Multivariate data evaluation of PCB and dioxin profiles in the general population in Sweden and Spain

Thirty-three polychlorinated biphenyls and 20 dioxin-like congeners were determined by GC-MS in blood and adipose tissue samples from two general population groups, one in Spain (n = 35) and one in Sweden (n = 28). The results were evaluated by multivariate projection (Simca), after normalisation to the most abundant and stable congener in each data set, in order to reveal differences in the "national" congener profiles. The mean values of each population group did not differ significantly. The sum of PCBs in the Spanish was 1450 ng/g and in the Swedish 1310 ng/g. The sum of the dioxin-like compounds in Spain was 1180 pg/g and in Sweden 804 pg/g. The congener profiles differed between the countries. Mainly the higher chlorinated congeners for both the dioxin-like compounds and the PCBs are more dominant in the Spanish group compared to the Swedish.     

PCDD/PCDF, dl-PCB and PBDE serum levels of Slovak general population

Blood serum specimens from 81 non-occupationally exposed adults residing in four areas close to municipal and waste incinerators as well as metallurgical industry plant and 44 adult subjects coming from control area of Slovakia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs). The concentration of total WHO(98)TEQ PCDD/F/dl-PCBs in whole group of donors from areas where known sources causing dioxin contamination are present was significantly higher than in control group of donors (p<0.001). Correlation between the age of donors and PCDD/F and dl-PCB levels was confirmed (Spearman's r(PCDD/Fs)=0.543, r(dl-PCBs)=0.521, p<0.001). Furthermore, this study presents first results concerning the PBDE congeners in human serum of Slovak general population. The total concentration (congeners 28, 47, 99, 100, 153, 154, 183) in control group was approximately 1.5-times higher in comparison to that of residents coming from areas with supposed environmental pollution. The most abundant congeners in all samples were BDE-47 and BDE-153 with median values of 0.24 ng g(-1) lipid and 0.23ngg(-1) lipid, respectively. The positive association between PBDE values and age of donors was not found.     

Sediment dioxin levels as the basis for risk assessment and human health criteria

Methods for assessing human health risks and establishing water quality criteria under the Clean Water Act are based on the assumption that fish accumulation of dioxin is correlated with the dissolved phase of the dioxin in the water column by a water-to-fish predictive factor called a bioconcentration factor. However, dioxin does not remain dissolved in the water column to any significant degree, but sorbs to organic matter in the water column and sediment. Under Toxic Substances Control Act regulations, dioxin's hydrophobicity is recognised, and fish dioxin levels are predicted with a solids-to-fish factor. These two different predictive methods can result in extremely variable predictions of fish contaminant levels. A methodology for establishing criteria under the Clean Water Act, which considers fish uptake of sorbed hydrophobic compounds by way of ingestion of contaminated sediment, is offered as an alternative to the methods used today.     

Agreement between breast milk dioxin levels by CALUX bioassay and chemical analysis in a population survey in Hong Kong

Chemically-activated luciferase gene expression (CALUX) bioassay and gas chromatography/mass spectrometry (GC/MS) are used to determine dioxin levels in food and humans. Valid measures of the agreement between the two methods would improve interpretation of bioassay results. Paired breast milk samples from 250 mothers, as 11 pooled samples, were analysed by GC/MS for total WHO-TEQ (7 polychlorinated dibenzo-para-dioxins, 10 polychlorinated dibenzofurans and 12 dioxin-like polychlorinated biphenyls) and as individual samples by CALUX. Mean difference between total WHO-TEQ (weighted by TEF system derived in 1997) and mean CALUX-TEQ in each pool was 1.6 pg/g fat (95% CI: 0.7, 2.4), indicating a statistically significant overestimation of CALUX-TEQ compared to WHO-TEQ, probably due to the presence of Ah-receptor agonists. CALUX estimated toxicity of 13 pg/g fat was greater than the WHO-TEQ by 0.9, 3.1 and 0.3 pg/g fat for mothers from Hong Kong, mainland China and overseas territories, respectively. When the 2005 TEF system was applied, a reduction of 14-26% in the WHO-TEQ and a larger but less disperse discrepancy between WHO-TEQ and CALUX-TEQ (3.9 pg/g fat, 95% CI: 3.5, 4.4) were observed. Our study suggested that the mothers' place of residence explained the discrepancy between CALUX-TEQ and WHO-TEQ and should be considered in inter-country comparisons for CALUX-TEQ. For regulatory purposes bioassays for detecting quantitative dioxin contents in any setting must be combined with adequate extraction, clean-up and validation with WHO-TEQs. The larger difference between the two measurements after using the new TEF system warrants further investigation.     

