沉淀分离富集-分光光度法测定海水中痕量活性磷酸盐

十六烷基三甲基溴化铵(cetyltrimethylammonium bromide,CTAB)可与磷钼蓝(phosphomolybdenum blue,PMB)生成水难溶的PMB-CTAB离子缔合物沉淀,从而分离富集水溶液中的PMB。该沉淀易溶于硫酸乙醇溶液,溶液在700 nm有强吸收,基于此建立了沉淀分离富集-分光光度法测定海水中痕量活性磷酸盐的新方法。对溶剂酸度、试剂用量、反应时间与温度等实验参数进行了优化选择,并考察了盐度对测定结果的影响。实验结果表明,PMB可被CTAB有效地定量沉淀;盐度在15~45范围内,对测定结果无影响。在优化的实验条件下,以盐度为35的人工海水为基底,做空白加P标实验,方法的线性范围为0.30~8.00μg/L,平均回收率为95.0%,方法检测限为0.10μg/L。对实际海水中痕量活性磷酸盐进行测定,相对标准偏差(RSD)为4.4%~7.1%,与广泛采用的MAGIC法比较,置信度为99%时结果无显著差异。新方法具有消耗试样体积少、测定速度快等优点。     

卤素类阻燃剂的阻燃基础理论

本文从阻燃化学反应,化学键能,热传递和反应动力学角度分析勖类阻燃剂的阻燃机理。     

Organophosphorus flame retardants and plasticizers in the atmosphere of the North Sea

Air samples collected in the German part of the North Sea from March to July 2010 were investigated for organophosphorus compounds (OPs) being applied as flame retardants and plasticizers. The ∑₈OPs concentration ranged from 110 to 1400 pg m⁻³ while tris(2-chloroisopropyl) phosphate (TCPP) dominated all samples with individual concentrations up to 1200 pg m⁻³. The highest concentrations were observed in continental air masses showing the high influence of industrialized regions including production sites on atmospheric emissions and concentrations. The occurrence of OPs even in oceanic/Arctic air masses shows that OPs can undergo long-range atmospheric transport. Dry particle-bound deposition fluxes from 9 to 240 ng m⁻² d⁻¹ for ∑₈OPs were estimated leading to a minimum annual flux of 710 ± 580 kg y⁻¹ OPs into the German North Sea. This study presents the first occurrence of OPs in the marine atmosphere together with important information on their long-range transport potential.     

Tissue distribution of Dechlorane Plus and its dechlorinated analogs in contaminated fish: high affinity to the brain for anti-DP

Information on tissue distribution of Dechlorane Plus (DP) and its dechlorinated analogs in wildlife is scarce. DP isomers and two dechlorinated compounds, anti-Cl₁₁-DP and anti-Cl₁₀-DP, were examined in the muscle, liver, and brain tissues of two bottom fish species collected from an electronic waste recycling site, South China. The median levels of syn-, anti-, and anti-Cl₁₁-DP isomers in the tissues ranged 0.18-39.1, 0.22-52.9, and 0.01-5.63 ng/g wet wt, respectively. Anti-Cl₁₀-DP was only detected in one muscle sample of mud carp (0.01 ng/g wet wt), although it was consistently detected in the sediments (0.42-0.83 ng/g dry wt). Preferential distribution in liver relative to muscle was observed for syn-DP and anti-Cl₁₁-DP. However, a high persistent retention in the brain compared to the liver was observed for anti-DP, suggesting that this isomer can across the blood-brain barrier of fish, and may cause adverse effects to the nervous system in the exposed biota.     

Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China

Dechlorane Plus (DP) has been determined in surface sediments from three Chinese coastal bays, e.g. Jiaozhou, Sishili and Taozi Bay in North China. DP concentrations ranged from <1.2 to 187 pg g⁻¹ dry weight (dw) (mean: 24.7 pg g⁻¹ dw) in Jiaozhou Bay, <1.2 to 135 pg g⁻¹ dw (mean 69.9 pg g⁻¹ dw) in Sishili Bay and <1.2 to 66.7 pg g⁻¹ dw (mean: 40.4 pg g⁻¹ dw) in Taozi Bay, respectively. Additionally, two dechlorinated species were quantified, which accounted for 0.6-5.1% of the ∑DP concentration.The f_syn values (syn-isomer/(syn- + anti-isomer)) in sediments from Jiaozhou Bay (mean 0.29) were close to the technical DP mixture (0.2-0.4), probably indicating local inputs of DP. In contrast, sediments in Sishili and Taozi Bay showed much lower f_syn values (mean 0.16). During transportation the DP isomers are subject to stereo selective degradation which partly resulted in the relative enrichment of anti-DP in coastal sediments.     

