Methodological aspects of a national population-based study of persistent organochlorine compounds in serum

Key methodological aspects are presented for a study of concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and organochlorine pesticides in the serum of a sample of the New Zealand population aged 15 years and older. The study took advantage of the sampling frame and sample collection and interview processes of the National Nutrition Study (NNS). An additional blood sample for this organochlorines study was collected by the NNS and questions added to the NNS questionnaire. Serum was obtained from the blood and, based on responses to questions in the questionnaire, samples with possible occupational exposure to organochlorines were excluded. Remaining samples providing at least 2 ml of serum were pooled within 80 strata defined according to geographic area, age group, sex and ethnicity. A minimum number of five individual serum samples was required for pooling within a stratum. Within strata with sufficient samples, two or three pooled samples were created for variance calculation. Eligible for inclusion in the study were 2497 individual serum samples. Sixty strata had sufficient serum samples for pooling and chemical analysis. This was the first study of organochlorine compounds with a national population-based sample. Two factors that made the study feasible deserve emphasis. First, being able to "piggy-back" on another study. Second, pooling of samples to reduce analytic expenses. It is hoped that the methods used in this study will form the basis for other studies investigating organochlorine concentrations in national populations.     

Hair analysis: another approach for the assessment of human exposure to selected persistent organochlorine pollutants

Hair analysis was used for the assessment of exposure to organochlorine pollutants in specimens from Greece, Romania and Belgium. A simple method (using 3 N HCI as incubation reagent, liquid-liquid extraction with hexane/ dichloromethane (DCM), alumina/acid silica clean-up and GC-ECD/GC-MS analysis) was used for screening of specimens. The highest organochlorine load (up to 148 ng/g hair for the sum of PCB, DDT and hexachlorocyclohexane (HCH) isomers) was found in samples from a group of Greek women with past occupational exposure to pesticides. DDTs were the main organochlorine pollutants in Greek samples (up to 70%), while in Belgian hair samples their contribution was reduced to 40%. PCB mean concentration was higher in Belgian specimens (up to 14 ng/g hair). Lindane (y-HCH) was the main HCH isomer found in the samples (up to 82% in the Greek samples). Contribution of p,p'-DDT to the sum of DDTs was higher in Greek samples and indicates recent exposure to technical DDT. Similar PCB 153/sum PCBs ratios were found for each of the three countries suggesting similar sources of pollution with PCBs (mainly dietary). Artificially coloured hair samples were found to have lower, but not statistically significant concentrations of organochlorine pollutants than the non-coloured hair.     

A simplified precise method for adjusting serum levels of persistent organohalogen pollutants to total serum lipids

In order to obtain biomarker values that reflect body burden of persistent organohalogen pollutants (POP), concentrations of lipophilic POP in serum or plasma are generally expressed on a lipid weight basis, and not on a fresh weight basis. There are two different approaches to determine the lipid content in serum and plasma. The gravimetric determination is more expensive, and longer experience is needed as compared with the preferable enzymatic determination. Clinical chemistry laboratories at most hospitals perform enzymatic determinations of cholesterol and triglycerides on a routine basis, whereas analysis of phospholipids is not part of these analyses. In the present study, therefore, we evaluated the association between the sum of measured triglyceride, cholesterol, and phospholipid levels in serum among 617 individuals with the sum of only triglyceride and cholesterol levels. There was a very strong linear association between the sums of serum concentrations of triglycerides and cholesterols and the total lipid concentrations. As much as 97.2% of the variation in total lipid concentrations was explained by the sum of the triglyceride and cholesterol concentrations, with the following regression: Total lipid=0.9+1.3 *(Cholesterol+Triglycerides). Almost identical relationships were recorded in subgroups with men, women and subjects of different age. Thus, total lipid concentrations in blood serum can be accurately estimated by analyzing only cholesterol and triglycerides in the matrix.     

Simplified method for determination of organochlorine pollutants in human serum by solid-phase disk extraction and gas chromatography

Solid-phase disk extraction (SPDE) was developed as an improved method for isolation of selected organochlorine pollutants from human serum. An Empore C18 bonded silica extraction disk cartridge was used for the initial extraction and enrichment of the analytes. Subsequent clean-up was done by adsorption chromatography on concentrated sulphuric acid:silica gel (1:1, w/w). Analysis was achieved by gas chromatography-mass spectrometry or electron capture detection on two different capillary columns. Recoveries for selected organochlorines range from 62% to 74% (RSD < 14%). The method was validated through successful participation to several interlaboratory tests and by analysis of human serum with different organochlorine loading.     

