零价铝对高氯酸盐污染物的去除

为了考察零价铝对高氯酸盐的去除影响因素和机制,对比了普通铝粉和酸洗铝粉对高氯酸盐的去除效果,并设计正交实验,分析温度、p H值、酸洗零价铝投加量和高氯酸根初始浓度4个因素对高氯酸盐的去除影响规律,另外,检测分析零价铝去除高氯酸盐过程中反应液Cl O-4、Cl-随时间的浓度变化。结果表明,酸洗预处理得到较高纯度的零价单质铝,并且对高氯酸盐具有较高的去除效率;正交实验极差分析结果表明,反应的最优水平:温度25℃、p H为4.5、投加量为35 g·L~(-1)、高氯酸根初始浓度为2 mg·L~(-1),高氯酸根去除效率各影响因素的主次关系为p H投加量温度初始浓度;初步表明,零价铝去除高氯酸根的主要机制并非零价铝的还原作用,而是老化铝粉固体表面吸附过程。     

纳米零价铁颗粒除磷反应机理

从溶液化学与固相表征两方面对纳米零价铁(NZVI)去除水中磷酸根(PO3-4)的机理进行初步探究。分别研究不同初始p H值、溶解氧(DO)对NZVI除磷效果的影响,结果表明,酸性环境(p H为3.0~7.0)有利于NZVI除磷,且初始p H值越低,磷去除率越高;好氧环境较厌氧环境更利于磷的去除,DO8.0 mg/L时对磷酸根的去除率是厌氧条件(DO0.1 mg/L)下的2倍。采用Na OH对反应后含磷NZVI进行解析,发现磷解析率不到30%,说明吸附并非NZVI除磷惟一作用机理。微米铁、NZVI和Ca(OH)2等7种不同去除材料中以Ca(OH)2的共沉淀作用去除率最大(99.9%),NZVI次之(87.2%),表明NZVI除磷机理中还存在共沉淀作用。采用多种固相表征手段对NZVI除磷前后进行分析:扫描电子显微镜(SEM)显示反应后出现不规则颗粒;X射线衍射(XRD)表明Fe3(PO4)2是主要反应产物;X射线光电子能谱(XPS)分析未发现磷被还原成低价态。研究表明,NZVI可有效去除水中磷酸根,主要去除机理包括:NZVI对磷酸根的吸附作用、NZVI在水中腐蚀产生的Fe2+离子对磷酸根的化学沉淀作用及铁氢氧化物与磷酸根的共沉淀作用。     

酸根离子对铝板电絮凝处理含镍废水的影响

电絮凝是去除废水中重金属离子的有效技术。本研究考察了常见酸根离子SO2-4、Cl-、NO-3和H2PO-2对铝板电絮凝除Ni2+的影响。结果表明,SO2-4、Cl-、NO-3均有利于Ni2+的去除,其中由于NO-3的还原可提高铝阳极溶解效率,因此,当其浓度从0.0186增至0.186 mol/L时,反应30 min后Ni2+去除率从77.9%升至99.8%。H2PO-2会降低絮体絮凝活性并钝化电极,从而显著降低Ni2+去除率,其浓度从0.0186 mol/L增至0.372 mol/L,反应60 min后Ni2+去除率从91.7%降至30.5%。另外,对各阴离子存在下溶解态铝絮体聚合度以及电解过程pH的检测,进一步揭示这4种离子对电絮凝影响机制。     

表面增强拉曼光谱技术检测高氯酸根离子

高氯酸根离子是水质污染物中常见的污染源之一.通过化学还原法制备稳定、分散性好的纳米银溶胶颗粒(粒径为30～40 nm),并以此为基底,探究了利用表面增强拉曼光谱技术迅速准确地检测质量浓度为10-6～10-1 g/L的高氯酸根离子溶液的表面增强拉曼光谱.结果表明,当高氯酸根离子质量浓度为10-5～10-1 g/L时,随着高氯酸根离子浓度的降低,表面增强拉曼光谱强度逐渐减弱.     

混凝法去除城市生活污水中抗性基因

采用聚合氯化铝(PACl)和聚合硫酸铁(PFS)混凝处理城市生活污水(格栅出水和二级出水),考察混凝剂投加量、p H值对污水中抗生素抗性基因(ARGs)的去除率影响。结果表明,随着PACl和PFS投加量的增加,污水中目标基因的去除率先升高后降低;在p H 3~10的范围内,PACl对目标基因的去除效果随p H值的增加而降低,PFS对目标基因的去除随着p H值的增加先升高后降低。对于格栅出水,PACl和PFS的最佳投加量为400 mg/L,基因的去除率分别达到2.33~2.97 log和0.98~2.11 log,对于二级出水,PACl和PFS的最佳投加量分别为200 mg/L和150 mg/L,基因的去除率分别为1.85~2.64log、1.81~2.46 log;混凝去除最优p H条件分别为p H=3(投加PACl)及p H=5~6(投加PFS)。PACl的处理效果优于PFS。     

