Analysis of human milk to assess exposure to PAHs,PCBs and organochlorine pesticides in the vicinity Mediterranean city Mersin,Turkey

Assessment of human exposure to environmental persistent organic pollutants such as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) based on the levels in human breast milk provides a reasonable tool not only to assess the contaminant burden in mothers but also to assess potential exposure of breast-fed neonates. There are limited data on levels of PCBs and OCPs in humans but no previous reports from Turkey on chemically determined levels PAHs in human milk. The aim of this study was to report the levels and accumulation profiles of OCPs, PCBs and PAHs in 47 breast milk samples obtained from a Mediterranean city, Mersin. High resolution analyses were performed by a gas chromatography coupled with mass spectrometer (GC–MS). Dichlorodiphenyldichloroethane (4.4′-DDE) was the dominant pollutant. Beta-hexachlorocyclohexane (ß-HCH), dichlorodiphenyltrichloroethane (4.4′-DDT), dieldrin, hexachlorobenzene, oxy-chlordane, cis-heptachlorepoxide were the other main OCPs detected. Mean levels of ΣPCB congeners and WHO_PCB-TEQ were 9.94 and 0.001 ng/g lipid, respectively. PCB 153 showed the highest concentration (3.37 ng/g lipid), followed by PCB 138 and 180. For the dioxin-like PCBs, PCB 118 was the dominant (0.97 ng/g lipid). Naphthalene, phenanthrene, pyrene and fluoranthene were the major PAHs among the 16 PAHs detected. The estimated daily intakes of DDTs, PCBs, HCHs and HCB were not exceeded the tolerable daily intake (TDI) proposed by the Health Canada Guideline. These results indicate that the neonates of Mersin city are exposed to persistent organic pollutants analyzed in this study. However, neonates born in Mersin province are less exposed than the ones born in other regions, considering OCP and PCB levels in breast milk.     

Mechanistic polychlorinated biphenyl exposure modeling of mothers in the Canadian Arctic: the challenge of reliably establishing dietary composition

BackgroundTraditional food (TF) consumption represents the main route of persistent organic pollutant (POP) exposure for indigenous Arctic Canadians. Ongoing dietary transitions away from TFs and toward imported foods (IFs) may contribute to decreasing POP exposures observed in these groups.MethodsTo explore this issue, we combined the global fate and transport model GloboPOP and the human food chain bioaccumulation model ACC-Human Arctic to simulate polychlorinated biphenyl (PCB) exposure in two indigenous Arctic Canadian communities from the Inuvik region, Northwest Territories and Baffin region, Nunavut. Using dietary survey information from initial (1996–98) and follow-up (2005–07) biomonitoring campaigns in Inuvik and Baffin, we simulated PCB exposures (PCB-118, -138, -153, and -180) for each individual study participant and also whole study populations.ResultsTF intake rates, particularly of marine mammals (MMs), were the most important predictors of modeled PCB exposure, while TF consumption did not associate consistently with measured PCB exposures. Further, reported mean TF intake increased from baseline to follow-up in both Inuvik (from 8 to 183 g d^− 1) and Baffin (from 60 to 134 g d^− 1), opposing both the expected dietary transition direction and the observed decrease in human PCB exposures in these communities (ΣPCB Inuvik: from 43 to 29 ng g lipid^− 1, ΣPCB Baffin: from 213 to 82 ng g lipid^− 1). However dietary questionnaire data are frequently subject to numerous biases (e.g., recall, recency, confirmation), and thus casts doubt on the usefulness of these data.ConclusionsUltimately, our model's capability to reproduce historic PCB exposure data in these two groups was highly sensitive to TF intake, further underscoring the importance of accurate TF consumption reporting, and clarification of the role of dietary transitions in future POP biomonitoring of indigenous Arctic populations.     

Maternal dietary intake of dioxins and polychlorinated biphenyls and birth size in the Norwegian Mother and Child Cohort Study (MoBa)