Simulation of dioxin accumulation in human tissues and analysis of reproductive risk

Polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofuran and dioxin-like polychlorinated biphenyl concentrations in human liver, kidney, fat, blood, muscle, richly perfused tissue (brain, lung etc.) and skin were simulated to assess the health risk for Japanese fetuses. A 40-year time course of dioxin accumulation via food ingestion was simulated using a physiologically based pharmacokinetic (PBPK) model. In richly perfused tissue, the concentration estimated by the PBPK model showed better agreement with measured concentrations than that calculated by the one-compartment model. Fetal dioxin concentration was simulated based on the assumption that the fetal concentration was almost equal to the concentration in the mother's richly perfused tissue. To assess the reproductive risk, the estimated concentration in human fetus was compared with that in rat fetus in which reproductive function showed signs of alteration by 2,3,7,8-TCDD in previous reports [Toxicol. Appl. Pharmacol. 114 (1992) 118; 146 (1997) 11; Toxicol. Sci. 53 (2000) 411; 57 (2000) 275]. The present daily intake of 2,3,7,8-TCDD is approximately 1/50 of the amount that leads to possible reproductive toxicity in the next generation. However, when 29 kinds of dioxin congeners are considered, the present level is 1/5 of the hazardous levels. For species extrapolation of dioxin risk, further study on tissue concentration versus toxicity is required.     

Development of dioxin toxicity evaluation method in human milk by enzyme-linked immunosorbent assay--assay validation for human milk

In this study, the development of a toxicity evaluation method for dioxins in human milk by enzyme-linked immunosorbent assay (ELISA) was reported. A total of 17 human milk samples were tested by ELISA and by gas chromatography/mass spectrometry (GC/MS) to assess whether the ELISA performed on samples obtained from primiparas could be considered as reliable enough for identifying a dioxins contamination in human milk. The concept of toxicity equivalent quantity (TEQ) screening was validated by comparing TEQ values for a set of human milk samples to the ELISA responses predicted for those samples. A fairly good correlation (r=0.920) between immunoassay and GC/MS was achieved for human milk. This ELISA should be useful for biological samples monitoring.     

Dioxin-like and non-dioxin-like PCBs in human serum of Slovak population

In the present study, non-ortho, mono-ortho and other ortho-substituted PCB congeners were analysed in individual blood serum samples taken from healthy adults (196 males and 119 females) in the polluted area of the Michalovce district and in the background area of the Stropkov/Svidnik districts in Eastern Slovakia by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). The samples from general population living in villages and towns of two regions were taken between August 2001 and February 2002 within the project of the EC's 5th Framework Programme (PCBRISK, ). The medians of dioxin-like PCBs (dl-PCBs)--expressed as TEQs on lipid basis--of all males (24.7 pg g(-1) lipid) and females (21.4 pg g(-1) lipid) were comparable, but there was a significant difference between both of the areas studied. In the district of Michalovce, the medians of males (47.3 pg g(-1) lipid) and females (41.1 pg g(-1) lipid) were 2.3 times higher than in the area of the Stropkov/Svidnik districts. The medians of total non-dioxin-like PCB concentration were 1,835 and 1,033 ng g(-1) lipid in males and females, respectively. The data show a trend toward higher concentrations of both dl- and non-dioxin-like PCBs in the older age groups. The substantial increase was observed for the 60+ age group. PCB-126 was the most abundant non-ortho congener. PCBs-118 and 156 were the predominant mono-ortho congeners. They were quantitated in all samples analysed. Congeners 153, 138(+163), 180 and 170(+190) were the main contributors to total non-dioxin-like PCB concentrations. Mean mutual ratio HexaCBs:HeptaCBs:OctaCBs in the non-dioxin-like group was 37:50:1. The results of this study represent the overall information about the congener distribution of dioxin-like and non-dioxin-like PCBs in human serum blood of adult Slovaks.     