Levels of persistent organic pollutant and their predictors among young adults

Exposure to persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), dichlorodiphenyldichloroethane (p,p′-DDE), and hexachlorobenzene (HCB) continues to be of concern due to their ubiquitous distribution and high persistence. Current toxicant body burden is still a primary concern within the Akwesasne Mohawk Nation since other studies conducted within the community have shown relationships between these POPs and endocrine disruption.In this article we describe the levels of these toxicants in young adults of the Akwesasne Mohawk Nation between the ages of 17 and 21 years of age (mean age 18.1 years), and investigate potential influences of their current body burden. Seventeen congeners in fourteen chromatographic peaks were detected in 50% or more of the individuals sampled (geometric mean [GM] of the sum of these congeners = 0.43 ppb). Congeners 118, 138[+163 + 164] and 153 had the highest rate of detection (?98%) within the Akwesasne young adults. Of the other organochlorines, HCB (GM = 0.04 ppb) and p,p′-DDE (GM = 0.38 ppb) were found in 100% and 99% of the sample respectively.Significantly higher levels of PCBs were found among individuals who were breastfed as infants, were first born, or had consumed local fish within the past year. When compared to levels of p,p′-DDE, HCB, and 13 specific congeners reported by the CDC for youth between the ages of 12 and 19 years, the geometric means of several congeners (CBs 99, 105, 110, and 118) among the Akwesasne were higher than the reported CDC 90th percentile. In contrast, levels of CB 28 in Akwesasne young adults were ∼50% or less than those of the CDC cohort. p,p′-DDE and HCB levels were generally higher in the CDC cohort (GM of 0.516 and 0.065 ppb, respectively for Mohawks vs. 2.51 and 0.123, respectively, for CDC). Concentrations of non-persistent PCBs among this sample of Akwesasne young adults were higher than those reported by the CDC suggesting continued exposure, but lower than those associated with severe contamination.Additional research into the concentration trends of individual PCB congeners within Akwesasne youth and young adults is warranted to further improve our insight into the determinants and influences of organochlorine concentrations within members of the Akwesasne community.     

Temporal and biogeographic comparisons of PCBs and persistent organochlorine pollutants in the blubber of fin whales from eastern Canada in 1971-1991

Concentrations of PCB congeners and organochlorine (OC) pesticides were studied in archived fin whale (Balaenoptera physalus) blubber samples collected in 1971-1972 from Newfoundland (Nfld) and Nova Scotia (NS) with the objective of obtaining a historical perspective on contaminant levels and proportions at a time when many persistent OCs were still in use. Concentrations of sigmaPCBs and sigmaDDTs in the blubber of 17 fin whales from historical whaling stations in 1971-1972 were generally in agreement with previously reported values for fin whales from Atlantic Canada. Although some differences in sex and body length (age) distribution of samples occurred, significant differences were detected in the concentrations and patterns of PCBs, DDTs and chlordanes in whales from Nfld and NS, supporting ecological evidence that whales from these regions represent relatively separate stocks. Temporal and geographical variations were examined by comparing data to those reported for fin whales from the St Lawrence Estuary (StL) in 1991 by Gauthier et al. (1997a). Significantly higher levels of sigmaDDT, sigmaCHL and HCB were found in the NS (1971-1972) stock compared with the StL (1991) animals, and in HCB between the Nfld stock (1971-1972) and the StL (1991) animals, as well as higher p,p'-DDE/sigmaDDT and lower p,p'-DDT/sigmaDDT ratios in the 1991 whales suggesting that temporal trends in these whales between the 1970s and 1990s were consistent with those in other marine mammals in Atlantic Canada. Evidence also suggests that geographical variations in patterns may occur for individuals from two relatively distinct stocks of fin whales in Atlantic Canada (NS, Nfld) and perhaps for one population (StL) related to, but recognisably different from the NS stock.     

Global-scale environmental transport of persistent organic pollutants

In order to realistically simulate both chemistry and transport of atmospheric organic pollutants, it is indispensable that the applied models explicitly include coupling between different components of the global environment such as atmosphere, hydrosphere, cryosphere and soil system. A model with such properties is presented.

The atmospheric part of the model is based on the equations in a general contravariant form which permits easy changes of the coordinate system by redefining the metric tensor of a specifically employed coordinate system. Considering a need to include explicitly the terrain effects, the terrain following spherical coordinate system is chosen from among many possible coordinate systems. This particular system is a combination of the Gal-Chen coordinates, commonly employed in mesoscale meteorological models, and the spherical coordinates, typical for global atmospheric models.

