超声波有机改性凹凸棒土的苯酚吸附性能研究

采用超声波技术,对凹凸棒土进行有机改性,提高凹凸棒土的苯酚吸附能力,比较了不同的阳离子表面活性剂的改性效果,并且通过正交实验得出了超声波改性的最优化工艺条件为:十八烷基三甲基氯化铵的添加比例为35mmol/100g,超声波处理时间10min,屏极电流0·5A。在此条件下,苯酚去除率可达酸处理凹凸棒土的80倍以上,是搅拌有机改性的1.5倍。     

有机改性凹凸棒土的制备表征及其对4-氯苯酚的吸附

利用十六烷基三甲基溴化铵（HDTMA）对凹凸棒土进行有机改性，并通过SEM、XRD、FT—IR、表面积及孔径分析对改性前后的凹凸棒土进行结构表征，结果表明，利用HDTMA对凹凸棒土改性仅是表面的负载修饰，并未改变凹凸棒土的内部结构；改性凹土对4-氯苯酚的吸附实验表明，吸附速率很快，30min即达到吸附平衡，吸附符合准二级动力学方程，吸附等温线符合H型吸附等温方程，在pH为中性的环境下有利于吸附。     

以凹凸棒土为载体的非均相Fenton催化剂处理苯酚废水研究

采用浸渍法制备载铁凹凸棒土,并用其作为非均相Fenton催化剂处理模拟苯酚废水,研究该体系中各影响因素对模拟苯酚废水处理效果的影响,确定适宜反应条件,并对载铁凹凸棒土进行简单造粒研究。结果表明,载铁凹凸棒土与原凹凸棒土相比吸附能力有所增强,是一种良好的非均相Fenton催化剂。对于50 mL质量浓度为500 mg/L的模拟苯酚废水,适宜的非均相Fenton反应条件为载铁凹凸棒土14g/L、H_2O_2 1.0mL,在此条件下反应2.5h后苯酚及总有机碳(TOC)的去除率分别在98%、56%以上,非均相Fenton反应在一定程度上拓宽了Fenton反应的pH范围。将载铁凹凸棒土手工制成2~3mm颗粒,重复使用8次仍具有较高的活性,铁溶量低,具有良好的稳定性和回收性。     

烷基胍有机改性凹凸棒土研究

利用十六烷基胍盐对凹凸棒土进行有机改性,通过红外(IR)、X-射线衍射仪(XRD)、电镜(SEM)、差热(TG)、比表面积测定(BET)等分析手段对改性前后凹凸棒土进行了表征。结果表明,有机改性剂以静电吸附形式存在于凹凸棒土表面。十六烷基胍盐改性降低了凹凸棒土的空隙度和表面积。改性凹凸棒土对甲基橙模拟废水的脱色率显著提高,由改性前的3%左右提高到98%。     

改性凹凸棒土负载纳米铁的制备及性能

以200目的天然凹凸棒土为原料,先对原土进行酸活化与微波改性,再以改性凹凸棒土为载体,采用液相还原法由Fe Cl3·6H2O和Na BH4制备改性凹凸棒土负载纳米铁。通过正交实验、扫描电镜(SEM)、能谱仪(EDS)及红外光谱(IR)对负载前后的凹凸棒土进行表征分析确定其最佳条件。并通过稳定性实验和去除实验对改性凹凸棒土负载纳米铁的性能分析。结果表明:改性凹凸棒土负载纳米铁的最佳条件是铁土比为2.5∶1,酸浓度为3 mol·L~(-1),微波时间为6 min,微波功率为600 W,改性时间为24 h。改性凹凸棒土负载纳米铁在常规水处理环境中能稳定存在。对水中的Cr(Ⅵ)有良好的去除效果,去除率可达97.67%。     

改性凹凸棒粘土脱硫剂脱除SO2

采用单因素法,在传统搅拌混合下,研究了煅烧温度、煅烧时间、酸碱浸渍等对改性凹凸棒粘土脱硫剂穿透硫容与最大硫容的影响.然后在超声波混合作用下,采用正交实验确定了超声时间、超声温度以及活性组分(CaO)、促进剂(V2O5)的复配比例.结果表明:(1)甘肃临泽凹凸棒粘土富Al、Mg、Fe,且其比表面积较大.(2)改性凹凸棒粘土脱硫剂最佳制备条件:煅烧温度300℃;煅烧时间2.0 h;酸碱浸渍最佳pH9～10;混合采用超声波,超声时间30 min;超声温度40℃;CaO质量分数30%;V2O5质量分数5%.采用在最佳条件下制备的改性凹凸棒粘土脱硫剂进行脱除SO2实验,其最大硫容为38.16%.(3)改性凹凸棒粘土脱除SO2的性能比工业Fe2O3脱硫剂强.(4)X射线衍射分析表明,改性凹凸棒粘土脱硫剂脱除SO2后,将SO2转变为SO2-4,从而达到完全脱除SO2的目的,这与红外光谱分析的结果一致.     

偶联剂改性凹凸棒土处理含汞(Ⅱ)废水的研究

利用一种含氮硅烷偶联剂γ-氨丙基三乙氧基硅烷改性凹凸棒土,对凹凸棒土改性前后的表面性质进行了分析,并通过静态吸附实验研究了材料对水中汞离子的吸附性能.研究结果表明,酸活化增加了凹凸棒土吸附材料的孔道直径,使吸附速度加快,30 min即达到吸附平衡.通过硅烷偶联剂对凹凸棒土的改性,在材料表面引入了大量氨基,提高了材料对汞...     

有机改性成都粘土预处理垃圾渗滤液

以成都粘土为原料,十六烷基三甲基溴化铵(HDTMA)为改性剂制备有机改性土,并将其应用于垃圾渗滤液的预处理。采用单因素静态吸附实验,以粘土对垃圾渗滤液COD和氨氮的去除率作为考查指标,初步探究有机改性土预处理垃圾渗滤液的适宜条件;并对有机改性粘土及原土进行性能表征,初步分析其吸附机理。研究结果表明,有机土的处理效果明显优于原土,处理效果上比原土提高了1.6~2.3倍;有机土预处理垃圾渗滤液适宜条件为:投加量120 g/L、搅拌速度200 r/min、搅拌时间50 min、pH=7、静置时间为6 h。     

固定化改性蒙脱土对苯酚吸附性能的研究

利用十六烷基三甲基溴化铵对天然蒙脱土进行改性,并用聚乙烯醇对改性蒙脱土进行固定化处理,然后进行柱状吸附和振荡条件的吸附试验。研究结果表明,HDTMA改性蒙脱土固定化后能有效吸附苯酚,不同环境条件对苯酚的柱状吸附能力产生不同的影响。在pH4~8的范围内,固定化改性蒙脱土对苯酚的吸附效果无显著性差异,pH在10以上,其吸附能力明显下降;温度对吸附效果影响不大;进水苯酚浓度越高,改性蒙脱土对苯酚的吸附量越大,但出水苯酚浓度也高;苯酚的流速越小,吸附容量越高,吸附效果越好。     

磷酸改性凹凸棒粘土对Pb^2＋的吸附研究

研究了不同浓度磷酸改性凹凸棒粘土的比表面积、孔结构性质以及其对水中Pb（Ⅱ）的吸附.结果表明,凹凸棒粘土磷酸改性后比表面积明显增大,具有明显的中孔分布;9 mol/L磷酸改性处理的凹凸棒粘土吸附能力最佳,在改性凹凸棒粘土加入量为20～30 g/L,水样pH=5条件下,废水中Pb（Ⅱ）的被吸附率接近99%.     

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.     

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.     

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.