Effects of Cu2+ and humic acids on degradation and fate of TBBPA in pure culture of Pseudomonas sp. strain CDT

Soil contamination with tetrabromobisphenol A(TBBPA) has caused great concerns;however, the presence of heavy metals and soil organic matter on the biodegradation of TBBPA is still unclear. We isolated Pseudomonas sp. strain CDT, a TBBPA-degrading bacterium, from activated sludge and incubated it with ~(14)C-labeled TBBPA for 87 days in the absence and presence of Cu~(2+)and humic acids(HA). TBBPA was degraded to organic-solvent extractable(59.4% ± 2.2%) and non-extractable(25.1% ± 1.3%) metabolites,mineralized to CO_2(4.8% ± 0.8%), and assimilated into cells(10.6% ± 0.9%) at the end of incubation. When Cu~(2+)was present, the transformation of extractable metabolites into non-extractable metabolites and mineralization were inhibited, possibly due to the toxicity of Cu~(2+)to cells. HA significantly inhibited both dissipation and mineralization of TBBPA and altered the fate of TBBPA in the culture by formation of HA-bound residues that amounted to 22.1% ± 3.7% of the transformed TBBPA. The inhibition from HA was attributed to adsorption of TBBPA and formation of bound residues with HA via reaction of reactive metabolites with HA molecules, which decreased bioavailability of TBBPA and metabolites in the culture. When Cu~(2+)and HA were both present, Cu~(2+)significantly promoted the HA inhibition on TBBPA dissipation but not on metabolite degradation. The results provide insights into individual and interactive effects of Cu~(2+)and soil organic matter on the biotransformation of TBBPA and indicate that soil organic matter plays an essential role in determining the fate of organic pollutants in soil and mitigating heavy metal toxicity.     

Degradation of nitrobenzene in wastewater by γ-ray irradiation

The degradation of nitrobenzene(NB) by γ-ray irradiation was studied. The influences of dose rate and initial NB concentration were investigated in details. At a dose rate of 55 Gy/min, the degradation kinetics was pseudo-first-order at NB concentrations from 0.2 mmol/L to 4.0 mmol/L. At an initial NB concentration of 0.8 mmol/L, the degradation of NB at various dose rates also followed pseudo-first-order kinetics. Dissolved oxygen was found to have a positive effect on NB degradation. The degradation products were identified as nitrophenol,nitrosobenzene, and hydroquinone, and so on. Based on the product analysis, possible degradation pathways of nitrobenzene were proposed.     

Biodegradation of tetrabromobisphenol A in the sewage sludge process

Anaerobic sewage sludge capable of rapidly degrading tetrabromobisphenol A(TBBPA) was successfully acclimated in an anaerobic reactor over 280 days. During the period from 0 to 280 days, the TBBPA degradation rate(DR), utilization of glucose, and VSS were monitored continuously. After 280 days of acclimation, the TBBPA DR of active sludge reached 96.0% after 20 days of treatment in batch experiments. Based on scanning electron microscopy(SEM) observations and denaturing gradient gel electrophoresis(DGGE) determinations,the diversity of the microorganisms after 0 and 280 days in the acclimated anaerobic sewage sludge was compared. Furthermore, eleven metabolites, including 2-bromophenol,3-bromophenol, 2,4-dibromophenol, 2,6-dibromophenol, tribromophenol and bisphenol A,were identified by gas chromatography–mass spectrometry(GC–MS). Moreover, the six primary intermediary metabolites were also well-degraded by the acclimated anaerobic sewage sludge to varying degrees. Among the six target metabolites, tribromophenol was the most preferred substrate for biodegradation via debromination. These metabolites degraded more rapidly than monobromide and bisphenol A. The biodegradation data of the intermediary metabolites exhibited a good fit to a pseudo-first-order model.Finally, based on the metabolites, metabolic pathways were proposed. In conclusion, the acclimated microbial consortia degraded TBBPA and its metabolites well under anaerobic conditions.     

Characterization of phenanthrene degradation by strain Polyporus sp. S133

Polyporus sp. S133, a fungus collected from contaminated soil, was used to degrade phenanthrene, a polycyclic aromatic hydrocarbon, in a mineral salt broth liquid culture. A maximal degradation rate (92%) was obtained when Polyporus sp. S133 was cultured for 30 days with agitation at 120 r/min, as compared to 44% degradation in non-agitated cultures. Furthermore, the degradation was a ected by the addition of surfactants. Tween 80 was the most suitable surfactant for the degradation of phenanthrene by Polyporus sp. S133. The degradation rate increased as the amount of Tween 80 added increased. The rate in agitated cultures was about 2 times that in non-agitated cultures. The mechanism of degradation was determined through the identification of metabolites; 9,10-phenanthrenequinone, 2,2’-diphenic acid, phthalic acid, and protocatechuic acid. Several enzymes (manganese peroxidase, lignin peroxidase, laccase, 1,2-dioxygenase and 2,3-dioxygenase) produced by Polyporus sp. S133 were detected during the incubation. The highest level of activity was shown by 1,2-dioxygenase (187.4 U/L) after 20 days of culture.     

