Differential accumulation of low-chlorinated (Delor 103) and high-chlorinated (Delor 106) biphenyls in human placental tissue and opposite effects on conversion of DHEA to E2

OBJECTIVE: Polychlorinated biphenyls (PCBs) and related compounds elicit a diverse spectrum of toxic responses. Additionally, they are able to pass through the human placenta. The aim of the presented data was to compare the action of low-chlorinated (Delor 103) and (Delor 106) high-chlorinated biphenyls on placental steroidogenesis. METHODS: Explants of human placental tissue were used to test differences in PCBs accumulation and influence on placental steroidogenesis. Delor 103 or 106, were added daily for six days at a dose of 200 pg from day 0 to day 6 of culture. The media in the control and experimental groups were changed every day, and collected and frozen for steroid analysis by RIA. Determinations of PCBs of tissue and medium were analysed by GC/MS/MS. RESULTS: Delor 103 was found at a higher level in the tissue than Delor 106. The first day of exposure to Delor 103 had no effect on the conversion of dehydroepiandrosterone (DHEA) to estradiol (E2) while there was a 2-fold decrease in E2 secretion from days 3 to 6. Conversely, Delor 106 caused an immediate increase in E2 secretion, which was maintained at higher levels throughout the exposure period. CONCLUSION: Differences between the accumulation of lower chlorinated and higher chlorinated biphenyls in human placental tissue and in the properties of the congeners can have multiple effects that may intensify or counteract the effects on uterine contraction by PCBs.     

Chlorinated herbicide (triallate) dehalogenation by iron powder

The reductive degradation of a chlorinated herbicide by iron powder was investigated at lab scale. The studied substrate was triallate (S-2,3,3-trichloroallyl di-isopropyl thiocarbamate) which contains a trichloroethylene moiety potentially reducible by zero-valent iron. Degradation reactions were carried out in batch, at 25 degrees C, in the absence of oxygen, by contacting electrolytic iron powder (size range: 20-50 microm) with a triallate aqueous solution (2.5 mgl(-1)). Herbicide decay, corresponding evolutions of TOC, TOX and chloride ion release were regularly monitored throughout the reactions. Furthermore, the main degradation by-products were identified by HPLC/MS. The results showed that, after 5 days, herbicide degradation extent was about 97% and that the reaction proceeded through the formation of a dechlorinated alkyne by-product (S-2-propinyl di-isopropyl thiocarbamate) resulting from the complete dechlorination of triallate. The subsequent reduction of such an alkyne intermediate gave S-allyl di-isopropyl thiocarbamate as main end by-product. The identified by-products suggested that dechlorination took place mainly via reductive beta-elimination. However, as traces of dichloroallyl di-isopropyl thiocarbamate were also detected, a role, although minor, was assigned even to hydrogenolysis in the overall dechlorination process.     

Enhanced dehalogenation of halogenated methanes by bimetallic Cu/Al

A low-cost and high effective copper/aluminum (Cu/Al) bimetal has been developed for treatments of halogenated methanes, including dichloromethane, in near neutral and high pH aqueous systems. Bimetallic Cu/Al was prepared by a simple two-step synthetic method where Cu was deposited onto the Al surface. The presence of Cu on Al significantly enhanced rates of degradation of halogenated methanes and reduced toxic halogenated intermediates. The stability of Cu/Al was preliminarily studied by a multi-spiking batch experiment where complete degradation of carbon tetrachloride was achieved for seven times although the Cu/Al aging was found. Roles of Cu may involve protecting Al against an undesirable oxidation with water, enhancing reaction rates through the galvanic corrosion, and increasing the selectivity to a benign compound (i.e., methane). Kinetic analyses indicated that the activity of bimetallic Cu/Al was comparable to that of iron-based bimetals (e.g., palladized iron) and zero-valent metals. Bimetallic Cu/Al could be a promising reactive reagent for remediation of halogenated solvents-contaminated groundwater associated with high pH problems.     

