Research on operating conditions at the catalytic reactor for the combined removal of NOx and PCDD/PCDFs from MWI plants

The management of municipal solid waste (MSW), particularly the role of incineration, is currently a subject of public debate. Incineration shows to be a good alternative of reducing the volume of waste and eliminating certain infectious components. Moreover, Municipal Waste Incinerators (MWI), are reported to be highly hygienic and apart from that MWIs are immediately effective in terms of transport (incinerators can be built close to the waste sources) and incineration's nature. Nevertheless, the emissions of many hazardous substances make the Municipal Waste Incineration (MWI) plants to be unpopular. Metals (especially lead, manganese, cadmium, chromium and mercury) are concentrated in fly and bottom ashes. Furthermore, incomplete combustion produces a wide variety of potentially hazardous organic compounds, such as aldehydes, polycyclic aromatic hydrocarbons (PAH), chlorinated hydrocarbons including polychlorinated dibenzodioxins (PCDD) and dibenzofurans (PCDF), and even acid gases, including NOx. Many of these hazardous substances are carcinogenic and some have direct systemic toxicity.

Modelagem e simulação da formação de hidrocarbonetos na combustão do gás natural

A exaustão de um veículo de motor a diesel é uma importante fonte de poluentes atmosféricos, pois forma uma matriz complexa composta de poluentes regulados e não regulados pelos órgãos governamentais. Dentre os poluentes regulados podemos citar óxidos de nitrogênio (NOx) e material particulado. Os poluentes não regulados são pouco estudados até hoje e dentre estes encontra-se a classe dos hidrocarbonetos policíclicos aromáticos e seus derivados nitrados (nitro-HPA). Estes são encontrados na exaustão do diesel na forma gasosa ou agregados ao material particulado. Hoje, o interesse em estudos destes compostos vem aumentando, devido às suas atividades carcinogênicas e mutagênicas às quais estão sujeitas as populações dos centros urbanos. O impacto causado pelos nitro-HPA emitidos por motores a ciclo diesel ao ambiente não está ainda completamente estabelecido. Este estudo consiste na modelagem e simulação do processo de combustão de hidrocarbonetos na faixa de C1 a C4 com o objetivo de descrever a formação de compostos aromáticos, principalmente HPA, e óxidos de nitrogênio a partir de modelos cinéticos de combustão propostos na literatura como referência e fazendo uso do software de simulação Kintecus. Este projeto tem como objetivo em longo prazo propor um modelo cinético para combustão do óleo Diesel. Foi iniciada a construção de um modelo cinético de combustão a partir de modelos de hidrocarbonetos simples de C1 a C4, com formação de aromáticos, HPA e óxidos de nitrogênio. Os modelos originais foram avaliados e modificados a fim de estudar como parâmetros do modelo afetam a concentração das espécies de interesse. Foi observado a tendência de formação de benzeno e fulveno em baixas temperaturas e a tendência de formação de antraceno, pireno, fenantreno a temperaturas mais altas. Foi avaliado que a conversão NO-NO2 ocorre em maiores proporções em reações iniciadas a baixas temperaturas, 600 K. Os resultados indicam que propano é o maior responsável por esta conversão. O modelo final obtido resultou da união dos modelos de combustão Hori e Marinov mais inclusão do GRI-Mech 3.0 e reações adicionais de NOx retiradas da base de dados NIST

Perfil dos HPA prioritários na exaustão de veículo a diesel, no combustível diesel utilizado durante os ensaios de emissão veicular e no óleo lubrificante do motor

