改性壳聚糖处理污水中Ni(Ⅱ)的效果

通过丁二酸酐与γ-氨丙基三甲氧基硅烷改性后的纳米SiO2(即可分散的纳米二氧化硅,简称DNS)反应,合成了羧基化的DNS,再经过与壳聚糖脱水生成酰胺的过程,合成了改性壳聚糖。通过红外光谱和扫描电镜对改性壳聚糖进行表征。研究了壳聚糖及改性壳聚糖微粒吸附Ni2+时溶液pH值、时间、吸附剂用量和Ni2+初始浓度等对吸附率的影响,并确定了最佳条件为:pH=7,吸附时间为120 min,吸附剂的投加量为0.3 g。改性壳聚糖比壳聚糖具有更强的吸附Ni2+的能力,吸附率达67.01%。     

活化粉煤灰改性壳聚糖絮凝除藻的研究

将活化后的粉煤灰滤液对壳聚糖进行改性,研究其絮凝除藻性能.实验表明,改性后的壳聚糖除藻性能优良,较少的用量(0.5 mL)可去除接近90%的藻.而分泌可溶性的胞外有机物(EOM)会优先争夺絮凝剂--壳聚糖,导致其投加量增加.适当增加改性壳聚糖投加量可以使藻絮体密实,增强抗水流冲击能力,由此展开改性壳聚糖投加量与絮凝除藻的动力学研究.最后,测定了絮凝上清液的藻光合活性,发现投加改性壳聚糖后有效降低了藻光合活性,防止水华二次爆发.     

改性壳聚糖-凹凸棒石复合絮凝剂絮凝采收小球藻

用3-氯-2-羟丙基氯化铵(CTA)季铵化改性壳聚糖(CTS),制备了季铵化改性壳聚糖(CTS-CTA);将壳聚糖(CTS)、阳离子淀粉(CS)、二甲基二烯丙基氯化铵(DMDAAC)进行三元接枝共聚,制备了三元接枝改性壳聚糖(CTS-DMDAAC-CS)。并且比较了壳聚糖(CTS)、季铵化改性壳聚糖(CTS-CTA)、三元接枝改性壳聚糖(CTS-DMDAAC-CS)对小球藻的絮凝效果,选择三元接枝改性壳聚糖与凹凸棒石进行复配,确定了最佳絮凝条件为:p H=8,絮凝剂与凹凸棒石的比例为1∶14,沉降时间为20 min,絮凝剂投加量为0.4 g。在该条件下进行了重复实验,得出小球藻的絮凝率为98.8%,并且絮体紧密、沉降速度快,不需要再次分离,具有很好的应用前景。     

微波辅助改性壳聚糖的制备及其絮凝性能

以壳聚糖、阳离子醚化剂二甲基二烯丙基氯化铵为原材料,采用微波辐射的方法,制备了壳聚糖接枝共聚物(壳聚糖-二甲基二烯丙基氯化铵),并通过红外光谱分析对改性壳聚糖进行了表征。以接枝率为标准,确定改性壳聚糖的最佳反应条件,并以高岭土悬浊液和实际生活污水作为处理对象,测定了改性壳聚糖的絮凝性能。结果表明,壳聚糖接枝共聚物的最佳制备条件是微波反应温度55℃,反应时间20 min,壳聚糖0.5 g,微波功率270 W,阳离子醚化剂的浓度20%,在此条件下,合成的改性壳聚糖的接枝率为80%。红外光谱分析结果显示,已成功地合成了壳聚糖-二甲基二烯丙基氯化铵接枝共聚物。在絮凝实验中,壳聚糖接枝共聚物的去浊率最高达到91%,COD去除率最高达到77%。其结果表明,壳聚糖接枝共聚物的絮凝性能明显高于原料壳聚糖。     

阳离子化壳聚糖改性黏土絮凝去除藻华

壳聚糖改性黏土可以用于治理藻华,但未经改性的壳聚糖具有电荷密度小、溶解度小、pH适用范围较窄以及分子质量较小等缺点,影响了壳聚糖改性黏土除藻的性能。为了优化壳聚糖的絮凝除藻性能,以二甲基二烯丙基氯化铵为阳离子醚化剂,在微波条件下对壳聚糖进行改性合成阳离子型壳聚糖,并研究了阳离子壳聚糖溶解度随pH的变化,以及用它改性后的黏土颗粒的表面电位的变化,并对阳离子壳聚糖改性黏土和壳聚糖改性黏土的絮凝除藻性能进行比较。结果表明,阳离子壳聚糖在酸性和碱性条件下都具有很好的溶解性,经其改性后的黏土颗粒的等电点(pH 10.8)显著高于壳聚糖改性黏土的等电点(pH 9.5)。在絮凝实验中,阳离子壳聚糖改性黏土的最大除藻率达到99%,藻絮体粒径为978μm,即使在pH为10时,仍有87%的去除率。结果表明,阳离子壳聚糖改性黏土的除藻性能明显优于未改性的壳聚糖改性黏土。     

