纳米零价铁的制备及其去除水中对氯硝基苯的研究

通过FeSO4与KBH4反应,利用液相还原法制备纳米零价铁颗粒(NZVI),用XRD、SEM和BET对其性能进行表征。在常温常压下利用纳米铁还原废水中的对氯硝基苯(p-CNB),探讨了反应条件对还原率的影响。结果表明,制备过程中碱性物质(NaOH)的添加可以明显减小颗粒粒径,增大比表面积,提高纳米铁还原反应的效率。NZVI对于对氯硝基苯有很好的去除效果,NZVI用量、p-CNB初始浓度和pH值均对其去除效率产生影响。在纳米铁投加量为1 g/L,pH=2的条件下,添加NaOH的纳米铁能在120 min内将质量浓度为50 mg/L的对氯硝基苯基本完全降解,降解率为98.8%。此外,还对NZVI还原对氯硝基苯的机理进行了初步探讨。     

麻质活性炭的制备及其对Cu2＋的吸附研究

以废麻为原料,KOH为活化剂制备粉状活性炭,通过静态吸附实验研究了活性炭对Cu2＋的吸附性能,探讨了溶液起始pH值、活性炭投加量、吸附时间、起始Cu2＋质量浓度等对Cu2＋吸附效果的影响。结果表明,溶液pH和活性炭投加量对吸附效果有较大影响,活性炭对Cu2＋的吸附率在60 min内超过50%,初始浓度在10~50 mg/L时,活性炭对Cu2＋的吸附量与起始浓度近似成正比。采用Langmuir、Freundlich吸附等温式对吸附平衡数据进行了拟合,结果表明吸附等温线符合Frenudlich模型。采用傅立叶红外光谱法（FT-IR）分析了活性炭的表面官能团,分析表明活性炭表面酸性官能团可能是吸附Cu2＋的活性中心。     

纳米钯?铝双金属对水中3-氯酚的脱氯降解研究

采用置换沉积法制备了纳米钯/铝双金属催化剂,氢解还原去除水相中难降解有毒有机物3-氯酚(3-CP),考察了溶液pH、钯负载量、纳米钯/铝双金属投加量、反应温度对脱氯效果的影响并解析相关反应机制。结果表明:(1)初始pH 3.0时,沉积液中93.25%(质量分数,下同)～96.67%的钯可有效负载于铝材上。(2)在pH为3.0、纳米钯/铝双金属投加量为2g/L、钯负载量为1.16%(质量分数)、反应温度为25℃下降解初始摩尔浓度为0.389mmol/L的3-CP,反应终了时脱氯率在99%以上。利用纳米钯/铝双金属降解氯代有机污染物具有高效低耗的优势,在实际应用上具有较好的前景。     

新型重金属捕集剂NBMIPA处理含铜汞废水

研究了以间苯二甲酰氯和巯基乙胺盐酸盐为原料合成的重金属捕集剂NBMIPA对单一Cu2＋、Hg2＋电镀废水的捕集性能。结果研究表明,NBMIPA对Cu2＋和Hg2＋的捕集性能优良,NBMIPA投加量越大,捕集性能越高;NBMIPA对pH具有较宽适应性。NBMIPA对于单一含铜废水可无需调pH,投加捕集剂量为废水中含量的4～5倍（摩尔比）,静置后其上层清夜中所含Cu2＋为0.38 mg/L,Cu2＋的去除率可达99.5%以上;当NBMIPA的投加量（摩尔比）是Hg2＋的3.5～4.5倍时,Hg2＋的去除率达到99.83%,残余Hg2＋浓度为0.032 mg/L。     

饮用水源水无机金属污染的应急处理

根据密云水库供水现状，针对突发性无机金属污染事件，采用聚合氯化铝辅助化学沉淀法进行应急处理。选用Cu2＋、Fe2＋、Zn2＋和Cd2＋ 4种金属离子为目标污染物，首先通过小试实验确立了最佳混凝处理条件。结果表明，调节pH值为8．0左右，可使初始浓度为5mg／L和10mg／L的Cu2＋浓度降至0．96mg／L和0．67mg／L；初始浓度为1．5mg／L和3mg／L的Fe2＋浓度降至0．27mg／L和0．24mg／L；初始浓度为0．05mg／L和0．1mg／L的Cd2＋浓度降为0．0089mg／L和0．0078mg／L；调节pH值为9．0时，可使初始浓度为5mg／L和10mg／L的Zn2＋浓度降至0．57mg／L和0．48mg／L。4种污染物出水浓度均低于国家饮用水标准。在小试基础上，在北京第九水厂开展无机金属污染处理的中试实验，结果表明所选用的聚合氯化铝辅助化学沉淀法简便易行，可实现污染物快速、有效去除。     

