Fe0/厌氧微生物联合体系处理2,4,6-三氯酚影响因素的研究

利用Fe0/厌氧微生物联合体系对2,4,6-三氯酚(2,4,6-TCP)进行降解研究.结果表明,Fe0/厌氧微生物联合体系可以有效降解2,4,6-TCP,Fe0与厌氧微生物之间存在明显的协同效应.Fe0/厌氧微生物联合体系处理2,4,6-TCP的最优条件为:微生物接种量0.434 g VSS/L,Fe0投加量15 g/L,体系初始pH值7.0～8.0.     

Fe0/厌氧微生物体系降解2,4,6-三氯酚特性研究

通过摇床间歇实验，研究了厌氧微生物与零价铁（Fe⁰）联合体系降解2,4,6-三氯酚（TCP）的特性，结果表明，在pH 7.5，35℃，150 r/min，Fe⁰ 10 g/L条件下，TCP初始浓度为30 mg/L时，TCP降解的拟一级反应速率常数为0.0207 h^-1，添加少量碳源可达到0.0390 h^-1，其降解速率是前者的1.88倍；添加碳源的体系在220 h内连续多次投加TCP降解率都达到80%以上，而不加碳源的体系在第2次投加TCP后降解率就只有30%左右；添加不同碳源，降解速率不同；添加2-溴乙烷磺酸钠（BESA）以及SO^2-₄、NO^-₃和S^2-对TCP降解有不同的抑制作用。     

天然沸石负载La2O3-ZnO-TiO2光催化降解活性艳红K-2BP

利用80目天然斜发沸石作载体制备La₂O₃(0.5%)-ZnO(20%)-TiO₂/沸石复合光催化剂，以20 W紫外灯为光源，在自制的光催化反应器中降解活性艳红K-2BP，考察了光照时间、空气通入量、催化剂用量、溶液初始浓度、H₂O₂与Fe³⁺投加量等对活性艳红K-2BP光催化降解率的影响。结果表明，当溶液初始浓度为60 mg/L，催化剂投加量为12 g/L，通气量为1 200 mL/min，光照2.5 h，活性艳红K-2BP的降解率可达99.2%；H₂O₂和Fe³⁺投加量为4 mL/L和3 g/L时，光照1 h活性艳红K-2BP降解率分别为100%和97.2%。紫外可见吸收光谱显示，LZTZ光催化剂可有效降解印染废水。     

超声强化Fe0去除阳离子红GTL的研究

采用US/Fe⁰系统去除阳离子红GTL，考察了pH值、Fe⁰用量、超声功率及活性炭、H₂O₂、盐分添加对阳离子红GTL去除率的影响，利用紫外-可见吸收光谱变化查明阳离子红GTL在不同条件下的去除差异性，利用SEM解析铁的形态与染料去除的相关性。结果表明： pH≥5.0时超声和Fe⁰具有协同效应，Fe⁰用量2 g/L，pH=7.0，超声功率135 W，阳离子红GTL去除率达到96.07%；一定量的活性炭、H₂O₂、盐分添加会加速染料去除，US加速Fe⁰反应速度，但不改变染料降解机理，添加活性炭能够彻底降解阳离子红GTL，添加H₂O₂提供的氧化环境抑制苯胺类化合物生成；铁的形态及与染料的接触是影响染料去除效果的重要原因。     

pH值对"Fe0-厌氧微生物"体系去除2,4,6-三氯酚过程的影响

考察了pH值对"Fe0-厌氧微生物"体系降解2,4,6,-三氯酚(2,4,6-TCP)效果的影响,结果表明:pH值是影响"Fe0-厌氧微生物"体系降解2,4,6-TCP效果的重要参数,初始pH值直接影响微生物活性和铁腐蚀,进而影响过程pH值变化,反过来又影响铁腐蚀和微生物活性,pH 7.0～9.0的中性偏碱范围较适于厌氧微生物生长。Fe0与微生物对目标污染物的降解具有协同促进作用,其协同促进机制表现在3方面:Fe0与微生物对体系过程pH值具有互补调节作用,可将体系的pH值调节值适于微生物生长的中性范围;Fe0腐蚀产生的Fe2+和H2可为微生物代谢提供电子对和营养物质,从而促进生物还原脱氯的进行;Fe0的腐蚀过程直接对氯代有机物还原脱氯,而微生物又可促进Fe0腐蚀。     

不同pH值条件下Fe3+、Cu2＋和Zn2＋对厨余垃圾两相厌氧消化水解酸化过程的影响

通过间歇实验研究了在pH=7和不调节pH两种情况下添加不同浓度的Fe^3＋、Cu^2＋和Zn^2＋对厌氧消化水解酸化阶段有机酸组分和含量的影响。结果表明，pH=7时，添加50 mg/L Fe^3＋和30 mg/L Cu^2＋，有利于厨余垃圾水解酸化过程的进行，反应生成的VFA（挥发性脂肪酸）含量增加。不调节pH时，添加100 mg/L以下的Fe^3＋和Cu^2＋对VFA含量也有所促进，但乳酸含量也增加。在2种pH条件下添加Zn^2＋对反应的促进或抑制作用均不明显。     

