Chlorinated and brominated organic contaminants in fish from Shanghai markets: a case study of human exposure

In the present study were two favorite edible fish species for local residents, i.e., mandarin fish and crawfish, collected from the Shanghai market and analyzed for selected organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), hexabromocyclododecane (HBCDD), polybrominated diphenyl ethers (PBDEs) and methoxylated PBDEs (MeO-PBDEs). Efforts were also made to identify the potential sources of these contaminants. Comparable concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and HBCDD were found in muscle tissue of mandarin fish from Guangdong (GDF), the Pearl River Delta and from Taihu Lake (TLF), the Yangtze River Delta. Levels of chlordanes, PCBs and PBDEs were about one magnitude lower in TLF compared to GDF. The concentrations of OCPs in the butter-like gland of the crawfish (CFB) were 2-5 times of those in the crawfish muscle (CFM) while concentrations of PCBs, PBDEs and MeO-PBDEs were comparable. The different patterns and levels of chlorinated and brominated organohalogen contaminants seen in mandarin fish from GDF and TLF indicates that different types of chemicals might be used in the two delta regions. The present study also shows a good correlation between the concentrations of hexachlorobenzene (HCB) and pentachloroanisol (PCA) in fish for the first time. Fish consumption limits based on chemical contaminants with non-carcinogenic effects were calculated. The estimated maximum daily consumption limit for GDF, TLF, CFM and CFB were 1.5, 2.6, 3.7 and 0.08 kg, respectively, indicating no significant risk regarding the persistent organic pollutants measured in the present study.     

多溴联苯醚降解和分析研究进展

介绍了多溴联苯醚(PBDEs)在环境中的分布情况,综述了近年来国内外对PBDEs测定方法以及化学催化降解、生物降解和热解等PBDEs降解技术的研究进展,并对PBDEs研究的未来发展方向进行了展望。     

Parental phenols exposure and spontaneous abortion in Chinese population residing in the middle and lower reaches of the Yangtze River

Widespread use of phenols has led to ubiquitous exposure to phenols. In experimental animals, phenols increased resorptions, reduced live litter size and fetal body weights. However, there are limited epidemiological evidences of the relationships between exposure to phenols and pregnancy outcomes. We evaluated the associations between parental urinary levels of various phenols and spontaneous abortion in a Chinese population residing in the middle and lower reaches of the Yangtze River. A case-control study was conducted that included 70 case couples with medically unexplained spontaneous abortion and 180 control couples who did not have a history of spontaneous abortion and had at least one living child. Both parental urinary phenols were measured by ultra-high performance liquid chromatography-tandem mass spectrometry including bisphenol A (BPA), benzophenone-3 (BP-3), 2,3,4-trichlorophenol (2,3,4-TCP), pentachlorophenol (PCP), 4-n-octylphenol (4-n-OP) and 4-n-nonylphenol (4-n-NP). Compared with the low exposure group, there was an increased risk of spontaneous abortion with high paternal urinary PCP concentration [odds ratio (OR) = 2.09, 95% Confidence Interval (CI), 1.05–4.14], and maternal exposure to 4-n-OP and alkylphenol(s) also significantly increased the risk of spontaneous abortion (OR = 2.21, 95% CI, 1.02–4.80; OR = 2.81, 95% CI, 1.39–5.65, respectively). Our study firstly provides the evidence that paternal PCP exposure, maternal 4-n-OP and alkylphenol(s) exposure are associated with spontaneous abortion in humans.     

Factors influencing on the bioaccessibility of polybrominated diphenyl ethers in size-specific dust from air conditioner filters

