复合淋洗剂柱淋洗法修复工业废弃地铬污染土壤

为了更好地修复铬污染土壤,以盐酸、柠檬酸为初始淋洗剂,配合去离子水、石灰水、氯化钙、碳酸钠和磷酸钠,制定了20种复合淋洗剂的淋洗方案对某工业废弃地铬污染土壤进行柱淋洗实验,研究复合淋洗剂对土壤pH、总铬和Cr(Ⅵ)去除效果及对各形态铬变化的影响。结果表明:(1)各淋洗方案对土壤总铬和Cr(Ⅵ)的去除量分别为197.4~1 671.6、113.2~316.8mg/kg,其中初始淋洗剂盐酸、柠檬酸结合使用对总铬有较好的去除效果。(2)石灰水和磷酸钠可以将淋洗后的土壤pH调至接近中性并固定尚未淋洗出的Cr(Ⅵ)。(3)当0.2mol/L柠檬酸、0.1mol/L盐酸、0.2mol/L盐酸、1%(质量分数)石灰水用量分别为2、2、1、2mL/g进行淋洗时,土壤pH为7.37,总铬和Cr(Ⅵ)去除量分别为1 659.8、316.8mg/kg,去除率分别为34.6%、72.7%,水溶态铬、可交换态铬和碳酸盐态铬已被大量淋出,有机态铬与残渣态铬占比较其他淋洗方案低,为最佳淋洗方案。     

基于粒径分布的不同异位修复工艺除Cr特性

以我国某铬盐厂的铬污染土壤为研究对象,采用改进的BCR顺序提取法研究了粒径对不同修复工艺(异位淋洗、异位稳定化、湿法解毒)去除土壤中各形态Cr的影响。实验结果表明:粒径是影响铬渣污染土壤总铬和Cr(VI)去除的关键影响因素之一,粒径越细,越有利于3种异位修复工艺对土壤中Cr(Ⅵ)的去除或还原,粒径越细越有利于异位淋洗工艺对总铬的消减。粒径对水溶态Cr、酸溶态Cr的去除影响显著,粒径越细,水溶态Cr、酸溶态Cr的去除率越高,水溶态Cr和酸溶态Cr的分离或去除是不同异位修复工艺实现铬渣污染土壤中Cr(Ⅵ)高效去除的有效手段;粒径对可还原态Cr的去除影响不显著,pH是影响可还原态Cr去除的主要影响因素;粒径对可氧化态Cr含量提升显著,尤其是对异位稳定化和湿法解毒工艺,粒径越细,可氧化态Cr增大倍数越高;粒径对残渣态Cr的去除影响不显著。     

生物炭-微生物复合材料修复Cr(Ⅵ)污染土壤条件优化及促生效果

生物炭和微生物在改善Cr(Ⅵ)污染土壤质量方面得到了广泛的应用,而以生物炭-微生物制备的复合材料(BC-MT)在Cr(Ⅵ)污染土壤修复中的促生效果鲜见报道。以玉米秸秆生物炭为载体吸附铬还原菌——藤黄微球菌(Micrococcus luteus)制备BC-MT,综合考察了BC-MT修复Cr(Ⅵ)污染土壤最佳条件及促生效果。结果表明:藤黄微球菌能成功附着在生物炭上,BC-MT对Cr(Ⅵ)污染土壤修复效果显著,在BC-MT投加量3%(质量分数,下同)、氮源投加量10g/kg、土壤含水率14%的条件下,修复25d,Cr(Ⅵ)去除率为64.35%,可提取态铬从27.01mg/L降至7.72mg/L。在3%BC-MT作用下,植物生长12周后地上、地下部分总铬含量分别降低了65.15%、49.76%,Cr(Ⅵ)分别降低了94.11%、87.74%,植物株高增加了17.7cm,生物量(以干重计)增加了132mg,叶绿素增加了4.65mg/g,可溶性糖增加了1.69mg/g。由此可见,BC-MT不但能有效降低土壤Cr(Ⅵ)含量,而且促生效果显著,具有广阔的应用价值。     

