H_2-O_2对柴油机尾气颗粒物组分的影响分析

针对柴油机进气通入H_2-O_2对尾气颗粒物组分的影响进行研究,利用热重分析仪和气相色谱/质谱联用(GC/MS)仪测量了通入2L/min H_2-O_2前后的尾气颗粒物组分,比较了尾气颗粒物中可溶有机物(SOF)的挥发特性及烃类、含氧类有机化合物,碳烟的质量分数变化。结果表明:通入H_2-O_2后,短链SOF占SOF的质量分数由11.90%增加到19.00%,长链SOF由88.10%下降为81.00%;SOF中的烃类有机化合物升高,含氧类有机化合物降低,先燃碳烟占柴油机尾气颗粒物的质量分数由23.91%降低为17.75%,后燃碳烟由24.79%升高为43.46%。因此,通入H_2-O_2可降低长链SOF和含氧类有机化合物。     

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。     

用数值模拟方法研究含硫颗粒物生成过程

为了研究不同燃烧条件对燃煤中含硫颗粒物生成的影响,利用数值分析方法模拟炉膛煤燃烧。通过改变燃烧环境温度、进口氧气所占总气体摩尔比,分析得到的碳烟(soot)颗粒、SO2和CO2等主要物质浓度场。模拟结果能够很好地反映炉膛内各物质生成趋势和历程。生成的碳烟颗粒中富集煤中一部分硫元素,燃烧后期未被氧化的碳烟颗粒是燃煤烟气含硫颗粒物的一个重要来源。进口O_2摩尔比从0.1~0.5时碳烟颗粒迅速被氧化,出口处产生含硫碳烟颗粒物减少。在1 200~1 600 K范围内,温度增高不利于碳烟颗粒的生成,来源于碳烟颗粒的含硫颗粒物也就逐渐减少。     

孔道结构对柴油机DPF压降及再生特性的影响

针对微粒捕集器(DPF)内部碳烟及灰分颗粒特征,运用AVL-Fire软件建立了六边形孔道结构柴油机微粒捕集器模型。针对不同排气流量、进口温度、孔密度、碳烟和灰分沉积量,对六边形孔道及四边形孔道DPF压降特性和碳烟再生特性进行分析,并研究灰分分布形式对不同孔道形状DPF的影响。结果表明:排气质量流量越大,进口温度越高,不同孔道结构的压降敏感性增大;与传统四边形孔道DPF相比,当碳烟沉积量较低时,六边形孔道DPF压降损失较高;随着碳烟沉积量的增加,六边形孔道DPF压降损失较低,且碳烟承载量较大;灰分在DPF孔道表面层状分布可以有效阻止碳烟深床捕集模式,降低压降损失;六边形孔道DPF能够有效提高碳烟及灰分容量,且碳烟捕集及再生效率较高,再生速率较快,热应力较小,可以降低DPF主动再生频率,延长使用寿命。     

La_(1-x)Ce_xCu_yMn_(1-y)O_3/HZSM-5催化剂低温去除柴油机碳烟和NO_x

为实现对柴油机碳烟和NOx的低温同步去除,采用柠檬酸络合法制备分子筛负载钙钛矿型金属复合氧化物催化剂,应用X衍射分析仪(XRD)和电镜扫描仪(SEM)对催化剂性能进行表征,并在微型固定床反应器中对催化剂低温去除碳烟和NOx进行活性评价。利用程序升温反应(TPR)技术,进行催化剂活性评价、柴油机负荷和排放等特性实验。结果表明,A位用适量Ce部分取代La,B位用适量Cu部分取代Mn,可使碳颗粒燃烧温度降低,CO2选择性好,NOx转化率升高。La0.4Ce0.6Cu0.2Mn0.8O3/HZSM-5催化剂的最大NOx转化率为81.0%,Ti、Tm和Tf分别为250、350和475℃,表明该催化剂具有较好的催化活性,能在低温条件下去除碳烟和NOx。     

