交联羧甲基玉米淀粉对水溶液中铅离子吸附性能的优化研究

以玉米淀粉为原料，采用先醚化后交联改性工艺合成了交联羧甲基玉米淀粉吸附剂。在单因素试验的基础上，采用Box-Benhnken的中心组合试验设计及响应面分析法，研究了交联羧甲基玉米淀粉吸附剂用量、吸附时间和pH值3因素对水溶液中铅离子吸附效果的影响，得出了吸附剂对铅离子吸附效果的回归模型。结果表明，最佳吸附工艺参数为吸附剂用量0.22 g，pH值为6.6，吸附时间32.9 min，交联羧甲基玉米淀粉对铅离子吸附容量可达44.72 mg/g，铅离子去除率达到98.38%。常温下吸附动力学模型符合Freundlich等温式Q=0.4152C^0.9894。采用0.9 mol/L盐酸溶液作为解析液，铅离子回收率可达97.55%。     

铝钒土—钢渣吸附剂去除铅的研究

天然铝钒土与钢渣混合制得的Al-Ca混合吸附剂性能稳定,能够有效地去除水中的铅离子。通过间歇式振荡吸附实验得到该吸附剂的最佳制作条件为:铝钒土/钢渣为1:2,在0.5mol/lH_2SO_4溶液中处理2小时后,500℃灼烧1小时。实验中对铅的最大吸附量达到746.6mg/g。     

膨胀石墨对U(Ⅵ)的吸附特性

高温加热可膨胀石墨制得膨胀石墨,用于去除溶液中的U(Ⅵ)。通过静态吸附实验,研究了初始p H、吸附剂投加量、U(Ⅵ)初始浓度、温度以及吸附时间对膨胀石墨吸附U(Ⅵ)效果的影响。实验结果表明,膨胀石墨吸附U(Ⅵ)的最佳p H为6.5,在温度为30℃,投加量为2.0 g/L,U(Ⅵ)初始质量浓度为10 mg/L时,对U(Ⅵ)的去除率达到98.08%,反应在4 h达到平衡。Langmuir等温吸附模型和准二级动力学模型较好地拟合了吸附过程,30℃时饱和吸附量为27.03 mg/g;热力学分析表明,膨胀石墨对U(Ⅵ)的吸附是自发的放热反应。比表面积测试、扫描电镜、X射线能谱与傅里叶红外光谱分析结果表明,膨胀石墨对U(Ⅵ)的吸附以物理吸附为主,表面官能团起辅助作用。解吸实验证明,膨胀石墨是可重复利用的吸附剂。     

改性纤维素吸附剂的合成及其对铜离子的吸附

建立了一种简单方便的纤维素改性的固相合成方法。采用普遍廉价的滤纸作为原料,用固相合成法将预处理后的滤纸纤维经琥珀酸酐进行酯化改性,制备成新型的纤维素吸附剂,通过质量增比、扫描电镜、傅里叶红外光谱仪和X射线衍射仪对制备的吸附剂进行了分析表征,并且探究了离子初始浓度、溶液p H和吸附时间对改性纤维素吸附铜离子的影响。结果表明,在室温下初始离子浓度为1 000 mg/L,离子溶液体积为50 m L,加入0.1 g纤维改性剂,p H为4.0~5.0,吸附平衡时间为50 min时,滤纸纤维改性后最大吸附铜离子质量可达470 mg/g,铜离子去除率达到94%。     

锆(Ⅳ)负载交联壳聚糖吸附硫酸根的性能

以甲醛、苯甲醛为交联剂,制备交联壳聚糖树脂,再与锆(Ⅳ)离子反应制备锆负载交联壳聚糖吸附剂。采用静态吸附法考察了该吸附剂对水中硫酸根离子(SO24-)的吸附性能。实验发现,吸附时间2 h,SO24-溶液初始浓度500 mg/L,pH值3.0,溶液温度35℃为较优的吸附条件;吸附过程符合Langmuir等温吸附模型,属于优惠吸附型,吸附容量可达78.65 mg/g;吸附过程较好地符合拟二级动力学模型;锆负载前后交联壳聚糖对硫酸根的吸附量提高了约4.5倍;该吸附剂具有良好的耐酸性和再生性能。     