Concentrations of organochlorine pesticides and polychlorinated biphenyls in human serum and their relation with age,gender, and BMI for the general population of Bizerte,Tunisia

Human serum samples (n?=?113) from Bizerte, northern Tunisia, collected between 2011 and 2012 were analyzed for 8 organochlorine pesticides (OCPs) including p,p′-dichlorodiphenyltrichloroethane (DDT) and its metabolites, hexachlorobenzene (HCB), hexachlorocyclohexane isomers, dieldrin, and heptachlor and 12 polychlorinated biphenyls (PCBs) congeners. Concentrations of these residues in serum were determined by gas chromatography with electron capture detector and total cholesterol (CHOL) and triglycerides (TG) levels were evaluated by enzymatic colorimetric method. HCB, p,p′-DDE, PCB-138, PCB-153, and PCB-180, were the most abundant organochlorine compounds (OCs) detected in >95 % of the study subjects. The mean levels of p,p′-DDE and HCB in serum were 168.8 and 49.1 ng?g^?1 lipid, respectively. The sum PCBs concentrations ranged from 37.5 to 284.6 ng?g^?1 lipid in the samples, with mean and median value of 136.1 and 123.2 ng?g^?1 lipid, respectively. The PCB profile consisted of persistent congeners, such as PCB-138, PCB-153, and PCB-180 which contributed for approximately 82.7 % to the ∑PCBs. Statistical analysis showed that most OCs correlated significantly with age, considering all samples together or with gender differentiation. The present study shows that the levels of p,p′-DDE and ∑DDTs were significantly higher in females than in males (p?<?0.05), while PCBs levels were significantly higher in male (p?<?0.05) than in females. No statistically significant association was found between body mass index and concentration of any organochlorine pesticide or PCB congeners 153, 138, 180, or ∑PCBs.     

Assigning concentration values for dioxin and furan congeners in human serum when measurements are below limits of detection: an observational approach

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in dietary sources for humans have been declining over the previous two decades. These declines have been accompanied by decreases in concentrations of these compounds in humans, as evidenced by measurements in blood and milk. Because of the decreasing concentrations of PCDD/PCDFs in the environment and in humans, measuring PCDD/PCDF congeners in humans has become increasingly difficult, despite advances in analytic methods. An observational approach was recently described to address the quandary of non-detectable results in determining toxic equivalents. This approach, called the congener ratio approach, is specifically for cases where concentrations of 2,3,7,8-TCDD (TCDD) are below the limit of detection (LOD), and where concentrations of 1,2,3,7,8-pentachlorodibenzo-p-dioxin (PeCDD) are equal to or above the LOD. Development of this approach relied on evaluating data on measured concentrations of TCDD and PeCDD in human serum from the general population. The congener ratio approach for TCDD and PeCDD was based on the concentration of TCDD being approximately 40% that of PeCDD in serum from the general population. Additional analyses presented here reveal that when concentrations of both congeners are above the LOD, the data appear to generally support the congener ratio approach for TCDD and PeCDD, with the caveat that gender may affect the ratio. However, the TCDD/PeCDD relation is less clear when TCDD is less than the LOD; in this situation, the relation overpredicts levels of TCDD approximately 80% of the time for the 2001-2002 NHANES database. Using the congener ratio approach for other PCDD/PCDF congeners requires assessing the correlation and the frequency of detection for both TCDD and PeCDD.     

