磁性CoFe_2O_4/MgAl-LDH去除水中的磷酸盐

采用共沉淀法制备了磁性复合材料Co Fe2O4/Mg Al-LDH,通过静态吸附实验研究了Co Fe2O4/Mg Al-LDH对磷酸盐的吸附性能,考察了吸附剂投加量、溶液p H值、吸附时间、温度、共存离子等因素对磷酸盐去除效果的影响。结果表明,在实验条件下,Co Fe2O4/Mg Al-LDH对磷酸盐的吸附量随溶液p H值的增大而逐渐降低,吸附的最佳p H值为1.5。磁性Co Fe2O4/Mg Al-LDH对磷酸盐的吸附动力学符合准二级动力学模型,吸附等温线符合Langmiur等温吸附模型,理论最大吸附容量为105.37 mg/g。吸附热力学参数表明,Co Fe2O4/Mg Al-LDH对磷酸盐的吸附是自发、吸热的过程。     

Fe3O4@SA/GO凝胶球的制备及对亚甲基蓝的吸附性能

以海藻酸钠为骨架,结合Fe3O4及氧化石墨烯制备了Fe3O4@SA/GO复合凝胶球.采用SEM、FT-IR、XRD、VSM等对制备的材料进行了表征分析,并且考察了Fe3O4@SA/GO对水中亚甲基蓝的吸附性能.结果 表明:Fe3O4@SA/GO凝胶球空隙较多,表面含有丰富的羧基、羟基等含氧官能团;材料磁性能良好,饱和磁化强度达到了17.88 emu·g-1,具有超顺的磁性;在25℃、pH=9的条件下,投加量为1 g·L-1的吸附剂对100mg·L-1亚甲基蓝吸附300 min,吸附率达到了92.4％,吸附量可达94 mg·g-1;吸附过程相对符合伪一级动力学方程,吸附过程偏向于物理吸附;Langmuir等温模型能够更好地反应吸附平衡,吸附以表面单层覆盖为主,最大吸附量为452 mg·g-1;在相同条件下,Fe3O4@SA/GO对混合液中亚甲基蓝的吸附效果优于碱性品红;该吸附剂具有良好的循环利用性能,5次脱附循环使用后对亚甲基蓝的吸附率依旧保持在70％以上.以上研究结果可为处理印染废水提供参考.     

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。     

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。     

城镇有机垃圾热解生物炭对水中亚甲基蓝的吸附

热解是一项极具前景的城镇垃圾资源化处理技术,对热解产物的合理利用有助于热解技术的推广应用。以1套垃圾分选、热解工程设备产生的生物炭为原料,研究生物炭对水中亚甲基蓝的吸附效果,分析吸附动力学和吸附等温线;通过红外光谱、比表面积、孔径及微观形貌的表征方法阐释其吸附机理,并进行经济性分析。结果表明,生物炭对亚甲基蓝的去除率随生物炭投加量的增加而增加,随亚甲基蓝溶液初始浓度的增加而降低,在pH为9时达到最高。生物炭对亚甲基蓝的吸附过程符合准二级动力学方程和Langmuir吸附等温线方程,为单分子层吸附,最大吸附量为35.7 mg·g~(-1)。生物炭具有较强的非均质性,其对亚甲基蓝的吸附主要发生在微孔中,且亚甲基蓝与生物炭表面的O—H、NH~(3+)、NH_2、C—O等基团发生了作用,说明亚甲基蓝在生物炭表面的吸附受生物炭孔结构和化学性质2个方面的影响。生物炭的制备过程可产生446～708元·t~(-1)的经济效益,作为废水处理的吸附剂具有较好的应用前景。     

