甲苯气体的动态吸附净化及吸附剂再生实验研究

研究了活性炭纤维(ACF)对甲苯气体的动态吸附净化过程及热空气解吸脱附再生过程.采用3种经验方程对ACF的吸附等温线进行拟合,其中Langmuir方程拟合效果最好,拟合相关系数R2 =0.9960,说明在给定的浓度范围内,ACF对甲苯的吸附是以单分子层吸附为主.穿透曲线实验表明,ACF对甲苯吸附效果较好,Yoon-Ne...     

活性炭和沸石分子筛处理非稳定排放VOCs气体的性能比较

通过对活性炭和沸石分子筛的表征和动态吸附/脱附实验,探索2类吸附材料固定床工艺用于非连续、非稳定类型的大风量、低浓度挥发性有机物(VOCs)排放控制的应用前景。结果表明:沸石分子筛孔径分布较为集中,约在0.8 nm,比表面积为393.76 m~2·g~(-1);活性炭孔径分布具有广谱性,微孔集中在1~2 nm之间,比表面积为1 026.71 m~2·g~(-1)。活性炭对二甲苯的平衡吸附量总体高于沸石分子筛,其平衡吸附容量随气相平衡浓度和温度的波动要大于沸石分子筛。动态吸附穿透实验结果显示沸石分子筛单位传质区长度的平均传质速率是活性炭的约1.42~1.66倍。相同吸附和脱附温度条件下,活性炭的工作容量要大于沸石分子筛。沸石分子筛在210℃时基本脱附彻底,且可得到48倍以上的浓缩脱附气体。50次的吸附、脱附重复实验对沸石分子筛的性能影响不大。沸石分子筛作为吸附材料脱附单位质量的二甲苯所需能耗是活性炭的2.9~4.2倍。活性炭和沸石分子筛可采用不同的工艺方式应用于低浓度、大风量、非稳定排放的VOCs气体的净化。     

活性炭吸附回收高含量油气的研究

利用3种活性炭吸附分离汽油蒸汽和空气的混合气,研究了其吸附回收油气的动力学、热力学性能.活性炭ACl、AC3在20℃时的吸附容量分别为0.295 g/g、0.189 g/g,30 ℃时为0.284 g/g、0.165 g/g.活性炭吸附高含量油气时,吸附热高,如吸附油气摩尔分数为0.3 mol/mol时,吸附床温升达50～60 ℃.活性炭导热系数为0.15～0.20 W/m·℃,吸附过程可视为绝热吸附.建立了活性炭吸附油气热效应估算式,可用来评价活性炭吸附容量、进料油气摩尔分数、油气回收率与活性炭温升的关系.活性炭解吸宜先采取真空解吸,在解吸后期适当加入微量微热空气吹扫而深度脱附.解吸操作压力应低于1 kPa,解吸时间可控制在60 min内,热空气温度宜控制在50℃以下.油气吸附分离方法将主要用作其他分离方法的深度处理,以确保油气回收设备尾气达标排放.     

活性炭纤维吸附废水中对硝基苯酚及其脱附研究

采用新型高效吸附剂--活性炭纤维吸附废水中对硝基苯酚,对其吸附和脱附影响因素进行了较详细的研究,确定了最佳工艺参数,并对动态吸附-脱附进行了稳定性实验.在最佳的吸附条件下,装填4 g活性炭纤维可处理含对硝基苯酚1000 mg/L的废水1400 mL,出水对硝基苯酚浓度＜2 mg/L,达到国家综合污水一级排放标准,活性炭纤维有效吸附量可达349.87 mg/g.在最佳脱附条件下,脱附率＞99%,并可从高浓度脱附液中回收对硝基苯酚.稳定性实验表明,吸附-脱附性能稳定,采用活性炭纤维吸附处理对硝基苯酚废水是一种行之有效的处理方法.     