La1-x Cex Cuy Mn1-yO3／HZSM-5催化剂低温去除柴油机碳烟和NOx

为实现对柴油机碳烟和NOx的低温同步去除，采用柠檬酸络合法制备分子筛负载钙钛矿型金属复合氧化物催化剂，应用x衍射分析仪（XRD）和电镜扫描仪（SEM）对催化剂性能进行表征，并在微型固定床反应器中对催化剂低温去除碳烟和NOx进行活性评价。利用程序升温反应（TPR）技术，进行催化剂活性评价、柴油机负荷和排放等特性实验。结果表明，A位用适量Ce部分取代La，B位用适量cu部分取代Mn，可使碳颗粒燃烧温度降低，CO2选择性好，NOx转化率升高。La0.4 Ce0.6 Cu0.2 Mn0.8O3／HZSM-5催化剂的最大NOx转化率为81．0％，Ti、Tm和Tf分别为250、350和475℃，表明该催化剂具有较好的催化活性，能在低温条件下去除碳烟和NOx。     

La—K—Co—Mn-O钙钛矿型复合氧化物同时去除碳颗粒和NOx的性能

采用柠檬酸络合燃烧法合成制备了La1-xKxCo0.5Mn0.5O3(x为K+取代量,x=0、0.1、0.2、0.3、0.4、0.5)系列钙钛矿型复合金属氧化物催化剂,以X射线衍射、红外光谱和比表面积等手段对该催化剂进行表征,以常压固定床微型反应器程序升温氧化还原反应技术评价该催化剂同时去除模拟柴油机尾气中炭黑颗粒(表征柴油机尾气中的碳颗粒)和NOX的催化性能.结果表明,K+部分取代LaCo0.5Mn0.5O3中的La3+后,催化剂催化性能得到明显改善,炭黑颗粒的起燃温度(Tig)、峰值温度(Tm)和燃尽温度(Tf)均降低,NOX的转化率提高,最高为16.6%;La0.6K0.4Co0.5Mn0.5O3具有最佳的催化性能,炭黑颗粒的Tig、Tm和Tf分别为305、350、379 ℃,炭黑颗粒燃烧产物中CO2的体积分数为98.8%,NOX转化率为15.5%.     

低温等离子体净化尾气中的颗粒相多环芳烃

利用低温等离子体(NTP)净化车用柴油机尾气中的颗粒相多环芳烃(PAHs),基于电晕放电的原理,设计了NTP发生装置。使用色谱质谱联用仪分析经过NTP净化前后柴油机尾气中颗粒相多环芳烃的含量,观察NTP对颗粒相多环芳烃的净化效果。结果表明,颗粒相小分子量PAHs除菲、蒽外,其他4种多环芳烃的含量显著增加,其中萘、苊变化率达1130.4%和758.57%;大分子量PAHs除苯并(ghi)芘外,多环芳烃的含量降低达80%以上;NTP对柴油机尾气中颗粒相多环芳烃含量及毒性当量的净化率分别达58.4%和82.8%。     

混合燃料中含氧量对柴油机有害物质排放量的影响

通过柴油机试验,研究了混合燃料中含氧量对柴油机有害物质排放量的影响.试验结果显示,在混合燃料中含氧量低于10.4%(质量分数,下同)时,CO和HC排放量随含氧量增加而减少;但随着混合燃料中乙醇所占比例增加,当混合燃料中含氧量达25.3%时,CO和HC排放量均增加到含氧量为10.4%时的2.5倍左右;当混合燃料中含氧量低于10.4%时,NOx排放量随其增加而少量增加.但当混合燃料中含氧量达25.3%时,NOx排放量较燃用柴油时减少50%以上;碳烟排放量则随着混合燃料中含氧量增加而不断减少.     

柴油车尾气碳烟颗粒物催化燃烧催化剂的最新研究进展

柴油车尾气排放的碳烟颗粒已经引起了严重的环境污染问题,必须加以净化处理.柴油车碳烟颗粒的低温燃烧离不开高活性的催化剂.针对柴油车排放的碳烟颗粒物后处理方法中的催化氧化技术,总结了近年来几种主要类型的碳烟燃烧催化剂(贵金属催化剂、碱金属催化剂、单组分过渡金属氧化物催化剂、多组分混合氧化物催化剂和固定结构复合氧化物催化剂)的最新研究进展,并对该研究方向存在的主要问题和应用前景进行了探讨.     

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.