吸附-氧化法应急处理饮用水源突发苯酚污染的研究

以黄浦江上游水源地突发苯酚污染为背景,重点考察了粉末活性炭（PAC）吸附、高锰酸钾（KMnO4）氧化及两者联用技术的除酚效能。结果表明,活性炭及氧化剂种类的选择是影响处理效果的重要因素,微孔发达、比表面积巨大的竹炭对苯酚的去除效果明显优于煤质炭、椰壳炭和木质炭;KMnO4对苯酚的氧化能力强于次氯酸钠和高铁酸钾。增大PAC和KMnO4的投加量,可有效提高对苯酚的去除率;PAC吸附-KMnO4氧化联用技术可大大提高除酚效能,投加50mg／LPAC,2mg／LKMnO4可将初始浓度为250／μg／L和500／μg／L的含酚原水分别处理至18μg／L和66／μg／L,是应对高浓度苯酚突发污染的有效应急措施。     

不同工艺对含高浓度腐殖酸地下水处理的可行性

针对内蒙古农村地区高腐殖酸地下水的处理问题,分别对（pH调节）-PAC强化混凝、高锰酸钾预氧化／混凝、活性炭吸附／混凝、Fenton氧化等技术处理的可行性进行了研究,同时利用三维荧光和高效体积排阻色谱分析处理前后水中有机物的组成变化特征。有机分析结果显示,水中的有机物为腐殖酸类物质,分子量分别为1600和3500,腐殖酸类物质为水中色度的主要贡献者。原水PAC强化混凝、高锰酸钾预氧化／PAC混凝对有机物的去除效果不佳,处理前后水样DOC浓度无明显变化,而pH调节．PAC强化混凝、微米活性炭吸附和Fenton氧化均能有效去除有机物。将原水pH调节至6．5,经300mg／LPAC混凝后出水DOC降至5．99mg／L。活性炭投加量为0．6g／L时,DOC降至7．6mg／L,然后采用60mg／LPAC混凝出去高度分散而不易沉降的小颗粒活性炭。此外,当反应初始pH值为3,过氧化氢投加量为0．5％（v／v）,亚铁和双氧水摩尔比为0．05时,出水DOC降至5．6mg／L,氧化后有小分子有机物生成。     

O3氧化工艺处理黄连素制药废水研究

采用臭氧（O3）氧化法处理含高浓度黄连素和COD的制药废水,探讨了废水初始pH、O3投加量及初始黄连素浓度等因素对O3氧化过程的影响,确定了O3氧化技术处理黄连素制药废水的最佳操作条件。结果表明,O3能够有效分解废水中的黄连素,降低其COD浓度;黄连素浓度为700mg／L、COD为3500mg／L、pH为0．88的废水,进气O3浓度为14．05mg／（L·min）,处理时间为180rain（即投加量为2529mg／L）时,黄连素和COD的降解率分别可达77．46％和41．28％,BOD,／COD比（B／C比）从0．06提高到0．34,增加了4．7倍;随着废水中初始黄连素浓度的升高,废水COD降解率逐渐降低。O3氧化法是一种有效的黄连素制药废水预处理技术,可以大大提高废水的可生化性。     

O3／GAC-常规处理珠江水系不同原水

以东江、西江和北江3种原水为研究对象,采用臭氧预处理-常规处理-臭氧活性炭系列处理,研究原水中有机物的去除及臭氧化副产物的产生和转化。结果表明,东江、西江和北江水中CODMn、UV254、甲醛和溴酸盐沿各处理单元过程变化规律基本一致;CODMn总去除率分别为60％、51％和39％,uV。总去除率分别为74％、96％和97％,最终出水甲醛浓度分别为0．004mg／L、0mg／L和0mg／L,B-O3-分别为3．1μg／L、8．7μg/L和35．5μg／L;CODMn的去除主要在预臭氧和活性炭过滤2个处理单元,预臭氧对UV254总去除率贡献最大,甲醛和溴酸盐浓度在主臭氧处理单元达到其峰值（西江甲醛除外）;氨氮和有机物浓度较低、pH值较高的北江原水,出水溴酸盐浓度最高。     

固相萃取毛细管气相色谱法分析水中有机磷农药残留

探索了采用固相萃取对样品进行提取富集，以及配备氮磷检测器的毛细管气相色谱(CGC)法分析水中有机磷农药痕量残留的方法。结果表明：敌敌畏、内吸磷、乐果、甲基对硫磷、马拉硫磷和对硫磷等6种农药在20min内有较好的分离；3个不同浓度的标准添加，其回收率范围为52．1％～93．7％，最低检出限范围为1．11～5．21ng／L；同时利用该方法分析太湖梅梁湾水源地和长江沿岸水厂取水口水质，6种有机磷农药均有一定程度检出，但仍未超出集中水源地供水标准。     

