化工制药工艺残渣燃烧过程固氯研究

采用管式固定床反应器对化工制药工艺残渣的燃烧分解进行了实验研究,进一步通过加入氧化钙/碳酸钙来防止燃烧过程残渣中氯的释放.实验结果表明,残渣在燃烧时氯主要以氯化氢形式排出,加入固氯剂后能有效地抑制氯化氢的生成,且固氯效果随着钙化物投加量的增加而明显提高.当氧化钙/残渣比(质量比)达到0.8时,固氯率可达97%以上;当碳酸钙/残渣比(质量比)提高到2.0时,固氯率为76%.与此对应的Ca/Cl摩尔比分别为30和40.继续增加钙投加量,固氯效果基本不变.同时发现添加一定量的木屑在助燃的同时有助于提高固氯效果.     

燃煤钙基固砷剂的影响因素研究

利用电石渣、CaCO3、CaCO3·Ca(OH)3和Ca(OH)2作为燃煤钙基固砷剂,通过正交试验研究了固砷剂种类、固砷剂用量、燃烧温度及煤粒径对固砷效果的影响.结果表明,燃烧温度是影响燃煤固砷的最显著因素,最佳为1 050℃;钙基固砷剂中CaCO3和电石渣的固砷效果最好,其次是CaCO3·Ca(OH) 2,Ca(OH) 2的固砷效果最差;钙基固砷剂用量按Ca、S摩尔比计量为2.0、煤粒径为160～200目时,钙基固砷剂具有较好的固砷效果,而且具有固砷固硫的双重作用.     

浙江湖州黄芝山煤在燃烧过程中氟的动态

本文探索煤燃烧时氟化物的排放规律以及加入CaO后的脱氟效果。试验表明:煤燃烧时,煤中大部分氟化物均排放出去。燃烧温度是影响氟排放的主要因素,而过量空气的通入对于氟的排放无大的影响。在燃煤时加入一定量的CaO有一定的脱氟作用,CaO/S为4时,氟的排放量降低近一倍。     

可燃固废复合燃料的固硫固氯效果

以可燃垃圾、污水污泥和煤粉为原料,添加园林残余、固硫剂等按L16(45)正交表配料,采用机械成型设备制备固废复合燃料,研究燃料组分对固硫固氯效果的影响。固硫率、固氯率实验数据的极差、方差分析结果显示:CaO添加量对固硫率、固氯率的影响最显著;MnO2添加量对固氯率的影响仅次于CaO添加量,但对固硫率没有影响。运用ForStat 2.0统计软件建立了固硫率、固氯率指标的预测方程,置信度大于95%。应用综合评分法筛选出最佳固硫固氯效果的燃料制备配方为:A2B3C2D3,即垃圾、污泥、煤粉以2∶1∶1比例混合,园林残余为10%,助燃剂MnO2添加量为0.17%,固硫剂CaO添加1.2%时所制备的燃料,燃烧中固硫率可达74.55%,固氯率可达77.35%。     

钙基矿物固硫剂对不同煤种固硫效果的影响研究

对肥城煤(FC)、淮南煤(HN)和大同煤(DT)3种典型的高中低硫煤作了煤岩学分析,利用DTA、XRD、SEM、光学显微镜和粒度分析仪对钙基矿物添加剂及其固硫灰渣进行了矿物学研究.主要研究了温度、钙硫比、矿物添加剂等因素对煤种固硫率的影响.实验表明,相同的燃烧条件下,不同煤种对碳酸钙适应性有很大差异,淮南煤和肥城煤对碳酸钙的适应性明显好于大同煤,高硫煤更有利于950℃和1050℃下固硫;煤样自身固硫能力较差,碳酸钙固硫效果显著,当Ca/S=4,燃烧温度分别为1050、850和950℃时,肥城煤、大同煤和淮南煤固硫率分别达到最高值(89%、72%和89%);膨润土促进大同煤固硫,却降低了肥城煤和淮南煤固硫率;钙基矿物添加剂协同作用能更有效地提高低硫煤的固硫效果,在1050℃时,可将固硫率由51%提高到74%.     

钙基矿物固硫剂对不同煤种固硫效果的影响研究

对肥城煤（FC）、淮南煤（HN）和大同煤（DT）3种典型的高中低硫煤作了煤岩学分析,利用DTA、XRD、SEM、光学显微镜和粒度分析仪对钙基矿物添加剂及其固硫灰渣进行了矿物学研究.主要研究了温度、钙硫比、矿物添加剂等因素对煤种固硫率的影响.实验表明,相同的燃烧条件下,不同煤种对碳酸钙适应性有很大差异,淮南煤和肥城煤对碳酸钙的适应性明显好于大同煤,高硫煤更有利于950℃和1050℃下固硫;煤样自身固硫能力较差,碳酸钙固硫效果显著,当Ca/S=4,燃烧温度分别为1050、850和950℃时,肥城煤、大同煤和淮南煤固硫率分别达到最高值（89%、72%和89%）;膨润土促进大同煤固硫,却降低了肥城煤和淮南煤固硫率;钙基矿物添加剂协同作用能更有效地提高低硫煤的固硫效果,在1050℃时,可将固硫率由51%提高到74%.     

