膜电解法在线再生酸性蚀刻液及回收铜新技术

采用极化曲线法研究了酸性蚀刻液阴、阳极电化学行为,并构建了离子膜电解反应体系,考察了在线再生酸性蚀刻液及回收铜的效果。结果表明,阳极氧化过程发生浓差极化,存在极限电流密度,Cu＋含量越高,极限电流密度越大;阴极还原分4步反应进行,存在极限电流密度;强化溶液传质可有效提高阴、阳极极限电流密度,有利于避免电解过程中析出氯气和氢气;在线实验表明,通过监控阳极液ORP,可避免析出氯气;分步降低电流电解有利于避免析出氢气,形成致密的金属铜块;在电流为9～24A范围内分4步电解23．5h可再生酸性蚀刻液23．5L,同时电沉积回收510g铜,纯度高达99．98％。阴极电流效率达到95．2％,吨铜电耗3251kWh。电解过程中无氯气和氢气析出,无废液排放,表明膜电解法在线再生酸性蚀刻液具有良好的应用前景。     

利用废旧线路板回收金属富集体再造超细铜粉

实验以氨性溶液溶浸废线路板中回收的金属富集体产出高浓度含铜浸出液作为电解原液,采用电沉积法循环再造超细铜粉。主要考察了电沉积过程中硫酸浓度、电流密度、电沉积时间和电沉积温度等条件对超细铜粉回收率的影响。实验结果表明,在硫酸浓度为12 g/L,电流密度为4 A/dm2,电沉积时间3 h,溶液温度为40℃的条件下,电沉积超细铜粉的回收率超过97%,所得铜粉的树枝状形貌完整,纯度高,粒径小,约为3～6μm。     

膜电解工艺处理碱性含铜蚀刻废液

实验对碱性含铜蚀刻废液膜电解工艺处理的可行性开展相关研究,考察了槽电压、电解时间和阳极液pH值等因素对膜电解电流效率的影响,并确定了最佳工艺条件:槽电压3.10 V、电解时间2 h、阳极液初始pH值9.20。在上述最优工艺条件下,膜电解电流效率达91.5%。实验结果表明,该工艺操作方便、简单可行,是处理蚀刻废液、回收铜的有效方法,具有一定的应用价值。     

悬浮电解法回收废旧电子印刷线路板中的铜

以废旧电子印刷线路板中的金属铜为处理对象,采用悬浮电解法制取纯铜粉。选择了4个影响铜粉的纯度、脱落率和电流效率的因素,每个因素3个水平进行正交实验。实验结果表明,硫酸铜的浓度、氯离子的浓度和电流密度对铜粉的纯度、脱落率和电流效率有较大的影响。通过对正交实验结果的分析得出最优的电解条件,在此电解条件下可得到铜粉的纯度99.8%、脱落率99.6%和电流效率99.7%。     

Lix54-100从印刷电路板蚀刻废液中回收铜

本文对Lix5 4 10 0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 15 6.96g/L ,相比为 2∶1条件下 ,用 80 %Lix5 4 10 0 -煤油经过三级错流萃取 ,铜的浓度可下降到 2 6.88g/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     

PTFE/C三相电极氧阴极还原法生产过氧化氢

设计了隔膜体系电解槽,制作了聚四氟乙烯(PTFE)/碳黑三相气体扩散电极,系统研究了隔膜、电流密度、电极间距、初始溶液酸度、电解质、空气量和时间等因素对过氧化氢累积产生浓度和电流效率的影响。结果表明,在有隔膜体系,电流密度为70 mA/cm2,电极间距为1 cm,初始pH=0.5,电解质为0.10 mol/L Na2SO4溶液,空气量为40 mL/min的条件下,电解时间1 h时过氧化氢累积浓度最高可至20 096.05 mg/L,此时对应的电流效率为63.37%。在确定的最佳条件下,进行电解液循环实验,1 h时电流效率升高到98.4%,12 h之后,过氧化氢累积浓度为46 042.43 mg/L。实验原位产生的高浓度酸性过氧化氢溶液可以直接应用于Fenton试剂。     

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。     

电子工业中三氯化铁废液中铜的回收

电子工业中,蚀刻工艺广泛应用于印刷线路板生产。蚀刻剂有多种,其中三氯化铁腐蚀液因其性能良好、价格低廉,在我国应用极为广泛,缺点是污染环境。 三氯化铁废液的治理,在国内,有采用电解法的,电解法回收铜纯度高,但电耗高、设备加工复杂;也有采用中和法的,但     

高铁酸钠电化学合成条件的研究

利用含铁材料为阳极,铜为阴极,NaOH溶液为电解液,于隔膜电解槽中电解制备高铁酸钠.探索了该工艺所必需的各种参数和反应条件,确定了隔膜材料,并对Na2FeO4浓度和电流效率的非一致性变化作出了解释.研究结果表明:在阳极距离为1.3 cm(极距2.3 cm)、阳极电解液浓度为14 mol/L,阴极电解液浓度为4 mol/L、温度为35℃、电压为8～9 V时,电解2 h后得到的Na2FeO4浓度为18.7g/L,电流效率为20%.     

转底炉粉尘酸浸净化液电沉积锌

对转底炉炉灰酸浸净化液电沉积锌的工艺条件和参数进行了研究,获得的电积锌最佳电积条件与参数为:锌离子浓度50 g·L-1,电解液pH=2,电解温度40 ℃,电流密度600 A·m-2,骨胶浓度6 mg·L-1。在最佳条件下,锌电沉积电流效率接近90%,电积出的锌表面光滑平整,其纯度可达99.9%。     

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.     

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.     

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.     

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.