生活垃圾与煤混合燃烧特性及动力学分析

利用热重分析仪对生活垃圾与煤混合试样的燃烧特性及热反应动力学进行了实验研究,考察了不同配比混合试样的着火温度、燃尽温度、最大燃烧速率及最大燃烧速率温度等燃烧特征参数,并用Coats-Redfern积分法对其进行了燃烧动力学分析,确定了燃烧动力学方程,求出了反应活化能Ea及指前因子A。实验结果表明:生活垃圾与煤混合燃烧时均保持各自的燃烧特性;混合燃料中随着生活垃圾掺量的增加,热重曲线向低温区转移,燃尽点逐渐降低,综合燃烧特性指数明显增大,生活垃圾能改善煤的燃烧性能;生活垃圾及其与煤混合燃烧出现两个燃烧阶段,分别遵循二级和一级反应机理,煤燃烧只出现一个燃烧阶段,遵循一级反应机理;混合燃料燃烧反应活化能Ea与指前因子A存在动力学补偿效应。     

餐厨垃圾分选有机废物热解动力学特性分析

针对餐厨垃圾生物处理过程中产生的有机废物,为了实现餐厨垃圾的资源化利用,使用热重分析仪对其典型组分:塑料、骨头及难降解生物质,进行了单独及混合热重(TG)特性研究。结果表明:难降解生物质(BRB)、骨头等生物质类物质失重温度较低,最大失重率温度分别为325和341℃,塑料的失重温度较高,最大失重率温度在475℃;通过对混合物料的热重曲线和动力学分析,在较低温度(400℃),塑料和骨头对热解过程有一定的抑制作用,而在高温(400℃)状态下,二者在热解过程中有协同作用;含有3种组分的实际物料在166~361℃条件下热解过程符合二维相界反应(函数为2(1-α)1/2);而在361~550℃热解符合三级动力学反应(函数为(1-α)3),在整个温度阶段(166~550℃)中的实际活化能低于模拟活化能(59.6986.57 k J·mol-1),表明3种物料混合热解有协同作用。     

造纸工业污泥燃烧特性及动力学实验研究

在不同升温速率及与其他污泥不同混合比例条件下，利用热重法对造纸污泥和含工业污水污泥进行了实验研究。结果表明，造纸污泥与含工业污水污泥表现出不同的DTG曲线形式，其中造纸污泥固定碳燃烧峰失重较为明显。随着升温速率的提高，造纸污泥的燃烧速率加大，燃尽时间缩短，提高了其综合燃烧特性；加入含工业污水污泥后，造纸着火性能及燃尽性能均得到改善。采用积分法（Coats-Redfern方程）计算得到各阶段燃烧反应的机理方程及相应的活化能参数，表明活化能的大小与试样的燃烧阶段是相对应的。     

矿物元素迁移对脱脂餐厨垃圾灰熔融特性的影响

为探究脱脂餐厨垃圾燃烧过程中矿物元素迁移对灰熔融特性的影响,对不同灰化温度下得到的脱脂餐厨垃圾灰(以下简称垃圾灰)进行灰熔点测试及灰成分分析,并利用X-射线粉末衍射(XRD)分析和扫描电子显微镜(SEM)对垃圾灰进行表征。结果表明,灰化温度对脱脂餐厨垃圾的灰熔融温度影响不大,K、Na、Cl元素在垃圾灰中的主要存在形式为NaCl、KCl,随着灰化温度从500℃升高至1 100℃,垃圾灰中K、Na、Cl元素质量分数分别下降86.57%、67.67%、95.92%,主要是以气态NaCl、KCl形式析出;升温过程中Ca元素质量总体变化不大,Ca元素的迁移主要经过2个过程,羧磷灰石到钠钙铝盐的混盐再到白磷钙石,脱脂餐厨垃圾灰熔点较高的主要原因是大量Ca、P元素形成的高熔点矿物质白磷钙石所致。     

石灰调质污泥的燃烧特性及动力学分析

采用热重-差示扫描量热同步分析仪,在空气气氛下对石灰调制污泥进行燃烧失重实验.通过分析获得的曲线,可以将调质污泥的热反应过程分为4个阶段:自由水和化学结合水析出阶段;易挥发有机质析出和燃烧阶段;难挥发有机质析出分解和燃烧阶段;无机质的分解阶段.添加石灰后,污泥的着火温度小幅上升,综合燃烧特性指数随添加量增加而减小.采用Coats-Redfern积分法对挥发分析出和燃烧阶段进行了热反应动力学求解,发现添加量小于30％时,石灰可以减少污泥燃烧的活化能,促进污泥挥发分的析出和燃烧.     

