Aircraft measurements of the vertical distribution of sulfur dioxide and aerosol scattering coefficient in China

Information on the vertical distribution of air pollution is important for understanding its sources and processes and validating satellite retrievals and chemical transport models. This paper reports the results of the measurements of sulfur dioxide (SO₂) and aerosol scattering coefficient (B_sp) obtained from several aircraft campaigns during summer and autumn 2007 in the north-eastern (NE), north-western (NW), and central-eastern (CE) regions of China. Their vertical profiles over the three regions with contrasting emission characteristics and climates are compared. Very high concentrations/values of SO₂ and B_sp (with a value of up to 51 ppbv and 950 Mm^?1, respectively) were recorded in the lower planetary boundary layer in CE China, indicating high SO₂ emissions in the region. The SO₂ column concentrations determined from the in-situ measurements were compared with Ozone Monitoring Instrument (OMI) SO₂ retrievals. The results show that the OMI data could distinguish the varying levels of SO₂ pollution in the study regions, but appeared to have underestimated the SO₂ column in the highly polluted region of CE China.     

A contribution of brown carbon aerosol to the aerosol light absorption and its radiative forcing in East Asia

Brown carbon aerosols were recently found to be ubiquitous and effectively absorb solar radiation. We use a 3-D global chemical transport model (GEOS-Chem) together with aircraft and ground based observations from the TRACE-P and the ACE-Asia campaigns to examine the contribution of brown carbon aerosol to the aerosol light absorption and its climatic implication over East Asia in spring 2001. We estimated brown carbon aerosol concentrations in the model using the mass ratio of brown carbon to black carbon (BC) aerosols based on measurements in China and Europe. The comparison of simulated versus observed aerosol light absorption showed that the model accounting for brown carbon aerosol resulted in a better agreement with the observations in East Asian-Pacific outflow. We then used the model results to compute the radiative forcing of brown carbon, which amounts up to ?2.4 W m^?2 and 0.24 W m^?2 at the surface and at the top of the atmosphere (TOA), respectively, over East Asia. Mean radiative forcing of brown carbon aerosol is ?0.43 W m^?2 and 0.05 W m^?2 at the surface and at the TOA, accounting for about 15% of total radiative forcing (?2.2 W m^?2 and 0.33 W m^?2) by absorbing aerosols (BC + brown carbon aerosol), having a significant climatic implication in East Asia.     

On the contribution of black carbon to the composite aerosol radiative forcing over an urban environment

This paper discusses the extent of Black Carbon (BC) radiative forcing in the total aerosol atmospheric radiative forcing over Pune, an urban site in India. Collocated measurements of aerosol optical properties, chemical composition and BC were carried out for a period of six months (during October 2004 to May 2005) over the site. Observed aerosol chemical composition in terms of water soluble, insoluble and BC components were used in Optical Properties of Aerosols and Clouds (OPAC) to derive aerosol optical properties of composite aerosols. The BC fraction alone was used in OPAC to derive optical properties of BC aerosols. The aerosol optical properties for composite and BC aerosols were separately used in SBDART model to derive direct aerosol radiative forcing due to composite and BC aerosols. The atmospheric radiative forcing for composite aerosols were found to be +35.5, +32.9 and +47.6 Wm^?2 during post-monsoon, winter and pre-monsoon seasons, respectively. The average BC mass fraction found to be 4.83, 6.33 and 4 μg m^?3 during the above seasons contributing around 2.2 to 5.8% to the total aerosol load. The atmospheric radiative forcing estimated due to BC aerosols was +18.8, +23.4 and +17.2 Wm^?2, respectively during the above seasons. The study suggests that even though BC contributes only 2.2–6% to the total aerosol load; it is contributing an average of around 55% to the total lower atmospheric aerosol forcing due to strong radiative absorption, and thus enhancing greenhouse warming.     