改性沸石对水中微量汞的吸附性能

为了更好的去除水体中微量汞,研究了采用二氧化锰和壳聚糖对天然斜发沸石进行改性,着重考察了pH、温度、离子强度、Hg~(2+)初始浓度和时间对改性前后沸石吸附Hg~(2+)的影响,并研究了其吸附机理。结果表明,改性沸石受pH、温度和离子强度影响较小,在pH、温度、离子强度和初始浓度为6、25℃、0.05 mol·L~(-1)和50μg·L~(-1)时,二氧化锰+壳聚糖改性沸石(ZCM)对Hg~(2+)的去除率高达99%,符合国家饮用水标准,并且二氧化锰+壳聚糖改性沸石(ZCM)具有更好的解吸再生性。3种沸石均较好的符合Langmuir等温吸附模型和假二级动力学模型,其中改性沸石对汞的吸附主要为离子交换和表面官能团的络合作用,二氧化锰+壳聚糖改性沸石(ZCM)和壳聚糖改性沸石(ZC)饱和吸附量由1.43 mg·g~(-1)提高到5和3.3 mg·g~(-1),吸附平衡时间由10 h减少至1和4 h,为治理汞微污染地表水提供一定的理论支持。     

壳聚糖衍生物的合成及其絮凝性能的研究

对从虾蟹壳中制备的壳聚糖进行改性,分别制得壳聚糖衍生物——壳聚糖季铵盐和羧甲基壳聚糖,用于味精废水的絮凝实验。实验结果表明,壳聚糖、壳聚糖季铵盐和羧甲基壳聚糖作为絮凝剂处理味精废水均有较好的效果,以壳聚糖季铵盐的效果最好,其pH值适用范围宽、絮体沉降快,是一种具有良好反应活性的高分子絮凝剂。     

水溶性巯基壳聚糖对污染土壤吸附态汞的解吸作用研究

用两种巯基化试剂半胱氨酸(Cys)和硫代乙醇酸(Thi)与壳聚糖(CTS)反应,制备了两种水溶性巯基壳聚糖,即Cys-CTS和Thi-CTS,对比研究了这两种巯基壳聚糖与CTS对被染毒土壤中吸附态汞的提取能力.结果表明,Thi-CTS在pH=3、质量浓度为0.5g/L、用量为20 mL的条件下.对汞的提取率为59.44%,相同条件下CTS和cys-CTS对汞的最高提取率只有31.81%和10.15%.     

壳聚糖接枝共聚物的合成及应用研究

在N2保护下,以浓度为0.8 mmol/L硝酸铈铵为引发剂,控制壳聚糖(CTS)和丙烯酰胺(AM)质量比为mCTS∶mAM=1∶6,于50℃下接枝共聚反应3 h,得改性的壳聚糖衍生物(CAM).用IR对产物进行表征.通过对废水的处理,研究了共聚产物在絮凝、COD去除、脱色上的应用.结果表明:CAM的絮凝效果好于聚丙烯酰胺和壳聚糖,CAM对COD的去除率达到84.7%,并有较好的脱色效果.     

壳聚糖改性对磁性Fe_3O_4吸附去除Pb(Ⅱ)和Cd(Ⅱ)的影响研究

利用壳聚糖改性磁性Fe_3O_4以提高其对重金属Pb(Ⅱ)和Cd(Ⅱ)的吸附性能,考察了改性前后磁性Fe_3O_4对Pb(Ⅱ)、Cd(Ⅱ)的吸附等温线及吸附动力学过程。结果表明,经壳聚糖改性后,壳聚糖-磁性Fe_3O_4比表面积大幅增加,由原来的76.12m2/g增加到142.67m2/g;壳聚糖-磁性Fe_3O_4对Pb(Ⅱ)、Cd(Ⅱ)的吸附性能优于磁性Fe_3O_4;当pH为2.0~7.0时,提高pH有助于促进两种磁性材料对Pb(Ⅱ)和Cd(Ⅱ)的吸附量;两种磁性材料对Pb(Ⅱ)和Cd(Ⅱ)的吸附符合准二级动力学模型,吸附过程属于吸热过程;重复吸附—脱附循环再生5次后,壳聚糖-磁性Fe_3O_4对Pb(Ⅱ)、Cd(Ⅱ)的去除率仍在80%以上,磁性Fe_3O_4对Pb(Ⅱ)、Cd(Ⅱ)的去除率在75%以上,两种磁性材料再生性能较好。     

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.