Reductive dehalogenation of tetrabromobisphenol-A by sediment from a contaminated ephemeral streambed and an enrichment culture

This study was aimed at improving our understanding of the physiology of the microorganisms that reductively dehalogenate tetrabromobisphenol-A (TBBPA). Activity was followed in contaminated sediments from a polluted streambed as well as from fracture filling material underlying the stream. Reductive dehalogenation was observed in surface sediments but not in fracture filling samples from a depth of 3m. Likewise, anaerobic microbial activity, represented by sulphate reduction, was much higher in the surface sediment. In the culture enriched from the surface sediment, optimal microbial debromination of TBBPA took place at a salinity of 2% and 3% NaCl, temperature of 30 degrees Celsius, and pH of 7-8. Ethanol, pyruvate and the combination of hydrogen with acetate were the most suitable electron donors and carbon sources for this culture. Alternative electron acceptors like Fe(3+), SO(4)(2-), SO(3)(2-), NO(3)(-) and 2,4,6-tribromophenol inhibited TBBPA debromination. The debrominating bacteria were heat sensitive (80 degrees Celsius, for 10min) but were not inhibited by bromoethanesulphonate or molybdate. This study allowed optimisation of our culturing conditions, but was also important for understanding the factors which influence TBBPA debromination in situ.     

Photolytic dehalogenation of the marine halogenated natural product Q1

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) has been detected in high-trophic level biota throughout the world. In this study we UV-irradiated Q1 in order to produce hexahalogenated 1'-methylbipyrroles (Cl(6)-MBPs). Q1 was transformed with half-lives of <5 min. Already after 5 min, all of the five existing Cl(6)-MBPs (H1-H5) were detected in the irradiated sample. Only one Cl(6)-MBP (2,3,3',4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-77, H2) has been previously described in the literature. H5 was identified as 2,3,3',4,4',5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-75) by a specific fragment ion detected by GC/ECNI-MS. Fractionations of the irradiation mixture by reversed-phase HPLC followed by (1)H NMR analysis led to the structure of H4, i.e. 2,3,3',4,4',5-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-74). H1 and H3 showed virtually identical (1)H NMR data. Therefore, it could not determined which of either isomers is 2,3,3',4,5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-76) and which is 2,3,4,4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-78). In addition, two pentachloro-MBPs (P1 and P3) could be traced back to MBP-62 and MBP-69. Cl(6)-MBPs were analyzed in whale blubber from Australia and skua adipose tissue from Antarctica. The marine mammals contained all Cl(6)-MBPs except for the most abundant in the irradiation experiment. The concentrations of the Cl(6)-MBPs amounted to 0.04-1.76% of the concentration of Q1. The highest concentrations of Cl(6)-MBP isomers in the biota samples were found for MBP-76, MBP-77, and MBP-78. These congeners appeared to be the most lipophilic ones owing to the highest retention time in RP-HPLC. Nevertheless, it remained unclear whether the Cl(6)-MBPs were actual halogenated natural products or environmental metabolites of Q1.     

N-甲基咪唑配体络合金属Cu(I)催化剂对水中2,4-二甲氧基溴苯还原脱溴

合成了以N-甲基咪唑为配体,Cu为活性中心的络合金属多相催化剂Cu(I)-NHC-SBA-15。通过1H-NMR、13C-NMR、有机元素分析和FTIR对各步合成反应产物结构经行了鉴定;用SEM、N2吸附脱附等方法对催化剂进行了表征;用ICP测定了催化剂Cu含量。对催化剂催化2,4-二甲氧基溴苯还原脱溴活性进行了测试。在反应时间为24 h,通过正交实验和单因素实验,考察了催化剂用量、反应温度、还原剂用量等因素对脱溴率的影响,并确定了最佳反应条件:催化剂用量为0.05 g、水合肼用量为2 mL、反应温度为80℃,脱溴效果较好,脱溴率达到98.5%。对催化剂重复使用进行了初步研究。对催化反应动力学进行了初步研究,结果表明,该多相催化反应是由表面反应速度控制,并符合一级动力学反应。对反应机理进行了初步探讨。     

