Atmospheric concentrations of PCDD/Fs,PAHs, and metals in the vicinity of a cement plant in Istanbul

The levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polycyclic aromatic hydrocarbons (PAHs), and metals (Al, As, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Tl, V, and Zn) in particulate matter (PM10) were determined in ambient air at selected two sampling points located under the influence of a cement plant and a background/control sampling point in Büyükçekmece Istanbul. The samplings of PM10, PCDD/Fs, and PAHs were carried out simultaneously from September 2011 to November 2012 with EN 12384, EPA TO-9A, and EPA TO-13A, respectively. Quartz-fiber filters and glass adsorbent cartridge containing the polyurethane foam (PUF) are installed in air sampler for PAHs and PCDD/Fs sampling. The mean concentrations of PCDD/Fs in SP-1, SP-2, and SP-3 (control point) were 5.5?±?1.7 fg I-TEQ m^?3, 8.5?±?2.6 fg I-TEQ (International Toxic Equivalents)?m^?3, and 0.2?±?0.1 fg I-TEQ m^?3, respectively. The higher PAHs and BaP concentrations during winter were probably due to increasing emissions from residential heating. Ca, Mg, Al, Fe, K, and Na showed elevated concentration values compared to other metals, with mean values of 10,401?±?1,050 and 3,934?±?397, 473?±?43 and 301?±?27, 1,478?±?177 and 1,465?±?176, 1,168?±?151 and 934?±?121, 700?±?69 and 1,380?±?137, and 1,181?±?94 and 434?±?35 ng m^?3 in the sampling and control points, respectively. The results of principal component analysis (PCA) and Pearson correlation analysis were consistent with those of literature for similar areas and showed a clear distinction between the sampling points and the source profiles. The ambient air concentrations of PCDD/Fs, PAHs, and metals in the vicinity of a cement plant were presented for the first time in Turkey through this work.     

人体胎盘组织二噁英和多溴联苯醚化合物负荷水平初步研究

目的 建立人体胎盘组织样品氯化二苯并二噁英(PCDD)和呋喃(PCDFs)、多氯联苯(PCBs)、多溴联苯醚(PBDEs)化合物同时准确定量检测分析方法,揭示上述持久性有机污染物人体负荷水平,并初步进行危险性评估.方法 采用国际权威标准方法--核素(同位素)稀释的高分辨气相色谱/高分辨双聚焦磁式质谱联用(HRGC/HRMS)技术,以多离子检测方法对人体胎盘组织样品中17个PCDD/Fs和12个共平面PCBs以及7个PBDEs化合物分别进行定性和定量分析,用WHO-TEF值计算所有样品的毒性当量浓度∑TEQ(PCDD+PCDFs+PCBs)和PBDEs浓度,进一步对人体二嗯英和PBDEs化合物负荷水平进行危险性评估.结果 6个胎盘组织样品中PCDD/Fs和PCBs化合物毒性当量总浓度∑TEQ(PCDD+PCDFs+PCBs)中位数是18.15 WHO-TEQ pg/g脂肪.范围分布在5.14～67.01 WHO-TEQ pg/g脂肪之间.2,3,4,7,8-PeCDFs、1,2,3,7,8-PeCDDs、PCB126是毒性当量的主要贡献者,合计占65%.以7个化合物计算PBDEs总浓度,6个样品的中位数值为2.73 ng/g脂肪,均数为7.17 ng/g脂肪,范围是0.95～25.99 ng/g脂肪.BDE47是最主要的污染同系物,占到35%.浓度最高的一个受试样品其毒性当量总浓度∑TEQ(PCDD+PCDFs+PCBs)已经达到世界上已知高暴露区人体二噁英污染负荷水平.结论 我们在本研究中建立了人体组织样品中持久性有机化合物二噁英和PBDEs化合物同时准确定量检测方法,高二噁英负荷水平的样品提供者可能对胎儿存在健康危害的高暴露风险,对于健康的远期影响还需要深入进行医学追踪研究.     