生物质基炭膜的制备及其对Pb(Ⅱ)的吸附

以生物质二层牛皮为原料,在控制热分解条件下制备了生物质基炭膜。利用TG/DTG、XRD、FT-IR、SEM、TEM和低温N_2吸附-脱附等方法对在不同炭化温度下(550~950℃)制备的生物质基炭膜形貌特征、孔隙结构及其表面化学性质进行了表征。考察了炭化温度、反应时间、溶液pH、加入量等因素对炭膜吸附溶液中铅离子的影响。表征结果表明:随着炭化温度的升高,生物质基炭膜碳微晶趋于石墨化发展,总孔容积持续增大,孔隙结构变得更加发达。实验结果表明:随炭化温度升高,生物质基炭膜对铅离子的吸附效果明显变好;在初始铅离子质量浓度为50 mg·L~(-1)、溶液pH为5.5、吸附剂加入量为1.5 g·L~(-1)、吸附时间为6 h的条件下,950℃下所制炭膜对铅离子有较好去除效果,去除率可达99.9%,吸附容量为32.76 mg·g~(-1)。     

聚甲亚胺酰胺树脂对水中Cu~(2+)的吸附

制备了聚甲亚胺酰胺树脂,对其进行傅里叶变换红外光谱分析。采用批处理方法实验了pH、铜离子初始浓度、吸附时间、吸附剂用量对吸附量的影响,研究了等温吸附模型和吸附动力学模型。优化后的吸附条件为:在铜离子溶液体积50 mL、初始浓度为300 mg/L、pH为6.0时,吸附剂投放量50 mg、吸附时间60 min,此时吸附量达到269.1 mg/g,去除率达89.7%。25℃时在研究浓度范围内,铜离子吸附过程用Langmuir等温线模型和Freundlich等温线模型描述均可;与准一级动力学方程、Elovich方程及内扩散方程相比,准二级动力学方程能更好地描述其吸附动力学过程。     

聚醚酰亚胺功能化磁性纳米微球吸附富集及测定水中痕量镉

利用聚醚酰亚胺修饰纳米磁性微球,制备了一种磁性纳米吸附材料,将其作为固相萃取吸附剂用于富集水体中的痕量镉Cd(Ⅱ)离子,并通过等离子电感耦合发射光谱法测定。利用透射电子显微镜(TEM)、傅里叶变换红外光谱(FIIR)和热重分析仪(TGA)对材料进行了表征,并考察了吸附剂对Cd(Ⅱ)离子的吸附性能,研究了溶液pH值、吸附时间、饱和吸附量、干扰离子、洗脱条件等因素对吸附性能的影响。结果表明,当水样的pH值为5时,振荡吸附15 min达到平衡,饱和吸附容量为5.61 mg/g。吸附在磁性纳米材料上的Cd(Ⅱ)离子可用5 m L 1.0 mol/L盐酸溶液完全洗脱,然后用等离子电感耦合发射光谱法测定此洗脱液中Cd(Ⅱ)离子的含量。将该方法用于环境水样中痕量Cd(Ⅱ)离子的吸附富集和测定,加标回收率在95.3%~97.8%之间。     

氧化石墨烯-氧化锌净化铅离子废水

利用改性Hummers法制备氧化石墨,并成功地将氧化锌负载到氧化石墨上催化降解铅离子。利用SEM、XRD、FTIR等对氧化石墨烯-氧化锌的形貌进行表征,并用以净化铅离子废水。通过实验分析得知废水净化的原因有两方面:光催化效应和吸附理论,然后考察其影响净化过程的因素。结果表明,氧化石墨烯-氧化锌对溶液中铅离子在紫外光下有较强的吸附和催化降解能力,在t=4 h,p H=7条件下,其最大净化量可达到184 mg/g。     

海藻酸钠固化香蕉皮粉吸附染料废水

利用海藻酸钠固化农业废弃物-香蕉皮粉制备成吸附剂,以甲基紫为例,对有机染料废水进行吸附研究,考察吸附时间,温度和甲基紫/吸附剂用量比对吸附的影响。实验结果表明,该吸附剂能有效地吸附掉溶液中的甲基紫,其吸附率随温度的增加而下降,最佳吸附时间为2 h,甲基紫/吸附剂的最佳用量比为1∶5。在25℃、pH 7、甲基紫起始浓度10 mg/L,吸附剂浓度50 mg/L的条件下,吸附2 h,吸附率为92.64%,吸附量为185.3 mg/g。研究了相应的Langmuir、Freundlich吸附等温线和准一级、准二级动力学方程,结果表明甲基紫的吸附动力学数据与Freundlich吸附等温线和准二级动力学方程有更好的相关性,同时该吸附剂具有较好的重复利用率。     

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.     

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.     

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 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.