As concentrações na exaustão e os fatores de emissão dos hidrocarbonetos policíclicos aromáticos (HPA) prioritários de um veículo a diesel e as suas respectivas concentrações no diesel usado durante os ensaios de emissão veicular foram determinados com a finalidade de estimar a contribuição dos HPA provenientes do combustível nas emissões. Os produtos da combustão foram coletados diretamente nas emissões brutas do escapamento, utilizando um sistema de amostragem a volume constante sem diluição dos gases da exaustão. Os HPA associados ao MP foram amostrados de forma estratificada, utilizando um impactador em cascata MOUDI e filtros de fibra de vidro como substratos, e os HPA em fase gasosa foram amostrados usando cartuchos de amberlite XAD-2. A concentração dos HPA no óleo lubrificante do motor também foi monitorada ao longo do tempo até a sua troca após 12.000 km de uso. Após a extração e tratamento das amostras, a identificação e quantificação dos HPA foram realizadas, utilizando cromatografia de fase gasosa acoplada à espectrometria de massas (CG-EM) com injetor de grande volume de vaporização com a temperatura programável (PTV-LVI). Cinco variáveis do PTV-LVI foram otimizadas, utilizando planejamento de experimentos, o que permitiu obter limites de detecção menores do que 2,0 g L-1. Somente 7 dos 16 HPA prioritários foram identificados na exaustão: NAP, ACY, ACE, FLU, FEN, FLT e PYR. Os ensaios de emissão veicular foram realizados com o veículo em modo estacionário, sem aplicação de carga e com baixa velocidade de rotação do motor (1500 rpm), utilizando um diesel com menor teor de enxofre (10 mg kg-1) e com 5% v/v de biodiesel. Esses fatores possivelmente contribuíram para reduzir as emissões dos outros 9 HPA a valores abaixo dos limites de detecção do método desenvolvido. Aproximadamente 80% da massa dos HPA totais associados ao MP estavam presentes em partículas com tamanho entre 1,0 m e 56 nm, e aproximadamente 4,5% estavam presentes em partículas menores do que 56 nm. Partículas menores que 2,5 m são facilmente inaladas e depositadas no trato respiratório e na região alveolar, justificando a preocupação com relação às emissões de HPA associados a partículas provenientes da exaustão veicular de motores a diesel. Somente 5 dos 7 HPA identificados na exaustão foram detectados no diesel: NAP, ACY, FLU, FEN e PYR. A razão entre os fatores de emissão (g L-1diesel) dos HPA na exaustão e suas respectivas concentrações do diesel (g L-1) variaram de 0,01 0,02 a 0,05 0,029, dependendo do HPA. Esses valores indicam que pelo menos 95 a 99% dos HPA identificados no diesel foram destruídos e/ou transformados em outros compostos durante a combustão, e/ou foram retidos no reservatório do óleo lubrificante. Por outro lado, os HPA que tiveram maiores concentrações no diesel também apresentaram maiores fatores de emissão, o que sugere que os HPA provenientes do diesel possuem uma contribuição significativa para as emissões dos HPA totais. O perfil dos HPA prioritários no óleo lubrificante mostrou-se semelhante ao perfil dos HPA no diesel e nas emissões totais, onde o NAP, FEN e PYR foram os HPA majoritários

Protocols for conducting dolphin capture-release health assessment studies

Marine mammals, such as dolphins, can serve as key indicator species in coastal areas by reflecting the effects of natural and anthropogenic stressors. As such they are often considered sentinels of environmental and ecosystem health (Bossart 2006; Wells et al. 2004; Fair and Becker 2000). The bottlenose dolphin is an apex predator and a key component of many estuarine environments in the southeastern United States (Woodward-Clyde Consultants 1994; SCDNR 2005). Health assessments of dolphins are especially critical in areas where populations are depleted, show signs of epidemic disease and/or high mortality and/or where habitat is being altered or impacted by human activities. Recent assessments of environmental conditions in the Indian River Lagoon, Florida (IRL) and the estuarine waters surrounding Charleston, South Carolina (CHS) highlight the need for studies of the health of local bottlenose dolphins. While the condition of southeastern estuaries was rated as fair in the National Coastal Condition Report (U.S. EPA 2001), it was noted that the IRL was characterized by poorer than expected benthic communities, significant sediment toxicity and increased nutrient concentrations. Similarly, portions of the CHS estuary have sediment concentrations of aliphatic aromatic hydrocarbons, select inorganic metals, and some persistent pesticides far in excess of reported bioeffect levels (Hyland et al. 1998). Long-term trends in water quality monitoring and recent scientific research suggest that waste load assimilation, non-point source runoff impacts, contaminated sediments, and toxic pollutants are key issues in the CHS estuary system. Several ‘hot spots’ with high levels of heavy metals and organic compounds have been identified (Van Dolah et al. 2004). High concentrations of anthropogenic trace metals, polychlorinated biphenyls (PCB’s) and pesticides have been found in the sediments of Charleston Harbor, as well as the Ashley and Cooper Rivers (Long et al. 1998). Two superfund sites are located within the CHS estuary and the key contaminants of concern associated with these sites are: polycyclic aromatic hydrocarbons (PAH), lead, chromium, copper, arsenic, zinc and dioxin. Concerns related to the overall health of IRL dolphins and dermatologic disease observed in many dolphins in the area (Bossart et al. 2003) initiated an investigation of potential factors which may have impacted dolphin health. From May-August 2001, 35 bottlenose dolphins died in the IRL during an unusual mortality event (MMC 2003). Many of these dolphins were diagnosed with a variety of skin lesions including proliferative ulcerative dermatitis due to protozoa and fungi, dolphin pox and a vesicular dermatopathy of unknown etiology (Bossart et al. 2003). Multiple species from fish to dolphins in the IRL system have exhibited skin lesions of various known and unknown etiologies (Kane et al. 2000; Bossart et al. 2003; Reif et al. 2006). On-going photo-identification (photo-ID) studies have documented skin diseases in IRL dolphins (Mazzoil et al. 2005). In addition, up to 70% of green sea turtles in the IRL exhibit fibropapillomas, with the highest rates of occurrence being seen in turtles from the southern IRL (Hirama 2001).