PCDD/Fs and Dioxin-Like PCBs in Sediments from Yellow Estuary and Yangtze Estuary, China

Twenty one surface sediments were analyzed for PCDD/Fs and dioxin-like PCBs by HRGC-HRMS in Yellow Estuary and Yangtze Estuary in China. The concentration ranges of 2,3,7,8-substituted PCDD/Fs, dioxin-like PCBs and WHO-TEQ were 2.33–253, 0.04–139 and 0.11–1.01 pg/g dw respectively in sediment from two estuaries. For PCDD/Fs and dioxin-like PCBs, OCDD, CB77, CB105 and CB118 were found to be dominant. The pollution levels in two estuaries were lower compared with that in other locations reported by previous studies.     

PCBs,PCDD/Fs,and PBDEs in blood samples of a rural population in South Germany

The body burden of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like (dl-PCBs) and non-dioxin-like (ndl-PCBs) polychlorinated biphenyls, and polybrominated diphenyl ethers (PBDEs) was determined in blood samples from 70 subjects between 4 and 76 years old. The participants of the study were recruited in the neighborhood of a reclamation plant located in a rural area in Southern Germany.The median concentrations (95th percentiles in parentheses), expressed as WHO₂₀₀₅-TEQ (toxic equivalents), for PCDD/Fs and dl-PCBs were 4.5 (17.9) pg g⁻¹ l.w. and 2.6 (13.2) pg g⁻¹ l.w., respectively. The dl-PCBs contributed 40% of the total TEQ (median values), and the most abundant congener was PCB 156. Combined, the sum of the 6 non-dioxin-like PCBs had a median of 0.773 μg L⁻¹ and a 95th percentile of 4.895 μg L⁻¹. For the six tetra to hepta PBDE congeners, the median was 1.8 ng g⁻¹ l.w. (95th percentile: 16.2 ng g⁻¹ l.w.). None of our study subjects had a body burden that exceeded the biomonitoring equivalents for dioxins or PBDE congener 99 or the human biomonitoring values for ndl-PCBs. Likewise the study group did not exceed German reference values or values obtained in similar investigations.Overall, our study did not exhibit elevated internal exposures. The results also hint further decreasing tendencies for PCDD/Fs, PCBs, and PBDEs in Germany and demonstrates that people in the vicinity of a reclamation plant with no indication of an environmental contamination did not exhibit elevated internal exposures.     

高分辨质谱法测定海鱼中二噁和多氯联苯

目的　采用同位素稀释的HRGC/HRMS法定量检测鱼体中 17种 2 ,3,7,8-氯取代的二 (PCDD/Fs)和 12种二多氯联苯 (PCBs)。方法　参照美国EPA16 13及EPA16 6 8A方法 ,采用索式抽提和自动纯化系统(FMS)对鱼体中的PCDD/Fs及PCBs进行纯化和富集、用同位素稀释气相色谱与高分辨质谱联用 -多离子检测方法检测。结果　该方法可对样品中的PCDD/Fs及PCBs同系物进行有效分离 ,PCDD/Fs同位素标准物的回收率为83 83%～ 98 4 8% ,PCBs同位素标准物的回收率为 5 0 0 6 %～ 90 5 6 %。 13种PCDD/Fs在鱼体中可检出 ,总毒性当量 (TEQ)为 0 86 pg/g ,12种二PCBs在鱼体中均可检测出 ,总TEQ值为 2 77pg/ g。结论　该方法可以同时对同一样品中的 17种PCDD/Fs及 12种二PCBs进行检测 ,检测效率高 ,结果准确可靠     

Assessment of PCBs and PCDD/Fs Along the Chinese Bohai Sea Coastline Using Mollusks as Bioindicators

