ng/g), beta-HCH (1.38 +/- 0.18 ng/g), gamma-HCH (0.83 +/- 038 ng/g), 2,4'-DDT (0.36 +/- 0.04 ng/g), 2,4'-DDE (0.29 +/- 0.02 ng/g), 2,4'-DDD (0.49 +/- 0.02), 4,4'-DDT (3.42 +/- 0.47 ng/g), 4,4'-DDD (1.29 +/- 0.17 ng/g), PCB 28 (0.11 +/- 0.01 ng/g), PCB 52 (0.09 +/- 0.003 ng/g), PCB 101 (0.07 +/- 0.003 ng/g), PCB 138 (0.06 +/- 0.003 ng/g) and PCB 153 (0.06 +/- 0.003 ng/g). Furthermore, indicative values for major and minor constituents as well as for polychlorinated dibenzodioxines and -furanes were measured.