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.     

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。     

高浓度汞污染土壤低温工程性修复复垦的可行性

低温热解技术修复高浓度汞污染土壤(≥100 mg·kg~(-1))工程除汞效果可达70%以上,仍残留20%~30%的惰性汞,是否对农作物安全存在一定风险仍属未知。为此,以低温热解工程性修复前的高浓度汞污染农田土壤为对照,研究修复后土壤在原位大田条件下残留汞的形态变化及对几种常见作物生物产量、质量及汞在植物组织间迁移的影响。结果表明:低温热解过程未对土壤肥力造成影响,经低温热解修复后土壤中有机结合态汞降低64.07%,残渣态汞降低56.38%;高浓度汞污染抑制了作物生长,修复后土壤耕种作物生长状况得以明显改善,作物产量提高了2~3倍;所研究作物可食部分土豆肉、玉米粒及稻米,汞含量分别降低了51.2%、43.8%和53.79%;汞在植株中的分布情况为:根叶茎,残留汞对植株根系的胁迫最为严重,且植株的根和叶汞含量,相比修复前明显降低了2~5倍。     

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.     

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.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Malathion-induced sublethal toxicity on the hematology of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on hematological parameters of the cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable hematological alterations were observed. The study on hematological parameters revealed a highly significant decrease (P < 0.01) in the total erythrocytes count in malathion-exposed animals from 24 hours to 96 hrs of exposure as compared to control. Significant decreases (P < 0.01) of hemoglobin and packed cell volume were also observed from 48 hrs to 240 hrs. A significant increase (P < 0.01) in leucocytes count was noted throughout the exposure period. Elevated numbers of lymphocytes and eosinophils as found in the present study revealed lymphocytosis as well as eosinophilia, suggesting that this was a result of direct stimulation of the immunological defense due to the presence of a toxic substance or may be associated with tissue damage. The cytomorphological and cytopathological study of erythrocytes and leucocytes in malathion-exposed frogs at 0.006 ppm concentration revealed various cytotoxic effects at different exposure times. It was noted that the size and the shape of the erythrocytes were subjected to variation in different blood disorders.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.