Maternal diet not only provides essential nutrients to the developing fetus but is also a source of prenatal exposure to environmental contaminants. We investigated the association between dietary intake of dioxins and PCBs during pregnancy and birth size. The study included 50,651 women from the Norwegian Mother and Child Cohort Study (MoBa). Dietary information was collected by FFQs and intake estimates were calculated by combining food consumption and food concentration of dioxins, dioxin-like PCBs and non-dioxin-like PCBs. We used multivariable regression models to estimate the association between dietary intake of dioxins and PCBs and fetal growth. The contribution of fish and seafood intake during pregnancy was 41% for dietary dioxins and dioxin-like PCBs and 49% for dietary non-dioxin-like PCBs. Further stratified analysis by quartiles of seafood intake during pregnancy was conducted. We found an inverse dose–response association between dietary intake of dioxins and PCBs and fetal growth after adjustment for confounders. Newborns of mothers in the upper quartile of dioxin and dioxin-like PCBs intake had 62 g lower birth weight (95% CI: − 73, − 50), 0.26 cm shorter birth length (95% CI: − 0.31, − 0.20) and 0.10 cm shorter head circumference (95% CI: − 0.14, − 0.06) than newborns of mothers in the lowest quartile of intake. Similar negative associations for intake of dioxins and dioxin-like PCBs were found after excluding women with intakes above the tolerable weekly intake (TWI = 14 pg TEQ/kg bw/week). The negative association of dietary dioxins and PCBs with fetal growth was weaker as seafood intake was increasing. No association was found between dietary dioxin and PCB intake and the risk for small-for-gestational age neonate. In conclusion, dietary intakes of dioxins and PCBs during pregnancy were negatively associated with fetal growth, even at intakes below the TWI.     

Associations between blood persistent organic pollutants and 25-hydroxyvitamin D3 in pregnancy

Persistent organic pollutants (POPs) are suggested to contribute to lower vitamin D levels; however, studies in humans are scarce and have never focused on pregnancy, a susceptibility period for vitamin D deficiency. We investigated whether serum levels of POPs were associated with circulating 25-hydroxyvitamin D3 [25(OH)D3] concentration in pregnancy. Cross-sectional associations of serum concentrations of eight POPs with plasma 25(OH)D3 concentration were analyzed in 2031 pregnant women participating in the Spanish population-based cohort INfancia y Medio Ambiente (INMA) Project. Serum concentrations of POPs were measured by gas chromatography and plasma 25(OH)D3 concentration was measured by high-performance liquid chromatography in pregnancy (mean 13.3 ± 1.5 weeks of gestation). Multivariable regression models were performed to assess the relationship between blood concentrations of POPs and 25(OH)D3. An inverse linear relationship was found between serum concentration of PCB180 and circulating 25(OH)D3. Multivariate linear regression models showed higher PCB180 levels to be associated with lower 25(OH)D3 concentration: quartile Q4 vs. quartile Q1, coefficient = − 1.59, 95% CI − 3.27, 0.08, p trend = 0.060. A non-monotonic inverse relationship was found between the sum of predominant PCB congeners (PCB 180, 153 and 138) and 25(OH)D3 concentration: coefficient (95% CI) for quartile Q2 vs. Q1 [− 0.50 (− 1.94, 0.94)], quartile Q3 vs. Q1 [− 1.56 (− 3.11, − 0.02)] and quartile Q4 vs. Q1 [− 1.21 (− 2.80, 0.38)], p trend = 0.081. No significant associations were found between circulating 25(OH)D3 and serum levels of p,p′-DDE, p,p′-DDT, HCB, and ß-HCH. Our results suggest that the background exposure to PCBs may result in lower 25(OH)D3 concentration in pregnant women.     

Determination of polybrominated diphenyl ethers in human semen

Some persistent organic pollutants (POPs) have been found in human semen but until this point it was unclear whether polybrominated diphenyl ethers (PBDEs) could be detected in human semen. In this study, PBDEs were found for the first time in human semen samples (n = 101) from Taizhou, China. The concentrations of total PBDEs (∑ PBDEs) varied from 15.8 to 86.8 pg/g ww (median = 31.3 pg/g ww) and 53.2 to 121 pg/g ww (median = 72.3 pg/g ww) in semen and blood samples, respectively. The ∑ PBDE level in semen was about two times lower than in human blood, which was different in the distribution in the two matrices from other POPs. A correlation of ∑ PBDE concentration was found between paired semen and in blood. The results suggest that semen could be used to detect PBDE burden in human body as a non-invasive matrix. In addition, the levels of BDE-209 and BDE-153, especially the latter, were much higher in blood than in semen, while the levels of BDE-28, BDE-47 and BDE-99 were comparable in the two matrices, suggesting that low brominated congeners could be more easily transferred to semen than high brominated congeners. Considering different toxicities among the PBDE congeners, it might be more significant to measure PBDEs in semen than in blood for evaluating male reproduction risks of PBDEs.     

