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...     

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.     

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。     

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     

等离子体修复对硝基酚污染土壤影响因素研究

使用自主研发的针板式高压放电等离子体装置处理对硝基酚(PNP)污染土壤,考察了放电电压、土壤含水率、土层厚度、污染物浓度、活化剂种类及其添加量在不同放电时间下对污染物降解效果的影响.结果表明,当土壤中PNP初始质量浓度为1024 mg/kg时,自然风干(含水率1％)土壤设定放电电压5 kV、土层厚度2 mm,添加10％...     

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。     

土壤柴油污染修复的抽气提取去除实验研究

为得到土壤气相抽提(SVE)去除柴油的优化条件,进行了一维土柱抽气提取去除柴油污染物的实验研究,研究不同初始含水率、不同抽气量对污染土壤中柴油去除率的影响及不同深度残留柴油的变化规律。结果表明：在本实验模拟的范围内,抽气量越大,SVE处理效果越好;初始含水率越低,处理效果越好;此外,不同深度去除率变化的规律基本上是随深度的增大而减小。实验结果可为土壤轻油污染实际治理提供实验数据基础。     

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。     

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%。     

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%。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.