硫酸锰废渣的浸出毒性及处理研究

研究了硫酸锰废渣的主要金属元素组成及浸出毒性,并采用锰渣加石灰混合的方法进行无害化处理,研究结果表明,硫酸锰废渣浸出液中Mn、Cd超标,锰渣加石灰混合处理的方法能有效降低废渣的浸出毒性,锰渣与石灰的重量比为25:2最佳.     

硫酸锰废渣浸出毒性及淋溶特性研究

长沙市兴镇13家硫酸锰厂的生产废渣使当地的生态环境造受到了严重破坏。本文在废渣浸出毒性实验、渣柱淋滤实验以及废渣的全分析基础上,全面地研究了废渣的组成、浸出毒性大小以及在当地酸沉降条件下的淋滤特征,为其安全处置提供了理论基础。研究证明,废渣中重金属种类多、含量高,尤其是锰,高达138800mg/kg。渣的浸出毒性虽未达到国家规定的危险废物鉴别标准,但远超过了《污水综合排放标准》,其衰减可用负指数方程来描述。在酸雨淋溶下,渣中的锰离子会在短时期内大量释放后,维持在一相对较低水平长期释放,对环境威胁巨大。     

硫酸锰废渣浸出毒性及淋溶特性研究

长沙市黄兴镇13家硫酸锰厂的生产废渣使当地的生态环境造受到了严重破坏。本文在废渣浸出毒性实验、渣柱淋滤实验以及废渣的全分析基础上，全面地研究了废渣的组成、浸出毒性大小以及在当地酸沉降条件下的淋滤特征，为其安全处置提供了理论基础。研究证明，废渣中重金属种类多、含量高，尤其是锰，高达138800mg／kg。渣的浸出毒性虽未达到国家规定的危险废物鉴别标准，但远超过了《污水综合排放标准》，其衰减可用负指数方程来描述。在酸雨淋溶下，渣中的锰离子会在短时期内大量释放后，维持在一相对较低水平长期释放，对环境威胁巨大。     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验,测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣,并为矿区重金属污染土壤的修复提供技术支持,采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理;通过浸出毒性实验对固化/稳定化处理效果进行综合分析,试图寻求一种最佳的稳定剂。结果表明,无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加,样品浸出液的pH都有升高,As、Cd的浸出浓度都有明显下降,而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中,粉煤灰混合堆肥化污泥的处理效果最好,浸出液的pH值达到7.82,As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳,同时具有以废治污的资源化生态效能。     

磷渣-粉煤灰基地聚物材料固化含砷废渣

为了处理有色金属冶炼厂产生的含砷废渣,利用磷渣-粉煤灰基地聚物材料对其进行固化处理。在磷渣：粉煤灰=60：40的基础上,通过单因素实验考察了石灰的掺量、化学激发剂水玻璃的模数及掺量、含砷废渣掺量等因素对砷固化体力学性能及砷毒性浸出特性的影响。结果表明：石灰外掺掺量为10%,水玻璃的模数为M=1.2,且其掺量为4%时,砷固化体的抗压强度和As毒性浸出浓度等指标综合效果达到最佳,地聚物材料对含砷废渣的最大固化容量为34%,其固化体抗压强度可达13.6 MPa,砷毒性浸出浓度为2.4 mg·L-1,满足危险废弃物堆存国家标准要求。通过XRD、SEM等手段分析可以得出,固化后砷通过化学键合的方式变成难溶盐的形式被地聚物材料牢牢地包裹,结构更加密实。     

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。     

洗涤方式对电解锰渣中锰回收效率及无害化处理的影响

以化浆-滤饼洗涤代替传统化浆洗涤回收锰渣中的硫酸锰及对洗涤后的锰渣进行无害化处置,对比洗涤方式对电解锰渣中锰回收效率及无害化处理的影响。结果表明,在同等6倍渣重用水量的情况下,化浆-滤饼洗涤比传统化浆洗涤硫酸锰回收率提高10%以上,可达到95.82%。同时回收锰后的锰渣用氢氧化钠无害化处置,在保证锰渣浸出液中锰、氨氮离子满足污水综合排放标准(GB 8978-1996)要求的前提下,药剂用量相比未水洗的节省70%以上,大幅度节约药剂成本。洗涤液以碳酸钠为沉锰药剂回收碳酸锰产品,可产生一定的经济价值,进一步降低锰渣无害化处理成本。     

