生物法和化学法回收制革污泥中铬的对比研究

研究了嗜酸性硫杆菌(Thiobacillus)生物沥滤法和1:1硫酸化学沥滤法分离回收制革污泥中的铬.比较了嗜酸性硫杆菌生物沥滤法和化学沥滤法回收制革污泥铬过程中pH、氧化还原电位(ORP)、沉降比(SV)以及铬的沥滤率的变化.试验结果表明,pH是影响制革污泥中铬的沥滤率的关键因素.生物沥滤法在使污泥pH大幅度降低的同时,能很好地改善污泥的沉降性能,对铬的沥滤效果好于化学沥滤法.     

生物沥滤-焚烧法处理制革污泥中铬迁移转化研究

采用生物沥滤-焚烧方法,先将制革污泥中大部分难溶的有毒重金属——铬从固相溶出转移至液相,之后将沥滤后制革污泥进行有效的固液两相分离,并对分离后的固相污泥进行焚烧处理实验,研究生物沥滤-焚烧处理法对制革污泥中的总Cr在不同介质中的浓度影响。结果表明,生物沥滤法处理制革污泥后,以金属离子交换形态存在的总Cr含量增加,其中68.56%的总Cr6+和87.70%的总Cr得以去除,去除效果十分明显;将沥滤脱水后的污泥进行焚烧处理,以残渣态形式存在的总Cr相对含量变大,迁移能力减弱;铬在高温下与其他重金属元素形成复杂的金属化合物及络合物:Cr1.3Fe0.7O0.5、Na4(CrO4)(SO4)、Ca5(CrO4)3O0.5,有助于今后进一步对整个生物沥滤-焚烧处理过程进行反应机理研究。     

提高生物法分离制革污泥中铬分离效率的研究

在已确定污泥驯化最佳条件的基础上,通过改变滤材、液固分离条件,添加营养物质继续降低pH等方法,进行提高生物沥滤法分离制革污泥中铬的分离效率的研究。同时考察化学沥滤法（1∶1硫酸）在相同条件下的分离效率。试验结果表明：用相应pH值酸液（1∶1硫酸配制）淋洗,淋洗+闷洗和抽真空＋酸液淋洗等过滤方式可提高铬的分离效率。生物沥滤中当pH值下降至1.8时,分离效率即可达到94.65%,与直接用蒸馏水淋洗相比要高得多。化学沥滤中当pH值下降到1时,分离效果可达96.7%,沥滤污泥中剩余铬含量可达到制革污泥农用标准。     

皮革含铬废水加碱处理研究

用加碱沉淀法处理制革铬鞣废水时 ,MgO CaO(1∶4 ,w∶w)取得较好的处理效果 ,其机理包括调节pH与混凝沉淀。铬鞣废水Cr3+ 和色度去除率大于 99% ,SS去除率大于 87% ,但COD去除率只有 4 7% ,主要依靠协同沉降。混合废水处理效果也很好 ,但铬泥沉降较差。有机杂质的存在较大地影响了Cr3+ 的去除 ,一定量的SS有利于铬泥的沉降。     

元素硫颗粒粒径对污泥重金属生物沥滤的影响

以城市污水处理厂剩余污泥作为处理介质,土著嗜酸氧化硫硫杆菌(Acidithiobacillus thiooxidans,A.thiooxi-dans)为主要沥滤微生物,采用序批式生物沥滤装置,就投加150~725μm的不同粒径元素硫对沥滤的酸化效果、硫酸根产率和重金属去除效果的影响进行了研究。结果表明,在元素硫投配量为3 g/L,曝气强度为1.0 L/(min.L)的条件下,元素硫粒径在165~215μm范围减小时能显著改善污泥酸化速度、提高酸化程度和硫酸根产率。底物元素硫的最佳粒径为165μm,此时沥滤体系pH下降速率为0.85个pH单位/d,硫酸根的产率为454.9 mg/(L.d),沥滤6 d后污泥中高浓度重金属Cu、Zn、Cd的去除率达到70.3%、81.2%、87.8%.     

