电晕放电等离子体对水中邻苯二甲酸二甲酯的降解

采用电晕放电等离子体降解水中的邻苯二甲酸二甲酯,研究了放电输出功率、溶液初始浓度、空气流量、初始p H、Fe2+和羟基自由基清除剂对邻苯二甲酸二甲酯去除效率的影响,并对其降解动力学进行了初步模拟。结果表明,电晕放电等离子体对水中邻苯二甲酸二甲酯有较好的去除效果。在放电功率45 W、初始浓度50 mg·L~(-1)、空气流速2 L·h-1、初始p H 6.31、初始电导率4.05μS·cm-1的条件下,反应30 min,邻苯二甲酸二甲酯的去除率可达到95%。酸性条件下有利于邻苯二甲酸二甲酯的降解。添加Fe2+,在反应初期可显著提高邻苯二甲酸二甲酯的降解率。羟基自由基清除剂的加入在一定程度上抑制了邻苯二甲酸二甲酯的降解。电晕放电等离子体降解邻苯二甲酸二甲酯的过程基本符合一级反应动力学。     

水体中酮硝基麝香的臭氧氧化降解研究

采用臭氧氧化水体中的酮硝基麝香,考察pH、H2O2等因素对降解程度的影响,结果表明提高初始pH能加快酮硝基麝香的氧化降解,当pH为12时,反应时间1 h,酮硝基麝香几乎完全去除,浓度为2 mol/L和5 mol/L的H2O2存在有利于O3分解生成·OH自由基,使得酮硝基麝香的氧化降解速率加快,当H2O2浓度超过5 mol/L,H2O2会成为·OH的清除剂,降低·OH利用率;无论O3单独作用和O3/H2O2协同作用,酮硝基麝香降解符合准一级动力学规律;酮硝基麝香氧化降解产物包括甲酸、二乙酸和硝酸根等,其中硝基从苯环上脱落降低了硝基麝香对环境的风险.     

旋转盘反应器光催化降解苯酚废水动力学

采用旋转盘反应器(SDR)降解苯酚废水,对苯酚初始浓度、溶液p H值、H2O2的添加对其光催化降解动力学的影响进行了研究。结果表明,SDR内的光催化降解动力学特征符合一级反应动力学规律。苯酚初始浓度越低,反应速率常数k值越大;溶液p H=2时的降解速率高于其他p H值;H2O2的协同作用使苯酚的降解速率明显提高,其速率常数k值为未添加H2O2时的78倍。     

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。     

光电芬顿矿化草甘膦有机废水

以有机磷农药-草甘膦为目标污染物,利用光电芬顿方法对其进行降解研究。研究汇总考察了电流强度、初始p H、Fe2+浓度、草甘膦初始浓度、光种类及通入背景气体种类对草甘膦降解效果的影响。实验结果表明:电流强度越大,草甘膦初始浓度越低,草甘膦降解效果越好;草甘膦在p H=2.0~3.0的酸性体系中降解效果最好;Fe2+浓度升高,草甘膦降解效果增强。在电流为0.36 A、初始p H=3.0、Fe2+浓度为1.0 mmol·L~(-1)、通入100 m L·min-1O2条件下,以365 nm紫外光照射的光电芬顿反应降解初始浓度为84.5 mg·L~(-1)的草甘膦溶液,处理360 min后溶液矿化率可达64.5%。     

磁性Fe_3O_4/石墨烯纳米复合材料催化降解水中17β-雌二醇

利用化学沉淀法制备磁性四氧化三铁/石墨烯(Fe3O4/GE)纳米复合材料,并将其与H2O2构成非均相Fenton体系用于催化降解水中微量的17β-雌二醇(E2),研究了初始p H值,初始H2O2浓度,催化剂用量对E2降解的影响。结果表明,Fe3O4/GE纳米复合材料在无需外加光源的条件下能够有效催化降解E2。在p H 7.0,E2初始浓度为1 mg/L,初始H2O2浓度为15 mmol/L,Fe3O4/GE投加量为15 mg/L的条件下,反应8 h后可去除92.9%的E2。Fe3O4/GE具有便捷的磁分离特性和稳定的催化活性,经过7次循环使用后对E2的降解效率仍保持在91.5%左右。     

纳米二氧化钛光催化氧化油田采出水中萘和芴的影响因素分析

利用纳米二氧化钛光催化氧化技术,分析了不同影响因素UV波长(UVA 365 nm、UVB 308 nm和UVC 254nm)、温度、p H、催化剂(Ti O2)、抑制剂(Bu OH)和氧化剂(O2、H2O2和O3)对油田采出水中多环芳烃萘和芴降解效率的影响,并进一步优化出单因子的最佳条件。实验结果表明,各因素对萘和芴降解有不同的影响,但其效果都随波长减小和酸度降低而得到增强。当其他条件为一致最优时(T=90℃,Ti O2=0.5 g/L和Bu OH=0.03 mol),当H2O2=0.01 mol或O2=30 m L/min时,萘的降解率最高,而当H2O2=0.1 mol或O3=30 m L/min对芴的降解效果最好。     