一种重金属螯合剂的制备及其性能

采用聚丙烯酰胺和磺胺在碱性条件下合成了一种新型的重金属螯合剂—PAS,并对合成原料PAM和产物PAS进行了红外光谱和紫外光谱表征,分析结果表明,PAS中有N—C—S和C-S生成。将PAS用于重金属离子的螯合实验,研究了温度、pH和初始浓度对PAS去除镍离子性能的影响,用PAS处理100 mg/L的Cu2＋、Zn2＋、Cd2＋和Pb2＋的单个离子模拟废水,去除率最高分别可达到90%、96%、99%和99%。用PAS处理含Pb2＋、Cd2＋、Zn2＋和Cu2＋混合废水,去除顺序为Pb2＋〉Cd2＋〉Zn2＋〉Cu2＋。PAS对重金属离子具有很好的螯合效果,应用前景广阔。     

核桃壳对模拟废水中Cu~(2+)的吸附性能研究

采用核桃壳作为吸附剂,对模拟废水中的Cu2+进行吸附去除,考察了吸附剂粒径、水样初始pH、吸附剂用量、Cu2+初始浓度、吸附时间等因素对Cu2+吸附效果的影响,确定最佳吸附参数,并进行了吸附动力学和吸附等温线分析。结果表明:最佳吸附参数为核桃壳吸附剂粒径1.25~1.60mm、水样初始pH 5.0、吸附剂用量2.5g,Cu2+初始质量浓度20mg/L、吸附时间360min,在此条件下100mL水样在200r/min、25℃条件下吸附的Cu2+去除率达70%以上,吸附量约为0.702mg/g;本实验过程采用伪二级动力学方程的拟合更好,R2均在0.9以上,Cu2+吸附速率与其浓度的二次方成正比;Langmuir方程可以较好地描述核桃壳吸附剂对Cu2+的吸附过程,此吸附过程是单分子层的吸附。     

电极-SBBR处理含铜有机污水

采用电极一SBBR系统去除Cu^2＋，考察了电流强度，IA竞争离子（阴离子SO4^2-、NO3^-、CL^-和阳离子Zn^2＋、Ph^2＋）、初始含Cu^2＋量及溶液pH值对除铜效除果的影响。结果表明，当电流强度为40mA时Cu^2＋去除率最高为98％。投加阴（SO4^2-、NO3^-、Cl^-）、阳（Zn^2＋、Pb^2＋）离子均会引起出水Cu^2＋浓度的增加，且Cl^-和Ph^2＋含量分别为45mg／L和30mg／L时对Cu^2＋去除的影响更为显著。进水Cu^2＋浓度为30mg／L时，Cu^2＋去除率最高为98．48％，当进水Cu^2＋≥70mg／L时，出水Cu^2＋浓度不能达标。酸性（pH4．0～4．5）与碱性（pH9．0～10．0）条件均不利于Cu^2＋的去除，且酸性条件的负面影响更显著．当pH为4．5～7．5时．Cu^2＋去除率最高为97．78％。     

木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂对二元重金属离子溶液中Pb^2＋的吸附

采用自制木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂R1、R2、R3对二元金属离子Cu2＋/Pb2＋和Zn2＋/Pb2＋溶液中的吸附性能进行了较系统考察。Pb2＋离子溶液中存在竞争离子Cu2＋、Zn2＋时,随竞争离子浓度增加,3种吸附树脂R1、R2、R3对Pb2＋的吸附量明显下降,而竞争离子吸附量显著增加。二元溶液中各金属离子浓度相同时,3种树脂对竞争离子Cu2＋、Zn2＋的吸附量大于对Pb2＋的吸附量;各溶液中分别加入NaCl及NaNO3、尿素后,对Pb2＋离子的吸附量下降迅速。随吸附树脂用量增加,竞争离子Cu2＋、Zn2＋的吸附量逐渐减小,Pb2＋的吸附量在吸附树脂用量0.10 g/L（Zn2＋/Pb2＋溶液）或0.15 g/L（Cu2＋/Pb2＋溶液）时出现最大值。溶液pH值对树脂吸附性能有显著影响。3.0     

生物膜细菌藻酸盐对Cu2+的吸附动力学研究

以生物膜中提取的细菌藻酸盐为原料制备藻酸钙为吸附剂,对水溶液中的Cu2+进行了吸附动力学研究.试验结果表明,吸附时间、溶液初始pH和吸附剂投加量对藻酸钙吸附Cu2+影响显著.当溶液初始pH为4.0、Cu2+初始质量浓度为100 mg/L、吸附剂投加量为0.7 g/L时,藻酸钙对Cu2+的平衡吸附量为56.15 mg/g.水溶液中Cu2+在藻酸钙上的吸附动力学过程可用准二级动力学方程来模拟.吸附等温线研究表明,藻酸钙吸附Cu2+的过程可用Langmuir和Freundlich模型来描述.100 mmol/L 乙二胺四乙酸(EDTA)可有效解吸95.6%的Cu2+,实现Cu2+的回收与吸附剂的重复利用.     

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.     

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.     

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.     

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.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.     

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.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.