工业废弃场地再开发的环境评估：Ⅱ健康风险评估

工业废弃场地往往受到严重的土壤地下水污染,再开发往往会给公众带来潜在健康风险。对河南某城市一工业废弃污染场地进行了健康风险评估。根据未来土地利用状况,分剐对居住场景和建筑场景的健康风险进行了评估。在居住场景下,总石油烃会引起较高的非致癌风险,而苯会通过口腔摄入和呼吸摄入导致较高的致癌风险。假如长期饮用MW—1附近区域的地下水时,苯和总石油烃会给居民带来不可接受的非致癌风险。同时苯还会带来较高的致癌风险。在建筑场景下,由于较短的暴露周期,场地污染不会带来不可接受的风险。为保护未来居民的健康,应当在场地开发为住宅小区前进行污染区域的修复。     

加油站泄漏污染物的迁移分布规律

选择某废弃加油站场地为研究对象,通过采集分析土壤和地下水样品中的铅（Pb）、总石油烃（TPH）、多环芳烃（PAHs）、苯系物（BTEX）、甲基叔丁基醚（MTBE）,分析了污染物在该区域地下环境中的迁移和分布特征.测试结果表明：场地包气带和含水层介质岩性以砂质粉土、粘质粉土和粉质粘土为主,土壤样品中总石油烃（C < 16）和苯均存在超标现象;垂向污染物高浓度值多出现在地下水面附近,其中上层滞水区总石油烃和苯大面积超标,潜水中总石油烃（C < 16）、苯及MTBE超标,承压水尚未被污染.在分析目前石油类污染场地修复技术的基础上,结合场地的实际条件,建议土壤和地下水的修复主要采用异位修复技术.     

暴露参数对苯污染场地健康风险评价的影响

由于工业活动的影响,工业废弃场地再开发往往会给公众健康带来许多风险,因此受到各国政府的关注。文章以某化工污染场地中挥发性有机物苯的环境风险评价为例,利用基于蒙特卡罗概率性风险评估的方法分析了我国居民暴露参数对苯污染场地环境风险评价结果的影响。研究结果表明:某苯污染场地的致癌风险值为6.42E-07~8.98E-06,非致癌风险值为6.48E-04~2.03E-01之间;室内吸入蒸汽途径、土壤摄入途径是健康风险的主要途径;参数不确定性分析表明土壤摄入量、暴露周期、室内暴露频率为敏感参数,其相关系数分别为0.084 2、0.711和0.177。因此,在该污染场地风险评估中,有必要重点获取敏感参数取值使场地风险评估结果更准确、可靠。另外,有必要加强暴露参数的调查研究,建立适合中国人群的暴露参数资料库。     

农药企业场地土壤中苯系物污染风险及管理对策

苯系物主要包括苯、甲苯、乙苯、二甲苯和苯乙烯等,是一类重要的环境污染物,可以通过呼吸道、消化道和皮肤等进入人体,对人体产生健康危害.采用吹扫捕集-气相色谱/质谱联用对河北省3个代表性农药企业场地内外土壤的苯系物进行分析,研究了土壤中苯系物的污染特征与健康风险.结果表明,A、B、C这3个企业场地土壤中的苯系物,除苯和苯乙烯外,甲苯、乙苯、二甲苯均有检出.苯系物总含量分别在673.50~32363.50 ng·g-1、nd~6 461.80 ng·g-1、461.70~8 740.80ng·g-1之间.检出的甲苯和乙苯含量(4619.50~7234.30 ng·g-1和364.60~7944.60 ng·g-1)超过加拿大工业用地指导值(370 ng·g-1和82 ng·g-1),场地A生产区灰尘中二甲苯含量甚至超过荷兰土壤干预值(17000 ng·g-1).对于场地外,区域Ⅰ(A周边)和区域Ⅱ(B、C周边)土壤苯系物浓度分别在nd~645.81 ng·g-1和nd~309.13 ng·g-1之间,均低于加拿大农业用地指导值.A、B、C场地内土壤中苯系物非致癌风险分别在2.90E-06~1.32E-04、nd~4.30E-05、1.29E-06~5.64E-05之间,远小于1,说明各场地土壤苯系物不存在明显的非致癌风险.场地外区域Ⅰ和Ⅱ苯系物的总非致癌风险分别在nd~2.02E-06和nd~1.10E-06之间,远低于1,同时也低于对应场地内非致癌风险的平均值.苯系物非致癌风险较高的区域主要集中在场地的下风向,此外,村庄和城镇周边土壤苯系物的非致癌风险略高于其他区域.整体来看,各场地内土壤和灰尘已受到不同程度的污染,场地外的农业用地环境质量也有所下降.据此,提出了企业环境管理和职工安全防护的具体对策建议.     

某污染场地地下水石油烃的健康风险评估及其微生物群落分析

有机污染场地地下水石油烃污染问题较为普遍,对周边环境和人体健康造成一定影响. 为探究污染场地地下水环境中石油烃含量、健康风险及其与微生物群落分布关系,对天津市某污染场地地下水石油烃开展健康风险评估调查,使用气相色谱法分析石油烃浓度,利用污染场地健康与环境风险评估软件进行健康风险评估,利用高通量测序技术进行地下水微生物群落特征分析. 结果表明:①5个监测井的石油烃污染情况有显著差异,A1～A4监测井石油烃浓度较低,健康风险处于可接受水平;A5监测井石油烃浓度是其他4个监测井的60～100倍,总石油烃危害商为44.990,为可接受值的45倍,健康风险较高. ②4个监测井地下水中均含有变形菌门(Proteobacteria)和厚壁菌门(Firmicutes),说明这两种细菌对石油烃污染有一定耐受能力. A5监测井细菌Chao指数和Shannon-Wiener指数最高,说明细菌多样性和丰富度最高,且该监测井变形菌门(Proteobacteria)和厚壁菌门(Firmicutes)绝对丰度均较高,说明一定浓度石油烃的存在会促进具有降解石油烃功能的细菌生长. 研究显示,一定浓度石油烃的存在使石油烃降解菌绝对丰度增加,从而增加了对石油烃的降解能力,增强了石油烃的自然衰减能力,有利于降低人体健康风险.      

