电催化氧化对制药废水二级出水的深度处理效能

以制药厂未达标二级出水为研究对象,采用二维和三维电催化氧化作为深度处理方法,考察了电催化氧化对制药废水深度处理效能。结果表明,二维和三维电催化氧化均能降低出水COD和色度,实现出水达标排放。在电流密度为7.5 m A·cm~(-2),电催化反应60 min时,与二维电催化反应器相比,三维电催化反应器可使COD去除率提高23.1%,色度降低20度,能耗降低8.2 k Wh·(kg COD)~(-1)。三维电催化体系内羟基自由基生成速率常数比二维电催化体系高2.38倍,这是三维电催化体系比二维电催化体系更具有效率高、能耗低的优势的本质原因。     

三维电催化氧化技术处理草铵膦农药废水

选用石墨板作为三维电催化装置的阳极、不锈钢板作为阴极,以活性炭颗粒作为粒子电极进行反应,研究了三维电催化氧化技术处理草铵膦农药废水的效果;并考察了电流密度、极板间距、电解时间、初始浓度、pH值和粒子电极用量等因素对其处理效果的影响。实验结果表明,在废水初始浓度为300 mg·L~(-1),反应时间为90 min,极板间距为4 cm,pH值为5,电流密度为31.5 m A·cm-2,粒子电极的用量为3.08 g·L~(-1)的条件下,废水的COD去除率为83.48%。三维电催化氧化技术通过减小粒子间距改善电荷传质效果;电流效率的提高也促使废水的处理效果显著提升。     

软锰矿粒子电极的制备及其对SMP的催化降解

针对二氧化锰对废水中氯离子电解生成活性氯具有较好催化活性的特点,以软锰矿为原料制备一种新型粒子电极,将其用于三维电极系统处理油气田高含氯废水,利用活性氯的强氧化性进一步强化废水中难降解有机物SMP的处理;并考察软锰矿粒子电极制备条件对电极性能和电解效果的影响。结果表明:软锰矿与石墨质量比6∶4、PTFE分散液加入量10%、330°C下灼烧2 h为软锰矿粒子电极最优制备条件;与常规活性炭粒子电极相比,软锰矿粒子电极电解活性氯的产生量、COD去除率均显著优于活性炭粒子电极;且软锰矿粒子电极在重复使用多次后,活性组分流失量较小,对SMP的降解效率仍较高,保持了稳定的电催化性能。     

活性炭三维电极法处理超高盐榨菜腌制废水

将粒状活性炭作为三维电极的粒子电极处理超高盐榨菜腌制废水。采用静态实验,对比了二维电极与三维电极对该废水COD和磷酸盐的去除效果,考察了三维电极条件下极板间距、活性炭填充量、电解时间、电解电流及初始pH等对该废水COD和磷酸盐去除率的影响。结果表明：三维电极对超高盐榨菜腌制废水COD和磷酸盐的去除率明显高于二维电极;在原水pH（4．3—5．0）,废水体积600mL,电流8A,活性炭填充量250g,极板间距6．5cm,电解时间150min时,处理效果良好,COD和磷酸盐去除率分别为76．47％和97．81％。由波长扫描图可初步认为部分有机物直接被氧化为二氧化碳。     

钢渣粒子电极的制备及其在三维电催化氧化除藻中的应用

为进一步提升电催化氧化除藻效果,制备出钢渣粒子电极,构建了三维电催化氧化系统并用以处理普通小球藻藻液,进而对除藻机理进行了探索。利用钢渣、蒙脱石和锯末在高温煅烧条件下制备钢渣粒子电极,通过制备条件的优化,获得了具有良好除藻性能的钢渣粒子电极。考察普通小球藻经过三维电催化氧化后,藻细胞密度、SOD、光合活性和叶绿素a的变化特征。结果表明:钢渣、蒙脱石、锯末的配比为60%∶28%∶12%,在800℃煅烧60 min制备出的钢渣粒子电极在三维电催化氧化系统8 V、 60 min条件下,对初始浓度为4×10~9～6×10~9 cells·L~(-1)小球藻的去除率为97.10%;处理1 m~3藻液的耗电量为3.78 kWh;经过10 min三维电催化氧化处理的藻细胞,其SOD活性会出现短暂升高,藻细胞的光合活性减弱、叶绿素a浓度下降,藻细胞的光合系统的抑制效应可维持较长时间。综合上述结果,应用钢渣粒子的三维电催化氧化系统能够高效除藻,并可长久抑制藻细胞的光合活性。     

