废旧手机电路板酸性硫脲浸金过程动力学

废旧手机是一种典型电子废弃物,手机电路板中含有较高含量的贵金属,而金的回收是废旧手机资源化研究的热点。以硫脲为络合剂、硫酸铁为氧化剂、硫酸为调节剂,在pH为1.5、固液比为1:30、硫酸铁质量分数为0.3%的条件下,分别考查了硫脲浓度、反应温度、浸出时间等因素对酸性硫脲浸出废旧手机电路板中金的影响,采用核收缩模型探讨了酸性硫脲浸金体系浸出过程表观动力学,结果表明,酸性硫脲浸金过程的总体控制步骤为固体产物层扩散控制,其浸出过程动力学方程为1-2/3η-(1-η)2/3=KDt,硫脲浓度的反应级数为一级反应,该浸出过程表观活化能Ea=19.378 kJ/mol。由此推断,在酸性硫脲浸金体系中通过提高反应温度或通过增加硫脲浓度的途径来提高金的浸出率是有限的。     

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(NH4+)、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(NH4+)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。     

盐酸浸出提取赤泥中铝和铁的工艺条件优化

系统研究盐酸浸出赤泥中铝和铁的过程,考察酸浸温度、盐酸浓度、酸浸时间、液固比以及赤泥粒度对铝、铁浸出率的影响。单因素实验和正交实验结果得出,在影响浸出率的酸浸温度、盐酸浓度、酸浸时间和液固比对铁、铝的浸出率的影响几个因素中,酸浸温度和盐酸浓度的影响最大,液固比和浸出时间其次。盐酸酸浸的最佳工艺条件为：赤泥粒度150 μm、酸浸温度80 ℃、盐酸浓度10 mol·L-1、液固比8∶1（V/m）、浸出时间150 min,此时铝的浸出率为96.7%,铁的浸出率为95.1%,铁铝总浸出率96.0%。     

氧化亚铁硫杆菌浸出废弃线路板中铜的研究

对废弃线路板中的铜进行了细菌浸出、只有硫酸亚铁环境下的浸出及酸浸出实验,研究了不同条件对比浸出效果,研究结果表明,细菌浸出比只有硫酸亚铁存在的浸出和酸浸要快得多。研究了在线路板粉末浓度12、24、40、60和120 g/L下浸出速率的变化,结果表明, 在考察范围内,浸出速度随着加入的废弃线路板粉末浓度的升高而降低,当线路板粉末的浓度＞60 g/L时,浸出速度维持在较低水平,选取24 g/L作为浸出的线路板粉末的浓度。分别在细菌培养0、24、48和72 h时加入线路板粉末24 g/L进行浸出实验,结果表明,细菌培养时间长,使得浸出过程进行得也更快。     

废弃脱硝催化剂碱浸提取钒和钨的浸出动力学研究

针对不同NaOH浓度和浸出温度进行碱浸提取废弃脱硝催化剂中钒、钨的实验研究。在NaOH浓度为7.5 mol·L~(-1),碱浸温度为100℃的条件下,V_2O_5和WO_3的碱浸效率分别可达到92.94%和97.30%。基于液-固浸出过程中的核收缩模型研究了碱浸过程中钒、钨的浸出动力学,考察了NaOH浓度、碱浸温度对V_2O_5、WO_3浸出反应速率的影响,进而确定浸出过程中的控制步骤。结果显示,在100℃温度下,NaOH浓度在0.5~7.5 mol·L~(-1)范围内,V_2O_5、WO_3的浸出过程为固膜扩散控制过程,其表观反应级数分别为0.305、0.436。在7.5 mol·L~(-1)NaOH浓度下,V_2O_5、WO_3的浸出过程在30~100℃的反应温度范围内均为固膜扩散控制过程,浸出反应的表观活化能分别为17.74和37.88 k J·mol-1。     

含锌铅废物碱法浸出工艺

各种工业过程中产生的大量含锌铅废物中含有大量的有毒重金属.必须在危险废物处置场所进行处置,这导致处置成本增加.采用强碱浸出的方法回收含锌铅废物中的Zn和Pb,考察了浸出温度、NaOH浓度、液固比(浸提液体积/原料质量)和搅拌速率等工艺参数对Zn、Pb和杂质金属浸出率的影响,得出其最佳工艺条件.在温度为70℃、液固比为13:1、搅拌速率为800r/min条件下.用5 mol/L的NaOH浸出含锌铅废物,浸出液中Zn和Pb的质量浓度分别达33.47、11.21 g/L,浸出率分别达到94.24%和93.47%.     