钙基固硫剂对污泥和煤燃烧过程中SO2和NOx释放的影响

在O2气氛下,研究了煤与污泥2种燃料中添加4种钙基固硫剂( CaO、Ca(OH)2、CaCO3和白云石(CaCO3·MgCO3))后的SO2和NOx的释放特性.结果表明:(1)煤燃烧时SO2的释放曲线和NO较相似,呈现2个析出峰;污泥燃烧过程中SO2和NO的释放规律一致,35 s时烟气中SO2和NO瞬时质量浓度达到峰值...     

粉煤灰的处理和利用

燃煤发电厂每年排出大量由煤的灰分形成的各种煤灰渣——粉煤灰、炉渣和熔渣,其中绝大部分是从煤燃烧后的烟气中收捕下来的细灰,我们称之为粉煤灰。 粉煤灰是我国当前排量较大、较集中的工业废渣之一。现阶段我国年排渣量已达三     

包裹块石煤固氟燃料制备工艺研究

以石灰或烧制白云岩与粘土、低氟无烟煤粉作为包裹材料,通过正交试验方法,对陕西省紫阳县蒿坪镇高氟块状石煤进行了固氟效果研究。结果表明,影响包裹石煤固氟效果的主要因素是无烟煤粉和石灰,影响顺序是无烟煤粉>石灰>粘土。最佳制备工艺条件为石煤块∶无烟煤粉∶石灰∶粘土=70∶10∶10∶5,固氟率达91.9%。     

粉煤灰、电石渣及其配合物碳酸化特性

为了促进粉煤灰和电石渣建材化高效利用和协同矿化CO_2减排,研究了粉煤灰、电石渣及其配合物的碳酸化特性。实验采用pH在线测试方法分别对粉煤灰、电石渣以及两者配合物的碳酸化过程的pH进行在线测试,并对原料和产物进行XRD、TGA和SEM表征。结果表明:相同条件下,粉煤灰碳酸化浆液pH降到7.0的平均速度约为电石渣的51倍;与等量电石渣单独碳酸化相比,粉煤灰与电石渣按照4:1(质量比)复配碳酸化pH降低到7.0的速度较纯电石渣提高了近5.6倍,且在相同电石渣配量的条件下,粉煤灰-电石渣复配料比碳酸钙-电石渣复配料的碳酸化反应完成时间缩短了31.6%,说明电石渣与粉煤灰复配后进行碳酸化反应具有明显协同促进作用。TGA分析表明,纯粉煤灰和纯电石渣的固碳率分别约为2%和61.3%,粉煤灰与电石渣复配料的固碳率较等量单一电石渣和粉煤灰的固碳率之和的计算值提高了19.6%。SEM分析表明,粉煤灰与电石渣复配料碳酸化产物碳酸钙颗粒在粉煤灰表面呈现异位分散附着形态,而单一电石渣碳酸化产物碳酸钙则在电石渣颗粒表面呈现原位聚集附着形态。这可能是复配料固碳率提高的主要原因。     

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 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.     

A History of Dry Cleaners and Sources of Solvent Releases from Dry Cleaning Equipment

Approximately 25, 000-35, 000 dry cleaning facilities currently operate in the U.S. The release of perchloroethylene and other solvents from these establishments represents a major source of soil and groundwater contamination. The manner in which dry cleaning solvents escape from dry cleaning plants is, for all practical purposes, identical for chlorinated and petroleum hydrocarbon solvents and is related to one of the following events: the catastrophic failure of a component of the dry cleaning system, the improper installation, operation or maintenance of the dry cleaning equipment or a combination of all of these causes. Acceptable customs, codes and regulations can also dictate what is authorized for operation of a dry cleaning facility in a particular community, geographic area during a particular time frame. Environmental litigation dealing with the origin of a solvent release from dry cleaners tends to focus on the design and manufacture of dry cleaning industry machines such as washers, washer extractors, tumblers, solvent filters, water separators, stills and spotting boards. A thorough analysis of the daily operations of dry cleaners often reveals that poor maintenance, failure to follow the manufacturer's instructions and the actions of the operator are the most likely causes of soil and groundwater pollution. In order to forensically evaluate the most probable origins of a solvent release and to examine issues regarding liability, a thorough understanding of the history of dry cleaning and a detailed analysis of the operation and maintenance of the dry cleaning equipment are necessary. The discovery of solvent plumes in the vicinity of dry cleaning plants may suggest that the solvent source is the dry cleaning plant; however, the presence of these plumes does not necessarily indicate that the dry cleaning equipment was defectively designed or manufactured. A thorough review of the type of equipment used over the life of the dry cleaning plant and verifiable solvent mileage records frequently indicates that operators of the plant have disposed of solvent and contaminated solids into the municipal sewer or on ground surfaces.     

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.