Total Toxic Equivalents Research Articles

Evaluation of serum markers of blood redox homeostasis and inflammation in PCB naturally contaminated heifers undergoing decontamination

Dioxins and polychlorinated biphenyls (PCBs) are widely spread and long persistent contaminants. The aim of this study was to evaluate physiological changes associated with the decontamination of animals previously exposed to environmental pollutants. Eight Limousine heifers were removed from a polluted area and fed a standard ration for six months. The extent of contamination was defined by measuring total toxic equivalents (TEQ) values of dioxin like-PCBs (DL-PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs), and NDL-PCBs amount in pericaudal fat two weeks after the removal from the contaminated area (day 0) and then bimonthly for six months during the decontamination (days 59, 125, and 188). The concentrations of both DL-PCBs+PCDD/Fs and NDL-PCBs at the start of decontamination (day 0) were higher than those legally admitted, and they were strongly decreased at the end of the experimental period. Specific indices of blood redox homeostasis and inflammation were also measured at each time. Serum concentrations of Retinol, Tocopherol and Ascorbate, the total antioxidant capacity (TAC) and the activities of superoxide dismutase and glutathione peroxidase were lower at day 0 than after 59, 125 or 188days of decontamination. Protein-bound carbonyls (PC), nitro-tyrosine (N-Tyr), and lipid hydroperoxides concentrations were higher at day 0 than during decontamination. In addition, TAC, PC and N-Tyr levels correlated with both DL-PCB and NDL-PCB concentrations only at day 0. Serum concentrations of TNF-alpha and Haptoglobin were higher in samples collected at day 0 than in those obtained during decontamination. As Haptoglobin and TNF-alpha levels correlated with both DL-PCB and NDL-PCB concentrations at day 0 and at day 59 (when these concentrations are still over legal limit), they might represent easily measurable parameters for assessing acute exposure to pollutants. Further both N-Tyr and TNF-alpha concentrations could be used as bio-monitoring markers of the decontamination procedure.

The exposure of the Croatian population to toxic environmental contaminants – “Dioxin-like” PCBs

We measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (PCBs), and non-dioxin-like PCBs in paired samples of blood and breast milk collected from 67 secundiparas in Sapporo City, Japan, and combined this data with those of the 30 secundiparas previously measured. The arithmetic mean total toxic equivalents (TEQ-WHO) concentrations of PCDDs, PCDFs, non-ortho PCBs, and mono-ortho PCBs in blood and breast milk of the 97 secundiparous subjects were 3.0–23 (mean: 13, median: 14) and 2.7–20 (mean: 8.6, median: 8.5) pg TEQ g−1 lipid, respectively. The sums of the concentrations of 56 non-dioxin-like PCB congeners that were measured in the subjects’ blood and breast milk were 16–326 (mean: 107, median: 100) and 12–252 (mean: 73, median: 67) ng g−1 lipid, respectively. The partitioning ratios of individual congeners of PCDDs, PCDFs, dioxin-like PCBs, and non-dioxin-like PCBs from blood to breast milk in secundiparas were almost the same as those of primiparas that have been recently reported, suggesting that the partitioning ratios of these compounds from maternal blood to breast milk in women is little affected by delivery. Furthermore, the partition of PCB congeners with chlorine at the 2-, 3-, 4′-, and 5-positions or the 2-, 4-, 4′-, and 5-positions of the biphenyl ring from the blood to the breast milk tended to occur at a higher level than that of other congeners. In particular, the levels of tetraCB-74 and hexaCB-146 in the breast milk for both primiparous and secundiparous mothers were slightly higher than those in the blood.

Heavy metals and polycyclic aromatic hydrocarbons in surface sediments of Karoon River, Khuzestan Province, Iran.

Karoon is the longest river in Iran and provides water for industries located along its banks, such as metal, petrochemical, and oil industries. It is also the source of drinking water for cities such as Ahwas, Abadan, and Khorramshahr. In this study, 34 and 18 surface sediment samples were collected and analyzed for heavy metals (Al, As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) and polycyclic aromatic hydrocarbons (PAHs). The measured concentrations of heavy metals were compared with US EPA sediment quality guidelines, and the results showed that Cu concentration was above the threshold effect level (TEL) in 65.67% of the samples and Hg concentration was above the effect range median (ERM) in some samples. The results revealed that Hg was severely enriched (5 < enrichment factor < 20) and classified in very high ecological risk index category. It is the major metallic contaminant in the study area. The total PAH concentrations ranged from 11.54-117,730 μg/kg, with the mean value of 7034.55 μg/kg dominated by lower molecular weight (LMW) PAHs. The total potentially carcinogenic PAHs (∑cPAHs) in sediment samples ranged from 2.09 to 31,930 μg/kg, indicating high carcinogenic potential of sediments in the study area. The total toxic equivalent (TEQ) values ranged from 1.06 to 7228.7 μg/kg. Maximum TEQ occurred in Abadan oil refinery station followed by Khorramshahr soap factory and Abadan petrochemical complex. Principal component analysis and cluster analysis also revealed the relationships between the studied parameters and identified their probable sources.