The effects of urbanization on populations of grass shrimp Palaemonetes spp. in small, high salinity estuaries

High salinity estuaries in the southeastern U.S. have experienced increased inputs of contaminants from nonpoint source (NPS) urban runoff and decreases in habitat due to filling of wetlands and dock/bulkhead construction. Urbanization may pose significant risks to estuarine fauna, particularly crustaceans. The grass shrimp of the genus Palaemonetes, is one of the dominant species found in estuarine tidal creeks, accounting for greater than 50% of all macropelagic fauna on an annual basis. Spatial analytical and geographic information system techniques were used to determine which factors influenced the Palaemonetes population structures in a South Carolina bar-built estuary surrounded by urban development. Impacts from land use practices were investigated using concentric circular buffers around study sites. Factors investigated included sediment-associated polycyclic aromatic hydrocarbons concentration, land use classification, percent impervious surfaces, and other selected urban factors. Geographic information system and statistical modeling showed quantitative relationships between land use class and impacts on Palaemonetes density. The study suggests that habitat loss is a major factor influencing grass shrimp densities. Multiple regression modeling suggests a significant relationship between habitat alterations and Palaemonetes densities.

Deepwater Horizon oil spill: assessment of potential impacts on the deep soft-bottom benthos; interim data summary report

A study was initiated in May 2011, under the direction of the Deepwater Horizon (DWH) Natural Resource Damage Assessment (NRDA) Deepwater Benthic Communities Technical Working Group (NRDA Deep Benthic TWG), to assess potential impacts of the DWH oil spill on sediments and resident benthic fauna in deepwater (> 200 meters) areas of the Gulf. Key objectives of the study were to complete the analysis of samples from 65 priority stations sampled in September-October 2010 on two DWH Response cruises (Gyre and Ocean Veritas) and from 38 long-term monitoring sites (including a subset of 35 of the original 65) sampled on a follow-up NRDA cruise in May-June 2011. The present progress report provides a brief summary of results from the initial processing of samples from fall 2010 priority sites (plus three additional historical sites). Data on key macrofaunal, meiofaunal, and abiotic environmental variables are presented for each of these samples and additional maps are included to depict spatial patterns in these variables throughout the study region. The near-field zone within about 3 km of the wellhead, where many of the stations showed evidence of impaired benthic condition (e.g. low taxa richness, high nematode/harpacticoid-copepod ratios), also is an area that contained some of the highest concentrations of total petroleum hydrocarbons (TPH), total polycyclic aromatic hydrocarbons (total PAHs), and barium in sediments (as possible indicators of DWH discharges). There were similar co-occurrences at other sites outside this zone, especially to the southwest of the wellhead out to about 15 km. However, there also were exceptions to this pattern, for example at several farther-field sites in deeper-slope and canyon locations where there was low benthic species richness but no evidence of exposure to DWH discharges. Such cases are consistent with historical patterns of benthic distributions in relation to natural controlling factors such as depth, position within canyons, and availability of organic matter derived from surface-water primary production.

