水环境中腐殖酸与镉离子结合作用的影响因素

通过测定不同化学条件下腐殖酸与镉离子作用后的游离态镉离子浓度及其结合率,研究各因素对腐殖酸与镉离子作用的影响。研究结果表明,pH值、离子强度、投加镉离子总浓度、腐殖酸浓度和反应温度均影响腐殖酸与镉离子的结合。pH值在4.5~6.5范围内,随pH值升高,腐殖酸与Cd²⁺的结合率增大,游离态Cd²⁺浓度减少。溶液的离子强度增大对结合反应有抑制作用。投加Cd²⁺总浓度的增大会导致结合态Cd²⁺浓度和游离态Cd²⁺浓度逐渐增加,而其结合率逐渐减小。腐殖酸浓度逐渐增大,使Cd²⁺和腐殖酸的结合率逐渐增大。在20℃~50℃范围内时,随反应温度升高,游离态Cd²⁺浓度逐渐减小,其结合率逐渐增加。     

煤泥对水溶液中Ca2+的吸附性能研究

在静态条件下,研究了Ca²⁺在煤泥表面的吸附动力学。考察了不同Ca²⁺初始浓度的吸附实验,并对实验结果进行了动力学方程的拟合,结果表明,煤泥对Ca²⁺的吸附过程较好地符合准二级动力学方程。研究了初始Ca²⁺浓度、溶液pH值、振荡速度和煤泥质量对Ca²⁺吸附量的影响,实验结果表明：（1）煤泥对Ca²⁺吸附量随着Ca²⁺溶液浓度的增加而增大,Ca²⁺浓度大于3.828 mmol/L时,吸附量基本保持不变;（2）溶液pH<9时煤泥颗粒对Ca²⁺的吸附主要是静电吸附,pH>9时Ca²⁺在煤泥表面主要是沉淀吸附和一羟基吸附;(3) Ca²⁺在煤泥表面吸附的最佳振荡强度为150 r/min。     

城市垃圾焚烧渗沥液中Ca2+对厌氧EGSB处理效果的影响简

研究了城市生活垃圾焚烧厂渗沥液中Ca²⁺对厌氧颗粒污泥膨胀床反应器（EGSB）处理效果的影响,并采用静态实验方法考察了Ca²⁺对厌氧颗粒污泥产甲烷活性的影响。实验结果表明,进水COD为17 000 mg/L的条件下,当Ca²⁺浓度低于6 000 mg/L时,EGSB对COD去除率达93%以上;当Ca²⁺浓度高于6 000 mg/L时,COD去除率随运行时间明显下降,并在污泥中形成大量沉淀。静态实验结果表明,废水中低浓度Ca²⁺促进了厌氧颗粒污泥的产甲烷活性,但高浓度Ca²⁺明显抑制了其产甲烷活性,这是导致高Ca²⁺浓度条件下EGSB对COD去除率降低的主要原因。研究表明,颗粒污泥产甲烷活性恢复程度随Ca²⁺浓度增加而减弱。     

纳滤去除饮用水中的PFOS

全氟辛烷磺酸类物质（PFOS）是一种新型持久性有机污染物,对人类健康存在很大威胁,目前世界范围内的水体中均检测到不同浓度的PFOS。研究如何安全有效去除这类新型污染物十分必要。利用HYDRA—COPe10纳滤膜进行PFOS去除研究,在不同操作压力下研究pH、电解质以及与腐殖酸共存对PFOS截留效果的影响。结果表明,随着pH值的增加,截留率上升;二价盐对PFOS截留率的影响要高于一价盐,并且随着二价盐离子强度的增加,截留率上升;腐殖酸共存时截留效率有显著增加,尤其在1mmol／L钙离子存在条件下,PFOS的截留率可达到95．8％,但会引起膜通量下降及膜污染的发生。     

Ca(II)在活性污泥生物絮凝中的作用研究

采用4个平行的序批式反应器(SBR),研究了进水Ca²⁺浓度对活性污泥絮体表面特性和结构稳定性的影响,并由此来确定Ca²⁺在生物絮凝中的作用。结果表明：随着进水Ca²⁺浓度的增加,污泥中的Ca含量逐渐增大。进水中Ca²⁺的加入,增大了污泥絮体的粒径和密度,进而改善了污泥的沉降性能;Ca²⁺的加入,使可供结合的蛋白质数量最高增至近1倍,污泥表面疏水性也相应增强;污泥絮凝性能的改善,主要和可供Ca²⁺结合的蛋白质含量增加有关,而非多糖;EDTA通过络合污泥絮体中的Ca²⁺,破坏了由Ca²⁺架桥形成的污泥絮体结构,这说明Ca²⁺可通过和胞外聚合物（extracellular polymeric substances, EPS）中的负电官能团架桥来促进污泥絮体的形成并维持絮体结构的稳定性。     

