水铁矿吸附磷酸根的影响因素

为了修复水体富营养化,选取了人工合成的水铁矿作为除磷吸附剂。通过批量实验研究了震荡速度、吸附时间、吸附剂投加量、溶液初始p H、含磷初始浓度、反应温度和共存离子等因素对吸附作用的影响。结果表明:水铁矿的吸附具有快速吸附,缓慢平衡的特点;随着投加量的增加,溶液中磷酸根的去除率逐渐增加;溶液初始p H在酸性条件下,溶液中磷酸根的去除率最好;在室温25℃下,水铁矿对不同浓度的磷酸根溶液均具有很好的吸附效果;溶液共存离子的存在对磷酸根去除率有一定影响,HCO_3~-的影响最大。     

2,6-二硝基甲苯在土壤中的吸附行为

采用静态吸附实验,对供试土壤吸附2,6-二硝基甲苯(2,6-DNT)的过程进行了研究,探讨了土壤对2,6-DNT吸附的动力学及热力学特征,并研究了溶液p H、土壤投加量对吸附的影响。结果表明:2,6-DNT在供试土壤上的吸附在24 h达到平衡,吸附过程符合拟二级动力学模型;Freundlich模型能够很好的拟合土壤对2,6-DNT的吸附等温曲线;热力学计算结果表明供试土壤对2,6-DNT的吸附反应是自发和吸热过程;p H对吸附过程影响不大,随着土壤投加量的增加,2,6-DNT去除率不断提高,单位土壤的平衡吸附量不断降低并且逐渐趋于平缓。     

壳聚糖包覆介孔微孔分子筛去除水中的氨氮

以壳聚糖包覆介孔-微孔复合分子筛(CS/MCM-41-A)为吸附剂去除水中的氨氮,研究了反应时间、溶液p H、溶液氨氮初始浓度、CS/MCM-41-A投加量、竞争离子对吸附的影响,分析了CS/MCM-41-A的吸附动力学和热力学特征。结果表明,298 K下,当CS/MCM-41-A投加量为5 g/L,溶液氨氮初始浓度50 mg/L,p H为7,吸附时间为40 min时,溶液中氨氮的去除率达到74.35%,CS/MCM-41-A对离子的选择吸附顺序为Mg2+K+Ca2+Na+。CS/MCM-41-A吸附氨氮符合拟二级动力学方程,吸附等温线更好地符合Freundlich方程,CS/MCM-41-A对氨氮的去除有良好的吸附性能。     

响应面法优化凹凸棒土吸附水中亚甲基蓝

以凹凸棒土为吸附材料,对亚甲基蓝模拟水样进行吸附研究。采用响应面方法(RSM)对吸附工艺进行优化,考察温度、初始p H、吸附剂投加量、染料初始浓度对脱色率的影响,提出采用该工艺的数学模型及优化后的最佳工艺参数。结果表明,各影响因子对脱色率影响显著性顺序为吸附剂投加量初始浓度温度初始p H。优化得到最佳的工艺参数:温度为55℃,p H为3.3,吸附剂投加量为0.15 g,染料初始浓度为100.02 mg·L-1,该条件下对亚甲基蓝模拟水样脱色率可达99.25%,与预测值98.68%接近。因此,建立的模型能真实地反映各主要因素的影响。     

腐殖酸修饰凹凸棒对U(VI)的吸附性能及机理

采用腐殖酸(HA)修饰凹凸棒(ATP)制备得到腐殖酸/凹凸棒(HA/ATP),用于去除废水中的U(VI)。通过静态吸附实验,研究了溶液初始p H、投加量、吸附时间和初始浓度对吸附的影响,并用扫描电镜(SEM),X射线能谱图(EDS),傅里叶红外光谱仪(FITR)分析吸附机理。实验结果表明,去除率随时间的增大而增大,在120 min内可以达到平衡;吸附剂投加量越大,溶液p H=6左右时越有利于U(VI)的去除;HA/ATP能多次重复使用,且经过5次吸附解吸后对U(VI)的去除率仍能达到96%。吸附过程均符合Langmuir和Frendlich等温方程。较之准一级动力学,准二级动力学模型能更好地拟合实验数据。SEM-EDS、FITR分析结果表明,U(VI)被成功地吸附到了HA/ATP的表面,吸附机理为络合作用。     

膨胀石墨对U(Ⅵ)的吸附特性

高温加热可膨胀石墨制得膨胀石墨,用于去除溶液中的U(Ⅵ)。通过静态吸附实验,研究了初始p H、吸附剂投加量、U(Ⅵ)初始浓度、温度以及吸附时间对膨胀石墨吸附U(Ⅵ)效果的影响。实验结果表明,膨胀石墨吸附U(Ⅵ)的最佳p H为6.5,在温度为30℃,投加量为2.0 g/L,U(Ⅵ)初始质量浓度为10 mg/L时,对U(Ⅵ)的去除率达到98.08%,反应在4 h达到平衡。Langmuir等温吸附模型和准二级动力学模型较好地拟合了吸附过程,30℃时饱和吸附量为27.03 mg/g;热力学分析表明,膨胀石墨对U(Ⅵ)的吸附是自发的放热反应。比表面积测试、扫描电镜、X射线能谱与傅里叶红外光谱分析结果表明,膨胀石墨对U(Ⅵ)的吸附以物理吸附为主,表面官能团起辅助作用。解吸实验证明,膨胀石墨是可重复利用的吸附剂。     