Deep-sea benthic footprint of the Deepwater Horizon blowout

The Deepwater Horizon (DWH) accident in the northern Gulf of Mexico occurred on April 20, 2010 at a water depth of 1525 meters, and a deep-sea plume was detected within one month. Oil contacted and persisted in parts of the bottom of the deep-sea in the Gulf of Mexico. As part of the response to the accident, monitoring cruises were deployed in fall 2010 to measure potential impacts on the two main soft-bottom benthic invertebrate groups: macrofauna and meiofauna. Sediment was collected using a multicorer so that samples for chemical, physical and biological analyses could be taken simultaneously and analyzed using multivariate methods. The footprint of the oil spill was identified by creating a new variable with principal components analysis where the first factor was indicative of the oil spill impacts and this new variable mapped in a geographic information system to identify the area of the oil spill footprint. The most severe relative reduction of faunal abundance and diversity extended to 3 km from the wellhead in all directions covering an area about 24 km2. Moderate impacts were observed up to 17 km towards the southwest and 8.5 km towards the northeast of the wellhead, covering an area 148 km2. Benthic effects were correlated to total petroleum hydrocarbon, polycyclic aromatic hydrocarbons and barium concentrations, and distance to the wellhead; but not distance to hydrocarbon seeps. Thus, benthic effects are more likely due to the oil spill, and not natural hydrocarbon seepage. Recovery rates in the deep sea are likely to be slow, on the order of decades or longer.

Assessing the impacts of the Deepwater Horizon oil spill: the National Status and Trends Program response; a summary report of coastal contamination

NOAA’s National Status and Trends Program (NS&T) collected oyster tissue and sediments for quantification of polycyclic aromatic hydrocarbons (PAHs) and petroleum associated metals before and after the landfall of oil from the Deepwater Horizon incident of 2010. These new pre- and post- landfall measurements were put into a historical context by comparing them to data collected in the region over three decades during Mussel Watch monitoring. Overall, the levels of PAHs in both sediment and oysters both pre- and post-landfall were within the range of historically observed values for the Gulf of Mexico. Some specific sites did have elevated PAH levels. While those locations generally correspond to areas in which oil reached coastal areas, it cannot be conclusively stated that the contamination is due to oiling from the Deepwater Horizon incident at these sites due to the survey nature of these sampling efforts. Instead, our data indicate locations along the coast where intensive investigation of hydrocarbon contamination should be undertaken. Post-spill concentrations of oil-related trace metals (V, Hg, Ni) were generally within historically observed ranges for a given site, however, nickel and vanadium were elevated at some sites including areas in Mississippi Sound and Galveston, Terrebonne, Mobile, Pensacola, and Apalachicola Bays. No oyster tissue metal body burden exceeded any of the United States Food and Drug Administration’s (FDA) shellfish permissible action levels for human consumption.

Chemical contamination in southwest Puerto Rico: a survey of contaminants in the coral Porites astreoides

Coral ( Porites astreoides ) from eight sites in southwest Puerto Rico were analyzed for approximately 150 chemical contaminants, to provide a preliminary characterization of environmental contamination in the corals, and assess the relationships between chemical contamination in corals and adjacent sediments. Overall, the concentration of PAHs (polycyclic aromatic hydrocarbons) and PCBs (polychlorinated biphenyls) detected in the limited number of coral samples collected were comparable to concentrations found in sediments. However, the concentration of a chemical contaminant (e.g., PAHs) in the corals at a site was often different from what was found in adjacent sediments. The level of PCBs and DDT (dichlorodiphenyltrichloroethane) in the corals appeared higher just outside of Guanica Bay, and there was some evidence of a downstream concentration gradient for these two contaminant classes. The trace elements copper and zinc were frequently detected in Porites astreoides , and the concentrations were usually comparable to those found in adjacent sediments. Chromium was an exception in that it was not detected in any of the coral samples analyzed, although it was detected in all of the sediment samples.

