上海市某污染场地土壤异位化学氧化修复方案设计

上海市某钢材剪切厂生产过程中机油泄漏等原因导致遗留场地被石油烃(C10～C40)和苯并(a)芘污染.在对场地开展污染状况调查和风险评估的基础上,确定了场地修复工程量和修复方案.采用过硫酸盐氧化+生石灰活化的异位化学氧化技术对污染场地土壤进行修复,确定过硫酸钠和生石灰的添加量都为1.5％(质量分数),根据实际情况控制在1...     

网络版论文摘要

正胶态微氧气泡强化修复甲苯污染土壤研究郑艳梅王远鹏孙道华(厦门大学化学化工学院,福建厦门361005)通过一维土柱实验研究了胶态微氧气泡(CGAs)强化曝气技术修复甲苯污染土壤的效果,考察了污染物的初始浓度、菌液加入量、CGAs加入量等对甲苯去除效果的影响。结果表明:无CGAs添加的条件下,常规的地下水曝气不能使低浓度的污染物去除,产生拖尾现象,而适量的CGAs和     

贝壳粉对污染土壤中Pb、Zn、Cd的稳定化作用

价廉易得且无二次污染的稳定剂开发是重金属污染土壤稳定化修复的关键。以铅蓄电池污染场地Pb污染土壤(CQ土壤样品)及铅锌冶炼厂周边Pb、Zn、Cd复合污染土壤(ZZ土壤样品)为研究对象,用贝壳粉进行稳定化研究,通过毒性特征浸出测试(TCLP)评价其稳定化效果。X射线衍射(XRD)和X射线荧光光谱(XRF)等分析结果表明,贝壳粉的主要成分为CaCO3。稳定化实验结果表明:贝壳粉在2%(质量分数,下同)~10%的添加量下,CQ土壤样品中Pb的浸出浓度降低22%~62%;ZZ土壤样品中Pb、Zn、Cd的浸出浓度分别降低11%~91%、26%~65%、18%~64%。贝壳粉添加后土壤pH升高可能会使重金属形成氢氧化物沉淀;部分重金属可能会通过离子交换作用形成碳酸盐沉淀。经贝壳粉稳定化后土壤中重金属浸出浓度降低,有效降低了重金属的迁移性,因此贝壳粉可作为稳定剂应用于重金属污染土壤的修复。     

土壤气相抽提法去除红壤中挥发性有机污染物的影响因素研究

土壤气相抽提技术(SVE)是一种安全、经济、高效的土壤治理技术,广泛应用于不饱和土壤中挥发性有机污染物的去除.本实验以我国南方典型土壤红壤(粘性较大的土壤)为实验土样,选用最常见的挥发性有机物苯作为污染物,采用一维土柱通风模拟SVE过程,研究了通风流量、土壤含水率以及间歇操作对苯污染红壤去污过程的影响.结果表明,在各土柱垂向气相中苯浓度变化趋势一致,通风初期浓度迅速降低后进入长时间的拖尾阶段,拖尾阶段初期进行间歇操作可降低能耗达到较经济的治理效果.通风流量与土壤含水率是影响净化时间和修复效果的重要因素,两者均存在最佳值.当通风流量为600 mL/min,含水率为17.2%时本实验净化时间降低为36 h,去除率为99.9%,达到了最佳的治理效果.     

泥浆系统中Fe~(2+)活化过碳酸钠降解三氯乙烯

主要探究泥浆系统中Fe2+活化过碳酸钠(SPC)降解三氯乙烯(TCE)的效果。通过批次实验研究土壤对TCE的吸附作用,并考察泥浆系统中SPC和Fe2+投加量对TCE去除效果的影响。结果表明,土壤对TCE具有一定的吸附作用;泥浆系统中,土壤含有的有机质越多,TCE去除效果越低;当SPC/TCE摩尔比为5/1~20/1时,SPC投加量对TCE去除影响不明显,TCE去除效果随Fe2+投加量增大而提高。当水土质量比为30/1,TCE初始浓度为20 mg/L时,SPC/Fe2+/TCE最优摩尔比为10/30/1,此时TCE最终去除率达到97.5%。综上所述,Fe2+活化过碳酸钠降解三氯乙烯快速高效,为应用于实际场地修复提供有效的理论依据。     

矿化垃圾修复石油污染土壤的影响因素及污染物的去除机制

利用矿化垃圾对石油污染土壤进行修复研究,以期在低成本、易操作、修复效果好的前提下达到以废治废的目的。分别研究了矿化垃圾与石油污染土壤的混合比例、土壤含盐量、含油量和含水率对矿化垃圾修复石油污染土壤的影响,并通过3D-EEM(三维荧光)和GC-MS(气相-质谱)技术分析了体系石油污染物的去除特性。结果表明:矿化垃圾对石油污染土壤具有较好的修复效果,在矿化垃圾与石油污染土壤的混合比例为6:4、土壤不添加盐分、含油量为4%、含水率为30%的条件下,运行94 d后土壤中石油去除率最高可达58.61%;同时,基于3D-EEM分析发现土壤中石油类物质的荧光峰位置在处理前后均出现在Ex/Em=300 nm/330 nm处,其去除率为44.89%,表明矿化垃圾床对三环及其同系物和单环及其同系物的芳烃去除效果较好;另外,基于GC-MS技术分析得出,经矿化垃圾修复后,土壤中石油总去除率为66.57%,除正十八烷去除率(19.84%)较低外,其他烷烃的去除率均高于56.8%。     

