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.     

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.     

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。     

利用CPS还原稳定化修复Cr(Ⅵ)污染土壤

通过研究多硫化钙(CPS)与水溶液中六价铬(Cr(Ⅵ))中的反应,得出CPS与Cr(Ⅵ)的化学计量关系及主要反应产物;以CPS为修复剂,开展还原稳定化法对Cr(Ⅵ)污染土壤的修复实验,并用Fe SO_4作对比,比较两者的稳定化效果。结果表明:CPS与水溶液中Cr(Ⅵ)反应的化学反应计量比为3∶2,对反应产物进行XRD表征,发现其主要成分为Cr(OH)3和单质S;CPS能够在短时间内大幅度降低砂土中总铬和Cr(Ⅵ)的浸出浓度以及土壤的Cr(Ⅵ)含量;经CPS处理之后的Cr(Ⅵ)污染土壤,pH值从原来的8.9下降至8.2,而经Fe2+处理的土壤明显酸化,其pH值降至7.5;土壤氧化还原电位(ORP)先显著下降,后期随着CPS的逐步消耗稍有上升;经CPS稳定化处理后,土壤可交换态铬和碳酸盐结合态铬均明显减少,铬的稳定性增强,环境风险显著减小。     

废铁屑-改性粉煤灰联用处理铬渣渗滤液

针对铬渣严重污染环境问题,以"以废治废"为研究目标,采用室内静态实验方法,进行废铁屑-改性粉煤灰联用处理铬渣渗滤液中Cr(Ⅵ)和总铬实验研究。实验结果表明,废铁屑与聚合氯化铝改性粉煤灰联用处理Cr(Ⅵ)和总铬效果优于单独采用其中一种物质;处理Cr(Ⅵ)浓度208 mg/L、总铬浓度260 mg/L的200 m L高浓度含铬废水最佳反应条件为:反应时间30 min,总投加量40 g,配比为1∶1,pH值4.1,对应Cr(Ⅵ)去除率99.93%,总铬去除率99.72%。处理后水质满足《污水综合排放标准》(GB 8978-1996)要求。     

不同营养条件对薏苡人工湿地去除Cr(Ⅵ)的影响

为研究不同营养水平下薏苡人工湿地对Cr(Ⅵ)的净化与形态转变化的影响,以生活污水(W)、1/2(体积比)Hoagland营养液(Y)、1/2Hoagland营养液+生活污水(Y+W)为灌溉水源,构建微型模拟垂直流薏苡人工湿地,采取间歇进水方式,进水分别以0、10、30mg/L左右Cr(Ⅵ)(以K2Cr2O7形式加入)进行处理。结果表明:(1)根、茎、叶中总铬均随处理时间的延长和Cr(Ⅵ)浓度的提高而提高;不同器官之间相比较,总铬依次为根叶茎。(2)在不同营养条件下,基质中可交换态、铁锰氧化物结合态、有机物结合态、残渣态铬含量均随着Cr(Ⅵ)浓度的增加而提高,而碳酸盐结合态铬则先升高后降低。(3)Y处理出水Cr(Ⅵ)较高,W、(Y+W)处理均能提高人工湿地对含铬污水的处理效果。     

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。     

餐厨垃圾与铬污染土壤混合堆肥中铬形态的转化

进行了不同比例铬污染土壤与餐厨垃圾混合堆肥实验,分析了堆肥过程铬形态的变化、浸出液毒性以及种子发芽指数.结果表明,堆肥实验后,堆肥物料中可交换态和碳酸盐结合态的铬含量逐渐减少,最多可分别减少82.6%和72.69%,有机结合态的铬含量明显增加,最大增幅为106.58%;堆肥物料浸出液铬的浓度低于国家危险废物鉴别标准,浸...     

铁系物还原稳定化技术修复铬污染土壤应用研究

铁系物还原与稳定化是修复铬(Cr)污染土壤的重要手段。采用硫化亚铁(FeS)、硫酸亚铁(FeSO₄)、四氧化三铁(Fe₃O₄)和纳米零价铁(nZVI)4种铁系物对Cr(Ⅵ)污染土壤进行修复，优化修复条件，并进一步联用3种稳定剂(石英砂、高岭土和石灰石)对Cr(Ⅵ)污染土壤进行修复。结果表明，4种铁系物对土壤Cr(Ⅵ)的还原效果为FeSO₄>nZVI>Fe₃O₄>FeS,3种稳定剂对土壤总Cr和Cr(Ⅵ)的稳定化效果为高岭土>石灰石>石英砂。其中，nZVI-石英砂和nZVI-高岭土联用对土壤Cr(Ⅵ)的还原率超过99%,修复后，土壤中可交换态和碳酸盐结合态的Cr含量减少，残渣态Cr含量增加。     

电动修复不同形态铬污染土壤的研究

研究了土壤中铬的价态对电动修复效率的影响以及电动修复前后土壤中铬形态的变化.结果表明,电动修复对于土壤中1 000 mg Cr(Ⅵ)/kg的去除效果明显,总铬去除率达59.7%;而对1 000 mg Cr(Ⅲ)/kg的去除效率较低,仅为6.2%;Cr(Ⅲ)和Cr(Ⅵ)(各500 mg/kg)同时污染的土壤,铬的去除率介于中间,为18.7%.电动修复前后,土壤中铬的形态也发生了明显的变化.其中,电动修复对土壤中Cr(Ⅵ)的提取形态影响最大,而对Cr(Ⅲ)提取形态并无太大的影响.总体上,电动修复后对于生物有效的弱酸可提取态铬的浓度都保持在较低水平,预期铬的环境风险(物理流动性和生态风险)将大大降低.     

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.     

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.     

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.     

土壤中砷的化学平衡

本文比较详细地综述了砷的化学特性,环境背景值及来源和循环,土壤中砷的三大化学平衡即沉淀溶解平衡,氧化还原平衡,吸附解吸平衡,以及微生物对砷的转化。     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 μ g g^{? 1} dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 μ g g^{? 1} and 150 μ g g^{? 1} dry weight, respectively. Aluminum concentrations were (in μ g g^{? 1} dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 μ g g^{? 1}) and aluminum (> 360 μ g g^{? 1}), while leaves had less than 200 μ g g^{? 1} of iron and 165 μ g g^{? 1} of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 μ g g^{? 1}), Zn (50 μ g g^{? 1}) and Cu (3.6 μ g g^{? 1}). Some presence of lead in leaves (2.0 μ g g^{? 1}) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.