交换电极法强化电动修复铬污染土壤

pH值是影响污染土壤电动修复的主要因素。为此提出了交换电极法强化电动修复，并对该技术进行了实验研究。实验土壤Cr污染浓度为506.36 mg/kg，工作电压为1 V/cm，结果显示，固定电极方向运行模式下，运行2 d，产生聚焦效应，运行8 d，碱性区Cr(III)残留量和酸性区Cr(VI)残留量较大，分别是97.88 mg/kg和328 mg/kg，总铬去除率为59.04%。采用交换电极法，交换频率为4 d，运行8 d，总铬去除率为70.18%；交换频率为2 d，运行8 d，总铬去除率高达86.10%，土壤中总铬平均含量从506.36 mg/kg降至73.56 mg/kg，达到酸性土壤环境质量一级标准。该技术可控制土壤pH值在中性范围，电流密度高，不添加化学试剂，操作简单。     

外源铅污染对紫色土中微生物酶活性的影响研究

以森林和耕地紫色土为研究对象,研究了外源铅在6种不同浓度水平下对土壤微生物酶活性的影响。结果表明:(1)森林土壤中微生物酶活性总体较耕地土壤高。(2)在连续培养56d后,森林土壤中除亮氨酸氨基肽酶(LAP)外其余4种酶活性与铅外源添加量和有效态铅呈显著或极显著正相关,外源铅污染促进了林地中C和P的矿化循环过程;耕地土中酸性磷酸酶(ACP)、β-葡萄糖苷酶、LAP活性与铅外源添加量和有效态铅呈显著或极显著负相关,在铅质量浓度≥250mg/kg时ACP基本失活,铅质量浓度达1 000mg/kg时,LAP抑制率为95.8%,外源铅污染抑制了耕地中养分元素的矿化循环过程。     

微生物矿化修复重金属污染土壤

以选矿厂附近土壤为研究对象,分析了土壤中交换态重金属含量,As、Pb、Cd、Zn和Cu的交换态浓度为14.01、4.95、0.64、33.46和12.95 mg/kg。基于生物矿化原理,利用碳酸盐矿化菌生长代谢过程产生的脲酶来分解底物尿素,产生碳酸根离子,固结重金属离子,使得土壤中活泼的重金属离子转变为碳酸盐矿物态,降低其危险。研究了温度、pH和重金属离子对酶活性的影响,发现环境30℃温度有利于促进酶活性;在弱酸性条件下,底物分解量减少15%;重金属离子在低浓度时对脲酶活性影响不大,浓度提高后对酶活性抑制作用没有加剧。将制备好的微生物矿化修复制剂喷洒于1 000 m2的污染土壤中,实验结果发现,土壤中交换态重金属离子含量在0～20 cm范围内明显减少,As、Pb、Cd、Zn和Cu的交换态浓度分别减少至2.37、1.25、0.31、16.67和3.42 mg/kg。     

2,4,6-三氯酚在盐城湿地土壤中的吸附行为

2,4,6-三氯酚(2,4,6-TCP)是造纸废水中的有机污染物之一,具有毒性强、难生物降解等特点。为了解盐城湿地土壤对2,4,6-TCP的吸附行为,采用批平衡实验研究了2,4,6-TCP在该土壤中的动力学和热力学吸附特征,并考察了不同溶液pH及离子强度对土壤吸附2,4,6-TCP的影响。结果表明,在水土比为10∶1的条件下,当溶液pH为3~9时,吸附系数Kd随pH的升高由8.01 L/g降到1.57 L/g;当Ca Cl2溶液浓度为0、0.01和0.1 mol/L时,该土壤对10 mg/L 2,4,6-TCP的吸附量则分别为20.64、26.62和39.57 mg/kg。与拟一级动力学模型和拟二级动力学模型相比,双室一级动力学模型能较好地描述湿地土壤对2,4,6-TCP的动态吸附过程。在288、298和308 K温度下Freundlich方程能较好地拟合2,4,6-TCP的吸附等温线,吸附系数Kf随温度的升高依次为5.91、7.35和11.14(mg/kg)/(mg/L)n,该吸附过程为自发的吸热反应。     

接种菌剂对城市污泥生物干化过程中干化效果和氮素转化的影响

以广州某污水处理厂压滤污泥为原料,木屑为调理剂,添加接种菌剂和碳源,采用间歇强制通风方式进行了周期8 d的生物干化实验,研究了不同接种菌剂量对生物干化过程中温度、含水率、pH、挥发分以及氮素形态转变的影响。实验共设4组,接种菌剂添加量分别为0、2‰、4‰和6‰,其他条件相同。实验结果表明,在接种菌剂添加量为4‰时,综合生物干化效果最好。堆体温度和pH在初期升高最快,含水率降低到51.73%,挥发分降低到42.04%。在氮素转化方面,污泥中的氮素在初期最容易向氨氮转化,而后期则较多的向硝氮转化。污泥的总氮含量从40.3 g/kg降低到27.6 g/kg,氮损失率为31.51%。     

矿化垃圾除磷特性及其影响因素的研究

主要研究了KH2PO4溶液在矿化垃圾中的吸附性能,静态和动态试验研究表明在静态试验条件下,初始浓度越高,固液比越小,矿化垃圾吸附磷量越多;pH对磷吸附性能具有较大的影响,当pH在8左右时,矿化垃圾吸磷量达到最大吸附量.在动态实验条件下,湿干比减小,配水速率减小,都有利于矿化垃圾除磷率的增加,当初始溶液的磷质量浓度为50 mg/L时,矿化垃圾有最佳除磷率.     

