Background levels of atmospheric hydrocarbons,sulphate and nitrate over the western Mediterranean

Aerosols collected on top of Alfabia ridge (∼1100 m; Mallorca Island) have been analysed for chloride, nitrate, sulphate, aliphatic, and polycyclic aromatic hydrocarbons. The results exhibit concentrations in the level of the lowest previously reported for the western Mediterranean atmosphere. However, they are significantly higher than those described for very remote sites, thus defining a background level of particulate atmospheric compounds in this region. Two natural and anthropogenic sources, namely higher plant waxes and coal combustion particles, have been recognized as the main organic inputs to these background aerosols. The former is represented by the major n-alkanes and the latter by the polycyclic aromatic hydrocarbons.     

Characterization of odorous charge and photochemical reactivity of VOC emissions from a full-scale food waste treatment plant in China

Food waste treatment plants (FWTPs) are usually associated with odorous nuisance and health risks, which are partially caused by volatile organic compound (VOC) emissions. This study investigated the VOC emissions from a selected full-scale FWTP in China. The feedstock used in this plant was mainly collected from local restaurants. For a year, the FWTP was closely monitored on specific days in each season. Four major indoor treatment units of the plant, including the storage room, sorting/crushing room, hydrothermal hydrolysis unit, and aerobic fermentation unit, were chosen as the monitoring locations. The highest mean concentration of total VOC emissions was observed in the aerobic fermentation unit at 21,748.2–31,283.3 μg/m³, followed by the hydrothermal hydrolysis unit at 10,798.1–23,144.4 μg/m³. The detected VOC families included biogenic compounds (oxygenated compounds, hydrocarbons, terpenes, and organosulfur compounds) and abiogenic compounds (aromatic hydrocarbons and halocarbons). Oxygenated compounds, particularly alcohols, were the most abundant compounds in all samples. With the use of odor index analysis and principal components analysis, the hydrothermal hydrolysis and aerobic fermentation units were clearly distinguished from the pre-treatment units, as characterized by their higher contributions to odorous nuisance. Methanthiol was the dominant odorant in the hydrothermal hydrolysis unit, whereas aldehyde was the dominant odorant in the aerobic fermentation unit. Terpenes, specifically limonene, had the highest level of propylene equivalent concentration during the monitoring periods. This concentration can contribute to the increase in the atmospheric reactivity and ozone formation potential in the surrounding air.     

Structure and disposition of particles from a spark-ignition engine

Particles generated in the exhaust of a spark-ignition engine operated with leaded and unleaded fuel exhibit significant changes of size, structure and surface chemical composition on changing the temperature T of the carrier gas.Total mass, mass of black carbon (BC), diameter and the photoelectric yield of the particles have been measured in situ as a function of temperature. Concomitantly the particles have also been deposited on a substrate and imaged by transmission electron microscopy.Diameter and total mass of the particles decrease significantly with increasing T, whereas the BC mass remains nearly unaffected. From diameter and photoyield vs T curve a shell structure of the particles emerges, where the outermost shell is made up of volatile organic components followed by a layer of polycyclic aromatic hydrocarbons (PAHs) with less volatility on a core of BC and, depending on the type of fuel, also lead. Transmission electron micrographs indicate that lead and carbonaceous fractions segregate at T = 275°C. For T > 275°C and almost perfect crystalline order of lead appears.     

Hydrocarbons in particulate samples from wildfire events in central Portugal in summer 2010

In summer 2010, twenty eight(14 PM_(2.5)samples plus 14 samples PM_(2.5–10)) smoke samples were collected during wildfires that occurred in central Portugal. A portable high-volume sampler was used to perform the sampling, on quartz fibre filters of coarse(PM_(2.5–10)) and fine(PM_(2.5)) smoke samples. The carbonaceous content(elemental and organic carbon) of particulate matter was analysed by a thermal–optical technique. Subsequently, the particulate samples were solvent extracted and fractionated by vacuum flash chromatography into three different classes of organic compounds(aliphatics, polycyclic aromatic hydrocarbons(PAHs) and carbonyl compounds). The organic speciation was performed by gas chromatography–mass spectrometry(GC–MS). Emissions were dominated by the fine particles, which represented around 92% of the PM_(10). A clear predominance of carbonaceous constituents was observed, with organic to elemental carbon(OC/EC)ratios ranging between 1.69 and 245 in both size fractions. The isoprenoid ketone6,10,14-trimethyl-2-pentadecanone, a tracer for secondary organic aerosol formation, was one of the dominant constituents in both fine and coarse particles. Retene was the most abundant compound in all samples. Good correlations were obtained between OC and both aliphatic and PAH compounds. Pyrogenic processes, thermal release of biogenic compounds and secondary processing accounted for 97% of the apportioned PM_(2.5)levels.     

