纳米零价铁颗粒去除污染土壤HCl浸提液中的Pb

主要研究了纳米零价铁颗粒对土壤HCl浸提液中重金属Pb的去除效果。通过批实验探讨HCl浓度、纳米零价铁投入量以及处理时间对Pb去除率的影响。实验结果表明,纳米零价铁颗粒对浸提液中Pb的去除反应符合langmuir和freundlich等温吸附方程;反应遵循准一级反应动力学方程,标准化后的反应速率常数KSA=0.018 mL/(m2.min);反应30 min时,0.5 g纳米零价铁对1.0 mol/L的HCl所提取Pb(51.7 mg/L)的去除率达到91.8%。研究结果表明,纳米零价铁对土壤HCl浸提液中Pb具有良好去除效果,但相对于处理水溶液中的Pb,反应速率偏低。     

CMS包覆纳米零价铁去除2,4-二氯酚的条件优化

针对纳米零价铁(Fe~0)去除2,4-二氯酚(2,4-DCP)时易团聚、易氧化、去除效率差等问题,采用环境友好材料羧甲基淀粉钠(CMS)对纳米零价铁进行了包覆,制成包覆型纳米零价铁。探究了包覆比例(CMS:Fe0)、pH、包覆型纳米零价铁投加量等单因素对去除率的影响。在单因素实验的基础上,以包覆比例、pH、包覆型纳米零价铁的投加量为考察因素,以2,4-DCP的去除率为响应值,采用二次多项式响应面探究多因素交互作用对包覆型纳米零价铁去除2,4-DCP的影响。利用响应面优化模型对包覆型纳米零价铁去除2,4-DCP进行优化。模型优化结果显示:包覆型纳米零价铁去除2,4-DCP的最佳条件为pH 3.0,纳米零价铁包覆比例3.59:1,包覆型纳米零价铁的投加量7.96 g·L~(-1),模型预测2,4-DCP的最高去除率为90.03%,实验值为85.77%,两者相对误差为4.73%,证明了优化模型的可靠性。     

修复铬污染地下水的可渗透反应墙介质筛选

通过实验研究筛选出一种经济、高效的用于修复铬污染地下水的可渗透反应墙(PRB)介质。实验以铬污染地下水为研究对象,分别对Fe0、Fe0+石英砂和包覆型零价铁填料进行了筛选实验,选取处理效果好且经济可行的包覆型零价铁材料作为PRB反应介质。结果表明,以包覆型零价铁材料作为PRB反应介质,大大提高了铁粉的利用效率,且缓解了系统堵塞严重的问题。以包覆型零价铁材料作为PRB反应介质修复Cr(VI)污染地下水是可行的。     

膨润土负载硫化纳米零价铁去除对硝基苯酚的研究

以具有较大比表面积和良好吸附性能的膨润土作为载体,制备了膨润土负载硫化纳米零价铁,并利用X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及比表面积等手段表征膨润土负载硫化纳米零价铁的特性。研究了膨润土负载硫化纳米零价铁的硫铁比(摩尔比)、投加量、初始pH对对硝基苯酚(PNP)去除的影响,并对PNP降解机理进行了初步探究。结果表明,膨润土负载硫化纳米零价铁比表面积为33.06m~2/g,大于膨润土的比表面积(26.72m~2/g),负载的纳米零价铁颗粒分散均匀。当硫铁比为0.011 2、投加量为0.5g/L、初始pH为5.0时,10min基本能把1L1.5mmol/L的PNP完全降解,具有最大的去除速率和去除率。PNP的最主要降解产物为对氨基苯酚。     

废布料活性炭吸附典型染料动力学研究

研究了废布料活性炭从水溶液中吸附2种典型染料(酸性蓝62和活性艳蓝KN-R)的吸附特性,从动力学角度探讨了吸附机理.结果表明,废布料活性炭对2种染料的平衡吸附量(qc)均随着初始浓度的增加而升高,相同条件下,qc的大小顺序为酸性蓝62＞活性艳蓝KN-R.吸附过程符合准二级动力学模型,对于酸性蓝62,粒子内扩散过程是该吸...     

有机配体对纳米零价铁还原硝基苯的影响与机理

通过FeSO4·7H2O与NaBH4反应,采用液相还原法制备纳米级零价铁(NZVI),并用XRD,SEM对其性能进行表征。研究了纳米零价铁还原硝基苯(NB)的动力学规律及柠檬酸、草酸、柠檬酸钠、草酸钠、乙二胺四乙酸二钠(EDTA二钠盐)几种有机小分子对其还原效率的影响,并对其机理进行了初步探讨。结果表明,纳米零价铁去除硝基苯反应符合准一级动力学方程,并且当硝基苯浓度一定时,增加NZVI投加量,去除率会显著增大;当NZVI浓度一定时,硝基苯浓度越低,去除率越高;柠檬酸和EDTA二钠盐在较低浓度时抑制还原反应进行,而在3 mmol/L左右时,具有促进还原反应进行的作用,而草酸、柠檬酸钠和草酸钠则为抑制作用。     

