化学改性对活性炭吸附磺胺甲恶唑和布洛芬的影响

以5种化学改性剂(NH3、HCl、H2SO4、HNO3和H2O2)对活性炭进行改性,考察了化学改性对活性炭吸附磺胺甲恶唑(SMX)和布洛芬(IBP)的影响,并结合活性炭改性前后孔结构和表面化学性质的变化特征,利用Pearson相关性分析法,分析了活性炭各项理化指标与其吸附量之间的相关性。结果表明,与原炭相比,各种改性炭对SMX和IBP的吸附能力均有较大幅度提高,24 h时吸附量分别提高了36%~59%和8%~42%。活性炭的比表面积、孔容等物理性质与吸附量的相关系数绝对值均在0.4以内,表现为弱相关。对于SMX,活性炭的羧基官能团与吸附量相关系数r值在0.6~0.8之间;对于IBP,羧基、内酯基分别在吸附的前期和中后期与吸附量表现为强正相关,r达到0.6~0.8以上。本研究中活性炭的表面含氧官能团对其吸附能力表现出更为显著的影响。     

活性炭表面酸性含氧官能团对吸附甲醛的影响

利用Bothem滴定法测定了化学浸渍处理的活性炭表面酸性含氧官能团浓度,研究表面酸性含氧官能团对甲醛吸附的效应。结果表明,HNO3浸渍处理能有效增大活性炭表面的羧基、酚羟基和内酯基浓度;H2O2浸渍处理主要增大了活性炭表面的酚羟基浓度;随着NaOH浓度的增大,活性炭表面的酚羟基、内酯基和羰基浓度大致呈先增大后减小的趋势,这是由于NaOH的化学清洗作用和酸碱中和反应所致;HNO3浸渍处理的活性炭表面的酸性含氧官能团浓度显著超过NaOH、H2O2浸渍处理的活性炭,而30%(质量分数)NaOH浸渍处理的活性炭和30%(体积分数)H2O2浸渍处理的活性炭吸附甲醛的饱和时间比HNO3浸渍处理的活性炭吸附甲醛最大饱和时间分别多4.0、1.5 h,说明酚羟基能够显著影响活性炭吸附甲醛的效果。     

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。     

粉末活性炭对水中农药的吸附性能研究

研究了粉末活性炭对2,4-滴、呋喃丹、甲萘威和莠去津的吸附过程和吸附规律以及投炭量和水质对粉末活性炭吸附性能的影响。结果表明,粉末活性炭能有效去除4种农药;吸附规律符合Freundlich吸附等温线和Langmuir吸附等温线;吸附时间为30 min时,去离子水中的去除率已达到80%以上;随着投炭量的增加,去除率提高,粉末活性炭的吸附容量降低;在不同水质条件下,粉末活性炭的吸附等温线可能不同,因此在应急处理中,首先应该确定该水质下的吸附等温线,然后求出投炭量。     

氧化、还原改性对活性炭吸附草甘膦的影响

研究了氧化、还原改性对活性炭吸附草甘膦的影响.以傅立叶红外光谱定性表面官能团变化,以扫描电镜观察表面形貌,以化学吸附分析仪测定后再通过测定样品的氮气吸附/脱附等温线计算比表面积和孔径.结果表明:(1)氧化改性使活性炭比表面积增大;还原改性使活性炭比表面积减小.还原阶段使先前氧化阶段中产生的孔道以及原有孔道均发生塌陷,导致还原改性活性炭比表面积减小.(2)在静态吸附的条件下,氧化改性和还原改性活性炭对草甘膦的吸附均为吸热反应.还原改性在活性炭表面产生的还原性官能团有利于活性炭对草甘膦的吸附,而氧化改性产生的氧化性官能团并不利于活性炭对草甘膦的吸附.(3)热力学参数的计算进一步表明,改性活性炭对草甘膦的吸附为吸热反应.     