Substantial decline of polychlorinated biphenyls serum levels 10 years after public health interventions in a population living near a contaminated site in Northern Italy

IntroductionPolychlorinated biphenyls (PCBs) are persistent pollutants classified among endocrine disruptors and human carcinogens. In an urban area in Northern Italy (Brescia), a chemical factory producing PCBs from 1938 to 1984 caused soil and food pollution. Since the discovering of the environmental pollution in the area in 2001, various public health interventions have been implemented to avoid human contamination.MethodsTwo independent surveys were carried out in 2003 and 2013 using the same study design and methods. A random sample of the adult general population living in four areas of the town with different soil contamination level was enrolled in both surveys. Investigation included serum levels of 24 PCB congeners and of other common clinical-chemical parameters and questions about residential and occupational history as well as current and past diet and consumption of locally produced food. 537 subjects were tested in the 2003 and 488 in the 2013 survey.ResultsTotal PCB serum levels showed a strong correlation with age (Spearman r = 0.71 in 2003 and r = 0.80 in 2013), but not with gender. Consumers of food produced in the most polluted area had higher total PCB serum levels (median 15.6 and 4.7 ng/ml in 2003 and 2013, respectively) than non-consumers (4.1 and 2.3 ng/ml) and consumers of food produced in non-polluted areas (6.5 and 1.9 ng/ml), with increasing trend of PCB serum levels with cumulative local food intake. PCB serum levels from 2003 to 2013 survey declined by around half in all age groups, especially among the youngest people. The total PCB reduction was found to be due to a combination of a birth cohort effect (− 41% every 10 years) and survey period effect (− 18% in 2013 versus 2003), with medium chlorinated CB congeners showing the most relevant reduction (− 30%) between the two surveys. High chlorinated CBs were more strongly associated with birth cohort (− 46% every 10 years): in the 2013 survey they represented 58% of total PCBs in 60–79 years old while they were 37% among the under 40s with a median value 20 times higher in the oldest than in the youngest (3.1 versus 0.16 ng/ml).ConclusionsPCBs serum levels declined from the 2003 to 2013 survey though they are still high in the elderly mainly because of past intake of locally produced contaminated food. Present findings suggest that PCBs food chain contamination and human absorption have been interrupted successfully in the area since discovery of the pollution in 2001.     

Circulating levels of Persistent Organic Pollutants (POPs) among elderly men and women from Sweden: Results from the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS)

Persistent Organic Pollutants (POPs) are a huge group of chemicals that have been linked to various adverse health effects in humans. Large epidemiological studies investigating gender differences in levels of POPs in the elderly are limited and the results from these are not always consistent. The present study was undertaken to examine the background levels of a broad range of POPs in human plasma samples among elderly men and women from Sweden and to assess the influence of gender. Levels of 23 POPs were determined in plasma samples collected during 2001–2004 from 1016 (50.2% women) 70 year-old participants from the population-based Prospective Study of the Vasculature in Uppsala Seniors (PIVUS). Measurements were performed using high resolution gas chromatography with high resolution mass spectrometry (HRGC-HRMS) and the POPs studied were 16 polychlorinated biphenyls (PCBs), five organochlorine (OC) pesticides, one dioxin, and one brominated flame retardant. The concentrations of the selected POPs were found similar, or comparable, to other studies of non-occupationally exposed populations from Sweden and Europe. Differences in levels of POPs between men and women were assessed by using Wilcoxon rank-sum (Mann–Whitney) test. Significant (p < 0.0001) gender differences in levels of specific POPs were observed and a number of POP concentrations were found to differ between men and women. More specifically, levels of HCB, OCDD, and PCB congeners #74, #105, and #118 were found to be higher in women, while the rest of the majority of POPs were higher in men.     

Dietary intake of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) from fish and meat by residents of Nanjing,China

Concentrations of 14 polybrominated diphenyl ether (PBDEs) and 28 polychlorinated biphenyl (PCBs) congers were measured in 137 samples of fish and meat from Nanjing, a city in the Yangtze River Delta, China. Total concentrations of PBDEs were less in fish (mean of 180 pg/g ww; range 8.0–1100 pg/g ww), but more in non fish foods (mean of 180 pg/g ww; range 15–950 pg/g ww) than those reported from other countries. The total dietary intake of PBDEs and PCBs by humans were 9.9 ng PBDE/d and 870 ng PCB/d, respectively. The daily intake by a 60 kg adult of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ_WHO) from PCBs was estimated to be 49 pg ^PCBTEQ_WHO/d (0.82 pg ^PCBTEQ_WHO/kg bw), which is less than the tolerable daily intake suggested by the World Health Organization (WHO). The daily intake of meat and fish accounted for 57.2% and 42.8% of the total intake of ^PCBTEQ_WHO.     

