The effects of aging processes on critical supersaturation ratios of ultrafine carbon aerosols

The condensation properties of polydisperse aged ultrafine carbon aerosols (particle diameter<1 μm) have been investigated by means of a variable supersaturation condensation nucleus counter. The critical supersaturation (S_c), as the point, where 50% of all particles have been activated and grew to droplets was compared to the median dry particle diameter for pure carbon aerosols, benzo[a]pyrene-tagged carbon aerosols and external mixtures of the carbon particles with sodium chloride and sulphuric acid aerosols. Additionally, ozone as oxidising gaseous compound was added in some of the experiments. Simple coagulation of pure and benzo[a]pyrene-tagged carbon particles resulted in only slightly lower values for S_c due to the increased median particle diameter. The formation of soluble functionalities on the particle surface, i.e. the coagulation with the soluble sodium chloride and sulphuric acid aerosols or the chemical decomposition of benzo[a]pyrene into polar, hydrophilic products due to the reaction with ozone resulted in significant lower values for S_c for the modified carbon aerosol. The necessary supersaturations for the increased hydrophilic particles dropped to atmospherically relevant values of 3% after 5 h reaction time (benzo[a]pyrene decomposition) and 15 h (coagulation with soluble particles), respectively.     

Morphologies of zinc oxide particles and their effects on photocatalysis

ZnO powders with different morphologies were synthesized by alkali precipitation, organo-zinc hydrolysis, and spray pyrolysis. Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these ZnO powders. We investigated the relationship between photocatalytic activity and crystallinity, surface area, or morphology. Results indicate that the photocatalytic activity of ZnO powder depends on crystallinity rather than surface area for the same original ZnO powders prepared by equal conditions other than the difference in calcination temperature. However, no direct relationship between photocatalytic activity and crystallinity or surface area was found for the differently original ZnO powders prepared by different methods, or the same method with different conditions. Instead, we find that the particle morphology significantly affects its photocatalysis.     

Electron microscopy of acidic aerosols collected over the northeastern United States

As part of the acid precipitation experiment (APEX) conducted in the northeastern U.S. by the National Center for Atmospheric Research and cooperating universities, aerosols were collected from an aircraft in different seasons, locations and meteorological conditions. Particles were impacted on electron microscope grids for morphological analysis and thin-film chemical tests for sulfate and nitrate. Under most conditions the accumulation mode aerosols (c. 0.1–1.0 μm diameter) collected in the boundary layer were composed of sulfate particles of uniform composition (i.e. an internally mixed aerosol), indicating that individual particle composition could be inferred from bulk measurements. Externally mixed aerosols (i.e. assemblages of different kinds of particles) were found to exist near certain sources (e.g. power plants), in urban plumes, and near fair weather cumulus clouds. Direct evidence of rapid oxidation of SO₂ to H₂SO₄ in cloud droplets was obtained in samples collected near clouds in northern New York and central Illinois, and this represents a potentially major pathway for SO₂ oxidation in the lower troposphere.     

Proinflammatory effect of fine and ultrafine particulate matter using size-resolved urban aerosols from Paris

Epidemiological and experimental studies have underlined that exposure to particulate matter (PM) leads mainly to airway inflammation, but the roles of particle size and chemical composition associated to such adverse health outcomes need to be better investigated. This study was performed to validate novel strategies of particle sampling, recovery and cell exposure in order to evaluate the pro-inflammatory potential of fine and ultrafine particles from a fractionated aerosol. Samplings of Paris background aerosols using 13-stage low pressure impactors (0.03-10 microm) gave bimodal mass distributions with an accumulation mode centered on a median diameter of 0.42 microm and a coarse one on 3.25 microm. PM 1 accounted for 70% and PM 0.1 for 12% of PM 10. The latter mainly comprised carbon-chained aggregates. The development of an efficient and reproducible method to recover fine (PM 1-0.1) and ultrafine (PM 0.1-0.03) particulate matter has permitted experimental comparison of the impact of such particles on human bronchial epithelial cells (HBECs). In this study we have compared the relative effects of fine and ultrafine particles at non-cytotoxic concentrations over 24h on the production of the pro-inflammatory cytokine GM-CSF by HBECs. Combining two cell exposure strategies to the size-fraction particles according to either their proportion (isovolume exposure) or their quantity in the aerosol (isomass exposure), we showed that both ultrafine and fine particles induced a concentration-dependent GM-CSF release by HBECs which is significant from 1 microg cm(-2). In conclusion, short duration samplings using 13-stage impactors enable to obtain size-resolved PM in sufficient quantities to carry out toxicological investigations. These findings are promising in view to conduct a more intensive study joining chemical and toxicological assays.     