Triple quadrupole tandem mass spectrometry: A real alternative to high resolution magnetic sector instrument for the analysis of polychlorinated dibenzo-p-dioxins, furans and dioxin-like polychlorinated biphenyls

This paper reports on the optimisation, characterisation, validation and applicability of gas chromatography coupled to triple quadrupole mass spectrometry in its tandem operation mode (GC-QqQ(MS/MS) for the quantification of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs, dioxins) and dioxin-like polychlorinated biphenyls (DL-PCBs) in environmental and food matrices. MS/MS parameters were selected to achieve the high sensitivity and selectivity required for the analysis of this type of compounds and samples. Good repeatability for areas (RSD = 1–10%, for PCDD/Fs and DL-PCBs) and for ion transition ratios (RSD = 0.3–10%, for PCDD/Fs, and 0.2–15%, for DL-PCBs) and low instrumental limits of detection, 0.07–0.75 pg μL−1 (for dioxins) and 0.05–0.63 pg μL−1 (for DL-PCBs), were obtained. A comparative study of the congener specific determination using both GC-QqQ(MS/MS) and gas chromatography-high resolution mass spectrometry (GC-HRMS) was also performed by analysing several fortified samples and certified reference materials (CRMs) with low (feed and foodstuffs), median (sewage sludge) and high (fly ash) toxic equivalency (TEQ) concentration levels, i.e. 0.60, 1.83, 72.9 and 3609 pg WHO-TEQ(PCDD/Fs) g−1. The agreement between the results obtained for the total TEQs (dioxins) on GC-QqQ(MS/MS) and GC-HRMS in all the investigated samples were within the range of ±4%, and that of DL-PCBs at concentration levels of 0.84 pg WHO-TEQs (DL-PCBs) g−1, in the case of feedstuffs, was 0.11%. Both instrumental methods have similar and comparable linearity, precision and accuracy. The GC-QqQ(MS/MS) sensitivity, lower than that of GC-HRMS, is good enough (iLODs in the down to low pg levels) to detect the normal concentrations of these compounds in food and environmental samples. These results make GC-QqQ(MS/MS) suitable for the quantitative analysis of dioxins and DL-PCBs and a real alternative tool to the reference sector HRMS instruments.

Increased levels of dioxin-like substances in adipose tissue in patients with deep infiltrating endometriosis.

Are the levels of biologically active and the most toxic dioxin-like substances in adipose tissue of patients with deep infiltrating endometriosis (DIE) higher than in a control group without endometriosis? DIE patients have higher levels of dioxins and polychlorinated biphenyls (PCBs) in adipose tissue compared with controls without endometriosis. Some studies have investigated the levels of dioxin-like substances, in serum samples, in patients with endometriosis, with inconsistent results. Case-control study including two groups of patients. The study group (DIE group) consisted of 30 patients undergoing laparoscopic surgery because of DIE. In all patients, an extensive preoperative work-up was performed including clinical exploration, magnetic resonance imaging (MRI) and transvaginal sonography. All patients with DIE underwent a confirmatory histological study for DIE after surgery. The non-endometriosis control group (control group), included the next consecutive patient undergoing laparoscopic surgery in our center due to adnexal benign gynecological disease (ovarian or tubal procedures other than endometriosis) after each DIE patient, and who did not present any type of endometriosis. During the surgical procedure 1-2 g of adipose tissue from the omentum were obtained. Dioxin-like substances were analyzed in adipose tissue in DIE patients and controls without endometriosis. The total toxic equivalence and concentrations of both dioxins and PCBs were significantly higher in patients with DIE in comparison with the control group (P < 0.05), mainly due to the significantly higher values of the two most toxic dioxins (2,3,7,8-tetrachlorodibenzo-p-dioxin [2,3,7,8-TCDD] and 1,2,3,7,8-pentachlorodibenzo-p-dioxin [1,2,3,7,8-PeCDD]) (P < 0.01 for each compound). The levels of furan 2,3,4,7,8-PeCDF were statistically higher in the DIE group compared with controls. Only four congeners of PCBs had toxic equivalence values and concentrations that were statistically higher in patients with DIE, but these included the most toxic and carcinogenic PCB-126 (PCB-114 P < 0.05; PCB-156 P < 0.05; PCB-189 P = 0.04; PCB-126 P < 0.01). Since few patients were recruited, the study is only exploratory. Our results need to be confirmed in larger and more heterogeneous population studies since environmental and even genetic factors involved in determining dioxins and PCBs widely vary in different countries. Furthermore, the strict eligibility criteria used may preclude generalization of the results to other populations and the surgery-based sampling frame may induce a selection bias. Finally, adipose tissue was obtained only from the omentum, and not from other adipose tissue of the body. Our results suggest a potential role of dioxin-like substances in the pathogenesis of DIE. Further studies are warranted to confirm our findings. None. Not applicable.

