基于现场试验的石油类污染物自然衰减能力研究

基于在北京地区某加油站开展的油类污染物自然衰减试验,通过氧平衡和碳平衡计算对加油站土壤内石油污染物的自然衰减方式进行了评价,利用一级衰减模型对该污染现场土壤中油污染物的降解速率和半衰期进行了计算,并在此基础上对该加油站包气带土壤的自然衰减能力和环境质量进行了评价.结果表明,该污染场地实际耗氧量小于污染物全部需氧降解所需要的理论耗氧量,检测到的CO2的量也远小于需氧降解的理论生成量;污染点石油污染物的半衰期约为50 d左右.根据以上结果得出以下结论：①该加油站地下土壤中实际发生的微生物降解既有需氧降解也有厌氧降解;②第一次监测时超过环境标准的苯浓度大约在250 d左右降至保护地下水的筛选值以下,污染点已经不存在环境风险,该污染现场的环境监控措施可以解除.     

工业园区TVOC和恶臭的电子鼻检测技术研究

根据工业园区中TVOC和恶臭可能存在的主要气体组分,筛选传感器阵列,构建用于检测工业园区内TVOC和恶臭的电子鼻系统.本研究设计了TVOC污染指数（TPI）和恶臭污染指数（OPI）及基于电子鼻的现场检测方法.在此基础上,结合嘉兴市乍浦港区内化工园区污染情况分析,选择6个检测点进行现场检测,各传感器响应值经PCA分析,提取了2个主成分即可将8个传感器分为2类：TVOC型（S1）和恶臭型（S2～S8）.将现场采集的气体样品用GC/MS进行定性分析,各采样点TVOC物质积分面积百分比在10%以上的累积起来大多都占总面积的90%以上,而恶臭类物质则大多都在10%以下.结果表明：①选用合适的传感器阵列,结合PCA分析,可以初步反映工业园区内TVOC和恶臭的污染情况;②结合电子鼻测得的污染指数与GC/MS定性分析结果,可以大体得出工业园区TVOC和恶臭总体污染情况及各种污染物分布情况;③电子鼻和GIS技术综合应用到工业园区TVOC和恶臭的检测,能初步用于评估工业园区空间污染情况.     

石油污染包气带中降解微生物的分布特性

包气带土层系统中油类污染物的性质和降解微生物的分布特性是影响污染物自然衰减和污染包气带强化生物治理的重要自然和生物学因素 .对淄河滩油污土层的石油类污染物的含量、污染物质组成的分析 ,以及微生物的分离和培养的研究结果表明 ,饱和烷烃、环烷烃和多环芳烃构成淄河滩油污土层中主要烃类污染组分 ,其含量高达 90～200 g· kg^-1干土 .淄河滩石油污染土层中降解菌主要为好氧异养菌 ,菌群数量高达 10⁶～10⁷个·g^-1干土 .为包气带土层石油类污染物的自然衰减和净化提供了良好的生物条件 .     

BTEX在地下环境中的自然衰减

通过室内模拟柱实验研究了BTEX在地下环境中的自然衰减过程,发现BTEX通过以细砂为介质的模拟地下环境时确实发生了自然衰减,挥发和生物降解作用是其自然衰减的重要机制.以苯为例,其在水中的质量浓度为11.40 mg/L左右时,挥发和生物降解作用占自然衰减的比例分别是16.36%和4.91%;而甲苯浓度为3.30 mg/L左右时,两者所占比例分别是11.04%和41.50%.可见BTEX中各组分衰减规律不同.BTEX浓度越大,其挥发得也越快,挥发对自然衰减的作用越大.微生物降解作用对甲苯更有效,占自然衰减的41.50%,间、对二甲苯次之占8.49%,而苯和乙苯很难被降解.     

基于土壤和农产品综合质量指数法的区域农田土壤环境质量评价

在云南539对土壤与农作物协同样品检测分析的基础上,采用土壤和农产品综合治理指数法对农田土壤环境质量进行评价。结果表明稻田土壤镉、砷含量均低于玉米地为代表的旱地。539个点位中清洁点位占41. 4%、轻微污染点位占26. 0%、轻度污染点位占13. 9%、中度污染点位占8. 0%、重度污染点位占10. 8%。     

