大分子络合超滤技术去除溶液中镍离子的研究

采用聚丙烯酸(PAA)和羧甲基纤维素钠(CMC)去除Ni2 ,首先将Ni2 离子络合在大分子上形成大分子络合物,进而通过超滤膜,将其截留在膜的一侧,从而达到分离镍离子的目的.研究表明,采用这两种聚合物进行络合超滤可以使镍离子去除率达到95%以上;当Ni2 与聚合物的反应时间为30 min时,镍离子(170 mg/L)与PAA(0.5 wt%)、CMC(0.5wt%)的适宜配比分别为1:2.5和1:1.在分离体系中加入Na 、Mg2 后,对镍离子的去除具有不利影响.此外,考察了用大分子络合超滤法处理含有镍离子的实际废水,结果在透过液中未检测出Ni2 .     

中和共沉淀—铁氧体法处理含镍、铬废水的实验研究

利用中和共沉淀—铁氧体法处理甘肃某稀有金属生产企业产生的含镍、铬废水,同时对该废水的处理工艺条件进行了实验研究。经测定,废水中Ni 2+质量浓度为50mg/L,Cr(Ⅲ)质量浓度为87mg/L。通过实验得到处理工艺的最佳条件:投料摩尔比(Fe2+/(Ni 2++Cr2O2-7))为9,pH=9,温度为70℃。出水中镍、铬均可达到《污水综合排放标准》(GB 8978—1996)中第一类污染物最高允许排放浓度的要求,为中和共沉淀—铁氧体法处理混合重金属废水的工艺条件研究提供了参考。     

离子浮选法处理电镀废水实验研究

进行离子浮选法处理电镀废水的研究,对影响因素pH、CA∶CMe(摩尔比)、离子强度、浮选时间和通气量等进行了实验研究。实验结果表明:离子分离选择性递减顺序为:Cd2+Zn2+Fe2+Cu2+Ni2+。当CA∶CMe为2.5～3∶1,pH为8.5～9,离子强度不高于0.0001 mol/L时,离子浮选对镉、锌、铜、镍等金属离子均有很高的去除率,Cd2+、Zn2+、Fe2+、Ni2+、Cu2+残余浓度最低分别可达0.05、0.20、0.22、0.28和0.33 mg/L,处理后的电镀废水各污染物浓度均达到排放标准。泡沫产品中镉、锌、铜、镍品位分别达到3.2%、9.3%、18.1%和13.2%,具有极高的资源回收价值。     

赤泥晶种法磷酸铵镁结晶工艺模拟废水磷的回收

以赤泥为晶种,研究不同工艺条件对磷酸铵镁(MAP)结晶法回收模拟废水中磷的影响。结果表明,在投加赤泥(60～80目)8 g/L,搅拌速度为180 r/min,搅拌时间30 min,沉淀时间30 min,N∶Mg∶P=1∶1∶1的条件下磷酸根离子的回收率随初始磷酸盐浓度的增加而增大,在初始磷酸盐浓度小于90 mg/L时增幅较大,初始磷酸盐浓度大于90 mg/L后增幅减小;pH值对磷酸根离子的回收率影响显著,结合铵根离子、镁离子的回收率变化,pH值为9.5时最优;磷酸根离子的回收率随着Mg∶P摩尔比和N∶P摩尔比增大而呈上升趋势,当Mg∶P摩尔比为1.4∶1、N∶P摩尔比为4∶1时,磷酸盐的回收率可达97.9%。运用扫描电子显微镜(SEM)、X射线能谱仪(EDS)和X射线衍射仪(XRD)对最优工艺条件下的结晶产物进行了表征,表明磷主要以磷酸铵镁形态回收。     

MAP-Fenton法预处理垃圾渗滤液的实验研究

采用MAP-Fenton法对垃圾渗滤液进行预处理研究,以氨氮和COD的去除率为衡量指标,根据单因素实验和正交实验确定其最佳工艺条件。MAP阶段的最佳工艺条件:pH=9.5、Mg2+∶NH+4∶PO3-4(摩尔比)=1.3∶1.0∶1.3、反应时间为25min;Fenton阶段的最佳工艺条件:pH=3.5、30%(质量分数)H2O2投加量20mL/L、H2O2∶FeSO4·7H2O(摩尔比)=5∶1、反应时间为2.0h。在上述最佳工艺条件下,垃圾渗滤液氨氮和COD去除率的平均值分别为93.89%和90.12%。     

气田高浓度含硫废水的化学氧化处理

采用亚硫酸钠(Na2SO3)氧化法对气田高含硫废水进行了实验研究。考察了硫化物初始浓度、Na2SO3/Na2S(摩尔比)、初始pH值和反应时间对Na2SO3氧化去除硫化物效果的影响,进行了对氧化产物的元素分析。结果表明,在Na2SO3/Na2S(摩尔比)为0.7、初始pH值为5和反应时间为5 min时,硫化物从1 100 mg/L降至1.80 mg/L,去除率高达99.84%,达到了气田回注水水质标准。元素分析发现,氧化产物中C、N、S、H和O元素的含量分别为0.11%、0.06%、98.73%、0.90%和1.10%,且其产率达到90.59%。     