Measurement of Chlorinated Dioxins and Furans in Cigarette Mainstream Smoke

Summary Chlorinated dioxins and furans (‘dioxins’) are not ordinarily detected in cigarette smoke at levels likely to exceed the recommended ‘safe’ limits recognised by health and environmental protection agencies. By convention they are measured in terms of their total toxic equivalence (TEQ). The method developed by this group utilises high sensitivity gas chromatography-tandem mass spectrometry (GCMS/ MS). The limit of detection (LOD) was determined to be 4.3 pg TEQ/cig; under ISO 3308 smoking conditions. Dioxins are not subject to any routine regulatory control in cigarette smoke. However, certain dioxin congeners are highly toxic and they have been cited by the United States Food and Drug Administration (FDA) as harmful and potentially harmful constituents (HPHC) of tobacco smoke. This raises the issue of how to monitor and measure uncertainty when the analyte(s) of interest are not normally present in the matrix of interest. In the absence of a reference cigarette containing levels of dioxins above the detection limit; we prepared test pieces containing known quantities of 17 dioxin congeners, regarded by the World Health Organisation (WHO) as significantly toxic. This paper provides data for the transfer rates performed under ISO 3308 (ISO) and Health Canada Intense (HCI) machinesmoking conditions; and proposes a means to estimate the uncertainty (U) based on TEQ. [Beitr. Tabakforsch. Int. 26 (2015) 214-218]

Comparison of the contributions of polychlorinated dibenzo-p-dioxins and dibenzofurans and other unintentionally produced persistent organic pollutants to the total toxic equivalents in air of steel plant areas

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and the “dioxin-like” (dl) compounds polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polybrominated dibenzo-p-dioxins (PBDDs), and dibenzofurans (PBDFs), were determined in the air samples collected from six steel plants. The toxic equivalent (TEQ) concentrations of the PCDDs, PCDFs, dl-PCBs, dl-PCNs, PBDDs, and PBDFs in the air were 0.01–0.19pgWHO-TEQNm−3, 0.01–0.69pgWHO-TEQNm−3, 0.001–0.089pgWHO-TEQNm−3, 0.002–0.011pgTEQNm−3, 0.004–0.02pgTEQNm−3, and 0.02–0.12pgTEQNm−3, respectively. The PCNs were the most abundant compounds (by mass concentration), contributing about 87% of the total mass concentrations of the analytes that were found in the air of the steel plant areas. The PCDFs contributed about 47% of the total TEQs, following by the PBDFs (28%) and the PCDDs (18%). The dioxin-like compounds together contributed up to 40% of the total TEQs, so their contributions to the toxic effects that could be caused by exposure to the air of the steel plant areas were significant. The congener profiles in the air were similar to the congener profiles that were found in stack gas emissions, indicating that the steelmaking plants were possible sources of the PCDDs, PCDFs, and dioxin-like compounds that were found in the air of the steel plant areas.