Fenton法制备污泥基活性炭及其性能表征

污泥基活性炭孔隙率低下是污泥资源化利用的主要制约因素,而Fenton法预处理污泥,可有效改善活性炭性质。通过考察H2O2投加量、H2O2/Fe2+、活化pH以及炭化条件等参数,确定了最佳污泥基活性炭制备条件:H2O2投加量为5%(质量分数),H2O2/Fe2+为5∶1(质量比),活化pH为3,活化时间为2.0h,污泥含固率为1.0%(质量分数),炭化温度为600℃,炭化时间为2.0h,炭化升温速率为10℃/min。此时,得到的污泥基活性炭吸附碘值为340mg/g,比表面积为353.563m2/g,孔容积为0.238cm3/g,微孔容积为0.095cm3/g。该活性炭对阳离子和阴离子染料(亚甲基蓝和甲基橙)具有良好的吸附性能,结果表明,对亚甲基蓝和甲基橙的吸附更符合Langmuir方程,且其饱和吸附量分别为71.53、57.73mg/g。对吸附动力学的拟合结果表明,该吸附更符合二级动力学方程。     

阳离子表面活性剂改性油茶果壳对水溶液中甲基橙的吸附

以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对油茶果壳进行改性,制备CTAB-油茶果壳(CTABCOS)吸附材料,并采用批实验法对其对水溶液中甲基橙的吸附去除进行了研究。考察了溶液p H、吸附剂用量和离子强度等对水溶液中甲基橙的吸附影响,并研究了体系的吸附动力学和吸附热力学特征。结果表明,向100 m L浓度为50 mg/L的甲基橙溶液中加入0.40 g CTAB-COS,在最佳实验条件下,CTAB-COS对甲基橙的去除率可达96.66%。溶液离子强度增大,甲基橙去除率降低。CTAB-COS对甲基橙的吸附行为符合拟二级动力学模型,吸附等温线可用Langmuir模型进行较好拟合,在20℃时最大吸附量为18.31 mg/g。吸附热力学结果表明,吸附过程为可自发进行的放热过程。再生性实验结果表明,再生6次后,CTAB-COS对甲基橙的吸附去除率仍可达到80%。该改性油茶果壳可应用于阴离子型染料废水的吸附法处理。     

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。     

复合型生物炭对废水中亚甲基蓝的吸附作用

以木屑、二氧化硅为原料,采用慢速热解法制备了木屑生物炭(BC)和木屑-二氧化硅复合型生物炭(CBC),并对其物理化学性质进行表征,同时研究其吸附水中亚甲基蓝的吸附等温方程、动力学过程和影响因素。结果表明,和BC相比,CBC的比表面积、孔体积和平均孔径分别增加了2.85、7.00、1.21倍。CBC和BC对亚甲基蓝的吸附符合Langmuir吸附等温方程,其最大吸附量分别为26.60、5.37mg/g,CBC对亚甲基蓝的吸附能力更强。CBC和BC对亚甲基蓝的吸附动力学过程遵循准二级动力学方程。此外,和BC相比,CBC对亚甲基蓝的吸附效果受pH和离子强度影响较小。     

亚甲基蓝在污泥活性炭上的吸附

以剩余污泥为原料,氯化锌为活化剂制备污泥活性炭。研究了初始pH值、吸附温度及离子强度对污泥活性炭吸附亚甲基蓝效果的影响。采用高分辨电子扫描电镜(SEM)和氮吸脱附曲线对污泥活性炭进行了表征。结果表明,随着pH值的升高,吸附量增大,碱性条件下最好。在15～55℃的范围内,亚甲基蓝的吸附量先增加后降低,温度为35℃时吸附量达到最大值。加入氯化钠后的污泥活性炭的吸附能力变弱,但随着离子强度的增大,变弱的强度减少。污泥活性炭以中孔为主和污泥活性炭具有不规则结构,预示着污泥活性炭较高的吸附能力。污泥活性炭对亚甲基蓝的吸附符合Lang-muir等温吸附方程。污泥壳活性炭对亚甲基蓝的吸附符合二级反应动力学方程反应特征。     

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.     

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 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.     

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.