Size-specific concentrations and bioaccessibility of polybrominated diphenyl ethers (PBDEs) in dust from air conditioner filters were measured, and the factors influencing the PBDE bioaccessibility were determined. Generally, the PBDE concentrations increased with decreasing dust particle size, and BDE209 (deca-BDE) was generally the predominant congener. The bioaccessibility ranged from 20.3% to 50.8% for tri- to hepta-BDEs, and from 5.1% to 13.9% for BDE209 in dust fractions of varied particle size. The bioaccessibility of most PBDE congeners decreased with increasing dust particle size. The way of being of PBDE (adsorbed to dust surface or incorporated into polymers) in dust significantly influenced the bioaccessibility. There was a significant negative correlation between the tri- to hepta-BDE bioaccessibility and organic matter (OM) contents in dust. Furthermore, tri- to hepta-BDE bioaccessibility increased with increasing polarity of OMs, while with decreasing aromaticity of OMs. The tri- to hepta-BDE bioaccessibility significantly positively correlated with the surface areas and pore volumes of dust. Using multiple linear regression analysis, it was found that the OM contents and pore volumes of dust were the most important factors to influence the tri- to hepta-BDE bioaccessibility and they could be used to estimate the bioaccessibility of tri- to hepta-BDEs according to the following equation: bioaccessibility (%) = 45.05 − 0.49 × OM% + 1.79 × pore volume. However, BDE209 bioaccessibility did not correlate to any of these factors.     

Exposure to inhaled THM: Comparison of continuous and event-specific exposure assessment for epidemiologic purposes

Trihalomethanes (THMs) (chloroform, bromoform, dibromochloromethane, and bromodichloromethane) are the most abundant by-products of chlorination. People are exposed to THMs through ingestion, dermal contact and inhalation. The objective of this study was to compare two methods for assessing THM inhalation: a direct method with personal monitors assessing continuous exposure and an indirect one with microenvironmental sampling and collection of time–activity data during the main event exposures: bathing, showering and swimming. This comparison was conducted to help plan a future epidemiologic study of the effects of THMs on the upper airways of children. 30 children aged from 4 to 10 years were included. They wore a 3M^™ 3520 organic vapor monitor for 7 days. We sampled air in their bathrooms (during baths or showers) and in the indoor swimming pools they visited and recorded their time–activity patterns. We used stainless steel tubes full of Tenax^® to collect air samples. All analyses were performed with Gas Chromatography and Mass Spectrometry (GC-MS). Chloroform was the THM with the highest concentrations in the air of both bathrooms and indoor swimming pools. Its continuous and event exposure measurements were significantly correlated (r_s = 0.69 p < 0.001). Continuous exposures were higher than event exposures, suggesting that the event exposure method does not take into account some influential microenvironments. In an epidemiologic study, this might lead to random exposure misclassification, thus underestimation of the risk, and reduced statistical power. The continuous exposure method was difficult to implement because of its poor acceptability and the fragility of the personal monitors. These two points may also reduce the statistical power of an epidemiologic study. It would be useful to test the advantages and disadvantages of a second sample in the home or of modeling the baseline concentration of THM in the home to improve the event exposure method.     

PBDEs的来源特征、环境分布及污染控制

多溴联苯醚(Polybrominated diphenyl ethers,PBDEs)生产应用、环境分布与生态风险之间的关系将如何影响我国的未来,具体涉及到工业、环境、健康、人类繁衍等的社会问题.由于PBDEs阻燃效率高,热稳定性好,价格便宜,作为添加剂被广泛应用在电子、电器、化工、交通、建材、纺织、石油等领域的阻燃产品中.PBDEs进入环境后迁移扩散并富集于沉积物和生物体内,进入人体后引起肝脏毒性、内分泌干扰、神经毒性和生育能力下降等而危害人类的健康.基于此,从生产应用、品种生产量、分子的物理化学特性以及毒性等的文献数据分析了PBDEs的来源特征与环境危害,分析这些性质对环境分布与污染控制的基础支持关系;从沉积物、水体、大气、水生生物、人体5个方面考察了PBDEs的环境本底浓度变化、分配关系、迁移规律、时间效应,分析了生产、应用与扩散的多因素影响关系,发现全球性PBDEs污染物蔓延的现象,沉积物是主要的归趋场所,室内空气中的浓度远高于室外,水中浓度较低,水生生物和人体均能富集PBDEs,通过饮食、母乳和呼吸摄入,可实现代际传播,污染的分布呈现介质与区域的不同特征;污染控制需要考虑点源技术与面源修复的联合,结合PBDEs的物理性质、分子结构及其化学特性,统计分析了微生物法、光化学降解法和零价铁还原法的原理及其有效性,根据PBDEs在产品中存在与分布的特点,提出收集-分离-富集-超临界催化还原和氧化毁毒的工艺,针对实际环境(以电子垃圾塑料和流域水体及沉积物为对象)中的PBDEs进行回收或处理,结合材料如催化剂的应用,从动力学和热力学方面提高PBDEs无害化的效率.最后,从生产管理、环境监测、风险评价、技术集成等方面提出了未来的努力方向.     