不同氮源对常中温条件下麦秆厌氧发酵的影响

通过自行设计的厌氧发酵装置,研究不同氮源对常温（20℃）和中温（35℃）条件下麦秆厌氧发酵的影响。结果表明,在常温和中温条件下进行麦秆沼气厌氧发酵时,适量添加外部氮源可加快产气速率,增加产气量,缩短产气停滞时间,其中添加牛粪效果最好,分别在182 d和84 d时发酵完全,总累积产气3 486.80 mL和4 210.70 mL,干物质累积产气量为217.93 mL/g和263.17 mL/g,且在实验期间未出现产气停滞。添加尿素处理次之,分别在累积产气215.70 mL和238.00 mL时进入61 d和20 d的产气停滞期,在196 d和143 d时发酵完全,在实验结束时,累积产气2 784.20 mL和3 454.00 mL,干物质累积产气量为174.01 mL/g和215.88 mL/g。可见,在以秸秆为原料的沼气发酵过程中,可通过添加适量的外部氮源和提高发酵温度来提高沼气产量,而且在条件允许的情况下,应尽量添加畜禽粪便等有机氮源。     

添加天然沸石和石灰对土壤镉形态转化的影响

采用土壤培养实验,研究镉污染土壤中添加沸石、石灰及两者配施对土壤pH值和土壤镉形态变化的影响。结果表明,土壤pH值随沸石用量的增加而增加,随培养时间呈现先增加后下降并逐渐趋于稳定的趋势,但均高于对照。高剂量石灰的处理对土壤pH的影响最大,与对照相比土壤pH提高了3.33个单位。在土壤5~50 d培养过程中,石灰处理的土壤交换态镉含量呈现先逐渐降低而后略有升高的趋势,其余处理均呈下降趋势。培养50 d后,高剂量的沸石、石灰及高剂量沸石与石灰配施处理的土壤交换态镉含量从5 d时的67.54、61.95和55.56 mg/kg降低至54.65、49.93和45.96mg/kg。相关分析表明,不同培养时期交换态镉含量与土壤pH值呈负相关关系。在10个处理中,L2Z3(石灰2 g/kg土和沸石60 g/kg土)组合处理效果最好,使土壤交换态镉含量下降了34.68%,碳酸盐结合态镉含量上升了4.30%,铁锰氧化结合态镉含量上升了16.97%,有机结合态镉含量上升了1.31%,残渣态镉含量上升了12.11%。     

淹水对土壤重金属浸出行为的影响及机制

为了明确淹水对土壤重金属浸出行为的影响及其作用机制,以实际场地重金属污染土壤为研究对象,开展了淹水实验。对淹水过程中土壤重金属的浸出浓度、氧化还原电位、pH、铁氧化物浓度及重金属形态等相关指标进行测定了分析。结果表明,淹水后,重金属浸出浓度随淹水时间呈现先增长后降低趋势。淹水初期(30 d),Cu、Zn、Cd和Pb浸出浓度分别增加了6.71%、4.03%、3.56%和4.55%。pH降低、有机质降解和铁氧化物还原溶解是导致重金属浸出浓度升高的主要原因。随淹水时间的持续增加,重金属浸出浓度逐渐降低并于90 d时趋于稳定。淹水结束时(180 d),Cu、Zn、Cd和Pb浸出浓度分别降低了23.78%、16.78%、15.48%和15.45%。重金属形态分析表明,淹水促使重金属赋存形态由酸可提取态转化为可还原态和可氧化态,降低了重金属活性;矿物成份分析证实了金属硫化铜物相的生成。新形成的无定形氧化铁对重金属的吸附作用和硫化物与重金属的化学沉淀作用是重金属浸出浓度降低的主要机制。该研究为淹水条件下重金属污染土壤风险控制提供了依据。     

南京市紫金山土壤中6种重金属的污染特征和污染水平评价

为探究人类活动对南京市紫金山国家森林公园土壤重金属污染的影响,研究了紫金山土壤中6种重金属(Cu、Zn、Pb、Cr、Ni、Mn)的污染特征,并采用单因子指数法和内梅罗综合指数法进行了污染水平评价。结果表明:Cu的质量浓度范围为4.21~249.75mg/kg,平均值为64.08mg/kg;Zn的质量浓度范围为155.26~418.75mg/kg,平均值为212.34mg/kg;Pb的质量浓度范围为112.19~608.91mg/kg,平均值为319.57mg/kg;Cr的质量浓度范围为29.54~201.25mg/kg,平均值为127.36mg/kg;Ni的质量浓度范围为46.64~142.48mg/kg,平均值为76.16mg/kg;Mn的质量浓度范围为182.59~1 634.48mg/kg,平均值为1 008.93mg/kg。总体而言,上层样(0~20cm)的重金属浓度高于下层样(20~40cm),高海拔的重金属浓度低于低海拔的。内梅罗综合指数表明,所有采样点均处于重度污染状态。分析6种重金属的单因子指数发现,主要是因为Pb的单因子指数较大。     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.