木质纤维素/蒙脱土纳米复合材料对Cr(Ⅵ)吸附性能研究

利用X射线衍射(XRD)和扫描电镜(SEM)方法,对木质纤维素/蒙脱土纳米复合材料的结构进行表征,并研究了溶液pH、Cr(Ⅵ)初始浓度、吸附时间和吸附温度对木质纤维素/蒙脱土纳米复合材料吸附Cr(Ⅵ)的影响.结果表明:(1)木质纤维素和蒙脱土复合后形成了插层一剥离型的纳米复合材料;(2)在溶液pH为2、Cr(Ⅵ)初始质量浓度为100mg/L、吸附温度为30℃、吸附时间为180 min的条件下,木质纤维素/蒙脱土纳米复合材料对Cr(Ⅵ)的吸附量达5.72mg/g;(3)木质纤维素/蒙脱土纳米复合材料对Cr(Ⅵ)的吸附符合伪二级动力学模型和Freundlich吸附等温式.     

不同黏土对盐酸环丙沙星和诺氟沙星的吸附特性

研究了不同振荡时间、溶液pH和金属离子浓度条件下,蒙脱土和硅藻土对水溶液中盐酸环丙沙星和诺氟沙星的吸附特性及其吸附动力学。结果表明,蒙脱土和硅藻土对抗生素的吸附均在4 h达到吸附平衡;强酸、强碱均有利于蒙脱土对盐酸环丙沙星的吸附,中性和碱性不利于蒙脱土对诺氟沙星的吸附;pH的升高不利于硅藻土对盐酸环丙沙星的吸附,强酸、强碱条件有利于硅藻土对诺氟沙星的吸附。pH≤6时,Na+和K+对吸附效果影响不大;pH=10时,Na+和K+显著降低2种吸附剂对抗生素的去除率。Ni2+有利于蒙脱土吸附盐酸环丙沙星,但不利于吸附诺氟沙星,不利于硅藻土在中性条件对抗生素的吸附。由吸附动力学可知,2种吸附剂对抗生素的吸附过程均符合准二级动力学模型。     

凹凸棒土对腐殖酸的低温吸附性能研究

首次研究凹凸棒土对饮用水中腐殖酸的低温吸附性能,考察5℃条件下,吸附时间与腐殖酸初始浓度、吸附剂投加量、pH对凹凸棒土吸附腐殖酸的影响,确定吸附剂的吸附等温线、吸附动力学和热力学等相关理论参数,研究凹凸棒土对腐殖酸的吸附性能与机理。结果表明,江苏盱眙凹凸棒土在温度5℃、pH=4、水中腐殖酸初始浓度为5 mg/L,投加量为15 g/L的条件下,吸附180 min后对腐殖酸的去除率可达97.26%。凹凸棒土对腐殖酸的吸附符合二级吸附动力学方程与Freundlich吸附等温式,吸附过程由孔隙内扩散过程控制,吸附为自发的吸热过程,包括物理吸附与化学吸附。根据Fre-undlich吸附等温式拟合计算,5℃、pH=7时理论最大吸附量为9 mg/g,说明凹凸棒土对于低温饮用水中腐殖酸具有良好的吸附效果。     

虾壳粉对水溶液中阴、阳离子型染料的吸附

采用废弃虾壳制备吸附剂处理含刚果红或亚甲基蓝的溶液。考察了温度、吸附时间、初始浓度、吸附剂投加量和初始溶液pH对吸附效果的影响并构建了去除率预测模型,并对吸附等温线、吸附动力学和吸附热力学进行系统研究。结果表明:虾壳粉对刚果红和亚甲基蓝的吸附分别在24 h和4 h时达到平衡,平衡吸附量随吸附时间、初始浓度及吸附剂投加量的增加而增大;刚果红平衡吸附量随pH升高而增大,亚甲基蓝平衡吸附量几乎不随pH变化。在15℃下,吸附剂投加量为1 g·L~(-1),刚果红吸附的最优条件为接触时间24 h、pH=4,在该条件下,虾壳粉对刚果红的饱和吸附量为276.64 mg·g~(-1);亚甲基蓝吸附的最优条件为接触时间4 h、pH=12,在该条件下,虾壳粉对刚果红的饱和吸附量为1.44 mg·g~(-1);虾壳粉对2种染料的吸附过程以物理吸附为主,符合准二级动力学方程。虾壳粉对阴离子型染料的吸附效果较优,对阳离子型染料有一定吸附性能,是一种经济高效的染料废水吸附材料。     

季铵纤维素对苋菜红染料的吸附特性研究

采用季铵醚化法制备季铵纤维素,研究季铵纤维素对苋菜红染料(AR)的吸附特性及其再生利用性能。结果表明:季铵纤维素的阳离子度与醚化剂用量呈正相关,季铵纤维素QC-7为最佳AR吸附剂;QC-7吸附AR以单分子层化学吸附为主,其吸附过程符合伪二级动力学模型,等温吸附曲线可用Langmuir和D-R等温吸附模型较好描述;QC-7对AR的吸附能力较强,在AR初始质量浓度为100mol/L、pH为7、QC-7投加量为100mg/L、温度为25℃、吸附90min时的饱和吸附量约为360mg/g,且QC-7对AR的吸附具有较宽pH适用范围(3~9)。依次经0.10mol/L NaOH解吸、0.1mol/L HCl再生的QC-7吸附效果良好,8次循环利用后的QC-7对AR的吸附量可达335.2mg/g,再生率超过90%。     