Mollusk samples such as bivalves and gastropods were collected from eight sampling sites along Bohai Sea coastline from northeastern China. The samples were analyzed for polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC-HRMS) to elucidate bioaccumulation of persistent organic pollutants in benthon. Residue levels of ΣPCBs and ΣPCDD/Fs were in the ranges of 66.1 to 583.6 ng/g and 0.9 to 15317 pg/g on a lipid-weight basis, respectively, The pollution source was identified using principal component analysis (PCA) in some coastal areas. It indicated that the typical pollution sources were characterized by PCB₃, which was one Chinese technical product of PCBs. PCA also revealed the similarity patterns of PCBs between identical species collected from the different sites. The higher gastropod PCB concentrations were related to a former capacitor factory and the paint factories in some coastal areas, but this was not the case with the bivalves. The results of this study suggest that some gastropod species may be a potential bioindicator or “sentinel” organism for marine PCBs monitoring.     

高分辨质谱法测定海鱼中二噁(口英)和多氯联苯

目的采用同位素稀释的HRGC/HRMS法定量检测鱼体中17种2,3,7,8-氯取代的二噁(口英)(PCDD/Fs)和12种二噁(口英)多氯联苯(PCBs).方法参照美国EPA1613及EPA1668A方法,采用索式抽提和自动纯化系统(FMS)对鱼体中的PCDD/Fs及PCBs进行纯化和富集、用同位素稀释气相色谱与高分辨质谱联用-多离子检测方法检测.结果该方法可对样品中的PCDD/Fs及PCBs同系物进行有效分离,PCDD/Fs同位素标准物的回收率为83.83%～98.48%,PCBs同位素标准物的回收率为50.06%～90.56%.13种PCDD/Fs在鱼体中可检出,总毒性当量(TEQ)为0.86 pg/g,12种二噁(口英)PCBs在鱼体中均可检测出,总TEQ值为2.77pg/g.结论该方法可以同时对同一样品中的17种PCDD/Fs及12种二噁(口英)PCBs进行检测,检测效率高,结果准确可靠.     

高分辨质谱法测定海鱼中二噁英和多氯联苯

目的采用同位素稀释的HRGC／HRMS法定量检测鱼体中17种2，3，7，8-氯取代的二噁英(PCDD／R)和12种二噁英多氯联苯(PCBs)。方法参照美国EPA1613及EPA1668A方法，采用索式抽提和自动纯化系统(FMS)对鱼体中的PCDD／Fs及PCBs进行纯化和富集、用同位素稀释气相色谱与高分辨质谱联用一多离子检测方法检测。结果该方法可对样品中的PCDD／Fs及PCBs同系物进行有效分离，PCDD／Fs同位索标准物的回收率为83．83％～98．48％，PCBs同位素标准物的回收率为50．06％～90．56％。13种PCDD／Fs在鱼体中可检出，总毒性当量(TEQ)为0．86pg／g，12种二噁英PCBs在鱼体中均可检测出，总TEQ值为2．77pg／g。结论该方法可以同时对同一样品中的17种PCDD／Fs及12种二噁英PCBs进行检测，检测效率高，结果准确可靠。     

Levels of PCDD/Fs,PBDEs, and PBDD/Fs in Breast Milk from Southern Taiwan

This study investigates the congener-specific concentrations of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polybrominated dibenzo-p-dioxins/furans (PBDD/Fs), and polybrominated diphenyl ethers (PBDEs) in 25 breast milk samples from southern Taiwan. Most investigated congeners in Taiwanese breast milk are detectable except for PBDD/Fs. The geometric means of PCDD/Fs and PBDEs in the breast milk are 2.44 pg WHO₂₀₀₅-TEQ/g lipid and 2810 pg/g lipid. Several PCDD/F and PBDE congeners were highly correlated to each other like 1,2,3,7,8-PeCDD and 2,3,4,7,8-PeCDF (r?=?0.919, p?<?0.001). The longest duration of menstruation could be predicted by BDE-153 (β?=?0.252) and 1,2,3,4,6,7,8-HpCDF (β?=?0.345) with adjustment of confounders using a multiple stepwise linear regression model (r?=?0.963, p?<?0.001).     

