重金属Pb、As污染土壤的稳定化修复评价方法研究

稳定化修复是广泛应用的土壤修复技术之一,然而目前对该项技术修复效果的评价方法并不完善。鉴于此,提出分层原位取样的淋溶实验及外源污染的截留柱实验作为评价方法,分别评价稳定化修复过程中重金属在土壤中的迁移风险和稳定化修复的适应性。结果表明,稳定化修复后5cm深度土壤浸出液中As和Pb浓度分别降低了92.6%和98.4%;而稳定剂对于25cm深度土壤中的Pb、As截留效果不同,稳定化修复后的As污染土壤对Cd有较好的截留效果,而稳定化修复后的Pb污染土壤对于Cd的截留能力低于对照组。基于淋溶实验和截留柱实验的评价方法具有良好的应用前景。     

贝壳粉对污染土壤中Pb、Zn、Cd的稳定化作用

价廉易得且无二次污染的稳定剂开发是重金属污染土壤稳定化修复的关键。以铅蓄电池污染场地Pb污染土壤(CQ土壤样品)及铅锌冶炼厂周边Pb、Zn、Cd复合污染土壤(ZZ土壤样品)为研究对象,用贝壳粉进行稳定化研究,通过毒性特征浸出测试(TCLP)评价其稳定化效果。X射线衍射(XRD)和X射线荧光光谱(XRF)等分析结果表明,贝壳粉的主要成分为CaCO3。稳定化实验结果表明:贝壳粉在2%(质量分数,下同)~10%的添加量下,CQ土壤样品中Pb的浸出浓度降低22%~62%;ZZ土壤样品中Pb、Zn、Cd的浸出浓度分别降低11%~91%、26%~65%、18%~64%。贝壳粉添加后土壤pH升高可能会使重金属形成氢氧化物沉淀;部分重金属可能会通过离子交换作用形成碳酸盐沉淀。经贝壳粉稳定化后土壤中重金属浸出浓度降低,有效降低了重金属的迁移性,因此贝壳粉可作为稳定剂应用于重金属污染土壤的修复。     

化学淋洗与生物质炭稳定化联合修复镉污染土壤

为探讨土壤淋洗与生物质炭稳定化联合修复技术对镉(Cd)污染黄棕壤修复效果的影响,研究通过振荡淋洗实验、BCR连续化学提取法和CaCl_2一次提取法,筛选确定污染土壤的最佳淋洗方案,并比较了淋洗修复、淋洗+稳定化修复技术对污染土壤中Cd生物有效性的影响。结果表明:3种淋洗剂的淋洗效率强弱顺序为EDTA-2NaHCl柠檬酸,最佳淋洗条件为0.12 mol·L~(-1)EDTA-2Na在固-液比1:4条件下振荡淋洗3 h,Cd的洗脱率为81.3%;淋洗后土壤中Cd的有效态(F1+F2)百分比减少了51.0%,显著降低了污染土壤的重金属总量及其环境风险;相比于单一淋洗修复技术,EDTA-2Na在添加体积(V_(添加))为最佳淋洗体积(V_(最优))的80%时,淋洗后再加入3%玉米秸秆炭稳定化15 d的联合修复技术能够将土壤中有效态Cd含量(CaCl_2-Cd)从8.13 mg·kg~(-1)降低到0.42 mg·kg~(-1)。因此,淋洗修复后施加玉米秸秆炭的联合修复技术,能够有效降低重金属污染土壤的生态环境风险,提高土壤环境质量。     

硫化亚铁稳定化修复重金属污染湖泊底泥的效率及机理

研究了硫化亚铁(FeS)对重金属污染湖泊底泥的稳定化修复效率及作用机制。结果表明:FeS能有效稳定化湖泊底泥中的重金属Cu、Pb和Cd。当水溶液初始pH=2,FeS的添加量为5%(质量分数)时,重金属Cu、Pb和Cd的稳定化率分别达到72.83%、55.25%和48.17%。水溶液初始pH在2~7范围内逐渐增加时,FeS对重金属的稳定化效率逐渐降低。在FeS稳定化重金属的过程中,Cu的稳定化主要通过形成CuS沉淀,Pb和Cd的稳定化均包含生成金属硫化物沉淀和Fe(OH)_3共沉淀过程,但Fe(OH)_3共沉淀对Pb的稳定化贡献显著大于Pb S沉淀,而Fe(OH)_3共沉淀和CdS沉淀对Cd的稳定化贡献相当。     

地质聚合物固化稳定化重金属复合污染土壤

以污染土壤部分替代偏高岭土,在碱激发剂的作用下制备地质聚合物稳定化处理Pb、As、Cd复合污染土壤,研究了其稳定化效果及处理后固化体中重金属的赋存形态。结果表明:污染土壤部分替代高岭土降低了固化体抗压强度,从力学性能上看,土壤掺量低于50%时,能满足建筑材料的强度要求(10 MPa),掺量为60%仅能满足固废填埋要求(5 MPa),土壤掺量≥70%均不能满足要求。随着土壤掺量增加,对土壤中重金属的稳定化效果也逐渐降低,当土壤Pb、As和Cd浓度分别为600、80和22 mg·L~(-1)(HJ 350-2007B)时,土壤掺量在20%~50%,固化体中3种元素浸出浓度均低于浸出标准;当土壤掺量达到60%时,Pb的浸出浓度不能满足标准要求,当土壤掺量增加至70%,固化体中Pb、Cd浸出浓度均超标。固定土壤掺量为30%,随着污染土壤中重金属含量的增加,浸出浓度也增加:土壤中3种重金属浓度为HJ 350-2007B时经过30 d的稳定化处理,浸出浓度满足标准要求;而当浓度达到HJ 350-2007B的2倍时,Pb浸出浓度超标;达到HJ 350-2007B的3倍时,3种Pb、As和Cd均超出浸出标准。固化体中Pb、As、Cd的形态研究表明,外源重金属进入土壤后多以活性较高的形态存在,经过固化稳定后活性态占比降低、残渣态占比增加。     