In addition to atmospheric transport, the model also simulates the exchange between air and different types of underlying surfaces such as water, soil, snow, and ice. This approach permits a realistic representation of absorption and delayed re-emission of pollutants from the surface to the atmosphere and, consequently, allows to capture hysteresis-like effects of the exchange between the atmosphere and the other components of the system. In this model, the most comprehensive numerical representation of the exchange is that for soil. In particular, the model includes a realistic soil module which simulates both diffusion and convection of a tracer driven by evaporation from the soil, precipitation, and gravity.

The model is applied to a long-term simulation of the transport of pesticides (hexachlorocyclohexanes in particular). Emission fluxes from the soil are rigorously computed on the basis of the realistic data of the agricultural application. All four modelled systems, i.e. atmosphere, soil, hydrosphere and cryosphere, are driven by objectively analysed meteorological data supplemented, when necessary, by climatological information. Therefore, the verification against the observed data is possible. The comparison of the model results and the observations taken at remote stations in the Arctic indicates that the presented global modelling system is able to capture both trends and short-term components in the observed time series of the concentrations, and therefore, provides a useful tool for the evaluation of the source–receptor relationships.     

Vertical distributions of persistent organic pollutants (POPs) caused from organochlorine pesticides in a sediment core taken from Ariake bay, Japan

Persistent organic pollutants (POPs) of organochlorine pesticides such as dichlorodiphenyl trichloroethane (DDTs) and its metabolites, hexachlorobenzene (HCB), heptachlor, chlordane compounds (CHLs), aldrin, dieldrin, endrin, mirex and isomers of hexachlorocyclohexane (HCHs), were analyzed in sediment cores collected from Ariake Bay, Japan. Although Chikugo River has the largest flow in Ariake Bay, the total concentration of POPs in surface sediment was found in St.3, mouth of the Yabe River, where that level was two times higher than St.1, mouth of the Chikugo River. It could be assumed that the potential source of POPs contamination is relatively close to this study area. Relatively high residue levels of HCB, HCHs and DDTs in sediment core were found during the period from 1967 to 1970. In this layer, the HCB concentration investigated in sediment cores of Ariake Bay was maximum, 2.6 ng g(-1) dry weight and higher than that of Tokyo Bay and subsequently detected in deeper sediment cores. The ratio of (DDD+DDE)/SigmaDDTs was high in top sediments (0-2 cm). Although there was a concentration of DDTs in the top sediment, it was noticed that DDT emission did not cause direct input of DDT recently. The HCHs determined in upper sediment cores might be originated from long-range accumulation in environment after dispersing of technical-grade HCH. Moreover, the CHLs, dieldrin and heptachlor concentrations were detected and recently increased in sediment core. POPs in sediment cores of Ariake Bay based on the possibility of PCP contamination during the early 1960s were reflected.     

Persistent organochlorine pollutants in children working at a waste-disposal site and in young females with high fish consumption in Managua, Nicaragua

The aim of this study was to assess persistent organochlorine pollutant (POP) levels in serum collected from children (11-15 years old) working and sometimes also living at the municipal waste-disposal site in Managua, located at the shore of Lake Managua, and in nonworking children living both nearby and also far away from the waste-disposal site. The influence of fish consumption was further evaluated by assessing POPs levels in serum from young women (15-24 years old) with markedly different patterns of fish consumption from Lake Managua. 2,2-bis(4-chlorophenyl)-1,1,1-trichloro-ethane (4,4'-DDT) and 2,2-bis(4-chlorophenyl)-1,1-dichloro-ethene (4,4'-DDE), gamma-hexachlorocyclohexane (gamma-HCH), polychlorinated biphenyls, pentachlorophenol, and polychlorobiphenylols were quantified in all samples. In general, the levels observed were higher than those reported in children from developed countries, such as Germany and United States. Toxaphene, aldrin, dieldrin, and beta-HCH could not be identified in any sample. The children working at the waste-disposal site had higher levels of POPs compared with the nonworking reference groups. In children not working, there were also gradients for several POPs, according to vicinity to the waste-disposal site. Moreover, in children, as well as in young women, there were gradients according to fish consumption. The most abundant component was 4,4'-DDE, but at levels still lower than those reported in children from malarious areas with a history of recent or current application of 4,4'-DDT for vector control.     