生物炭携载纳米零价铁对溶液中Cr(Ⅵ)的去除

利用液相还原法,使生物炭携载纳米零价铁,可以有效解决纳米零价铁在水处理应用中自身团聚问题,从而提高Cr(Ⅵ)的去除效率。研究发现:在添加相同剂量纳米的条件下,当炭铁质量比为5∶1时,生物炭携载纳米零价铁对溶液中Cr(Ⅵ)的去除率可达到96.8%,比纯纳米零价铁去除Cr(Ⅵ)的效率高35.9%;TEM和BET分析表明,生物炭携载纳米零价铁比纯纳米零价铁有更好的分散性和更高的比表面积,这是其去除Cr(Ⅵ)效果更好的主要原因;当溶液中Cr(Ⅵ)的反应初始浓度从25 mg/L提升至125 mg/L时,表观速率常数kobs从0.104 1 min~(-1)降低至0.023 5 min~(-1),说明反应速率随着Cr(Ⅵ)初始浓度的增大而降低;当反应溶液初始p H在4.5~8.5之间时,携载纳米零价铁的生物炭对溶液中Cr(Ⅵ)的去除率均达到92.1%以上,表明生物炭携载纳米零价铁具有较广的p H适应范围,且对Cr(Ⅵ)具有较好的去除效果。     

湿式过氧化氢氧化活性艳蓝KN-R

为了有效地处理印染废水,采用湿式过氧化氢氧化法(wet peroxide oxidation,简称WPO)降解活性艳蓝KN-R。通过筛选反应因子,获得了最佳反应条件。当初始浓度为200 mg/L时,在最优条件下,活性艳蓝KN-R的脱色率和TOC去除率分别为100%和68.54%。在120~150℃考察了该反应的动力学,结果表明,活性艳蓝KN-R的湿式过氧化氢氧化反应符合准一级动力学方程,并且通过计算得到了反应活化能为73.9 k J/mol。利用气相色谱/质谱联用仪(GC-MS)鉴定活性艳蓝KN-R降解产物主要为几种小分子有机酸,如丁二酸、已二酸、邻苯二甲酸。通过添加自由基捕获剂(叔丁醇)研究了自由基反应机理,结果表明羟基自由基对活性艳蓝KN-R的降解起着主要作用。     

CTAB改性纳米零价铁的制备与橙黄Ⅱ的降解

以十六烷基三甲基溴化胺(CTAB)为分散剂,制备改性纳米零价铁颗粒(CNZVI)。比表面积、XRD、SEM和TEM表征结果表明改性的CNZVI比未改性纳米零价铁颗粒(BNZVI)粒径更小、更均匀,具有更好的分散性能和抗氧化性。首次考察了CNZVI对于水中染料橙黄Ⅱ的脱色降解效果。CNZVI对橙黄Ⅱ的脱色率和降解速率均优于未改性纳米铁颗粒BNZVI,脱色率在反应进行10 min后趋于稳定。考察了溶液p H、初始浓度、NZVI投加量和温度对反应脱色率的影响。p H值和初始浓度越高,脱色率越低;脱色率随着投加量和温度提高而增大。最后优化反应条件为:p H值5.96,初始浓度100mg/L,NZVI投加量0.2 g/L,反应温度293 K,CNZVI对橙黄Ⅱ的脱色率为91.8%,比BNZVI的脱色率高出16.1%。动力学分析表明,CNZVI对橙黄Ⅱ降解反应符合伪一级反应动力学。     

无定型纳米TiO2吸附去除饮用水中的低浓度As(Ⅲ)

研究了纳米无定型TiO2颗粒对饮用水中低浓度的三价砷As(Ⅲ)吸附行为。纳米TiO2颗粒吸附剂的BET表面积为205 m2/g,计算的BJH吸附平均孔径为4.02 nm(4 V/A)。对起始As(Ⅲ)浓度为150μg/L的模拟含砷水,经过5h的吸附处理后残余浓度不足4μg/L,As(Ⅲ)去除率达到97%。反应起始阶段吸附速率较快,84%的As(Ⅲ)能够在20min内去除。As(Ⅲ)吸附动力学较好地符合拟二级动力学模式。最佳As(Ⅲ)吸附pH为9.3,低于此值,随酸性增加吸附速率有所降低;而高于此值的强碱性pH对吸附有强烈抑制作用。在平衡浓度较低的情形下(10～220μg/L),Lang-muir,Freundlich和Dubinin-Radushkevich(D-R)吸附等温式均可较好拟合吸附行为,但中性和弱碱性条件下更符合Fre-undlich吸附等温式;平衡浓度大于220μg/L,吸附容量随平衡浓度增加而迅速增加,最大吸附容量在低浓度下达到4.79 mg/g。     

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.