活性碳纤维电极法去除水中敌草隆的研究

实验研究了活性炭纤维电极对敌草隆的去除作用。考察了电流强度以及敌草隆浓度对敌草隆去除的影响，对活性炭纤维用于吸附和用作电极去除敌草隆的效应进行了比较分析。结果表明，在0.01～0.05 A内，敌草隆的去除随着电流强度的增加而增加，其去除率为58%～91%。敌草隆浓度在5～40 mg/L时，其去除率随着浓度的增加而减小，但至1.5 h 时，去除率均可达95%以上。对于20 mg/L的敌草隆，活性炭纤维对其吸附去除率为90%左右，重复使用导致去除效率下降；活性炭纤维电极电化学氧化对其去除率达95%，并且重复使用其效果未见下降。活性炭纤维电极电化学氧化导致敌草隆分子结构破坏、苯环开环发生分解而最终得以去除。活性炭纤维电极可用于水中敌草隆的去除。     

碳酸根型镁铝水滑石对铬酸根和磷酸根离子的吸附性能

为研究水滑石类材料对水体中铬酸根和磷酸根离子的同时吸附去除性能,采用共沉淀法合成碳酸根型镁铝水滑石(Mg-Al-CO3LDHs),利用傅立叶转换红外光谱、X射线晶体衍射、表面积、X光吸收近边结构等手段对合成材料进行表征,并研究Mg-Al-CO3LDHs在不同初始浓度、p H、吸附时间、阴离子干扰条件下同时去除铬酸根和磷酸根离子的性能。结果表明,Mg-Al-CO3LDHs对铬酸根和磷酸根离子最大吸附量分别为0.042 mmol/g和0.146 mmol/g。吸附动力学实验数据的拟合结果以Elovich为最佳。竞争实验表明,溶液中含有少量磷酸根离子即可抑制铬酸根离子的吸附,但铬酸根离子对磷酸根离子的吸附影响不大。X光吸收近边结构结果表明,铬与构造中心的铝产生键结而吸附。     

硫酸钛混凝去除无机砷(Ⅲ)的效能

使用硫酸钛作为混凝剂,研究了混凝去除As(Ⅲ)过程中溶液pH值、混凝剂投加量、砷的初始浓度以及阴离子对除砷效果的影响.硫酸钛的水解沉淀物颗粒等电点为pH =5;当pH =6时,水解沉淀物的粒径最大.在pH =5 ～8范围内,As(Ⅲ)的去除率高且基本稳定;而沉淀物颗粒Zeta电位降低较大.说明水解沉淀物Zeta电位对As(Ⅲ)的去除影响不大.混凝剂投加量为2.5 ～10 mg/L时,As (Ⅲ)的去除率随投加量的增加而显著增加;混凝剂投加量大于15 mg/L时,As(Ⅲ)去除率随混凝剂投加量的增加变化趋于平缓.水中阴离子(硅酸根和磷酸根离子)的存在会降低混凝对As (Ⅲ)的去除效率.     

RPB-O3/H2O2法处理硝基苯模拟废水

在超重力场中,研究了硝基苯模拟废水的臭氧/双氧水(O3/H2O2)法处理效果,考察了超重力因子β、H2O2浓度、初始p H、液体流量及处理时间等因素对硝基苯去除率的影响。结果表明,硝基苯去除率随超重力因子β和处理时间的增加而增大,而随H2O2浓度、初始p H和液体流量的增加呈先增大后降低的趋势。当硝基苯初始浓度300 mg/L,工艺条件β=80、p H=10.0、臭氧质量浓度约为40 mg/L、H2O2浓度为4.9 mmol/L、液体流量为120 L/h时,循环处理35 min硝基苯去除率可达96.7%。处理时间60 min后,废水中硝基苯含量1.4 mg/L,COD为39 mg/L,达国家一级排放标准(GB 8978-1996)。在此条件下,硝基苯的降解过程符合准一级反应动力学。     

处理苯胺废水的电化学研究

采用电化学法处理苯胺废水 ,系统的氧化电极以恒电位法聚合制成高导电聚苯胺并压制成颗粒填料分多级填充在塔中形成固定床式电极。实验研究了不同的电位扫描速度、苯胺浓度及温度对电化学氧化还原反应的影响。实验表明 ,采用导电聚苯胺作为处理苯胺废水的氧化电极 ,可以有效地降低电化学反应的电解电位 ,提高氧化电流和反应速度 ,它是采用铂电极处理苯胺废水消耗电能的 1/ 2 .78。     

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.