The effect of humidity and state of water surfaces on deposition of aerosol particles onto a water surface

Deposition processes of particles with dry diameter larger than about 10 μm are dominated by gravitational settling, while molecular diffusion and Brownian motion predominate the deposition processes of particles smaller than 0.1 μm in dry diameter. Many air pollution derived elements exhibit characteristics common to sub-micron particles. The objective of the present study is to examine the effects of meteorological conditions within the turbulent transfer layer on the deposition velocity of particles with dry diameter between 0.1 and 1 μm. It is for these sub-micron particles that particle growth by condensation in the deposition layer, the broken water surface effect and the enhanced transfer process due to atmospheric turbulence in the turbulent transfer layer play important roles in controlling the particle deposition velocity. Results of the present study show that the `dry air’ assumption of Williams’ model is unrealistic. Effects of ambient air relative humidity and water surface temperature cannot be ignored in determining the deposition velocity over a water surface. Neglecting effects of ambient air relative humidity and water surface temperature will result in defining atmospheric stability incorrectly. It is found that the largest effect of air relative humidity on deposition velocity occurs at an air–water temperature difference corresponding to the point of `displaced neutral stability'. For a given wind speed of U=5 m s⁻¹ the additive effects of water surface temperature, T_w, changes from 5 to 25°C and ambient air relative humidity variations from 85 to 60%, respectively, lead to a maximum difference in v_d of about 20%. For a higher wind speed of 10 m s⁻¹, however, the corresponding change in v_d reduces to less than 5%. This is further confirmation that wind speed is one of the strongest variables that governs the magnitude of v_d. The present study also found that the broken surface transfer coefficient, k_bs, given as a multiple of the smooth surface transfer coefficient, k_ss, is physically more meaningful than assigning it a constant value independent of particle size. The method used in this study requires only a single level of atmospheric data coupled with the surface temperature measurement. The present method is applicable for determining deposition velocity not only at the conventional measurement height of 10 m but also at any other heights that are different from the measurement height.     

Partitioning of formaldehyde between air and ice at −35°C to −5°C

The equilibrium partitioning of formaldehyde (HCHO) between air and snow was studied in a series of laboratory experiments conducted at −5°C, −15°C, and −35°C, in order to understand how partitioning of HCHO between air and polar snow varies with temperature, and thus seasonally on the ice sheet. Measured partitioning coefficients were 56, 93, and 245 mol l⁻¹ atm⁻¹ for −5°C, −15°C and −35°C, respectively, showing a similar trend as the values previously estimated from field observations. Estimates of the pseudo-first-order rate coefficient for air–snow exchange for the same three temperatures were 4.1×10⁻⁴, 1.1×10⁻⁴, and 1.1×10⁻⁵ s⁻¹, respectively. This implies a time scale for air–snow equilibration of the order of hours to days for HCHO accumulated at or near the ice–air interface on snow grains. Comparing the current laboratory partitioning coefficients with those estimated from measurements of air and freshly fallen snow in Greenland during summer demonstrates that the snow is supersaturated and should degas HCHO to the surrounding air. During this degassing, polar snow should be a significant source of HCHO to the lower troposphere.     

Henry’s law constant measurements for formaldehyde and benzaldehyde as a function of temperature and water composition

Henry’s law constants H of formaldehyde and benzaldehyde were determined using a dynamic system based on the water/air equilibrium at the interface within the length of a microporous tube. The measurements were conducted over the range 273–293 K in (i) deionized water, (ii) 35 g L^?1 solution of NaCl simulating seawater and (iii) two nitric acid solutions, i.e. 0.63 and 6.3 wt%.In pure water, the obtained data were used to derive the following Arrhenius expressions: ln H = (6423 ± 542)/T ? (13.4 ± 2.0) and ln H = (6258 ± 280)/T ? (17.5 ± 1.0) for formaldehyde and benzaldehyde, respectively. The H values, calculated at 293 K from Arrhenius expressions cited above were the following (in units of M atm^?1): H = 5020 ± 1170 (formaldehyde), H = 47 ± 5 (benzaldehyde). The temperature dependence of H permits then to derive the solvation enthalpies for both compounds: ΔH_solv = ?(53.4 ± 4.5) kJ mol^?1 and ΔH_solv = ?(52.0 ± 2.3) kJ mol^?1 for formaldehyde and benzaldehyde, respectively.In 35 g L^?1 salt solution, the H values were 27–66% and 12–21% lower than their respective determinations in deionized water, for formaldehyde and benzaldehyde respectively. The observed salt effect was used to estimate the following Setschenow coefficients at 293 K for 0.6 M NaCl: formaldehyde (0.21) and benzaldehyde (0.09).In 6.3 wt% nitric acid solution, H values of benzaldehyde were approximately 30% higher than those found in pure water although no significant influence was observed for formaldehyde.Finally, our experimental data were then used to estimate the fractions of formaldehyde and benzaldehyde in atmospheric aqueous phase and their derived atmospheric lifetimes.     