Carbon isotope fractionation during abiotic reductive dehalogenation of trichloroethene (TCE)

Dehalogenation of trichloroethene (TCE) in the aqueous phase, either on palladium catalysts with hydrogen as the reductant or on metallic iron, was associated with strong changes in delta13C. In general, the delta13C of product phases were more negative than those of the parent compound and were enriched with time and fraction of TCE remaining. For dehalogenation with iron, the delta13C of TCE and products varied from -42/1000 to +5/1000. For the palladium experiments, the final product, ethane, reached the initial delta13C of TCE at completion of the dehalogenation reaction. During dehalogenation, the carbon isotope fractionation between TCE and product phases was not constant. The variation in delta13C of TCE and products offers a new monitoring tool that operates independently of the initial concentration of pollutants for abiotic degradation processes of TCE in the subsurface, and may be useful for evaluation of remediation efficiency.     

Isomer-specific analysis of chlorinated biphenyls,naphthalenes and dibenzofurans in Delor: polychlorinated biphenyl preparations from the former Czechoslovakia

Technical polychlorinated byphenyl (PCB) preparations--Delors 103, 104, 105, and 106--produced in the former Czechoslovakia were analyzed for their chlorobiphenyl (CB), chloronaphthalene (PCN) and chlorinated dibenzofuran (PCDF) composition and content using high resolution gas chromatography-mass spectrometry techniques. The congener patterns of Delors 103, 104, 105, and 106 resembled Aroclors 1242, 1248, 1254, and 1260. Delors contained PCNs and PCDFs, as impurities, at microgram per gram concentrations. Concentrations of PCNs and PCDFs in Delors were greater than those found in the corresponding Aroclors. The potential for the emissions of PCNs and PCDFs from Delor was estimated to be 3680 and 860 kg, respectively. Non- and mono-ortho PCBs were the major contributors to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents in Delor mixtures.     

Aerobic dehalogenation potentials of four bacterial species isolated from soil and sewage sludge

In Polar regions subject to acid precipitation, the spring flood period is swift and can be divided into three phases. In phase one, dilution and anion substitution by SO4 controls episodic acidification. Phase two is characterized by interaction of snowmelt water with the catchment. A combination of several factors contributes to declines in pH and ANC. In forest and wetland ecosystems, organic acids greatly contribute to the pH depression in the streams. In the coastal tundra and forest-tundra zones, "salt-effect" acidification predominantes. The increase in toxic forms of trace (Ni, Cu) and rare (Fe, Al, Mn) elements during pH depressions may create stress conditions for the fauna of polar fresh waters during a flood period.     

废旧电路板与碳酸钙共热解脱卤的研究

采用热重分析仪和石英管式炉热解反应器,分别对以酚醛树脂为基板的废旧电路板和混合碳酸钙后的废旧电路板进行热解实验研究,着重考察了添加碳酸钙后的酚醛树脂基板废旧电路板热解特性及添加量不同对卤素脱除效果的影响。实验结果表明,碳酸钙的加入对废旧电路板的降解行为和热解油的基本组成没有明显的影响,但热解油的各组分含量有所差异;随着热解温度的提高或者CaCO₃含量的增多,卤素可以更多地由有机卤向无机卤转变并束缚在固体残渣中,由此得到较好的脱卤效果。当60%PR-WPCBs与40%CaCO₃共热解,热解油中的溴化物也减少了7.6% 。在600℃等量CaCO₃与PR-WPCBs共热解时生成75.6%无机卤,其中70.62%束缚于固体残渣中,可见达到较好的脱卤效果。     

次氯酸钠氧化降解水杨酸

采用次氯酸钠对PPCPs(药品和个人护理用品)类污染物水杨酸(SA)的氧化消除及动力学规律进行研究,考察了pH值、温度、Br-浓度以及水体中常见有机物等各因素对降解效果的影响。结果表明,次氯酸钠对SA的氧化降解过程符合二级反应动力学;pH值对该降解反应影响较大,随着pH值的降低,反应速率增大;温度对该降解反应的影响明显且符合Van't Hoff规则,提高反应温度,有利于降解进行。向体系中加入Br-,可以加快次氯酸钠对SA的氧化降解,并随着Br-浓度的增加,SA降解的速率逐渐增加。水体中有腐殖酸和表面活性剂存在时,对水杨酸的氧化反应也会产生一定的影响。     