Levels of selected persistent organic pollutants in blood from delivering women in seven selected areas of São Paulo State,Brazil

Persistent organic pollutants (POPs) present in the living environment are thought to have detrimental health effects on the population, with pregnant women and the developing foetus being at highest risk. We report on the levels of selected POPs in maternal blood of 155 delivering women residing in seven regions within the São Paulo State, Brazil.The following selected POPs were measured in the maternal whole blood: 12 polychlorinated biphenyls (PCBs) congeners (IUPAC Nos. 99, 101, 118, 138, 153, 156, 163, 170, 180, 183, 187, 194); dichlordiphenyltrichloroethane p,p′-DDT, diphenyldichloroethylene p,p′-DDE and other pesticides such as hexachlorocyclohexanes (α-HCH, β-HCH, γ-HCH), hexachlorobenzene (HCB), chlordane derivatives cis-chlordane, trans-chlordane, oxy-chlordane, cis-nonachlor and trans-nonachlor.Statistical comparisons between regions were performed only on compounds having concentrations above LOD in 70% of the samples. PCB118 congener was found to be highest in the industrial site (mean 4.97 ng/g lipids); PCB138 congener concentration was highest in the Urban 3 site (mean 4.27 ng/g lipids) and congener PCB153 was highest in the industrial and Urban 3 sites with mean concentration of 7.2 ng/g lipids and 5.89 ng/g lipids respectively. Large differences in levels of p,p′-DDE between regions were observed with the Urban 3 and industrial sites having the highest concentrations of 645 ng/g lipids and 417 ng/g lipids, respectively; β-HCH was found to be highest in the Rural 1 site; the γ-HCH in Rural 1 and industrial; the HCB in the Rural 1 and industrial sites and oxy-chlordane and t-NC in the Rural 2 sites. An association between levels of some contaminants and maternal age and parity was also found.     

Background exposure to persistent organic pollutants predicts stroke in the elderly

Background exposure to persistent organic pollutants (POPs), lipophilic xenobiotics that accumulate mainly in adipose tissue, has recently emerged as a new risk factor for cardiovascular diseases. This prospective study was performed to evaluate if plasma concentrations of selected POPs predict incident stroke among the elderly. Twenty‐one POPs (including 16 polychlorinated biphenyl (PCB) congeners, 3 organochlorine (OC) pesticides, 1 brominated diphenyl ether (BDE), and 1 dioxin) were measured in plasma collected at baseline in 898 participants aged 70 years of the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS). Stroke diagnosis was validated by hospital records. During the five year follow-up, 35 subjects developed hospital-treated stroke. After adjusting for known stroke risk factors, most PCBs with 4, 5, or 6 chlorine atoms, p,p′-DDE, trans-nonachlor, and octachlorodibenzo-p-dioxin significantly predicted the risk of stroke. Across quartiles of summary measures of PCBs and OC pesticides, the adjusted ORs were 1.0, 0.8 (95% confidence interval: 0.2–2.5), 1.2 (0.4–3.4), and 2.1 (0.7–6.2) for PCBs and 1.0, 1.2 (0.3–4.2), 2.3 (0.7–6.9), and 3.0 (1.0–9.4) for OC pesticides (P for trend = 0.11 and 0.03, respectively). The adjusted ORs among participants ≥ 90th percentile of the summary measures were 5.5 (1.7–18.1) for PCBs and 4.0 (1.1–14.6) for OC pesticides; corresponding ORs for those ≥ 95th percentile were 7.8 (2.1–29.6) and 9.5 (2.3–38.9). Background exposure to POPs may play an important role in development or progression of stroke in the elderly.     

Human dietary intake of organohalogen contaminants at e-waste recycling sites in Eastern China

This study reports concentrations and human dietary intake of hexabromocyclododecanes (HBCDs), polychlorinated biphenyls (PCBs) as well as selected “novel” brominated flame retardants (NBFRs) and organochlorine pesticides, in ten staple food categories. Samples were sourced from areas in Taizhou City, eastern China, where rudimentary recycling and disposal of e-waste is commonplace, as well as from nearby non-e-waste impacted control areas. In most instances, concentrations in foods from e-waste recycling areas exceeded those from control locations. Concentrations of 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) and bis-(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (BEH-TBP) in samples from e-waste sites were 3.09–62.2 ng/g and 0.81–16.3 ng/g lipid weight (lw), respectively; exceeding consistently those in foods acquired from control sites by an order of magnitude in many cases. In contrast, while concentrations of HBCD in some foods from e-waste impacted areas exceed those from control locations; concentrations in pork, shrimp, and duck liver are higher in control samples. This highlights the potential significance of non-e-waste sources of HBCD (e.g. building insulation foam) in our study areas. While concentrations of DDT in all foods examined except pork were higher in e-waste impacted samples than controls; our exposure estimates were well below the provisional tolerable daily intake of 0.01 mg/kg bw/day derived by the Joint FAO/WHO Meeting on Pesticide Residues. Concentrations of ΣPCBs resulted in exposures (650 and 2340 ng/kg bw/day for adults and children respectively) that exceed substantially the Minimal Risk Levels (MRLs) for ΣPCBs of 20 ng/kg bw/day derived by the Agency for Toxic Substances & Disease Registry. Moreover, when expressed in terms of dioxin-like toxicity equivalency based on the four dioxin-like PCBs monitored in this study (DL-PCBs) (PCB-105, 118, 156, and 167); concentrations in e-waste impacted foods exceed limits set by the European Union in 6 of the 8 food groups studied and result in dietary exposures for children (10.2 pg TEQ/kg bw/day) that exceed the WHO tolerable daily intake of 1–4 pg TEQ/kg bw/day.     