三价铁改性活性炭对水中微量砷的吸附特性

研究了三价铁改性对不同活性炭(颗粒和粉末)对水中砷的吸附特性的影响。结果表明,三价铁改性有效提高了活性炭对不同形态砷的吸附性能。其中,对于2种活性炭,As(Ⅲ)和As(Ⅴ)的最佳铁离子改性浓度分别为0.1和0.05 mol/L。此时,通过Langmuir等温线方程拟合得到:粉末和颗粒活性炭对As(Ⅲ)的最大吸附量qm分别为2.38 mg/g和9.39 mg/g;而对As(Ⅴ)的qm分别为5.12 mg/g和2.32 mg/g。此外,当溶液的p H从3升高到9的过程中,吸附量先增加后有所下降,当p H为7时,改性前后的活性炭对砷的吸附量达到最高。     

硝酸铁改性活性炭的制备及其对Cu(Ⅱ)的吸附性能研究

通过硝酸铁溶液浸渍—加热的方法对颗粒活性炭进行改性,采用BET比表面积测定、扫描电子显微镜(SEM)观察、Boehm官能团滴定等分析方法对改性前后的活性炭理化特性进行表征,考察吸附剂投加量、吸附时间、pH、吸附质初始浓度、温度等对Cu(Ⅱ)吸附性能的影响。结果显示,活性炭表面化学性质的改变对吸附性能的提高起主导作用;吸附过程与Langmuir吸附等温线方程及Lagergren准二级动力方程拟合较好,相关系数R2都在0.990 0以上。     

微波诱导改性活性炭催化降解邻苯二甲酸二甲酯

通过HNO_3、H_2O_2、NaOH对活性炭进行浸渍改性,采用BET、SEM、Boehm、FT-IR对改性前后的活性炭进行表征,研究了改性前后的活性炭在不同反应体系对DMP的降解效果和动力学,探讨了微波诱导改性前后的活性炭催化降解DMP的机理。结果表明,3种改性活性炭的BET比表面积、总孔容、微孔孔容和平均孔径均有所增加。HNO_3、H_2O_2改性后表面酸性基团增加、碱性基团减少,而NaOH改性呈现相反的理化特征变化。活性炭理化特征的变化可能与化学改性剂溶液的酸碱性、氧化还原性有关。微波诱导改性前后的活性炭催化体系对DMP的降解率大于单独吸附或单纯微波辐射体系,且均符合一级反应动力学。在微波诱导改性前后的活性炭催化体系中,改性前后的活性炭通过表面吸附-微波诱导氧化协同作用极大地提高了对DMP的降解率。     

改性活性炭对废水中铬离子的吸附

改性活性炭被广泛应用于吸附水体中重金属离子,但关于铁改性活性炭吸附性能的研究报道甚少。本研究对活性炭进行铁改性处理,并将之应用于水中的铬离子吸附,考察了吸附时间、溶液p H对改性活性炭吸附Cr(Ⅵ)效果的影响。实验结果表明,在25℃下,p H为3,吸附时间为300 min时,其对Cr(Ⅵ)的去除率为91.4%。铁改性活性炭对铬离子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,饱和吸附量为28.82 mg/g。     

稻壳基活性炭的制备及其对亚甲基蓝吸附的研究

以稻壳为原料，采用K2CO3活化法和H3P04活化法制备了比表面积为1312m^2／g和682m^2／g的活性炭，通过扫描电子显微镜（SEM）、X-射线衍射仪（XRD）对样品进行了表征，并将孔隙发达的活性炭样品用于对亚甲基蓝的吸附，结果表明，K2CO3活化法制备的活性炭样品具有更多的微孔结构；随着亚甲基蓝溶液初始浓度的增加、活性炭吸附时间的延长，亚甲基蓝的去除率呈现逐渐降低和逐渐增大的变化规律，当pH值为6时，活性炭对亚甲基蓝的吸附效果最佳；稻壳基活性炭对亚甲基蓝的吸附等温线符合Langmuir模型，Qm最高可达476．2mg／g；热力学参数△G^0△H^0和△S^0均为负值，表明稻壳基活性炭对亚甲基蓝的吸附是一个自发的放热反应。     

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.     

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 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.     

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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.