Pesticide exposure and serum organochlorine residuals among testicular cancer patients and healthy controls

The incidence of testicular cancer (TC) has been increasing worldwide during the last decades. The reasons of the increase remains unknown, but recent findings suggest that organochlorine pesticides (OPs) could influence the development of TC. A hospital-based case-control study of 50 cases and 48 controls was conducted to determine whether environmental exposure to OPs is associated with the risk of TC, and by measuring serum concentrations of OPs, including p,p’-dichlorodiphenyldichloroethylene (p,p’-DDE) isomer and hexachlorobenzene (HCB) in participants. A significant association was observed between TC and household insecticide use (odds ratio [OR] = 3.01, 95 % CI: 1.11-8.14; OR_adjusted = 3.23, 95 % CI: 1.15-9.11). Crude and adjusted ORs for TC were also significantly associated with higher serum concentrations of total OPs (OR = 3.15, 95 % CI: 1.00-9.91; OR_adjusted = 3.34, 95 % CI: 1.09-10.17) in cases compared with controls. These findings give additional support to the results of previous research that suggest that some environmental exposures to OPs may be implicated in the pathogenesis of TC.     

Pesticide exposure and serum organochlorine residuals among testicular cancer patients and healthy controls

The incidence of testicular cancer (TC) has been increasing worldwide during the last decades. The reasons of the increase remains unknown, but recent findings suggest that organochlorine pesticides (OPs) could influence the development of TC. A hospital-based case-control study of 50 cases and 48 controls was conducted to determine whether environmental exposure to OPs is associated with the risk of TC, and by measuring serum concentrations of OPs, including p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) isomer and hexachlorobenzene (HCB) in participants. A significant association was observed between TC and household insecticide use (odds ratio [OR] = 3.01, 95 % CI: 1.11-8.14; OR(adjusted) = 3.23, 95 % CI: 1.15-9.11). Crude and adjusted ORs for TC were also significantly associated with higher serum concentrations of total OPs (OR = 3.15, 95 % CI: 1.00-9.91; OR(adjusted) = 3.34, 95 % CI: 1.09-10.17) in cases compared with controls. These findings give additional support to the results of previous research that suggest that some environmental exposures to OPs may be implicated in the pathogenesis of TC.     

On enumeration of congeners of common persistent organic pollutants

Congeners are molecules based on the same carbon skeleton but different by the number of substituents and/or a substitution pattern. Various Persistent Organic Pollutants (POPs) exist in the environment as families of halogen substituted congeners and/or their hydroxyl and methoxy substituted derivatives. Numbers of possible congeners resulting from substitution of a parent POP molecule with only one type of chemical group are generally available. At the same time, numbers of mixed-substituent congeners have not been counted and presented yet, although there is an increasing interest in such as is the increasing number of research articles presenting results on already identified Cl−/Br−mixed type congeners and/or their HO-/CH₃O-mixed metabolites. We have enumerated and counted possible mixed-substituent congeners of common POPs. This article presents the obtained numbers for congener families of benzene, naphthalene, biphenyl, diphenyl ether, dibenzo-p-dioxin, dibenzofuran, anthracene, pyrene and others and obtained by substitution of up to five chemical group types.     

Storage of organochlorine pesticides in human adipose tissues of Jordanian males and females

Adipose tissue of 50 human patients (5-96, years old) were taken and analysed by gas chromatography equipped with electron capture detector (63Ni) for determination of storage levels of HCH's (alpha, beta, and gamma-hexachlorcyclohexanes), DDT and its metabolites DDE and DDD, the cyclodiens (heptachlor, heptachlorepoxide, dieldrin, aldrin and endrin) and HCB (hexachlorbenzene). The data is reported according to age groups and sexes. The results show relatively moderate concentrations of all studied pesticides and that Jordanian men are more exposed to DDT and HCH's than women.     

Weight and height at 4 and 7 years of age in children born to mothers with a high intake of fish contaminated with persistent organochlorine pollutants

In Sweden the main exposure route for persistent organochlorine pollutants (POP) is through consumption of fatty fish from the Baltic Sea (off the eastern coast). The present study aimed to investigate whether intrauterine exposure for POP may have negative impact on children's weight and height at 4 and 7 years of age, respectively. The study included 174 fishermen's wives from the Swedish east coast who had given birth to an infant with either low (n=55) or normal (n=119) birth weight, and 88 and 206 corresponding women from the Swedish west coast (where the fish is less polluted). Comparisons between the east and west coast cohorts were performed. In addition, blood samples were collected among the east coast women and the concentrations of 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153) in plasma was analyzed and estimated for the year of childbirth. There were no significant differences between the east and west coast cohorts regarding weight and height at 4 and 7 years of age. There were, however, significant negative associations between the estimated plasma concentrations of CB-153 during year of childbirth and weight at 4 and 7 years of age, respectively, among the normal birth weight children. The study gives only very weak support for the hypothesized association.     