Methods for the analysis of PCBs in human food, faeces and serum.

A method was developed to determine trace concentrations of a range of individual PCB congeners in biological samples (serum, food and faeces) using GC-MS, to prepare a mass balance of PCBs in humans. A simple method for the analysis of PCBs in human serum, which excluded an extraction step, was first employed. Results indicated that the recoveries of 13C12 PCB spikes were variable. A soxhlet extraction step was added and was found to be efficient and reproducible. A quality control routine and method validation results are presented. In batch tests of the methods presented it was found that the serum analysis method gave within batch mean 13C12 spike recoveries of 98-120% and standard deviations between 6 and 20%. The food/faeces analysis method gave within-batch mean 13C12 spike recoveries of 88-100%, and within batch standard deviations between 4 and 12%. The batch to batch mean recovery for serum analysis was 100%, with an RSD of 9% for high spikes and 10% for low spikes. For food/faeces analysis the batch to batch average recovery was 110%, with an RSD of 5% for high spikes and 9% for low spikes.     

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.     

Human milk survey for dioxins in the general population in Japan

BACKGROUND: Much attention has been paid to the level of dioxins in breast milk in Japan but few large-scale studies have been conducted on the subject. METHODS: From 1997 to 2002, we collected 839 samples of breast milk from primiparas residing throughout Japan. Starting in 1999, breast milk was also collected from secundiparas. Seven isomers of polychlorinated dibenzo-p-dioxins (PCDDs), 10 of polychlorinated dibenzofurans (PCDFs), 4 of coplanar polychlorinated biphenyls (Co-PCBs) and 8 of mono-orthochlorinated polychlorinated biphenyls (mono-ortho PCBs) were analyzed by employing gas chromatography and mass spectrometry. A correlation between the level of dioxins in human milk and the age of the mothers was noted for the primiparas and the secundiparas; and the levels were compared between the first and the second deliveries. Grouped by parity and prefecture in each year, observations were also made on the trends in these levels. Dioxin levels are shown by using geometric means because their distributions were skewed to the left. RESULTS: The sum of PCDDs and PCDFs, Co-PCBs, mono-ortho PCBs, and total dioxins in the breast milk of primiparas were 13.9, 5.4, 3.4, and 22.7 pg TEQ/g fat, respectively. In the samples obtained from secundiparas, these levels were 63-68 percents of those taken from the primiparas. The correlation coefficients between the PCDDs/DFs, Co-PCBs, mono-ortho PCBs, and total dioxins and the age of the primiparas were 0.19, 0.17, 0.36, and 0.24, respectively. All these correlations were statistically significant (p < 0.001). The positive correlations between these contaminants and the age of the secundiparas were also examined. The total dioxins as well as PCDDs/DFs, Co-PCBs, and mono-ortho PCBs in the breast milk of the primiparas declined significantly between 1998 and 2002 (regression coefficients: -0.04, -0.05, -0.03, and -0.03, respectively). However, no significant decline in these levels was observed when sorted by prefectures. CONCLUSIONS: Much attention should be paid to the age and parity of nursing mothers when investigating the relationship between the level of dioxins in breast milk and the body burden of infants.     

沈阳市环境空气不同功能区二噁英含量与暴露风险分析

以沈阳市不同功能区为研究对象,进行不同功能区的二噁英含量与暴露风险分析.研究表明:沈阳市不同功能区的二噁英质量浓度大小顺序为工业区＞居民区＞文化区＞商业区＞公园＞风景区;6个功能区均检测出多氯二苯并二噁英(PCDDs)、多氯二苯并呋喃(PCDFs)和多氯联苯(PCB)3种污染物,除风景区外,PCDFs所占比例最大,PCDDs居第二位,PCB所占的比例最小;毒性当量的计算结果表明,不同功能区的二噁英毒性当量浓度与其质量浓度大小顺序一致;呼吸暴露量计算结果表明,儿童的呼吸暴露量高于成人,说明儿童受到空气二噁英的呼吸暴露风险更大.     