Laboratory studies on the uptake of aromatic hydrocarbons by ice crystals during vapor depositional crystal growth

Uptake of aromatic hydrocarbons (AH) by ice crystals during vapor deposit growth was investigated in a walk-in cold chamber at temperatures of 242, 251, and 260 K, respectively. Ice crystals were grown from ambient air in the presence of gaseous AH namely: benzene (C₆H₆), toluene (methylbenzene, C₇H₈), the C₈H₁₀ isomers ethylbenzene, o-, m-, p-xylene (dimethylbenzenes), the C₉H₁₂ isomers n-propylbenzene, 4-ethyltoluene, 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,2,3-trimethylbenzene (1,2,3-TMB), and the C₁₀H₁₄ compound tert.-butylbenzene. Gas-phase concentrations calculated at 295 K were 10.3–20.8 μg m⁻³. Uptake of AH was detected by analyzing vapor deposited ice with a very sensitive method composed of solid-phase micro-extraction (SPME), followed by gas chromatography/mass spectrometry (GC/MS).Ice crystal size was lower than 1 cm. At water vapor extents of 5.8, 6.0 and 8.1 g m⁻³, ice crystal shape changed with decreasing temperatures from a column at a temperature of 260 K, to a plate at 251 K, and to a dendrite at 242 K. Experimentally observed ice growth rates were between 3.3 and 13.3×10⁻³ g s⁻¹ m⁻² and decreased at lower temperatures and lower value of water vapor concentration. Predicted growth rates were mostly slightly higher.Benzene, toluene, ethylbenzene, and xylenes (BTEX) were not detected in ice above their detection limits (DLs) of 25 pg g_ice⁻¹ (toluene, ethylbenzene, xylenes) and 125 pg g_ice⁻¹ (benzene) over the entire temperature range. Median concentrations of n-propylbenzene, 4-ethyltoluene, 1,3,5-TMB, tert.-butylbenzene, 1,2,4-TMB, and 1,2,3-TMB were between 4 and 176 pg g_ice⁻¹ at gas concentrations of 10.3–10.7 μg m⁻³ calculated at 295 K. Uptake coefficients (K) defined as the product of concentration of AH in ice and density of ice related to the product of their concentration in the gas phase and ice mass varied between 0.40 and 10.23. K increased with decreasing temperatures. Values of Gibbs energy (ΔG) were between −4.5 and 2.4 kJ mol⁻¹ and decreased as temperatures were lowered. From the uptake experiments, the uptake enthalpy (ΔH) could be determined between −70.6 and −33.9 kJ mol⁻¹. The uptake entropy (ΔS) was between −281.3 and −126.8 J mol⁻¹ K⁻¹. Values of ΔH and ΔS were rather similar for 4-ethlytoluene, 1,3,5-TMB and tert.-butylbenzene, whereas 1,2,3-TMB showed much higher values.     

Concentration-dependent NH3 deposition processes for mixed moorland semi-natural vegetation

Dry deposition modelling typically assumes that canopy resistance (R_c) is independent of ammonia (NH₃) concentration. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to a moorland composed of a mixture of Calluna vulgaris (L.) Hull, Eriophorum vaginatum L. and Sphagnum spp. Ammonia was applied at a wide range of concentrations (1–100 μg m⁻³). The physical and environmental properties and the testing of the chamber are described, as well as results for the moorland vegetation using the ‘canopy resistance’ and ‘canopy compensation point’ interpretations of the data.Results for moorland plant species demonstrate that NH₃ concentration directly affects the rate of NH₃ deposition to the vegetation canopy, with R_c and cuticular resistance (R_w) increasing with increasing NH₃ concentrations. Differences in R_c were found between night and day: during the night R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 95 s m⁻¹ at 80 μg m⁻³, whereas during the day R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 48 s m⁻¹ at 80 μg m⁻³. The lower resistance during the day is caused by the stomata being open and available as a deposition route to the plant. R_w increased with increasing NH₃ concentrations and was not significantly different between day and night (at 80 μg m⁻³ NH₃ day R_w=88 s m⁻¹ and night R_w=95 s m⁻¹). The results demonstrate that assessments using fixed R_c will over-estimate NH₃ deposition at high concentrations (over ∼15 μg m⁻³).     

