油泥废弃物的生物修复技术研究

本文利用正交试验，探讨了堆腐法处理油泥废弃物过程中调控因子（肥料，客土，水分和pH值）的影响，结果发现，投加一定量的客土是影响处理效果的重要因子，通过正交试验选择和确定的最佳处理条件为：在自然温度＞20℃的情况下，客土投加量20％，肥料10％，菌剂5％，控制水分30％（烘干基）和pH7。优化条件的建立为油泥废弃物的深度处理提供了理论依据。     

热化学清洗法洗涤油泥-回收石油的工艺条件研究

以辽河油田落地油泥为样品,采用热化学清洗法洗涤油泥,净化土壤,回收石油,并获取工程所需的必要参数.通过筛选、复配,确定十二烷基苯磺酸钠(LAS):NazSiO3=1:2(质量比)为最佳清洗剂配比.考察了清洗温度、清洗液pH、液固比(即清洗剂与落地油泥的质量比)和清洗剂投加量等因素对清洗效率的影响,通过正交实验优化工艺参数,实验表明,当清洗时间为30min、清洗温度为75℃、搅拌器转速为200 r/min、液固比为8:1、清洗液pH为11、LAS Na2SiO3投加量为2.8 g/L时,含油率为21.2%(质量分数)的落地油泥样品经一级清洗,油泥残油率降为0.8%(质量分数,下同);经二级清洗,油泥残油率降为0.3%.清洗后,石油浮于水面,无明显乳化,易于分离.     

零价铁Fenton技术处理含聚乙烯醇的印染退浆废水

采用零价铁Fenton技术处理含聚乙烯醇(PVA)的印染退浆废水。通过单因素实验和正交实验,考察了初始pH、H2O2投加量、铁屑粒径及投加量和反应时间对实验结果的影响。结果表明,初始pH和H2O2投加量对处理效果影响很大。最佳反应条件是初始pH=4.0,H2O2投加量为100mmol/L,铁屑(粒径为1~3mm)投加量为15g/L,反应时间为30min。在该条件下,出水PVA质量浓度为0.9mg/L,PVA去除率为99.9%,COD去除率为23.6%,BOD5/COD由0.12升高至0.34,可生化性明显提高。无论从处理效果考虑还是从成本考虑,零价铁Fenton技术都优于传统Fenton技术。     

锰矿尾渣改性壳聚糖对Pb~(2+)的吸附

将工业废弃物锰矿尾渣与壳聚糖混合制得一种高效吸附剂,并应用扫描电镜、X射线衍射对其结构进行了表征.采用正交表设计试验,分别考察了 pH值、吸附时间、温度、复合吸附剂的投加量等4个影响因素对Pb2+吸附的影响,最伟吸附条件为:pH值为7,吸附时间为40 min,温度为20℃,复合吸附剂的投加量为0.10 g.处理后的水符合国家污水综合排放标准(GB8978-1996)中的一级标准.复合吸附剂时Pb2+的吸附符合Langmuir和Freundlich吸附等温方程.     

Fe~0/GAC-Fenton异相耦合深度处理焦化废水

采用由Fe0/GAC和H_2O_2构建的微电解与Fenton异相耦合降解体系对焦化废水进行深度处理,通过单因素影响实验和正交优化实验,考察了H_2O_2投加量、进水pH、HRT和mFe0/mGAC对处理效果的影响并确定了最佳反应条件。结果表明:随着各工艺参数取值的增大,系统对有机物的去除效率呈先上升后下降或趋于稳定的趋势;各影响因素的主次顺序为:H_2O_2投加量进水pHHRTmFe0/mGAC,H_2O_2投加量和进水pH为显著性影响因素;当H_2O_2投加量为1.2 m L·L~(-1),进水pH=3,HRT=90 min,mFe0/mGAC=3时,系统处理效果最佳,COD由306 mg·L~(-1)降至94 mg·L~(-1),去除率稳定达到69.2%,满足《炼焦化学工艺污染物排放标准》(GB 16171~(-2)012)对现有企业直接排放的要求。     

锰矿尾渣改性壳聚糖对Pb^2＋的吸附

将工业废弃物锰矿尾渣与壳聚糖混合制得一种高效吸附斛，并应用扫描电镜、X射线衍射对其结构进行了表征。采用正交表设计试验，分别考察了pH值、吸附时间、温度、复合吸附剂的投加量等4个影响因素对Pb^2＋吸附的影响，最佳吸附条件为：pH值为7，吸附时问为40mjn，温度为20℃，复合吸附剂的投加量为0．10g。处理后的水符合国家污水综合排放标准（GB8978．1996）中的一级标准。复合吸附剂对Pb^2＋的吸附符合Langmuir和Freundlich吸附等温方程。     

