硅藻土强化混凝去除微污染原水中的有机物

研究了联用硅藻土与聚合氯化铝（PAC）强化混凝对有机微污染原水中不同性质溶解性有机物的去除效果。采用超滤膜和XAD系列树脂对微污染原水中溶解性有机物进行分级表征,物理分级表明分子量〈4 kD的溶解性有机物占50%以上,化学分级表明原水中以憎水酸（HoA）和亲水物质（HiM）为主。硅藻土助凝去除溶解性有机物,实验结果表明,当PAC投加量30 mg/L,硅藻土投加量0.5 g/L时,溶解性有机碳去除率由22.5%提高到26.3%。     

城市污水二级生化出水中溶解性有机物的特性及其深度处理研究

在对某城市污水二级生化出水中溶解性有机物(DOM)特性进行深入分析的基础上,对比了混凝、活性炭吸附、树脂吸附等深度处理工艺对DOM的处理效果。结果表明,水样中溶解性有机碳(DOC)为12.32mg/L,其中疏水性组分占46.65%,亲水性有机物(HPI)占33.33%,过渡亲水性组分占20.02%;酸碱滴定结果表明,HPI的总酸度最强;MIEX树脂对所有组分尤其是疏水性组分的去除效果都较好,它在城市污水二级生化出水(尤其是富含疏水性物质的水体)的深度处理中具有更广阔的应用前景;凝胶渗透色谱分析结果表明,水样中DOM的分子量呈宽分布特征,主要包含平均分子量为230~750u的低分子量小分子有机物,也包含12 000u左右的中等分子量有机物,而经MIEX树脂吸附处理后,分子量在12 000u左右的组分基本去除,分子量在230~750u的组分也有显著的减少。     

混凝对二级出水中有机物分布特性的影响

以城市污水处理厂二级出水为研究对象,通过烧杯实验,确定了以三氯化铁(FeCl3)和聚合氯化铝(PAC)为混凝剂时两种混凝剂的最佳投加量,在此基础上采用XAD树脂分离技术和超滤膜法对水中溶解性有机物(DOM)进行分级表征,研究了混凝前后水中DOM的亲疏水特性、分子量分布规律以及比紫外吸收值(SUVA)和E4/E6(A465nm/A665nm)的变化.结果表明,当FeCl3和PAC投加量分别达到30 mg/L和60 mg/L时,可以使出水水质满足《城镇污水处理厂污染物排放标准》(GB18918-2002)中的一级A标准;FeCl3对含碳碳不饱和双键及芳香环的有机物的去除效果优于PAC;FeCl3对小分子有机物的去除效率更高,而PAC对分子量＞100 000的大分子有机物的去除效果优于FeC13;混凝处理对疏水性有机物的去除效果优于对亲水性有机物的去除效果,同时其对酸性物质的去除效率高于对非酸性物质的去除效率.     

SBR-混凝处理渗滤液过程中有机物的变化特征

考察了SBR-混凝组合工艺对垃圾渗滤液中溶解性有机物(DOM)不同分子量区间物质及组分腐殖酸(HA)、富里酸(FA)和亲水性有机物(Hy I)的去除效果,同时利用傅里叶红外光谱及三维荧光光谱对处理过程中DOM各组分变化特性进行了分析。结果表明,组合工艺对表观分子量为2 000~4 000及2 000的DOM去除率分别为89.3%和72.1%;对渗滤液DOM组分HA、FA和Hy I的去除率分别为-52.0%、73.1%和77.1%。红外光谱显示,DOM各组分都含有醇、羧酸、脂等多种有机物,SBR对糖、醇、羧酸等去除效果较好,而混凝对脂肪族及芳香族化合物去除效果较好;三维荧光光谱分析表明,经组合工艺处理,DOM各组分荧光峰强度及复杂化程度明显降低,且SBR工艺对色氨酸等类蛋白物质去除效果较好,混凝工艺对类腐殖酸、类富里酸等大分子物质的去除效果较好。     

水体溶解性有机物的化学分级表征:原理与方法

综述了水体溶解性有机物(DOM)的化学分级表征法即树脂吸附分级法(RA)的研究与进展,同时基于该方法存在的一些问题结合我国典型水质体系,从树脂的选择、净化、分级的定义、水样过柱流速、水样树脂体积比的确定等方面进行了研究探讨,给出了完整的实验参数和操作方法.     

