不同电极材料对阴极硝化耦合阳极反硝化微生物燃料电池性能的影响

为解决传统MFC反硝化菌在好氧阴极难以富集且脱氮效果差的问题,通过构建石墨MFC和碳刷MFC以阴极硝化耦合阳极反硝化的方式脱氮除碳,并对比分析2种不同电极MFC的性能。结果表明:在相同条件下石墨MFC的最大功率密度为6.71 W·m~(-3)NC,开路电压为902.13 mV;碳刷MFC的最大功率密度为5.11 W·m~(-3)NC,开路电压819.04 m V。启动阶段前15 d碳刷MFC的总氮去除率更高,之后石墨MFC的总氮去除率接近100%,碳刷MFC的总氮去除率在95%左右。石墨MFC的COD去除率高达93%,碳刷MFC的COD去除率在83%左右。相比于传统MFC,阴极硝化耦合阳极反硝化MFC不需要调节pH。相比于碳刷电极,石墨电极MFC可以启动和挂膜同时进行,缩短挂膜时间,且产电性能和脱氮除碳效果更好。     

AC/PTFE微生物燃料电池阴极去除罗丹明B及同步产电性能

采用辊压成型法制备了活性炭(AC)/聚四氟乙烯(PTFE)质量比分别为6、5和3的AC/PTFE电极,并利用SEM对电极表面进行表征。结果表明,随着质量比的降低电极表面活性炭颗粒间的连接更为紧密。以制得的AC/PTFE电极,碳毡分别为微生物燃料电池(MFC)的阴极、阳极,利用AC/PTFE阴极在曝气条件下产生的过氧化氢在阴极处理模拟的罗丹明B废水。研究了不同质量比AC/PTFE阴极对罗丹明B的去除效果及同步产电情况,结果表明以AC/PTFE质量比为6的AC/PTFE阴极在96 h内对罗丹明B的去除率达到96%,MFC获得的最大功率密度为105 mW·m~(-2);同时研究了在阴极液加入0.2 g·L-1Fe~(2+)的条件下,阴极液为不同pH值时,阴极对罗丹明B的去除效果及MFC产电情况。结果表明在阴极液pH=3的情况下,罗丹明B的去除率在36 h内达到了98.9%,MFC的最大功率密度达到210 mW·m~(-2),罗丹明B的去除速率及MFC能量的输出得到了明显提高。     

反硝化生物滤池用于再生水脱氮效能及动力学研究

采用反硝化生物滤池处理城市污水厂二级出水,研究了反硝化生物滤池脱氮效能及其影响因素,构建了反硝化生物滤池脱氮动力学模型。结果表明,反硝化生物滤池启动7d后出水水质稳定,对NO-3-N的去除率达到90%以上,NO-2-N积累现象消失;当外加乙酸钠作碳源并使C/N≥4.7时,对NO-3-N的去除率达到90%以上,出水NO-3-N浓度在1.0mg/L以下;反硝化生物滤池具有较高的处理负荷,当HRT≥5 min时,对NO-3-N的去除率能达到90%以上;在实验水质条件下,滤池反硝化反应遵循一级反应动力学,且反应速率常数与流速成正比。     

微生物燃料电池处理含铜废水的研究

构建了以乙酸钠为阳极基质、Cu~(2+)为阴极电子受体的双室微生物燃料电池(MFC),考察了该MFC处理含铜废水的效果及Cu~(2+)浓度对MFC产电性能的影响。通过改变阴极液中CuSO_4的质量浓度(20~130mg/L),测试了MFC运行过程中的输出电压、输出功率密度、内阻、Cu去除率等指标。结果表明:Cu~(2+)可作为MFC的阴极电子受体;在外电路电阻为1 000Ω的条件下,Cu~(2+)质量浓度为130mg/L的MFC性能最佳,其稳定输出电压为0.33V、最大输出功率密度为114.42mW/m~2,内阻为231.62Ω,最高Cu去除率为84.59%;通过X射线衍射测试发现,阴极还原产物为Cu_2O。     

不同阴极对微生物燃料电池产电性能的影响比较

阴极催化性能及材料对微生物燃料电池(microbial fuel cells,MFCs)的产电特性及制造成本有很大影响。本研究选用金属铂(Pt)、活性炭作为催化剂、聚四氟乙烯(PTFE)和道康宁1-2577作为阴极的扩散层、碳布和不锈钢网作为阴极的基体材料制备得4种阴极,分别考察了相应MFC的产电性能和阴极特性。结果表明,采用传统Pt催化剂+PTFE扩散层+碳布制备成的阴极(Pt-PTC),MFC的最大输出电压为560 mV,最大功率密度为808 mW/m2,而采用活性炭+道康宁1-2577+不锈钢网制备成的阴极(AC-DCS),MFC的最大输出电压为510 mV,最大功率密度为726 mW/m2,两者的MFC产电性能极为接近。SEM结果表明,活性炭催化层表面和道康宁1-2577扩散层分别比Pt催化层及PTFE扩散层的更均匀光滑。阴极线性伏安测定结果表明,AC-DCS与Pt-PTC的电化学氧化性能较为接近。AC-DCS阴极成本仅为Pt-PTC的1/300左右,是一种低成本扩大化生产MFC阴极的新方法。     

