水体中悬浮颗粒物对十溴二苯醚的吸附/解吸特性研究

采用室内试验法,以沉积颗粒物和浮游植物颗粒(铜绿微囊藻和普通小球藻)作为水体中悬浮颗粒物(SPM),研究了SPM对十溴二苯醚(BDE-209)的吸附/解吸特性.结果表明,沉积颗粒物和浮游植物颗粒对BDE-209的吸附分别在1.5h和0.5h内达到最大,在3h内可以充分达到平衡;沉积颗粒物和浮游植物颗粒对BDE-209的吸附能力存在差异,这与颗粒物中有机质的浓度和类型有关;在实验浓度范围内,BDE-209在SPM上的吸附可用Freundlich等温吸附方程较好地拟合;解吸过程表现出一定的迟滞性,且沉积颗粒物比浮游植物颗粒物具有更明显的迟滞性;pH中性、温度20～30℃的水体有利于SPM对BDE-209的吸附.     

Human maternal and umbilical cord blood concentrations of polybrominated diphenyl ethers

Polybrominated diphenyl ethers (PBDEs), widely used as flame retardants in commercial products, have become ubiquitous environmental contaminants. Although adult human exposure to PBDEs is well documented, developmental exposure is less well characterized. The objectives of this study were to measure maternal and fetal exposure to nine PBDE congeners and to investigate potential associations with birth weight. PBDE congeners were quantified in maternal serum at 24-28 weeks of pregnancy, delivery, and umbilical cord serum (UCS) by gas chromatography-mass spectrometry (GC/MS/MS). Complete blood sample sets were obtained from 97 pregnant women (mean age 33.1 ± 0.5 years). PBDE-28, -47 and -99 were quantified in all samples tested and PBDE-47 was the most abundant congener measured in both maternal (mid-pregnancy and delivery samples geometric mean = 26.9 and 26.9, respectively) and UCS (GM = 56.0 ng g⁻¹ lipid). The UCS concentration for all congeners with the exception of PBDE-153 was higher vs. maternal delivery samples (p < 0.001). Only the UCS concentration of PBDE-17 and -99 were significantly associated (β = −49.860, p = 0.032, and β = −3.645, p = 0.05) with birth weight. However, after adjustment for potential confounders only the association between PBDE-99 and birth weight remained significant (β = −3.951 and p = 0.016). We conclude that: the fetus is exposed to PBDEs from at least the second trimester of pregnancy onward; PBDE congeners are higher in UCS compared to maternal serum samples collected at delivery; and that developmental PBDE exposure is potentially associated with lower birth weight.     

光源和溶剂对十溴联苯醚光降解的影响

研究了不同光源和溶剂对十溴联苯醚(DecaBDE)光降解特性的影响,并对其降解产物进行了探讨.结果表明,在所试光源和溶剂条件下,DecaBDE均有一定程度的光降解,且都近似符合一级降解动力学.同一光源下,不同溶剂对DecaBDE降解表现出不同的影响.在太阳光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷>正己烷/丙酮>甲醇/水>乙醇/水;在模拟光源照射下,DecaBDE降解速率为甲苯>甲醇>甲醇/水>乙醇/水>正己烷>正己烷/丙酮;在紫外光照射下,DecaBDE降解速率为甲苯>甲醇>正己烷/丙酮>正己烷>甲醇/水>乙醇/水.同一溶剂中,DecaBDE降解速率均为紫外光>太阳光>模拟光源.尽管光源和溶剂对DecaBDE降解速率产生了一定影响,但降解途径基本一致,均为DecaBDE经光解脱溴产生低溴联苯醚.     

Photocatalytic debromination of preloaded decabromodiphenyl ether on the TiO(2) surface in aqueous system

There have been serious concerns about polybromodiphenyl ethers (PBDEs) in the environment because of their global distribution and bioaccumulation. Owing to strong hydrophobicity of PBDEs, the regular photocatalytic system, in which the substrate is solvated in the bulk solution, is not applicable to the removal of the PBDEs in water. In this work, the photocatalytic reduction degradation of decabromodiphenyl ether (BDE209), the most-used PBDEs, was investigated in aqueous system, by pre-adsorbing it on the surface of photocatalyst. It was found that the preloaded BDE209 underwent efficient reductive debromination in aqueous system under irradiation with wavelength larger than 360 nm in the presence of electron donors such as methanol. Our experiments further show that such a preloaded system exhibits different characteristics from that in the organic solution. The meta-debrominated intermediate is predominant in the present system, while the ortho-debrominated one is the main nona-BDE products in the organic solution. In addition, different from other photocatalytic system, the pH has little effect on the photocatalytic reaction. We propose that these differences are originated from the formation of overlayer of hydrophobic BDE209 to limit the motion of BDE209 and the access of water and H⁺/OH⁻ to the TiO₂ surface.     

