高铁酸钠电化学合成条件的研究

利用含铁材料为阳极，铜为阴极，NaOH溶液为电解液，于隔膜电解槽中电解制备高铁酸钠。探索了该工艺所必需的各种参数和反应条件，确定了隔膜材料，并对Na2FeO4浓度和电流效率的非一致性变化作出了解释。研究结果表明：在阳极距离为1．3cm（极距2．3cm）、阳极电解液浓度为14mol／L，阴极电解液浓度为4mol／L、温度为35℃、电压为8～9V时，电解2h后得到的Na2FeO4浓度为18．7g／L，电流效率为20％。     

PTFE/C三相电极氧阴极还原法生产过氧化氢

设计了隔膜体系电解槽,制作了聚四氟乙烯(PTFE)/碳黑三相气体扩散电极,系统研究了隔膜、电流密度、电极间距、初始溶液酸度、电解质、空气量和时间等因素对过氧化氢累积产生浓度和电流效率的影响。结果表明,在有隔膜体系,电流密度为70 m A/cm2,电极间距为1 cm,初始p H=0.5,电解质为0.10 mol/L Na2SO4溶液,空气量为40 m L/min的条件下,电解时间1 h时过氧化氢累积浓度最高可至20 096.05 mg/L,此时对应的电流效率为63.37%。在确定的最佳条件下,进行电解液循环实验,1 h时电流效率升高到98.4%,12 h之后,过氧化氢累积浓度为46 042.43 mg/L。实验原位产生的高浓度酸性过氧化氢溶液可以直接应用于Fenton试剂。     

隔膜电解法回收利用电厂锅炉EDTA清洗废水研究

以涂Ir/Sn钛网板作阳极,以不锈钢网板作阴极,采用隔膜电解法处理电厂锅炉EDTA清洗废水.实验结果表明,电流、阴极电解液初始pH值和Fe/EDTA摩尔比对粉末铁析出速率影响较大,粉末铁电解析出的适宜条件是电解电流为1.0 A、阴极电解液初始pH值为5.6、阴极电解液Fe/EDTA摩尔比足够高.采用隔膜电解结合反渗透膜系统处理电厂锅炉EDTA清洗废水,可同时高效回收纳米级粉末铁和EDTA.     

电-Fenton法处理4-氯酚废水

采用电解法对 4 氯酚废水进行了处理。以活性炭纤维 (ACF)为阴极 ,铁为阳极 ,并向阴极不断通入空气 ,电解过程中生成的H2 O2 与阳极溶解的Fe2 + 形成Fenton(芬顿 )试剂 ,Fenton试剂在电解的过程中可以产生大量活性羟基·OH ,能够很好地氧化降解废水中的 4 氯酚。在最佳试验条件下 :室温 ,氯酚浓度为 5 0mg/L ,电解时间为 6 0min ,pH值为4 5 ,电流密度为 15 38A/m2 ,Na2 SO4浓度为 3g/L时 ,4 氯酚去除率为 85 70 %。     

铁阳极电化学对直接大红4BE模拟废水脱色

对铁阳极电化学处理直接大红4BE染料废水脱色率和脱色能耗的影响因素进行研究。考察了电流密度、染料溶液初始pH值、染料初始浓度和支持电解质Na2SO4浓度对脱色性能的影响。结果表明,电流密度、染料废水初始pH、染料初始浓度、支持电解质浓度对脱色率和脱色能耗产生较大影响。在电流密度1.667 mA/cm2、pH值6.54、染料浓度50mg/L、Na2SO4浓度0.01 mol/L、温度20℃、搅拌速度600 r/min、电解时间60 min条件下,脱色率达到92.1%,脱色能耗1.298 kWh/kg染料、铁阳极消耗量41 mg/400 mL染料模拟废水。     

隔膜槽中ACF电极成对电解脱色活性艳蓝KN-R

同时以活性炭纤维(ACF)为阳极和阴极,在隔膜电解槽中研究了不同电流密度下蒽醌染料活性艳蓝KN-R的电化学脱色.考察了ACF阳极和ACF阴极各自对染料的脱色性能.结果表明,当电流密度为1.0～1.5 mA/cm2时,电解槽中发生阳极电氧化和阴极电还原同时进行的成对电解脱色.在ACF电极上,活性艳蓝KN-R的电氧化脱色比电还原脱色容易进行,1.0 mA/cm2时,阴阳两极室脱色率分别为69%和93%,而1.5 mA/cm2时,阳极室脱色率保持在93%,阴极室脱色率达到79%.     

电解絮凝法处理老龄垃圾渗滤液的实验研究

为考察简便低耗的电解材料处理效果,采用铸铁阳极电解絮凝法对老龄垃圾渗滤液进行了处理,通过正交实验和单因素实验考察了电解液浓度、电流密度、pH、极板间距对处理效果的影响.结果表明,电解絮凝法对该老龄垃圾渗滤液有较好的处理效果,当电流密度为50 mA/cm2、pH值为9、极板间距为2 cm、电解75 min后,COD和NH...     

电化学氧化法去除超高盐榨菜废水中的氨氮

采用电化学氧化法去除超高盐榨菜废水中的氨氮,阳极为Ti/RuO2-TiO2-IrO2-SnO2网状电极,阴极为网状钛电极,考察了电流密度、电解时间、极板间距、初始pH以及极水比对氨氮去除率的影响,并分析了电流密度对氨氮能耗和阳极效率的影响。结果表明,在初始氨氮浓度为472.73 mg/L,电流密度为156 mA/cm2,极板间距为1.5 cm,极水比为0.8dm2/L,原水pH为4.3～5.0时,电解30 min和60 min时氨氮的去除率分别为89.75%和99.94%,电解30 min时,氨氮能耗最低为96 kWh/kg,阳极效率最高为8.47 g/(h.m2.A)。     

电-Fenton法处理4-氯酚废水

采用电解法对4-氯酚废水进行了处理。以活性炭纤维(ACF)为阴极，铁为阳极，并向阴极不断通入空气，电解过程中生成的H2O2与阳极溶解的Fe^2 形成Fenton(芬顿)试剂，Fenton试剂在电解的过程中可以产生大量活性羟基 OH，能够很好地氧化降解废水中的4-氯酚。在最佳试验条件下：室温，氯酚浓度为50mg／L，电解时间为60min，pH值为4．5，电流密度为15．38A／m^2，Na2SO4浓度为3g／L时，4-氯酚去除率为85．70％。     

2-乙基蒽醌修饰石墨毡催化电极电化学降解土霉素废水二级出水

采用自制的2-乙基蒽醌修饰石墨毡阴极,通过SEM、X射线衍射、循环伏安扫描曲线(CV)等方法对其微观形态和催化活性进行表征,并进行电化学降解土霉素废水二级出水实验研究。结果表明,2-乙基蒽醌修饰石墨毡阴极是良好的空气扩散电极,2-乙基蒽醌晶体的存在使石墨毡具有更高的电催化活性;当以钛涂钌铱DSA电极为阳极、2-乙基蒽醌修饰石墨毡为阴极,在电流密度0.06 A/cm2、极板间距4 cm、电解质浓度0.2 mol/L和不调节废水初始pH的条件下,电解60min,土霉素废水二级出水COD可由258.7~269.2 mg/L降低至105.0~118.6 mg/L,出水水质满足《化学合成类制药工业水污染物排放标准》(GB21904-2008)要求,COD降解动力学符合一级动力学方程。     

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.