三维电极/电-Fenton法降解苯酚

采用电-Fenton耦合三维电极法处理苯酚模拟废水，研究了活性炭作为第三电极的三维电极体系中苯酚的去除效果，重点考察了常温下初始pH值、电流强度、Fe²⁺浓度等因素对苯酚降解的影响。结果表明：在常温下，曝气速率20 L/min，初始pH=3，电流强度为0.3 A/m²，Fe²⁺浓度为0.1 mmol/L，反应时间60 min时，废水的苯酚的氧化降解率为91%，COD去除率为64%。在此条件下，三维电极/电-Fenton表现出较强的氧化能力，具有较好的去除效果，可应用于含苯酚废水的处理。     

Fe3+(NTA)还原菌的固定化小球制备及还原特性

采用海藻酸钠包埋驯化得到的优势铁还原菌，用于还原络合吸收法脱除NOx过程中形成的中间副产物Fe³⁺(NTA)。结果表明，最佳包埋条件为海藻酸钠质量浓度4%，菌体质量浓度0.2%，CaCl₂质量浓度3%，此条件下制备的小球还原性能好，在微生物用量为20 g（湿重）/L时还原10 mmol/L Fe³⁺(NTA)，经12 h反应后还原率达到96.1％，而相同条件下游离微生物的还原率仅为11.8％，但反应16 h后游离微生物与固定化小球的还原率相近，均为97％左右。但此法制备的小球机械强度不高，溶胀、破裂现象严重。通过添加聚乙烯醇和硅藻土改良固定化小球，可强化小球的机械强度、降低小球的溶胀及破裂现象，对Fe³⁺(NTA)的还原效果也较改良前的小球有所提高，两者最佳添加量均为20 g/L。改良后的小球与游离微生物相比，耐酸性增强，在pH=5的条件下，仍具有79.8％的还原效率，远高于相同条件下游离微生物的39.5％，但对温度的适应范围两者基本一致。     

UV/Fenton法预处理N-甲基苯胺生产废水

采用UV/Fenton法对N-甲基苯胺生产废水进行预处理。当原水COD约为3 400 mg/L时，在适宜操作条件（H₂O₂投加量为50 mL/L，Fe²⁺投加量为1.209 g/L，pH＝5.0，反应时间为30 min）下的COD去除率可达90％以上。同时得到Fenton试剂处理该废水的适宜条件为：H₂O₂投加量为60 mL/L，Fe²⁺投加量为1.692 g/L，pH为5.0，反应时间30 min；单独UV辐照处理该废水的较适宜条件为：反应时间为20 min， pH＝5.0。最后就3种处理方法进行了比较，发现UV对Fenton试剂处理N-甲基苯胺生产废水具有一定促进作用。反应前后的紫外光谱说明，经UV/Fenton反应后，原水中的含苯环物质已得到了彻底的氧化分解。     

Fe(Ⅱ)EDTA/H2O2电催化降解甲基橙模拟废水的研究

在无隔膜电解槽中,采用SPR(Ru-Ir-Ti0₂)为阳极,石墨为阴极,考察了Fe(Ⅱ)EDTA/H₂O₂电催化降解甲基橙(methyl orange)模拟废水的影响,发现EDTA很大程度上促进了类电Fenton试剂对甲基橙模拟废水的降解。实验研究表明,在外加电压为5.0 V,EDTA∶Fe²⁺=2∶1(摩尔比,Fe²⁺=40 mmol/L),H₂O₂=48 mmol/L,电解质Na₂SO₄=40 mmol/L,废水pH值为(6.5±0.1)的条件下,降解260 mg/L的甲基橙模拟废水90 min, EDTA的加入可以使甲基橙模拟废水的脱色率由29.5%上升到78.4%,COD由571.429 mg/L降至80 mg/L,COD的降解率为86%，EDTA在此过程中既是催化剂又是反应物,可有效避免EDTA带来二次环境污染的可能性。     

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.     

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.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.     

Influence of crop residues on trifluralin mineralization in a silty clay loam soil

Trifluralin is typically applied onto crop residues (trash, stubble) at the soil surface, or onto the bare soil surface after the incorporation of crop residues into the soil. The objective of this study was to quantify the effect of the type and amount of crop residues in soil on trifluralin mineralization in a Wellwood silty clay loam soil. Leaves and stubble of Potato (Solanum tuberosum) (P); Canola (Brassica napus) (C), Wheat (Triticum aestivum) (W), Oats (Avena sativa), (O), and Alfalfa (Medicago sativa) (A) were added to soil microcosms at rates of 2%, 4%, 8% and 16% of the total soil weight (25 g). The type and amount of crop residues in soil had little influence on the trifluralin first-order mineralization rate constant, which ranged from 3.57E-03 day^?1 in soil with 16% A to 2.89E-02 day^?1 in soil with 8% W. The cumulative trifluralin mineralization at 113 days ranged from 1.15% in soil with 16% P to 3.21% in soil with 4% C, again demonstrating that the observed differences across the treatments are not of agronomic or environmental importance.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.