Mineral dust is a sink for chlorine in the marine boundary layer

Dust particles affect the budgets of important traces gases by providing a surface on which heterogeneous reactions can occur. The uptake of soluble species on dust alters the physical, chemical, and optical properties and the overall ability of dust to act as cloud condensation and ice nuclei. It is commonly assumed that all measured chloride in particulate filter samples is associated with sea-salt particles and any chloride in dust occurs as the result of internal mixtures of sea-salt and dust particles, formed by cloud processing. Here we show high temporal resolution data demonstrating the direct uptake of chlorine by dust via heterogeneous reaction with HCl(g). This reaction added significant amounts of chlorine to the dust particles during a major dust storm, representing 4–9% of the individual dust particle mass. Up to 65±4% of the dust particles contained chlorine due to this heterogeneous reaction during the dust front. Ignoring this process leads to an overestimation of sea-salt concentrations from bulk measurements, and an underestimation of the degree of sea-salt aging. The uptake of chloride will change the pH and hygroscopic properties of the dust and thus can influence the budgets of other reactive gases. Including this heterogeneous process in atmospheric measurements and chemical transport models will improve our ability to predict the atmosphere's composition and radiation budget with greater accuracy.     

Using Si depletion in aerosol to identify the sources of crustal dust in two Chinese megacities

Depletion of Si in transported dust has been recognized for many years. It can be used to distinguish between transported and local dust in cities, although it rarely has been. Here we use the variations of the Si/Al ratio in 15 months of continuous PM_2.5 samples at Beijing (northern China) and Chongqing (southwestern China) to reveal the seasonal patterns of their dust sources. For both cities, peaks of concentration for Si and Al in PM_2.5 corresponded with minima of Si/Al, and could often be linked to pulsed air flow from deserts to the northwest. With significant depletion (up to 80%) and homogeneous distribution at urban and rural sites, Si/Al showed a clear seasonal evolution, which decreased from spring to summer, increased from fall to winter, and collapsed during Chinese Spring Festival, indicating the dominance of transported dust, local fugitive dust and firework influence, respectively. The low ratios implied that desert dust is a common source during spring at Chongqing, whereas its presence during cold season at Beijing was also more frequent than expected. Failing to recognize the depletion of Si may lead to an overestimate of desert dust by 15%–65% when using the average abundance of Al in crust (6%–8%), as in previous studies. The difference in Si/Al ratio between local and transported dust implies that >60% of the dust at Beijing came from outside the city during the springs of 2004–2006. This result can help resolve the contradictory findings on this topic that have been presented earlier.     

Climatology of diurnal trends and vertical distribution of ozone in the atmospheric boundary layer in urban North Carolina

Vertical measurements of ozone were made on a 610-m-tall tower located about 15 km southeast of Raleigh, NC, as part of an effort by the state of North Carolina to develop a state implementation plan (SIP) for ozone control in the Raleigh Metropolitan Statistical Area. During summer 1993, 1994, and 1995, ozone was monitored at ground level, 250 m, and 433 m. Boundary layer wind, temperature, and other meteorological variable profiles were determined from balloon soundings. During summer 1996 and 1997, ozone was monitored at ground level, 76 m, 128 m, and 433 m. This paper presents the analysis and discussion of the five-year data. The evolutions of the convective boundary layer during daytime and the stable nocturnal boundary layer (NBL) were found to have marked impacts on ozone concentrations. A strong diurnal pattern, with an afternoon maximum and an early morning minimum, was dominant at ground level, but it was much weaker at elevated levels and insignificant above the NBL at night. Ozone deposition velocities at night during the measurement periods were estimated to range from 0.09 to 0.64 cm/sec. We found evidence of regional transport of ozone and/or its precursors from northwest and north of the site, which may play a role in high ozone events in the Raleigh-Durham area. Ozone concentrations between the various elevated levels were well correlated, while correlations between the ground and upper levels were much weaker. However, a strong correlation was found between the nighttime and early morning ozone concentrations (CR) in the residual layer above the NBL and the maximum ground level concentration (Co max) the following afternoon. Based on this correlation, the latter may be predicted by an observational model Co max = 27.76e 0.016 CR.     

