还原焙烧电镀污泥中的金属形态和浸出性

分别以煤粉和稻杆为还原剂对电镀污泥进行还原焙烧,并通过酸浸回收焙烧渣中的金属。研究了焙烧温度、焙烧时间和还原剂投加量对目标金属Cu浸出率的影响以及主要杂质金属的浸出性,并采用BCR逐级提取法分析了焙烧前后污泥中的金属形态分布。结果表明,当在电镀污泥中投加30％的煤粉在600℃下焙烧1h后Cu的浸出率达到97．78％,当投加50％的稻杆时浸出率为89．47％,而氧化焙烧后浸出率仅为37．71％;并且还原焙烧渣中多数杂质金属的浸出率较低,从而可以实现Cu与杂质金属的初步分离。氧化焙烧容易导致金属从易浸出的非残渣态向难浸出的残渣态转化,而还原焙烧则能抑制这种转化过程,金属形态是决定其浸出性的重要因素。     

电子废弃物的预处理技术

主要探讨硝酸-硫酸这一混酸体系溶解电子废弃物的条件。试验表明：在60℃下，1．23mol／L硝酸和3．22mol／L．硫酸组成的混酸体系与电子废弃物在机械搅拌下反应2h，就可使得电子废弃物的溶解率达到93％以上，铜的浸出率达到99％以上。     

中温焙烧/钠化氧化法回收电镀污泥中的铬

采用中温焙烧/钠化氧化法从电镀污泥中回收铬.结果表明,影响铬浸出率的最主要因素为焙烧温度.电镀污泥与碳酸钠质量比、焙烧时间、水浸时间对铬浸出率的影响较接近,在水浸水固比为10.0 ; 1.0(质量比)、室温、焙烧温度为650℃、焙烧时间为2.0h、电镀污泥与碳酸钠质量比为1:1、水浸时间为60 min的最佳浸出条件下,铬浸出率为99.3%;去除氢氧化铝、氢氧化锌的最佳反应温度和pH分别为90～95℃和7.5;去除硫酸钠晶体的最佳pH为4.0,在最佳试验条件下,铬回收率为90.57%.     

废旧锂离子电池中钴的回收

采用高温煅烧-酸浸-化学沉淀工艺回收废旧锂离子电池中的钴,根据电极材料的热重性质确定煅烧温度,探究不同因素对钴的浸出和沉淀效果的影响,利用响应面技术优化酸浸过程,并对酸浸液进行回收处理。实验结果表明:煅烧温度为500℃时可充分去除黏结剂;优化实验得出H_2SO_4+H_2O_2体系浸出钴的最佳实验条件为液固比(m L:g)6.15,浸出温度96.34℃,浸出时间44.52 min,H_2SO_4浓度1.20 mol·L~(-1),浸出率97.51%;当浸出液pH为1.5,[C_2O_4~(2-)]/[Co~(2+)]比值为1.10,反应温度为70℃,沉淀时间为50 min时,钴的沉淀率为95.69%。回收得到的Co C2O4纯度高,晶体结构较好。     

砷华生产废渣中硫的回收利用研究

高温下氧化焙烧细磨后的砷华生产废渣，利用软锰矿浆吸收产生的SO2气体，吸收液经净化除杂、浓缩结晶等工序可制备工业产品硫酸锰。适宜的焙烧条件如下：焙烧温度为650℃，焙烧时间为60min，废渣粒度为-97μm。选择合适的吸收工艺，Mn的浸出率可达96．20％，此时SO2脱除率为87．20％。     

失效锂离子电池材料真空热处理及氨性浸出

研究了失效锂离子电池中塑料、电极隔膜等有机物的真空脱除,并以电池级纯钴酸锂(LiCoO2)为原料,与活性炭粉混合,在真空中进行热还原,还原产物用含NH3和NH4HCO3的氨性水溶液浸出。实验结果表明,当加热温度大于450℃,真空压力<400 Pa时,失效锂离子电池中有机挥发物基本被脱除。在400℃真空温度下纯LiCoO2不被炭粉还原;当还原温度达到600℃,LiCoO2转变为CoO、Co和Li2CO3;在800℃时,还原产物主要为六方相、立方相金属钴及少量的CoO。还原产物中的钴易于被氨性水溶液浸出,浸出3 h后,钴基本进入溶液中,锂的浸出率也达到97%以上。     

用钛白废酸和副产锌泥制备活性氧化锌

以次硫酸氢钠甲醛副产锌泥和钛白废酸为原料,经高剪切乳化、酸浸、锌粉置换、除杂、碱锌合成等工艺制得碱式碳酸锌,再经过滤、洗涤、干燥、煅烧制备活性氧化锌。考察了浸取工艺液固比(硫酸与副产锌泥的质量比)和硫酸质量分数对锌浸出率的影响,以及煅烧温度和时间对活性氧化锌质量的影响。实验结果表明,锌泥酸浸工艺的最佳液固比4,硫酸质量分数30%,在此工艺条件下,锌浸出率达95%。活性氧化锌的最佳煅烧温度为600℃,煅烧时间为240 min,在此条件下测定产品质量,氧化锌质量分数大于96%,比表面积大于50 m2/g,堆积密度小于0.35 g/m L。     

钒钛磁铁矿制备絮凝剂用于有机污水处理的研究

以钒钛磁铁矿为原料,利用盐酸浸出工艺制备铁、钛、钒三元絮凝剂,对工艺条件进行优化后用于处理模拟有机污水,并与聚合氯化铁(PFC)的絮凝效果进行对比.结果表明:在浸出时间为4 h、浸出温度为80℃、液固质量比为5、盐酸初始质量分数为20％时,浸出效果最佳,钒、铁、钛的浸出率分别为99.98％、97.77％、10.41％;...     

湿法回收砷碱渣中锑的工艺研究

本研究先以水浸实现砷碱渣中的砷锑分离，再对水浸渣进行盐酸浸出，得到了可作为工业原料氯化锑溶液。研究结果表明，在液固比为6：1，温度40℃，浸出时间40min的条件下，可使水浸过程中锑的浸出率低于3％，砷的浸出率达到99％；盐酸浸出中，控制酸浓度为1：1，液固比10：1，温度60℃，授出时间30min，能使锑的浸出率达到88％以上。经过水浸和盐酸浸出，锑的直接回收率为85．36％。     

高砷烧渣酸浸-深度还原-磁选提铁除杂

对云南某高砷烧渣进行了酸浸-深度还原-磁选实验研究,采用HSC、SEM-EDS、XRD等检测技术分析了提铁脱杂的机理。研究结果表明,原料中Fe品位为57.35%,含As高达2.78%,As主要以金属砷酸盐形式赋存,Cu和Zn的品位分别为0.52%和0.57%。在浸出温度60℃,硫酸质量分数25%的条件下,浸出作业As脱除率为86.43%。浸出渣碳热深度还原最佳实验条件为:还原温度1 050℃,还原时间120 min,煤粉质量分数30%,砷的作业挥发率78.23%。焙烧样品经磁选后,最终获得铁品位71.19%,总回收率约92%,含As 0.08%,含Cu 0.29%,含Zn 0.10%的铁精矿。基础理论分析及样品特性研究结果表明,酸浸促使难溶性金属砷酸盐中As转变为易溶性的H_3AsO_4,碳热深度还原实现了氧化铁矿物向金属铁相的转变以及As的进一步脱除。研究为类似硫酸烧渣的综合利用提供了一定的理论基础和技术支撑。     

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.