Novel quantitative structure activity relationship models for predicting hexadecane/air partition coefficients of organic compounds

Predicting the logarithm of hexadecane/air partition coefficient (L) for organic compounds is crucial for understanding the environmental behavior and fate of organic compounds and developing prediction models with polyparameter linear free energy relationships. Herein, two quantitative structure activity relationship (QSAR) models were developed with 1272 L values for the organic compounds by using multiple linear regression (MLR) and support vector machine (SVM) algorithms. On the basis of the OECD principles, the goodness of fit, robustness and predictive ability for the developed models were evaluated. The SVM model was first developed, and the predictive capability for the SVM model is slightly better than that for the MLR model. The applicability domain (AD) of these two models has been extended to include more kinds of emerging pollutants, i.e., oraganosilicon compounds. The developed QSAR models can be used for predicting L values of various organic compounds. The van der Waals interactions between the organic compound and the hexadecane have a significant effect on the L value of the compound. These in silico models developed in current study can provide an alternative to experimental method for high-throughput obtaining L values of organic compounds.     

Unraveling the size distributions of surface properties for purple soil and yellow soil

Soils contain diverse colloidal particles whose properties are pertinent to ecological and human health, whereas few investigations systematically analyze the surface properties of these particles. The objective of this study was to elucidate the surface properties of particles within targeted size ranges (i.e. > 10, 1–10, 0.5–1, 0.2–0.5 and < 0.2 μm) for a purple soil (Entisol) and a yellow soil (Ultisol) using the combined determination method. The mineralogy of corresponding particle-size fractions was determined by X-ray diffraction. We found that up to 80% of the specific surface area and 85% of the surface charge of the entire soil came from colloidal-sized particles (< 1 μm), and almost half of the specific surface area and surface charge came from the smallest particles (< 0.2 μm). Vermiculite, illite, montmorillonite and mica dominated in the colloidal-sized particles, of which the smallest particles had the highest proportion of vermiculite and montmorillonite. For a given size fraction, the purple soil had a larger specific surface area, stronger electrostatic field, and higher surface charge than the yellow soil due to differences in mineralogy. Likewise, the differences in surface properties among the various particle-size fractions can also be ascribed to mineralogy. Our results indicated that soil surface properties were essentially determined by the colloidal-sized particles, and the < 0.2 μm nanoparticles made the largest contribution to soil properties. The composition of clay minerals within the diverse particle-size fractions could fully explain the size distributions of surface properties.     

Availability of phosphorus to algae from eroded soil fractions

A study was conducted to determine the concentrations of algal-available P (P_aa) in unfractionated samples and size-classified separates of soil eroded from wheat stubble plots during a simulated rainfall experiment conducted in Warren County, Indiana, U.S.A. Run-off samples were collected, concentrated, dispersed by sonification, separated according to size and incubated with algal cells (Selanastrum capricornutum) in P-free nutrient medium for 2 weeks. Algal-available P in soil separates was determined by decreases in sediment inorganic P (P_i) over the incubation period. The initial concentrations of dissolved molybdate-reactive P_i (DMRP), P_i extractable with NaOH (NaOH-P_i), P_i extractable with HCl (HCl-P_i), organic P (P_o, and total P increased with decreasing particle size. A higher proportion of P_i was HCl-extractable in fractions > 2 μm than in clay-size separates. The level of P_aa in samples increased with decreasing particle size. Available P concentrations in separates < 0.2, 0.2–2, 2–50, > 50 μm and unfractionated samples averaged 447, 282, 113, 26 and 261 μg g^?1, respectively. From 42 to 69% of the P_i and 20–37% of the total P in unfractioned samples was P_aa. A lower proportion of P_i in the > 50 μm fraction was P_aa than in the other size fractions (34 vs. 50%). There was no relationship between particle size and the proportion of total P that was available. The majority (> 84%) of P_aa originated in the P_i fraction extractable with NaOH, whereas HCl-P_i only contributed small amounts of P_aa. The proportion of initial NaOH-P_i assimilated by algae in 2 weeks ranged between 43 and 77%, whereas an average of 16% of HCl-P_i in separates was P_aa. On average, a greater proportion of NaOH-P_i was assimilated by algae in samples from no-till plots as compared to those from chisel-plowed plots.     

