煤质炭制备条件的优化及对酚类吸附性能与吸附动力学

KOH为活化剂,正交实验方法优化了煤质炭的制备条件。对2种酚类有机物苯酚、氯苯酚进行了静态吸附,观察了温度、时间、初始浓度及投加量对吸附性能的影响,优化了吸附条件。实验数据与Langmuir、Freundlich和Temkin吸附等温线进行了拟合,并对准一级、准二级动力学模型和内扩散模型拟合。结果表明,优化得煤质炭制备条件为:碱碳质量比3∶1,浸泡时间12 h,活化时间80 min,活化温度800℃。在温度为25℃,投加量为0.05 g时,苯酚的平衡时间为60 min,初始浓度为200 mg/L时的吸附量为58.89 mg/g;氯苯酚的吸附平衡时间为90 min,初始浓度为300 mg/L时的吸附量为84.32 mg/g。煤质炭对苯酚的吸附过程与Langmuir吸附等温线,氯苯酚的吸附过程与Temkin吸附等温线拟合得较好。二级动力学模型能够较好地描述这2个吸附过程,且颗粒内扩散不是唯一的速率控制步骤。     

东京根霉对重金属Cr3+、Mn2+和Zn2+的吸附研究

利用固定化发酵中产生的废菌体--东京根霉(Rhizopus tonkinesis)去除废水中Cr3 、Mn2 和Zn2 ,研究了预处理、pH、温度、金属离子初始浓度、吸附时间等条件对吸附量的影响.结果表明,用NaOH浸泡4～6 h、在pH=5～6,温度25～35℃时吸附效果最好,用Langmuir、Freundlich和Temkin方程对其吸附等温线进行拟合,相关性都比较好;用不同的吸附动力学方程描述东京根霉吸附金属离子的最优和最次模型分别为Elovich方程和一级扩散方程,双常数方程和抛物线扩散方程拟合介于前二者之间.     

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。     

核桃壳对模拟废水中Cu~(2+)的吸附性能研究

采用核桃壳作为吸附剂,对模拟废水中的Cu2+进行吸附去除,考察了吸附剂粒径、水样初始pH、吸附剂用量、Cu2+初始浓度、吸附时间等因素对Cu2+吸附效果的影响,确定最佳吸附参数,并进行了吸附动力学和吸附等温线分析。结果表明:最佳吸附参数为核桃壳吸附剂粒径1.25~1.60mm、水样初始pH 5.0、吸附剂用量2.5g,Cu2+初始质量浓度20mg/L、吸附时间360min,在此条件下100mL水样在200r/min、25℃条件下吸附的Cu2+去除率达70%以上,吸附量约为0.702mg/g;本实验过程采用伪二级动力学方程的拟合更好,R2均在0.9以上,Cu2+吸附速率与其浓度的二次方成正比;Langmuir方程可以较好地描述核桃壳吸附剂对Cu2+的吸附过程,此吸附过程是单分子层的吸附。     

东京根霉对重金属Cr^3＋、Mn^2＋和Zn^2＋的吸附研究

利用固定化发酵中产生的废菌体——东京根霉（Rhizopustonkinesis）去除废水中Cr^3＋、Mn^2＋和Zn^2＋,研究了预处理、pH、温度、金属离子初始浓度、吸附时间等条件对吸附量的影响。结果表明，用NaOH浸泡4—6h、在pH=5—6，温度25-35℃时吸附效果最好，用Langmuir、Freundlich和Temkin方程对其吸附等温线进行拟合，相关性都比较好；用不同的吸附动力学方程描述东京根霉吸附金属离子的最优和最次模型分别为Elovich方程和一级扩散方程，双常数方程和抛物线扩散方程拟合介于前二者之间。     

