城市污泥重金属在高级厌氧消化工艺系统中的迁移转化及风险评价

采用改进的BCR连续提取法,研究了4座再生水厂高级厌氧消化系统中热水解和厌氧消化对污泥所含重金属(As、Cd、Cr、Cu、Hg、Ni、Pb、Zn)赋存形态的影响,并利用风险评价指数法(RAC)和潜在生态风险指数法(PERI)评估了消化产物进行土地利用时的重金属迁移风险和潜在生态风险.结果显示,4座再生水厂热水解污泥中的...     

燃烧条件对灰渣中重金属元素形态的影响

根据改进了的BCR连续提取法,重金属元素形态分为酸可提取态、氧化物结合态、有机物结合态和残渣态,实验研究了不同燃烧温度、空气流量和燃烧气氛对燃煤重金属(Cr、Mn、Ni、Cu、Zn、As、Cd和Pb)的形态分布和挥发特性的影响规律。结果表明:在原煤和灰渣中,各重金属元素均主要以稳定的残渣态存在;8种重金属元素的挥发性难易程度顺序为Pb、Cd、ZnAs、Cr、Ni、CuMn;燃烧温度从650℃升至1 050℃过程中,各重金属元素4种存在形态的逸出率逐渐升高,逸出率最低增大幅度为20%,最高达60%;随空气流量的增大,重金属元素的有机物结合态和残渣态加速分解和挥发,各重金属元素的逸出率不断增大;除元素Mn和Ni较易于在贫氧气氛中挥发外,元素Cr、Cu、Zn、As、Cd和Pb均在富氧气氛中比较易于挥发气化。     

废弃等离子显示屏玻璃中重金属化学形态分布

通过BCR3步和BCR4步连续提取法,对等离子体显示屏玻璃中重金属的化学形态进行研究。结果表明,BCR3步连续提取法对废弃等离子体显示屏玻璃中重金属的提取比BCR4步连续提取法更稳定。废弃等离子体显示屏玻璃中Zn、Cu和Ag化学形态分布存在差异。BCR3步和BCR4步连续提取法均认为Ag以残渣态为主要赋存形态,对环境影响比较小;Cu的可交换与弱酸可溶态或交换态和碳酸盐结合态含量较少,潜在的环境风险也比较小;BCR3步和BCR4步连续提取法对Zn的形态分布结果评价不一致,BCR3步连续提取法表明Zn主要以可交换与弱酸可溶态为主,对环境影响较大,而BCR4步连续提取法结果认为Zn是以铁锰氧化态为主要存在形态。     

污泥微波热解过程重金属转化特性与风险评估

利用微波反应器在500~900℃的目标温度下,高温热解干污泥与Si C混合物(质量比为2.5∶1)以制取不同污泥焦,选取改进欧盟BCR逐级提取法对微波热解前后污泥焦中重金属(Cr、Cu、Pb、Ni)形态变化进行分析。同时对微波污泥热解焦进行RAC风险评估,探寻微波热解固定效能与污泥焦使用安全性与可行性。结果表明,随着微波热解温度的升高,重金属中残渣态(F4)大幅增加稳定性显著改善,与原样相比,Cr与Pb的可氧化态(F3)明显减少,分别由原样中73.86%和51.96%下降至5.98%和4.47%,Cu的可氧化态(F3)在500℃以上变化不明显。此外,微波热解焦中Ni的风险系数显著降低,其RAC形态风险系数由33.23骤降至0.78,其他3种重金属的风险系数也有不同程度的降低。     

不同粒级土壤磁化率与重金属污染特征的相关关系

采集辽宁省葫芦岛锌厂周边农田耕作层土壤,将其分为500μm、100~500μm、50~100μm、2~50μm、2μm 5个粒级,测定每一个粒级土壤的低频磁化率(χ_(lf))和高频磁化率(χhf),用BCR连续提取法对5个粒级及未分级土样中的Pb和Cd赋存形态进行分析,并计算各粒级土壤污染负荷指数(PLI)和频率磁化率(χ_(fd))等参数,以此探讨不同粒级土壤磁性与Pb和Cd含量、形态及PLI的关系。结果表明,粒径100μm时,随粒径减小,土壤中Pb和Cd含量、PLI、χ_(fd)均增加;各个粒级土壤中Pb的可还原态(F2)含量高于其他形态,而Cd的弱酸可溶态(F1)含量高于其他形态;未分级土壤中Pb含量、Cd含量和PLI与χ_(lf)和χ_(fd)具有显著相关性,且均在0.05水平及以上;各个粒级土壤中Pb和Cd的F2含量与χ_(lf)、χ_(fd)和PLI基本达0.01水平显著相关,其显著性均高于其他形态含量与χ_(lf)、χ_(fd)和PLI的显著性。     