Fenton氧化-混凝联合工艺处理络合铜镍废水的研究

采用Fenton试剂氧化-混凝联合工艺对难处理络合铜镍电镀废水进行了研究,考察了废水初始pH值、H2O2初始浓度、[Fe2 ]/[H2O2]、反应时间和温度、混凝液pH、混凝剂质量浓度对处理过程的影响,探讨了废水的降解途径和机理.结果表明,在体系初始pH=4,温度30℃,H2O2投加量为800mg/L,[Fe2 ]/[H2O2]=0.1,反应时间60 min,混凝液pH=8及混凝剂质量浓度为500mg/L的条件下,废水的COD去除率为96.98%,Cu2 为99.91%,Ni2 为99.92%,处理水完全达到国家一级排放标准.同时依据GC/MS对X-GN降解最终产物的分析结果,推导出废水的基本降解机理和途径.     

水体中常见无机阳离子对TiO_2薄膜光催化还原Cr(Ⅵ)的影响

选择了6种水体中常见的阳离子(Na+、Mg2+、Ca2+、Al3+、Cu2+、Ni2+),分别考查了其对TiO2薄膜光催化还原Cr(Ⅵ)的影响;从光吸收、无机离子本身的性质对光生电子的捕获及传递等讨论了上述离子影响TiO2薄膜光催化还原Cr(Ⅵ)的反应速率的原因。结果表明:由于其不能捕获光生电子,Na+、Mg2+、Ca2+本身对TiO2薄膜光催化还原Cr(Ⅵ)的反应速率影响不大;Al3+吸引电子能力较强,成为光生电子和Cr(Ⅵ)之间的桥梁,促进了Cr(Ⅵ)的还原;浓度为1 mmmol/L时,Cu2+显著地促进了Cr(Ⅵ)的光催化还原,其主要原因是Cu2+捕获光生电子的能力很强,起到了催化剂的作用,而浓度大于10 mmol/L时,Cu2+形成单质Cu以及对紫外光的吸收都使促进作用降低;Ni2+未充满的d轨道具有获得并传递光生电子的能力,也促进了Cr(Ⅵ)的还原;在浓度同为1mmol/L时,对Cr(Ⅵ)光催化还原的促进作用依次为:Cu2+Al3+Ni2+Na+、Ca2+、Mg2+。     

Mg-Fe-Al复合氧化物的制备及其对刚果红吸附性能的研究

通过共沉淀法制备了Mg-Fe-Al复合氧化物,并将其应用于水中刚果红的吸附研究。考察了Mg∶Fe∶Al(摩尔比)、pH、煅烧温度等因素对刚果红吸附性能的影响,并进行了吸附热力学和动力学研究。采用扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)和X射线衍射仪对Mg-Fe-Al复合氧化物进行表征。结果表明,Mg-Fe-Al复合氧化物的最佳制备条件为Mg∶Fe∶Al=2∶1∶1、pH=10、煅烧温度为500℃,并经结构表征确认,对刚果红的最大吸附量达到768.9mg/g。吸附过程符合Langmuir等温吸附方程和准二级速率方程。     

4种重金属离子对间接火焰原子吸收光谱法测定铝的干扰

空气-乙炔间接火焰原子吸收法是我国目前运用较多且易于推广的铝检测方法,研究了Mg2+、Ca2+、Zn2+和Ni2+4种离子对此法测定0.40 mg/L Al3+的干扰情况。得出如下结论:(1)在±5%误差范围内,15.10 mg/L Mg2+、105.00mg/L Ca2+、0.23 mg/L Zn2+、0.88 mg/L Ni2+对0.40 mg/L Al3+无干扰。(2)本方法虽然操作复杂,但成本较低、灵敏度高,检测的浓度范围宽、稳定性好,加标回收率为96%~99%,检出限为0.04 mg/L,适宜测定范围为0.05~100.00 mg/L,适用于饮用水、河水及地下水中Al3+的测定。     

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.     

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 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.     

Malathion-induced sublethal toxicity on the intestine of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on intestinal parameters of cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable histopathological alterations were observed. The study on intestinal parameters revealed acute pathological conditions in the intestinal wall. The toxic effect became evident as the cytoplasm of the cells disintegrated and the cells became empty and vacuolated. The cell membranes were also ruptured. Degenerative changes of the absorptive surface (villi) of the intestine in the different periods of exposure were pronounced. Severe atrophic nature (necrotic mucosa) of the intestine began from 48 hrs onwards to 96 hrs of exposure.     

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.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

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.