Tri-decabrominated diphenyl ethers and hexabromocyclododecane in indoor air and dust from Stockholm microenvironments 2: indoor sources and human exposure

Data on polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) concentrations from Stockholm, Sweden, indoor microenvironments were combined with information from detailed questionnaires regarding the sampling location characteristics, including furnishing and equipment present. These were used to elucidate relationships between possible flame-retarded sources and the contaminant concentrations found in air and dust. Median concentration ranges of ΣPenta-, ΣOcta-, ΣDecaBDE and HBCD from all microenvironments were 19-570, 1.7-280, 29-3200 and < 1.6-2 pg/m³ in air and 22-240, 6.1-80, 330-1400 and 45-340 ng/g in dust, respectively. Significant correlations were found between concentrations of some PBDEs and HBCD in air and/or dust and the presence of electronic/electrical devices, foam furniture, PUF mattresses and synthetic bed pillows in, as well as floor area and construction year of the microenvironment. Car interiors were a source to indoor air in dealership halls. Using median and maximum concentrations of ΣPenta-, ΣOcta-, ΣDecaBDE and HBCD in air and dust, adult and toddler (12-24 months) intakes from inhalation and dust ingestion were estimated. Toddlers had higher estimated intakes of ΣPenta-, ΣDecaBDE and HBCD (7.8, 43, 7.6 ng/d, respectively) from dust ingestion than adults (5.8, 38, 6.0 ng/d, respectively). Air inhalation in offices was also an important exposure pathway for ΣPenta-, ΣOcta- and ΣDecaBDE in adults. For ΣPentaBDE and HBCD, air inhalation and dust ingestion play minor roles when compared to previously published Swedish dietary intakes (median exposures). However, in worst case scenarios using maximum concentrations, dust ingestion may represent 77 and 95% of toddler intake for ΣPentaBDE and HBCD, respectively.     

活性炭纤维吸附模拟废气中的乙醇和乙醚

采用动态吸附法研究了5种活性炭纤维（ACF）对乙醇、乙醚及模拟混合废气中的乙醇和乙醚的吸附性能。实验结果表明：当ACF-1,ACF-2,ACF-3,ACF-4分别吸附乙醇和乙醚时,在室温、乙醇质量浓度12.0 mg/L、乙醚质量浓度13.0 mg/L的条件下,4种ACF对乙醇的穿透吸附量和饱和吸附量分别为60~70 mg/g和339~409 mg/g,对乙醚的穿透吸附量和饱和吸附量分别为50~65 mg/g和301~344 mg/g;在室温、模拟混合废气中乙醇和乙醚的质量浓度均为11.6 mg/L、吸附时间120 min的条件下,具有较大的比表面积和微孔体积的ACF-5对乙醇的吸附量为205 mg/g,对乙醚的吸附量为223 mg/g;在脱附真空度-0.95 Pa、脱附时间20 min的条件下,经17 次使用的ACF-5对模拟混合废气中乙醇和乙醚的穿透吸附量均为87 mg/g,穿透时间均为12 min。     

地下水浅埋区某加油站特征污染物空间分布简

加油站渗漏污染地下水已经是一个世界性的问题。由于浅埋区加油站储罐与地下水密切接触,更加剧储罐的腐蚀。为揭示加油站渗漏的典型污染物石油烃（TPH）、苯系物（BTEX）、萘和甲基叔丁基醚（MTBE）在该水文地质条件下的迁移变化,在浅埋区某加油站开展了平、枯、丰水期的地下水监测工作。在水平分布上,TPH、BTEX、萘基本相似,均在加油岛附近形成高浓度区,而MTBE则更易随地下水流动而迁移,呈现出不同的污染晕。在垂直分布上,地下水的水位变动是污染物浓度分布的主要影响因素。     

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.     

2,2',4,4'-四溴联苯醚的好氧微生物降解

从北京高碑店污水处理厂活性污泥中筛选出1株能好氧降解2,2’,4,4’-四溴联苯醚(BDE-47)的细菌,并对其降解特性及有关蛋白质进行分析,目的是了解好氧条件下BDE-47的微生物降解机制.BDE-47降解菌通过平板划线法获得,其16S rDNA与不动杆菌(Acintobacter sp.)的相似度最大,为90%.采用250 mL锥形瓶研究了所得菌对BDE-47的降解情况,在BDE-47初试浓度为146μg.L-1的条件下,经过63 d的培养,所得菌降解了45.44%的BDE-47,降解产物主要为4-OH-联苯醚,菌量增加了7倍左右.分别以BDE-47和酵母提取物为碳源培养所得菌2周,然后各自提取蛋白质,通过蛋白质双向电泳及质谱检测,发现了与BDE-47降解有关的一些特异蛋白质.本研究表明,在好氧条件下,细菌可以BDE-47为碳源生长,其过程涉及多种蛋白质的作用.     

铜绿假单胞菌胞内酶粗提液对十溴联苯醚的降解

探讨了铜绿假单胞菌粗酶液对十溴联苯醚(BDE-209)的降解特性,结果表明,该菌株胞内酶在12 h内对1 mg.L-1的BDE-209降解率达到了69.22%,温度、pH值、酶蛋白浓度及底物BDE-209浓度均会影响胞内酶粗提液对BDE-209的降解效率.当BDE-209浓度为1 mg.L-1时,BDE-209适宜的酶促降解条件为:温度30℃,反应pH值7.5,且降解率随着酶浓度的增加而增大.胞内酶对BDE-209的降解过程符合一级动力学反应模型,底物浓度为1 mg.L-1时降解速率最快,半衰期为6.9 h.胞内酶降解BDE-209符合高浓度底物抑制的酶促反应类型,其基本降解动力学参数为rmax=0.133 mg.(L.h)-1,Km=0.642mg.L-1,Ki=1.558 mg.L-1.