紫外光促进盐酸聚苯胺催化H_2O_2氧化处理罗丹明B废水

以苯胺和过硫酸铵为主要原料合成了盐酸聚苯胺（HClPANI）催化剂,并通过FTIR、XRD、SEM和EDS对催化剂进行了表征。研究了在紫外光照下、HClPANI催化H2O2氧化处理罗丹明B染料废水工艺参数,探讨了各种因素对废水脱色效果的影响,并对催化氧化机理进行了初步探讨。结果表明,催化剂HClPANI对催化H2O2氧化处理罗丹明B具有较好的催化活性、稳定性和重复使用性能。UV-H2O2-HClPANI体系产生了明显的协同效应,在pH=3、200 mg/L的罗丹明B废水中,30%H2O2用量为1.2 mL/L、HClPANI用量1 g/L、反应温度25℃、紫外灯功率500 W、光照70 min,罗丹明B脱色率达到了98.2%。     

Cu-SBA-15催化湿式过氧化氢氧化水溶液中罗丹明B

采用水热晶化法合成了不同含铜量的Cu-SBA-15介孔分子筛,并且用XRD、N2吸附、TEM以及UV-vis对所合成的样品进行表征。以Cu-SBA-15为催化剂,H2O2为氧化剂,催化湿式过氧化水溶液中的罗丹明B,主要考察H2O2浓度、催化剂用量、处理温度、初始pH等因素对罗丹明B氧化效果的影响。结果表明,在同样的处理条件下罗丹明的脱色率明显高于TOC去除率,处理温度、初始pH对罗丹明B的脱色与氧化有重要影响。在罗丹明B初始浓度100 mg/L,H2O2初始浓度1.8 g/L,催化剂量0.3 g/L,温度60℃,pH为7.0,处理时间100 min时,罗丹明B的脱色率为98.6%,TOC去除率为62.8%。     

Cu-SBA-15催化湿式过氧化氢氧化水溶液中罗丹明B

采用水热晶化法合成了不同含铜量的Cu—SBA-15介孔分子筛，并且用XRD、N2吸附、TEM以及uV—vis对所合成的样品进行表征。以Cu—SBA-15为催化剂，H2O2为氧化剂，催化湿式过氧化水溶液中的罗丹明B，主要考察H2O2浓度、催化剂用量、处理温度、初始pH等因素对罗丹明B氧化效果的影响。结果表明，在同样的处理条件下罗丹明的脱色率明显高于TOC去除率，处理温度、初始pH对罗丹明B的脱色与氧化有重要影响。在罗丹明B初始浓度100mg／L，H2O2初始浓度1．8g／L，催化剂量0．3g／L，温度60℃，pH为7．0，处理时间100min时，罗丹明B的脱色率为98．6％，TOC去除率为62．8％。     

H2O2处理酸性大红GR染料废水的研究

通过对废水pH值、H2O2用量、催化剂用量、反应时间、反应温度等工艺条件的考察,确定了H2O2催化氧化处理酸性大红染料废水的最佳工艺条件pH 4、H2O2用量6 mL/L、催化剂用量3 g/L、反应时间100 min、反应温度70℃.在该条件下,COD和色度的去除率分别为76.7%和99.4%;通过反应前后的紫外-可见光光谱分析表明,H2O2催化氧化处理酸性大红GR染料废水有比较好的效果,为该工艺处理酸性大红GR染料废水提供了科学依据.     

粉煤灰负载铁离子催化氧化活性黄染料废水

以粉煤灰为载体,制备铁/粉煤灰负载型催化剂,并利用该催化剂催化H2O2氧化降解活性黄染料废水,探讨了H2O2投加量、催化剂投加量、染料初始浓度和初始pH值等因素对染料废水COD去除率和脱色率的影响。结果表明,当染料废水COD初始浓度为200 mg/L,初始pH值为1.7,投加0.5 g/100 mL催化剂及加入1.0 mL浓度为1.13 mol/L的H2O2溶液时,处理效果最好,此时染料废水的COD去除率和脱色率分别达到63%和99%,并且废水的可生化性得到很大的提高。利用该负载催化剂能够有效地减少活性黄染料废水中Fe3+的残留量。     

膨胀珍珠岩负载TiO2光催化脱色性能的研究

以钛酸四丁酯为原料,膨胀珍珠岩为载体,用溶胶-凝胶法制备可漂浮于水面的负载型TiO2.利用该负载型TiO2对罗丹明B(RB)进行光催化脱色实验,结果表明,浸渍3次的负载型TiO2光催化活性最高,催化剂最佳用量为500mg/100mL RB,经5 h光照,对100mL浓度为1 mg/L和2.5 mg/L RB脱色率分别为76.67%和47.27%;该催化剂使用寿命长,25h后催化剂脱色性能没有减弱,可重复使用;经8 h光照,染料废水脱色效果好.     