微波催化氧化修复技术处理有机氯污染土壤

采用微波催化氧化修复技术处理常州某农药厂有机氯农药污染场地和南通某化工厂有机氯污染场地土壤,考察不同参数条件下实验装置对污染土壤的处理效能。结果表明,在微波功率18kW、微波辐射时间20min、土壤处理量400kg/h、土壤含水率15%、活性炭添加量0.03kg/kg的最佳条件下,实验装置运行稳定,有机氯农药污染土壤中氯丹去除率可达70%左右;有机氯污染土壤中邻二氯苯、石油烃总量、1,2-二氯乙烷、苯酚去除率分别可达到99.98%、91.29%、98.52%、74.74%。研发的污染土壤微波催化氧化修复技术及实验装置对有机氯污染土壤的修复具有一定的普适性。     

生物处理镉污染土壤及其酶活性研究

以添加镉的天津农田土壤为对象,分别设定空白处理、添加诺沃肥处理及生物强化处理(添加1株紫外线诱变工程菌和诺沃肥).研究土壤在不同pH、温度和含水率条件下可提取有效态镉(E-Cd)、过氧化氢酶及脲酶活性的变化情况.结果表明,添加诺沃肥处理可以有效降低E-Cd含量.而生物强化处理可进一步促进镉的固定效果;最适合生物修复的环境条件为PH 7.0、温度30℃和土壤含水率50%;添加诺沃肥处理和生物强化处理的土壤中过氧化氢酶和脲酶活性明显高于空白处理,说明生物修复后,土壤酶活性已经恢复,表明这2种处理能改善土壤结构和性能,提高土壤的肥力.     

磷基材料对铅酸蓄电池污染场地土壤铅的稳定化研究

运用不同磷基材料对铅酸蓄电池污染场地土壤进行稳定化修复,通过毒性特征浸出测试、简单生物提取测试和效果—成本分析确定适用于铅酸蓄电池污染场地的磷基材料,并采用MINTEQ化学平衡模型模拟磷基材料添加后土壤中铅赋存状态的改变、识别土壤中铅的迁移受控相。结果表明:(1)优选的3种磷基材料(磷酸二氢钾(KP)、磷酸二氢钾+轻烧氧化镁(KPM)和磷酸二氢钾+贝壳粉(SKP))对铅的稳定率高于92%,可使铅的生物可给度降低幅度达到12百分点以上,修复成本为65～180元/t。(2)3种磷基材料可明显降低土壤中Pb~(2+)活度。KP和SKP添加后土壤中铅的迁移性主要受Pb_5(PO_4)_3Cl控制;KPM添加后土壤中铅的迁移性主要受Pb_5(PO_4)_3OH和Pb_5(PO_4)_3Cl控制。     

生物强化修复石油污染土壤

筛选高效石油降解菌,考察菌株的降解性能及降解机理,进行花盆模拟高效外源菌强化修复石油污染土壤实验,在降解后期添加激活剂H2O2以及木屑来试图改善微生物的修复环境,减缓微生物的衰亡,并考察修复效果。结果表明,菌株L-1的降解效果较好,其对pH和温度有较大范围的适应性,能分泌较多的表面活性物质,细胞疏水性较强。将其应用于土壤修复中,经过50 d的修复,石油残留率达到50.6%左右,生物强化比自然修复残留率降低了8%左右。在第45天添加激活剂能有效改善修复效果,70 d时添加外源菌的土样最小石油残留率达到37.9%。     

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.     

A History of Dry Cleaners and Sources of Solvent Releases from Dry Cleaning Equipment

Approximately 25, 000-35, 000 dry cleaning facilities currently operate in the U.S. The release of perchloroethylene and other solvents from these establishments represents a major source of soil and groundwater contamination. The manner in which dry cleaning solvents escape from dry cleaning plants is, for all practical purposes, identical for chlorinated and petroleum hydrocarbon solvents and is related to one of the following events: the catastrophic failure of a component of the dry cleaning system, the improper installation, operation or maintenance of the dry cleaning equipment or a combination of all of these causes. Acceptable customs, codes and regulations can also dictate what is authorized for operation of a dry cleaning facility in a particular community, geographic area during a particular time frame. Environmental litigation dealing with the origin of a solvent release from dry cleaners tends to focus on the design and manufacture of dry cleaning industry machines such as washers, washer extractors, tumblers, solvent filters, water separators, stills and spotting boards. A thorough analysis of the daily operations of dry cleaners often reveals that poor maintenance, failure to follow the manufacturer's instructions and the actions of the operator are the most likely causes of soil and groundwater pollution. In order to forensically evaluate the most probable origins of a solvent release and to examine issues regarding liability, a thorough understanding of the history of dry cleaning and a detailed analysis of the operation and maintenance of the dry cleaning equipment are necessary. The discovery of solvent plumes in the vicinity of dry cleaning plants may suggest that the solvent source is the dry cleaning plant; however, the presence of these plumes does not necessarily indicate that the dry cleaning equipment was defectively designed or manufactured. A thorough review of the type of equipment used over the life of the dry cleaning plant and verifiable solvent mileage records frequently indicates that operators of the plant have disposed of solvent and contaminated solids into the municipal sewer or on ground surfaces.     

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.     

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

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on intestinal parameters of cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable histopathological alterations were observed. The study on intestinal parameters revealed acute pathological conditions in the intestinal wall. The toxic effect became evident as the cytoplasm of the cells disintegrated and the cells became empty and vacuolated. The cell membranes were also ruptured. Degenerative changes of the absorptive surface (villi) of the intestine in the different periods of exposure were pronounced. Severe atrophic nature (necrotic mucosa) of the intestine began from 48 hrs onwards to 96 hrs of exposure.     

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.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

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.