交联壳聚糖冠醚的合成及其对金属离子的吸附性能

本文合成了交联壳聚糖苯并－１５－冠－５醚和交联壳聚糖苯并－１８－冠－６醚,研究了它们对Ａｇ（Ⅰ）Ｐｄ（Ⅱ）,Ｐｂ（Ⅱ）,Ｃｄ（Ⅱ）,Ｃｒ（Ⅲ）等金属离子的吸附性能和选择性,实验结果表明：无论是在单一金属离子体系还是在二元或三元金属离子体系中,ＣＣＴＳ－ＢＸ和ＣＣＴＳ－ＢＹ对Ａｇ（Ⅰ）和Ｐｄ（Ⅱ）者有较高的吸附选择性。     

Prediction of polychlorinated dibenzofuran congener distribution from gas-phase phenol condensation pathways

A model for predicting the distribution of dibenzofuran and polychlorinated dibenzofuran (PCDF) congeners from a distribution of phenols was developed. The model is based on a simplified chemical mechanism. Relative rate constants and reaction order with respect to phenol precursors were derived from experimental results using single phenols and equal molar mixtures of up to four phenols. For validation, experiments were performed at three temperatures using a distribution of phenol and 19 chlorinated phenols as measured in municipal waste incinerator exhaust gas. Comparison of experimental measurements and model predictions for PCDF isomer distributions and homologue pattern shows agreement within measurement uncertainty. The R-squared correlation coefficient exceeds 0.9 for all PCDF isomer distributions and the distribution of PCDF homologues. These results demonstrate that the distribution of dibenzofuran and the 135 PCDF congeners from gas-phase condensation of phenol and chlorinated phenols can be predicted from measurement of the distribution of phenol and the 19 chlorinated phenol congeners.     

The fate of prazosin and levonorgestrel after electrochemical degradation process: Monitoring by-products using LC-TOF/MS

Prazosin (PRZ) and levonorgestrel (LNG) are widely used as an anti-disease drugs due to their biological activity in the human body. The frequent detection of these compounds in water samples requires alternative technologies for the removal of both compounds. After electrochemical degradation of PRZ and LNG, the parent compounds could be completely removed after treatment, but the identification and characterization of by-products are necessary as well. In this study, the effects of NaCl concentration and applied voltage were investigated during the electrochemical degradation process. The results revealed that the increase of NaCl concentration and applied voltage could promote the generation of hypochlorite OCl? and then enhance the degradation of PRZ and LNG. After initial study, 6 V and 0.2 g NaCl were selected for further experiments (96% and 99% removal of PRZ and LNG after 40 min, respectively). Energy consumption was also evaluated and calculated for PRZ and LNG at 3, 6 and 8 V. Solid phase extraction (SPE) method plays an important role in enhancing the detection limit of by-products. Furthermore, characterization and identification of chlorinated and non-chlorinated by-products were conducted using an accurate liquid chromatography-time of flight/mass spectrometry LC-TOF/MS instrument. The monitoring of products during the electrochemical degradation process was performed at 6 V and 0.2 g NaCl in a 50 mL solution. The results indicated that two chlorinated products were formed during the electrochemical process. The toxicity of by-products toward E. coli bacteria was investigated at 37°C and 20 hr incubation time.     

Ecotoxicological effects of mixed pollutants resulted from e-wastes recycling and bioaccumulation of polybrominated diphenyl ethers in Chinese loach (Misgurnus anguillicaudatus)

To understand potential ecotoxicological effects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguillicaudatus) as experimental fish was performed. Larval loaches were kept into net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant difference of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological effects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied in this e-wastes recycling site, the mean concentrations of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.