BTEX在乙醇汽油和传统汽油污染地下水中的衰减行为对比

地下燃油储藏罐泄漏造成苯、甲苯、乙苯和二甲苯（BTEX）影响生态环境和公众健康的问题一直备受关注,随着乙醇汽油的推广使用,乙醇对BTEX修复策略的影响成为需要重视的新问题.为揭示乙醇汽油污染地下水中BTEX的衰减行为,本文通过室内两个独立砂槽投注实验和近3年的监测,对比了乙醇汽油和传统汽油中BTEX自然衰减和基于硫酸盐-硝酸盐补充的增强生物修复行为.结果表明,传统汽油BTEX自然衰减较快,乙醇汽油BTEX自然衰减较慢,一级衰减速率常数分别为0.0055~0.0329 d^-1和0.0045~0.0124 d^-1;苯衰减最快,其次为甲苯.补充硫酸盐和硝酸盐能促进生物修复,单独补充硫酸盐时其利用率为89.7%~92.9%,同时补充硝酸盐时硫酸盐利用被抑制,硝酸盐利用率为79.9%~87.2%.水位波动会促进BTEX溶解和迁移,增大质量通量.乙醇汽油不仅能消耗更多电子受体,使得BTEX衰减被抑制,而且可能会扩大水位波动引起的增溶效应.     

不同开垦年限黑土温室气体排放规律研究

以东北黑土区荒地土壤(H)、开垦2 a(L)、30 a(S)和100 a(Y)土壤为对象,在25℃和60%WHC水分条件下,通过7 d的室内培养试验,研究了不同开垦年限黑土温室气体N2O、CO2和CH4的排放规律.结果表明,黑土开垦后理化性质发生了显著改变,进而影响了温室气体的排放.N2O排放量随开垦年限的增加而增加,开垦30 a和100 a土壤的N2O排放量显著高于荒地土壤.净硝化量和N2O排放量与土壤水溶性有机氮和粉粒含量呈显著正相关关系,与土壤pH和砂粒含量呈显著负相关关系.CO2排放量随开垦年限的增加而逐渐降低,开垦30 a和100 a土壤与荒地土壤差异显著.土壤有机碳和水溶性有机碳含量与CO2累积排放量呈显著正相关关系.好氧条件下,荒地土壤和开垦土壤在培养前4 d表现为对CH4的微量排放,然后表现为对CH4的微量吸收,开垦土壤的CH4排放量随开垦年限的增加而增加.不同开垦年限黑土可能因土壤pH、有机碳、水溶性有机碳含量以及土壤机械组成的差异而产生CO2和CH4排放的差异.     

室内空气污染预测方法的实证研究

在大型(30m3)、小型(1m3)环境箱实验获得数据的基础上构建释放模型,并将模拟结果和现场监测得到的浓度水平进行对比,对开发的室内空气污染预测方法进行了实证研究.以一新装修房间为例,分别利用大型和小型环境箱实验,研究了复杂整装材料和简单层状材料的释放规律,建立了相应材料的污染物释放模型;依据单元内物质守恒理论和污染物充分混合的假设将释放模型组合,建立了室内空气污染预测方法,并预测了该房间甲醛和TVOC(total volatile organic compounds)浓度的变化过程.在考虑了0.03ACH(air change per hour)的换气率之后,模型预测与现场监测的污染物浓度变化趋势基本吻合,甲醛和TVOC污染预测误差(正则化标准差)分别为2.8%和1.6%.模型分析表明,各污染源对于甲醛污染的贡献,家具＞涂料＞地板;对于TVOC污染的贡献,涂料＞地板＞家具.结论表明,该预测方法可以真实反映现场污染物浓度变化趋势,可以用来分析各污染源对于整体污染的贡献、指导装修材料的选择和作为室内污染评估和控制的有效工具.     

大气中CO2与O3浓度升高对植物光合作用影响研究

随着工业化进程的加快,两种温室气体CO2和O3在大气中浓度不断升高,对植物光合作用产生重要影响.通过从气体交换参数、光合色素含量、叶绿素荧光特性、光合酶、生物量及产量等多方面分析国内外CO2O3单独作用及复合作用对植物光合过程和机理、光合作用物质基础及光合产物的影响,深入了解两种污染气体作用下植物光合响应机制,以期为植物光合作用分子水平的研究以及有效应对未来全球大气变化提供理论依据.     

保护性耕作对后茬冬小麦土壤CO2和N2O排放的影响

为研究保护性耕作对后茬冬小麦土壤CO2和N2O排放的影响,在前茬进行常规耕作(T)、免耕(NT)、免耕+秸秆覆盖(NTS)、常规耕作+秸秆施用(TS)这4种处理,采用静态箱-气相色谱法分析土壤CO2和N2O排放通量.结果表明,保护性耕作没有改变后茬土壤CO2和N2O排放的季节性规律,对冬小麦生物量无明显影响;保护性耕作显著减少了土壤CO2和N2O累积排放量.与T相比,TS、NT、NTS的全生育期土壤CO2累积排放量分别降低了5.95%(P=0.132)、12.94%(P=0.007)和13.91%(P=0.004),土壤N2O累积排放量分别减少了31.23%(P=0.000)、61.29%(P=0.000)和33.08%(P=0.000).本研究表明免耕与秸秆施用能减少后茬作物生长季土壤的CO2和N2O排放量.     