On the vertical diffusion from a ground level source in a developing mixing layer

The quasi-stationary condition of vertical diffusion in a mixing layer is discussed using dimensional analysis, and some numerical calculations are carried out to evaluate the concentration in a non-stationary state. General relationships of vertical diffusion from a ground level source are suggested using several scale times of the mixing layer and it is shown that the quasi-stationary condition of diffusion can be satisfied when the travel time and averaging time of the diffusing matter are smaller than the time scale of the development of the mixing layer.Calculated results show that in a non-stationary state, the normalized concentration and spread of a plume using convective layer scaling are not essentially different from those in a stationary state. However, the real concentration in a non-stationary state increases with the increase in averaging time, due to the effect of development in the mixing layer.     

Simulation of aerosol radiative properties with the ORISAM-RAD model during a pollution event (ESCOMPTE 2001)

The aim of this study is to present the organic and inorganic spectral aerosol module-radiative (ORISAM-RAD) module, allowing the 3D distribution of aerosol radiative properties (aerosol optical depth, single scattering albedo and asymmetry parameter) from the ORISAM module. In this work, we test ORISAM-RAD for one selected day (24th June) during the ESCOMPTE (expérience sur site pour contraindre les modèles de pollution atmosphérique et de transport d’emissions) experiment for an urban/industrial aerosol type. The particle radiative properties obtained from in situ and AERONET observations are used to validate our simulations. In a first time, simulations obtained from ORISAM-RAD indicate high aerosol optical depth (AOD)0.50–0.70±0.02 (at 440 nm) in the aerosol pollution plume, slightly lower (10–20%) than AERONET retrievals. In a second time, simulations of the single scattering albedo (ω_o) have been found to well reproduce the high spatial heterogeneities observed over this domain. Concerning the asymmetry parameter (g), ORISAM-RAD simulations reveal quite uniform values over the whole ESCOMPTE domain, comprised between 0.61±0.01 and 0.65±0.01 (at 440 nm), in excellent agreement with ground based in situ measurements and AERONET retrievals. Finally, the outputs of ORISAM-RAD have been used in a radiative transfer model in order to simulate the diurnal direct radiative forcing at different locations (urban, industrial and rural). We show that anthropogenic aerosols strongly decrease surface solar radiation, with diurnal mean surface forcings comprised between −29.0±2.9 and −38.6±3.9 W m⁻², depending on the sites. This decrease is due to the reflection of solar radiations back to space (−7.3±0.8<ΔF_TOA<−12.3±1.2 W m⁻²) and to its absorption into the aerosol layer (21.1±2.1<ΔF_ATM<26.3±2.6 W m⁻²). These values are found to be consistent with those measured at local scale.     

Influence of a slight urban pollution on the size distribution of a marine aerosol

Size measurements of atmospheric aerosol, using impactors and Nuclepore filters have been carried out. Analysis were made by electron and optic microscopy. Thus we obtain a size distribution from D_p = 10^?2μm to D_p = 70 μm over the Atlantic Ocean and at urban location. The statistical analysis of the curves allows to compare the results and to point out the effect of an urban pollution on a marine aerosol.     

Sensitivity analysis of a parameterization of the stomatal component of the DO3SE model for Quercus ilex to estimate ozone fluxes

A sensitivity analysis of a proposed parameterization of the stomatal conductance (g(s)) module of the European ozone deposition model (DO(3)SE) for Quercus ilex was performed. The performance of the model was tested against measured g(s) in the field at three sites in Spain. The best fit of the model was found for those sites, or during those periods, facing no or mild stress conditions, but a worse performance was found under severe drought or temperature stress, mostly occurring at continental sites. The best performance was obtained when both f(phen) and f(SWP) were included. A local parameterization accounting for the lower temperatures recorded in winter and the higher water shortage at the continental sites resulted in a better performance of the model. The overall results indicate that two different parameterizations of the model are needed, one for marine-influenced sites and another one for continental sites.     