核桃壳对模拟废水中Cu~(2+)的吸附性能研究

采用核桃壳作为吸附剂,对模拟废水中的Cu2+进行吸附去除,考察了吸附剂粒径、水样初始pH、吸附剂用量、Cu2+初始浓度、吸附时间等因素对Cu2+吸附效果的影响,确定最佳吸附参数,并进行了吸附动力学和吸附等温线分析。结果表明:最佳吸附参数为核桃壳吸附剂粒径1.25~1.60mm、水样初始pH 5.0、吸附剂用量2.5g,Cu2+初始质量浓度20mg/L、吸附时间360min,在此条件下100mL水样在200r/min、25℃条件下吸附的Cu2+去除率达70%以上,吸附量约为0.702mg/g;本实验过程采用伪二级动力学方程的拟合更好,R2均在0.9以上,Cu2+吸附速率与其浓度的二次方成正比;Langmuir方程可以较好地描述核桃壳吸附剂对Cu2+的吸附过程,此吸附过程是单分子层的吸附。     

生物膜细菌藻酸盐对Cu2+的吸附动力学研究

以生物膜中提取的细菌藻酸盐为原料制备藻酸钙为吸附剂,对水溶液中的Cu2+进行了吸附动力学研究.试验结果表明,吸附时间、溶液初始pH和吸附剂投加量对藻酸钙吸附Cu2+影响显著.当溶液初始pH为4.0、Cu2+初始质量浓度为100 mg/L、吸附剂投加量为0.7 g/L时,藻酸钙对Cu2+的平衡吸附量为56.15 mg/g.水溶液中Cu2+在藻酸钙上的吸附动力学过程可用准二级动力学方程来模拟.吸附等温线研究表明,藻酸钙吸附Cu2+的过程可用Langmuir和Freundlich模型来描述.100 mmol/L 乙二胺四乙酸(EDTA)可有效解吸95.6%的Cu2+,实现Cu2+的回收与吸附剂的重复利用.     

木质素基水凝胶对亚甲基蓝染料的吸附性能

以木质素磺酸钠(LS-Na)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)为原料,采用微波辐射法,通过接枝共聚反应合成了生物质LS-g-PAMPS/AA水凝胶吸附剂,利用FTIR分析了水凝胶的结构。研究了吸附剂用量、染料初始浓度、吸附时间对亚甲基蓝(MB)染料的吸附性能的影响,结果显示,在MB初始浓度为1 000 mg/L,吸附剂为0.1 g时,吸附量和吸附率分别达1 914 mg/g和95%。平衡吸附数据满足Langmuir吸附等温模型,吸附动力学曲线较好地符合准二级动力学反应模型。木质素水凝胶对MB染料废水具有显著的吸附效果,可以作为阳离了染料废水处理用的生物质吸附剂。     

发酵麸皮对酸性含铬废水中Cr(Ⅵ)的吸附与解吸研究

以发酵行业产生的发酵麸皮废弃物为生物吸附剂处理酸性含铬废水中的Cr(Ⅵ),研究了pH、吸附时间、Cr(Ⅵ)初始浓度、发酵麸皮投加量对Cr(Ⅵ)吸附效果的影响,确定发酵麸皮吸附去除Cr(Ⅵ)的适宜条件。分别以NaOH、HCl、NaCl为解吸剂处理吸附饱和的发酵麸皮,利用正交实验研究解吸剂种类、解吸时间、解吸剂浓度、发酵麸皮投加量等因素对Cr(Ⅵ)解吸效果的影响。结果表明,在强酸条件下发酵麸皮对Cr(Ⅵ)的吸附效果最好,发酵麸皮吸附Cr(Ⅵ)的适宜条件为pH=1,吸附时间90min,Cr(Ⅵ)初始质量浓度20mg/L,发酵麸皮投加量0.35g。发酵麸皮解吸Cr(Ⅵ)的正交实验结果表明,最佳解吸条件为以0.20mol/L NaOH为解吸剂,发酵麸皮投加量0.50g,解吸时间60min。各因素对Cr(Ⅵ)解吸效果的影响程度排序为解吸剂种类解吸时间解吸剂摩尔浓度发酵麸皮投加量。吸附饱和后的发酵麸皮可以通过解吸再生,但再生第4次已经失去了重复利用的价值。     

草酸改性柚子皮对废水中镉离子的吸附性能

以粗柚子皮(PP)为吸附剂原材料,以草酸为改性剂制备出了改性柚子皮吸附剂(MPP)。采用批量实验研究了改性吸附剂对水中Cd(Ⅱ)吸附的影响因素(如溶液pH、吸附剂用量、接触时间和Cd(Ⅱ)初始浓度)、吸附动力学、吸附等温线和吸附热力学等,并讨论了其吸附机理。在溶液初始pH为5.0、吸附剂投加量为5 g/L、Cd(Ⅱ)初始浓度为50 mg/L条件下,吸附剂MPP对Cd(Ⅱ)的吸附平衡时间为120 min,其吸附率可维持在95.63%以上。吸附过程可以很好地用准二级动力学方程和Langmuir吸附等温模型描述。热力学分析结果显示,吸附剂(MPP)对Cd(Ⅱ)的吸附是吸热反应,且能自发进行。     

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.     

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.     

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 in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

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.