低频超声辐照降解间苯二酚水溶液的研究

利用低频超声波对模拟间苯二酚废水进行研究，主要讨论间苯二酚本身性质以及超声操作声强对降解的影响，并通过自由基清除剂实验判定该反应的反应类型。结果表明，间苯二酚本身性质以及超声声强对间苯二酚的超声降解影响都比较大，并且该超声降解反应过程以自由基氧化反应为主，同时该反应遵循表观一级动力学反应特征。初始浓度为200mg／L的间苯二酚反应液经强度0．4W／cm^２的超声波辐照4h后，降解率为48．6％。     

超声波降解水溶液中对二氯苯

采用超声波降解含对二氯苯(p-DCB)的溶液,研究了p-DCB降解的动力学和影响因素.结果表明:(1)超声波降解水溶液中的p-DCB,随着p-DCB初始浓度的增加降解率减小;p-DCB的超声波降解反应符合表观一级动力学规律.(2)增大超声波频率和功率以及双频率联合使用可以增大p-DCB的降解率和一级反应速率常数.(3)弱酸性或中性环境更有利于p-DCB的降解进行.(4)反应时的搅拌和自由基清除剂的投加都降低了p-DCB的降解率,这是因为超声波降解时空化气泡内的热裂解和自由基作用的削弱.(5)在单一体系中,p-DCB比对氯苯胺(p-ClA)更易降解.在混合体系中,p-ClA的加入没有显著降低p-DCB的去除效果,因为亲水的p-ClA不易挥发,难以进入空化气泡竞争能量和自由基,其存在对空化气泡内混合气体的比热容比影响较小;而p-DCB的存在却明显降低了p-ClA的降解效果,因为疏水的p-DCB易挥发进入空化气泡竞争能量和自由基,并降低混合气体的比热容比.     

超声波-光催化联合降解苯酚废水研究

超声降解和光催化降解均为自由基历程的高级氧化技术,同时,超声空化能够改善传质效果,因此,二者耦合能否产生协同效果是值得研究的。本文考察了苯酚溶液的超声降解、光降解、光催化降解、超声-光催化降解以及温度对光降解和光催化降解的影响。结果表明,40kHz,0.4w/cm2的超声波对苯酚没有明显的降解作用,而对光催化降解只有轻微的促进作用。光降解和光催化降解的过程曲线显著不同,但温度对二者均有显著的促进作用。     

超声波/零价铁降解对氯苯胺性能及机理研究

在超声波/零价铁体系中考察了溶液初始pH值、浓度对对氯苯胺降解的影响.在pH值为3～11范围内最佳条件为pH=9;初始浓度为0.1、0.2和0.4 mmol/L时的降解率(180 min)分别为83.2%、63.5%和36.1%.对氯苯胺在单纯铁粉、单纯超声波和超声波/零价铁3种体系中降解符合拟一级反应动力学规律,速率常数分别为6.83×10-4、3.95×10-3和1.01×10-2 min-1,增强因子为218%,表明铁粉与超声波对对氯苯胺降解有明显的协同效应.在体系中加入自由基捕捉剂正丁醇能抑制对氯苯胺的降解,证实对氯苯胺降解主要是依靠羟基自由基的氧化作用.     

US-UV-Fenton降解硝基苯

采用超声波(US)、紫外光(UV)和Fenton联合降解硝基苯,初步探讨了其作用规律。研究结果表明,UV可以促进双氧水转化自由基的效率,而US同时具有强化传质作用和超声氧化作用,两者均能够强化Fenton氧化硝基苯的降解过程。正交实验结果表明,H2O2初始浓度是硝基苯降解和矿化的最显著影响因素,反应时间和超声功率是矿化的显著影响因素。最佳反应条件为:H2O2500 mg/L、Fe2+10 mg/L、反应时间60 min、超声波功率100 W,此时,硝基苯完全降解,TOC去除率达到73.0%。Fenton、UV/Fenton和US/UV/Fenton降解硝基苯过程均符合伪一级反应动力学模式,反应速率常数分别为3.37×10-2、3.81×10-2和5.10×10-2min-1。     