海带对镉的吸附动力学与热力学研究

采用批量平衡法研究了海带对镉的吸附的动力学与热力学,并采用Lagrange假一级动力学方程、假二级动力学方程、Langmuir等温线方程、Freundlich等温线方程以及Dubimim-Radushkevich等温线方程对实验数据进行了拟合.结果表明,在4种温度下海带对镉的吸附率均随吸附反应时间增加而增大,在60 min时达到最大,此后基本保持不变,随着温度由20℃升高至50℃,其最大吸附率呈下降趋势,由90.2%降至77.5%;海带对镉的吸附动力学符合Lagrange假二级动力学方程;海带对镉的吸附热力学符合Langmuir等温线方程和Dubimim-Radushkevich等温线方程,表明吸附主要发生在海带表面的活性区位,属于单分子层吸附,其吸附平均活化自由能E为11.4 kJ/mol,表明该吸附过程为化学吸附,在4种温度下吉布斯自由能变化量△AG°均为负值,吸附焓变△H°也为负值,表明海带对镉的吸附为放热反应,能自发进行.     

胺化木质素对水中Cu（Ⅱ）、Cd（Ⅱ）的吸附

以胺化木质素作吸附剂对水中Cu2＋、Cd2＋的去除进行了研究，主要考察了吸附时间、溶液pH值、温度和金属离子初始浓度对吸附去除率的影响，并研究了其吸附等温线和动力学。结果表明，胺化木质素能有效去除水溶液中的Cu2＋、Cd2＋，且对Cd2＋的吸附能力大于Cu2＋吸附动力学符合准二级动力学方程，吸附等温线均可以很好地用Langmuir方程描述。     

牛粪生物炭对Cd~(2+)的吸附影响因素及特性

为了考察以牛粪为原料制备的生物炭对水溶液中Cd2+的吸附效果,进行了吸附影响因素、吸附等温线和动力学研究。结果表明,当热解温度为700℃、投加量为20 g/L、溶液初始pH为5、水溶液Cd2+初始浓度为10 mg/L、吸附平衡时间为60 min和溶液温度为25℃时,对Cd2+的吸附效果最佳,Cd2+去除率可达99%以上。提高溶液温度有利于吸附。降低生物炭热解温度和投加量对吸附效果影响不大。Langmuir方程能更好地拟合生物炭对Cd2+的吸附等温过程,吸附过程符合准二级动力学方程。牛粪生物炭是性能优良、价格经济的水溶液中Cd2+的吸附剂。     

香菇下脚料对水体中十二烷基苯磺酸钠的吸附

香菇下脚料经甲醛/硫酸混合溶液处理后制备成吸附剂。研究了吸附剂对SDBS的吸附性能,考察了溶液pH值、吸附剂粒径、初始浓度、吸附时间、浓度和温度的影响。结果表明,吸附适宜条件的为:pH 4.0,吸附时间60 min,吸附过程可以很好地用准二级动力学方程描述,吸附等温线用Langmuir方程的拟合效果优于Freundlich和Tempkin方程。在热力学研究中,ΔG0<0,ΔH0>0,ΔS0>0,表明此吸附过程是自发、吸热和熵增加的过程。     

大孔树脂吸附去除水中的2,4,6-三硝基甲苯

研究了2种大孔树脂XAD-4和NDA-804对水中的TNT的吸附行为。2种树脂对TNT的吸附等温线表明,温度的升高有利于吸附,在35℃条件下XAD-4树脂与NDA-804树脂对TNT的最高平衡吸附量分别达82.86 mg/g和94.26mg/g。采用Langmuir方程和Freundlich方程用于吸附等温线的解释,结果表明,吸附等温线更加符合Langmuir模型,相关系数均大于0.99。TNT在2种树脂上的吸附符合准二级动力学方程,TNT初始浓度越低,达到吸附平衡所需时间越短,在1 h内可达到吸附平衡。采用NDA-804处理对TNT废水,废水中TNT浓度由103.58 mg/L降至0.4 mg/L,去除率达99.6%,吸附后的树脂采用pH=2的乙醇和盐酸的混合液脱附可再生,高浓度再生溶液经蒸馏可回收TNT,实现了废水治理与资源化。     

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.