Assessment of exposure to PCDD/F, PCB, and PAH at a basic oxygen Steelmaking (BOS) and an iron ore sintering plant in the UK

An assessment was carried out at a UK integrated steelworks to investigate the exposure of workers via inhalation to dioxins [polychlorinated dibenzo-p-dioxins (PCDD/F)], polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAH) including benzo[a]pyrene (B[a]P). Investigations focused on a basic oxygen steelmaking (BOS) plant and an iron ore sintering plant. The highest concentrations of PCDD/F and dioxin-like PCB were found at the BOS vessels and sinter strand area at the BOS and sinter plant, respectively. A risk assessment was carried out by comparing the daily intake of PCDD/F and PCB via inhalation with the recommended tolerable daily intake (TDI) proposed by the World Health Organisation (WHO). For the most exposed category of worker in this study (i.e. sinter plant workers inside the strand area), the estimated daily intake via inhalation was estimated to be 0.25 pg WHO-toxic equivalent concentrations (TEQ) kg(-1) body weight (bw). Considering that the average UK adult exposure to PCDD/F from the diet is 1.8 pg WHO-TEQ kg(-1) bw day(-1), the results indicated that the estimated daily intake of PCDD/F and PCB via inhalation for sinter plant workers would not result in the recommended range of the TDI (1-4 pg WHO-TEQ kg(-1) bw day(-1)) being exceeded. Cancer risks for a 40-year occupational exposure period were determined by multiplying the estimated intake by the inhalation cancer potency factor for 2,3,7,8-tetrachlorodibenzo-p-dioxin. For the most exposed category of worker, cancer risks from exposure to PCDD/F and PCB ranged from 2.5 × 10(-6) to 5.2 × 10(-5). Under most regulatory programmes, excess cancer risks between 1.0 × 10(-6) and 1.0 × 10(-4) indicate an acceptable range of cancer risk, suggesting a limited risk from PCDD/F and PCB exposure for workers in the sinter plant. With regard to PAH, B[a]P concentrations were typically <10 ng m(-3) at all locations at both the sinter plant and the BOS plant. In several cases, particularly at the sinter plant, B[a]P concentrations were well below or only marginally above the target value of 1 ng m(-3) specified in ambient air by the European Commission in the fourth 'Daughter' Directive of the Air Quality Framework Directive suggesting a very low risk of exposure for workers. For PAH, excess cancer risks ranged from 2.4 × 10(-6) to 7.3 × 10(-6) for BOS plant workers and from for 5.3 × 10(-7) to 1.5 × 10(-5) for sinter plant workers, well within the acceptable range proposed by the US EPA.     

Evidence of PCDD/Fs and PCBs Contamination in Trees Grown in Forests Far from Their Production and Contamination-Free Areas

Polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in trees grown in pathless forests were analyzed to investigate their dispersal patterns in the atmosphere. The pg/g levels of 23 PCCD, 22 PCDF, and 54 PCB congeners were identified. The total amount of PCDDs in the red pine tree sample (95.8 pg/g) was approximately 7 times that in the beech tree sample (13.2 pg/g). The total amount of PCDFs in the red pine tree sample (71.1 pg/g) was also approximately 7 times that in the beech tree sample (11.1 pg/g). The total amounts of PCBs in the red pine tree and beech tree samples were 1,380 and 1,150 pg/g, respectively. The (Cl₁–Cl₃)-PCBs comprised 63.1 % and 67.6 % of total PCBs in the red pine and in the beech, respectively. The results of the present study indicate that PCDD/Fs and PCBs are transferred over long distances in the atmosphere and accumulated in the contamination-free areas.     

