Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

Fate of ah receptor agonists during biological treatment of an industrial sludge containing explosives and pharmaceutical residues

GOAL, SCOPE AND BACKGROUND: Sweden is meeting prohibition for deposition of organic waste from 2005. Since 1 million tons of sludge is produced every year in Sweden and the capacity for incineration does not fill the demands, other methods of sludge management have to be introduced to a higher degree. Two biological treatment alternatives are anaerobic digestion and composting. Different oxygen concentrations result in different microbial degradation pathways and, consequently, in a different quality of the digestion or composting residue, It is therefore necessary to study sludge treatment during different oxygen regimes in order to follow both degradation of compounds and change in toxicity. In this study, an industrial sludge containing explosives and pharmaceutical residues was treated with anaerobic digestion or composting, and the change in toxicity was studied. Nitroaromatic compounds, which are the main ingredients of both pharmaceutical and explosives, are well known to cause cytotoxicity and genotoxicity. However, little data are available concerning sludge with nitroaromatics and any associated dioxin-like activity. Therefore, we studied the sludge before and after the treatments in order to detect any changes in levels of Ah receptor (AhR) agonists using two bioassays for dioxin-like compounds. METHODS: An industrial sludge was treated with anaerobic digestion or composting in small reactors in a semi-continuous manner. The same volume as the feeding volume was taken out daily and stored at -20 degrees C. Sample preparation for the bioassays was done by extraction using organic solvents, followed by clean up with silica gel or sulphuric acid, yielding two fractions. The fractions were dissolved in DMSO and tested in the bioassays. The dioxin-like activity was measured using the DR-CALUX assay with transfected H4IIE rat hepatoma pGudluc cells and an EROD induction assay with RTL-W1 rainbow trout liver cells. RESULTS AND DISCUSSION: The bioassays showed that the sludge contained AhR agonists at levels of TCDD equivalents (TEQs) higher than other sludge types in Sweden. In addition, the TEQ values for the acid resistant fractions increased considerably after anaerobic digestion, resulting in an apparent formation of acid resistant TEQs in the anaerobic reactors. Similar results have been reported from studies of fermented household waste. There was a large difference in effects between the two bioassays, with higher TEQ levels in the RTL-W1 EROD assay than in the DR-CALUX assay. This is possibly due to a more rapid metabolism in rat hepatocytes than in trout hepatocytes or to differences in sensitivities for the AhR agonists in the sludge. It was also demonstrated by GC/FID analysis that the sludge contained high concentrations of nitroaromatics. It is suggested that nitroaromatic metabolites, such as aromatic amines and nitroanilines, are possible candidates for the observed bioassay effects. It was also found that the AhR agonists in the sludge samples were volatile. CONCLUSIONS: The sludge contained fairly high concentrations of volatile AhR agonists. The increase of acid resistant AhR agonist after anaerobic digestion warrants further investigations of the chemical and toxic properties of these compounds and of the mechanisms behind this observation. RECOMMENDATION AND OUTLOOK: This study has pointed out the benefits of using different types of mechanism-specific bioassays when evaluating the change in toxicity by sludge treatment, in which measurement of dioxin-like activity can be a valuable tool. In order to study the recalcitrant properties of the compounds in the sludge using the DR-CALUX assay, the exposure time can be varied between 6 and 24 hours. The properties of the acid-resistant AhR agonists formed in the anaerobic treatment have to be investigated in order to choose the most appropriate method for sludge management.     

Study of oil-water partitioning of a chemical dispersant using an acute bioassay with marine crustaceans

The toxicity of seawater dispersions of a chemical dispersant to two marine crustaceans was investigated in the presence and absence of various quantities of a non-toxic mineral oil. From the results and a physical-chemical partitioning analysis, a limiting value of the oil-water partition coefficient of the toxic compounds is deduced suggesting that essentially all of the toxic compounds in the dispersant will partition into solution in water following dispersant application to an oil spill. This conclusion simplifies interpretation and prediction of the toxic effects of a dispersed oil spill.The combined bioassay-partitioning procedure may have applications to the study of the toxicity of other complex mixtures such as industrial effluents.     