Novel brominated flame retardants in food composites and human milk from the Chinese Total Diet Study in 2011: Concentrations and a dietary exposure assessment

On the basis of the fifth Chinese total diet study (TDS) performed in 2011, the dietary exposure of the Chinese population to novel brominated flame retardants (NBFRs) was assessed. Six NBFRs were determined in 80 composite samples from four animal origin food groups and 29 pooled human milk samples. Based on gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS) analysis, the levels of the total NBFRs ranged from < LOD to 70.2 ng/g lipid weight (lw) in food composites and from 2.48 to 23.9 ng/g lw in human milk samples. Decabromodiphenyl ethane (DBDPE), with mean levels of 9.03 ng/g lw in food composites and 8.06 ng/g lw in human milk, was the most abundant compound in the total NBFRs. No obvious spatial distribution patterns in China were observed in food samples or human milk. The average estimated daily intake (EDI) of total NBFRs via food consumption for a “standard Chinese man” was 4.77 ng/kg bodyweight (bw)/day, with a range of 0.681 to 18.9 ng/kg bw/day. Meat and meat products were the main dietary source of NBFRs, although levels of NBFRs in aquatic food were found to be the highest among the four food groups. The average EDI of total NBFRs for nursing infants was 38.4 ng/kg bw/day, with a range of 17.4 to 113 ng/kg bw/day, which was approximately eight-fold higher than the EDI for adults, suggesting the heavy body burden of NBFRs on nursing infants. The levels and EDI of DBDPE in the present study were similar to or higher than those of legacy BFRs (i.e., PBDEs and HBCD) in the TDS 2007, indicating that DBDPE, as a main alternative to PBDEs, might have become the primary BFR used in China.     

Country specific comparison for profile of chlorinated,brominated and phosphate organic contaminants in indoor dust. Case study for Eastern Romania, 2010

We have evaluated the levels and specific profiles of several organohalogenated contaminants, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), novel brominated FRs (NBFRs), and organophosphate FRs (OPFRs), in 47 indoor dust samples collected in 2010 from urban locations from Iasi, Eastern Romania. The dominant contaminants found in the samples were OPFRs (median sum OPFRs 7890 ng/g). Surprisingly, OCPs were also measured at high levels (median 1300 ng/g). Except for BDE 209 (median 275 ng/g), PBDEs were present in dust samples at relatively low levels (median sum PBDEs 8 ng/g). PCBs were also measured at low levels (median sum PCBs 35 ng/g), while NBFRs were only occasionally detected, showing a low usage in goods present on the Romanian market. The results of the present study evidence the existence of a multitude of chemical formulations in indoor dust. FRs are usually associated to human exposure via ingestion of dust, but other chemicals, such as OCPs, are not commonly reported in such matrix. Although OCPs were found at comparable levels with OPFRs in Romanian dust, OCPs possess a higher risk to human health due to their considerably lower reference dose (RfD) values. Indeed, the OCP exposure calculated for various intake scenarios was only 2-fold lower than the corresponding RfD. Therefore, the inclusion of OCPs as target chemicals in the indoor environment becomes important for countries where elevated levels in other environmental compartments have been previously shown.     

Development and validation of prediction models for blood concentrations of dioxins and PCBs using dietary intakes