Polychlorinated naphthalene concentrations and profiles in cheese and butter, and comparisons with polychlorinated dibenzo-p-dioxin, polychlorinated dibenzofuran and polychlorinated biphenyl concentrations

Polychlorinated naphthalenes (PCNs) are candidates for inclusion in the Stockholm Convention on persistent organic pollutants. PCNs are structurally and toxicologically similar to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) and its analogues. Intake in food is considered to be an important human exposure pathway for PCNs. In this preliminary study, cheese and butter samples were analysed for PCNs, polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) using an isotope dilution gas chromatography high-resolution mass spectrometry method. The aim of this study was to evaluate the PCN concentrations in the cheese and butter samples and to compare them with the PCDD, PCDF and PCB concentrations. The PCN concentrations were 5.6–103 pg g−1 of wet weight in the seven cheese samples tested and 5.0–199 pg g−1 of wet weight in the seven butter samples tested. The mass concentrations of lower chlorinated congeners were greater than those of the higher chlorinated congeners. Congeners of CN45/36, CN27/30 and CN33/34/37 were much more abundant than other congeners found in tetrachlorinated PCNs. Congeners of CN51, CN66/67 and CN73 were determined to be the predominant congeners in penta-, hexa- and heptachlorinated homologs, respectively. The PCNs contributed around 5% of the total PCN, PCDD, PCDF and PCB toxic equivalence (TEQ) values. CN73 was found to be the dominant PCN congener and contributed more than 40% to the PCN TEQ value. Congeners CN66/67, CN69 and CN63 were also found at relatively high levels. The PCB congener CB118 was the predominant congener (by mass-based concentration) of the 12 dioxin-like PCBs (dl-PCBs). The PCBs contributed 53.8% of the total TEQ, and congener CB126 contributed more than any other compound that was analysed to the total TEQ. The PCDDs and PCDFs contributed 11.6% and 29.7% of the total TEQ values, respectively.

Performance of the CalTOX fate and exposure model in a case study for a dioxin-contaminated site.

Soil with high levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) is found at contaminated sites all over the world. Transfer of PCDD/Fs from contaminated soil to the food chain could lead to elevated human exposure. As a complement to available monitoring data, multimedia fate and exposure modeling can be applied to support risk assessment of sites with PCDD/F contaminated soil. In this study, we evaluated the performance of the CalTOX fate and exposure model for 2,3,7,8-substituted PCDD/Fs against measured concentrations in air, soil, grass, carrots, potatoes, milk, meat, and eggs from a contaminated site in northern Sweden. The calculated total toxic equivalent (TEQ) concentrations agree with measurements within a factor of 10 for all exposure media but one. Results for individual congeners demonstrated that the model did not always perform well at describing key processes that mobilize PCDD/Fs out of soils, such as transfer into root crops and ingestion of soil by chickens. Uncertainty in only a small subset of input parameters affects the model output. Improved information and models describing transfer of soil particles onto leafy vegetation by rain splash and biotransfer factors for PCDD/Fs to milk, meat, and eggs are particular research needs to reduce uncertainties in model-based assessments.

Chlorinated dibenzo-p-dioxin and dibenzofuran congener and homologue distributions in tree bark from Sauget, Illinois, U.S.

Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) are ubiquitous urban/industrial contaminants found in tree bark, which acts as a long-term passive atmospheric sampler. Twenty seven bark samples (tree age 8–92 years) were collected from residential and industrial areas near Sauget, IL to identify the trends of 2,3,7,8-Cl PCDD & PCDF congener distributions, toxic equivalents (TEQ), and PCDD & PCDF homologue distributions. The Sauget area is heavily industrialized, with a long history of chlorine production, and is the largest single contributor to air pollution exposure risk in St. Louis. Analysis of seven 2,3,7,8 Cl-substituted PCDD and 10 PCDF congeners showed ∑PCDD7 ranging from 2214 to 71821 pg g(–1) lipid and ∑PCDF10 from 355 to 13707 pg g(–1) lipid, the highest in trees <20 years old in both cases. OctaCCD and octaCDF respectively dominated ∑PCDD7 (89% average) and ∑PCDF10 (57% average). The 2,3,7,8-Cl congener profiles showed slight differences among samples showing that all were affected by similar sources but at different magnitudes. ∑TEQ ranged from 35 to 624 pg g(–1) lipid, dominated by 1,2,3,7,8-PeCDD (average = 41.3% of total TEQ). Tetra-Cl through hepta-Cl homologues were dominated by non-2,3,7,8-Cl compounds for both CDD and CDF. Homologue profiles for 26 samples had a “sink” profile dominated by octaCDD, whereas one sample showed effects of a local source.