机动车尾气排放VOCs源成分谱及其大气反应活性

选取轻型汽油车、重型柴油车和摩托车等城市典型机动车种分别采用底盘测功机及实际道路实验,结合SUMMA罐采样的方法,获得了小轿车、出租车、公交车、卡车、摩托车和LPG助动车的尾气VOCs样品,利用气相色谱-质谱分析了各车型机动车尾气VOCs的浓度及其物种组成.结果表明,轻型汽油车尾气VOCs以甲苯、二甲苯等芳香烃为主,占43.38%～44.45%;重型柴油车以丙烷、n-十二烷及n-十一烷等烷烃组分为主,占46.86%～48.57%,还有13.28%～15.01%的丙酮等含氧特征组分;摩托车与LPG助动车的主要成分为乙炔,分别占39.75%和76.67%左右.各车型中,摩托车和轻型汽油车尾气VOCs的化学活性显著高于重型柴油车辆,以上海市为例,其大气化学活性贡献分别占55%和44%左右,是影响城市和区域大气氧化能力的关键污染源,其中以甲苯、二甲苯、丙烯、苯乙烯等关键活性物种的贡献最大.     

Study on the numerical modeling of particulate matter in Shanghai

A diffusion model for industrial sources and a chemical element balance (CEB) method for non-industrial sources are combined to estimate the contributions of various sources to the suspended particulate matter (SPM), dust fall and total suspended particles (TSP) in Shanghai. The SPM is defined as those particles with diameters d < 10 μm. The mass proportions of the particulate matter with diameters d<10 μm, d = 10–40 μm and d > 40 μm, to TSP are also acquired. Settlings of particles, reflection and washout by rain are considered in the diffusion model, in which the emission rates of particulate matter are associated with size distributions, depending on different types of boilers and dust collectors. The data of mass-spectrum of chemical elements associated with two size-ranges, d < 10 μm and d ≥ 10μm are used in the CEB calculations. Combined results show that industrial sources play the most important role in contributing to atmospheric concentrations of the particulate matter, contributing more than 70% to atmospheric concentrations, in which the area sources are about 50% of the total contributions. The proportions of the particulate mass are 57% for d < 10 μm and 43% for d ≥ 10 μm, of the mass of TSP, respectively. It implies that, for alleviating the particulate matter pollution in Shanghai, emission control on the industrial sources, especially on the area sources, is still an emergent task.     

大同市大气颗粒物及有机污染物的分析研究

对大同市不同功能区的可吸入尘（＜１０μｍ）浓度进行了测定,并探讨了可吸入尘与总悬沙颗粒物的相关比例。总悬浮颗粒物上二氯甲烷萃取物含量达２０％,对其中的有机污染物用ＧＣ／ＭＳＴ和ＨＰＬＣ进行了分析,鉴定出的主要有机污染物有苯系物及芳烃类化合物３８种,烷烃类化合物３１种,以及酚类,酮类,含氮化合物和增塑剂１４种,总计８３种。     