Seasonal soil and leaf CO2 exchange rates in a Mediterranean holm oak forest and their responses to drought conditions

We measured the soil and leaf CO₂ exchange in Quercus ilex and Phillyrea latifolia seasonally throughout the year in a representative site of the Mediterranean region, a natural holm oak forest growing in the Prades Mountains in southeastern Catalonia. In the wet seasons (spring and autumn), we experimentally decreased soil moisture by 30%, by excluding rainfall and water runoff in 12 plots, 1×10 m, and left 12 further plots as controls. Our aim was to predict the response of these gas exchanges to the drought forecasted for the next decades for this region by GCM and ecophysiological models.Annual average soil CO₂ exchange rate was 2.27±0.27 μmol CO₂ m⁻² s⁻¹. Annual average leaf CO₂ exchange rates were 8±1 and 5±1 μmol m⁻² s⁻¹ in Q. ilex and P. latifolia, respectively. Soil respiration rates in control treatments followed a seasonal pattern similar to photosynthetic activity. They reached maximum values in spring and autumn (2.5–3.8 μmol m⁻² s⁻¹ soil CO₂ emission rates and 7–15 μmol m⁻² s⁻¹ net photosynthetic rates) and minimum values (almost 0 for both variables) in summer, showing that soil moisture was the most important factor driving the soil microbial activity and the photosynthetic activity of plants. In autumn, drought treatment strongly decreased net photosynthesis rates and stomatal conductance of Q. ilex by 44% and 53%, respectively. Soil respiration was also reduced by 43% under drought treatment in the wet seasons. In summer there were larger soil CO₂ emissions in drought plots than in control plots, probably driven by autotrophic (roots) metabolism. The results indicate that leaf and soil CO₂ exchange may be strongly reduced (by ca. 44%) by the predicted decreases of soil water availability in the next decades. Long-term studies are needed to confirm these predictions or to find out possible acclimation of those processes.     

Survey of polyfluorinated chemicals (PFCs) in the atmosphere over the northeast Atlantic Ocean

High volume air sampling in Bermuda, Sable Island (Nova Scotia) and along a cruise track from the Gulf of Mexico to northeast coast of the USA, was carried out to assess air concentrations, particle-gas partitioning and transport of polyfluorinated chemicals (PFCs) in this region. Samples were collected in the summer of 2007. Targeted compounds included the neutral PFCs: fluorotelomer alcohols (FTOHs), perfluoroalkyl sulfonamides (FOSAs) and perfluoroalkyl sulfonamido ethanols (FOSEs).Among the FTOHs, 8:2 FTOH was dominant in all samples. Sum of the concentration of FTOHs (gas+particle phase) were higher in Bermuda (mean, 34 pg m^?3) compared to Sable Island (mean, 16 pg m^?3). In cruise samples, sum of FTOHs were highly variable (mean, 81 pg m^?3) reflecting contributions from land-based sources in the northeast USA with concentrations reaching as high as 156 pg m^?3.Among the FOSAs and FOSEs, MeFOSE was dominant in all samples. In Bermuda, levels of MeFOSE were exceptionally high (mean, 62 pg m^?3), exceeding the FTOHs. Sable Island samples also exhibited the dominance of MeFOSE but at a lower concentration (mean, 15 pg m^?3). MeFOSE air concentrations (pg m^?3) in cruise samples ranged from 1.6 to 73 and were not linked to land-based sources. In fact high concentrations of MeFOSE observed in Bermuda were associated with air masses that originated over the Atlantic Ocean.The partitioning to particles for 8:2 FTOH, 10:2 FTOH, MeFOSE and EtFOSE ranged from as high as 15 to 42% for cruise samples to 0.9 to 14% in Bermuda. This study provides key information for validating and developing partitioning and transport models for the PFCs.     