Chemical contaminants in the coral Porites astreoides from southwest Puerto Rico

This report presents an initial characterization of chemical contamination in coral tissues (Porites astreoides) from southwest Puerto Rico. It is the second technical report from a project to characterize chemical contaminants and assess linkages between contamination and coral condition. The first report quantified chemical contaminants in sediments from southwest Puerto Rico. This document summarizes the analysis of nearly 150 chemical contaminants in coral tissues. Although only eight coral samples were collected, some observations can be made on the correlations between observed tissue and sediment contaminant concentrations. The concentrations of polycyclic aromatic hydrocarbons (PAHs), typically associated with petroleum spills and the combustion of fossil fuels, and polychlorinated biphenyls (PCBs) in the coral tissues were comparable to concentrations found in adjacent sediments. However, the concentration of a chemical contaminant (e.g., PAHs) in the coral tissues at a particular site was not a good predictor of what was in the adjacent sediments. In addition, the types of PAHs found in the coral tissues were somewhat different (higher ratios of alkylated PAHs) than in sediments. The levels of PCBs and DDT in coral tissues appeared higher just outside of Guanica Bay, and there was evidence of a downstream concentration gradient for these two contaminant classes. The trace elements copper, zinc and nickel were frequently detected in coral tissues, and the concentration in the corals was usually comparable to that found in adjacent sediments. Chromium was an exception in that it was not detected in any of the coral tissues analyzed. Additional work is needed to assess how spatial patterns in chemical contamination affect coral condition, abundance and distribution.

渤海湾海岸带表层沉积物中黑炭和多环芳烃的分布特征

黑碳（BC）是生物质和化石燃料不完全燃烧产生的高度聚合的碳质混合物，包括木炭 （char/charcoal）和烟炱碳（soot）等形式。黑碳产生后大部分储存在燃烧原地，而烟炱碳 由于粒径较小，易进入大气，滞留一到数周后回到地表。部分土壤黑碳随河流和大气的搬 运作用进入海洋环境，主要汇集在海岸带沉积物中。由于黑碳涉及到气候变化、碳循环、 环境危害、人体健康等诸多问题而成为当前气候与环境领域的研究热点。黑碳在环境介质 中比较稳定，因而可以较好的指示人类能源使用及其对环境质量的影响；同时黑碳具有很 强的吸附性，能显著影响周围介质中持久性有机污染物(如多环芳烃等)的赋存状态和生态 毒理效应。 多环芳烃（PAHs）是指两个或两个以上的苯环以稠环形式结合的芳香族化合物，主要 来源于含碳物质的不完全燃烧过程，在环境中广泛存在。由于PAHs 具有潜在的致癌性、 致畸性和致突变性（“三致”效应）而在环境研究领域中备受关注。另外由于具有主体的 同源性，PAHs 可以指示BC 的来源和环境过程。 海岸带沉积物是包括BC 和PAHs 在内的众多污染物在环境地球化学迁移过程中的主 要载体和归宿，由于受到陆地和海洋双重作用，海岸带对环境污染物尤其敏感。环渤海地 区是我国北方的社会经济中心，工业、农业和交通发达、人口稠密，污染严重。前人的研 究表明渤海湾的BC 和PAHs 污染程度明显高于我国其他海岸带，但受限制于采样区域和 样品数量，不能全面地反应BC 和PAHs 在渤海湾海岸带的分布状况及人类活动对海岸带 环境质量的影响。 本次研究在渤海湾海岸带潮间带、近海及主要入海河流系统布设了多条采样剖面，采 集表层沉积物样品85 个。首先，对国际上较为常用的化学热氧化法（CTO-375）处理沉积 物黑碳样品的方法进行了比对实验和优化，然后对全部样品进行黑碳分析；利用GC-MS 方法对样品中的PAHs（USEPA 的16 种优控物）进行了定量检测；对全部沉积物样品还进 行了粒度分析。 结果表明，该区域内黑碳的含量为0.09 到22.8 mg/g dw，其中，潮间带样品的BC 平 均含量为0.52 ± 0.39 mg/g dw，近海样品为0.84 ± 0.38 mg/g dw，河流样品（海河样品除外） 为1.88 ± 0.89 mg/g dw。BC占总有机碳的比例在潮间带、近海、河流区域分别为18.4 ± 8.3%、 14.5 ± 5.3%、14.2 ± 4.1%。潮间带黑碳存在明显的“北高南低”的趋势（以天津港码头和 海河为界），与近海和河流样品的BC 浓度有相似的变化趋势，反映了BC 在海岸带的运移 扩散具有一定的继承性；河流输入可能是近岸沉积物BC 的主要来源。同时，潮间带沉积 物粒度分析结果表明“北区细”(以粘土质粉砂主)而“南区粗”(以砂为主)，反映了两个区 域不同的水动力条件和沉积环境，可能是造成BC 浓度空间分异的主要原因。 摘要 II 多环芳烃的含量分布为33.1-7658.7 ng/g dw，其中，潮间带样品的PAHs 平均含量为 147.0 ng/g dw，近海样品为170.9 ng/g dw，河流样品（海河样品除外）为1228.5 ng/g dw。 主要成分均为三环和四环多环芳烃。PAHs 也呈现出了与BC 相似的“北高南低”的趋势， 多环芳烃与黑碳的相关性研究表明两者相关性较好（R2=0.59），表明多环芳烃和黑碳的同 源性和继承性。运用比值法（菲/蒽，荧蒽/芘，低环/高环等）对多环芳烃的来源解析显示， 整个研究区域内多环芳烃主要为燃烧源。