Human Exposure to PCDD/F in Contaminated Soil at a Former Sawmill Site in Sweden - Now a Residential Area

In a residential area in mid-Sweden, built in 1993, a sawmill was previously situated between 1920 and 1980. The sawmill used pentachlorophenol in dip tanks as a wood preservative. In 2012 and 2013 the authorities analyzed 56 soil samples in the residential area of 50,000 m2. The highest level of PCDD/F (polychlorinated dibenzo-p-doxins and dibenzofurans), contaminants in pentachlorophenol, found in the soil was 1,500 ng total toxic equivalent (TEQ) per kg dry weight (dw). PCDD/F is suspected, even at low concentrations, to cause reproductive and developmental problems, disturbance of the immune system, interfere with hormones, contribute to cardiovascular diseases and also to cause cancer. For this reason a risk assessment was made by calculation of the intake of PCDD/F, based on methods developed by The US Environmental Protection Agency (EPA). Children (&lt; 2 years) playing outdoors have been found to put soil in their mouth with an average oral intake of 120 mg soil per day. Soil contaminated with 1,500 ng TEQ per kg dw could therefore in a child result in an exposure of 9.0 pg TEQ per kg body weight (bw)/day. A single oral intake of 5 grams could result in 375 pg TEQ/kg bw (for a child weighing 10 kg). For an adult the corresponding intake was 0.5 TEQ/kg bw (50 mg soil/day) and 53 pg TEQ/kg bw (70 kg). Dermal uptake for PCDD/F, at 3% absorption, was 4.5 TEQ/kg bw for children and 0.6 TEQ/kg bw for adults. Inhalation of contaminated dust was regarded as negligible. There is no local food production in the area and groundwater was not used for drinking water. In the nearby lake the maximum PCDD/F concentration in the sediment was 41 ng TEQ/kg dw. An involuntary gulp of sediment-mixed lake water could result in exposure of 2.0 pg TEQ/kg bw for children and 0.3 pg TEQ/kg bw for adults. The tolerable daily intake of 2 pg TEQ per kg bw/day set by the European Union could be exceeded for children when playing in the contaminated soil or in shallow areas of the lake.

Dioxin-Like Chemicals Exposure Leads to an IL-22-Related Autoimmune Trait in Human

Dioxin-Like Chemicals Exposure Leads to an IL-22-Related Autoimmune Trait in HumanAbstract Number:2092 Nian-wei Lee*, Yue-liang Guo Nian-wei Lee* National Taiwan University Hospital Department of Environmental and Occupational Medicine, Taiwan, E-mail Address: [email protected] Search for more papers by this author and Yue-liang Guo National Taiwan University Hospital Department of Environmental and Occupational Medicine, Taiwan, E-mail Address: [email protected] Search for more papers by this author AbstractBackground: Over 2000 Taiwanese ingested cooking rice oil contaminated with polychlorinated biphenyls (PCBs) and polychlorinated dibenzofurans (PCDFs) in 1979. A Yucheng (‘oil-disease’ in Chinese) registry was established for long-term follow-up, including 1991 exposed subjects. A highly-increased mortality of systemic lupus erythematosus (SLE) was observed in the exposed women starting 10 years after the exposure. This study determined whether serum markers of autoimmunity were related to dioxin-like chemicals (DLCs) exposure.Methods: A total of 24 Yucheng women and 48 age/neighborhood-matched referent women, both without clinical SLE, donated blood for this study. Serum interleukin (IL)-17A, IL-22, IL-4, interferon (IFN)-gamma, and antinuclear antibody (ANA) were measured.Results: Serum IL-17A level was mildly elevated in Yucheng women (mean±standard deviation, 18.1±6.8 pg/ml) compared to referents (14.4±5.3 pg/ml; p=0.03), whereas serum IL-22 level was significantly higher in Yucheng women (65.7±32.3 pg/ml) than in referents (32.4±11.1 pg/ml; p<0.0001). No differences were observed in IL-4 and IFN-gamma. Serum IL-22 level was further found to be positively correlated with serum total toxic equivalent (TEQ) in Yucheng women (R squared=0.64, p<0.0001). Serum concentration of IL-17A and total TEQ were uncorrelated in Yucheng women (R squared=0.04, p=0.37). In addition, a higher percentage of Yucheng women (71%) had elevated serum ANA compared to referents (33%; p=0.002). While Yucheng and referent women were divided respectively into two groups, ANA (-) and ANA (+) [ANA (-): ANA titer<40 (+); ANA (+): ANA titer≥1:40 (+)], serum IL-22 level was highest in Yucheng women with ANA (+) (p<0.0001).Conclusion: IL-22-secreting, aryl hydrocarbon receptor-bearing T helper cells seem to play a key role in the DLC-triggering autoimmune trait.