An international survey of decabromodiphenyl ethane (deBDethane) and decabromodiphenyl ether (decaBDE) in sewage sludge samples

Decabromodiphenyl ethane (deBDethane) is an additive flame retardant marketed as a replacement for decabromodiphenyl ether (decaBDE). The structures of the two chemicals are similar, and hence deBDethane may also become an environmental contaminant of concern. Environmental data on deBDethane are scarce. Since sewage sludge is an early indicator of leakage of these chemicals into the environment, an international survey of deBDethane and decaBDE levels in sludge was conducted. Samples were collected from 42 WWTPs in 12 different countries and analyzed with GC/LRMS. DeBDethane was present in sludge from all countries and may therefore be a worldwide concern. The levels of deBDethane in sludge samples from the Ruhr area of Germany were the highest so far reported in the literature (216 ng g⁻¹ d.wt.). The [deBDethane]/[decaBDE] quotient for the whole data set ranged from 0.0018 to 0.83. High ratios were found in and around Germany where deBDethane imports are known to have been high and substitution of decaBDE with deBDethane is likely to have occurred. Low ratios were found in the USA and the UK, countries that have traditionally been large users of decaBDE. An estimate of the flux of deBDEthane from the technosphere via WWTPs to the environment within the European Union gave 1.7 ± 0.34 mg annually per person. The corresponding value for decaBDE was 41 ± 22 mg annually per person.     

Calibration and testing of a dynamic flow-through chamber for field determination of methyl bromide volatilization flux

Accurate emission measurement of highly volatile chemicals such as methyl bromide (MeBr) is a crucial step in assessing their potential for environmental contamination. Use of flux chambers is a simple method for measuring emission rate under field conditions. To validate the applicability of a dynamic flow-through chamber for measuring MeBr emission, we provide a complete presentation of calibration and testing of the chamber. The calibration was made under a controlled system subject to ambient temperature changes. Two field experiments were conducted to test the chamber for measuring MeBr flux under conditions similar to commercial soil fumigation practices. In both the calibration and the two field experiments, the chamber provided accurate emission estimates. The maximum mass balance error was < 10% which is comparable to the micrometerological method. Because of its simplicity, we believe this dynamic flux chamber can be used reliably in quantifying the emission dynamics of highly volatile chemicals such as MeBr.     

Occurrence, sources, and inventory of hexabromocyclododecanes (HBCDs) in soils from Chongming Island, the Yangtze River Delta (YRD)

Hexabromocyclododecanes (HBCDs) is a concern due to their large usage combining with physico-chemical properties and toxicity to wildlife and human. However, very limited data were reported on HBCDs in soils, especially from rural area. In this study, 22 soil samples were collected from Chongming Island at estuary of the Yangtze River Delta, to investigate the level, diasteroisomer profile, potential sources, and mass inventory of HBCDs. The total concentrations ranged from not detected to 93.8 pg g⁻¹ dry weight (dw) with a mean of 23.3 pg g⁻¹ dw, which was at the low end of the global levels. The wide distribution of HBCDs in soils suggested that the local emissions of HBCD-containing materials and/or the inputs via atmospheric transport from other regions were two possible sources. Variation of HBCDs levels was observed in different types of soils. Woodland, tideland and road soils contained slightly higher HBCDs than those of farmland and grassland. Overall, γ-HBCD was the dominant diasteroisomer in soils, followed by α-HBCD and β-HBCD. Significant but weak correlations were only found between α-HBCD and β-HBCD versus TOC content in soils. Currently, the mass inventory of HBCDs in soils of Chongming Island was 5.3 kg. Based on these data, we gave perspective on human intake of HBCDs via soil ingestion by age. Local resident’s intakes ranged from 15.5 to 97.8 fg kg body weight⁻¹ d⁻¹, in which children are exposed more than adults.     

广州市居民家庭室内灰尘中传统和新型阻燃剂与塑化剂的污染特征及健康风险评估

近年来,随着阻燃剂多溴联苯醚（PBDEs）和以邻苯二甲酸酯（PAEs）为代表的传统型塑化剂（LPs）的逐步禁用或限用,有机磷系阻燃剂（PFRs）等新型阻燃剂及替代型塑化剂（APs）的生产和使用呈逐年增长的趋势,其环境污染特征和人体暴露健康风险值得引起广泛关注. 目前,灰尘已广泛用于室内环境中PBDEs、PFRs和LPs等半挥发性有机污染物（SVOCs）的污染特征评估,而关于室内灰尘中APs的污染特征则鲜有报道.本研究以广州市42户普通居民家庭为研究对象,采集家庭室内灰尘并分析了PFRs、PBDEs、LPs和APs的含量及组成特征.结果表明,PFRs、PBDEs、LPs和APs在室内灰尘中均有广泛检出,其含量分别为593.28~11531.56、13.45~27029.13、40494.83~1154497.16和15365.19~1013352.51 ng·g^-1.大多数家庭中,PFRs和部分APs在灰尘中的含量呈现高于PBDEs和LPs的特征,PFRs和APs等新型污染物的人体暴露健康风险需引起高度关注.采用暴露模型评估人体经灰尘摄入和皮肤接触对目标污染物的日均暴露量,结果表明,幼儿对PFRs、PBDEs、LPs和APs的暴露量分别为6.488、1.425、854.009和433.922 ng·kg^-1·d^-1,成人的暴露量分别为0.403、0.091、54.239和27.557 ng·kg^-1·d^-1.进一步使用危险熵进行健康风险评价,结果显示,4类污染物对幼儿和成人的健康风险均在可接受范围内.