ANTHROPOGENIC ORGANIC CONTAMINANTS IN WATER AND SURFACE SEDIMENTS OF LARGE SHALLOW EUTROPHIC CHAOHU LAKE, CHINA

To characterize the contamination of anthropogenic organic contaminants in the aquatic environment of Chaohu Lake, China, 7 samples for both water and surface sediment were collected in the lake. Organic contaminants were extracted by solid phase extraction (SPE) and Soxhlet extraction from the water and surface sediment samples, respectively, and then analyzed by GC-MS. One hundred and twenty kinds of organic chemicals were detected in these samples including phenol, benzene series, benzaldehydes, ethanol, polycyclic aromatic hydrocarbons (PAHs), sulfur compounds, alcoholic halides, amines, ketones, esters, alkenes and alkanes. Among them, 13 kinds of chemicals were identified as priority pollutants listed by the U.S. Environmental Protection Agency (EPA), such as phthalate esters (PAEs) and PAHs. Besides, the concentrations of 19 of PAEs and PAHs including, priority pollutants identified were also determined. Bis(2-ethylhexyl)phthalate, the predominant component of the analyzed pollutants, was in the range from 72.34 ng g(-1) DW to 613.71 ng g(-1) DW, 14.80 ng L-1 to 47.05 ng L-1 in sediment and water, respectively. The results indicated that the northwest part of the lake was heavily polluted by domestic and industrial wastewater.

Determination of PAH, PCB, and OCP in water from the Three Gorges Reservoir accumulated by semipermeable membrane devices (SPMD)

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) were measured in the water column from Three Gorges Reservoir (TGR) collected in May 2008 using semipermeable membrane devices (SPMDs). The sampling sites spanned the whole reservoir from the upstream Chongqing to the great dam covering more than 600 km long distance with water flow velocities ranging from <0.05 to 1.5 m s(-1). This is the first experience of SPMD application in the biggest reservoir in the world. The results of water sampling rates based on performance reference compounds (PRC) were tested to be significantly correlated with water flow velocities in the big river. Results of back-calculated aqueous concentrations based on PRC showed obvious regional variations of PAH, PCB and OCP levels in the reservoir. Total PAH ranged from 13.8 to 97.2 ng L-1, with the higher concentrations occurring in the region of upstream and near the dam. Phenanthrene, fluoranthene, pyrene and chrysene were the predominant PAH compounds in TGR water. Total PCB ranged from 0.08 to 0.51 ng L-1, with the highest one occurring in the region near the dam. PCB 28, 52, 101, 138, 153, 180, 118 were the most abundant PCB congeners in the water. The total OCP ranged from 2.33 to 3.60 ng L-1 and the levels showed homogenous distribution in the whole reservoir. HCH, DDT and HCB, PeCB were the major compounds of OCP fingerprints. Based on water quality criteria, the TGR water could be designated as being polluted by HCB and PAH. Data on PAH, PCB and OCP concentrations found in this survey can be used as reference levels for future POP monitoring programmes in TGR. (C) 2009 Elsevier Ltd. All rights reserved.