Variation of dust layer height in the northern Taklimakan Desert in April 2002

LIDAR observations were conducted in the northern Taklimakan Desert to investigate the vertical distribution of dust in April 2002. During the observation period, a dust outbreak occurred on 13 April, remaining over the desert for several days. Despite only slight variations being observed in dust layer height before the dust event, marked diurnal variation in dust layer height was observed after the dust event. In this study, we conducted two numerical simulations to investigate differences in the variation exhibited by the dust layer heights before and after the dust event, and assessed the influence of meteorological conditions on this variation. The simulated results show that the clearly diurnal variation in dust layer height is strongly influenced by local circulation which is affected by the characteristic topography and synoptic conditions of the Tarim Basin.     

Impact of stratospheric volcanic aerosols on climate: Evidence for aerosol shortwave and longwave forcing in the Southeastern U.S.

Major volcanic eruptions inject massive amounts of dust and gases into the lower stratosphere and upper troposphere. Stratospheric volcanic aerosols can scatter incoming solar radiation to space, increasing planetary albedo, reducing the total amount of solar energy reaching the troposphere and the earth's surface, and decreasing the daytime maximum temperature (aerosol shortwave forcing). They can also absorb and scatter outgoing terrestrial longwave radiation, increasing the nighttime minimum surface temperature (longwave forcing). However, persuasive evidence of climate response to this forcing has thus far been lacking. Here we examine patterns of annual and seasonal variations in mean maximum and minimum temperature trend during the periods 1992–1994 and 1985–1987 relative to that during the period 1988–1990 at 47 stations in the southeastern U.S. for evidence of such climate responses. The stratospheric volcanic aerosol optical depths over the southeastern U.S. during the period 1985–1994 were inferred from the Stratospheric Aerosol and Gases Experiment (SAGE) 11 satellite extinction measurement. After the long-term trend signals are removed, it is shown that the dominant decreasing trend of mean maximum temperature and the dominant increasing trend of mean minimum temperature over periods 1992–1994 and 1985–1987 relative to that over the period 1988–1990 are consistent with the distribution of stratospheric volcanic aerosols and predictions from aerosol radiative forcing in the southeastern U.S.     

Frequency distribution of dust concentration in Barbados as a function of averaging time

Two sets of daily-averaged dust concentration data from Barbados, West Indies, have been analyzed to determine the affect of averaging time, ranging from 1 to 7 days, on the dust concentration frequency distribution. On each of the time scales examined, the frequency distribution is characterized as a bimodal lognormal distribution. The major effects of increasing the averaging are a major reduction in the percentage of the samples represented by the lower of the two modes and a significant increase in the geometric mean concentration of that mode. Consequently, predictions of the distributions on a shorter time scale are likely to substantially underestimate the frequency of low concentration samples.     

Application of neutral electrolyzed water spray for reducing dust levels in a layer breeding house

Reducing airborne dust is an essential process for improving hen housing environment. Dust reduction effects of neutral electrolyzed water (pH 8.2) spray were investigated in a commercial tunnel-ventilated layer breeding house during production in northern China. A multipoint sampler was used to measure airborne dust concentration to study the dust reduction effects and distribution in the house. Compared with the control treatment (without spray), airborne dust level was reduced 34% in the 3 hr after spraying 216 mL m^?2 neutral electrolyzed water in the breeding house. The dust concentration was significantly higher during the periods of feed distribution (1.13 ± 0.13 mg m^?3) and artificial insemination (0.72 ± 0.13 mg m^?3) compared with after spray (0.47 ± 0.09 mg m^?3) and during lights-off period (0.29 ± 0.08 mg m^?3) in the three consecutive testing days (P < 0.05). The experimental cage area was divided into four zones along the length of the house, with zone 1 nearest to the evaporative cooling pad and zone 4 nearest to the fans. The air temperature, relative humidity, airflow rate, and dust concentration were measured at the sampling points of the four zones in 3 consecutive days and mortality of the birds for the duration of a month were investigated. The results showed that the air temperature, airflow rate, dust concentration, and number of dead birds increase from zone 1 to zone 4 in the tunnel-ventilated layer breeding house.

