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。     

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.     

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.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.