絮凝-Fenton试剂氧化处理印染废水

采用Fenton试剂对某染袜厂2种印染废水(印染红和印染蓝)进行处理。考察了硫酸亚铁投加量、双氧水投加量、反应时间及pH值对印染废水的色度及COD去除率的影响,通过正交实验确定了Fenton试剂处理该废水的最佳操作条件为:反应时间30 min、双氧水(30%)投加量4 mL/L、硫酸亚铁投加量300 mg/L、pH值为4左右。在最佳条件下,印染蓝废水经氧化处理后COD去除率大于80%,色度去除率95%以上;印染红废水需经絮凝预处理后再用Fenton试剂氧化处理,其脱色率达到了99.6%,COD去除率为91.2%,出水COD浓度为96 mg/L,可达标排放。     

鼓泡式UV-Fenton法处理二甲苯废气

采用UV-Fenton法在自制鼓泡反应装置中处理二甲苯废气,考察了pH值、H_2O_2投加量、Fe~(2+)浓度和气体停留时间等操作条件对二甲苯废气处理效果的影响,并分析了UV与Fenton技术的协同效应。研究表明,pH、停留时间(EBRT)、双氧水投加量及气液接触效率对二甲苯去除效果影响显著,少量批次投加双氧水可以显著提高其利用效率。UV-Fenton体系的最佳反应条件为:pH=3,H_2O_2每隔半小时投加一次且投加量为0.01%·次-1,Fe~(2+)浓度为40 mg·L~(-1),EBRT为55 s,紫外波长为254 nm。UV和Fenton在反应过程存在较强的协同效应,协同因子达到81%以上。     

微波-Fenton法处理EDTA-Cu-Ni废水的工况与效能

为了探索微波-Fenton反应体系中的反应机理,进行了正交实验、单因素影响实验和微波-Fenton与水热-Fenton的对比实验。通过正交实验,确定了微波-Fenton法处理络合态重金属废水的主要影响因子为Fe2+投加量、初始pH、H2O2投加量及反应温度,COD与Ni去除效率的影响因子的权重次序一致,而Cu去除的权重次序则与前两者不同;单因素优化实验结果表明,微波-Fenton法处理EDTA-Cu-Ni废水在反应时间为9 min时的最优条件为:Fe2+投加量为0.5 mmol/L,H2O2投加量为185 mmol/L,初始pH为2.5,反应温度为80℃;此时COD∶Fe2+∶H2O2为1∶0.06∶15(mg/L),各影响因子对有机物与金属离子的去除影响效应不同;微波水浴对比实验结果表明,在微波-Fenton体系中,微波主要起加热和提高反应速率的作用。     

发酵麸皮对酸性含铬废水中Cr(Ⅵ)的吸附与解吸研究

以发酵行业产生的发酵麸皮废弃物为生物吸附剂处理酸性含铬废水中的Cr(Ⅵ),研究了pH、吸附时间、Cr(Ⅵ)初始浓度、发酵麸皮投加量对Cr(Ⅵ)吸附效果的影响,确定发酵麸皮吸附去除Cr(Ⅵ)的适宜条件。分别以NaOH、HCl、NaCl为解吸剂处理吸附饱和的发酵麸皮,利用正交实验研究解吸剂种类、解吸时间、解吸剂浓度、发酵麸皮投加量等因素对Cr(Ⅵ)解吸效果的影响。结果表明,在强酸条件下发酵麸皮对Cr(Ⅵ)的吸附效果最好,发酵麸皮吸附Cr(Ⅵ)的适宜条件为pH=1,吸附时间90min,Cr(Ⅵ)初始质量浓度20mg/L,发酵麸皮投加量0.35g。发酵麸皮解吸Cr(Ⅵ)的正交实验结果表明,最佳解吸条件为以0.20mol/L NaOH为解吸剂,发酵麸皮投加量0.50g,解吸时间60min。各因素对Cr(Ⅵ)解吸效果的影响程度排序为解吸剂种类解吸时间解吸剂摩尔浓度发酵麸皮投加量。吸附饱和后的发酵麸皮可以通过解吸再生,但再生第4次已经失去了重复利用的价值。     

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.