非均相UV/Fenton氧化法降解水中六氯苯的研究

采用超声辐照促进浸渍法制备了非均相UV/Fenton催化剂Fe/Al2O3,并对其进行了表征.以制备的催化剂对水中六氯苯进行非均相UV/Fenton法氧化降解.考察了铁的负载量、初始pH、H2O2投加量、催化剂投加量和反应时间对六氯苯降解效果的影响,并探讨了六氯苯的降解动力学规律.结果表明,制备的催化剂表面活性组分分散均匀,对六氯苯具有较高的催化活性和重复利用性.非均相UV/Fenton法降解六氯苯的最佳实验条件为:铁的负载量为2%,废水初始pH为3,H2O2和Fe/Al2O3催化剂的投加量分别为34 mg/L和150 mg/L,反应时间为20 min.在此条件下,浓度为500μg/L的六氯苯降解效率达94.5%.HCB的降解反应动力学规律可用Langmuir-Hinshwood方程很好地描述.六氯苯在催化剂表面的吸附常数为1.962 L/mg,表面反应速率常数为0.08 mg/(L·min).     

超声波/Fenton工艺降解微量邻苯二甲酸二甲酯和壬基酚效能的研究

研究了在超声波、Fenton不同体系中邻苯二甲酸二甲酯(DMP)和壬基酚(NP)的降解效果.通过正交实验得到超声波/Fenton工艺各个因素影响程度的大小为:H2O2投加量＞初始pH＞反应时间＞Fe2+投加量＞超声功率.最后得到降解250mL质量浓度为100 μg/L的DMP的最佳条件:H2 O2投加量为2 mmol/L、Fe2+投加量为0.40 mmol/L、初始pH为3.00、超声功率为1 800W、反应时间为120 min,降解率可达到85.96％;降解250mL质量浓度为100 μg/L的NP的最佳条件:H2O2投加量为4mmol/L、Fe2+投加量为0.50 mmol/L、初始pH为3.00、超声功率为1 800W、反应时间为120 min,降解率可达到78.70％.     

Fenton试剂氧化处理火炸药污染土壤淋洗液

采用Fenton试剂对火炸药污染土壤淋洗液进行氧化处理,研究了Fe SO4·7H2O投加量、H2O2投加量、初始pH、反应时间及温度对处理效果的影响,采用发光细菌发评价处理前后水样的急性毒性变化。结果表明,Fenton试剂氧化可有效去除火炸药污染土壤淋洗液的COD,当Fe SO4·7H2O投加量为8.0 g/L,H2O2投加量为64 m L/L,初始pH为3,反应时间120 min及反应温度30℃时,污染土壤淋洗液的COD由4 553.9 mg/L降至800.1 mg/L,COD去除率82.4%,COD的降解符合二级动力学模型。经Fenton氧化处理后,水样的急性毒性降低94.7%,B/C由0.007升至0.22,可生化性得到明显改善。     

Fenton氧化法对磺胺类抗生素的降解动力学

采用Fenton氧化法同时降解水溶液中磺胺吡啶(SPY)、磺胺二甲基嘧啶(SMZ)和磺胺甲噁唑(SMX)。系统考查了初始H2O2浓度、Fe2+浓度、pH对3种磺胺类抗生素降解性能的影响。结果表明,3种磺胺抗生素被完全降解的最佳Fenton氧化条件是:H2O2浓度为2.0 mmol/L,Fe2+浓度为0.10 mmol/L,pH为3.0~3.5,反应时间为20 min。Fenton试剂对3种磺胺类抗生素的降解符合一级反应动力学,速度常数为0.0318~0.2002 min-1。     

Fenton氧化法深度处理甲醛废水

采用Fenton氧化法深度处理经生化降解后的甲醛废水,结果表明,Fenton氧化法深度处理甲醛废水是可行的,在合适的反应条件下,降解初始COD为150 mg/L左右的甲醛废水,COD去除率达30%以上;Fe2+与H2O2的投加比例、投加量及投加方式、反应温度、pH、反应时间对处理效果都有不同程度的影响。     

