虾壳粉对水溶液中阴、阳离子型染料的吸附

采用废弃虾壳制备吸附剂处理含刚果红或亚甲基蓝的溶液。考察了温度、吸附时间、初始浓度、吸附剂投加量和初始溶液pH对吸附效果的影响并构建了去除率预测模型,并对吸附等温线、吸附动力学和吸附热力学进行系统研究。结果表明:虾壳粉对刚果红和亚甲基蓝的吸附分别在24 h和4 h时达到平衡,平衡吸附量随吸附时间、初始浓度及吸附剂投加量的增加而增大;刚果红平衡吸附量随pH升高而增大,亚甲基蓝平衡吸附量几乎不随pH变化。在15℃下,吸附剂投加量为1 g·L~(-1),刚果红吸附的最优条件为接触时间24 h、pH=4,在该条件下,虾壳粉对刚果红的饱和吸附量为276.64 mg·g~(-1);亚甲基蓝吸附的最优条件为接触时间4 h、pH=12,在该条件下,虾壳粉对刚果红的饱和吸附量为1.44 mg·g~(-1);虾壳粉对2种染料的吸附过程以物理吸附为主,符合准二级动力学方程。虾壳粉对阴离子型染料的吸附效果较优,对阳离子型染料有一定吸附性能,是一种经济高效的染料废水吸附材料。     

氢氧化钾改性亚麻对亚甲基蓝的吸附性能研究

以亚麻为原料,氢氧化钾为改性剂,制备了一种吸附剂,用红外光谱和扫描电子显微镜对其结构进行表征,并对其吸附亚甲基蓝的性能进行了研究。结果表明,经120℃、0.8mol/L氢氧化钾改性的亚麻对亚甲基蓝的吸附量和去除率明显提高。经优化,当pH=5、超声功率为50%(125W)、超声时间为25min、亚甲基蓝初始质量浓度为300mg/L、改性亚麻投加量为0.3g时,亚甲基蓝的去除率为95.1%,吸附量为28.54mg/g。其中,pH=5~9、亚甲基蓝初始质量浓度为300~500mg/L时,亚甲基蓝的去除率和吸附量变化不大。改性亚麻对亚甲基蓝的吸附过程符合Freundlich吸附等温式,其动力学过程符合准二级动力学方程。     

氯化钙改性凹凸棒处理亚甲基蓝废水的研究

采用氯化钙改性凹凸棒,并对其进行了透射电镜、红外光谱分析。用改性后的凹凸棒泥浆处理亚甲基蓝废水,讨论了动力学和热力学吸附性质。结果表明:(1)利用氯化钙改性凹凸棒,泥浆粘度在21Pa.s条件下对亚甲基蓝废水的吸附动力学和热力学性质进行了研究。在研究范围内,改性凹凸棒泥浆对亚甲基蓝的吸附符合准二级反应动力学方程,并且Langmuir等温方程能更好地描述吸附过程。(2)改性凹凸棒泥浆对亚甲基蓝的平衡吸附量随亚甲基蓝初始浓度的增加而增大,随pH的增大而减小。(3)改性凹凸棒泥浆对亚甲基蓝主要以表面吸附为主。ΔG00、ΔH00表明吸附过程可以自发进行,并且为放热反应。ΔS00意味着随温度的增加,改性凹凸棒泥浆对亚甲基蓝的吸附趋于有序性。     

飞灰吸附亚甲基蓝的影响因素研究及其吸附模型探讨

垃圾焚烧产生的飞灰处理处置和资源化利用已成为城市可持续发展的新挑战。将飞灰作为亚甲基蓝废水的吸附剂,研究吸附时间、飞灰投加量、亚甲基蓝初始浓度对吸附性能的影响,同时探讨是否有必要对飞灰进行改性。结果表明,无需对飞灰进行水热改性就能达到很好地吸附亚甲基蓝的效果,其吸附机制符合Langmuir模型,为单分子层的均一吸附。单因素实验结果表明,飞灰吸附亚甲基蓝的最佳条件为亚甲基蓝初始质量浓度300mg/L、飞灰投加量2.0g、吸附时间60min,此时亚甲基蓝的去除率可达99.9%。     

松树锯末对亚甲基蓝（MB）的吸附研究

采用松树锯末以及改性松树锯末对模拟废水中的亚甲基蓝进行吸附实验研究。研究结果表明，当亚甲基蓝的初始浓度为50 mg/L、pH为6、锯末投加量为1 g/L时，改性前后的锯末对亚甲基蓝的吸附量最大，分别为29.9 mg/g和60.6 mg/g。同时，对改性前后的锯末做了吸附等温线拟合及动力学研究。结果表明，吸附等温线均能很好地符合Langmuir吸附模式，吸附过程符合拟二级动力学方程。     