Fly ash-mediated formation of polychlorinated naphthalenes during secondary copper smelting and mechanistic aspects

Thermal experiments (at 250–450°C for 10–240min) on fly ash from secondary copper smelting process (SeCu) were performed to study the polychlorinated naphthalene (PCN) formation in the post-zone of a secondary copper smelter. Unexpectedly high concentrations of PCNs were formed. Total PCN concentrations and toxic equivalents were 47–104 and 44–80 times higher than the initial concentration and toxic equivalent, respectively. The thermal disposal of SeCu fly ash should therefore be reconsidered. The kinetic of each homolog was determined under different thermal conditions. Less chlorinated homologs favored 350°C and more chlorinated homologs favored higher temperature. Most of the homologs reached an equilibrium of formation and degradation within 30min, except octachloronaphthalene which did not appear to reach such an equilibrium even after 240min. Chlorine substitution of the formed PCNs was identified and a similar pattern was found in chlorination products starting with naphthalene and chlorine. Furthermore, inorganic chlorine and unsubstituted naphthalene were found in the reaction products, confirming that the formation of naphthalene and the chlorination of that naphthalene could occur and could be suggested to be an important PCN formation route. A detailed formation pathway from naphthalene through octachloronaphthalene is proposed.

Contribution of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) to the toxic equivalency of dioxin-like compounds in archived biosolids from the U.S. EPA's 2001 national sewage sludge survey.

The World Health Organization recently proposed the inclusion of brominated congeners in addition to chlorinated congeners when computing the toxic equivalency (TEQ) of dioxin-like compounds (DLCs) in assessments of human health risks. In the present study, 12 polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) were analyzed by gas chromatography/high resolution mass spectrometry in the composited, archived biosolids that were collected in 32 U.S. states and the District of Columbia from 94 wastewater treatment plants by the United States Environmental Protection Agency in its 2001 national sewage sludge survey. Two PBDDs and five PBDFs were detected in the biosolids composites at varying frequencies (40–100%) with a total mean concentration of 10,000 ng/kg dry weight (range: 630–42,800), of which 1,2,3,4,6,7,8-hepta-BDF constituted about 95% by mass. Relative to commercial polybrominated diphenyl ether (PBDE) formulations, the ratio of PBDD/Fs to PBDEs in biosolids was 55-times higher (∼0.002% vs ∼0.11%), which indicates potential PBDE transformation or possibly additional sources of PBDD/Fs in the environment. The TEQ contribution of PBDD/Fs was estimated at 162 ng/kg 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) (range: 15–672), which is equivalent to 75% (range: 12–96%) of the total TEQ in biosolids. The TEQ of DLCs released annually to U.S. soils as a result of the land application of biosolids was estimated at 720 g (range: 530–1600 g). Among all known DLCs determined in biosolids, brominated analogs contributed 370% more TEQ than did chlorinated congeners, which indicates the need to include brominated DLCs in the exposure and risk assessment of land-applied biosolids.

Unintentional formed PCDDs, PCDFs, and DL-PCBs as impurities in Chinese pentachloronitrobenzene products.

Pentachloronitrobenzene (PCNB) products have been reported to contain relatively high levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) as impurities. No data was available for Chinese PCNB products which are still produced and used in China. Therefore, we analysed Chinese PCNB products, including two raw pesticides and three formulations available on the market. In all samples, PCDDs, PCDFs, and dioxin-like polychlorinated biphenyls (DL-PCBs) were detected at levels exceeding Japanese regulation limits. The concentrations of PCDDs and PCDFs (0.16 to 0.93 ng TEQ g(-1)) were lower than the PCNB formulations measured from the Australian market (3.9 ng TEQ g(-1)). However, the Toxic Equivalent (TEQ) contribution from DL-PCBs (0.7 to 2.5 ng TEQ g(-1)) to total TEQ was higher compared to PCDDs and PCDFs. This discovery demonstrated that it is necessary to consider the DL-PCBs impurity in organochlorine pesticides and other organochlorine chemicals in particular chlorinated aromatic compounds for adequate risk assessment. In addition to DL-PCBs, other unintentionally POPs-hexachlorobenzene (HCB) (3.7 to 52 ng g(-1)) and pentachlorobenzene (PeCBz) (0.04 to 0.3 ng g(-1)) which are listed in the Stockholm Convention-were detected in the PCNB samples. The PCNB production steps were assessed for their unintentional POPs formation potential. Thermolysis of the aromatic compounds using iron chloride (FeCl3) as catalyst is suggested as relevant production step for (DL-)PCBs formation. Since the levels in the formulated PCNB recalculated to active ingredient were higher compared to the raw pesticide, the formulation process (e.g., milling) may also have had an influence on additional PCDD/Fs and PCBs formation.