皮革含铬废水加碱处理研究

用加碱沉淀法处理制革铬鞣废水时，MgO／CaO(1：4，w：w)取得较好的处理效果，其机理包括调节pH与混凝沉淀。铬辣废水Cr^3 和色度去除率大于99％，SS去除率大于87％，但COD去除率只有47％，主要依靠协同沉陷。混合废水处理效果也很好，但铬泥沉降较差。有机杂质的存在较大地影响了Cr^3 的去除，一定量的SS有利于铬泥的沉降。     

制革废水沉淀污泥的资源化处理试验研究

介绍了制革污泥资源化处理的工艺流程 ,并用试验考察了各工序的技术指标。结果表明 :制革污泥经焚烧处理后其质量和体积均减少为原来的 15 %左右 ,经过化学处理后 ,铬灰分溶解液中的总铬浓度从 38.8g/L左右降到 1.2 8mg/L ,其回收率几乎达到 10 0 % ,工艺过程中产生的废水和废渣均可达标排放。     

底物对生物沥滤去除污泥中Cu、Zn的影响

分别以FeSO2·7H2O、单质S粉为底物,对污泥中的重金属进行生物沥滤试验.通过分析生物沥滤过程中pH、Fe2+、SO22-的变化及Cu、Zn的滤出率.探讨不同底物对重金属生物沥滤的影响.试验结果表明,以FeSO2·7H2O或单质S粉为底物.利用污泥中固有的硫杆菌可以降低污泥的pH.从而使重金属滤出.以单质S粉为底物的处理中,污泥pH最低下降到2.1;以FeSO2·7H2O为底物的处理中,pH最低下降到2.6.经14 d的生物沥滤,以单质S粉为底物时,底物为6 g/L的污泥样品Cu、Zn滤出率最高,分别为18.8%和34.8%;以FeSO2·7H2O为底物时,底物为25 g/L的污泥样品Cu、Zn滤出率最高,分别为29.1%和36.8%.优于以单质S粉为底物的滤出效果.     

污泥酸化速率影响因子的探讨

采用城市污水厂污泥作为嗜酸微生物菌株来源,通过添加一定量的单质硫,使其中的嗜酸硫杆菌群大量增殖,并使污泥pH大幅降低.取得的培养物可用于废旧干电池中重金属沥滤等的处理.由于培养物对重金属沥滤效率和污泥的酸化速率密切相关,为此进行了不同的污泥种类、加硫量、污泥浓度和曝气强度对污泥酸化速率影响的实验.实验表明,初沉泥、二沉泥和混合浓缩污泥都能迅速利用硫产酸;加硫量(以100 mL污泥计)在0.5、1.0、2.0、4.0 g时,快速酸化的趋势相同.0.5 g的加硫量显示出略微慢的酸化速率,最后达到的最低pH在1.2左右,其他三个都降至1.0以下.污泥质量分数在0.5%、1.0%、2.0%、3.0%、4.0%时,也具有相同的酸化趋势,0.5%质量分数的污泥下降速率最快,这与较低浓度下污泥对pH的缓冲能力较小有关;曝气强度在0.45 L/min和0.3 L/min差别较小,5 d内能迅速降低pH,0.2 L/min的酸化速率较慢,足够长的时间(12 d)也能将pH降至2.5左右,0.1 L/min的曝气强度的酸化速率最慢,不能达到预期的酸化效果.     

复合酸化剂对电镀污泥中铬、铜的去除效果

以电镀加工厂产生的污水污泥作为主要研究对象,研究了柠檬酸、硝酸、过氧化氢为复合酸化剂,Fe3+为增效剂对电镀污泥中铬和铜的去除效果,考察了酸化剂的浓度、反应时间、摇床转速、污泥pH、Fe3+浓度等因素对污泥中重金属去除效率的影响。结果表明:在室温下,含0.15 mol/L柠檬酸、1.5%过氧化氢、0.25 mol/L硝酸的复合酸化剂与增效剂2.0g/L Fe3+溶液共同处理污泥,固液比为1∶10,以150 r/min的转速振荡4 h,对污泥中Cr的去除效率达到80.02%,Cu的去除效率可达到92.89%,使污泥中残留Cr、Cu含量均符合国家污泥农用标准。     

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.     

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.     

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.     

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)