不同来源溶解态腐殖酸与Cu2+作用的荧光特性

利用三维荧光等高线图以及其所确定的荧光峰荧光强度随溶液化学条件的变化,研究不同来源溶解态腐殖酸与Cu²⁺作用的荧光特性。研究结果表明：溶解态天然腐殖酸中主要存在二类发射荧光的有机物官能团能与Cu²⁺发生络合作用。位于激发波长和发射波长分别为271～281 nm和335～351 nm的荧光峰1所代表的有机物官能团是与Cu²⁺发生络合配位的主要点位;pH值为4～6时,其络合受pH值影响较显著;而受溶液离子强度影响较小。位于激发波长和发射波长分别为223～246 nm和335～371 nm的荧光峰2所代表的有机物官能团与Cu²⁺的络合作用受溶液pH值影响较小,受溶液离子强度影响较显著。溶解态商品腐殖酸荧光峰1′所代表的有机物官能团与Cu²⁺的络合作用荧光特性,与天然腐殖酸荧光峰1所代表的有机物官能团和Cu²⁺络合作用荧光特性相似,在pH值为3～7时,其络合受pH值影响较显著。     

几种阴阳离子对磷钨酸光催化降解甲基橙的影响

以磷钨酸为光催化剂,在紫外灯照射下,对甲基橙溶液进行光催化降解,考察了几种阴阳离子对磷钨酸光催化降解甲基橙溶液的影响。结果表明：Mg²⁺、Ca²⁺、NO^-₃、SO^2-₄和CO^2-₃均对催化活性有促进作用,其中Mg²⁺和Ca²⁺仅有微弱的促进作用;NO^-₃和SO^2-₄随着浓度的增加促进作用也有所增加;CO^2-₃则随着浓度的增加促进作用呈下降趋势;Mn²⁺、Al³⁺和Cl^-对光解反应存在较强的抑制作用,且Al³⁺和Cl^-随着其浓度的增加,抑制作用增强。     

TiO2光催化复合分离膜对水中天然有机物的去除

在水源污染越来越严重、水质标准日益严格的背景下,超滤(UF)已逐渐成为替代饮用水常规处理技术的最佳选择之一。本研究中采用相转化法,将聚偏氟乙烯(PVDF)、聚乙二醇(PEG)和二氧化钛(TiO₂)共混制得光催化复合分离膜并对其进行扫描电子显微镜(SEM)、原子力显微镜(AFM)和X射线能谱仪(EDS)等相应的表征。比较了有无光照条件下,PVDF-PEG和PVDF-PEG-TiO₂膜对腐殖酸(HA)的截留和超滤过程中的膜污染情况。研究结果表明,TiO₂光催化复合分离膜能提高对水中天然有机物的去除并同时降低膜污染。紫外光照强度越强,PVDF-PEG-TiO₂膜的抗污染性能越好。另外,光催化能更有效地减少超滤初始浓度较低的腐殖酸溶液过程中的膜通量衰减。     

共存物质对重金属絮凝剂 MCC 除镉性能的影响简

为进一步拓展天然高分子絮凝剂壳聚糖的应用范围,以壳聚糖、L-半胱氨酸为原料,通过酰胺化反应制备一种具有重金属捕集功能的高分子重金属絮凝剂-2-氨基-3-巯基丙酰壳聚糖（MCC）,研究了水体中常见的阴阳离子、有机配位剂及浊度对MCC除镉性能的影响,探讨了絮体形貌与絮体分形维数及絮凝除镉效果间的关系。结果表明,Na⁺、Cl^-、NO₃^-、F^-、SO₄^2-的存在对MCC除Cd²⁺均有促进作用,Ca²⁺表现为明显的抑制作用;低浓度的EDTA对除镉有促进作用,随着EDTA浓度的增大,逐渐转为抑制作用;低浓度的腐殖酸对MCC去除Cd²⁺有显著的促进作用;在一定范围内,浊度可促进 MCC对Cd²⁺的去除;絮体间空隙越多,絮体分形维数越小,除镉效果越好。     

沸石负载淀粉对Pb2+、Cu2+和Ni2+的吸附性能

将淀粉负载到沸石表面得到新型重金属离子复合吸附剂ZLS。分别从沸石与淀粉质量比、吸附温度、吸附时间、pH与重金属初始浓度不同方面考察了复合吸附剂ZLS吸附 Pb²⁺、Cu²⁺、Ni²⁺的影响。实验结果表明:当沸石与淀粉质量比为10:1,pH为6,吸附温度在30℃时,复合型吸附剂ZLS对Pb²⁺、Cu²⁺和Ni²⁺ 3种重金属离子的吸附效果最好;吸附动力学研究发现,ZLS对Pb²⁺、Cu²⁺和Ni²⁺的吸附行为均符合准二级动力学以及颗粒内部扩散模型;等温吸附数据符合Freundlich模型,吸附状态属于多层吸附。     

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.     

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.     

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.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

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.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

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.