磁性花生壳基活性炭对亚甲基蓝的吸附特性

以花生壳为原料,在K2CO3和Fe3O4共活化条件下制备了磁性花生壳基活性炭(MPSAC)。通过扫描电子显微镜、氮气吸附脱附等温线、X射线衍射和振动样品磁强计等手段表征了材料的结构和性质,测定了其对亚甲基蓝的吸附特性,考察了初始pH、吸附时间、MPSAC投加量、亚甲基蓝初始浓度和温度对吸附的影响。结果表明:(1)初始pH对亚甲基蓝的吸附影响较小;吸附时间对亚甲基蓝的吸附效率有明显的影响,在120min时吸附达到平衡,吸附过程符合准二级动力学方程。(2)吸附平衡数据更好地符合Langmuir方程,在25、35、45℃下,MPSAC的理论饱和吸附量分别为617.28、617.28、666.67mg/g。(3)热力学参数吉布斯自由能变0J/mol、焓变0J/mol、熵变0J/(mol·K),说明MPSAC对亚甲基蓝的吸附属于熵变增加的自发吸热反应过程。     

硫酸活化市政污泥对亚甲基蓝的吸附

采用市政剩余污泥作为原料,以硫酸作为活化剂制备吸附剂,并将其应用到含亚甲基蓝废水处理中。系统地研究了溶液初始pH值、亚甲基蓝初始浓度和吸附时间等因素对硫酸活化市政污泥吸附性能的影响。研究结果表明,在吸附剂投加量2 g/L,pH7.5,温度293 K条件下,硫酸活化市政污泥对亚甲基蓝的最大吸附量为38.4794 mg/g。吸附动力学和热力学研究结果表明,吸附剂对亚甲基蓝的吸附过程可用准二级动力学模型(R2=0.9910)、Freundlich吸附等温式(R2=0.9935)来描述。颗粒内扩散速率也是其吸附反应限制因素,但不是惟一限制因素。该研究表明,硫酸活化剩余污泥可以作为含亚甲基蓝染料废水的处理材料。     

改性木屑吸附除亚甲基蓝性能

为提高对亚甲基蓝的去除效果,采用热解+Na OH浸泡方法制备了改性木屑,用SEM研究了改性对木屑表面结构的影响,并以该改性木屑为吸附剂,进行了从水溶液中吸附亚甲基蓝的性能研究。研究结果显示,改性木屑表面光滑,并出现多发熔孔。常温下,改性木屑对亚甲基蓝的吸附等温线符合Langmuir方程,最大吸附量322.58 mg/g,是原始木屑的10倍,是活性炭的3倍,改性效果显著;对浓度为200 mg/L、p H值为7的亚甲基蓝溶液,改性木屑投加量为0.8 g/L时,去除率达到了99.01%,去除效果理想。吸附动力学符合伪二级速率方程。     

纳米羟基铁改性活性炭对亚甲基蓝的吸附性能研究

采用乙醇分散法制备了纳米羟基铁修饰的玉米苞叶和竹笋壳的活性炭复合物(记为nFeOOH@AC),分析了nFeOOH@AC对水样中亚甲基蓝的吸附性能及动力学机理。研究表明，nFeOOH@AC对亚甲基蓝的吸附以化学吸附为主，符合准二级动力学模型。在亚甲基蓝初始质量浓度为3～120 mg/L,体积为50 mL,nFeOOH@AC投加量为10 mg, pH为3～12,吸附时间为1～24 h时，吸附率随着pH升高而增大，随着亚甲基蓝初始浓度的增大先增后减，随着吸附时间的增加而增加。nFeOOH@AC可以作为一种新型环境友好型吸附剂应用于亚甲基蓝废水处理。     

微波活化中孔酸性生物质炭对亚甲基蓝的吸附行为与机理

以甘蔗渣为原料,采用微波辅助磷酸活化法制备了同时富含中孔结构和含氧酸官能团的生物质炭,以氮气吸附、红外光谱FT-IR等技术对炭样品表面物化性质进行了表征,通过静态实验法测定了生物质炭对水中亚甲基蓝的吸附特性,分析了溶液pH、初始浓度、温度对吸附的影响,研究了不同pH下蔗渣生物质炭对亚甲基蓝的吸附行为,并从热力学及动力学角度探讨了生物质炭对亚甲基蓝的吸附机理。结果表明,不同制备参数下生物质炭的得率均大于39.2%,但表面物化性质因参数变化有较大差异。在浸渍比1∶1,烘干时间10 h,活化功率900 W,活化时间22 min的条件下,制得的生物质炭的比表面积为1 021 m2/g,亚甲基蓝值超过国家一级品标准1.70倍,表面富含微中孔结构和羟基、羰基、羧基等酸性官能团,中孔约占总孔的40%。静态吸附实验表明,溶液初始浓度对吸附有较大的影响,吸附量随初始浓度的增加,pH的升高及温度的上升而增大,Freundlich方程、Redlich-Peterson方程与Temkin方程能较好地描述等温吸附行为;吸附动力学结果表明,数据符合Elovich方程,吸附行为更倾向于化学吸附;热力学研究表明,吸附吉布斯自由能(ΔG0)0,吸附标准焓变(ΔH0)70 kJ/mol,说明该吸附为自发的吸热反应,且化学反应在吸附过程中发挥了重要作用。     

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.