切削液废水处理过程中溶解性有机物分子质量分布和光谱特征的转化规律

以隔油-混凝沉淀-水解酸化-好氧共代谢为组合工艺处理切削液废水,探究各处理单元对不同种类有机物的转化规律和去除能力;对各处理单元出水中的溶解性有机物(DOM),采用超滤膜法进行分子质量分级,应用紫外-可见吸收光谱、三维荧光光谱等方法对各单元出水及其滤后液进行了分析。结果表明,隔油池出水DOM分子质量主要分布在1 kDa小分子质量区间和100 kDa的大分子质量区间,分子质量占比分别为46.04%、42.79%,混凝沉淀对大分子质量的DOM有较好的去除效果,混凝沉淀出水、水解酸化池出水、好氧池出水的DOM主要分布在1 kDa区间。切削液废水处理过程中出现5个荧光峰,其中峰A和峰B可能为多环芳香烃和杂环化合物的混合物;峰C为石油类;峰D可能是废切削液中滋生的微生物和细菌的细胞物质及其分泌物或单环芳香烃;峰E可能为杂环化合物或多环芳烃类腐殖酸。经一级处理(隔油和混凝沉淀)后峰A和峰B的去除率分别为60%和35%;峰C和峰D去除率均大于99%。经二级处理(水解酸化和好氧共代谢),峰A和峰B的去除率分别为23%和48%。该工艺流程对切削液废水中的有机物有较好的去除效果,石油类、COD、TOC、BOD_5的总去除率可达99.99%、98.81%、98.74%、99.78%,达到了《污水排入城镇下水道水质标准》中的B级标准。     

水体溶解性有机物的化学分级表征：原理与方法

综述了水体溶解性有机物（DOM）的化学分级表征法即树脂吸附分级法（RA）的研究与进展，同时基于该方法存在的一些问题结合我国典型水质体系，从树脂的选择、净化、分级的定义、水样过柱流速、水样树脂体积比的确定等方面进行了研究探讨，给出了完整的实验参数和操作方法。     

组合工艺处理填埋场渗滤液中溶解性有机污染物的去除特性

以采用"SBR+混凝+Fenton氧化+BAF"组合工艺处理的晚期垃圾渗滤液各级出水为研究对象,考察了HA、FA和HyI等溶解性有机物(DOM s)在各个工艺处理过程中的变化。结果表明,组合工艺COD和NH3-N去除率分别达到98.4%和99.3%;对DOM s的去除率为98.3%,其中胡敏酸(HA)、富里酸(FA)和亲水性有机物(HyI)的去除率分别为98.3%、99.5%和95.7%。各处理工艺中SBR和混凝工艺对HA和HyI的去除贡献较大,Fenton氧化工艺对FA去除率较高。Fenton氧化和BAF联用,可以有效去除难降解的溶解性有机污染物,使出水达到《生活垃圾填埋污染控制标准》(GB16889-2008)排放标准。     

沈阳市黑臭水体溶解性有机物组分及其光学特征

以沈阳市5条黑臭水体作为研究对象,其中支流I和支流II为重度黑臭,支流III、IV和V为轻度黑臭。运用三维荧光光谱结合平行因子方法对黑臭水体中水溶性有机物(DOM)组分进行了表征,并通过与光谱数据相结合的方法,建立了DOM各组分最大荧光强度(F_(max))与归一化遥感反射率的一元线性回归方程。三维荧光分析结果显示,DOM分为2个类别3种不同组分,分别为类蛋白荧光组分C1(235nm/360nm)、类腐殖质荧光组分C2(220nm/430nm)和C3(255nm/520nm)。水体光谱分析结果表明:在250～800 nm处,有色可溶性有机物吸收系数(a_g)、总悬浮物吸收系数(a_p)曲线均随着波长的增大逐渐减小,空间变化特征明显;在特征波长440 nm处,轻度黑臭水体的有色可溶性有机物吸收系数总体上大于重度黑臭水体,重度黑臭水体总悬浮物吸收系数总体大于轻度黑臭水体。与正常水体相比,在可见光波段,沈阳市黑臭水体遥感反射率普遍较低,出现3个反射峰和1个反射谷。但支流I与其他黑臭水体不同,表面呈白灰色,导致其遥感反射率(R_(rs))呈现与正常水体类似的明显的波峰和波谷,是一类特殊的黑臭水体。线性回归分析表明,由归一化遥感反射率比值R_(688)/R_(555)与DOM组分最大荧光强度所建立的线性模型估算精度最理想。R_(688)/R_(555)与轻度黑臭水体DOM组分F_(max)的拟合程度好于重度黑臭水体。进一步研究表明,R_(688)/R_(555)与色氨酸类物质拟合程度较好,与腐殖质类物质没有明显的线性关系。     

UV/H2O2/Fe-FeOxH2x-3和UV/H2O2工艺降解水中富里酸的研究

采用硼氢化钠还原法制备核-壳结构的Fe-FeOxH2x-3复合材料,研究了富里酸在UV/H2O2和UV/H2O2/FeFeOxH2x-3两种不同反应体系下的降解情况.结果表明,核-壳结构Fe-FeOxH2x-3的存在,提高了UV/H2O2降解富里酸的反应速率,TOC去除达到84%.采用XAD树脂吸附法对反应前后的富里酸进行化学分级表征,结果表明,富里酸经反应后憎水酸(HoA)、弱憎水酸(WHoA)和憎水中性物质(HoN)都有所减少,进而转化为亲水性物质(HiM);用超滤膜法对富里酸进行物理分级表征,考察了富里酸在反应前后分子量分布的变化情况.同时,富里酸经过反应后生成的中间产物降低了三氯甲烷生成趋势.     

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.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

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.     

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.     

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.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.