H2O2处理酸性大红GR染料废水的研究

通过对废水pH值、H2O2用量、催化剂用量、反应时间、反应温度等工艺条件的考察，确定了H2O2催化氧化处理酸性大红染料废水的最佳工艺条件：pH4、H2O2用量6mL／L、催化剂用量3g／L、反应时间100min、反应温度70℃。在该条件下，c0D和色度的去除率分别为76．7％和99．4％；通过反应前后的紫外一可见光光谱分析表明，H2O2催化氧化处理酸性大红GR染料废水有比较好的效果，为该工艺处理酸性大红GR染料废水提供了科学依据。     

负载铁分子筛催化H2O2对活性艳蓝的脱色

以13X分子筛为载体制备负载铁催化剂,比较了经稀硫酸和氢氧化钠2种不同预处理液处理后催化剂的催化效果。利用制备的负载铁分子筛催化剂协同H2O2对活性艳蓝进行脱色研究,得出当pH=2.03,Ⅱ型催化剂投加量为4.0 g/L,过氧化氢投加量为1.1 g/L,反应时间为4 h时,脱色率最佳可达92%。     

微波催化反应中Fe2O3/γ-Al2O3的制备及催化性能研究

以γ-Al2O3为载体,通过等体积浸渍法制备一种载铁催化剂。以微波非均相Fenton反应对甲基橙的脱色效果作为判断催化剂活性的依据,分别考察浸渍液(Fe(NO3)3.9H2O溶液)浓度、焙烧温度、焙烧升温速率、焙烧时间对催化性能的影响,并对复杂协同体系中的反应机制进行初步探讨。结果表明,在浸渍液浓度为8%(质量分数)、焙烧温度为300℃、焙烧升温速率为10℃/min、焙烧时间为2h时催化剂Fe2O3/γ-Al2O3活性最优;复杂协同体系作用机制表现为微波非热效应降低甲基橙分子化学键强度,热效应促使催化剂表面产生"热点",3者(微波、H2O2、催化剂)协同强化催化氧化反应。然而,在微波催化过程中,催化剂孔道坍塌可能影响催化剂活性。     

超声辐射浸渍法制备Fe-Ni-Mn/Al2O3催化剂及性能研究

以Al2O3为载体,分别采用超声辐射浸渍法和普通浸渍方法制备Fe-Ni-Mn/Al2O3催化剂。采用BET、XRD和SEM对催化剂的理化性质和孔结构进行了分析,以模拟酸性绿B废水为研究对象考察催化剂的催化性能。实验结果表明,浸渍溶液pH值和焙烧温度显著影响催化剂的性能。与普通浸渍法相比,超声浸渍法制备的Fe-Ni-Mn/Al2O3催化剂对酸性绿B脱色反应表现出较高的催化活性。     

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.     

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.     

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 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.     

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.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

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

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on hematological parameters of the cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable hematological alterations were observed. The study on hematological parameters revealed a highly significant decrease (P < 0.01) in the total erythrocytes count in malathion-exposed animals from 24 hours to 96 hrs of exposure as compared to control. Significant decreases (P < 0.01) of hemoglobin and packed cell volume were also observed from 48 hrs to 240 hrs. A significant increase (P < 0.01) in leucocytes count was noted throughout the exposure period. Elevated numbers of lymphocytes and eosinophils as found in the present study revealed lymphocytosis as well as eosinophilia, suggesting that this was a result of direct stimulation of the immunological defense due to the presence of a toxic substance or may be associated with tissue damage. The cytomorphological and cytopathological study of erythrocytes and leucocytes in malathion-exposed frogs at 0.006 ppm concentration revealed various cytotoxic effects at different exposure times. It was noted that the size and the shape of the erythrocytes were subjected to variation in different blood disorders.