回流式无膜生物阴极微生物燃料电池脱氮

为有效提高脱氮效率、降低MFC运行成本,设计了一种新构型回流式无PEM膜的生物阴极微生物燃料电池,处理生活污水,回收电能。研究了该系统的启动情况及稳定运行时的污水脱氮效果和产电性能。结果表明,系统稳定运行后,输出电压0.53 V,反应器内阻406.8Ω,最大功率密度201.9 mW/m3。连续进水、停留时间12 h、回流比为1及阴极连续曝气条件下,COD去除率85%以上,氨氮去除率93.94%,总氮去除率44.96%,总氮去除较作参比的A2/O系统提高8.17%。     

双室微生物燃料电池处理硝酸盐废水

基于双室微生物燃料电池(microbial fuel cell,MFC),针对阴极分别接种活性污泥(A-MFC)和反硝化细菌(D-MFC),研究其产电情况和硝酸盐废水去除效果。结果表明,在产电的同时都可有效去除废水中的硝酸盐污染物。在外接电阻100Ω的情况下,2种MFC均具有良好的产电性能,A-MFC和D-MFC达到的最大输出电压分别为119.6 mV和117.2mV,最大功率密度分别为23.40 mW/m2和26.63 mW/m2;同时两者在阴极室的平均反硝化速率分别为1.86 mg/(L.d)和2.19 mg/(L.d),阳极室的平均COD去除率分别为81.9%和82.4%。另外,通过扫描电镜观察可知,A-MFC和D-MFC阴极碳布表面形貌存在差异,并且阳极与阴极碳布表面形貌差异显著。     

微生物燃料电池阴阳两级分步降解对氯酚效果

构建一种微生物燃料电池(MFC),首先将对氯酚在阴极室降解为苯酚,随后将阴极处理液在阳极室降解。研究了对氯酚废水经过阴阳双室分步处理后的去除效果和该MFC的产电性能,结果表明,在外电阻1 000Ω时,阴极脱氯阶段最大输出电压为216 m V,产电周期为132 h;阳极降解阶段最大输出电压为277 m V,产电周期为48 h,对氯酚的总去除率为96.2%。实验结果表明该MFC能较好处理对氯酚废水,且与传统的生化处理技术相比,有较大的优势。     

MFC强化同步短程硝化反硝化工艺的启动

微生物燃料电池(MFC)可在阴极实现反硝化、短程反硝化和同步硝化反硝化并产生电能,但在MFC阴极实现同步短程硝化反硝化的研究尚未见到报道。为了探讨MFC阴极同步短程硝化反硝化工艺的性能,将双室曝气阴极MFC与A/O脱氮工艺结合处理人工模拟低碳氮比废水。通过静置运行15 d使得MFC阴极室亚硝态氮得以积累,氨氧化菌得以富集。随即改为连续运行后第21天成功启动同步短程硝化反硝化MFC;阴极出水氨氮浓度为0.3 mg/L,亚硝态氮浓度为15.9 mg/L,硝态氮浓度为0.6 mg/L,亚硝化率达到95%以上,阴极电极自养反硝化去除率达到50%以上,COD去除率达到85%以上。结果表明,将MFC与同步短程硝化反硝化工艺结合,通过阴极室中氧气得电子获得高p H,可以强化同步短程硝化反硝化工艺,完成生物脱氮的同时回收电能,并具有减少外加碱度的优势。     

微生物燃料电池化学阴极与生物阴极处理含铬废水

采用双室微生物燃料电池(MFC)反应器,考察了不同初始Cr(VI)浓度下化学阴极与生物阴极MFC的产电及Cr(VI)去除情况。结果表明,在各Cr(VI)浓度梯度(20、28、32、36、40和44mg/L)下生物阴极MFC的产电及Cr(VI)去除性能均较化学阴极MFC更优,生物阴极最大输出电压为180.1mV,是化学阴极的1.3倍。随着初始Cr(VI)浓度的递增,两者对Cr(VI)去除的差异越明显,最终在Cr(VI)浓度为44mg/L时,生物阴极MFC的Cr(VI)去除率为66.4%,较化学阴极提高了55.1%。进一步由循环伏安扫描、电镜扫描及X-射线能谱分析证实生物阴极MFC较化学阴极MFC产电及去铬性能优越的主要原因除了生物阴极电极上电化学活性微生物的催化作用外,Cr(VI)还原产生的不导电Cr(III)沉积物在其电极上附着较少也是一个关键因素,该Cr(III)沉积物中含有Cr2O3。     

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.