典型铬渣污染场地健康风险评价及修复指导限值

通过对青海某化工厂铬渣污染场地钻孔采样,分析了样品质地及铬含量,得到场地的水文地质及铬污染状况.根据场地区域生活现状,运用美国环保局健康风险计算模型,评估了现有条件下该场地对周边居民的潜在健康风险.同时,结合场地的修复目标,应用地下水溶质运移方程及土壤中Cr6+的解吸曲线,探讨了场地污染物的修复指导限值.结果表明:场地表层0～4m为黄土状土,4～22m为砾砂,铬污染区域面积约4×104m2;现有条件下场地Cr6+对人体的健康风险值为9.39,需要对Cr6+进行修复治理,而Cr3+的健康风险值在可接受范围内;通过计算得到场地表层0～4m黄土状土Cr6+的修复值为60mg·kg-1;4～22m砾砂Cr6+修复值为15mg·kg-1.     

VOCs污染场地风险管理策略的筛选及评估

以某VOCs(volatile organic compounds,挥发性有机化合物)污染场地为例,结合实地调查,将健康风险评估用于场地风险管理策略的筛选. 结果表明:①该场地不同深度土壤均受到氯仿、二氯甲烷和苯的污染,污染物垂向迁移特征明显,最大迁移深度达25.8 m,其中深度≤15.0 m的土壤污染较重. ②基于保守的通用场地概念模型对将其规划为居住用地时的健康风险进行评估显示,氯仿、二氯甲烷和苯的致癌风险分别达6.0×10-2、2.9×10-4、7.4×10-5,均超过可接受风险水平(1.0×10-6),三者修复目标分别为0.22、12.00和0.64 mg/kg. 如采取策略一,即将场地内超过修复目标的土壤进行清除,需修复的土壤深度达24.0 m,修复土方量为33.4×104 m3. ③结合污染物垂向分布及场地未来地下空间开发规划,提出策略二,即对0~15.0 m深度范围内重污染土壤进行清除异位修复、>15 m深度范围内土壤采取工程控制措施. 实施策略二后的风险评估结果显示,虽然>15.0 m深度范围内土壤中依然存在w(氯仿)超过修复目标的采样点,但致癌风险(8.3×10-8)远低于可接受水平;概率风险评估显示,该风险值对应的累计频率为99.5%,考虑各参数取值的不确定性后,风险模拟结果最大值也仅为1.06×10-7. 可见,策略二足够保守,能够保障未来居民的身体健康;与策略一相比,策略二可减少修复土方量6.4×104 m3,因此更具经济性,为风险管理策略的优选方案.      

基于保护地下水的土壤修复目标层次化制订方法

按照复杂程度将污染物从土壤经地下水迁移到下游饮水井的过程划分为3个层次,采用分层评估框架建立了基于保护地下水的土壤修复目标的制订方法,并利用该方法确定了某污染场地的土壤修复目标值. 结果表明,在污染场地下游200 m处的饮水井内水质标准不降低的前提下,随着评价层次的不断提高,需要修复的污染物由4种(苯、甲苯、乙苯、二甲苯)减至1种(苯),待修复土方量由23.1×104 m3降至4.7×104 m3,可极大地节约修复成本. 该场地污染土壤的第一层次和第二层次修复目标值与部分国家/地区的有关标准限值较为一致;第三层次修复目标值考虑的污染物迁移过程更加完整,更能反映场地的实际情况. 参数的敏感性分析表明,对土壤修复目标值计算结果影响最大的参数为土壤有机质质量分数、土壤有机碳-水分配系数和入渗速度. 在确定修复方案时,应该通过试验或补充调查获取这些参数,以降低结果的不确定性. 研究显示,将第三层次评估结果作为该污染场地的修复目标能充分保证下游饮水井内水质满足要求,并且可以避免过度修复.      