Comparative effects of zinc oxide and zinc oxide nanoparticle as feed additives on growth,feed choice test,tissue residues,and histopathological changes in broiler chickens

Environmental Science and Pollution Research - Zinc is an essential nutritional trace mineral required for growth and health. The aim of the current work is to compare the effects of bulk zinc...     

热镀锌厂酸洗废水和锌灰中回收硫化锌

从热镀锌厂的酸洗废水和锌灰中回收硫化锌,采用X射线能谱仪(EDS),X射线衍射仪(XRD),傅里叶红外光谱仪(FTIR)和场发射透射电镜(FETEM)表征样品ZnS性质,电感耦合等离子发射体(ICP-OES)分析上清液性质,并研究该反应动力学过程。EDS和ICP分析表明,样品ZnS纯度达到85.45%,其上清液含有高浓度铁,含量为2 g/L,可用于制备复合亚铁絮凝剂,而其他重金属离子浓度均低于电镀废水排放标准。XRD分析表明,样品ZnS是立方晶型,调节pH和采用滴加方式能有效改善样品ZnS的晶型。采用Scherrer公式计算晶体粒径,结果表明,晶粒大小在3~6 nm之间。FTIR分析表明,样品ZnS呈现良好的红外透明性,且温度、pH和滴加方式对样品的红外透光性基本没有影响。FETEM结合XRD图表明,该纳米晶呈片状,近似为球形,呈多层叠加,分散性不明显,有团聚现象。动力学实验表明,逆一级动力学方程适合描述硫化沉淀的反应动力学过程,活化能为39.04 kJ/mol,沉淀过程受化学反应和扩散联合控制。     

Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface

Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe⁰) is mediated by the thin film of iron (hydr)oxides found on Fe⁰ under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl₄) degradation by Fe⁰ was studied under the influence of various anions, ligands, and initial CCl₄ concentrations ([P]_o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl₄ disappearance (k_CCl4), and zero order for the appearance of dissolved Fe²⁺ (k_Fe²⁺). The rate of dechlorination exhibits saturation kinetics with respect to [P]_o, suggesting that CCl₄ is transformed at a limited number of reactive surface sites. Because oxidation of Fe⁰ by CCl₄ is the major corrosion reaction in these systems, k_Fe²⁺ also approaches a limiting value at high CCl₄ concentrations. The adsorption of borate strongly inhibited reduction of CCl₄, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased k_CCl4 (and k_Fe²⁺). Thus, it appears that the relatively strong complexation of these ligands at the oxide–electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.     

Enhancement of the deposition of ultrafine secondary organic aerosols by the negative air ion and the effect of relative humidity

Deposition is an important process for the removal of aerosol particles. Negative air ion (NAI) generators can charge the ultrafine airborne particles and enhance their deposition rate. However, many NAI generators may also emit ozone and increase the concentration of particles in the presence of biogenic volatile organic compounds owing to the secondary organic aerosol (SOA) production. To validate the effectiveness of NAI generator, the authors investigated the enhancement effect of an NAI generator on the deposition of the ultrafine SOAs generated from the ozonolysis of d-limonene in a test chamber under controlled ventilation rate and relative humidity (RH). The experimental results demonstrated that compared with other effects, including the gravity, particle eddy diffusion, and the Brownian diffusion, the effect of NAIs is the most dominate one on the deposition of SOA particles onto the wall surface in the near-wall region (<1 cm away from the wall). According to these experiments, the tested NAI generator could efficiently enhance the deposition rate by an enhancement factor ranging from 8.17 ± 0.38 to 25.3 ± 1.1, with a low ozone production rate. This NAI generator had better performance on the deposition of the SOAs with smaller particle sizes and it performed even better under higher RH. The enhancement effect of the NAI generator was related to its high NAI production and electric field strength.

Implications: This study investigated a novel technique of negative air ion (NAI) generator that can enhance the precipitation of nano-scale secondary organic aerosol (SOA). The tested NAI generator can significantly improve the deposition rate of SOA with an enhancement factor of about 8.17 ± 0.38 to 25.3 ± 1.1. The enhancement factor rose when relative humidity increased.     

