Lix54—100从印刷电路板蚀刻废液中回收铜

本文对Lix54-100萃取剂萃取铜氨料液中铜的性能做了研究，发现其具有动力学速率快，饱和容量高，分离效果好，反萃容易及不萃氨等特点，并把其应用于印刷电路板蚀刻废液中铜的回收，在铜初始浓度为156．96g/L，相比为2：1条件下，用80％Lix54-100－煤油经过三级错流萃取，铜的浓度可下降到26．88g/L，三级总萃取率达82．87％，由此设计推荐了无废排放工艺流程，实现了经济效益和环境效益的统一。     

碱性蚀刻废液中的铜回收

考察N910、Lix84-I、N902和RE609 4种不同类型的萃取剂从高浓度铜氨溶液中萃取铜的效率,选取萃取效果较好的N910作为重点研究对象,并研究其从铜氨溶液萃取铜的萃取性能。实验发现,N910具有萃取速率快、饱和容量高、分离效果好、反萃完全及不易萃氨等特点;并用80%N910+煤油溶液,在pH=9.5,温度25℃,相比(O/A)1∶1条件,进行真实料液萃取实验,振荡10 min,萃取中铜离子的浓度达到69.66 g/L。因此,N910能够作为一种高效的铜萃取剂,从碱性蚀刻废液中回收铜。     

含重金属水处理污泥的固化和浸出毒性研究

工业危险固体废物在进行安全填埋前需要进行固化稳定处理。针对电镀厂和皮革厂含重金属的水处理污泥 ,用不同比例的水泥、粉煤灰进行固化稳定处理。考虑酸雨环境 ,浸出实验采用TCLP标准。电镀厂污泥单独固化时 ,其浸出液中铜离子浓度由 78 0mg/L下降到 1 5mg/L ;镍离子浓度由 2 2 4 5mg/L下降到 2 2 2mg/L ,高于危险废物允许进入填埋区 15mg/L的控制限值。电镀厂污泥与皮革厂污泥混合后固化 ,浸出液毒性明显降低。铜离子的浸出浓度降低到1 98mg/L ,镍离子降低到 4 10mg/L ,总铬降低到 0 4 0mg/L ,各项指标均低于国家危险废物允许进入填埋区的控制限值 ,可安全填埋。     

1-2-4酸生产废水资源化技术研究

以萃取—反萃取体系处理萘系染料中间体 1-2 -4酸生产废水 ,通过静态实验和正交实验确定最佳萃取—反萃取工艺条件。 1-2 -4酸生产废水包括 1-2 -4酸母液和 1-2 -4酸氧体废水 ,两种废水的萃余液平均 CODcr<60 0 mg/ L,萃取效率分别达 95 %和92 % ,反萃取效率 10 0 % ,萃取剂可以循环使用 ,有机物浓缩倍数分别为 9～ 10倍和 5～ 6倍 ,该浓缩液可回用。并对 1-2 -4酸生产废水资源化进行了运行费用分析 ,结果表明 ,该工艺有良好的经济效益、社会效益和环境效益     

氧化氨浸工艺回收硫化砷渣中的铜

对在(NH4)2S2O8-NH3-H2O体系中氧化浸出硫化砷渣(砷渣)中的铜进行热力学分析;讨论了浸出温度、c(NH3)/c(NH+4)、液固比、浸出时间及总氨浓度对铜浸出率的影响,确定了从砷渣中回收铜最佳浸出工艺条件;采用XRD和SEM对浸出渣进行表征。结果表明,氧化氨浸回收铜工艺具有热力学可行性;在浸出温度35℃,c(NH3)/c(NH+4)1∶7,液固比6∶1,浸出时间3 h,总氨浓度4 mol/L的条件下,铜的浸出率为70.74%;大量S0均匀分布在浸出渣中。     