Airborne lead levels in the Korean peninsula: characterization of temporal and spatial patterns and cancer risk analysis

Introduction

This study collected long-term airborne lead concentrations in the Korean peninsula and analyzed their temporal, spatial, and cancer risk characterization.

Methods

Approximately, 12,000 airborne samples of total suspended particulate (TSP) were collected from 30 ambient air monitoring stations in inland (Daegu, Daejeon, Gwangju, and Seoul) cities and portal cities (Incheon, Busan, and Ulsan) over a period of 7?years (2004?C2010). High volume air samplers were employed to collect daily TSP samples during the second week of the consecutive months throughout the entire study period. The concentrations of Pb extracted from the TSP samples were analyzed using either inductively coupled plasma-atomic emission or flame atomic absorption spectrometry.

Results

The long-term high mean Pb concentrations were observed in the port cities including Incheon (88?±?18?ng/m³), Ulsan (61?±?7?ng/m³), and Busan (58?±?6?ng/m³). In the temporal analysis, seasonal mean Pb levels were relatively higher in winter and spring than those in summer and fall. In the spatial analysis, the mean Pb levels in spring, winter, and fall from Incheon, which showed the highest seasonal concentrations except summer, were 110?±?19, 101?±?18, and 76?±?23?ng/m³, respectively. In summer, the highest seasonal mean Pb level was observed in the largest industrial city and the second port city, Ulsan (78?±?15?ng/m³), followed by Incheon (65?±?13?ng/m³).

Conclusion

The estimated excess cancer risk analysis showed that inhalation of Pb could result in cancer for one or two persons per million of population in the Korean peninsula.     

小球藻生长及其净化猪场废水条件的优化

为提高小球藻净化猪场废水的效果,在户外条件下系统比较了预处理方式、管道光反应器的种类和光径对蛋白核小球藻生长及其对猪场废水净化效果的影响。结果表明,猪场原废水COD、NH4+、PO43-、TN、TP含量分别为710、491、54、590和108 mg·L-1 时,蛋白核小球藻对经过3级过滤预处理后的猪场废水净化效果最好,其中脱色率及NH4+去除率分别高达88.56%和83.48%,显著高于对原废水的处理效果(P-1。采用直径为5 cm的立式光生物反应器培养蛋白核小球藻,通过循环采收,藻粉产量可达到0.93 g·L-1,其蛋白质含量最高达到58.9%,汞、砷、镉、铅含量分别小于0.1、1.0、0.5和4.0 mg·kg-1,符合《饲料用小球藻粉》(DB32/T 564-2010)标准。采收小球藻后的出水中,NH4+、PO43-、色度的去除率均高达90%以上,基本达到国家排放要求。该研究结果可为制定猪场废水的净化及蛋白核小球藻的工业化生产方案提供参考。     

The relation between levels of selected PCB congeners in human serum and follicular fluid

Individual congener and total PCB concentrations were determined in serum and follicular fluid obtained from women undergoing assisted reproductive technologies (in-vitro fertilization and embryo replacement). Although the mean individual PCB levels revealed varying degrees of contamination, the results fall in the same range as that observed by other investigators. Except for PCB 118, correlations between levels in serum and follicular fluid were strong, and statistically significant at p < 0.05. Moreover PCB 153, a major and very stable PCB congener has been shown to correlate to the total amount of PCBs (r = 0.994, and r = 0.987, for serum and follicular fluid, respectively). The same accumulation patterns of PCBs for serum and follicular fluid have been observed.