Comparative studies of the Fe–UV, H2O2–UV, TiO2–UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.     

Identifikation der kfz-bürtigen Schadstoffbelastung mit Hilfe der Verh?ltnisse der stabilen Isotope von Kohlenstoff und Schwefel

Zusammenfassung  Reifen-, Ru?-, Motoren?l-, Asphalt-, Plastik- und Lackproben aus dem Stra?enverkehr wurden auf ihre Kohlenstoff- und Schwefel-isotopenverh?ltnisse mit dem Ziel untersucht, die Frage zu beant-worten, ob diese Isotopenverh?ltnisse als Indikatoren für die Belastungssituation und die Schadstoffquellen bei der Untersuchung von stra?ennahen B?den eingesetzt werden k?nnen. Die δ¹¹C-Werte der technischen Substrate lagen zwischen-30‰ und-18‰ relativ zum PDB-Standard, Dabei zeigte sich aufgrund der unterschiedlichen Herstellungsverfahren eine deutliche Abgrenzung der Substrate untereinander. Asphalt hatte Werte zwischen-23 und-18‰, Ru? zwischen -27 und -22‰ Die Ru?proben unterschieden sich je nach Art des verwendeten Kraftstoffs. Plastik, Lack und Motor?le zeigten ?hnliche δ¹³C-Werte, die zwischen-30 und-27‰ lagen. Reifen haben relativ konstante δ¹³C-Werte um -26‰ Der Einflu? des Stra?enverkehrs auf die δ¹³C-Werte im Stra?ensediment und in stra?ennahen B?den konnte anhand verschiedener Kohlenstoffspezies an einem Transekt an einer Landstra?e aufgezeigt werden. Ein Vergleich mit verkehrstypischen Schwermetallemissionen ergab bei einzelnen Kohlenstoffspezies einen ?hnlichen Verlauf der Schwermetallkonzentrationen und der δ¹³C-Werte. Die δ³⁴S-Werte lagen zwischen -6 und +8‰ relativ zum CDT-Standard. Eine Abgrenzung der Substrate in ihren δ¹⁴S-Werten war hierbei nicht m?glich.      

Dechlorination of 1,2,4-trichlorobenzene in the sediment of Ise Bay

The relation between dechlorination activities of 1,2,4-trichlorobenzene and anaerobic microbial activity were studied in the sediment collected at three sites in Ise Bay in Japan. The degradation rate of spiked 1,2,4-trichlorobenzene (3nmol ml⁻¹) ranged from 15 to 35 pmol day⁻¹ ml⁻¹ wet sediment and about 1/3 to 1/2 of degraded the trichlorobenzene was recovered as dechlorinated products. Among the dichlorobenzenes, the 1,2-isomer had the highest and 1,3-isomer had the lowest production rate. Comparing the three sampling sites, the trichlorobenzene degradation and dichlorobenzenes production rates were related to the sulfate reducing activity for the unit number of sulfate reducing bacteria. Production rates of dichlorobenzenes were completely inhibited by adding molybdate (20 mM), nitrate (60 mM), and formaldehyde solution (4 %). These results indicated that dechlorination activity in the Ise Bay sediment was supported by sulfate reduction activity in the sediment, and not supported by any other anaerobic microbial activity.     