广州城区大气PM10中二(恶)英季节分布特征及健康风险评估

目的 了解广州城区大气PM10中二(恶)英(PCDD/Fs)季节分布特征并进行健康风险评估.方法 于2013年7月(夏)、10月(秋)采集大气PM 10样品,每月连续采样10d,利用高分辨率气相色谱-高分辨质谱(HRGC/HRMS)分析了颗粒物中二(恶)英含量,在此基础上分析了PCDD/Fs组成变化特征和来源,并对其进行健康风险评价.结果 夏秋两季PM10浓度为0.065～0.208 mg/m3,PM10中17种PCDD/Fs总浓度为0.483～12.166 pg/m3.秋季PCDD/Fs总浓度高于夏季,但PCDD/Fs单体含量水平无明显季节变化特征.秋季PCDD/Fs的毒性当量浓度是夏季的2.38倍;PM10中PCDD/Fs致癌风险为4.69×10-1L5.51×10-12.结论 本次调查的广州城区大气PM10中二(恶)英水平有明显季节特征,秋季高于夏季,致癌风险低于可接受水平.     

浙江省部分地区河塘底泥及鲫鱼中二噁英和多氯联苯的污染特征研究

目的了解浙江省典型污染地区河塘底泥和鲫鱼中二噁英和多氯联苯的污染状况。方法样品加入同位素标记内标物,经有机溶剂提取浓缩后,再经凝胶色谱、多层硅胶柱和氧化铝柱净化,以高分辨气相色谱高分辨质谱仪测定二噁英和多氯联苯残留。结果5个地区河塘底泥和鲫鱼中二噁英和多氯联苯的浓度范围分别为379.6～9811.6pg/g干重、10000～762433pg/g干重和0.084～12.168pg/g湿重、149.03～57304pg/g湿重;总毒性当量范围为11.2～2162pg/g干重和0.234～39.251pg/g湿重。结论二噁英和多氯联苯在5个地区的底泥和鲫鱼中均有不同程度的检出,但以路桥地区为最严重,废旧电器拆解产业是当地环境中多氯联苯的主要排放源,该地区二噁英类物质的污染状况已不容忽视。     

Comparison of Historical Record of PCDD/Fs, Dioxin-Like PCBs, and PCNs in Sediment Cores from Jiaozhou Bay and Coastal Yellow Sea: Implication of Different Sources

The concentrations of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) were measured in two sediment cores collected from Jiaozhou Bay. The concentrations of PCDD/Fs, dioxin-like PCBs, and PCNs in the cores were in the range of 2.8–26.3, 7.1–82.4 and 3.9–56.4 pg/g dw, respectively. The depth profiles of total concentrations PCDD/Fs and dioxin-like PCBs were similar in the sediment core J37 inside Jiaozhou Bay, but different from those in the sediment core J94 outside the bay, suggesting the different sources. In both cores Tri-CNs and Tetra-CNs were dominant, similar to the PCNs composition of some Halowax technical products. The maximal PCNs contamination occurred in the mid-1970s (outside the Bay) and early-1990s (inside the Bay). An increase of the indicator CN congeners characteristic for thermal source in the top layers of the sediment core inside the bay indicated that the contribution from the municipal solid waste incineration has been more important in recent years.     

Polytopic vector analysis of soil, dust, and serum samples to evaluate exposure sources of PCDD/Fs

As part of the University of Michigan Dioxin Exposure Study, soil, household dust, and serum samples were collected from more than 750 households in five populations around the city of Midland and in Jackson and Calhoun Counties, Michigan, USA. Polytopic vector analysis, a type of receptor model, was applied to better understand the potential sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans found in these samples and to quantify the contributions of the sources in each matrix across populations. The results indicated that source signatures found in soil are similar to those found in dust, reflecting various combustion profiles, pentachlorophenol, and graphite electrode sludge. The profiles associated with contamination in the Tittabawassee River, likely related to historical discharges from the Dow Chemical Company facility in Midland, exhibited the largest differences among the regional populations sampled. Differences in serum source contributions among the study populations were consistent with some of the regional differences observed in soil samples. However, the age trends of these differences suggested that they are related to past exposures, rather than ongoing sources. Environ. Toxicol. Chem. 2012; 31: 2191-2200. ? 2012 SETAC.     