Aerosol-soil fractionation for Namib Desert samples

Four soil samples, collected in the central Namib Desert, were fractionated by dry sieving and aerosol generation into 16 size fractions in the range 0.15–300 μm diameter. The mass-size function of each soil and the dust (mineral aerosol) generated from the soil were studied. Due to the preferential lifting of smaller soil particles by the air stream, the soil underwent strong physical fractionation resulting in the bulk of the dust being found in the range of 1.3–10.3 μm, whereas the bulk of the soil was found in the range 63–300 μm. The concentrations of 11 elements in eight soil size fractions (from <45 to >300 μm) obtained by dry sieving were measured by X-ray fluorescence analysis while the concentration for these elements in eight size ranges (from <0.15 to >10.3 μm) obtained by aerosol generation were determined by particle-induced X-ray emission. The concentrations of the elements Al, Si, K, Rb and Sr were found to vary by less than a factor of two throughout the particle size range studied. However, the concentration of the elements Ca, Ti, Mn, Fe, Y and Zr increased when the particle size decreased below 150 μm to reach a maximum around 63-45 μm and then to decrease. The concentrations of the elements in the generated aerosol particles were found to be more similar to those in the bulk soil than any particular size fraction. For the aerosol size fraction, elemental enrichment factors were calculated with respect to the composition of average crustal rock, average soil, the bulk Namib soil and the small size fraction of the Namib soil. For several elements, the enrichment factors varied quite significantly, depending on the choice of the reference material. The elemental ratios in the mineral aerosol were also compared to those in the atmospheric aerosol from the Namib Desert. It was confirmed that there is a marine contribution for S, Cl and Sr in the Namib natural aerosol. The composition of the mineral aerosol generated in this study should be useful in source apportionment studies for the Namib Desert and sorrounding regions.     

2-丁烯醛生产废水中溶解性有机物的分级解析

采用超滤膜法将2-丁烯醛生产废水中的有机物分为相对分子质量不同的7个级分,并应用溶解性有机碳(dissolved organic carbon,DOC)、紫外吸收光谱(ultraviolet spectrum,UV)、傅里叶变换红外光谱(fourier transform infrared spectrometer,FT-IR)和气相色谱/质谱联用仪(gas chromatography with mass spectrometry,GC-MS)技术对不同相对分子质量区间的有机物所占比例及物质结构进行了研究.结果表明,废水中相对分子质量1×103的有机物所占比例最高,达到88.57%;采用GCMS对废水中相对分子质量1×103的级分进行分析,定性出27种化合物,包含醛、酮、酯、醇、酚、酸、烷烃类及其他苯系物等,其峰面积占有机物峰面积总和的比例分别为6.9%、5.3%、35.4%、13.2%、4.6%、0.4%、1.7%、16.8%,总和为84%.UV和FT-IR分析结果均显示不同相对分子质量区间的光谱吸收特征没有明显差别,级分中存在含有不饱和双键、羟基、羰基化合物及芳香族化合物,与GC-MS检测结果相吻合.研究结果为废水处理工艺的开发与优化提供了重要的指导作用.     

Particle size distribution and characteristics of heavy metals in road-deposited sediments from Beijing Olympic Park

Due to rapid urbanization and industrialization, heavy metals in road-deposited sediments (RDSs) of parks are emitted into the terrestrial, atmospheric, and water environment, and have a severe impact on residents' and tourists' health. To identify the distribution and characteristic of heavy metals in RDS and to assess the road environmental quality in Chinese parks, samples were collected from Beijing Olympic Park in the present study. The results indicated that particles with small grain size (< 150 μm) were the dominant fraction. The length of dry period was one of the main factors affecting the particle size distribution, as indicated by the variation of size fraction with the increase of dry days. The amount of heavy metal (i.e., Cu, Zn, Pb and Cd) content was the largest in particles with small size (< 150 μm) among all samples. Specifically, the percentage of Cu, Zn, Pb and Cd in these particles was 74.7%, 55.5%, 56.6% and 71.3%, respectively. Heavy metals adsorbed in sediments may mainly be contributed by road traffic emissions. The contamination levels of Pb and Cd were higher than Cu and Zn on the basis of the mean heavy metal contents. Specifically, the geoaccumulation index (I_geo) decreased in the order: Cd > Pb > Cu > Zn. This study analyzed the mobility of heavy metals in sediments using partial sequential extraction with the Tessier procedure. The results revealed that the apparent mobility and potential metal bioavailability of heavy metals in the sediments, based on the exchangeable and carbonate fractions, decreased in the order: Cd > Zn ≈ Pb > Cu.     

