Fenton氧化-混凝联合工艺处理络合铜镍废水的研究

采用Fenton试剂氧化-混凝联合工艺对难处理络合铜镍电镀废水进行了研究,考察了废水初始pH值、H2O2初始浓度、[Fe2 ]/[H2O2]、反应时间和温度、混凝液pH、混凝剂质量浓度对处理过程的影响,探讨了废水的降解途径和机理.结果表明,在体系初始pH=4,温度30℃,H2O2投加量为800mg/L,[Fe2 ]/[H2O2]=0.1,反应时间60 min,混凝液pH=8及混凝剂质量浓度为500mg/L的条件下,废水的COD去除率为96.98%,Cu2 为99.91%,Ni2 为99.92%,处理水完全达到国家一级排放标准.同时依据GC/MS对X-GN降解最终产物的分析结果,推导出废水的基本降解机理和途径.     

UV/Fenton法处理间-甲酚废水

利用UV/Fenton工艺对模拟间-甲苯酚废水进行了处理,研究了H2O2加入量、FeSO4加入量、pH、原水初始COD值、环境温度、反应时间等因素对COD去除率的影响.实验表明：间-甲苯酚浓度为100mg/L、初始COD值251 mg/L的废水,在30℃下,pH为4.Q,[H2O2]/[Fe^2＋]=15（质量浓度比）,紫外灯照射3 h后,COD去除率达86.3%,若再经Ca（OH）2絮凝沉降,则COD去除率提高到92.6%.同时,对Fenton及UV/Fenton的处理效果进行了比较,实验表明：UV/Fenton的处理效果明显优于Fenton法.     

Fenton氧化法深度处理丙烯腈废水的研究

以丙烯腈(AN)废水为研究对象，在正交实验基础上深入研究了Fenton反应体系中pH值、Fe^2 浓度、H2O2浓度、温度、uv和C2O^2-4对降解效果的影响，分析了不同因素作用机理，确定了最佳操作条件：pH=3、[Fe^2 ]=400mg／，L、[H2O2]=400mg／L、反应温度40℃，在此条件下丙烯腈降解率达80％以上。同时发现在紫外光、C2O^2-4对Fenton试剂的协同作用下，降解率可提高10％左右。     

Fenton法处理垃圾渗滤液的参数优化及反应动力学模型

采用Fenton法处理垃圾渗滤液,研究反应时间、初始浓度、pH、Fenton试剂用量对垃圾渗滤液TOC去除率的影响。研究结果表明,最优反应条件是反应时间30 min,初始pH为3.0,初始[H2O2]0=7 310 mg/L,最佳[H2O2]/[Fe2+]摩尔比为5,反应温度为室温,此时渗滤液的TOC去除率达到70.3%。渗滤液矿化过程符合一级反应动力学,并建立了符合该渗滤液的反应动力学模型。     

混凝-Fenton氧化-Fe0还原预处理高浓度硝基苯生产废水

采用混凝-Fenton氧化-Fe0还原工艺预处理高浓度硝基苯废水,考察各反应阶段硝基苯去除效果及影响因素。研究表明,聚铁混凝性能优于聚铝;初始COD为17 350 mg/L、硝基苯浓度为10 050 mg/L的废水,在pH=4,聚铁投加浓度3 300 mg/L时,COD和硝基苯去除率分别为63%和62%;混凝沉降后的上清液用Fenton试剂氧化,可在较宽pH(3～6)范围内降解硝基苯,当H2O2(30%)浓度为6 000 mg/L,Fe2+浓度为168 mg/L时,氧化效率最高;聚铁混凝-Fenton氧化后的出水用Fe0还原,最佳还原条件为:pH=3,Fe0浓度1 500 mg/L。原水经聚铁混凝-Fenton氧化-Fe0还原后,COD和硝基苯总去除率分别达90%和98%,总药剂成本约12.4元/t。处理后废水硝基苯浓度为168 mg/L,适宜进行后续的厌氧-好氧生物处理。     