BackgroundDioxins and PCBs accumulate in the food chain and might exert toxic effects in animals and humans. In large epidemiologic studies, exposure estimates of these compounds based on analyses of biological material might not be available or affordable.ObjectivesTo develop and then validate models for predicting concentrations of dioxins and PCBs in blood using a comprehensive food frequency questionnaire and blood concentrations.MethodsPrediction models were built on data from one study (n = 195), and validated in an independent study group (n = 66). We used linear regression to develop predictive models for dioxins and PCBs, both sums of congeners and 33 single congeners (7 and 10 polychlorinated dibenzo-p-dioxins and furans (PCDDs/PCDFs), 12 dioxin-like polychlorinated biphenyls (PCBs: 4 non-ortho and 8 mono-ortho), sum of all the 29 dioxin-like compounds (total TEQ) and sum of 4 non dioxin-like PCBs (∑ CB-101, 138, 153, 183 = PCB₄). We used the blood concentration and dietary intake of each of the above as dependent and independent variables, while sex, parity, age, place of living, smoking status, energy intake and education were covariates. We validated the models in a new study population comparing the predicted blood concentrations with the measured blood concentrations using correlation coefficients and Weighted Kappa (К_W) as measures of agreement, considering К_W > 0.40 as successful prediction.ResultsThe models explained 78% (sum dioxin-like compounds), 76% (PCDDs), 76% (PCDFs), 74% (no-PCBs), 69% (mo-PCBs), 68% (PCB₄) and 63% (CB-153) of the variance. In addition to dietary intake, age and sex were the most important covariates.The predicted blood concentrations were highly correlated with the measured values, with r = 0.75 for dl-compounds 0.70 for PCB₄, (p < 0.001) and 0.66 (p < 0.001) for CB-153. К_W was 0.68 for sum dl-compounds 0.65 for both PCB₄ and CB-153. Out of 33 congeners 16 (13 dl-compounds and 3 ndl PCBs) had К_W > 0.40.ConclusionsThe models developed had high power to predict blood levels of dioxins and PCBs and to correctly rank subjects according to high or low exposure based on dietary intake and demographic information. These models underline the value of dietary intake data for use in investigations of associations between dioxin and PCB exposure and health outcomes in large epidemiological studies with limited biomaterial for chemical analysis.     

Development and application of simple pharmacokinetic models to study human exposure to di-n-butyl phthalate (DnBP) and diisobutyl phthalate (DiBP)

In a published controlled dosing experiment, a single individual consumed 5 mg each of labeled di-n-butyl phthalate (DnBP) and diisobutyl phthalate (DiBP) on separate occasions and tracked metabolites in his blood and urine over 48 h. Data from this study were used to structure and calibrate simple pharmacokinetic (PK) models for these two phthalates, which predict urine and blood metabolite concentrations with a given phthalate intake scenario (times and quantities). The calibrated models were applied to a second published experiment in which 5 individuals fasted over the course of a 48-h weekend (bottled water only), and their full urine voids were captured and measured for DnBP and DiBP metabolites. One goal of this model application was to confirm the validity of the calibrated models — their validity would be demonstrated if a profile of intakes could be found which adequately duplicated the metabolite concentrations measured in the urine. A second goal was to study patterns of exposure for this group. It was found that all metabolites could be duplicated very well with individual-specific “best-fit” intake scenarios, with one exception. It appears that the model predicted much lower concentrations of the metabolite, 3carboxy-mono-propylphthalate (MCPP), than were observed in all individuals. Modeled as a metabolite of DnBP, this suggests that DnBP was not the major source of MCPP in the urine. For all 5 individuals, the reconstructed dose profiles of the two phthalates were similar: about 6 small bolus doses per day and an intake of about 0.5 μg/kg-day. The intakes did not appear to be associated with diary-reported activities (personal hygiene and medication) of the participants. The modeled frequent intakes suggested one (or both) of two possibilities: ongoing exposures such as an inhalation exposure, or no exposure but rather an ongoing release of body stores of the phthalate metabolites from past exposures.     

Levels of polychlorinated dibenzo-p-dioxins,dibenzofurans (PCDD/Fs) and biphenyls (PCBs) in blood of informal e-waste recycling workers from Agbogbloshie,Ghana, and controls