Influence of the surface microlayer on atmospheric deposition of aerosols and polycyclic aromatic hydrocarbons

Atmospheric dry deposition is an important process for the introduction of aerosols and pollutants to aquatic environments. The objective of this paper is to assess, for the first time, the influence that the aquatic surface microlayer plays as a modifying factor of the magnitude of dry aerosol deposition fluxes. The occurrence of a low surface tension (ST) or a hydrophobic surface microlayer has been generated by spiking milli-Q water or pre-filtered seawater with a surfactant or octanol, respectively. The results show that fine mode (<2.7 μm) aerosol phase PAHs deposit with fluxes 2–3 fold higher when there is a low ST aquatic surface due to enhanced sequestration of colliding particles at the surface. Conversely, for PAHs bound to coarse mode aerosols (>2.7 μm), even though there is an enhanced deposition due to the surface microlayer for some sampling periods, the effect is not observed consistently. This is due to the importance of gravitational settling for large aerosols, rendering a lower influence of the aquatic surface on dry deposition fluxes. ST (mN m⁻¹) is identified as one of the key factor driving the magnitude of PAH dry deposition fluxes (ng m⁻² d⁻¹) by its influence on PAH concentrations in deposited aerosols and deposition velocities (v_d, cm s⁻¹). Indeed, v_d values are a function of ST as obtained by least square fitting and given by Ln(v_d)=−1.77 Ln(ST)+5.74 (r²=0.95) under low wind speed (average 4 m s⁻¹) conditions.     

利用高炉瓦斯泥中的锌制备活性氧化锌的研究

利用高炉炼铁瓦斯泥中的锌,采用火法富集和湿法浸取制取活性氧化锌。考察了温度、时间对火法富集产品中氧化锌含量和原料瓦斯泥中锌挥发率的影响,确定了富集工艺的最佳条件为:在氮气氛围下,温度从常温以10℃/min升温至1 000℃并且在1 000℃下保持1 h,得到的富集产品中氧化锌含量82.24%;瓦斯泥中锌挥发率97%。同时考察了温度、氨水用量、碳酸氢铵用量和液固比等因素对氧化锌浸取率的影响。确定的最佳工艺条件为:浸取温度40℃,氨水用量为理论量的2倍,碳酸氢铵用量为理论量的2倍,液固比4∶1,浸取时间2 h,氧化锌浸取率达99.9%。湿法制得的活性前驱体碱式碳酸锌,经煅烧得到纯度为98.4%的活性氧化锌产品,氧化锌的总回收率达95.3%。     

The effects of roadside structures on the transport and dispersion of ultrafine particles from highways

Understanding local-scale transport and dispersion of pollutants emitted from traffic sources is important for urban planning and air quality assessments. Predicting pollutant concentration patterns in complex environments depends on accurate representations of local features (e.g., noise barriers, trees, buildings) affecting near-field air flows. This study examined the effects of roadside barriers on the flow patterns and dispersion of pollutants from a high-traffic highway in Raleigh, North Carolina, USA. The effects of the structures were analyzed using the Quick Urban & Industrial Complex (QUIC) model, an empirically based diagnostic tool which simulates fine-scale wind field and dispersion patterns around obstacles. Model simulations were compared with the spatial distributions of ultrafine particles (UFP) from vehicular emissions measured using a passenger van equipped with a Differential Mobility Analyzer/Condensation Particle Counter. The field site allowed for an evaluation of pollutant concentrations in open terrain, with a noise barrier present near the road, and with a noise barrier and vegetation present near the road.Results indicated that air pollutant concentrations near the road were generally higher in open terrain situations with no barriers present; however, concentrations for this case decreased faster with distance than when roadside barriers were present. The presence of a noise barrier and vegetation resulted in the lowest downwind pollutant concentrations, indicating that the plume under this condition was relatively uniform and vertically well-mixed. Comparison of the QUIC model with the mobile UFP measurements indicated that QUIC reasonably represented pollutant transport and dispersion for each of the study configurations.     

