活性半焦用于油田含油污水除油的研究

以经济廉价的半焦为原料,制备用于处理油田含油污水的吸附剂。采用高温焙烧活化、水蒸气活化、高压水热活化以及硝酸、氢氧化钾活化等方法对半焦进行活化处理,通过静态吸附实验测定除油率来评价活化效果,重点讨论了氢氧化钾活化条件对除油效果的影响。结果表明:KOH与半焦质量比为6∶1,80℃浸渍3 h,550℃焙烧1.5 h时,制备的活性半焦吸附除油效果最好,除油率可以达到75.6%;活性半焦对油的吸附符合Freund lich吸附方程。利用酸碱滴定法对样品表面酸碱官能团进行分析,发现KOH活化后半焦表面碱性亲油官能团明显增多;通过SEM对半焦的微观结构进行分析,发现KOH活化后半焦产生大量有利于吸附的孔结构。     

分子筛负载型吸附剂对典型VOCs的吸附行为特性

以浸渍法制备的分子筛负载铜锰铈(Cu-Mn-Ce/ZSM)为吸附剂,以甲苯、乙酸乙酯和丙酮作为挥发性有机物(VOCs)的典型代表,考察了单组分和混合组分VOCs在吸附剂固定床上的吸附行为。研究表明,Cu-Mn-Ce/ZSM吸附单组分VOCs时,甲苯的吸附穿透时间与饱和吸附量分别为110 min和32.47 mg/g,乙酸乙酯为150 min和52.29 mg/g,丙酮为210 min和86.40 mg/g,可见Cu-Mn-Ce/ZSM对单组分VOCs的吸附能力大小为:丙酮乙酸乙酯甲苯。Cu-Mn-Ce/ZSM吸附混合组分VOCs时,在甲苯与乙酸乙酯的穿透曲线上出现了明显的"驼峰",吸附穿透过程中存在共吸附和竞争吸附行为,甲苯的吸附穿透时间与饱和吸附量降至50 min、10.42 mg/g,乙酸乙酯为95 min、15.12 mg/g,丙酮为105 min、44.37 mg/g。通过Yoon-Nelson模型对单组分VOCs吸附穿透曲线的拟合,表明吸附模型参数可以准确地预测吸附质在固定床上的穿透行为。速率参数k'值计算表明,不同VOCs在固定床上的吸附速率大小为丙酮乙酸乙酯甲苯。     

木镁基碳质吸附剂的制备及其性能

用木镁聚合物(PML)制备碳质吸附剂,探讨了影响产物吸附性能的主要制备因素。结果表明,当活化温度为400℃,磷料比为2∶1和活化时间为2.5 h时,木镁基碳质吸附剂(MLCA)的吸附性能较好,其亚甲基蓝吸附值为142.5 mg/g,碘吸附值为946.43 mg/g。红外光谱分析表明,经过高温处理后,产物保持了PML的基本结构特征,而其比表面积由0.07 m2/g增大至642.38 m2/g。MLCA对染料亚甲基蓝的吸附过程符合Langmuir吸附等温式。     

污泥含炭吸附剂对挥发性有机废气吸附实验研究

研究了污泥含炭吸附剂对挥发性有机污染物的吸附特性。结果表明,污泥含炭吸附剂对苯系物的吸附为典型的物理吸附,其吸附甲苯等温线的类型系优惠型吸附等温线,表明具有良好的吸附能力;在吸附反应温度为20℃,气体流量为500 mL/m in(停留时间为0.424 s),甲苯浓度为2 700 mg/m3时,甲苯的饱和吸附容量为150.0 mg/g;同时,研究表明污泥含炭吸附剂对苯系物的饱和吸附容量和吸附强弱次序为二甲苯甲苯苯。结果表明污泥含炭吸附剂适合对中低浓度有机废气的吸附净化。     

半焦吸附养殖废水中的重金属

采用生物质半焦作为吸附剂处理养殖废水中的重金属,并对半焦吸附重金属的吸附容量及吸附效率进行了分析和评估。实验结果表明,生物质半焦对养殖废水中Cu、Zn、Pb和Cd 4种重金属具有较好的吸附效果,吸附容量分别为22.4、19.03、17.30和16.94 mg/g,且吸附率均达到70%以上,氮磷的影响吸附不超过30%。重金属离子在半焦表面上的吸附过程符合Langmuir等温吸附模型,且主要为单分子层表面吸附。由此生物质半焦作为廉价高效的吸附剂处理养殖废水中重金属技术上可行,为养殖废水中重金属吸附研究及生物质半焦资源化利用提供新途径。     

海藻酸钠包埋凹凸棒土颗粒吸附剂的制备及其对单宁酸的吸附

利用海藻酸钠和氯化钙成球原理,包埋制备有机凹凸棒土颗粒(GOAT)吸附剂,通过SEM图和红外谱图进行表征,通过批量实验考察了凹凸棒土颗粒吸附剂对水体天然有机质单宁酸的吸附行为,结果表明,凹凸棒土颗粒吸附剂内部形貌和粉体吸附剂(POAT)相比无明显变化;平衡吸附量(142 mg/g)稍低于粉体吸附剂(148 mg/g);吸附速率较快,100min时吸附趋于平衡,吸附行为符合准二级动力学方程;吸附等温线符合Freundlich等温方程,吸附为放热反应;p H为6时吸附性能最佳。     