溶液化学环境对给水厂废弃铁铝泥吸附草甘膦的影响

考察了给水厂废弃铁铝泥(ferric and alum water treatment residuals,FARs)对有机磷农药草甘膦的吸附特征,探究了溶液初始p H、阳离子种类及其离子强度、磷酸盐和小分子有机酸浓度等对FARs吸附草甘膦的影响。研究结果表明:FARs对草甘膦的吸附较符合伪二级动力学模型(R2=0.942),Freundlich方程能较好地描述FARs对草甘膦的等温吸附过程(R2=0.994),其草甘膦吸附容量KF值达10.35,是已报道铝泥的2倍。溶液化学环境对FARs吸附草甘膦影响较大,随着溶液p H的增加,FARs对草甘膦的吸附量显著降低。与K+相比,Ca2+的存在能显著提高草甘膦的吸附量。此外,溶液中小分子有机酸(苹果酸和柠檬酸)对FARs吸附草甘膦存在明显的抑制作用,且抑制作用随着有机酸浓度的升高而增强。解吸实验结果进一步表明FARs吸附的草甘膦能稳定存在,不易被溶液中的磷酸盐所取代。     

NiFe_2O_4/ZnAl-LDH吸附去除水中Cr(Ⅵ)

采用共沉淀法合成磁性复合材料NiFe_2O_4/ZnAl-LDH,通过静态吸附试验考察复合材料去除水中Cr(VI)的性能,系统地研究了溶液初始p H值、吸附剂投加量、吸附时间和温度等因素对Cr(VI)去除效果的影响。结果表明,当溶液初始p H值为2、初始Cr(VI)浓度为50 mg·L-1、吸附剂投加量为4 g·L-1时,吸附过程在240 min内达到平衡,此时Cr(VI)的去除率为89.5%。动力学和吸附等温式的研究表明:NiFe_2O_4/ZnAl-LDH吸附Cr(VI)的过程符合准二级动力学和Langmuir等温吸附模型。热力学参数表明该吸附过程为自发、放热的反应过程,低温有利于吸附剂对Cr(VI)的吸附。吸附剂经4次再生后对Cr(VI)仍有83.1%的去除率,且其在外加磁场的作用下能快速与水溶液分离,因此NiFe_2O_4/ZnAl-LDH可作为去除水中Cr(VI)的良好吸附剂。     

大肠杆菌配合植酸对铀的吸附

研究了用植酸处理后大肠杆菌对铀进行吸附,考察了p H、初始浓度、反应时间以及菌液投加浓度对吸附效果的影响。实验结果表明,植酸能够提高大肠杆菌菌悬液对铀的吸附效果。植酸处理后的大肠杆菌能有效结合UO2+2,在p H=4.0时,菌液投加浓度为90%时,吸附效果最好,吸附300 min达到平衡,吸附率为90%。大肠杆菌配合植酸吸附铀前后电镜图及EDX表明,反应能使铀酰离子络合沉淀,沉积在菌体表面。     

鸡蛋壳废料对水体中Cr(Ⅵ)的吸附特征与机理

利用鸡蛋壳废料对水中的Cr(Ⅵ)进行吸附处理,研究溶液p H、振荡时间、投加量和温度对鸡蛋壳废料吸附水体中Cr(Ⅵ)的特征和吸附机理。结果表明,在含有1 mg/L的Cr(Ⅵ)溶液的100 m L吸附体系中,鸡蛋壳废料可在30 min内完成吸附过程。溶液p H=2.5时,吸附量最大。鸡蛋壳投加量为1.0 g时,平衡吸附容量为0.0917 mg/g。利用鸡蛋壳去除水中Cr(Ⅵ)的最佳工艺参数为振荡时间30 min,初始p H为3.0,投加量2.0 g,体系温度35℃。鸡蛋壳对Cr(Ⅵ)的吸附过程用Langmiur和Freundlich方程能较好拟合,其中理论饱和吸附量在20℃、30℃和40℃时分别为0.1944、0.2034和0.2096 mg/g。吸附的焓变为8.76×10-3k J/mol,熵变为-45.96 J/(mol·K),吉布斯自由能变均为正值,变化范围是4.357~9.693 k J/mol。鸡蛋壳对Cr(Ⅵ)的吸附过程主要为物理性的单分子层和多分子层吸附。     

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.     

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.     

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.     

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.