On radiative effects of black carbon and sulphate aerosols

Most aerosol particles, such as sulphate and sea-salt particles, mainly scatter solar radiation, whilst soot (in the form of elemental carbon or “black” carbon, BC) in addition leads to considerable absorption. This scattering and absorption by the aerosol particles constitute the so-called direct aerosol effect. In this paper, we present results from a study of possible direct effects of tropospheric BC and sulphate aerosols, with an emphasis on BC aerosols, along a line from North Africa through Europe into the Arctic. Radiative budgets in a cloud-free atmosphere are estimated. Based on model-calculated distributions of BC and sulphate (provided by Seland and Iversen, 1998) and assumed size distributions of the background aerosol, new size distributions are obtained by adding natural, biomass burning and fossil fuel contributions to the background aerosol. Added nucleation mode particles are assumed externally mixed, whereas added accumulation mode BC and sulphate is internally mixed with the background according to condensational growth and Brownian coagulation theory. Humidity effects are taken into account by use of the Köhler equation. Mie calculations provide the resulting optical parameters, and the forcing is finally estimated by use of a radiative transfer model. A reference run and a series of eleven test-runs are performed to investigate the sensitivity of various assumptions on the contribution to upward TOA irradiance from BC and non-sea-salt sulphate. The tests suggest a high sensitivity to presence of BC and to particle swelling due to humidity. The sensitivity to assumed distribution of BC on particle size is more moderate. The same is true for the vertical resolution and the number concentration of the background aerosol. The effect of mixing organic carbon (OC) internally with biomass burning BC nucleation mode particles is characterized as moderate. The role of OC is, however, still uncertain. The same holds true for the optical thickness of the background atmosphere, for which we found a high sensitivity in this study. Other assumptions that were investigated had only small effects on the forcing. For the reference run we find a minimum in the aerosol forcing of approximately −5 W m^-2 near the most polluted areas in Europe, and a maximum of approximately 2 W m^-2 over North Africa. A warming effect is also found for the Arctic region, with forcing values up to 0.4 W m^-2.     

Measurements of SOx,NOx and aerosol species on Bermuda

During August 1982 and January and February 1983, General Motors Research Laboratories operated an air monitoring site on the southwest coast of Bermuda. The data show that the levels of the NO_x and SO_x species reaching Bermuda are determined by the direction of the air flow. The highest levels of sulfate (mean = 4.0 μg m⁻³), nitric acid (126 ppt) and other species are observed when air masses arrive from the northeastern United States while the lowest levels (sulfate = 1.1 μg m⁻³; nitric acid = 41 ppt) occur during air flow from the SE direction. With westerly air flow, increases in many anthropogenic constituents such as particulate sulfate, lead, elemental carbon, sulfur dioxide, nitrogen dioxide, nitric acid and ozone are observed. These species are generally the lowest during SE winds which bring high concentrations of soil- and crustal-related aerosol species. The source of this crustal material appears to be the Sahara Desert. On the average, the levels of anthropogenic constituents are higher in winter because of frequent intrusions of N American air masses. Conversely, the levels of crustal materials are higher in summer when the SE flow is more prevalent.     

Molecular cloning, characterization of CAT, and eco-toxicological effects of dietary zinc oxide on antioxidant enzymes in Eisenia fetida

The full-length cDNA of catalase (EfCAT) from Eisenia fetida was cloned (GenBank accession no. JN617999). Sequence characterization revealed that EfCAT protein sequence contained proximal heme-ligand signature sequence (³⁵¹RLFSYSDTH³⁵⁹), two glycosylation sites (N₁₄₅ and N₄₃₆), the proximal active site signature (⁶¹FDRERIPERVVHAKGAGA⁷⁸), and 12 amino acids (N₁₄₅, H₁₉₁, F₁₉₅, S₁₉₈, R₂₀₀, N₂₁₀, Y₂₁₂, K₂₃₄, I₂₉₉, W₃₀₀, Q₃₀₂, and Y₃₅₅), which were identified as putative residues involved in NADPH binding. These conserved motifs and catalase signature sequences were essential for the structure and function of EfCAT. The present study also investigated the effect of the veterinary food additive zinc oxide on antioxidant processes in E. fetida, at different concentrations and exposure durations. A significant increase (by 106.0 % compared to controls) in CAT activity at 500 mg/kg was registered at day 15. The superoxide dismutase (SOD) activity at 500 mg/kg increased to the maximum value (by 44.0 %) measured at day 15. There was a significant increase in glutathione peroxidase (GPx) activity for all concentrations after 5 days. The results showed that dietary Zn (500 mg/kg) causes oxidative damage to earthworms. At early stages of earthworms exposed to ZnO, GPx is the main enzyme to impair the oxidative status; while at later stages the enzymes CAT and SOD were the main indicators of oxidative stress. The antioxidant enzymatic variations may be an adaptive response of earthworms to survive in contaminated soils.     