中国持久性有机污染物嫌疑物质的计算机辅助筛选研究

按照《关于持久性有机污染物的斯德哥尔摩公约》中持久性有机污染物（POPs)的确定标准,借鉴荷兰建设规划和环境部开发的持久的生物富集性有毒化学物质（PBTs)筛选流程,利用计算机辅助工具《中国现有化学物质名录》最新版中收录的所有26707种化学物质进行了初步筛选,最后得到111种POPs嫌疑物质。对结果的深入讨论表明计算机工具用于持久性有机污染物初步筛选是可行的。     

Partitioning of persistent organic pollutants (POPs) between human serum and breast milk: A literature review

The literature was reviewed to assess the relationship between the lipid adjusted concentration in human serum and breast milk (expressed as the serum/milk ratio) of a broad range of POPs in paired samples. Thirteen studies were identified, including seven studies that reported serum/milk ratios for polychlorinated dibenzo-dioxins and -furans (PCDD/Fs), ten for polychlorinated biphenyls (PCBs), five for polybrominated diphenyl ethers (PBDEs), and five for organochlorine pesticides (OCPs). Mean serum/milk ratios ranged between 0.7 and 25 depending on the compound and congener. For PCDD/Fs, PCBs and PBDEs, a clear trend of increasing mean serum/milk ratio by increasing molar volume, hydrophobicity and number of halogen substitutes was observed. The mean serum/milk ratios reported by the 13 studies summarized here will aid comparison between human POPs exposure studies using either serum or milk samples. More studies are needed to allow a valid comparison between data obtained from analysis of breast milk and serum samples for a broader range of POPs. Furthermore such studies may shed light on compound specific factors as well as other determinants that may affect the partitioning and partition kinetics of POPs between serum and breast milk.     

Lowered birth weight among infants born to women with a high intake of fish contaminated with persistent organochlorine compounds

In Sweden fatty fish from the Baltic Sea (at the Swedish east coast) constitute the main exposure route for persistent organochlorine compounds (POC). The present study assessed reproductive outcomes among fishermen's sisters from the Swedish east coast, who were shown to had had a relatively high consumption of contaminated fish in early life. For relevant comparison, we used a similar cohort from the Swedish west coast, where the contamination of fish is considerable less. The east coast cohort women had an increased risk of having an infant with low birth weight (LBW; <2500 g) as compared with the west coast cohort women (odds ratio (OR) 1.6. 95% confidence interval 1.1-2.3). The results strengthen the hypothesized association between exposure to POC during childhood and adolescence and an increased risk for LBW.     

EU-wide survey of polar organic persistent pollutants in European river waters

This study provides the first EU-wide reconnaissance of the occurrence of polar organic persistent pollutants in European river waters. More than 100 individual water samples from over 100 European rivers from 27 European Countries were analysed for 35 selected compounds, comprising pharmaceuticals, pesticides, PFOS, PFOA, benzotriazoles, hormones, and endocrine disrupters. Around 40 laboratories participated in this sampling exercise. The most frequently and at the highest concentration levels detected compounds were benzotriazole, caffeine, carbamazepine, tolyltriazole, and nonylphenoxy acetic acid (NPE₁C). Only about 10% of the river water samples analysed could be classified as “very clean” in terms of chemical pollution. The rivers responsible for the major aqueous emissions of PFOS and PFOA from the European Continent could be identified. For the target compounds chosen, we are proposing “indicative warning levels” in surface waters, which are (for most compounds) close to the 90th percentile of all water samples analysed.     

Prediction of the bioaccumulation of persistent organic pollutants in aquatic food webs

Predictive correlations of the bioaccumulation factor of persistent organic pollutants in aquatic biota are presented as functions of their octanol/water partition coefficient. The correlations demonstrate the importance of differentiating among the different levels in the food web and of accounting for the pollutant's bioavailability by considering the amount freely dissolved in water instead of the total concentration. They also reveal the significance of the pollutant's octanol/water partition coefficient value on its biomagnification along the levels of the trophic chain. Prediction results, finally, demonstrate that the correlations provide reasonably accurate estimates of bioaccumulation, typically within an order-of-magnitude.