超声波—光催化联合降解苯酚废水研究

超声降解和光催化降解均为自由基历程的高级氧化技术，同时，超声空化能够改善传质效果，因此，二者耦合能否产生协同效果是值得研究的，本文考察了苯酚溶液的超声降解、光降解、光催化降解、超声-光催化降解以及温度对光降解和光催化降解的影响，结果表明，40kHz,0.4W/cm^2的超声波对苯酚没有明显的降解作用，而对光催化降解只有轻微的促进作用。光降解和光催化降解的过程曲线显著不同，但温度对二者均有显著的促进作用。     

过硫酸钠/钴离子/超声波协同降解酸性橙7

以酸性橙7(AO7)为目标污染物,研究了过硫酸钠(Na_2S_2O_8)/钴离子(Co~(2+))/超声波(US)协同降解水体中AO7的过程及其降解机理,并分别考察了Na_2S_2O_8初始浓度、AO7初始浓度、催化剂投加量和超声波功率对AO7降解率的影响。实验结果表明,过硫酸钠/钴离子/超声波协同工艺能有效的降解水中的酸性橙7。初始AO7浓度越低降解效果越好。超声功率在200~450 W之间时,AO7的降解率随着超声波功率的增大同样先升高后降低。在体系中加入乙醇和叔丁醇后明显抑制AO7的降解,证明该体系中主要氧化物种为硫酸根自由基(SO-4·)和羟基自由基(·OH)。     

超声波处理难降解有机物影响参数研究

考察了多种操作参数对多氯联苯、溴苯超声波降解的影响。结果表明,高频率、高声强、高流速、混合气体可以提高超声反应速率, 358kHz下降解速率比20kHz提高了848%, 34mL/min流速下比4 4mL/min提高了140%,参入Ar比单纯使用O2 提高83% ( +80%Ar)或66% ( +50%Ar)。然而高声强也造成了较多的能量消耗。自由基清除剂的存在则较大地降低了超声反应速率, 200mmol/LCO2- 存在时反应速率下降了79%。     

超声降解水中的磺胺嘧啶

以磺胺嘧啶(SD)为研究对象,探讨了超声功率、初始浓度、pH值以及超声协同H2O2、Fenton、TiO2等组合工艺对超声降解SD效率的影响。实验结果表明,超声可有效降解水中低浓度的SD,尤其在酸性条件下,超声降解更为显著,降解过程遵循准二级反应动力学模型。加入H2O2或TiO2可在一定程度上促进SD的超声降解,加入Fenton试剂则显著提升SD的去除率。依据量化计算以及LC-MS测定结果,探讨了SD的超声降解机理。超声降解水中SD主要是基于.OH自由基的氧化过程。     

超声辅助电催化氧化降解苯酚的研究

对电催化氧化和超声辅助电催化氧化降解苯酚过程中的UV扫描吸收光谱研究表明:在苯酚的氧化降解反应过程中,都有对紫外光有吸收的中间体生成;对吸光度峰值随降解反应时间的变化关系进行非线性最小二乘法拟合(NLSF),发现溶液的相对吸光度峰值的衰减均符合表观零级反应动力学规律,其相应的表观反应速率常数(k0)分别为(0.0051±0.0005)min-1和(0.0052±0.0003)min-1;但超声波对电催化降解苯酚的速度和效果并无显著影响.同时GC-MS也检测到苯酚超声辅助电催化氧化降解60 min后,发现除苯酚仍然存在外,还有中间产物苯酚乙酸酯、甲酸、乙酸,从而证实苯酚在羟基自由基作用下,开环氧化降解生成乙酸和甲酸等小分子有机物,最后降解为二氧化碳和水.     

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.     

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.     

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.     

土壤中砷的化学平衡

本文比较详细地综述了砷的化学特性,环境背景值及来源和循环,土壤中砷的三大化学平衡即沉淀溶解平衡,氧化还原平衡,吸附解吸平衡,以及微生物对砷的转化。     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 μ g g^{? 1} dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 μ g g^{? 1} and 150 μ g g^{? 1} dry weight, respectively. Aluminum concentrations were (in μ g g^{? 1} dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 μ g g^{? 1}) and aluminum (> 360 μ g g^{? 1}), while leaves had less than 200 μ g g^{? 1} of iron and 165 μ g g^{? 1} of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 μ g g^{? 1}), Zn (50 μ g g^{? 1}) and Cu (3.6 μ g g^{? 1}). Some presence of lead in leaves (2.0 μ g g^{? 1}) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.