Development of indirect competitive fluorescence immunoassay for 2,2′,4,4′-tetrabromodiphenyl ether using DNA/dye conjugate as antibody multiple labels

An indirect competitive fluorescence immunoassay using a DNA/dye conjugate as antibody multiple labels was developed on 96-well plates for the identification and quantification of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) in aqueous samples. A hapten, 2,4,2′-tribromodiphenyl ether-4′-aldehyde, was synthesized, and was conjugated to bovine serum albumin to form a coating antigen. Specific recognition of the antigen by anti-PBDE antiserum was confirmed by a surface plasmon resonance measurement. In the immunoassay, the coating antigen was adsorbed on a 96-well plate first, and a sample, antiserum and biotinylated goat anti-rabbit secondary antibody were then added and reacted sequentially. A biotinylated, double-stranded DNA with 219 base pairs was attached to the secondary antibody by using streptavidin as a molecular bridge. In situ multiple labeling of the antibody was accomplished after addition of a DNA-binding fluorescent dye, SYBR Green I. The working range of the immunoassay for the BDE-47 standard was 3.1-390 μg/L, with an IC₅₀ value of 15.6 μg/L. The calculated LOD of the immunoassay is 0.73 μg/L. The immunoassay demonstrated relatively high selectivity for BDE-47, showing very low cross-reactivity (< 3%) with BDE-15, BDE-153 and BDE-209. With a spiked river water sample containing 50 μup g/L BDE-47, quantification by the immunoassay was 41.9 μg/L, which compared well with the standard GC-ECD method (45.7 μg/L). The developed immunoassay provides a rapid screening tool for polybrominated diphenyl ethers in environmental samples.     

Imazaquin degradation and metabolism in a sandy loam soil amended with farm litters

Irnazaquin applied in legume crops has a long residual time in soil, which often impacts safety of the susceptible crops. To increase safety of imazaquin application, two composted litters, bovine manure （BM） and chicken manure （CM）, were used to determine their effects on imazaquin environmental behavior by incorporating each kind of manure into the tested sandy loam soil at 10% （w/w）. The degradation of imazaquin in BM- and CM-amended soil was about 2.4 and 1.5 times, respectively, faster than that in unamended soil. The half-lives of imazaquin in BM-amended soil varied between 6.7 and 15.4 d over the temperature range of 20 to 40℃, and the degradation rate constant （k） increased by a factor of about 1.5 for every 10℃ change. Higher mix ratio did not significantly increase the degradation, and the optimal active degradation of imazaquin was observed approximately at the mix ratio of 10：1 of soil to BM. The different moisture levels had negligible effect on imazaquin degradation. In both unamended and BM-amended treatments, two metabolites were observed at 5, 10 and 30 d after treatment. One metabolite at retention time （RT） of 8.4 rain was identified as 2-（4- hydroxyl-5-oxo-2-imidazolin-2-yl） quinoline acid, originating from the loss of isopropyl group and hydroxylation at the 4-position of imidazolinone ring. The other at RT of 12.9 rain was identified as quinoline-2,3-dicarboxylic anhydride, resulting from detachment of imidazolinone ring and the forming of dicarboxylic anhydride. This finding suggested that the addition of farm litters into soil might be a good management option since it can not only increase soil fertility but also contribute to increase safety of imazaquin application to the following susceptible crops.     

Enhanced photoelectrocatalytic degradation of ammonia by in situ photoelectrogenerated active chlorine on TiO2 nanotube electrodes