长沙市夏季大气颗粒物中重金属的形态及其源解析

对长沙市高开区、经开区、开福区以及马坡岭4个采样点夏季的大气颗粒物(TSP)浓度以及颗粒物中的重金属元素Cu、Zn、Mn、Pb和Cd的浓度和形态分布进行了研究分析,利用污染因子(Cf)对重金属元素的可保持能力进行了评价,并利用因子分析方法(PCA)分析TSP中重金属元素的主要来源。结果显示长沙市夏季TSP平均浓度为220.7μg/m3,表明长沙市颗粒物污染较严重。TSP中重金属元素浓度大小顺序为:ZnPbCuMnCd。从形态分布来看,大约63.3%~89.0%的Cu主要存在于可氧化态(F3),而Mn在这一态中分布最少。元素Zn、Cd则主要分布在弱酸提取态,分别占了70%和35%。Pb主要分布在残渣态,大约为24%~43%。由污染因子计算可知Cu、Cd和Zn比Mn、Pb有更高的迁移性。     

滇西北剑湖表层沉积物重金属分布特征和生态风险

采用电感耦合等离子体发射光谱(ICP-OES)仪测定剑湖表层沉积物4种重金属Cd、Cu、Pb、Zn含量,采用改进BCR连续提取法提取4种重金属各形态含量,结合空间插值方法对4种重金属空间分布特征和生态风险进行了分析。结果表明,剑湖表层沉积物呈碱性,以砂砾为主,湖周浅水区总有机碳含量高于湖心区,重金属迁移转化能力弱,主要以残渣态为主,可氧化态含量最低。同时,剑湖表层沉积物中Cd和Cu以人为富集为主,Pb和Zn以自然富集为主,重金属均处于轻微或中等风险程度。湖周浅水区富集程度高于湖心区,而湖心区生态风险高于湖周浅水区。     

铅锌厂重金属污染土壤的螯合剂淋洗修复及其应用

为探讨螯合剂淋洗法在修复铅锌厂周边重金属污染土壤的修复效果及淋洗后土壤利用价值,研究采用振荡淋洗的方法比较了乙二胺四乙酸(EDTA)、次氮基三乙酸三钠盐(NTA)、[S,S]-乙二胺-N,N-二琥珀酸三钠盐(EDDS)乙二醇-双-(2-氨基乙醚)四乙酸(EGTA)4种螯合剂对不同污染程度土壤中Cd、Cu、Zn、Pb的去除效果,并用BCR连续提取法分析了淋洗前后土壤重金属形态的变化,最后通过黑麦草盆栽实验及土壤酶分析,探讨了土壤经淋洗后的利用价值。结果表明,4种螯合剂中EDTA对Cd、Cu、Zn和Pb的去除率比其他螯合剂的去除率高,其中对高污染土壤4种重金属离子的去除率最大,分别为Cd 90.98%、Cu 42.10%、Zn 56.98%和Pb 52.03%,4种重金属中Cd的去除效果分别为EDTANTAEDDSEGTA;EDTA能有效去除酸溶态、可还原态土壤重金属,而对可氧化态和残余态土壤重金属作用效果不明显;EDTA淋洗土种植黑麦草后土壤脱氢酶、碱性磷酸酶和β-葡糖苷酶活性均高于NTA淋洗后土壤中酶活性。综合考虑淋洗效率、淋洗剂的成本和利用价值等因素,可以认为,采用EDTA和NTA淋洗修复重金属污染土壤具有一定的实用性,并以EDTA效果较佳。     

南京仙林地区大气PM2.5中金属化学形态分析及其风险评估

采用四步连续提取法提取不同季节南京仙林地区PM_(2.5)中不同化学形态的金属组分。结果显示:(1)PM_(2.5)日均值平均为84.93μg/m3,75%的样品超过了《环境空气质量标准》(GB 3095—2012)中PM_(2.5)日均值二级标准值(75μg/m~3)。(2)PM_(2.5)中Fe、Zn和Pb浓度最高,As和Cd浓度最低。(3)Zn、Cd和Mn主要以弱酸提取态(F1)存在,Pb以可还原态(F2)为主,As主要以F1和F2存在,Ni和Cr以F1和可氧化态(F3)为主,Cu主要为F1、F2、F3,Fe和Ti大部分以残渣态(F4)存在。(4)Zn具有非常高的环境风险,Cd、As、Cu和Mn均表现出高风险,Pb、Ni和Cr具有中等风险,Fe、Ti具有低风险。(5)对于儿童,Cr具有潜在致癌风险;对于成人,As和Cr具有潜在致癌风险。     

非道路柴油机排放颗粒物中的重金属形态及其风险评价

采集6种典型非道路柴油机排放的颗粒物样品,利用BCR连续提取法分析了颗粒物中重金属的形态。结果表明,6种典型非道路柴油机的颗粒物比排放达154~343mg/(kW·h),小功率的非道路柴油机颗粒物比排放较高;各重金属平均质量浓度排序为ZnCrAsMnPbNi≈Cu≈Cd,重金属总量约占颗粒物质量的2.22%;Ni和Cu以有机物结合态为主,其他重金属均以残渣态为主,约占总提取形态的71.83%~96.74%;所有非道路柴油机颗粒物中均存在有机物结合态重金属且比例较高,说明排放颗粒物中有机污染物和重金属结合紧密。基于风险评价法和污染系数法对重金属的生态风险进行评价,结果表明,非道路柴油机排放颗粒物中Cd的生态风险最高,Pb、Cr和Mn的风险次之。     

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.     

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.     

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.