不同消毒剂对饮用水中可同化有机碳的影响

以某地表水为原水（TOC为5．3mg／L），研究了氯、氯胺和臭氧3种消毒剂对可同化有机碳（AOC）的影响。结果表明，投加1mg／L氯氧化30min就会使AOC升高近3倍。投加3种剂量（1、2、3mg／L）的氯胺，氧化30min时AOC增加不到1倍；氧化24h时AOC浓度均比30min时的高，这说明氯胺的作用机理与氯不同。投加臭氧2．0mg／L氧化30min时可使AOC增加2．4倍；当臭氧质量浓度大于2．0mg／L时，AOC开始下降，这说明一部分中间产物进一步被氧化成了二氧化碳和水。     

新型复合预氧化技术控制副产物的试验研究

臭氧被广泛应用于饮用水预氧化工艺中,但是成本较高,而且会生成臭氧化副产物,如可同化有机碳(AOC)、溴酸盐和甲醛.因此,提出臭氧/高锰酸钾复合预氧化技术,并对照预臭氧化技术,进行了消毒副产物前质及臭氧化副产物控制的小试试验研究.结果表明,与预臭氧化(1.5 mg/L臭氧)相比,复合预氧化(0.6 mg/L臭氧 0.4 mg/L高锰酸钾)能促进混凝沉淀对消毒副产物前质的去除,总去除率与单独预臭氧化的去除率相当.而且又能降低AOC生成量,并促进混凝沉淀对AOC的去除,合计AOC去除率达43%左右.此外,对溴酸盐和甲醛生成量也有明显去除效果,比单独预臭氧化降低了78.4%和21.2%.     

臭氧活性炭-后置砂滤工艺对水中农药的控制效能

选择我国饮用水水质标准中有相关规定,以及部分用量较大或虽被禁用但仍有残留的农药共25种,对黄浦江水源水以及采用臭氧活性炭-后置砂滤工艺的某水厂工艺段出水中的浓度分布进行了调查,评估了砂滤后置工艺条件下相应农药的实际处理效果。结果表明:原水中有包括莠去津、乐果、六氯苯、敌敌畏、乙草胺、丁草胺、仲丁威和p,p’-DDT的8种农药检出,且总浓度较高达到760 ng/L,其中莠去津和乙草胺含量较高,最高浓度分别达到531 ng/L和277 ng/L;从季节性分布来看,春季总农药浓度最高达760 ng/L,秋季最低为175 ng/L。从工艺去除效果来看,臭氧活性炭砂滤后置工艺对农药的总体去除率为62%~78%,与冬春季相比,夏秋季节的农药的去除率提高约10%左右,这可能与高温期微生物活性较高有关。值得关注的是,砂滤后置工艺与同期常规臭氧活性炭工艺相比农药的总去除率要低10%左右,应结合总体出水水质情况对其进一步评估。     

水相和泥浆系统中地下水成分对高锰酸钾氧化TCE的影响

三氯乙烯（TCE）是污染土壤和地下水中检出率较高的氯代有机物。以TCE为研究对象,考察了地下水无机成分和腐殖酸对高锰酸钾氧化TCE的影响,研究了不同离子强度下的MnO,颗粒行为,并测定了泥浆系统中TCE的氧化效果,结果表明：当TCE初始浓度为20mg／L、高锰酸钾与TCE的摩尔比为2：1,离子浓度〈0．1mol／L时,TCE去除率可达98％以上,Na^＋、Cl^-、HCO3-对TCE的去除率影响甚微,但离子强度对MnO2的沉淀生成影响显著;0．1mol／L的K^＋对TCE的去除有一定程度的抑制;0．1mmol／L的Fe^2＋和腐殖酸对TCE的氧化有显著负面影响。泥浆系统实验进一步验证了有机质对高锰酸钾氧化TCE的影响很大。     

微气泡曝气O3／H2O2处理RO浓水的效能及影响因素

采用O3／H2O2高级氧化工艺处理炼油厂反渗透（RO）浓水,用溶气泵加压溶气并产生微气泡强化传质,确定装置运行条件,考察气体中臭氧浓度、O3／H2O2初始摩尔比、pH和温度对O3／H2O2处理RO浓水效果的影响,并对RO浓水处理效能进行研究。结果表明,随着气体中臭氧浓度的增加,COD的去除率基本呈线性增加;加入适当量H,0,能提高臭氧氧化RO浓水的效果,O3／H2O2初始摩尔比在0～0．8范围内,COD的去除率先增加后下降,O3／H2O2初始摩尔比为O．5时COD去除率最大;pH从6．84增加到9．01,COD去除率逐渐增大,pH为10．03时COD去除率反而降低;在14～28℃范围内,温度低时,升高温度COD去除率增加较大,温度较高时,升高温度对COD去除率的影响较小。为考察该工艺的稳定性,在H：0：／0,初始摩尔比为O．5、溶液pH为8～9、臭氧浓度为80～100mg／L、温度为10-28℃条件下,对COD为90～140mg／L的RO浓水氧化处理4～10h,出水COD维持在39．9～49．9mg／L,达到《城镇污水处理厂污染物排放标准（GB18918—2002）》中的一级A标准;去除1gCOD消耗031．4～3．3g,消耗0,与H,02的总氧量为2．2～4．4g。     

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.     

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.     

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.     

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)