小麦秸秆生物碳质吸附剂对硝基苯的吸附性能

在炭化温度为300℃下,用小麦秸秆制备生物碳质吸附剂,研究生物碳质吸附剂对硝基苯废水的吸附性能.考察了pH值、温度、吸附时间和吸附剂投加量对吸附效果的影响,分析了吸附剂在水中对硝基苯的吸附机理.结果表明,在pH值为7,温度为25℃,吸附时间为8h,吸附剂投加量为3 g/L条件下,生物碳质吸附剂对硝基苯的去除率达到90％.等温吸附曲线符合Freundlich方程,最大吸附量约为92.37 mg/g.定量描述了分配作用与表面吸附对生物碳质总的吸附作用的贡献,炭化后的小麦秸秆非极性增强,使硝基苯与其的极性更为匹配,引起分配作用增大.     

利用滩涂污灌土壤制备吸附剂

研究了滩涂污灌土壤吸附剂的制备方法。通过正交实验,比较了氯化锌、磷酸、氢氧化钾、盐酸几种活化剂在不同秸秆加入量、活化剂浓度、活化时间、活化温度的情况下制备的吸附剂,对水中邻硝基甲苯的吸附效果影响。实验结果表明,选择盐酸活化法制备吸附剂,在秸秆加入量为15%,经2 mol/L的盐酸按液固比为1∶1浸泡处理滩涂污灌土壤后,用氮气做保护气在400℃的条件下碳化1 h,制备的土壤吸附剂对水中邻硝基甲苯的吸附效率可以达到90%以上。     

镧改性凹凸棒土的制备及其对水中磷酸盐的吸附

锁磷剂的应用与推广加快了人们对镧改性粘土的不断研究。为了探讨2种制备方法所得的镧改性凹凸棒土吸附剂对水体中磷酸根的去除效果,首先制备了镧改性凹凸棒土(La-ATP)及镧改性酸活化凹凸棒土(La-H-ATP)2种吸附剂,然后在不同条件下研究比较了二者对磷酸根的吸附效果。结果表明:La-ATP和La-H-ATP对磷酸根吸附曲线适合Langmuir方程,饱和吸附量(qm)均大于12 mg·g~(-1)。高温有利于La-ATP和La-H-ATP对磷酸根的吸附,并且La-ATP的平衡吸附量(qe)在35、25和10℃条件下均大于La-H-ATP。在酸性条件下,La-ATP具有比La-H-ATP更好的除磷效果。两种吸附剂对磷酸根具有较好的吸附选择性,几种常见共存离子存在时的吸附量无明显变化。     

改性玉米秸秆对水中砷的吸附

以玉米秸秆做原材料,筛选出异丙醇-氢氧化钠-草酸作改性剂,利用改性后的玉米秸秆吸附水体中的三价砷;探讨了其吸附过程的热力学和动力学行为;研究了p H及吸附剂量对吸附效果的影响。实验结果表明,改性玉米秸秆对水中砷具有很好的吸附能力,当进水浓度为1.25 mg/L、吸附剂投加量为0.25 g、温度为25℃、p H值为9时,60 min达到吸附饱和;在此条件下,改性玉米秸秆对三价砷的吸附去除率为94.28%;吸附过程符合准二级动力学方程,等温吸附规律能够同时满足Langmuir和Freundlich吸附等温吸附模型。     

响应面法优化微波热解制备污泥-秸秆吸附剂的工艺研究

以氯化锌为活化剂,采用微波诱导热解法制备秸秆-污泥复合吸附剂,根据Box-Behnken响应面优化法的设计原理,在单因素实验基础上,以氯化锌质量分数、微波功率、微波时间为考察因素,以秸秆-污泥复合吸附剂的碘值为响应值,建立了考察因素和响应值之间的二次多项式模型。回归分析结果表明,在热解时间和微波功率之间存在交互作用,氯化锌浓度和热解时间以及氯化锌浓度微波功率之间交互作用不明显。调整后的最佳制备参数为微波时间250 s,微波功率540 W,氯化锌含量1.0。在此优化条件下,制得秸秆-污泥复合吸附剂的碘值为621.45 mg/g。     