Exposure assessment and sensitisation in workers exposed to organic acid anhydrides

Objectives: To clarify whether the intensity of exposure to organic acid anhydrides (OAAs) is associated with the risk of sensitisation to these allergens. Methods: The investigations were carried out in three different manufacturing plants (A, B, and C) where OAAs were used in the production of epoxy resins. Methyltetrahydrophthalic acid anhydride (MTHPA) was used in all three plants. The exposure assessment included stationary and ambient air monitoring (OAAs in the air) and biological monitoring (metabolites in urine). In plant A 20, in plant B 86 and in plant C 113 employees were examined by a physician (anamnesis, skin-prick test, specific IgE, spirometry). In plants B and C, the exposure areas were classified as high, medium, and low, without the results of the exposure assessment being known. Results: The ambient air concentrations (in μg/m³) of MTHPA were 37.2 and 58.5 in plant A (number of samples n=2), ranged from <0.5–26.2 in plant B (n=5) and from 2.1–57.9 in plant C (n=3) with stationary air collecting, and from 8–45 (n=6), from <4.7–35.7 (n=3) and from 2–37.8 (n=3) with personal air collection. The metabolites of OAAs in urine (in nmol/mmol creatinine) ranged from 5.7–645 (median of MTHPA: 346) in plant A, from <1–213 (median of MTHPA: 10.1) in plant B and from 0.1–830 (median of the sum of the OOA metabolites: 108.6) in plant C. The prevalence of sensitisation was 35% in plant A, 21% in plant B and 29% in plant C. A higher prevalence in the highly exposed areas, however, could not be seen. Levels of IgE specific for conjugates of MTHPA were not associated with the metabolites in the end of shift urine. Levels of IgG specific for conjugates of MTHPA, however, were associated with the metabolites in the end of shift urine. Conclusions: The data showed that biological monitoring is a useful tool in the exposure assessment of OAAs. Comparing the prevalence of sensitisation and the results of biological monitoring, between the three plants, we found that sensitisation increased with increasing exposure. Within a plant a higher risk of sensitisation in persons working in highly exposed areas at the time of the examination could not be seen, possibly due to frequent job rotation. Received: 2 August 1999 / Accepted: 29 January 2000     

典型地区食品中二噁英的污染水平分析

目的 评价典型行业所在地区食品样品中17种PCDD/Fs的污染水平.方法 使用同位素稀释技术以高分辨气相色谱-高分辨质谱(HRGC-HRMS)测定采自于垃圾焚烧厂、氯化工厂、铸造厂周边以及对照组地区的猪肉、牛肉、鸡肉、牛奶、鸡蛋、水产类及蔬菜样品中的17种二嗯英(PCDD/Fs).结果 OCDD是主要的污染物,平均含量值为0.75 pg/g wet weight;其次,垃圾焚烧厂、氯化工厂、铸造厂周边地区的食品样品中17种PCDD/Fs的毒性当量浓度(TEQ)会显著高于对照组,蔬菜样品中TEQ值会明显低于其他样品;另外,结合已有的食物消费量,计算标准人的二噁英类物质的每月膳食暴露量会远低于JECFA规定的PTMI(70 pg/kg bw/month).结论 垃圾焚烧厂,铸造厂和对照组周边地区人群目前由膳食摄入PCDD/F而导致的潜在健康风险处于较低的水平.     

Evaluation of ocular hazards due to electric arc flash at an in-line switch

We investigated the ocular damage resulting from operation of a solid blade pole-mounted in-line electrical switch at between 16 and 17 kV with current loads between 38 A and 340 A. Spectroradiometric data for the electric arcs produced as the switch was opened were obtained over the waveband 200 to 1500 nm. The eyes of adult pigmented rabbits were exposed to the arc flash at a distance of 2 m. The ocular tissues were assessed clinically and histologically up to 48 h postexposure. Threshold damage was clinically detectable only in eyes exposed to a 340 A arc. We conclude that at the normal current loads on a 17-kV electric power transmission line, the principal oculovisual hazards are due to molten metal fulminated from the switch by the arc, and after-images due to the bright visible light flash. At a working distance of 2 m, the ultraviolet ocular hazard is negligible. Adequate eye protection is provided by clear polycarbonate safety lenses.