Implications: It is difficult to effectively reduce hen house airborne dust levels and limited information is available on airborne dust distribution in tunnel-ventilated hen houses. This work investigates (i) the application of neutral electrolyzed water spray for reducing dust in a layer breeding houses; (ii) dust concentration variations in 24-hr house operation; as well as (iii) the effects of location on dust concentrations. It was demonstrated that neutral electrolyzed water spray can be efficiently used for dust reduction in poultry houses. Further, a better understanding of the dust concentration variations in 24-hr house operation and in different spatial zones can contribute to bird housing environment management and poultry house design so as to improve bird health.     

Analysis and simulation of wintertime light scattering by the urban aerosol in Dallas-Fort Worth

Wintertime atmospheric light scattering in Dallas, TX, was estimated through the use of aerosol models. Input data for the aerosol models were provided by measurements of aerosol chemistry, physical particle size distributions, and distributions of particulate sulfur by particle size, and by predictions by an atmospheric simulation model. Light scattering measurements provided a basis for testing the aerosol models. The SCAPE thermodynamic equilibrium model was used to estimate the amount of liquid water associated with particles and the ELSIE Mie scattering model was applied to estimate the resulting light scattering. The calculations were based on aerosol properties measured in Dallas during December 1994 and February 1995, and changes in scattering due to hypothetical changes in the aerosol were predicted. The predicted light scattering was compared to scattering measured by an Optec nephelometer; agreement was within 20% in every case.     

Drifting towards the surface: a shift in newborn pipefish's vertical distribution when exposed to the synthetic steroid ethinylestradiol

Endocrine disrupting chemical (EDC) effects during early life have the potential to modulate population structure, either directly through increased mortality or by causing inappropriate aggregation events, thus affecting the number of young that will reach adulthood. An alteration in the dispersal and recruitment patterns can also impair the connectivity among geographically distant populations. However, the detection of EDC-induced effects occurring after egg hatch, when newborns increase their chances of contacting with environmentally dispersed contaminants, is not a simple process as effects might be masked by the large natural mortality rates that usually occur during fish early life.Since there is a lack of information regarding the impact of EDCs on fish early life dispersal patterns, particularly on vertical migrations patterns, the effects of environmentally relevant concentrations of EE₂ on the vertical distribution of newborn fish was assessed through an ex situ exposure experiment. Syngnathus abaster newborns were exposed to EE₂ (nominal concentrations of 8, 12 and 36 ng L⁻¹) and the dynamics of their vertical distribution was monitored for up to 40 d. No significant differences in overall mortality were observed between treatments or in the dynamics of the registered death curves. Nevertheless, an alteration in the distribution patterns was observed. The commonly benthic newborn tended to shift their vertical distribution towards the surface, in a dose-dependent manner. Curiously, a follow up of the exposed pipefish confirmed that EE₂ effects were also noticeable upon sexual maturity, namely by the alteration of several primary and secondary sexual characters. The observation that vertical distributional patterns, at least in pipefish, are clearly altered at environmentally relevant EE₂ concentrations indicates that EDC’s impact in fish larvae behaviour should be considered when addressing the effects of contaminants, given the obvious implications on population connectivity, stability and persistence.     

Aqueous free radical chemistry of mercury in the presence of iron oxides and ambient aerosol

The effect of goethite (α-FeOOH), hematite (α-Fe₂0₃) and maghemite (γ-Fe₂0₃) on the aqueous photoreduction of divalent mercury with organic acids (oxalate, formate and acetate) is investigated. Laboratory photochemistry experiments with synthetic iron oxides and simulated sunlight were performed to assess the role of the oxides on the photoreduction. Ambient aerosol was also collected and introduced as the solid phase to compare its effect with that of synthetic oxides. It is observed that the presence of various iron oxides or aerosol particles enhances the photoreduction. It is also found that the hydroxyl radicals produced in the hematite-oxalate systems can re-oxidize the reduced mercury back to Hg(II). Based on the experimental observations, mechanisms responsible for the Hg(II) reduction are proposed. The kinetics of Hg⁰ oxidation by hydroxyl radicals was also studied by a steady-state kinetic technique using nitrate photolysis as the * OH radical source. The second-order rate constant is determined to be 2.0 × 10⁹ M⁻ s⁻¹. The implications of the studied reactions on the atmospheric chemistry of mercury are discussed.     

