城市工业污染场地修复技术筛选方法探讨

近年来,随着城市化进程加速和产业结构调整,因城市工业企业搬迁而遗留的污染场地已成为制约中国土地资源再利用的新环境问题。面对不断涌现的城市工业场地污染问题,如何筛选出适宜的修复技术进行场地修复已成为中国城市土地资源安全再利用的关键。分析了中国城市工业污染场地的产生及污染特征,概述了中国城市工业场地污染的修复研究现状,并参考美国的场地污染修复经验,提出了适用于中国的城市工业污染场地修复技术选择基本流程,探讨了运用决策矩阵对修复技术进行筛选的方法,最后在此基础上提出了城市工业污染场地修复技术的发展建议。     

热解吸对污染土壤中不同形态汞的去除作用

选取贵州省万山矿区的汞污染土壤样品进行不同形态汞的热解吸去除行为研究。研究了热解吸过程中∑Hg的去除效果及动力学,以及温度和时间对污染土壤中不同形态汞的去除作用。结果表明,热解吸修复技术可有效去除土壤中的汞,土壤中∑Hg的热解吸过程符合二级动力学方程。固定热解吸时间在10 min时,随着热解吸温度的升高,土壤中水溶态汞、盐酸溶态汞和碱溶态汞含量呈现先下降后上升再下降的趋势,王水溶汞和盐酸溶态汞始终呈现下降趋势,说明不同形态的汞之间发生了转化。热解吸温度为250℃时,随着热解吸时间的增加,环境风险大的水溶态汞、盐酸溶态汞、碱溶态汞和硝酸溶态汞的去除率大幅增加,土壤的有机质损失较少,说明在低温下,延长热解吸时间,对生物毒性强的形态汞有良好的修复效果,且此温度下处理后的土壤更容易恢复农田耕作。     

关于硝酸工业污染物排放标准的研究

中国近10年来硝酸工业快速发展,但该行业的污染治理和环境管理情况却没有得到同步发展和应有的重视,对环境已造成了严重污染.现行综合排放标准已无法对硝酸工业污染起到控制作用.分析了硝酸工业污染排放情况和国内外相关的排放标准,针对中国实际情况提出了该行业污染物排放标准制定思路,严格控制硝酸工业NOx 和总氮排放,并建议利用国际清洁发展机制对温室气体N2O实施减排控制.     

关于制定地下水修复目标上限值(风险管制值)的建议

修复目标值是评判场地修复是否合格以及修复后地块能否安全利用的唯一标准,因此制定合理的修复目标值对于污染场地修复治理和安全利用起着至关重要的作用。大部分污染场地需要同时进行土壤和地下水修复,生态环境部发布了《建设用地土壤污染修复目标值制定指南(试行)》,然而地下水修复目标值制定的指南标准尚未发布。少数项目制定的地下水修复目标值过于宽松,无法保障地块的风险可控和安全利用。因此,建议借鉴土壤环境管理的思路,制定一个类似于“土壤管制值”的“地下水修复目标上限值(风险管制值)”。该值的制定不能只基于风险评估计算的结果,而应充分考虑每种污染物各自的理化性质、迁移转化归趋机制、环境赋存特征、健康和环境风险、国外同类标准的取值、检测方法的准确度和成本、经济社会承受能力等因素,力争做到合规合法、科学严谨、综合平衡。     

污染场地土壤生态毒性诊断方法的筛选

污染场地环境的调查诊断是污染场地风险管理的重要环节和依据,迄今为止中国在污染场地土壤生态毒性诊断方面尚未形成系统的技术方法。借鉴了发达国家在土壤生态毒性诊断方面的相关经验,从保护土壤功能(保持功能、栖息地功能)的角度出发,结合污染场地现在或未来土地利用类型,建立了污染场地土壤生态毒性诊断方法的筛选程序,包括污染场地初步调查、生态毒性诊断方法初筛和生态毒性诊断方法复筛3个阶段。该筛选方法在某铅蓄电池污染场地进行了应用,为中国污染场地土壤生态毒性诊断的规范化提供了参考。     

某聚氯乙烯树脂厂退役场地土壤汞污染特征分析

场地重金属污染是工业化进程的产物,污染来源多为原料及副产物的泄漏或不达标排放,给人类和环境造成不同程度的危害。本文以武汉某退役聚氯乙烯(PVC)树脂厂为研究对象,结合氯化汞催化工艺特点,探究场地土壤重金属汞的污染来源及分布特征,为同类型场地土壤重金属汞的污染调查、防治、修复提供案例支撑。研究结果表明:1)参与调查的33个点位中有27.3%已达到相当严重的污染水平,潜在生态风险单项指数Ei值最高达57 900,污染分布范围主要集中于氯化汞催化乙炔生产氯乙烯(VCM)工艺段,水平迁移扩散能力不强;2)重金属汞的垂直迁移受土壤性质影响,粘土对重金属汞的截留效果佳,粘土层中0.8~1.0 m至1.8~2.0 m最大汞浓度衰减量达2 040 mg·(kg·m)~(-1),衰减率达97.2%,而疏松的杂填土则有利于汞的垂直下渗;3)调查区域受重金属汞污染呈现典型点源污染特征。     