碱激发电解锰渣制备水泥掺合料

电解锰渣是湿法冶炼金属锰的残渣,为降低其对环境的浸出毒性影响并提高其在水泥产品中的掺入量,利用碱激发技术处理电解锰渣制备水泥掺合料是一种可行的方法。主要研究了碱激发剂种类、掺量对电解锰渣的激发效果,并将碱激发电解锰渣用作水泥掺合料与水泥按不同比例混合研究对水泥抗压强度和浸出毒性的影响。结果表明：碱激发电解锰渣活性显著提高,NaOH中Na2O当量为10%时试件M-SH10的3、7、28 d抗压强度最高,分别为7.15、9.46、10.03 MPa;将此条件下激发的电解锰渣按质量比取15%与85%的水泥混合制得的掺合料其抗压强度较净水泥试件有一定程度的提高;浸出毒性结果显示Cd、Cr、Pb、Ni、Mn和Zn浓度均下降,且低于GB 8978-1996限值。     

SDS和PVP强化生物淋溶锰渣的性能

在生物淋溶锰渣的过程中,设置一系列浓度梯度(0～100 mg/L)的离子型表面活性剂SDS(十二烷基硫酸钠)和非离子型表面活性剂PVP(聚乙烯吡咯烷酮),研究两种活性剂对硫杆菌生长和对锰渣中锰的浸出率的影响.结果表明,两种表面活性剂均能有效强化硫杆菌对锰渣的淋溶性能,SDS和PVP的最佳浓度分别为35 mg/L和15 mg/L,在最佳浓度条件下,两者均能显著降低培养液的pH值,提高锰的浸出率,其浸出率分别达到88％和83％,均高于对照组的72％.进一步分析表明,SDS比PVP更能有效提高浸出体系的ORP电位,促进锰的浸出.电镜结果表明,在最佳浓度条件下,SDS比PVP更能有效促进硫杆菌对锰渣表面的侵蚀,降低锰渣的表面粒度,提高锰渣中锰的浸出率.     

细菌浸出电解锰废渣中锰的机制研究

从电解锰废渣中分离出一株高效浸锰菌,经鉴定为沙雷氏菌(Serratia sp.).考察了电解锰废渣培养液、MnO2培养液在有菌和无菌条件下的锰浸出情况,以及有菌液和无菌液在加入不同还原剂后的锰浸出情况.结果表明,在初始pH为6.0、固液质量比为1:10、温度为37 ℃的浸出条件下,在电解锰废渣培养液中,无菌条件下的锰浸出率远小于有菌条件下的,反应72 h后,无菌、有菌条件下的锰浸出率分别为8.030 00%、78.670 00%;无论在有菌还是无菌条件下,MnO2培养液中的锰浸出率都较低,反应72 h后,无菌、有菌条件下的锰浸出率分别为0.000 39%、0.041 00%;有菌液加入ZnS、FeS、FeSO4、Fe2(SO4)3、CuS还原剂后,反应72 h的锰浸出率分别为73.340 00%、70.980 00%、69.680 00%、10.260 00%、1.670 00%;无菌液中加入4种还原剂(不包括CuS)后的锰浸出率都相当低, 反应72 h后,锰浸出率相对较高的是FeS和ZnS,均为0.006 20%,锰浸出率相对最低的是Fe2(SO4)3,为0.005 00%;沙雷氏菌对电解锰废渣中锰的浸出既不是直接氧化浸出作用,也可能不是间接产酸浸出作用,而可能是一种催化还原作用.     

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.     

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.     

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.     

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.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)