Effects of DOM characteristics from real wastewater on the degradation of pharmaceutically active compounds by the UV/H2O2 process

The characteristics of dissolved organic matter (DOM) can significantly affect the degradation of target compounds by the advanced oxidation processes. In this study, the effects of the different hydrophobicity/hydrophilicity fractions, molecular weight (MW) fractions, fluorescence components and molecular components of DOM extracted from municipal wastewater on the degradation of 4 pharmaceutically active compounds (PhACs), including carbamazepine, clofibric acid, atenolol and erythromycin by the UV/H₂O₂ process were investigated. The results showed that the degradation rate constants of 4 PhACs decreased dramatically in the presence of DOM. The linear regressions of 4 PhACs degradation as a function of specific fluorescence intensity (SFI) are exhibited during the degradation of 4 PhACs and the SFI may be used to evaluate effect of DOM on target compounds in wastewater. The hydrophobic acid (HPO-A) exhibited the strongest inhibitory effect on degradation of 4 PhACs during oxidation process. The small MW fractions of DOM significantly inhibited the degradation of 4 PhACs during oxidation process. Among three fluorescence components, hydrophobic humic-like substances may significantly inhibit the degradation of 4 PhACs during oxidation process. At the molecular level, the formulas may be derived from terrestrial sources. CHO compound may significantly inhibit the degradation of 4 PhACs during oxidation process on formula classes. The unsaturated hydrocarbons, carbohydrates and tannins compounds may significantly inhibit the effectiveness of the UV/H₂O₂ process on compound classes.     

河南省某典型垃圾焚烧发电厂的VOCs排放特征

为评估河南省生活垃圾焚烧发电厂排放的挥发性有机物(VOCs)对臭氧生成的贡献,选取某典型企业进行调研. 采用气袋、苏玛罐和吸附管进行采样,通过气质联用(GC/MS)和高效液质(HPLC/MS)联用分析方法对117种VOCs物种排放水平进行监测,并计算本地化VOCs排放因子. 采用最大增量反应活性(MIR)法计算臭氧生成潜势(OFP),并识别OFP贡献率较大的物种. 结果表明:①主排放口实测的VOCs总浓度为4.28 mg/m3,VOCs排放量为3.5 t/a,计算的VOCs排放因子为0.016 g/kg (以垃圾计,下同). ②MIR系数法计算的有组织OFP总排放量为9.3 t/a,对应的MIR系数平均值为2.67. ③排放量占比较大的VOCs组分依次为芳香烃(38.37%)、卤代烃(28.79%)、含氧化合物(14.32%)和烷烃(12.75%). 对OFP贡献率较大的VOCs组分为芳香烃(53.91%)和含氧化合物(28.16%),OFP贡献率排名前5位的VOCs物种分别为乙醛(20.5%)、间/对-二甲苯(20.2%)、正丁烯(6.2%)、1,2,4-三甲苯(5.4%)和正丁醛(4.9%). ④固废间、锅炉房、锅炉房外、渗滤液泵房及房顶采样点测得的VOCs无组织排放总浓度分别为83.6、6.19、1.24、5.71、1.79 mg/m3. 研究显示,该垃圾焚烧发电厂固废间VOCs浓度较高,需要进一步提高车间内VOCs收集率,以减少无组织VOCs排放,同时可在主排放口安装合适的VOCs去除装置以进一步削减VOCs有组织排放量.      

典型内燃叉车尾气挥发性有机物与正构烷烃的排放特征

非道路柴油车尾气是影响我国空气质量的重要排放源,但目前针对其化学组分及其影响因素的了解仍然非常有限.以6台内燃叉车为研究对象,利用气态组分在线监测结合样品采集离线分析方法,重点探讨了柴油机颗粒物过滤器(DPF)对叉车尾气中的关键化学组分挥发性有机物(VOCs)和正构烷烃含量及其特征的影响.结果 表明,含氧挥发性有机物(...     