On-line CO, CO2 emissions evaluation and (benzene, toluene, xylene) determination from experimental burn of tropical biomass

Atmospheric pollution and global warming issues are increasingly becoming major environmental concerns. Fire is one of the significant sources of pollutant gases released into the atmosphere; and tropical biomass fires, which are of particular interest in this study, contribute greatly to the global budget of CO and CO₂. This pioneer research simulates the natural biomass burning strategy in Malaysia using an experimental burning facility. The investigation was conducted on the emissions (CO₂, CO, and Benzene, Toluene, Ethylbenzene, Xylenes (BTEX)) from ten tropical biomass species. The selected species represent the major tropical forests that are frequently subjected to dry forest fire incidents. An experimental burning facility equipped with an on-line gas analyzer was employed to determine the burning emissions. The major emission factors were found to vary among the species, and the specific results were as follows. The moisture content of a particular biomass greatly influenced its emission pattern. The smoke analysis results revealed the existence of BTEX, which were sampled from a combustion chamber by enrichment traps aided with a universal gas sampler. The BTEX were determined by organic solvent extraction followed by GC/MS quantification, the results of which suggested that the biomass burning emission factor contributed significant amounts of benzene, toluene, and m,p-xylene. The modified combustion efficiency (MCE) changed in response to changes in the sample moisture content. Therefore, this study concluded that the emission of some pollutants mainly depends on the burning phase and sample moisture content of the biomass.     

Co-adsorption of gaseous benzene, toluene, ethylbenzene, m-xylene (BTEX) and SO2 on recyclable Fe3O4 nanoparticles at 0-101% relative humidities

We herein used Fe3O4 nanoparticles(NPs) as an adsorption interface for the concurrent removal of gaseous benzene, toluene, ethylbenzene and m-xylene(BTEX) and sulfur dioxide(SO2), at different relative humidities(RH). X-ray diffraction, Brunauer–Emmett–Teller, and transmission electron microscopy were deployed for nanoparticle surface characterization.Mono-dispersed Fe3O4(Fe2O3·Fe O) NPs synthesized with oleic acid(OA) as surfactant, and uncoated poly-dispersed Fe3O4 NPs demonstrated comparable removal efficiencies.Adsorption experiments of BTEX on NPs were measured using gas chromatography equipped with flame ionization detection, which indicated high removal efficiencies(up to(95 ± 2)%) under dry conditions. The humidity effect and competitive adsorption were investigated using toluene as a model compound. It was observed that the removal efficiencies decreased as a function of the increase in RH, yet, under our experimental conditions, we observed(40 ± 4)% toluene removal at supersaturation for Fe3O4 NPs, and toluene removal of(83 ± 4)% to(59 ± 6)%, for OA-Fe3O4 NPs. In the presence of SO2, the toluene uptake was reduced under dry conditions to(89 ± 2)% and(75 ± 1)% for the uncoated and coated NPs, respectively, depicting competitive adsorption. At RH 100%,competitive adsorption reduced the removal efficiency to(27 ± 1)% for uncoated NPs whereas OA-Fe3O4 NPs exhibited moderate efficiency loss of(55 ± 2)% at supersaturation.Results point to heterogeneous water coverage on the NP surface. The magnetic property of magnetite facilitated the recovery of both types of NPs, without the loss in efficiency when recycled and reused.     

3种金属氧化物纳米材料在不同土壤中运移行为研究

采用实验室柱淋溶方法,考察了纳米CeO2、纳米TiO2和纳米Al2O3材料在不同土壤中的运移行为,分析了纳米材料在土壤中运移能力与土壤性质的相关性,并采用胶体运移动力学模型估算了纳米材料在土壤中的最远运移距离.结果表明,纳米CeO2和纳米TiO2在试验的大部分土壤中有很强的运移能力,而纳米Al2O3仅在试验的酸性土壤中有较强的运移能力,在其他土壤中几乎被全部截留.纳米材料在土壤中运移的机制非常复杂,静电作用、土壤表面电荷异质性、团聚作用、张力作用(straining)以及过滤熟化作用(ripening)均对纳米材料的运移有着重要的影响.纳米CeO2的运移能力与土壤Zeta电位显著负相关;纳米TiO2的运移能力与土壤黏粒含量显著负相关,与土柱渗透系数显著正相关;纳米Al2O3的运移能力与土壤pH显著负相关,与土柱渗透系数显著正相关.模型估算的纳米CeO2、纳米TiO2和纳米Al2O3在试验土壤中的最远运移距离分别为52~69 043、31~332和<10~5 722 cm.纳米材料在一些土壤中的最远运移距离远远大于30 cm表层土壤的深度,意味着纳米材料在这些土壤中有向深层土壤运移的可能.     

