磷石膏预分解的热分析研究

采用热分析的方法对磷石膏在不同掺碳量、不同气氛条件下的热反应过程进行了研究，针对近年来提出的利用水泥新型干法技术实现磷石膏预分解制硫酸联产水泥的设想，研究了磷石膏的热分解过程对预热分解炉的适应性。结果表明，在碳与磷石膏的混合体系中，碳仅能在一定程度上促进磷石膏分解，其完全分解温度接近1 300℃。而在较强还原气氛中，磷石膏+碳系统生成硫化钙，在约1 260℃时才完全分解。因此新型干法水泥工艺分解磷石膏制酸联产水泥新工艺在实际过程中将受限于硫酸盐及硫化物熔点较低与硫酸钙分解温度较高这对矛盾而不宜直接采用。     

CuMnO_x/γ-Al_2O_3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu-Mn复合氧化物催化剂和加入不同稀土含量的Cu-Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加人稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T_(99)(催化处理效率达到99%时的温度)比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

活性组分稀土氧化物对甲苯催化燃烧性能的影响

以活性组分氧化铜、氧化锰为基础,加入活性组分稀土氧化物,研究对甲苯催化燃烧性能影响。研究结果表明,在所选稀土氧化物中,加入氧化铈时甲苯的起燃温度和完全燃烧温度最低;在一定的负载量下,Cu∶Mn∶Ce摩尔比为1∶2∶0.7时,制备的Cu Mn Ce/Zr O2整体催化剂甲苯完全燃烧温度最低;催化剂合理的焙烧温度为500℃,此时甲苯的起燃温度约200℃,完全燃烧温度为220℃;催化剂合理的焙烧时间为3 h。     

CuMnOx／γ-Al2O3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu—Mn复合氧化物催化剂和加入不同稀土含量的Cu—Mn复合氧化物催化剂，通过实验优选出加入稀土催化剂中稀土含量的最优配比，以气相色谱为检测手段，考察了加入稀土和不加稀土催化剂的催化燃烧性能，结果表明，加入稀土的催化剂T99（催化处理效率达到99％时的温度）比不加稀土的催化剂降低30～40℃，具有更好的低温活性，且对多种VOCs均能降低反应温度。     

CuMnOx/γ-Al2O3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu-Mn复合氧化物催化剂和加入不同稀土含量的Cu-Mn复合氧化物催化剂，通过实验优选出加入稀土催化剂中稀土含量的最优配比，以气相色谱为检测手段，考察了加入稀土和不加稀土催化剂的催化燃烧性能，结果表明，加入稀土的催化剂T₉₉（催化处理效率达到99%时的温度）比不加稀土的催化剂降低30～40℃，具有更好的低温活性，且对多种VOCs均能降低反应温度。     

温度对污泥与底泥烧结陶粒性能的影响

研究了温度对污泥与底泥烧结制备陶粒的主要性能(抗压强度、吸水率、比表面积和密度)的影响,并结合电镜扫描(SEM)和热重红外(TG-FTIR)分析对温度影响陶粒的膨胀特性和孔隙结构的机理进行分析。研究发现,随着烧结温度的升高,陶粒比表面积和吸水率降低,而抗压强度和表观密度有所提高。SEM分析表明,温度对烧结体内部形态影响显著:800℃时烧结体呈现出松散堆积状态,1 000℃时陶粒开始产生液相,1 050℃时烧结体出现大量液相,并且陶粒中有非常丰富的气孔。TG-FTIR分析表明,有机物所发生的分解产气反应只能起到轻质化的作用,并不能使陶粒膨胀;1 000℃以上发生产气反应的主要是铁的化合物和固定碳,污泥中有机物形态存在的碳有利于将碳元素保留到陶粒高温烧结阶段,这一过程使得铁的化合物得以与碳元素发生产气反应,对陶粒多孔结构起到重要作用。     

N_2O直接分解催化剂的研究进展

本文详细综述了用于Ｎ２Ｏ直接分解催化剂的研究进展情况。Ｎ２Ｏ分解催化剂大致可以分作以下几类，即：（１）稀土氧化物及相关氧化物；（２）复合金属氧化物；（３）沸石催化剂；（４）水滑石热分解产物催化剂。前两类催化剂注重探讨催化分解Ｎ２Ｏ的机理；而后两类催化剂主要研究催化分解Ｎ２Ｏ的活性。     

脱水污泥热调质的特性

热调质方法是污泥深度脱水的有效办法之一。研究结果表明,污泥热调质过程中反应温度和反应时间对污泥热调质效果影响较大,搅拌速度影响较小。当反应温度从160℃升至180℃,反应时间从30 min增至60 min时,污泥溶液中挥发性悬浮固体(VSS)急剧溶解,释放出细胞里的结合水,表明污泥细胞破壁的温度条件为160～180℃,时间条件为45～60 min。热调质后污泥的比阻变化较大。随着反应温度的不断提高,比阻不断减小,污泥的脱水性能越来越好。实验确定了污泥热调质的最佳反应条件为:反应温度180℃,反应时间60 min,搅拌转速30 r/min。在此条件下,压滤后泥饼含水率约50%,滤液中COD浓度可达19 000 mg/L,有利于后续污泥的消化。     

水热条件下碳酰肼分解二噁英的研究

研究了保温温度为245、260℃水热条件下使用碳酰肼分解垃圾焚烧飞灰中二噁英的分解效果.结果表明,在高温水热条件下使用碳酰肼作为添加剂有利于二噁英的分解;在245、260℃下保温1 h,二噁英的分解率分别达到80%和90%以上,但二噁英毒性当量因2,3,7,8-TCDD的再生成减小很少,甚至增大;同时,在水热条件下,垃圾焚烧飞灰中的重金属取得了良好的稳定效果.     

LaxCe1-xMnO/γ-Al2O3催化剂的制备及其催化燃烧甲苯的性能

为了研究镧、铈2种稀土元素共掺金属氧化物催化剂对甲苯的去除效果,采用等体积浸渍法制备了LaxCe1-xMnO/γ-Al2O3稀土改性催化剂。考察了活性组分负载量、焙烧温度对催化剂催化活性的影响,确定了催化剂的最佳制备工艺。同时对镧、铈两种稀土元素不同原子配比对催化活性的影响进行研究。实验结果表明,LaxCe1-xMnO负载量为12%,催化剂的焙烧温度为450℃,La、Ce物质的量比为4∶1,制得的催化剂催化活性最强,催化效率最高,在6 000 h-1空速下,反应温度为320℃时即可将甲苯气体完全燃烧。运用BET、XRD、SEM、XRF等方法对催化剂的结构进行表征,结果表明,催化剂表面活性组分具有高分散性,氧化物颗粒粒径均一且分散均匀。稀土共掺催化剂与单一稀土改性催化剂相比,活性组分易于负载在载体表面,负载效果有着显著的提高。     

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.