粤港澳大湾区典型化工场地苯系物污染特征及迁移规律

以粤港澳大湾区某典型化工污染场地为例,共采集了247个土壤样品和20个地下水样品,探讨了场地苯系物的污染分布特征,利用GMS分别从水平和垂直方向模拟分析了该场地苯系物在土壤与地下水的污染迁移扩散规律.结果表明,场地土壤样品中苯、乙苯、间,对-二甲苯、邻-二甲苯超筛选值,其中苯系物超筛选值的土壤样品主要集中在0. 5～4 m深度范围;地下水样品中苯、乙苯、间,对-二甲苯和邻-二甲苯超标较严重,最大超标倍数分别为140. 00、101. 33、212. 00和103. 40倍,主要分布在浅层地下水.地下水中的苯污染物在水平方向主要以对流/弥散运移方式从西北往东南方向迁移,而在垂向上浮苯主要集中在地下水面处,溶解态苯主要在水动力作用下迁移.模拟验证分析结果表明,MT3D模型能较准确地反映场地苯系物的空间分布和迁移特征,可为粤港澳大湾区化工类污染场地的精准化管控与修复提供科学指导.     

某场地土壤苯系物空间分布特征和健康风险评价

对某场地土壤苯系物浓度空间分布特征描述以及结合场地未来土地利用类型,采用健康风险评价模型对土壤苯系物污染可能给未来入住人群带来的空间健康风险进行评价。结果表明,场地土壤中苯系物的污染主要以苯、氯苯和硝基苯为主。从苯系物浓度的空间分布看出,场地土壤存在一定范围的污染,亚表层污染土壤面积远大于表层土壤。空间健康风险评价结果:不同土地利用类型下均存在一定的致癌和非致癌风险,且居民用地风险远高于商业用地风险,亚表层土壤风险高于表层土壤。     

轻质非水相流体污染场地的双相抽提修复

某化工生产场地受到了苯系物的污染,并在现场浅层地下水上方形成了由甲苯构成的轻质非水相流体层.采用原位单泵双相抽提技术对该场地进行了修复的中试研究.结果表明,双相抽提技术能通过真空作用同时去除场地中的自由相污染物、受污染的地下水以及受污染的土壤气体,可有效适用于中～低渗透性场地LNAPL污染的原位修复;直接回收自由相污染物是双相抽提工艺修复场地LNAPL污染的主要途径.     

硫酸厂搬迁遗址土壤和地下水特征污染物分布研究

以浙江某硫酸厂搬迁遗留场地为研究对象进行环境调查评估。共布设土壤与地下水监测点19个,采集土壤样品38个,地下水样品16个。实验室检测项目包括挥发性有机物、半挥发性有机物、总石油烃、重金属、氟化物和硫酸盐等。根据场地特征污染因子超标情况及其在土壤与地下水中的分布规律分析,得出如下结论:(1)原硫酸厂矿石堆场、普钙生产车间等区域污染最严重;(2)土壤中主要是重金属与多环芳烃超标,地下水超标污染物主要包括重金属、石油烃、氟化物和硫酸盐等;(3)一般说来重力因素、雨水的冲刷和淋溶会使污染因子纵向迁移。而该硫酸厂拆迁时土壤翻动、横移和回填造成不同生产区域土壤混合,导致了污染因子横向扩散。     

近10年来我国污染场地再利用的案例分析与环境管理意义

及时掌握污染场地修复过程中所关注污染物和修复后再利用土地类型信息对深化建设用地环境管理具有重要意义. 本文基于文献调研和信息公示平台资料查询等途径获取了我国537个污染场地案例信息数据,分析了我国近10年来污染场地修复与再利用的变化情况. 统计分析结果表明:我国537个污染场地中约有66%集中在北京市、上海市、浙江省、江苏省和重庆市等先行地区;从2016年《土壤污染防治行动计划》颁布实施开始,场地修复管控数量增势凸显,2018年污染场地修复管控数量达到峰值;原用地类型归属化学工业、金属制品、冶炼等行业的比例较大,且重金属、苯系物为主的再利用挥发性有机物、多环芳烃类为主的半挥发性有机物和总石油烃是典型污染物;在GB 36600—2018《土壤环境质量 建设用地土壤污染风险管控标准(试行)》实施前后,包含苯系物、多环芳烃类和总石油烃等污染物的出现频次增加趋势最为明显,而有机农药类和多氯联苯(总量)的出现频次有所减少;污染场地用途大部分是敏感用地类型中的居住用地,且这类场地的原行业类型为化学工业、金属制品等特征污染物危害较大的行业. 研究显示,利好政策和标准的颁布与实施促进了我国经济欠发达地区污染场地的修复管控工作,以多环芳烃类为主的半挥发性有机物是我国未来场地土壤环境治理工作的重点,需要进一步提升对再利用类型为敏感用地类型场地的关注.      

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.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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