The formation and environmental release of highly toxic organohalogen compounds associated with informal recycling of waste electric and electronic equipment (e-waste) is a growing problem at e-waste dumps/recycling sites (EWRSs) in many developing countries worldwide. We chose a cross-sectional study design to measure the internal exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) as well as polychlorinated biphenyls (PCBs) of individuals working on one of the largest EWRSs of Africa, located at Agbogbloshie, Accra, Ghana, and in controls from a suburb of Accra without direct exposure to EWRS activities. In whole blood samples of 21 age matched male exposed individuals (mean age: 24.7 years, SD 6.0) and 21 male controls (mean age: 24.4 years, SD 5.7) 17 PCDD/F congeners were determined. Moreover three indicator PCB congeners (#138, #153 and #180) were measured in blood of 39 exposed (mean age: 27.5 years, SD 11.7) and 19 non-exposed (mean age: 26.8 years, SD 9.7) patients. Besides a health examination, biometric and demographic data, residential and occupational history, occupational exposures and working conditions were recorded using a standardized questionnaire. In the exposed group, median PCDD/F-concentrations were 6.18 pg/g lipid base WHO₂₀₀₅-TEq (range: 2.1–42.7) and significantly higher compared to the control group with 4.60 pg/g lipid base WHO₂₀₀₅-TEq (range: 1.6–11.6). Concentrations were different for 2,3,7,8-TetraCDD, three HexaCDD and all 10 PCDF congeners, indicating a combustion pattern. Using a multivariate regression analysis exposure to EWRS activities was the most important determinant for PCDD/F exposure. Median PCB levels for the indicator congeners #138, #153 and #180 were 0.011, 0.019 and 0.008 μg/l whole blood (ranges: 0.002–0.18, 0.003–0.16, 0.002–0.078) in the exposed group and, surprisingly, significantly higher in the controls (0.037, 0.062 and 0.022; ranges: 0.005–0.46, 0.010–0.46, 0.004–0.21). In a multivariate regression approach e-waste related activities had no positive influence on internal PCB exposure, but rather the time living in Accra. The internal PCB exposure is in particular notable for a country where PCBs have historically never been produced or used. The impact of EWRS activities on organohalogen compound exposure of individuals working at and living in the surroundings of the Agbogbloshie EWRS, and the surprisingly high PCB exposure of people living in Accra not involved in e-waste activities require further investigation.     

Fish ingestion and congener specific polychlorinated biphenyl and p,p'-dichlorodiphenyldichloroethylene serum concentrations in a great lakes cohort of pregnant African American women

A cohort of low income, city dwelling, pregnant African American Women (delivered from 1994–1999) was assembled to identify factors related to organochlorine exposure through consumption of Great Lakes resources. The cohort is known as the Great Lakes Cohort of Pregnant African American Women (GLCPAAW). Pregnant women from metropolitan Chicago, IL area clinics were administered a questionnaire on diet, demographics, and health history. Weight, height, and serum lipids were measured at delivery along with serum organochlorines such as PCBs and DDE. Congener specific concentrations of PCBs and p,p'-DDE found in the maternal serum are reported. Dominant PCB congeners found in the serum of the pregnant women at delivery included PCB 101, 118, 138, 153, and 180. The high prevalence and magnitude of PCB 101 (greater than the limit of detection in > 80% of the women in the cohort) are unique characteristics of this cohort.Great Lakes fish has been identified as a source of exposure to organochlorines in several studies. Spearman correlations and robust regression models were utilized to identify the impact of Great Lakes fish ingestion on cohort serum organochlorine concentrations. Several potential confounders of the relationship between serum organochlorines and Great Lakes fish consumption were identified. Covariates related to organochlorines in correlations as well as regression models included age, body surface area, fish ingestion, lipids, parity, race and smoking. Lower chlorinated PCB congeners do not follow the same trends as the higher chlorinated congeners and DDE. The higher chlorinated PCB congeners (PCB 138, 153, and 180) and DDE were correlated with age while the lower chlorinated congeners were not. PCB 153 and 180 regression models included age as a significant covariate. None of the higher chlorinated congeners correlated to race, while both lower chlorinated congeners were correlated to race. Race was also significant in both lower chlorinated congeners' regression models. PCB 101, a lower chlorinated congener seldom found in human serum, is readily found in the cohort. Airborne PCB exposure as well as diminished metabolism of PCB 101 in African Americans may explain the increased presence of PCB 101 and it's correlation with race.High end sport fish consumers (≥ 1meal per week) carried elevated levels of DDE and higher chlorinated PCB congeners (138, 153, and 180) compared to non-sport fish eaters. Unexpectedly, DDE was correlated more consistently with fish ingestion and age (a marker of bioaccumulation) in comparison to PCBs. Small correlations were found between serum PCBs and fish ingestion (Spearman correlation = 0.19 for total PCBs and fish meals per year). Additionally, Serum PCBs in low end Great Lakes sport fish consumers were not higher than non-consumers. These findings suggest the women of the cohort are being exposed to PCBs through other routes in addition to Great lakes sport fish. One major route of exposure may be Chicago air. The observed trends amongst individual PCB congeners has important ramifications because lower chlorinated congeners or their metabolites may be mediators of toxicity. Organochlorine exposure through Great Lakes fish ingestion was clearly identified in high end fish consumers while associations with race, metabolism, and possible airborne exposures pose new questions.     