Persistent organic pollutants and liver dysfunction biomarkers in a population-based human sample of men and women

Background and objectivePersistent organic pollutants (POPs) are stable organic compounds generated through different industrial activities. Liver is involved in the metabolism of POPs, and hence exposure to POPs may interfere with liver function. Although a few studies have shown adverse effects of POPs on liver function, large-scale studies involving humans are lacking. We performed this large population-based cross-sectional study to assess the associations between different POPs and liver dysfunction biomarkers. MethodsA total of 992 individuals (all aged 70 years, 50% males) were recruited as part of Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) cohort. The total toxic equivalency (TEQ) value was calculated for seven mono-ortho and two non-ortho substituted polychlorinated biphenyls (PCBs) and octachloro-p-dibenzodioxin (OCDD) to assess their toxicological effects. The association of TEQ values, summary measures of 16 PCBs (sum of PCBs) and three organochlorine pesticides (sum of OC pesticides) with liver dysfunction biomarkers (bilirubin; alkaline phosphatase, ALP; alanine aminotransferase, ALT; and gamma-glutamyltransferase, GGT) was analyzed utilizing linear regression analysis. ResultsThe mono-ortho PCB TEQ values were found to be significantly positively associated with bilirubin (β=0.71, P=0.008), while sum of OC pesticide concentrations was negatively associated with ALP (β=−0.02, P=0.002) after adjusting for various potential confounders. When analyzed individually, a number of different POPs were associated with ALP, ALT and bilirubin. No such association with GGT was observed. ConclusionVarious POPs including PCBs, OCDD and pesticides were associated with the liver dysfunction biomarkers bilirubin, ALT and ALP, suggesting adverse effects on liver function from these environmental pollutants.

Gas chromatography–triple quadrupole mass spectrometry for the determination of atmospheric polychlorinated naphthalenes

Atmospheric polychlorinated naphthalenes (PCNs) ranging from mono-CNs to octa-CNs were detected using isotope-dilution gas chromatography coupled with triple quadrupole mass spectrometry (GC–MS/MS). The developed instrumental method was successfully applied to the determination of PCNs in technical products. It was observed that there were significant differences in concentrations, homologue profiles, chlorinated contents and total toxic equivalents (∑TEQs) of PCNs for four Halowax products. Subsequently, the validation of the analytical method was evaluated for the determination of PCNs in air samples in terms of method detection limit (MDL), recovery and matrix effect. The results demonstrated that this method could provide satisfactory sensitivity and adequate selectivity with lower cost. It was conducted to comprehensively evaluate the levels, composition patterns, ∑TEQs, and daily intake exposure of PCNs in indoor and outdoor air samples. Concentrations and ∑TEQs of PCNs in air samples ranged 47.7–832.7pgm−3 and 1.31–5.99fgm−3, respectively, and the predominant homologues were di- and tri-CNs in the gas phase. The results indicated that this analytical method was useful for the accurate and specific evaluation of dioxin-like toxicity and human exposure levels of PCNs in the atmosphere.

Influence of persistent organic pollutants on the complement system in a population-based human sample

BackgroundPersistent organic pollutants (POPs) are toxic compounds generated through various industrial activities and have adverse effects on human health. Studies performed in cell cultures and animals have revealed that POPs can alter immune-system functioning. The complement system is part of innate immune system that helps to clear pathogens from the body. We performed a large-scale population-based study to find out associations between summary measures of different POPs and different complement system markers. MethodsIn this cross-sectional study, 16 polychlorinated biphenyls (PCBs), 3 organochlorine (OC) pesticides, octachloro-p-dibenzodioxin, and 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) were analyzed for their association with levels of protein complement 3 (C3), 3a (C3a), 4 (C4) and C3a/C3 ratio. A total of 992 individuals (all aged 70years, 50% females) were recruited from the Prospective Investigation of the Vasculature in Uppsala Seniors cohort. Regression analysis adjusting for a variety of confounders was performed to study the associations of different POP exposures (total toxic equivalency value or TEQ and sum of 16 PCBs) with protein complements. ResultsThe TEQ values were found to be positively associated with C3a (β=0.07, 95% CI=0.017–0.131, p=0.01) and C3a/C3 ratio (β=0.07, 95% CI=0.015–0.126, p=0.01) taking possible confounders into account. The association observed was mainly driven by PCB-126. ConclusionIn this study involving 992 elderly individuals from the general population, we showed that POPs, mainly PCB-126, were associated with levels of complement system markers indicating that the association of these toxic compounds with downstream disease could be mediated by activation of immune system.