交换电极法强化电动修复铬污染土壤

pH值是影响污染土壤电动修复的主要因素。为此提出了交换电极法强化电动修复，并对该技术进行了实验研究。实验土壤Cr污染浓度为506.36 mg/kg，工作电压为1 V/cm，结果显示，固定电极方向运行模式下，运行2 d，产生聚焦效应，运行8 d，碱性区Cr(III)残留量和酸性区Cr(VI)残留量较大，分别是97.88 mg/kg和328 mg/kg，总铬去除率为59.04%。采用交换电极法，交换频率为4 d，运行8 d，总铬去除率为70.18%；交换频率为2 d，运行8 d，总铬去除率高达86.10%，土壤中总铬平均含量从506.36 mg/kg降至73.56 mg/kg，达到酸性土壤环境质量一级标准。该技术可控制土壤pH值在中性范围，电流密度高，不添加化学试剂，操作简单。     

Cr(Ⅵ)污染土壤的热解还原无害化处理

提出了用热解还原法对含铬土壤进行无害化处理的新技术,研究了热解温度、热解时间及土壤有机质对铬无害化处理的影响,分析了热解前后土壤中铬的元素形态的变化.同时还探讨了热解还原过程中Cr(Ⅵ)的无害化机制.结果表明,土壤中的有机质在热解还原过程中产生的挥发分对Cr(Ⅵ)的无害化起核心作用;在200～600℃范围内,Cr(Ⅵ)的还原量随着热解温度升高而增大,500.0℃最适合于经济有效地实现Cr(Ⅵ)的热解还原处理;Cr(Ⅵ)的热解还原过程较快.铬的形态分析结果表明,热解后可交换态和碳酸盐结合态铬量大大降低,大部分铬转化成了活性低的残渣态,极大地降低了铬的危害.     

铬渣的热解无害化处理

采用热解工艺无害化处理铬渣,探讨了稻秆在铬渣无害化处理中的作用.研究了热解温度、稻秆与铬渣质量比、铬渣粒径及保温时间对铬渣热解无害化处理的影响,并分析了热解前后热解产物中铬元素形态的变化.结果表明,热解工艺能有效地将铬渣中Cr(Ⅵ)还原,稻秆热解过程中产生的气相挥发分对Cr(Ⅵ)的还原起核心作用.较为适宜的热解条件:热解温度为400 ℃,稻秆与铬渣质量比为0.10,铬渣粒径<2 000 μm,保温时间为10 min.在该热解条件处理下,热解产物中的Cr(Ⅵ)质量浓度为121 mg/kg,低于热解前铬渣中的Cr(Ⅵ)(3 400 mg/kg).热解后,可交换态及碳酸盐结合态铬含量降低,大部分铬转化成了稳定的有机结合态和残渣态,极大地降低了铬渣的危害.第一作者:张大磊,男,1982生,博士研究生,研究方向为固体废弃物热处理.     

pH和有机质对铬渣污染土壤中Cr赋存形态的影响

选用3种不同的铬渣污染土壤作为试验样,通过调节其pH和有机质含量,并采用碱消解-共沉淀法和改良BCR顺序提取法,研究了pH和有机质含量对土壤中铬的价态及形态的影响。结果表明,总体上Cr(Ⅵ)含量随pH降低和有机质投加量增大而减小,Cr(Ⅲ)则增加,但土1各水平间差异均显著(F8.89),土2和土3只有部分水平间差异显著。同时,随pH降低和有机质投加量增大,酸可提取态Cr含量减小,可氧化态Cr增加,可还原态略有增加,表明酸性条件和有机质有利于Cr(Ⅵ)的还原和酸可提取态Cr向可还原态和可氧化态Cr的转化。     