微生物固定化方法修复多环芳烃污染土壤

针对传统游离微生物修复技术的缺点和弊端，提出了采用固定化微生物技术修复受多环芳烃污染的非流体介质的新课题。本文筛选出2株高效降解菌，并进行了固定化载体筛选，优化并确定了3种固定化工艺。通过实验室模拟实验，考察了固定化菌对PAHs污染非流体介质的修复能力，最后通过扫描电子显微镜（SEM）分析，对固定化微环境强化修复机制进行了初步探讨。 细菌芽孢杆菌（Bacillus sp.，SB02）和真菌毛霉（Mucor sp.，SF06）对土壤中的Pyr、BaP降解率高，降解速率快，为高效降解微生物。 碱化后的泥炭土适宜作为细菌固定化载体；玉米芯适宜作为真菌固定化载体；改性后蛭石适宜作为混合菌固定化载体。这些载体来源广泛，成本低廉，工艺简单，安全无毒。 将固定化菌应用于Pyr、BaP污染土壤的修复，考察了初始接种量、环境温度、土壤含水量对固定化菌降解Pyr、BaP的影响，固定化菌对不同系列浓度Pyr、BaP的降解，以及固定化菌在不灭菌土壤中对Pyr、BaP的降解，表明固定化菌对土壤中Pyr和BaP的降解率均高出游离菌20%，固定化混和菌降解效果最好，其次是固定化真菌，再次是固定化细菌。 SEM分析了固定化颗粒的微观结构和微生物在颗粒内部的形态变化，结果表明颗粒内部丰富的疏松多孔结构和巨大的比表面积为微生物提供了适宜的生存空间，使吸附固定化成为可能。 固定化菌对沈抚灌区PAHs污染土壤修复效果非常理想，经过6个月，土壤中总PAHs的去除率达70.3%，高于游离菌。

土壤中PAHs的光催化降解动力学及机制研究

本文以土壤为介质，以三环的菲（Phe）、四环的芘（Pyr）和五环的苯并[a]芘（BaP）为目标污染物，研究了紫外灯照射下土壤中多环芳烃（PAHs）的降解，并以半导体纳米TiO2和Fe2O3为催化剂研究了土壤中PAHs的催化降解，对光降解及光催化降解的动力学进行了研究，在室内条件下考察了土壤条件和环境因子对光降解及光催化降解PAHs的影响；研究了太阳光照条件下土壤pH值对光降解和催化降解的影响和腐殖酸对光降解的影响；初步探讨了纳米TiO2催化光降解土壤中PAHs的机制。 研究结果表明：土壤中PAHs的紫外光降解符合一级动力学模型，土壤中PAHs光降解与土壤厚度呈显著负相关，土壤粒径对紫外光解PAHs有显著影响，温度从20 ℃升高到30 ℃，光解速率逐渐增加，在PAHs污染土壤的光降解中腐殖酸起敏化作用，随着紫外辐射强度的增加，光降解速率加快。 纳米TiO2和Fe2O3均能促进土壤中PAHs的紫外光降解，PAHs光催化降解符合一级动力学模型，在酸性和碱性土壤条件下，光催化降解PAHs的速率均高于中性，在不同光质条件下，TiO2 、Fe2O3催化光降解PAHs的速率发生变化，随着紫外辐射强度的增加，光催化降解速率常数增加，半衰期减少；腐殖酸促进TiO2 、Fe2O3催化土壤中PAHs的光降解，腐殖酸在这个过程中起着敏化作用。 在太阳光照射下酸性和碱性土壤中PAHs的降解快于中性，PAHs污染土壤中在加入腐殖酸后光降解速率加快，在酸性条件下催化降解最快，在碱性和中性条件下相差不大。 土壤中PAHs存在着PAH的光致电离、电子向O2的转移的两种降解途径；在有催化剂TiO2条件下，由于催化剂在光照后形成的电子-空穴能够氧化还原污染物，PAH的光致电离、电子向O2的转移的引起的降解，共同促进了土壤中PAHs的光催化降解。