Influence of persistent organic pollutants on oxidative stress in population-based samples

Persistent organic pollutants (POPs) are a large group of chemicals widely used and produced in various industrial applications. Many cell culture/animal studies have shown that POPs can induce oxidative stress. Since such data is lacking in humans, we conducted a large population-based study to analyze associations between POPs and oxidative stress markers. We measured following POPs; 16 polychlorinated biphenyls (PCBs), 5 organochlorine (OC) pesticides, octachlorinated dibenzo-p-dioxin, and polybrominated diphenyl ether 47, and oxidative stress markers; homocysteine, reduced [GSH] and oxidized glutathione [GSSG], glutathione ratio [GSSG/GSH], total glutathione, oxidized low-density lipoprotein [ox-LDL], ox-LDL antibodies, conjugated dienes, baseline conjugated dienes of LDL, and total anti-oxidative capacity in plasma samples collected from 992 70-year old individuals (50% women) from the population-based Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) cohort. Linear regression analyses were performed to study the associations between oxidative stress markers and summary measures of POPs including the total toxic equivalence (TEQ), sums of PCBs and OC pesticides (main exposures) while adjusting for potential confounders. In multivariable-adjusted analyses, sum of PCBs showed strong associations with ox-LDL (β=0.94; P=2.9*10−6). Further, sum of PCBs showed association with glutathione-related markers (GSSG: β=−0.01; P=6.0*10−7; GSSG/GSH: β=−0.002; P=9.7*10−10), although in reverse direction. Other summary measures did not show any significant association with these markers. In our study of elderly individuals from the general population, we show that plasma levels of POPs are associated with markers of increased oxidative stress thereby suggesting that even low dose background exposure to POPs may be involved in oxidative stress.

Persistent organic pollutants and inflammatory markers in a cross-sectional study of elderly Swedish people: the PIVUS cohort.

Background: Persistent organic pollutants (POPs) are compounds that are generated through various industrial activities and released in the surrounding environment. Different animal studies have shown effects of different POPs on various inflammatory markers.Objective: Because very few studies have been conducted in humans, we assessed the associations between different POPs and inflammatory markers in a large population-based sample of elderly men and women (all 70 years of age) from Sweden.Methods: This cross-sectional study investigated the concentrations of several polychlorinated biphenyls (PCBs), organochlorine pesticides, polychlorinated dibenzo-p-dioxin, and brominated diphenyl ether congeners and their association with a number of inflammatory markers [vascular cell adhesion molecule 1 (VCAM-1), intercellular adhesion molecule 1 (ICAM-1), E-selectin, C-reactive protein (CRP), total leucocyte count, tumor necrosis factor α (TNF-α), monocyte chemotactic protein 1 (MCP-1), and interleukin 6 (IL-6)] in 992 individuals. These individuals were recruited from the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) cohort. We used a total toxic equivalency (TEQ) value that measures toxicological effects with the relative potencies of various POPs.Results: Following adjustment for potential confounders, the TEQ value (driven mainly by PCB-126) was significantly associated with levels of ICAM-1 (p < 10–5). A similar trend was also observed between sum of PCBs and VCAM-1 (p < 0.001). No significant associations were observed between levels of POPs and other inflammatory markers.Conclusions: TEQ values were associated with levels of ICAM-1, to a lesser degree also with VCAM-1, but not with CRP and several other inflammatory markers. These findings suggest an activation of vascular adhesion molecules by POPs, and particularly by PCB-126.Citation: Kumar J, Lind PM, Salihovic S, van Bavel B, Ingelsson E, Lind L. 2014. Persistent organic pollutants and inflammatory markers in a cross-sectional study of elderly Swedish people: The PIVUS cohort. Environ Health Perspect 122:977–983; http://dx.doi.org/10.1289/ehp.1307613