电催化氧化技术处理制革综合废水

选择DSA电极中的钛基掺硼金钢石膜电极(Ti/BDD),用于制革综合废水的电催化氧化处理研究,考察了在不同的电流密度、电压、电解质、pH值和电解时间等因素对COD去除率和电流效率的影响。结果表明,控制电流密度为30mA/cm2,电压为8.0 V,电解质(NaCl)浓度为2.0 g/L,pH为4.0,电催化氧化处理2 h后,废水的COD和NH4+-N的去除率分别达到了83.6%和90.3%,BOD/COD为0.45,比能耗为35.34 kWh/kg COD,电流效率为37%。     

废椰壳制备活性炭负载CuO处理活性艳红X-3B废水的工艺优化

为了综合利用废椰壳,进行了废椰壳制备活性炭并负载氧化铜处理活性艳红X-3B废水的研究。采用正交实验法,以COD和色度去除率为目标函数确定了活性炭的最佳制备工艺条件为：磷酸浓度65%（质量百分数）,m（磷酸）/m（椰壳）比3∶1,活化时间2.5 h,活化温度500℃。在该活性炭上负载氧化铜处理活性艳红X-3B染料废水,其COD和色度去除率分别为83.70%和99.72%。用扫描电镜（SEM）和X衍射仪（XRD）对裸活性炭和载铜活性炭样品表面形貌和结构进行了表征和分析。通过单因素实验法确定了废水处理的最佳工艺条件为：pH值5,曝气时间4 h和催化剂用量0.55 g,在此条件下,COD和色度去除率分别为86.70%和99.75%,相应的出水指标为75 mg/L和32稀释倍数。     

活性炭负载CuO催化过硫酸盐去除活性艳红X-3B染料

利用活性炭吸附法及基于SO-4·的高级氧化技术,以活性炭和过渡金属氧化物Cu O为催化剂,催化过硫酸盐产生SO-4·降解活性艳红X-3B染料。结果表明,活性炭负载Cu O催化过硫酸盐可有效去除活性艳红X-3B,色度去除率达90%以上,显著优于活性炭(21.53%)、过硫酸盐(46.88%)、活性炭催化过硫酸盐(53.67%)(P0.05)。活性艳红X-3B的催化降解效果受Cu O负载量、pH、过硫酸盐投加量、温度的影响。单因素法研究表明,各因素最佳条件为:负载量活性炭与Cu O质量比为1∶5,投加量0.2 g,pH为3,过硫酸钠投加量0.2 g,反应温度40℃,活性艳红X-3B的色度去除率分别达到91.34%、95.57%、98.54%和98.81%,COD去除率分别为82.73%、88.89%、87.60%和93.46%。     

Mn_3O_4催化臭氧化钻井废水的作用机理

通过静态实验,探讨了Mn3O4对钻井废水臭氧化过程的催化作用机理,考察了Mn3O4及Cl-对臭氧分解、水体湍动程度、羟基自由基抑制剂碳酸氢根和叔丁醇的加入对COD去除率的影响,分析了反应过程中TOC和p H的变化。结果表明,催化剂加量为100 mg/L时,臭氧分解率由单独臭氧时的38.2%增加到81.4%,Mn3O4对钻井废水中有机物的吸附去除率仅为2%,O3/活性炭体系对COD去除率与单独臭氧效果接近,说明臭氧在催化剂表面存在吸附作用,促进臭氧分解;水体不搅拌与搅拌速度增加为900 r/min时,COD去除率由52%增加到58%,搅拌程度对钻井废水COD去除效果影响不大;HCO-3浓度为100 mg/L时,COD去除率降低到41.2%,说明了体系中有羟基自由基产生;氯离子浓度为1 000 mg/L,臭氧的分解率降低了9.2%,证明了臭氧在催化剂表面的吸附作用;羟基自由基抑制剂叔丁醇的加入,使得COD去除率由54.3%降低为40.8%,证实了反应体系中存在羟基自由基。同时在反应过程中,体系的TOC由191.9 mg/L降低至37.6mg/L;p H由原来的11.2降低到6.3。实验现象说明,臭氧吸附在Mn3O4催化剂表面,分解产生羟基自由基,进而氧化去除钻井废水中有机物,这在某种程度上证明了Mn3O4催化臭氧化对有机物的降解遵循羟基自由基机理。     

三维电极法处理丙烯酸丁酯生产废水的研究

对比了二维电极与三维电极对丙烯酸丁酯生产废水的处理效果,考察了三维电极条件下废水初始COD浓度、曝气强度、极板间距对废水处理效果的影响,并研究了丙烯酸丁酯生产废水中特征污染物的去除过程.结果表明:三维电极对丙烯酸丁酯生产废水COD的去除率明显高于二维电极;三维电极电流效率和能耗受污染物浓度影响较大,污染物浓度越高,电流...     

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)