零价铁与双氧水异相Fenton降解活性艳橙X-GN

采用Fe0与H2O2构成异相Fenton体系降解偶氮染料活性艳橙X-GN,考察了初始pH、H2O2和Fe0投加量、温度等对反应过程的影响。实验结果表明,在初始pH值为3.0、Fe0投加量为0.8 g/L、H2O2投加量为5 mmol/L和反应温度30℃的条件下,反应60 min后活性艳橙降解率达到96.2%。Fe0与H2O2投加量都存在一个最佳范围,当Fe0与H2O2浓度大于0.8 g/L和5 mmol/L时,羟基自由基会通过其他方式消耗,致使活性艳橙降解率下降。酸性条件和提高温度均有利于反应的进行。反应符合准一级动力学,表观反应速率常数k为0.064 min-1(30℃),反应活化能为80.62 kJ/mol。UV-Vis光谱扫描表明,反应过程中活性艳橙的发色基团及苯环结构均被破坏。     

Fenton法氧化处理水中土霉素的研究

为了评价Fenton法预处理抗生素生产废水中残留的高浓度土霉素的可行性,对Fenton试剂(Fe2 -H2O2)法催化氧化降解水溶液中的土霉素进行了研究.探讨了H2O2与Fe2 投加比例、投加量以及起始pH值对降解效果的影响,同时考察了土霉素废水中大量共存的草酸根离子对氧化过程的影响.结果表明,当H2O2与Fe2 按照5:1的比例投加时降解效率最高,最佳初始pH值在3.0-4.0之间.在最佳投加比例下,H2O2投加量为0.9 mmol/L,100 mg/L的土霉素可在10 min内得到完全降解.最佳反应条件下经过处理后土霉素水溶液TOC的去除率达40%左右,可生化性(BOD5/COD)也得到明显的改善.水中共存的草酸根离子对氧化效率具有明显的影响,但通过增加亚铁离子的量可以消除草酸的影响.     

Fenton氧化法深度处理抗生素废水二级出水

采用Fenton氧化法对青霉素和土霉素混合废水二级处理出水进行深度处理,通过正交和单因素实验研究了废水初始反应pH值、H2O2投加量、Fe2+/H2O2摩尔比及反应时间等因素对废水处理效果的影响。实验结果表明,Fenton氧化法处理的最佳反应条件为:初始pH值4、H2O2(30%)投加量50 mL/L、Fe2+/H2O2摩尔比1/20和反应时间60 min,处理后出水COD小于120 mg/L,COD去除率在75%以上,急性毒性(HgCl2毒性当量)小于0.07 mg/L,满足《发酵类制药工业水污染物排放标准》(GB21903-2008)表2标准要求。     

赤泥协同Fenton法处理焦化废水的研究

采用赤泥吸附协同Fenton法处理焦化废水,两者协同处理对COD的去除率高于其单独处理之和.考察了赤泥投加量、初始pH值、反应温度、H2O2浓度和Fe2+浓度等因素对降解效果的影响,实验结果表明,在20 g/L的赤泥、初始pH=3、80 mmol/L的H2O2、224 mg/L的Fe2+的最佳条件下,经过120 min...     

Fenton法处理石化废水混凝泥及其剩余液的氧化回用研究

运用Fenton法氧化石化废水混凝泥,考察了体系pH、H2O2投加量、H2O2与Fe2+的摩尔比(简称H2O2/Fe2+)、反应时间等因素对氧化效果的影响,并将氧化后的剩余液回用作混凝剂,用于石化废水的混凝,考察了其连续多次氧化回用后的混凝效果.结果表明.混凝泥的最佳Fenton法氧化条件;pH为3,H2O2投加量为0...     

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.