Light scattering characteristics of aerosols as a function of relative humidity: Part I--A comparison of measured scattering and aerosol concentrations using the theoretical models

The Southeastern Aerosol and Visibility Study (SEAVS) was undertaken to characterize the size-dependent composition, thermodynamic properties, and optical characteristics of the ambient atmospheric particles in the southeastern United States. The field portion of the study was carried out from July 15 to August 25, 1995. As part of the study a relative humidity controlled inlet was built to raise or lower the relative humidity to predetermined levels before the aerosol was passed into an integrating nephelometer or particle-sizing device. Five other integrating nephelometers were operated in various configurations, two of which were fitted with a 2.5 microns inlet. Fine particle (< 2.5 microns) samplers were operated to measure concentrations of sulfate, nitrate, and ammonium ions, organic and elemental carbon, and fine soil. Mass size distributions were measured with an eight-stage, single orifice cascade impactor. Four different strategies for estimating scattering were used. First, an externally mixed model with constant specific scattering coefficients, sulfate ion mass interpreted as ammonium bisulfate, and ammonium bisulfate growth as a function of relative humidity, is assumed. Second, an externally mixed aerosol model, assuming constant dry specific scattering but with sulfate ammoniation and associated composition-dependent hygroscopicity explicitly accounted for, is used. Third, an externally mixed aerosol model, but with sulfate ammoniation, associated growth as a function of relative humidity, and sulfate size distributions, is applied. Fourth, an internally mixed aerosol model with measured sulfur size distributions and estimated size distributions for other species is used with the growth characteristics of the mixture being estimated using the Zdanovskii-Stokes-Robinson (ZSR) assumptions. Only ionic species were considered to be hygroscopic. The second, third, and fourth approaches yield similar results with reconstructed scattering comparing quite favorably with measured scattering. Accounting for sulfate ammoniation and associated water uptake was the most important detail in achieving closure between measurements and modeled scattering. In general, differences between estimated scattering, assuming internally or externally mixed models, was small. These same models were used to estimate wet to dry scattering ratios. The R2 for an ordinary least-squares regression between measured and predicted ratios was high (0.71-0.92), and in most cases the scattering ratio was insensitive to modeling assumptions. However, during some sample periods differences between predicted scattering ratios for the different modeling assumptions were as high as 30%.     

Occurrence of Fipronil in residential house dust in the presence and absence of pets: a hint for a comprehensive toxicological assessment

The presence of the insecticide Fipronil and its main products of toxicological relevance, namely Sulfone and Desulfinyl, was assessed in 161 residential house dust samples in the absence (N?=?101) and presence (N?=?60) of cats and dogs in Italy. High-resolution mass spectrometry analysis revealed a significant difference (p?<?0.001) in the dust contamination in the presence of pets (median: 467 vs. 24?ng/g dry weight), even if the highest value was found in the absence of pets (82,069 vs. 67,799?ng/g dry weight). Fipronil intake estimates from dust in toddlers, computed according to US-EPA and EU-ECHA guidelines, ranged from 333 to 556 and from 20 to 34?ng/kg per day for acute and chronic scenario, respectively. Dust seemed not able itself to lead to Fipronil overexposure with respect to acute and chronic toxicity health-based guidance values. Kittens were potentially overexposed to Fipronil under both acute (26,076?ng/kg per day) and chronic (1,633?ng/kg per day) scenarios. The mild symptomatology associated with acute intoxication could possibly determine case underreporting within pharmacosurveillance schemes. Its administration was estimated in 7.3–9.7 tons per year. Such a range suggests its prudent use under strict veterinary control to prevent pest resistance and ecotoxicological outcomes.