成都东郊稻田土中汞的分布特征研究

选取成都东郊唯一的火力发电厂周围的稻田土为研究对象,对稻田土中各种形态汞的分布特征进行了调查与研究,探讨稻田土中汞的分布规律,为分析和判断稻田土中汞的迁移和转化行为及该区汞污染土壤的修复提供重要依据。结果表明,处于火力发电厂烟尘排污口下风向的1#、2#、3#、4#采样点土样受到了严重的汞污染,呈现出高含汞特征,总汞平均质量浓度在9～41mg/kg,平均值为24.546mg/kg,远远超出《土壤环境质量标准》(GB 15618—1995)二级标准所规定的限值(0.5mg/kg),而处于排污口上风向的5#、6#、7#、8#土样没有受到明显的汞污染,大部分土样的总汞含量与成都市土壤汞平均含量接近;1#、2#、3#、4#土样中5种形态汞的垂直分布均呈现出随着土壤深度增加而减少的特征;1#、2#、3#、4#土样中的各形态汞平均百分比为有机结合态汞>硝酸溶汞>残渣态汞>铁锰氧化态汞>水溶和可交换态汞,土壤中含有的大部分汞化学性质比较稳定,难以被植物吸收利用,而易被植物吸收利用的水溶和可交换态汞虽然仅占极小一部分,但含量还是高于成都市土壤中水溶和可交换态汞的背景值。     

几种硫化物对紫色土汞的稳定化效果及优化稳定条件

以西南地区广泛分布的紫色土-灰棕紫泥为对象,探讨了硫化物种类(S、Na_2S、FeS、Na_2S_2O_3和DTCR(二硫代氨基甲酸盐))、用量对不同水平汞污染土壤的稳定化效果。结果表明5种硫化物对土壤汞均具有显著的稳定化效果。固定S:Hg摩尔比为1:1条件下,在1.5～250 mg·kg~(-1)汞污染土壤中,几种硫化物稳定效率相对大小顺序:DTCRNa_2SNa_2S_2O_3SFeS。Na_2S和DTCR在高浓度汞污染土壤中均表现较高的稳定化效果,在不同汞污染浓度下均能在3d内使土壤浸出汞浓度满足美国固体废弃物毒性浸出程序(TCLP)浸出标准要求(0.2 mg·L~(-1)),Na_2S_2O_3稳定效果相对较差,对250 mg·kg~(-1)的汞污染土壤,稳定化处理时间需要15d才能达到浸出标准要求,当汞污染浓度≥150 mg·kg~(-1)时,S和FeS不能满足浸出标准要求。固定汞污染浓度为150 mg·kg~(-1)稳定化效果取决于硫化物的用量,其中,仍然以DTCR效果最好,S:Hg=1稳定化处理3 d时即可达汞浸出标准。Na_2S和Na_2S_2O_3则均需要在较高的浓度下才能实现汞的稳定化,但是过高的用量会导致土壤中HgS再次溶解,两者的最佳施用量为S:Hg=5。元素S和FeS则需要以S:Hg5稳定化处理7 d以上才能达到浸出标准要求。土壤中汞的浸出活性与其赋存形态有关,交换态(Exc-Hg)和碳酸盐结合态汞(Carb-Hg)与土壤浸出汞浓度呈显著正相关,高效稳定剂显著促进了汞向有机质结合态(OM-Hg)和残渣态(Res-Hg)转化。硫化物稳定化处理9个月内土壤中浸出汞浓度始终维持在极低水平,满足持续稳定化要求。     

中国台湾地区土壤及地下水污染整治管理与经验

中国台湾地区土壤及地下水污染整治基金管理会自2001年成立以来,不断完善管理架构和管理体系,发布相关领域的法律法规、行政规则和公告,有效运行污染整治基金的财务筹措和使用等经济管理机制。开展了一系列行之有效的预防、监测、调查、评估等管理工作,为污染场地的识别和筛选奠定了坚实的基础。对于污染场地的整治工作,采用标准和风险评估相结合的验收方式,推行场地可持续利用的绿色修复技术。重点研究台湾地区土壤及地下水污染整治工作的管理政策、模式和措施,总结相关经验,为中国土壤及地下水污染防治工作提供借鉴和参考。     

桂林市表层土壤总汞分布特征研究

为了研究桂林市表层土壤汞污染情况,采集了不同功能区(包括校园区、风景旅游区、交通运输区、居民区、商业区、农业用地区和其他区域)的表层(0~10cm)土壤样品36个,采用硫酸-硝酸混合液浸提、原子荧光方法测定土壤中的总汞。结果表明,桂林市表层土壤的总汞质量浓度在0.136~1.873mg/kg,平均值为0.557mg/kg,中值为0.440mg/kg。各功能区土壤中汞的平均值均超过《土壤环境质量标准》(GB 15618—1995)的一级标准(0.15 mg/kg),以风景旅游区最高,为0.900 mg/kg,其次为商业区,为0.595 mg/kg。进一步对桂林市表层土壤总汞浓度与环境参数的关系进行了研究,结果表明,各采样点土壤的总汞浓度与有机质显著相关,与土壤pH无相关关系。     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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 in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.