Development of a synthetic PCB mixture resembling the average polychlorinated biphenyl profile in Chicago air

Studies of environmental and toxic effects of polychlorinated biphenyls (PCBs) are ideally performed with PCB mixtures reflecting the composition of environmental PCB profiles to mimic actual effects and to account for complex interactions among individual PCB congeners. Unfortunately, only a few laboratory studies employing synthetic PCB mixtures have been reported, in part because of the challenges associated with the preparation of complex PCB mixtures containing many individual PCB congeners. The objective of this study was to develop a PCB mixture that resembles the average PCB profile recorded from 1996 to 2002 at a satellite station of the Integrated Atmospheric Deposition Network located at the Illinois Institute of Technology (IIT) in Chicago, Illinois, using commercial PCB mixtures. Initial simulations, using published Aroclor profiles, showed that a mixture containing 65% Aroclor 1242 and 35% Aroclor 1254 was a good approximation of the target profile. A synthetic Chicago air mixture (CAM) was prepared by mixing the respective Aroclors in this ratio, followed by GC/MS/MS analysis. Comparison of the PCB profile of the synthetic mixture with the target profile suggests that the synthetic PCB mixture is a good approximation of the average IIT Chicago air profiles (similarity coefficient cos θ = 0.82; average relative percent difference = 84%). The synthetic CAM was also a reasonable approximation of the average of 184 PCB profiles analyzed in 2007 at 37 sites throughout Chicago as part of the University of Iowa Superfund Basic Research Program (isbrp), with a cos θ of 0.70 and an average relative percent difference of 118%. While the CAM and the two Chicago air profiles contained primarily di- to pentachlorobiphenyls, higher chlorinated congeners, including congeners with seven or eight chlorine atoms, were underrepresented in the synthetic CAM. The calculated TCDD toxic equivalency quotients of the synthetic CAM (2.7 ng/mg PCB) and the IIT Chicago air profile (1.6 ng/mg PCB) were comparable, but lower by two orders of magnitude than the isbrp Chicago air profile (865 ng/mg PCB) due to surprisingly high PCB 126 levels in Chicago air. In contrast, the calculated neurotoxic equivalency quotients of the CAM (0.33 mg/mg PCB) and the two Chicago air profiles (0.44 and 0.30 mg/mg PCB, respectively) were similar. This study demonstrates the challenges and methods of creating and characterizing synthetic, environmental mixtures of PCBs.     

Identification of fipronil metabolites by time-of-flight mass spectrometry for application in a human exposure study

Fipronil is a phenylpyrazole insecticide commonly used in residential and agricultural applications. To understand more about the potential risks for human exposure associated with fipronil, urine and serum from dosed Long Evans adult rats (5 and 10 mg/kg bw) were analyzed to identify metabolites as potential biomarkers for use in human biomonitoring studies. Urine from treated rats was found to contain seven unique metabolites, two of which had not been previously reported—M4 and M7 which were putatively identified as a nitroso compound and an imine, respectively. Fipronil sulfone was confirmed to be the primary metabolite in rat serum. The fipronil metabolites identified in the respective matrices were then evaluated in matched human urine (n = 84) and serum (n = 96) samples from volunteers with no known pesticide exposures. Although no fipronil or metabolites were detected in human urine, fipronil sulfone was present in the serum of approximately 25% of the individuals at concentrations ranging from 0.1 to 4 ng/mL. These results indicate that many fipronil metabolites are produced following exposures in rats and that fipronil sulfone is a useful biomarker in human serum. Furthermore, human exposure to fipronil may occur regularly and require more extensive characterization.     

Three decades (1983–2010) of contaminant trends in East Greenland polar bears (Ursus maritimus). Part 1: Legacy organochlorine contaminants

Legacy organochlorine contaminants were determined in adipose tissues from 294 polar bears (Ursus maritimus) sampled in East Greenland in 23 of the 28 years between 1983 and 2010. Of 19 major legacy contaminants and congeners (ΣPCB, 4 PCB congeners (CB153, 180, 170/190), ΣDDT, p,p′-DDE, p,p′ -DDD and p,p′-DDT, α- and β-hexachlorocyclohexane (HCH), HCB, octachlorostyrene, dieldrin, oxychlordane, cis- and trans-chlordane, cis- and trans-nonachlor, heptachlor epoxide and BB-153), 18 showed statistically significant average yearly declines of − 4.4% (range: − 2.0 to − 10.8%/year) among subadult polar bears (i.e. females < 5 years, males < 6 years). For example, the ∑ PCB concentrations declined 2.7 fold from 22 730 ng/g lw (95% C.I.: 12 470–32 990 ng/g lw) in 1983–1986 to 8473 ng/g lw (95% C.I.: 6369–9776 ng/g lw) in 2006–2010. Similar but fewer statistically significant trends were found for adult females and adult males likely due to smaller sample size and years. Despite declines as a result of international regulations, relatively high levels of these historic pollutants persist in East Greenland polar bear tissues.