O_2/CO_2气氛下市政污泥混煤燃烧及动力学特性

采用差示扫描量热法对市政污泥、神华烟煤和淮北烟煤单独及不同比例混合物在O2/CO2气氛下进行燃烧特性的实验研究,结果表明,市政污泥综合燃烧特性最好,神华烟煤次之,淮北烟煤最差;随着污泥掺混比例的增加,混合试样着火温度和燃尽温度提前,综合燃烧特性得到改善,但燃烧放热量减少。利用Freeman-Carroll法对淮北烟煤、市政污泥及两者混合物的燃烧动力学参数进行计算,得到市政污泥、淮北烟煤和神华烟煤的平均反应活化能E分别为48.34、68.32和51.47 k J/mol。     

污水污泥流化床空气气化焦油的燃烧特性

利用热重分析法,研究了气化温度(650、750和850℃)和污泥性质对污泥流化床气化焦油燃烧特性的影响变化规律。结果表明:6种污泥气化焦油的燃烧过程均分为轻质有机物挥发和燃烧、重质有机物分解和燃烧以及微量残炭燃烧3个阶段;其中第一阶段失重率均明显高于第二阶段,且第一阶段和第二阶段的失重率随气化温度的升高而分别呈现为升高和降低的变化趋势。来自于活性污泥法工艺未消化污泥气化焦油在第一阶段的失重率高于消化污泥的,而A2/O工艺未消化污泥气化焦油在第一阶段的失重率则低于消化污泥的。6种气化焦油的机理函数不完全相同,但反应级数均在1~2.5之间,且第一阶段的表观活化能均低于30 k J·mol-1。污泥流化床空气气化焦油的着火点和表观活化能均比其固定床空气气化焦油的低。     

不同升温速率下城市污水污泥热解特性及动力学研究

利用差热-热重分析法和Coats-Redfern积分法,对杭州某污水处理厂污泥在不同升温速率下的热解特性及反应动力学特征进行研究。实验结果表明,热解温度从室温升至900℃时,污泥热解过程可分为4个失重阶段;升温速率对污泥热解转化率、挥发分析出温度以及最大失重率等热解特性参数都有显著影响。升温速率越高污泥最大失重率越大;而较低的升温速率延迟了污泥热解反应时间,导致污泥失重量相对较大。根据Coats-Redfern积分法计算结果,污泥在氮气氛围下的热解反应为二级反应模式。提高升温速率可显著增加污泥热解的表观活化能和频率因子。     

废润滑油再生燃油及其碳烟热重特性研究

为合理评价废润滑油再生燃油的热稳定性及其燃烧生成碳烟的氧化活性,采用热重分析法研究了废润滑油再生燃油及碳烟的热重特性,同时采用Coats-Redfern方程计算了燃油与碳烟的热动力学参数。结果表明:(1)分别采用一级、二级动力学模型求解2种燃油及其碳烟的热动力学参数,热动力学参数的拟合直线的线性相关性较好。(2)再生燃油的热稳定性比柴油好。最大失重速率对应的温度接近燃油的着火温度。再生燃油、柴油的活化能分别为44.2、39.2kJ/mol。(3)碳烟存在3个明显的质量损失阶段。(4)再生燃油燃烧生成碳烟的10%失重时对应的起燃温度高于柴油,两者燃烧生成碳烟的50%失重时对应的起燃温度相差不多。     

餐厨垃圾与剩余污泥混合消化产沼气协同效应

在(35±0.2)℃温度下,以餐厨垃圾和剩余污泥为原料,设置餐厨垃圾和剩余污泥混合比例(VS)分别为1∶0、2∶1、1∶1、1∶2和0∶1,研究其单独消化与混合消化的系统性能、产甲烷潜力及脱氢酶活性和F420浓度变化。结果表明,混合消化提高了系统稳定性,与餐厨垃圾单独消化相比,添加剩余污泥能调节pH、氨氮浓度和VFA浓度,缩短产气周期;与剩余污泥单独消化相比,添加餐厨垃圾能显著提高沼气产量。混合比例为1∶1组混合消化产甲烷潜力最佳,消化作用的协同效应最为明显,沼气和甲烷产量分别达358.2 mL/g VS和224.1 mL/g VS,较餐厨垃圾和污泥单独消化估计值分别提高了23.09%和36.80%。1∶1混合消化组脱氢酶活性最高达437.33 TFμg/(mL·h),比餐厨垃圾和剩余污泥单独消化分别提高93.60%和40.69%,辅酶F420浓度最高为1.718μmol/L,分别提高17.3%和100.7%。     

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.