钝化剂在烟草植物修复铅镉污染土壤中的作用简

重金属钝化剂可以改变土壤中重金属的形态,降低其在土壤中的有效浓度、植物毒性及生物有效性,影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe⁰）和纳米TiO₂（nTiO₂）对烟草植物修复铅镉污染土壤的作用。结果表明,HA降低土壤中Pb、Cd的有效性、促进烟草生长、增加了烟草叶、茎、根中Cd的吸收量和根系中Pb的吸收量,有利于Pb、Cd的钝化和植物修复。nHA也可以降低土壤中Pb、Cd的有效性,增加了烟草叶中Cd的吸收量,有利于Pb、Cd的钝化和Cd的植物提取。nFe⁰和nTiO₂对于土壤Pb和Cd的钝化作用和植物修复均没有显著影响。综合来看,HA最适合应用于烟草植物修复铅镉污染土壤。     

氯化铁和硫酸铁对酸性土壤中有效态镉和铅污染的修复作用

采用浸泡实验法研究了氯化铁和硫酸铁对酸性土壤中有效态镉和铅污染的修复效果,结果表明,氯化铁和硫酸铁均能有效去除土壤有效态镉和铅污染,Fe(Ⅲ)用量为50～100 mmol/kg时,有效态Cd和Pb的去除效果可达70％～96％.氯化铁和硫酸铁能去除土壤中的水溶态、碳酸盐结合态、腐殖酸结合态、铁锰氧化物结合态和强有机结合态Cd和Pb及交换态Cd.氯化铁和硫酸铁对Cd均既有洗脱修复作用又有固定修复作用,且洗脱修复作用的贡献稍大;氯化铁用量较小时(50 mmol/kg)对Pb既有固定修复又有洗脱修复作用,固定修复作用稍大;用量较大时(100 mmol/kg),对Pb只有洗脱修复作用.硫酸铁对Pb的修复作用则以固定修复作用为主,洗脱修复作用很小.     

重金属复合污染土壤稳定化研究及效果评价

用自制稳定化试剂CTS-AC01试剂对广西河池某砒霜厂遗址As、Cd、Pb、Zn复合污染土壤进行稳定化研究并进行效果评价。结果表明:(1)CTS-AC01试剂可以降低土壤中重金属的毒性特征浸出程序(TCLP)浸出液浓度,使As、Cd、Pb、Zn的稳定效率分别达到87.7%、93.7%、90.9%、99.5%;(2)经过20次模拟淋溶,淋溶液中As、Cd、Pb、Zn的质量浓度分别为0.199、0、0、0.017mg/L,除As浓度超过《地表水环境质量标准》(GB 3838—2002)的Ⅴ类水质标准外,其他3种重金属均已达标;(3)通过土壤中重金属形态分析发现,稳定化主要是将可交换态和氧化结合态向残渣态转化,但20次模拟淋溶对土壤中重金属形态的影响不大,更长期的淋溶作用有待进一步研究。     

生物炭复配磷酸盐对Pb-Cd污染土壤原位钝化修复的研究

采用小区试验方法,选取生物炭、磷酸盐及两者复配材料作为钝化剂原位修复工业遗留场地Pb-Cd污染土壤,通过毒性浸出方法(TCLP)以及欧共体标准物质局(BCR)连续提取法分析钝化修复效果,以期获取最优化的钝化修复方法。结果表明,生物炭、磷酸盐及两者复配材料均能够有效降低土壤Pb、Cd的生物有效性和迁移能力。生物炭能提高土壤pH,使TCLP提取态Pb、Cd分别降低56.26%和83.54%,生物炭能促进重金属沉淀的形成进而提升残渣态Pb、Cd比例;磷酸盐主要通过矿物沉淀作用促使重金属由弱结合态向强结合态方向的转化,使TCLP提取态Pb、Cd分别降低70.66%、89.94%,残渣态Pb、Cd比例显著提升,进而有效降低Pb、Cd的生物有效性和迁移能力。生物炭和磷酸盐复配材料相比单一钝化剂材料未表现出协同作用,但复配材料在保证钝化修复效果的前提下,能补偿酸性磷酸盐造成的土壤酸化,在修复实践中更具应用优势。     

观赏植物与驯化污泥联合修复垃圾渗滤液污染土壤

垃圾填埋场渗滤液污染土壤具有重金属-有机物复合污染的特性。研究了观赏植物广东万年青、白掌、孔雀竹芋和经垃圾渗滤液驯化的污泥对该污染土壤的修复效果,结果表明:采用单一植物修复时,广东万年青较白掌和孔雀竹芋对土壤污染物具有更强耐性,能在污染土壤中生长良好,对重金属Cd和Pb的富集能力也更强;驯化污泥能明显提高污染土壤中有机污染物的降解率,并使重金属Cd和Pb稳定态比例分别提高了34.7%和36.6%,降低了重金属的生物有效性。当采用广东万年青和驯化污泥联合修复时,污泥能促进植物的生长,且当污泥添加量为480 mg·kg~(-1)时,联合修复对土壤中Cd、Pb及有机污染物的去除率分别较不加污泥的对照提高了51.7%、25.5%和40.2%。     

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.