基于地下水暴露途径的健康风险评价及修复案例研究

以北京某大型焦化厂苯污染地下水为例,对该场地不同功能地块苯呼吸暴露途径的致癌风险进行了评价,计算了苯的修复目标、修复范围并提出了相应的修复策略.结果表明,室内呼吸含苯的蒸气为关键暴露途径.该途径下,规划为商业用地的地块A苯的致癌风险为6.37×10-8,未超过1.0×10-6,风险可接受.但规划为工业遗址公园的地块B及规划为综合开发区的地块C苯的致癌风险分别为2.20×10-4、7.49×10-5,均超过可接受风险水平.为使风险可接受,该场地地下水应修复至118μg.L-1以下,需修复的地下水面积约为16.5万m2.综合考虑该场地地下水含水层的高渗透性及苯的强挥发性,确定削减污染源强度的空气注射技术并辅以切断暴露途径的工程控制措施为该场地苯污染地下水的优先修复策略.     

修复达标土壤回填对地下水环境影响的层次化评估方法应用研究

以含1,2-二氯乙烷等10种有机物污染土壤异位修复后回填为例,采用层次化方法评估将按原厂址健康风险评价确定的修复目标进行达标修复后的土壤回填对回填区地下水下游700 m处饮用水井水质的影响.第一层次预测结果显示8种污染物在回填土层淋溶液中的浓度将超过评价标准,可能对目标水井水质造成污染.考虑回填区非饱和带土壤的吸附截留进行第二层次评价的结果显示,到达回填区地下水水面处浓度依然超过评价标准的污染物降低至6种,不能排除对目标水井的水质影响.进一步考虑地下水混合稀释进行第三层次评估的结果显示,经地下水混合稀释后,超过评价标准的污染物降低至4种.最后,考虑饱和带吸附截留作用进行第四层次评估的结果显示,目标水井中超过评估标准的污染物仅1种.由此可见,随着评估层次的不断深入,虽然所需开展的工作及获取的场地参数增加,但是污染物预测浓度更接近目标预测点的浓度,需调整修复目标的污染物数量逐渐减少,污染防治成本将逐渐降低.     

原位生物稳定固化技术在铬污染场地治理中的应用研究

原位生物稳定固化方法是控制铬污染场地地下水风险的有效方法,通过实地工程试验,初步验证了原位生物稳定固化法治理南方某铬污染场地的修复效果.实地工程试验的场地面积约600 m2,位于整个污染场地的上游,受高浓度铬污染,总铬含量高值为11 850 mg.kg-1,六价铬含量高值为349 mg.kg-1,污染最为严重的土层为-0.5～-2 m.通过对在试验场地范围内设置注射井注射还原剂和微生物调节剂等,并通过监测井监测分析不同时间不同深度范围内在药剂注射的作用下地下水中六价铬和总铬的浓度变化.工程试验结果表明,原位生物稳定固化技术显著改变了土壤中铬的形态,进而降低了铬的迁移性,消减了地下水污染风险.注入的药剂对注入井(有效范围)内的地下水六铬污染治理效果很好,六价铬转成三价铬并固定稳定率达到94%～99.9%,总铬固定稳定率达到83.9%～99.8%.试验结果对于浅层地下水深度较浅、土壤以粉质黏土和砂质黏土为主的污染场地修复具有重要的参考价值.     

某林丹生产企业搬迁遗留场地土壤中六六六的残留特征

为了解有机氯农药生产企业搬迁遗留场地土壤的污染状况,于2010年11月对原新乡市某林丹生产企业搬迁遗留场地进行了调研,采用索氏提取-气相色谱-电子捕获检测器(SE-GC-ECD)法对其污染土壤中六六六(HCH)进行分析检测.结果表明,在所有采样点位中,六六六的4种异构体的检出率均为100%.0～20 cm表层土壤中六六六的浓度变化具有波动性,总残留量(ΣHCH)范围在0.034 3～19.560 8 mg·kg-1;前后院中心0～80 cm垂向土壤中六六六浓度随土壤深度的增加呈现先增加后减小的趋势,总残留量(ΣHCH)范围在0.031 3～0.294 7 mg·kg-1.通过对污染物的组成分析发现,4种异构体的含量顺序符合β-HCH>δ-HCH>γ-HCH>α-HCH,β-HCH异构体的平均含量在50%左右,远远高于其它异构体的含量,表明该场地并没有新的六六六输入.采用《土壤环境质量标准(GB 15618-1995)》对污染场地土壤残留六六六进行风险评价,结果表明,经过十几年的降解,大部分采样点位六六六的污染浓度(67.9%)低于土壤环境质量二级标准0.5 mg·kg-1,处于安全级别,厂区后院西部及东部靠近生产车间的土壤污染仍较为严重,超出土壤环境质量三级标准(1.0 mg·kg-1)1.5～20倍,存在较大的安全隐患和风险.     