铜氰溶液的电子束辐照降解

研究了铜氰溶液中总氰初始浓度、pH、铜浓度等对总氰降解效率的影响,比较了KCN溶液和铜氰溶液的总氰降解率,初步推断了铜氰溶液在辐照过程中的降解机制.实验结果表明,在同样的辐照剂量下,随着总氰初始浓度的增加,总氰降解率降低,相应的总氰降解G值增大;铜浓度越低,总氰降解率越高;pH越小的铜氰溶液总氰降解率越高.电子束辐照KCN溶液和铜氰溶液的总氰降解反应属于表观一级反应.在相同的辐照剂量下,KCN溶液的总氰降解率比铜氰溶液要高得多.铜氰溶液的电子束辐照降解过程非常复杂,主要是铜氰络合离子逐步离解出的CN-与·OH的反应.     

电解液条件对苯酚降解及羟自由基生成的影响

以钛基Pb O2电极为活性阳极,通过电化学氧化法降解处理苯酚模拟废水,系统考察了羟自由基(·OH)抑制剂、支持电解质、酸碱性等电解液条件对苯酚水溶液COD去除率的影响。同时,以水杨酸(SA)为·OH捕捉剂,通过高效液相色谱分析技术对不同电解液条件下·OH的生成量进行间接检测。结果发现,Pb O2电极上苯酚水溶液的COD去除符合一级反应动力学规律,其表观反应速率常数在分别加入·OH抑制剂Na HCO3、Na2CO3和叔丁醇时显著下降,表明苯酚的电化学氧化降解遵循·OH反应机理;支持电解质对电解液体系中·OH生成量的影响不明显,主要通过在阳极氧化生成的氧化剂参与苯酚的降解,以Na Cl为支持电解质时降解效率最高,其次是Na2SO4,最后为Na NO3;随电解液p H值的增加,苯酚水溶液的COD去除速率不断提高,而·OH的生成量在碱性条件下亦显著增加。     

沸石负载Cu_2O光催化剂降解甲基橙

采用化学沉积法,以Cu SO4·5H2O和Na2SO3为原料,以人造沸石为载体,在HAC-Na AC缓冲溶液中制备了沸石-Cu2O复合型光催化剂。在仿日光光源照射下,分别从降解时间、甲基橙初始浓度及初始p H、降解温度等不同方面考察了对复合光催化剂降解甲基橙的影响。结果表明,当甲基橙初始浓度为25 mg/L、初始p H在7.00~10.00之间,降解温度为40℃,复合型光催化剂对甲基橙的降解效果最好;样品重复性使用实验表明,沸石-Cu2O复合光催化剂在可见光区具有良好的光催化活性和稳定性;离子干扰实验证明,Cl-浓度控制在1.2 g/L之内时对甲基橙降解效果影响较小。     

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.     

A History of Dry Cleaners and Sources of Solvent Releases from Dry Cleaning Equipment

Approximately 25, 000-35, 000 dry cleaning facilities currently operate in the U.S. The release of perchloroethylene and other solvents from these establishments represents a major source of soil and groundwater contamination. The manner in which dry cleaning solvents escape from dry cleaning plants is, for all practical purposes, identical for chlorinated and petroleum hydrocarbon solvents and is related to one of the following events: the catastrophic failure of a component of the dry cleaning system, the improper installation, operation or maintenance of the dry cleaning equipment or a combination of all of these causes. Acceptable customs, codes and regulations can also dictate what is authorized for operation of a dry cleaning facility in a particular community, geographic area during a particular time frame. Environmental litigation dealing with the origin of a solvent release from dry cleaners tends to focus on the design and manufacture of dry cleaning industry machines such as washers, washer extractors, tumblers, solvent filters, water separators, stills and spotting boards. A thorough analysis of the daily operations of dry cleaners often reveals that poor maintenance, failure to follow the manufacturer's instructions and the actions of the operator are the most likely causes of soil and groundwater pollution. In order to forensically evaluate the most probable origins of a solvent release and to examine issues regarding liability, a thorough understanding of the history of dry cleaning and a detailed analysis of the operation and maintenance of the dry cleaning equipment are necessary. The discovery of solvent plumes in the vicinity of dry cleaning plants may suggest that the solvent source is the dry cleaning plant; however, the presence of these plumes does not necessarily indicate that the dry cleaning equipment was defectively designed or manufactured. A thorough review of the type of equipment used over the life of the dry cleaning plant and verifiable solvent mileage records frequently indicates that operators of the plant have disposed of solvent and contaminated solids into the municipal sewer or on ground surfaces.     

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.     

Malathion-induced sublethal toxicity on the intestine of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on intestinal parameters of cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable histopathological alterations were observed. The study on intestinal parameters revealed acute pathological conditions in the intestinal wall. The toxic effect became evident as the cytoplasm of the cells disintegrated and the cells became empty and vacuolated. The cell membranes were also ruptured. Degenerative changes of the absorptive surface (villi) of the intestine in the different periods of exposure were pronounced. Severe atrophic nature (necrotic mucosa) of the intestine began from 48 hrs onwards to 96 hrs of exposure.     

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.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.