5,11,17,23,29,35-六羧基-37,38,39,40,41,42-六羟肟酸甲氧基杯[6]芳烃对铀(Ⅵ)的萃取

以上沿羧基化的杯[6]芳烃羟肟衍生物-5,11,17,23,29,35-六羧基-37,38,39,40,41,42-六羟肟酸甲氧基杯[6]芳烃(HHMHC)为萃取剂,利用HHMHC萃取U(Ⅵ),探讨U(Ⅵ)溶液初始p H值、萃取剂浓度、温度、萃取时间、初始U(Ⅵ)浓度等因素对HHMHC萃取U(Ⅵ)的影响。实验结果表明,在萃取剂浓度为2×10-4mol/L,U(Ⅵ)初始浓度为2.1×10-5mol/L,温度为25℃时,HHMHC萃取U(Ⅵ)的最佳p H值为6.0,萃取平衡时间为30 min,且最佳萃取分配比大于10。用准二级动力学模型(R20.99)和Freundlich等温模型(R20.999)均可较好地拟合其萃取过程,通过计算萃取过程的热力学参数焓变(ΔH0)小于0,表明此萃取反应是一个放热反应。以0.1 mol/L的HCl溶液作为反萃取液,初次反萃取率达96%,证明HHMHC具有一定的重复利用价值。     

UV/H_2O_2-NaOH沉淀法处理铜-酒石酸络合体系模拟电镀废水的研究

含铜电镀废水中酒石酸等络合剂的存在,使得采用普通氢氧化物或硫化物沉淀法难以满足达标排放的要求。采用UV/H2O2-NaOH沉淀法处理铜-酒石酸络合体系模拟电镀废水,考察了光照时间、初始pH、H2O2投加量等因素对处理过程的影响。结果表明,对于铜-酒石酸络合体系(酒石酸质量浓度为418mg/L,CuSO4·5H2O质量浓度为196mg/L),得出的最佳处理条件为:光照时间70min,H2O2投加量1.07g/L,初始pH 3.0,出水中铜质量浓度可以低于0.3mg/L的排放标准,为后续工业化应用奠定了基础。     

金属离子对厌氧氨氧化污泥脱氮效能影响

通过接种厌氧氨氧化污泥研究不同浓度Fe~(3+)、Cu~(2+)和Zn~(2+)对厌氧氨氧化污泥的脱氮效能影响,以及在其最适金属离子浓度下对厌氧氨氧化污泥的长期影响。实验结果表明,进水Fe~(3+)、Cu~(2+)和Zn~(2+)质量浓度分别为0～10、0～2、0～4mg/L对厌氧氨氧化污泥活性有促进作用;当进水Fe~(3+)质量浓度为10～40mg/L时,厌氧氨氧化污泥活性未受到较大影响,而进水Cu~(2+)和Zn~(2+)质量浓度分别为1～30、4～30mg/L时,随着金属离子浓度升高,脱氮效能逐渐下降,浓度越高,对厌氧氨氧化污泥活性的抑制效果越明显。分别在最适Fe~(3+)、Cu~(2+)和Zn~(2+)质量浓度为6、1、4mg/L的条件下,对厌氧氨氧化污泥进行2个月的长期影响实验发现,加入Fe~(3+)对厌氧氨氧化污泥活性一直有良好的促进效果,而加入Cu~(2+)和Zn~(2+)分别在第19天和第21天开始出现明显的活性下降现象,并且在停止投加金属离子后,短期内活性也未能恢复,混合组未发现明显的抑制或促进现象。     

溶剂萃取法提取电镀污泥浸出液中的铜

研究了N_(510)-煤油-H_2SO_4体系分离电镀污泥氨浸液中的Cu~(2+)的工艺过程,确定萃取铜的最佳工艺参数,以及负铜有机相反萃取较优工艺条件。研究结果表明,以N_(510)为萃取剂,经四级逆流萃取,铜的萃取效率达99％,共存的Ni~(2+)和Zn~(2+)损失量接近0,不影响后续有价金属的回收。铜在工艺过程中以铜盐CuSO_4·5H_2O或电解纯铜的形式得以回收,具有较高的经济效益。     

以有机酸为共基质硝基酚厌氧生物降解性研究

在中温厌氧消化条件下 ,以有机酸 (乙酸与丙酸的混合酸 )为共基质 ,通过测定甲烷累积产量 ,研究了 2 硝基酚、2 ,4 二硝基酚的厌氧生物降解性。试验条件为 :温度 35℃ ,COD 110 0～ 12 0 0mg/L ,pH 7 0～ 7 5 ,COD/VSS为 0 1,接种污泥未驯化 ,其产甲烷活性CH4/VSS为 195mL/g。研究结果表明 ,在所选的浓度范围内 (≤ 4 4mg/L) ,2 硝基酚对产甲烷过程没有产生抑制作用 ;2 ,4 二硝基酚是抑制性较强的物质 ,浓度为 12～ 2 0mg/L时产生中度抑制 ,大于 2 8mg/L时产生重度抑制     

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.