不同环境因素下太湖中四环素的自然消减

四环素已经广泛应用于兽药生产和疾病治疗中,并通过禽畜粪便等途径进入环境中,基于四环素残留物的危害性,采用了模拟自然环境状态的实验方法,研究了四环素在不同环境状态(光照、底泥、重金属)下的自然消减过程.结果表明,四环素在自然光照下的消减不明显;未杀菌底泥水体中,四环素的消减速率大于杀菌底泥水体;实验初期,含硝酸铅水体中四环素消减缓慢,随着时间延长,消减速率加快,而在硝酸镉水体中四环素短时间内消减趋势已经十分明显,且消减速率大于硝酸铅水体;以0.08 mmol·L-1四环素为例,四环素在光照下各环境因素中的消减速率依次为:未杀菌底泥(87.2%)>杀菌底泥(70.37%)>硝酸镉水体(64.2%)>硝酸铅水体(32.3%)>空白组(6.6%),各环境因素均促进了四环素的消减.避光时,各环境因素中四环素的消减趋势与光照组相同,但消减速率较光照组小,表明光照对四环素的自然消减具有一定的促进作用.     

Fabrication of Bi2O3/TiO2 nanocomposites and their applications to the degradation of pollutants in air and water under visible-light

A nanoheterojunction composite photocatalyst Bi2O3/TiO2working under visible-light(λ 420 nm) was prepared by combining two semiconductors Bi2O3 and TiO2 varying the Bi2O3/TiO2molar ratio. Maleic acid was employed as an organic binder to unite Bi2O3 and TiO2 nanoparticles. The SEM, TEM, XRD and diffuse reflectance spectra were utilized to characterize the prepared Bi2O3/TiO2nanoheterojunction. The nanocomposite exhibited unusual high photocatalytic activity in decomposing 2-propanol in gas phase and phenol in aqueous phase and, evolution of CO2 under visible light irradiation while the end members exhibited low photocatalytic activity. The composite was optimized to 5 mol% Bi2O3/TiO2. The remarkable high photocatalytic efficiency originates from the unique relative energy band position of Bi2O3 and TiO2 as well as the absorption of visible light by Bi2O3.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O³ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ >> NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

黄绵土中碳酸钙含量和有机肥施用对土壤有机碳组分及CO2排放的影响

为探讨碳酸钙(CaCO_3)和有机肥对土壤有机碳矿化和CO_2排放的影响,本研究通过向一种黄绵土中分别添加0、30、50 g·kg~(-1)CaCO_3模拟陕西省境内具有不同CaCO_3含量(9%~15%)的黄绵土,随后再添加0、20 g·kg~(-1)有机肥(M),交互组合设L0、L0-M、L30、L30-M、L50和L50-M等6个处理进行室内培养试验(105 d),测定了土壤pH、微生物量碳(MBC)、水溶性有机碳(DOC)、颗粒碳(POC)、易氧化有机碳(ROC)和CO_2释放量.结果表明:未施用有机肥时,土壤pH和MBC含量随CaCO_3含量的增加而增加,但CaCO_3含量对DOC、POC、ROC和有机碳氧化稳定性(Kos)无显著影响,其差异亦不会对土壤CO_2排放产生显著影响.当施用有机肥后,随着土壤CaCO_3含量增加,土壤pH上升、活性有机碳(MBC、DOC、POC和ROC)含量增加、Kos降低,土壤CO_2排放也随之增加.CaCO_3不仅能促进有机肥的矿化分解,而且它和有机肥会对土壤CO_2排放产生显著的交互效应,其效果与CaCO_3含量密切相关.低量CaCO_3和有机肥对土壤CO_2的释放具有负的表观交互效应,但高量CaCO_3和有机肥对其产生正的表观交互效应.因此,CaCO_3对土壤有机碳转化的影响不能一概而论,它与土壤中CaCO_3含量密切相关.在农业管理中,根据土壤CaCO_3含量合理施用有机肥对土壤碳素循环和温室气体(CO_2)排放都具有重要意义.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O₃ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ ? NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the “cold start” problem.     

包气带水气二相流CO2运移规律

利用土柱实验装置模拟CO₂在土壤中的迁移转化规律,重点研究湿润峰处水、气二相间污染物转化实验土柱长1m,过饱和CO2溶液浓度为748mg/L.分析表明水相运移受对流、弥散、反应及水-气质量传输机制控制,气相运移受对流、扩散和水-气质量传输机制控制.对土柱中水气二相动态条件下的取样方法进行了探索,确定了CO₂在渗透湿润峰水-气二相间分配系数为0.00061,表明水相向气相有一定传输,但不显著.可进一步为低中水平放射性废物地质处置安全评价及固体废物填埋处置环境影响评价提供定量科学依据.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.