污泥活性炭固定床吸附甲苯

采用ZnCl2化学活化法制备的污泥活性炭用于固定床吸附甲苯实验,研究了吸附剂床层厚度、甲苯初始浓度、气体线速等操作条件对其吸附性能的影响,并建立了污泥活性炭吸附甲苯的传质模型,计算不同操作条件下的传质区长度和物质总传质系数。结果表明,当床层厚度从3 cm增加到7 cm,传质区长度基本不变,物质总传质系数增加了66.66%;当甲苯初始浓度增大3.36倍,传质区长度增加了17.19%,而物质总传质系数降低了22.05%;在实验流速范围内,气体线速变为原来的2倍,物质总传质系数增加了65.27%,说明污泥活性炭对甲苯吸附属于外扩散控制。     

Y型与ZSM-5型分子筛吸附VOCs性能的对比

从疏水性较好的分子筛中筛选出2类吸附性能优良的分子筛,通过实验考察其对VOCs的吸附量、脱附量、吸附穿透曲线、脱附活化能等,评价其对VOCs的吸附脱附性能;评估了所选分子筛经多次吸附再生后的性能稳定性,建立了一套分子筛工业应用性能指标体系.结果 表明:Y型分子筛性能优于ZSM-5型分子筛;同种分子筛比表面积及孔径越大,单位质量能吸附的VOCs量越多;在甲苯/乙酸丁酯的竞争吸附体系中,Y型分子筛及ZSM-5型对甲苯的吸附量较单组分情况下分别下降了50.1％、40.1％,而对乙酸丁酯的吸附量分别增加了189％、102％;甲苯在Y型分子筛上的脱附活化能为76.7 kJ·mol-1,在ZSM-5分子筛上的脱附活化能为64.7 kJ·mol-1;Y型分子筛和ZSM-5型分子筛均具有较好的循环使用性,吸附性能稳定;Yoon-Nelson模型能较好地拟合分子筛吸附穿透曲线,拟合系数在0.97以上.     

活性炭纤维吸附废水中对硝基苯酚及其脱附研究

采用新型高效吸附剂——活性炭纤维吸附废水中对硝基苯酚，对其吸附和脱附影响因素进行了较详细的研究，确定了最佳工艺参数，并对动态吸附一脱附进行了稳定性实验。在最佳的吸附条件下，装填4g活性炭纤维可处理含对硝基苯酚1000mg/L的废水1400mL，出水对硝基苯酚浓度〈2mg／L，达到国家综合污水一级排放标准，活性炭纤维有效吸附量可达349．87mg／g。在最佳脱附条件下，脱附率〉99％，并可从高浓度脱附液中回收对硝基苯酚。稳定性实验表明，吸附-脱附性能稳定，采用活性炭纤维吸附处理对硝基苯酚废水是一种行之有效的处理方法。     

活性炭负载I-TiO_2对气体中甲苯的吸附

利用溶胶凝胶-浸渍烧结法制备了碘掺杂二氧化钛修饰的活性炭复合吸附剂。利用XRD、SEM、BET、Boehm滴定、亚甲蓝吸附值等手段研究了活性炭负载前后表面结构与性质。利用动态吸附实验研究了活性炭负载I-TiO_2复合材料(IT/AC)和再生IT/AC对气体中甲苯的吸附。考察了活性炭粒径、气体的流速、吸附床层高度和气体中甲苯的浓度对活性炭吸附性能的影响及甲苯在活性炭固定床上的吸附动力学。结果表明:由于介孔I-TiO_2和活性炭的协同作用,负载适量I-TiO_2对活性炭结构和吸附性能影响较小。活性炭的粒径越小、复合材料的吸附穿透点和饱和吸附量越大;气体的流速和甲苯的初始浓度越大,复合材料的吸附穿透点越小但饱和吸附量越大。YOON-NELSON模型可以预测复合材料吸附甲苯的动力学过程。     

微波辐照载甲苯活性炭再生研究

研究在微波辐照条件下,活性炭量、微波功率、载气量、加热时间等因素对载甲苯活性炭脱附的影响,在正交实验中,各个影响因素的重要性排序为:氮气流量、活性炭量、辐照时间、微波功率,最佳的操作工况为:活性炭量9 g、载气流量300 mL/min、辐照时间120 s、微波功率500W,活性炭的脱附率在99.74%.     

微波辐照载甲苯活性炭再生研究

研究在微波辐照条件下,活性炭量、微波功率、载气量、加热时间等因素对载甲苯活性炭脱附的影响,在正交实验中,各个影响因素的重要性排序为：氮气流量、活性炭量、辐照时间、微波功率,最佳的操作工况为：活性炭量9 g、载气流量300 mL/min、辐照时间120 s、微波功率500W,活性炭的脱附率在99.74%.     

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.