Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

Bioaccumulation of polybrominated diphenyl ethers in harbor seals from the northwest Atlantic

Polybrominated diphenyl ethers (PBDEs) were analyzed in blubber of harbor seals (Phoca vitulina concolor) collected between 1991 and 2005 along the northwest Atlantic. ∑PBDE concentrations (mono- to hexa-BDEs) detected in blubber samples (n = 42) ranged from 80 to 25 720 ng g⁻¹ lw, (overall mean 2403 ± 5406 ng g⁻¹ lw). By age, mean ∑PBDE concentrations were: 3645 ± 7388, 2945 ± 5995, 1385 ± 1265, and 326 ± 193 ng g⁻¹ lw in pups, yearlings, adult males, and adult females, respectively. Unlike the trend for PCBs, no decreasing gradient from urban to rural/remote areas was observed for PBDEs in these samples, likely reflecting inputs from local sources. No significant temporal trend was observed for PBDEs in harbor seals between 1991 and 2005, although congener profiles shifted over time. Tetra-BDE-47 was the dominant congener, followed by BDEs-99, -100, -153, -154, and -155 in varying order, suggesting exposure to the penta-BDE product. In adult males, the hexa-BDEs contributed more to the total (22%) than BDEs-99 and -100 (14%), and concentrations of BDE-155 were elevated compared with -154. Higher BDEs were detected in a subset of seals (n = 12) including hepta-BDE-183, the marker for the octa-BDE mixture, and octa-BDE-197, along with several unidentified hepta- and octa- congeners. BDE-209 was detected in seal blubber at concentrations ranging from 1.1 to 8 ng g⁻¹ lw, indicating that deca-BDE is bioavailable in this marine food web. This is the first study to document the accumulation of BDE-209 at measurable levels in wild harbor seals. While the PBDE patterns in blubber indicate exposure to all three BDE commercial mixtures, the data also suggest that BDE-209 debromination by seal prey fish may contribute to the loading of lower brominated congeners (hexa- to octa-BDEs) in these seals.     

Detailed analysis of polybrominated biphenyl congeners in bird eggs from Norway

Individual eggs of six species of birds from Norway representing different food chains were analysed for residues of polybrominated biphenyls (PBBs). In all species, the residue pattern was dominated by hexaBBs. The dominating congeners were PBB 153, PBB 154, and PBB 155. Whereas PBB 153 is present in technical hexabromobiphenyl, PBB 154 and PBB 155 are formed by the reductive debromination of decabromobiphenyl. This was evidenced by the detection of several heptaBBs and octaBBs all of which are typical degradation intermediates of PBB 209. Hepta- and octaBBs were more than one order of magnitude less abundant than the hexaBBs. The second most prevailing homologue group was pentaBBs. The most relevant pentabrominated isomers were PBB 99 and PBB 101. Concentrations of the three hexaBBs - PBB 153, PBB 154, and PBB 155 - amounted to 1.3-13 ng/g wet weight or 3-23% of the contamination with polybrominated diphenyl ethers.     

黄淮地区纳滤膜苦咸水软化分离性能研究

针对我国黄淮地区华北山前冲积平原与中部冲积平原交接部位的模拟苦咸水,构建纳滤(NF)膜法软化系统,考察了跨膜压差(0.6~2.1 MPa)、进水端切向流速(0.09~0.38 m/s)和进水温度(7~35 ℃)等操作条件对NF膜软化分离性能的影响。结果表明:在跨膜压差为1.2 MP,进水端切向流速为0.28 m/s,进水温度为15 ℃时,NF膜软化系统有较高的膜产水通量〔52.04 L/(m ²·h)〕,对主要成垢离子Ca ²⁺、Mg ²⁺、$CO_{3}^{2-}$和$SO_{4}^{2-}$的去除率分别达44.13%、73.72%、81.05%和99.13%,对总硬度的平均去除率达53.31%,NF膜有良好的软化性能;随着跨膜压差、进水端切向流速的增加及进水温度的下降,NF膜产水的pH逐渐降低,而浓水的pH呈逐渐升高的趋势。     

水华藻斑漂移速度时变特征研究

以太湖水华藻斑为研究对象,采用自主研发的藻斑漂移原位观测技术,研究分析了不同时间尺度下太湖蓝藻水华易发区藻斑漂移速度的变化特征.结果表明：日内藻斑漂移速率在（0.0793±0.0135）~（0.146±0.0318）m/s范围内变化,藻斑漂移速度的北向分量在-0.0896~0.0247m/s之间,东向分量在-0.0157~0.0029m/s之间.漂移速率日均值变化呈现出锯齿式交替特征即增加-减少-再增加的往复循环,变化范围为（0.0499±0.0141）~（0.1580±0.0120）m/s,漂移方向以北向为主.藻斑漂移速度的月际变化明显,6月~8月,向东漂移的占比逐渐降低,而向西漂移的占比逐渐增加,此期间漂移方向均以北向为主.漂移速率6月上旬最小,均值为0.0680m/s,7月上旬达到最大,均值为0.1350m/s,7月中旬~8月下旬水华藻斑漂移速率在0.0800m/s附近波动.     