Sorption of sodium dodecylbenzene sulfonate by montmorillonite

Sorption of linear alkylbenzene sulfonates by soils and sediments is an important process that may affect their fate, transport, toxicity and their application in remediation of contaminated soil and groundwater. In this study, batch experiments were conducted to elucidate the sorption of a widely used anionic surfactant, sodium dodecylbenzene sulfonate (SDBS), by montmorillonite. It was observed that: (i) SDBS was sorbed significantly by montmorillonite saturated with Ca(2+), but little by Na-saturated montmorillonite; (ii) the amount of SDBS sorbed by Ca(2+)-montmorillonite was enhanced by NaCl; and (iii) no significant intercalation of SDBS into Ca(2+)-montmorillonite was observed by X-ray diffraction (XRD) analysis. These results indicate that the removal of SDBS by Ca(2+)-montmorillonite was primarily attributed to the precipitation between DBS(-) and Ca(2+) in solution which was released from montmorillonite via cation exchange. These results will help us to understand the sorption behavior and environmental effects of anionic surfactants.     

真空紫外光降解五氯酚钠以及过硫酸盐对反应的促进作用

研究了真空紫外光(VUV,185 am)对于水溶液中五氯酚钠的降解,反应2 h后,初始浓度为10 mg/L的五氯酚钠的去除率达到99%以上,有机氯的脱除率达到70%以上,有效地实现了五氯酚钠的脱毒.溶液初始pH值对五氯酚钠的真空紫外光解有很大影响,pH=10.9时的降解速率常数是pH=3.1时的3倍.表观一级反应速率常数随初始浓度的增加而线性下降.在反应溶液中加入过硫酸盐,可有效提高五氯酚钠的真空紫外光降解速率和矿化速率,过硫酸盐和五氯酚钠摩尔比为24时,降解速率提高3倍,反应4 h后TOC去除率达到95%.     

次氯酸钠降解水中萘普生的效果

探究了次氯酸钠(NaClO)对萘普生(NPX)的氧化降解效果。分析了次氯酸钠投加量对NPX去除率和体系总有机碳(TOC)的影响,同时分析了此过程中次氯酸钠投加量与次氯酸钠利用效率之间的关系。结果表明,NPX的降解率随着次氯酸钠投加量增加而增加,直至NPX的降解率达100%。溶液中TOC去除率随NaClO与NPX摩尔比的增大先增加后趋于平缓,最后溶液中TOC去除率稳定在22.5%左右。次氯酸钠的利用效率会随NaClO与NPX摩尔比的增大先增后减,在NaClO与NPX摩尔比为7.5:1时,次氯酸钠的利用效率达最大值。同时研究了不同pH对NPX氧化降解反应的影响,实验显示,溶液处于较低的pH更有利于NPX被氧化降解。最后通过对比实验,研究了医用萘普生胶囊中所添加辅料对NPX的氧化反应的影响,结果表明,萘普生医用药品中所添加成分对NPX的氧化降解有一定的抑制作用。     

Continuous-flow column study of reductive dehalogenation of PCE upon bioaugmentation with the Evanite enrichment culture