改性膨润土对水体中多环芳烃的吸附

改性膨润土被广泛地应用于吸附水体中重金属离子和有机污染物,但关于改性膨润土吸附水体中多环芳烃混合物的动力学研究鲜见报道。利用十二烷基三甲溴化铵和十二烷基磺酸钠对膨润土进行改性,并将之应用于吸附水体中萘、蒽、菲和芘4种多环芳烃,考察了吸附剂投加量、时间和温度等条件对吸附效果的影响。实验结果表明,在25℃、吸附时间40 min、起始浓度为1.25 mg/m L、改性膨润土的投加量为4 g/L的条件下,该吸附剂对萘、蒽、菲和芘的吸附率分别为99.1%、99.6%、98.7%和98.9%。改性膨润土对水体中4种多环芳烃的吸附机理服从准二级动力学方程,该吸附剂吸附等温线服从Langmuir方程。     

改性核桃果皮基活性炭对Cu~(2+)的吸附

以核桃外果皮制备活性炭及改性活性炭,对制得的活性炭进行表征,研究了5种活性炭对重金属Cu~(2+)的吸附性能。研究表明,以氯化锌为活化剂制得的活性炭,其碘吸附值及表面酸性基团含量均高于磷酸活化制备的活性炭,改性后的活性炭吸附性能明显增强,碘吸附值最高达到678.53 mg·g~(-1),对Cu~(2+)的最高去除率达到91.43%。吸附量和Cu~(2+)去除率随时间、温度和p H的升高而增大,5种活性炭投加量增加,导致吸附量减小,但Cu~(2+)去除率增大,吸附平衡时间为3 h。5种活性炭对Cu~(2+)的吸附均符合准二级动力学模型。磷酸和氯化锌活化的活性炭吸附等温线符合Tempkin模型,而3种改性活性炭的吸附等温线则较好地符合Langmuir模型。     

羧基化小麦秸秆对Pb~(2+)的吸附及再生性能研究

利用作物秸秆治理环境污染具有很好的环境效益。用氯乙酸对小麦秸秆进行羧基化改性,制得羧基化小麦秸秆,对其结构进行了表征,并考察其对水中Pb~(2+)的吸附和再生性能。结果表明,羧基化小麦秸秆与改性前相比,活性位点得到暴露,比表面积增大,其对Pb~(2+)吸附的最适pH为4.5。Ca~(2+)会竞争羧基化小麦秸秆上的活性位点,降低Pb~(2+)的平衡吸附量,但与商用阳离子交换树脂D001相比,羧基化小麦秸秆对Pb~(2+)具有更高的选择吸附性。羧基化小麦秸秆对Pb~(2+)的吸附过程符合Langmuir吸附模型,R2=0.92,最大吸附量为166.11mg/g。经过7次循环再生实验,羧基化小麦秸秆对Pb~(2+)去除率无明显下降,证明该吸附剂再生性能良好,具有很好的应用潜力。     

生物基质活性炭对挥发性有机物的吸附

以咖啡渣和柚子皮生物基质为原料用磷酸活化法制成活性炭,探讨了制备条件对活性炭制备的影响,并研究了其对正丁烷的吸附行为。磷酸活化过程中磷酸的用量为生物基质质量的1.5倍为宜,咖啡渣采用超声干燥法,柚子皮采用水热法制备。制备的活性炭对正丁烷均有较好的吸附能力,以柚子皮为原料、磷酸用量为原料质量两倍活化制成的活性炭吸附性能最佳,最大吸附量约为商用活性炭的2倍。吸附剂均能较好地与兰格缪尔曲线相拟合,计算了不同正丁烷覆盖度下的等量吸附热,其变化规律与吸附曲线变化规律相一致。     

改性油菜秸秆对Co(Ⅱ)的吸附

利用ZnCl_2对油菜秸秆进行改性,制得生物吸附剂。通过单因子优化实验,研究其对水溶液中的重金属Co(Ⅱ)的吸附效果。结果表明:在298 K下,pH为6.5,吸附剂用量2 g/L时,对初始浓度为10.0 mg/L Co(Ⅱ)水溶液的吸附率达95%。利用Langmuir和Freundlish等温线模型对实验数据进行拟合分析,Langmuir等温线模型很好地描述了油菜秸秆对Co(Ⅱ)的吸附过程。热力学参数表明,吸附是一个自发放热反应。改性油菜秸秆对Co(Ⅱ)的吸附符合准二级动力学方程。在室温下秸秆对Co(Ⅱ)的饱和吸附量为10.3 mg/g。     

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.