剩余污泥制备活性炭及其应用研究

以城市污水处理厂二沉池排出的剩余污泥为原料，采用不同活化方法制备活性炭，同时对比活化效果，研究了制备工艺条件对污泥活性炭吸附性能及产率的影响。结合比表面积、孔径分布和扫描电镜表征分析，对制备的污泥活性炭的性能进行评价，并探讨了污泥活性炭作为水处理吸附剂的去除效果。结果表明，以ZnCl₂为活化剂制备的活性炭性能较好，其最佳制备条件为：活化温度550℃，活化时间45 min，ZnCl₂浓度40％，固液比1∶2。制得的污泥活性炭的碘吸附值为496 mg/g，产率为51.8％，比表面积为301.4 m²/g,孔体积为0.37 mL/g，微孔体积为0.08 mL/g，平均孔径为5.78 nm。将该产品用于处理城市污水，投加量为0.8％，吸附平衡时间约为60 min时，对COD的去除率为81％，吸附容量为42.53 mg/g。     

泥炭对甲苯的吸附-解吸行为研究

用热处理方法对泥炭进行活化改性,探讨了对甲苯的吸附性能及影响因素,并研究了甲苯在泥炭上的吸附/解吸行为。结果表明,粒径在0.6～1 mm之间的泥炭在160℃热处理5 h,在pH为7的条件下对甲苯有良好的吸附效果,对甲苯的吸附量为0.32 mg/g。泥炭对甲苯的吸附在20 min内基本达到平衡,可用二级吸附速率方程进行拟合。甲苯在泥炭上的吸附和解吸均呈现明显的非线性,用Langmuir模型能较好地描述,泥炭对甲苯的饱和吸附量为0.939 mg/g。甲苯在泥炭上的平均解吸率为6.393%,并且出现了滞后现象,表明苯系物与泥炭有较强的结合能力。研究结果为应用泥炭作为PRB装填介质进行原位修复甲苯污染的地下水提供了理论依据。     

非活体生物质对水中活性艳红X-3B的吸附研究

研究了4种非活体生物质(米酒糟、花生壳、柚子皮、稻草秸秆)对模拟废水中活性艳红X-3B的吸附条件及吸附机理。结果表明,活性艳红X-3B初始浓度为100 mg/L、pH为1.0~2.0、吸附剂浓度为10 mg/L时,4种吸附剂对活性艳红X-3B的吸附率可达到80%。吸附在60 min左右达平衡后最大吸附量的顺序为:米酒糟(58.8 mg/g)花生壳(28.0mg/g)柚子皮(23.6 mg/g)稻草秸秆(19.5 mg/g)。在达最大吸附率时,米酒糟的用量可减少一半、pH范围可宽为1.0~6.0,且吸附量是另三者的2倍以上。综合比较,米酒糟具有较强的吸附废水中活性艳红X-3B的能力,可作为废水中活性染料的吸附剂使用。而花生壳、柚子皮和稻草秸秆的吸附能力相对较弱,不是理想的吸附材料。数学模型模拟表明,米酒糟和柚子皮的吸附过程更符合Freundlich方程,而花生壳和稻草秸秆更符合Langmuir方程;动力学研究表明4种吸附剂的吸附拟合更符合拟二级动力学方程。     

改性膨胀石墨对含铅废水吸附特性

采用微波法在1 000 W下微波膨胀60 s制备了膨胀石墨,以乙醇为分散剂,采用超声沉淀法制备了纳米氢氧化镁,同时将纳米氢氧化镁负载到膨胀石墨孔隙中,制备出一种新型吸附剂,并采用静态吸附的方法研究了该吸附剂对铅离子的吸附效果,实验证明当改性膨胀石墨的用量为0.035 g,铅溶液的pH=4,铅溶液初始浓度为300 mg/L,吸附温度为25℃时,该吸附剂对铅离子的去除率能达到48%,吸附容量能达到105 mg/g左右。同时该吸附反应能够较好地符合Lang-muir吸附等温式以及二级动力学模型。     

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.     

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.     

Influence of crop residues on trifluralin mineralization in a silty clay loam soil

Trifluralin is typically applied onto crop residues (trash, stubble) at the soil surface, or onto the bare soil surface after the incorporation of crop residues into the soil. The objective of this study was to quantify the effect of the type and amount of crop residues in soil on trifluralin mineralization in a Wellwood silty clay loam soil. Leaves and stubble of Potato (Solanum tuberosum) (P); Canola (Brassica napus) (C), Wheat (Triticum aestivum) (W), Oats (Avena sativa), (O), and Alfalfa (Medicago sativa) (A) were added to soil microcosms at rates of 2%, 4%, 8% and 16% of the total soil weight (25 g). The type and amount of crop residues in soil had little influence on the trifluralin first-order mineralization rate constant, which ranged from 3.57E-03 day^?1 in soil with 16% A to 2.89E-02 day^?1 in soil with 8% W. The cumulative trifluralin mineralization at 113 days ranged from 1.15% in soil with 16% P to 3.21% in soil with 4% C, again demonstrating that the observed differences across the treatments are not of agronomic or environmental importance.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.