氧化亚铁硫杆菌浸提废旧线路板铜的浸出率与时间的关系

探讨氧化亚铁硫杆菌SW-02(Thiobacillus ferrooxidans SW-02)浸提废旧印刷线路板Cu的适宜浸出时间,对Cu的浸出率与时间的关系进行了研究。通过摇瓶培养的方式,在30℃,摇床转速为170 r/min条件下进行浸出实验,按不同时间间隔取样测定溶液Cu2+浓度,pH值与氧化还原电位。分析发现,线路板加入量在30 g/L及以上时,浸出40 h后浸出反应停止,而线路板加入量在15 g/L时,浸出40 h后Cu的浸出率达到70%,继续浸出,浸出率不再显著增加。研究结果表明,铜的适宜浸出时间为40 h。     

Pb/Zn冶炼废渣中重金属的生物浸出-盐浸处理

利用中温嗜热菌对某铅锌冶炼废渣进行生物浸出盐浸处理研究,并根据国家固体废物浸出毒性方法(HJ/T299-2007)对盐浸后余渣进行毒性分析。研究结果表明,在pH 1.5、温度65℃、矿浆浓度5%的优化条件下生物浸出3 d后,废渣中Cu、In、Ga和Zn的浸出率分别达到了91.5%、91.8%、84.9%和93.4%;盐浸生物浸出渣,其浸出液中Ag、Pb浓度分别为7.6和247.5 mg/L,可从废渣中有效回收Cu、In、Ga、Zn、Ag和Pb。生物浸出盐浸处理后余渣约为原渣量的70%;毒性分析浸出液中重金属元素Ag、As、Cd、Cu、Pb和Zn浓度分别为2～3.5、2～3、0.3～0.5、30～50、2～4、20～60 mg/L,低于国家危险废物鉴别标准(GB5085.3-2007)。根据试验结果,提出了针对冶炼废渣资源化、减量化、无害化的生物浸出盐浸联用工艺。     

盐酸分级浸出赤泥中有价金属元素

采用盐酸2段分级浸出工艺回收氧化铝赤泥中的有价金属元素。通过考察液固比、反应温度、反应时间及盐酸使用量对浸出率的影响,确定了2段浸出的实验工艺。结果表明:在盐酸用量为理论用量的40%、90 ℃液固比为7∶1、反应时间1 h的条件下,Ca的浸出率为96.2%,Na的浸出率为82.47%,Al的浸出率为42.87%,其他元素几乎不浸出,这是第1段浸出;在盐酸用量为理论量的130%、90 ℃、盐酸浓度8.8 mol·L-1的条件下,浸出1段酸浸渣,Fe的浸出率99.65%,Sc的浸出率88.76%,V的浸出率93.58%,其他稀土元素的浸出率均达到了70%左右,这是第2段浸出。     

有机磷酸HEDP稳定垃圾焚烧飞灰重金属的研究

研究了有机磷酸羟基亚乙基二膦酸(HEDP)对生活垃圾焚烧飞灰中重金属的稳定方法.通过对不同HEDP投加量处理后的飞灰试样作危险废物浸出毒性鉴别试验,分析HEDP最佳使用剂量,并评价了稳定化飞灰的长期稳定性.结果表明,HEDP最适使用剂量为0.03 Ml/g(以商品级HEDP与飞灰的体积质量比计),处理后飞灰与原状飞灰相比,Pb、Zn和Hg的浸出浓度分别降低了98.3%、99.5%和85.0%.HEDP对飞灰中重金属稳定效果排序为:Pb＞Zn＞Hg＞Ni＞Cu＞Cd＞CrHAs.重金属pH相关浸出测试(pH-dependent leaching tests)表明:经0.03mL/g HEDP稳定处理的飞灰,在0.3 mol/L HNO3和0.3 mol/L NaOH的浸取条件下,其重金属浸出浓度均低于国家危险废物鉴别标准,显示具有良好的长期稳定性.     

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.