液化和压缩气体半球形扩散模型集的构建和应用

国内外液化和压缩气体的泄漏爆炸事故屡见不鲜,针对其性质和短时间近地面扩散的特点,总结、修正和扩展了瞬时泄漏下的平均半球形扩散模型。对于连续泄漏,利用数学积分理论建立了静风下的半球形扩散模型。接着对有风时的情况进行建模推导,将风速和气体自身扩散速度进行矢量合成,得到了半椭球形扩散和半椭圆锥与1/4椭球体组合扩散下气体的质量浓度和质量浓度变化趋势。最后用实例验证了该模型的先进性。该模型集能较好地反映液化和压缩气体泄漏后不同泄漏情况、时间、近地面区域和风速下的扩散浓度空间分布及其动态变化过程,为事故后果预估和应急救援决策提供参考。     

海藻酸钠包埋活性炭与细菌的条件优化及其对Pb~(2+)的吸附特征研究

利用海藻酸钠固定化包埋活性炭与多黏类芽孢杆菌GA1,通过正交试验研究海藻酸钠溶液浓度、包炭量及包菌量吸附Pb2+的最佳配比,并研究了这种新型的固定化小球对Pb2+的吸附特征.结果表明,固定化活性炭与多黏类芽孢杆菌GA1小球最佳制备条件为海藻酸钠质量分数2.5%、包炭量1:20和包菌量1:2,在该制备条件下吸附率达到93.74%.固定化小球的最佳吸附条件为pH5、温度30℃和Pb2+初始浓度300mg·L-1,活性炭与GA1经固定后对pH、温度和Pb2+初始浓度适应范围扩大.吸附平衡曲线表明,对Pb2+的吸附在30min内是一个快速的过程,在2h时基本趋于平衡,且平衡曲线能较好地用Langmuir模型和Freundlich模型来描述,其吸附过程主要为单分子层吸附,最大单分子层吸附量为370.37mg·g-1.解吸结果表明固定化小球能有效地循环利用.     

Isolation of Cr(VI) reducing bacteria from industrial e uents and their potential use in bioremediation of chromium containing wastewater

The present study is aimed at assessing the ability of Bacillus sp.JDM-2-1 and Staphylococcus capitis to reduce hexavalent chromium into its trivalent form.Bacillus sp.JDM-2-1 could tolerate Cr(Ⅵ) (4800 μg/mL) and S.capitis could tolerate Cr(Ⅵ) (2800 μg/mL).Both organisms were able to resist Cd2+ (50 μg/mL),Cu2+ (200 μg/mL),Pb2+ (800 μg/mL),Hg2+ (50 μg/mL) and Ni2+ (4000 μg/mL).S.capitis resisted Zn2+ at 700 μg/mL while Bacillus sp.JDM-2-1 only showed resistance up to 50 μg/mL.Bacillus sp.JDM-2-1 and S.capitis showed optimum growth at pH 6 and 7,respectively,while both bacteria showed optimum growth at 37℃.Bacillus sp.JDM-2-1 and S.capitis could reduce 85% and 81% of hexavalent chromium from the medium after 96 h and were also capable of reducing hexavalent chromium 86% and 89%,respectively,from the industrial effluents after 144 h.Cell free extracts of Bacillus sp.JDM-2-1 and S.capitis showed reduction of 83% and 70% at concentration of 10 μg Cr(Ⅵ)/mL,respectively.The presence of an induced protein having molecular weight around 25 kDa in the presence of chromium points out a possible role of this protein in chromium reduction.The bacterial isolates can be exploited for bioremediation of hexavalent chromium containing wastes,since they seem to have the potential to reduce the toxic hexavalent form to its nontoxic trivalent form.     

取代芳烃对呆鲦鱼急性毒性的QSAR研究

应用密度泛函方法(DFT)在B3LYP/6-311G**水平上全优化计算25个取代芳烃的量子化学参数,结合疏水性参数与化合物对呆鲦鱼的急性毒性进行定量构效关系研究(QSAR)。经逐步回归筛选变量后,所建多元线性回归方程的相关系数R及去一法交互检验复相关系数R2cv分别为0.967和0.907。用预测集样本进行了外部预测,所得外部预测样本复相关系数R2ext和外部预测集交互检验Q2ext分别为0.881和0.836。模型结果显示:分子疏水性参数logP较大时具有较大的脂溶性,化合物的毒性较大;取代基的吸电子能力越强,苯环的正电性越大,化合物的毒性越大。