锌、铁等离子对氧化锌烟气脱硫工艺中亚硫酸锌氧化的影响简

在氧化锌法脱除烟气SO₂工艺中,脱硫产物亚硫酸锌的氧化是实现锌、硫资源回收的关键环节。在pH为4~5,25℃等条件下,考察了锌、铁、镉离子对亚硫酸锌氧化过程的影响。结果发现,铁离子对亚硫酸锌氧化过程有较强的催化作用,锌离子有一定的催化作用,而低浓度的镉离子几乎不影响氧化过程。进一步的研究表明,锌、铁离子的独自催化氧化速率对各自的浓度均为0.5级响应,但在混合状态下,锌离子对铁离子的催化过程有抑制作用。     

锌、铁等离子对氧化锌烟气脱硫工艺中亚硫酸锌氧化的影响

在氧化锌法脱除烟气SO2工艺中,脱硫产物亚硫酸锌的氧化是实现锌、硫资源回收的关键环节。在pH为4～5,25℃等条件下,考察了锌、铁、镉离子对亚硫酸锌氧化过程的影响。结果发现,铁离子对亚硫酸锌氧化过程有较强的催化作用,锌离子有一定的催化作用,而低浓度的镉离子几乎不影响氧化过程。进一步的研究表明,锌、铁离子的独自催化氧化速率对各自的浓度均为0．5级响应,但在混合状态下,锌离子对铁离子的催化过程有抑制作用。     

Inorganic element concentrations in near surface aerosols sampled on the northwest slopes of Mount Kenya

Eight trace elements, Si, Cl, K, Ca, Ti, Mn, Fe and Zn in the near-ground atmospheric aerosols were evaluated in the northwestern part of Mount Kenya using a dichotomous sampler and an EDXRF spectrometer. The samples were taken at 2 sites situated in Nanyuki area, which is roughly on the Equator. The sampler segregated the aerosol into two aerodynamic diameter (ad) size fractions, fine (<3.5 μm ad) and coarse (>3.5 and <18 μm ad). The elemental concentrations in the two size fractions were quantified and the elements assigned to known sources. Local wind blown dust related to agricultural activities and fire burning was found to dominate the lower tropospheric aerosols. There was inconclusive evidence of long range-transported aerosols being moved by night transport from the middle to the lower parts of the troposphere. Influence of the Indian Ocean marine aerosol was suggested but conclusive evidence was lacking.     

Light-absorbing aldol condensation products in acidic aerosols: Spectra,kinetics, and contribution to the absorption index

The radiative properties of aerosols that are transparent to light in the near-UV and visible, such as sulfate aerosols, can be dramatically modified when mixed with absorbing material such as soot. In a previous work we had shown that the aldol condensation of carbonyl compounds produces light-absorbing compounds in sulfuric acid solutions. In this work we report the spectroscopic and kinetic parameters necessary to estimate the effects of these reactions on the absorption index of sulfuric acid aerosols in the atmosphere. The absorption spectra obtained from the reactions of six different carbonyl compounds (acetaldehyde, acetone, propanal, butanal, 2-butanone, and trifluoroacetone) and their mixtures were compared over 190–1100 nm. The results indicated that most carbonyl compounds should be able to undergo aldol condensation. The products are oligomers absorbing light in the 300–500 nm region where few other compounds absorb, making them important for the radiative properties of aerosols. Kinetic experiments in 96–75 wt% H₂SO₄ solutions and between 273 and 314 K gave an activation energy for the rate constant of formation of the aldol products of acetaldehyde of −(70±15) kJ mol⁻¹ in 96 wt% solution and showed that the effect of acid concentration was exponential. A complete expression for this rate constant is proposed where the absolute value in 96 wt% H₂SO₄ and at 298 K is scaled to the Henry's law coefficient for acetaldehyde and the absorption cross-section for the aldol products assumed in this work. The absorption index of stratospheric sulfuric acid aerosols after a 2-year residence time was estimated to 2×10⁻⁴, optically equivalent to a content of 0.5% of soot and potentially significant for the radiative forcing of these aerosols and for satellite observations in channels where the aldol products absorb.