筑坝河流水动力条件对浮游植物动态变化的影响

河流筑坝后水动力条件发生改变,影响了浮游植物的动态变化,目前对这一过程的研究相对较少。为此,本研究对乌江河流-水库体系浮游植物和流速及相关环境因子进行了季度调查。研究区域水体平均流速为032 m/s,变化范围为001～132 m/s;浮游植物中硅藻、蓝藻、甲藻对水体流速变化最敏感:在流速小于005 m/s时,蓝藻与硅藻占比最大,甲藻次之,其他藻类占比较低;流速在005～010 m/s之间,蓝藻占比下降,硅藻、甲藻及绿藻占比上升,其他藻类占比较低;流速大于010/s时,硅藻占比达到绝对优势。浮游植物细胞丰度随着流速的增加表现出先增加后减小的趋势,两者之间存在单峰关系;不同流速下浮游植物会出现较明显的聚类特征。     

上流式斜流沉淀去除率公式的理论推导

结合斜流沉淀结构的特点，分析了流道内液芬布对颗粒沉淀过程的影响；污水中颗粒粒径分布对去除率的影响，从而理论上推导上流式斜流沉去除率的计算公式     

火焰原子吸收法与邻菲口罗啉光度法测定水中铁的方法比对

火焰原子吸收法与邻菲口罗啉光度法测定水和废水中铁具有精密度高、准确度好的持点。用两种方法测定的考核样为1 37mg/L及1 35mg/L,均为合格。两种方法均具有很强的可比信,都能满足水和废水中铁的测定,测定结果准确、可靠。     

海螺沟植物和积雪中有机磷酸酯的分布及来源

为研究大气传输以及干湿沉降对偏远地区环境中有机磷酸酯(OPEs)含量及分布的影响,本研究以海螺沟景区为例,采集了海螺沟的植物和积雪样品,用气相色谱-质谱联用仪(GC-MS)定量分析了样品中7种典型有机磷酸酯[磷酸三丁酯(Tn BP)、磷酸三氯乙酯(TCEP)、磷酸三氯丙酯(TCPP)、磷酸三(2,3-二氯丙基)酯(TDCPP)、磷酸三苯酯(TPh P)、磷酸三丁氧乙酯(TBEP)和磷酸三异辛酯(TEHP)]的含量及分布特征.结果表明,海螺沟景区常见的9种植物中7种OPEs(Σ7OPEs)的含量(以DW计)水平在43. 1～1 050. 8 ng·g-1之间,其中TBEP和TPh P含量最高,分别占Σ7OPEs总含量的36%～70%和24%～80%.冰川积雪中主要污染物与植物中一致,TBEP含量最高,占Σ7OPEs总含量的47%,其次为TPh P,占24%.采用Grads、后向轨迹模型及历史风向数据分析得出海螺沟环境显著受到人类活动扰动,其OPEs主要受来自成都方向和云南昭通与宜宾、泸州、西昌交界处方向的大气传输的影响,需要进一步研究其环境行为并加强城市污染控制.     

成都市大气PM2.5中有机磷阻燃剂的污染水平及来源

应用气相色谱-质谱联用仪定量分析成都市大气PM2.5中有机磷酸酯阻燃剂(OPEs)的质量浓度水平,讨论了其分布特征,并采用后向气流轨迹模型及相关性分析探析PM2.5中OPEs的来源.结果表明,成都市市区采样点大气PM2.5中Σ7OPEs年平均质量浓度为6.46 ng·m-3,郊区采样点为9.38 ng·m-3.受郊区废旧物质拆解产业和常年主导风向的影响,郊区采样点大气PM2.5中OPEs的质量浓度高于市区采样点(P=0.013).大气混合程度影响郊区和市区OPEs的分布,外源污染对成都市OPEs贡献小,OPEs质量浓度高低可能主要受采样点周围局地源的影响.