基于特定场地的挥发/半挥发有机化合物(VOC/SVOC)空间分布与修复边界确定

选择我国某典型的废弃化工污染场地为研究对象,在对场地全面调查的基础上,采用美国试验与材料学会(ASTM)规范的场地环境评价方法,对场地中污染物类型、污染程度和空间分布进行了描述.同时,以人体健康风险为基础对场地修复目标进行推算,并界定修复边界和测算污染土壤体积.结果表明,四氯化碳、四氯乙烯、五氯乙烷、六氯丁二烯、六氯乙烷和六氯苯等挥发/半挥发性有机化合物为场地土壤中的主要污染物类型,其含量超过我国现有标准.根据场地特性,以最大可接受风险水平1×10-4、1×10-5和1×10-6计算得出的修复目标值界定修复边界,场地中对应区域的污染土壤体积分别为20457、25600和37300m3.最后,根据综合场地利用规划和成本投入要求,对场地中污染土壤分类处理和修复提出了技术建议.     

有机氯农药污染场地表层土壤有机-矿质复合体中污染物的分布

采用湿法物理分级方法将北京市某农药厂遗留场地表层土壤分成4种粒径的有机-矿质复合体组分:粘粒、粉粒、细砂和粗砂(<2 ìm、2～20ìm、20～200ìm、>200 ìm),研究有机氯农药在其中的分布特征及土壤不同有机-矿质复合体组分中有机质和矿物质组成的差异对污染物赋存分布的影响.结果表明,污染物质六六六(HCHs)和滴滴涕(DDTs)在粉粒中分布较多,含量分别为463.1 mg·kg-1和1225.6 mg·kg-1,粗砂中分布最少,含量仅为157.8 mg·kg-1和384.5 mg·kg-1.1gKoc与污染物质在粘粒上的分布量存在显著的相关关系.通过对有机-矿质复合体进行x射线衍射分析发现,场地土壤粘粒和粉粒中粘土矿物含量较高.由于有机-矿质复合体中粘土矿物组成和含量存在差别,这在一定程度上影响了污染物质在其中的分布.同时,所研究的场地土壤中污染物易于富集的粒径范围与报道的北京大气颗粒物上HCHs和DDTs有较多吸附的粒径相近.因此,应当重视污染场地表层土壤对大气污染的可能贡献及其环境风险.     

基于住宅用地规划及建筑结构暴露模型的场地健康风险评估

以某拟建高层住宅的苯污染场地为例,结合场地土壤环境调查结果以及场地用地规划和高层住宅结构的特点,修正了通用污染暴露模型,构建了住宅用地规划及建筑结构暴露模型,分别采用两种污染暴露模型对该污染场地的健康风险进行了评估,并比较了两种污染暴露模型下该污染场地土壤中苯的健康风险水平、修复目标、修复量和修复费用的差异。结果表明:两种污染暴露模型的评估结果均显示该污染场地土壤中苯的健康风险高于可接收水平(1×10~(-6)),须对污染场地进行修复;采用通用污染暴露模型评估时,评估过程较为简单,但评估结果相对保守,可能会导致污染场地的过度修复,而采用住宅用地规划及建筑结构暴露模型评估时,该污染场地土壤中苯的修复目标值提高了约240倍,污染土壤的修复量减少了约82.03%,土壤修复费用减少了约86.87%,其评估结果比通用污染暴露模型更具科学性。可见,对于污染场地风险评估项目,应结合场地用地规划及建筑结构特点对现有污染暴露评估模型进行修正,以避免评估结果偏离实际。     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.