还原稳定化法修复六价铬污染土壤的中试研究

为探索还原稳定化法修复六价铬污染土壤的工程可行性,以某化工厂铬渣堆存场内六价铬污染土壤为研究对象,开展还原稳定化法修复六价铬污染土壤的中试研究。结果表明,DARAMEND-M、硫酸亚铁(Fe SO4)和多硫化钙(CPS)3种药剂对土壤中Cr(Ⅵ)的还原率超过了99%,糖蜜对Cr(Ⅵ)的还原率达93.9%。经糖蜜和DARAMEND-M处理的下层土壤,水溶态铬+交换态铬由原来的21.77%分别下降至6.26%和2.95%;经Fe SO4和CPS处理的渣土混合物,水溶态铬+交换态铬由22.12%分别下降至4.58%和2.94%,铬的稳定性明显增强。采用糖蜜、DARAMEND-M和Fe SO4处理后可以降低土壤p H值,而CPS处理则提高土壤p H值;糖蜜和DARAMEND-M有助于提高土壤微生物量碳含量。总体而言,糖蜜和DARAMEND-M适合修复低Cr(Ⅵ)污染土壤,在还原稳定化效果和长效性方面,DARAMEND-M药剂优于糖蜜;Fe SO4和CPS在修复高Cr(Ⅵ)污染土壤方面具显著效果。     

铸铁和椰壳活性炭混合介质修复高浓度Cr(Ⅵ)污染地下水研究

铬是人体和动物必需的微量元素之一。但高浓度的铬,尤其是地下水中的Cr(Ⅵ)可能对人体健康和环境造成很大的危害,因此研究高浓度Cr(Ⅵ)污染地下水的修复技术至关重要。应用铸铁和椰壳活性炭作为模拟柱中渗透反应格栅(PRB)的反应介质,为了防止实验过程发生堵塞,添加适当河沙,通过铸铁的还原作用及椰壳活性炭的吸附作用研究PRB对高浓度Cr(Ⅵ)污染地下水的修复效能。结果表明:铸铁、椰壳活性炭、河沙的质量比为3∶1∶4、Cr(Ⅵ)为400 mg/L条件下,完全穿透时反应材料对Cr(Ⅵ)整体去除率为67.0%,PRB反应介质寿命为165d;侧孔Cr(Ⅵ)浓度随时间延长而逐渐增大,离进水口越近,材料去除Cr(Ⅵ)的能力降低越快;出水及沿程在没有Cr(Ⅵ)检出时pH为4.5～7.0,出水有Cr(Ⅵ)检出时pH均大于7.0;出水中无Cr(Ⅵ)检出时,总铁(TFe)含量较高,Fe(Ⅲ)含量较少,有大量Fe(Ⅱ)产生,出水有Cr(Ⅵ)检出时,对应的Fe(Ⅲ)和TFe检出浓度均较低,说明柱体内铸铁材料基本钝化完全。     

酒石酸强化重金属复合污染模拟土壤电动修复过程及机理分析

为提高电动修复重金属复合污染土壤的效率,通过配制重金属复合污染模拟土壤,构建电动修复实验装置,利用2因素完全随机实验设计研究了酒石酸浓度和时间对重金属去除效果的影响;采用BCR法对土壤金属赋存形态进行了分析表征。结果表明:与对照相比,以酒石酸为电解液显著提高了重金属的去除率;重金属去除率受酒石酸浓度和修复时间影响显著;以0.05 mol·L~(-1)酒石酸为电解液修复120 h后,重金属去除效果最好,重金属总去除率为86.15%,Cu~(2+)、Mn~(2+)、Cd~(2+)、Pb~(2+)、Zn~(2+)的去除率分别为75.67%、98.11%、85.1%、70.75%和90.9%。BCR分析表明,酒石酸有助于提高土壤中弱酸提取态重金属含量,提高了重金属的迁移性能,从而有利于电动修复过程。     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.