TiO_2 nanotube(Ti NT) electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy(FE-SEM) and X-ray diffraction(XRD) were performed to characterize the TiNT electrodes. The linear voltammetry results under irradiation showed that the TiNT electrode annealed at 450°C presented the highest photoelectrochemical activity. By combining photocatalytic with electrochemical process, a significantly synergetic effect on ammonia degradation was observed with Na_2SO_4 as supporting electrolyte at pH 10.7. Furthermore, the photoelectrocatalytic efficiency on the ammonia degradation was greatly enhanced in presence of chloride ions without the limitation of pH. The degradation rate was improved by 14.8 times reaching 4.98 × 10~(-2) min~(-1) at pH 10.7 and a faster degradation rate of 6.34 × 10~(-2) min~(-1)was obtained at pH 3.01. The in situ photoelectrocatalytic generated active chlorine was proposed to be responsible for the improved efficiency. On the other hand, an enhanced degradation of ammonia using TiNT electrode fabricated in fluorinated organic solution was also confirmed compared to TiNT electrode anodized in fluorinated water solution and TiO_2 film electrode fabricated by sol–gel method. Finally, the effect of chloride concentration was also discussed.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Degradation of indomethacin in river water under stress and non-stress laboratory conditions: degradation products, long-term evolution and adsorption to sediment

The pharmaceutical compound indomethacin is not totally removed in wastewater treatment plants,whose effluents flow into aquatic environments;concentrations in the 0.1-100 ng/L range are commonly found in surface waters,and its fate is unknown.Here,biological,photochemical and thermal degradation assays were conducted under stress and non-stress conditions to estimate its degradation rate in river water and establish its degradation products over time.The results revealed that direct sunlight irradiation promoted the complete degradation of indomethacin(2 μg/L) in less than 6 hr,but indomethacin was detected over a period of 4 months when water was kept under the natural day-night cycle and the exposure to sunlight was partially limited,as occurs inside a body of water.The biological degradation in water was negligible,while the hydrolysis at pH 7.8 was slow.Residues were monitored by ultra-pressure liquid chromatography/quadrupole time-of-flight/mass spectrometry after solid-phase extraction,and six degradation products were found;their structures were proposed based on the molecular formulae and fragmentation observed in high-resolution tandem mass spectra.4-Chlorobenzoic and 2-acetamido-5-methoxybenzoic acids were the long-term transformation products,persisting for at least 30 weeks in water kept under non-stress conditions.Furthermore,the degradation in the presence of sediment was also monitored over time,with some differences being noted.The adsorption coefficients of indomethacin and degradation products on river sediment were calculated;long-term degradation products did not have significant adsorption to sediment.     

Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.     

土壤整体质量的生态毒性评价

土壤样品采自沈阳西部污灌区 .进行了污染物 (重金属和矿物油 )含量分析和生态毒性试验 .重金属采用原子吸收分光光度仪测定 ,矿物油采用紫外分光光度计测定 .生态毒性试验分别参照国际标准组织 (ISO)和OECD指南 ,进行了植物毒性试验、蚯蚓毒性试验和蚕豆根尖微核试验 .植物试验以小麦种子发芽根伸长抑制率为试验终点 ,试验周期50h ,蚯蚓毒性试验以蚯蚓死亡率、体重增长抑制率为试验终点 ,试验周期28d .土壤中矿物油含量在145mg/kg～1121mg/kg ,重金属Cd为0.34mg/kg～1.81mg/kg .土壤对植物和蚯蚓显示不同程度的毒性效应 ,土壤的蚕豆根尖微核率明显高于对照 .种子发芽根伸长抑制率为2.0%至-35.1% ,蚯蚓死亡率为0%～40%.体重增长抑制率由14d的-2.3%～-19.4%在28d增加到-2.1%～10.7% ,蚕豆根尖微核率最高达6.62/100.研究表明 ,土壤中的污染物积累较低 ,但具有明显的生态毒性 .     

国际化学危险品分类体系简介

介绍了当前国际化学危险品的各种分类体系,对比了GHS与TDG、EU_CLP、DOT、WHMIS等对化学危险品的具体分类。有助于GHS的理解与掌握,全面推进GHS在我国的实施。     

多目标规划在预测区域总产值-排污-水质协调解中的应用研究

以某区域水环境－经济系统为研究实例，寻求值－排污－水质综合协调解方法，寻求净收益最大时的总体规划方案。建立目标参数规划模型，寻求不同生产规模条件下的产值－排污－水质协调解，又探讨了水环境标准约束下的某化工区废水治理费用的计算方法，提出了以供决策者选择的方案。     

滇池富营养化特性评价

介绍了滇池水质状况,对滇池富营养化特性进行了分析和评价,并提出了对策.     