A continuous-flow anaerobic column experiment was conducted to evaluate the reductive dechlorination of tetrachloroethene (PCE) in Hanford aquifer material after bioaugmentation with the Evanite (EV) culture. An influent PCE concentration of 0.09 mM was transformed to vinyl chloride (VC) and ethene (ETH) within a hydraulic residence time of 1.3 days. The experimental breakthrough curves were described by the one-dimensional two-site-nonequilibrium transport model. PCE dechlorination was observed after bioaugmentation and after the lactate concentration was increased from 0.35 to 0.67 mM. At the onset of reductive dehalogenation, cis-dichloroethene (c-DCE) concentrations in the column effluent exceeded the influent PCE concentration indicating enhanced PCE desorption and transformation. When the lactate concentration was increased to 1.34 mM, c-DCE reduction to vinyl chloride (VC) and ethene (ETH) occurred. Spatial rates of PCE and VC transformation were determined in batch-incubated microcosms constructed with aquifer samples obtained from the column. PCE transformation rates were highest in the first 5 cm from the column inlet and decreased towards the column effluent. Dehalococcoides cell numbers dropped from approximately 73.5% of the total Bacterial population in the original inocula, to about 0.5% to 4% throughout the column. The results were consistent with estimates of electron donor utilization, with 4% going towards dehalogenation reactions.     

Efficient dehalogenation of automobile shredder residue in NaOH/ethylene glycol using a ball mill

We investigated the effectiveness of sodium hydroxide/ethylene glycol (NaOH/EG) for dehalogenation of automobile shredder residue (ASR) using a ball mill. Efficient dehalogenation was achieved at atmospheric pressure by combining the use of EG (196 degrees C b.p.) as a replacement solvent for NaOH with ball milling, which improved contact between ASR and OH(-) in solution. Moderate NaOH concentrations and increased ball mill rotation speeds produced high dechlorination that was not significantly affected by the weight ratio of ASR to EG. NaOH/EG dechlorination increased with temperature with an apparent activation energy of 50 kJ mol(-1) confirming that the reaction proceeded under chemical reaction control. The modified shrinking-core model was appropriate to explain the dechlorination process. Low chloro levels in our NaOH/EG-treated ASR suggested that this material could be used for feedstock recycling and the wet process may be applicable for dehalogenation of other important waste streams.     

The kinetics of reductive dehalogenation of a set of halogenated aliphatic hydrocarbons in anaerobic sediment slurries

Disappearance rate constants are reported for the reductive transformation of 17 halogenated aliphatic hydrocarbons in anaerobic sediment-water samples. Statistical experimental design in combination with multivariate chemical characterization of their chemical properties was used to select the compounds. Degradation followed pseudo first-order kinetics through at least two half-lives for 15 of the 17 compounds. Of all the compounds investigated, 1,2,3-trichloropropane and dichloromethane were unique in that they were dehalogenated according to zero-order kinetics. Reductive dehalogenation was the sole transformation reaction taking place.     

乙酸钠修复铬污染土壤的机制研究

选择乙酸钠作为农家肥中羧酸类物质的代表,在确定其对铬污染土壤修复效果的基础上,通过化学分析和红外图谱研究,探索乙酸钠与土壤中Cr(Ⅵ)之间可能存在的5种作用方式,并对其有效作用方式的机制进行研究。结果表明:乙酸钠能显著降低铬污染土壤中的Cr(Ⅵ)含量,其有效作用方式是乙酸钠和土壤中有机组分的共同作用;乙酸钠的加入使土壤有机组分中的一些不溶于水的羧酸类物质进入液相,从而促进铬污染土壤的修复。     

硫化物沉淀法处理含铅废水

采用硫化物沉淀化处理含铅废水,考察了Na2S投加量、反应初始pH等操作条件对铅离子去除效果的影响,以及硫化铅沉淀反应过程的动力学特征,并采用激光粒度分析仪对反应生成的硫化铅沉淀的粒径分布进行了测定。实验结果表明,S2-与废水中Pb2+之间的沉淀反应能较好地符合一级反应动力学特征;Na2S与Pb2+的最佳物质的量之比为3;最佳的反应初始pH为6～9。在最佳操作条件下,Pb2+的平均去除率为99.60%,反应出水中Pb2+平均浓度为0.13 mg/L,低于污水综合排放标准(GB8978-1996)中铅的排放浓度限值。反应生成的硫化铅沉淀的平均粒径为2.62μm,具有较好的沉淀性能,能够通过沉淀的方式与废水分离。