一个沿海城市大气臭氧的本地生成过程及其对前体物的敏感性

在威海市两个采样点用苏码罐采集了全空气样品,利用三级冷阱预浓缩-GC/MS方法离线测定了空气样品中109种大气挥发性有机物(VOCs).使用基于观测的MCM机理大气化学模式(OBM-MCM)分析了大气臭氧生成对VOCs组分的敏感性及本地生成过程.结果表明:观测期间两个采样点的总挥发性有机物(TVOCs)平均浓度分别为27.84×10~(-9)和17.85×10~(-9),对TVOCs贡献最大的均是烷烃.模拟分析表明,大气臭氧生成与前体物的控制关系存在空间差异性,在一个观测点受VOCs控制,而在另一个观测点受NO_x和VOCs共同控制;模拟结果还表明,臭氧生成对活性烃类最为敏感,但是,含氧有机物、卤代烃和高碳烷烃对臭氧生成的影响和贡献也不可忽视;此外,计算了日平均臭氧净生成速率P(O_3)_(net),分别为6.41×10~(-9) h~(-1)和3.22×10~(-9) h~(-1),臭氧的本地生成过程扮演重要角色.     

Controls on the phosphorus content of fine stream bed sediments in agricultural headwater catchments at the landscape-scale

There have been no landscape-scale assessments which quantify the relative importance of the organic and mineral properties of BS (bed sediment) and associated catchment characteristics (geology, land cover and mean topsoil phosphorus (P) content) for BSP concentration. Mid infra red diffuse reflectance spectrometry was applied to estimate the quantities of organic matter, dithionite extractable aluminium- (Al_d) and iron (Fe_d), kaolinite, dioctahedral clay and mica (D&M) minerals in 1052 snapshot samples of fine (<150 μm) BS in small to medium-sized (5-55 km²) agricultural headwater catchments across a large area (15 400 km²) of central England. Analyses included estimates of BS specific surface area, cerium (Ce) concentrations (enriched in P-bearing apatite and P-fertilsers), and catchment average topsoil P content.Simple linear regression demonstrated that the proportion of variance in BSP explained by specific components of BS across all catchments declined in the following order: Al_d > Fe_d > topsoil P = kaolinite = residual iron> organic matter = Ce> D&M > mineral SSA. No single component accounted for more than 36% of the variance in BSP. Multiple regression - including a classification of bedrock lithology and proportions of arable and grassland by area - accounted for 61.9% of the variance in BSP. The proportion of arable and grassland by area in each catchment was also a statistically significant predictor of BSP. Across this large region - with widely differing geology and soils - Fe_d in BS is more strongly associated with kaolinite than D&M minerals because iron-oxyhydroxides and kaolinite form contemporaneously during pedogenesis. The SSA of fine bed sediments is largely determined by catchment area, fitted accurately using a power function.     

造纸废水二级生化出水的电离辐射深度处理

探讨了采用电离辐射对造纸废水二级生化出水进行深度处理的可行性.结果表明,二级生化出水主要由相对分子质量为1000～3000和3000以上的有机物组成,它们对COD的贡献分别为69.5%和6.9%,它们对溶解性有机质（DOC）的贡献分别为40.6%和31.6%.电离辐射促使废水中的一些大分子有机物向小分子有机物转化,相对...     

泡沫塑料鞋制造区VOCs污染特征及臭氧生成潜势

于泡沫塑料鞋制造集中区和周边设置了5个采样点,研究其大气VOCs的污染特征和对臭氧生成的潜在影响.结果显示泡沫塑料制鞋行业大气VOCs组成以烷烃（38.4%）、含氧挥发性有机物（33.5%）和芳香烃（19.5%）为主,80种VOCs浓度为137.1~169.0μg/m³（均值149.1μg/m³）.正戊烷、异戊烷、正丁烷、异丁烷、甲醛、甲苯、间/邻二甲苯、丙酮、丁酮、环己酮、甲基丙烯酸甲酯、乙酸乙酯为泡沫塑料鞋制造行业的特征VOCs.总VOCs、特征VOCs类型（含氧挥发性有机物、芳香烃）和特征VOCs组分（甲苯、邻二甲苯、间二甲苯、丁酮、乙酸乙酯）的浓度空间变化趋势依次为污染区 > 受影响区（下风向） > 对照区（上风向）.同时,采用最大增量反应活性（MIR）方法估算了VOCs的臭氧生成潜势（OFP）,均值为544.6μg/m³,表明泡沫塑料鞋制造导致了周边环境空气VOCs污染且对臭氧生成存在明显潜在影响.