氯苯类化合物的生物降解

经过2个月的驯化,从某染料厂和某毛纺厂活性污泥中分离出能够生长于1,4-二氯苯、1,2,4-三氯苯和六氯苯的4种微生物.通过测定该混合菌降解氯苯类化合物过程中的累积好氧量、微生物生长曲线及降解产物Cl^-的释放,证明在好氧条件下该混合菌能够以1,4二氯苯和1,2,4-三氯苯为唯一碳源和能源,降解产物Cl^-浓度的变化与微生物生长周期有关.通过好氧振荡瓶培养法测得3种氯苯的生物降解顺序为:1,4-二氯苯[356.7μg/(L·d)]>1,2,4-三氯苯[110.4μg/(L·d)]>六氯苯[～6μg/(L·d)],说明氯取代数越多,氯苯类化合物越难被好氧降解.     

生态保护地协同管控成效评估

分区分类管理是我国生态保护的重要管控制度,生态保护地是事关国家生态安全的关键区域,开展生态保护地保护成效评估及不同类型生态保护地之间的协同管控成效评估具有重要意义。以吉林省自然保护地和重点生态功能区等生态保护地（即禁止开发区和限制开发区）为研究对象,以重要生态空间、植被生态、水源涵养功能为主要内容,基于“禁止开发区—限制开发区—省域”的管控梯度差异,评估分析了生态保护地的协同管控成效。结果表明：（1）从重要生态空间协同管控成效来看,自然保护地的重要生态空间面积比例最高、人类活动干扰指数最低,这与生态保护管控严格程度呈现很好地正相关。但是1980—2015年间重要生态空间面积比例均有所减少,减少幅度与管控严格程度没有表现出正相关。（2）从植被生态协同管控成效来看,植被覆盖总体呈现出自东向西逐步降低的特点,与东部分布有重点生态功能区和森林类自然保护区、西部分布较多的湿地类自然保护地的空间特征一致。但是,由于湿地及水域类型自然保护地面积占比较高,且分布在吉林西部草原和平原区的面积比例较高,自然保护地的年际变化较大、且植被覆盖稳定度低于重点生态功能区。（3）从水源涵养功能协同管控成效来看,水源涵养能力呈现出东部和西部高、中部低的特点,与这两个区域主要分布有森林、草地和湿地等重要生态空间密切相关,也与分布着大面积的重点生态功能区和各类自然保护地密切相关。自然保护区的水源涵养能力最高,且年际变化最小、稳定性最高。     

燃煤电厂脱硫副产物资源化利用可行性分析——上海案例研究

未来5年(2006～2010年)上海进行脱硫的机组将达957.2万kW,文章对上海市未来5年中脱硫副产物的资源化利用,进行了技术、经济分析,预计每年可节省SO2排污费用约1.02、1.28亿元,如以原煤计,则为1.51亿元/a和1.89亿元/a,到2010年将达1.67～2.09亿元/a,折成原煤则为2.34～2.93亿元/a,如排污费提高,效益还将扩大;电厂脱硫石膏销售将获得约2160～2880万元/a,折算成原煤应为3024万元/a和4032万元/a,如加工成球或利用余热烘干成粉,利润还会增加;到2010年脱硫石膏销售收入还将进一步放大。上海石膏板或水泥企业利用54～72万t的脱硫石膏,可使企业的原料购买成本节约3250～3650万元/a,如将FGD石膏40%SO3含量与天然石膏34%相比算入成本,使用FGD石膏的水泥生产企业原料购置费节约将更显著。     

哈尔滨松北区城市湿地的生态安全分析

以哈尔滨松北区城市湿地为研究对象,选择10个指标,采用因子分析法和聚类分析法,研究了松花江发生污染事故前后城市湿地的生态安全状况.结果表明:发生污染前哈尔滨松北区城市湿地东区的生态安全程度最高,发生污染后中区的生态安全程度最低;西区的抗干扰能力较差.各主因子中以水因子的下降幅度最大,说明水污染直接影响了哈尔滨松北区城市湿地的生态安全.最后有针对性地提出了哈尔滨松北区城市湿地的生态安全对策.      

工业锅炉烟尘浓度测量的不确定度评定

如何对测量结果的不确定度进行合理评定,一直是困扰检测实验室的一个难题。根据环境检测的特点,通过实例,阐述了烟尘排放浓度测量的不确定度评定的方法,对监测领域测量不确定度评定具有现实意义。     

学生食堂优化管理的数学模型

从学生食堂的设备及场所、物资的储存与购入、工作人员的管理及就餐者对食堂的要求这4个方面描述了各自对学生食堂管理的影响,得出了评估学生食堂优劣的一般公式Y=n∑i=1ωixi,并着重解决了学生就餐排队等待时间太长的问题,分析了该等待问题在排队论中所属的模型,解决了该课题要研究的问题的一般情况和个别案例,确定了各参数之间的关系.通过分析,得出了最优排队模型、费用模型及服务台数,并证明了最优模型的一般性.