日光/H2O2/草酸铁体系对垃圾渗滤液深度处理的试验研究

以草酸铁络合物／H2O2作光氧化剂,利用日光对垃圾渗滤生化出水进行了光氧化降解试验。结果表明,在溶液的初始体系pH=3．0,H2O2投加量为460mg／L,Fe^3＋质量浓度为20mg／L条件下,反应60min后,CODCr去除率可达80％以上;溶液初始体系的pH、H2O2和Fe^3＋的投加量及废水的水质对光解过程有显著影响,而且在太阳光照射下,CODCr去除率比紫外光照射下高。研究表明,在一定试验条件下,用日光／H2O2／草酸铁体系对城市垃圾渗滤液处理效果较好,可作为垃圾渗滤液的深度处理。     

用H2O2/Fe^3＋处理高浓度含甲醛废水的研究

研究采用H2O2/Fe^3＋催化氧化处理高浓度含甲醛废水,探讨了双氧水和催化剂投加量、反应pH及反应温度等操作条件对处理效果的影响,并通过酸溶解回用失活催化剂。结果表明,较优的操作条件为：H2O2/COD（质量比）=2.2～2.6,Fe^3＋/H2O2（摩尔比）=0.048～0.058,反应pH1.80～2.68,反应温度50℃,反应时间40 min;在上述操作条件下,甲醛去除率达到99%以上,COD去除率达到85%以上。失活的催化剂可通过稀酸溶解后循环使用,其效果与三价铁盐作催化剂的基本相同。采用H2O2/Fe^3＋处理含甲醛废水具有比采用H2O2/Fe^2＋较优的效果。     

Fenton试剂处理选矿废水机理研究

研究了用Fenton试剂处理选矿废水中残余的黄药,分别考查了氧化时间、反应初始pH值、Fe2+浓度及H2O2用量对黄药降解效果的影响,用正交试验确定了4个因素的最好条件。结果表明:初始pH值和H2O2用量是影响去除效果的主要因素;氧化时间为60 m in,反应初始pH=4,[Fe2+]=20 mg/L,[H2O2]=20 mg/L,黄药的浓度为125 mg/L时,黄药的去除率达到99.5%;初步探讨了Fenton试剂净化废水中黄药的机理是.OH自由基先将黄药氧化为过氧化黄原酸盐,再将其氧化为CO2,黄药得到去除。     

Fenton氧化法深度处理丙烯腈废水的研究

以丙烯腈(AN)废水为研究对象,在正交实验基础上深入研究了Fenton反应体系中pH值、Fe2+浓度、H2O2浓度、温度、UV和C2O2-4对降解效果的影响,分析了不同因素作用机理,确定了最佳操作条件pH=3、[Fe2+]=400mg/L、[H2O2]=400mg/L、反应温度40℃,在此条件下丙烯腈降解率达80%以上。同时发现在紫外光、C2O2-4对Fenton试剂的协同作用下,降解率可提高10%左右。     

Fenton试剂氧化处理火炸药污染土壤淋洗液

采用Fenton试剂对火炸药污染土壤淋洗液进行氧化处理,研究了Fe SO4·7H2O投加量、H2O2投加量、初始pH、反应时间及温度对处理效果的影响,采用发光细菌发评价处理前后水样的急性毒性变化。结果表明,Fenton试剂氧化可有效去除火炸药污染土壤淋洗液的COD,当Fe SO4·7H2O投加量为8.0 g/L,H2O2投加量为64 m L/L,初始pH为3,反应时间120 min及反应温度30℃时,污染土壤淋洗液的COD由4 553.9 mg/L降至800.1 mg/L,COD去除率82.4%,COD的降解符合二级动力学模型。经Fenton氧化处理后,水样的急性毒性降低94.7%,B/C由0.007升至0.22,可生化性得到明显改善。     

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)