Measurement of the vapor phase deposition of polychlorinated bipheyls (PCBs) using a water surface sampler

A water surface sampler (WSS) was employed in combination with greased knife-edge surface deposition plates (KSSs) to measure the vapor phase deposition rates of PCBs to the sampler at an urban site, Chicago, IL. This sampler employed a water circulation system that continuously removed deposited PCBs. Total (gas+particle) and particulate PCB fluxes were collected with the WSS and KSSs, respectively. Gas phase PCB fluxes were then calculated by subtracting the KSS fluxes (particulate) from the WSS fluxes (gas+particle). The calculated gas phase PCB fluxes averaged 830±910 ng m⁻²d⁻¹. This flux value is, in general, higher than the fluxes determined using simultaneously measured air–water concentrations in natural waters and is in the absorption direction. This difference is primarily because the PCBs were continuously removed from the WSS water keeping the water PCB concentration near zero.Concurrently, ambient air samples were collected using a modified high volume air sampler. The gas phase PCB concentrations ranged between 1.10 and 4.46 ng m⁻³ (average±SD, 2.29±1.28 ng m⁻³). The gas phase fluxes were divided by the simultaneously measured gas phase ambient concentrations to determine the overall gas phase mass transfer coefficients (MTCs) for PCBs. The average gas phase overall MTCs (K_g) for each homolog group ranged between 0.22 and 1.32 cm s⁻¹ (0.54±0.47 cm s⁻¹). The average MTC was in good agreement with those determined using similar techniques.     

Fungi and bacteria in mould-damaged and non-damaged office environments in a subarctic climate

The fungi and bacterial levels of the indoor air environments of 77 office buildings were measured in winter and a comparison was made between the buildings with microbe sources in their structures and those without such sources. Penicillium, yeasts, Cladosporium and non-sporing isolates were the commonest fungi detected in the indoor air and in settled dust, in both the mould-damaged and control buildings. Aspergillus ochraceus, Aspergillus glaucus and Stachybotrys chartarium were found only in environmental samples from the mould-damaged buildings. Some other fungi, with growth requiring of water activity, a_w, above 0.85, occurred in both the reference and mould-damaged buildings, but such fungi were commoner in the latter type of buildings. The airborne concentrations of Penicillium, Aspergillus versicolor and yeasts were the best indicators of mould damage in the buildings studied. Penicillium species and A. versicolor were also the most abundant fungi in the material samples. This study showed that the fungi concentrations were very low (2–45 cfu m⁻³ 90% of the concentrations being <15 cfu m⁻³) in the indoor air of the normal office buildings. Although the concentration range of airborne fungi was wider for the mould-damaged buildings (2–2470 cfu m⁻³), only about 20% of the samples exceeded 100 cfu m⁻³. The concentrations of airborne bacteria ranged from 12 to 540 cfu m⁻³ in the control buildings and from 14 to 1550 cfu m⁻³ in the mould-damaged buildings. A statistical analysis of the results indicated that bacteria levels are generally <600 cfu m⁻³ in office buildings in winter and fungi levels are <50 cfu m⁻³. These normal levels are applicable to subarctic climates for urban, modern office buildings when measurements are made using a six-stage impactor. These levels should not be used in evaluations of health risks, but elevated levels may indicate the presence of abnormal microbe sources in indoor air and a need for additional environmental investigations.     

Biogenic emission of dimethylsulfide (DMS) from the North Yellow Sea,China and its contribution to sulfate in aerosol during summer

Seawater, atmospheric dimethylsulfide (DMS) and aerosol compounds, potentially linked with DMS oxidation, such as methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄^2?) were determined in the North Yellow Sea, China during July–August, 2006. The concentrations of seawater and atmospheric DMS ranged from 2.01 to 11.79 nmol l^?1 and from 1.68 to 8.26 nmol m^?3, with average values of 6.20 nmol l^?1 and 5.01 nmol m^?3, respectively. Owing to the appreciable concentration gradient, DMS accumulated in the surface water was transferred into the atmosphere, leading to a net sea-to-air flux of 6.87 μmol m^?2 d^?1 during summer. In the surface seawater, high DMS values corresponded well with the concurrent increases in chlorophyll a levels and a significant correlation was observed between integrated DMS and chlorophyll a concentrations. In addition, the concentrations of MSA and nss-SO₄^2? measured in the aerosol samples ranged from 0.012 to 0.079 μg m^?3 and from 3.82 to 11.72 μg m^?3, with average values of 0.039 and 7.40 μg m^?3, respectively. Based on the observed MSA, nss-SO₄^2? and their ratio, the relative biogenic sulfur contribution was estimated to range from 1.2% to 11.5%, implying the major contribution of anthropogenic source to sulfur budget in the study area.     

Transport of SO2 and aerosol over the Yellow sea

Aircraft measurements of air pollutants were made to investigate the characteristic features of long-range transport of sulfur compounds over the Yellow Sea for the periods of 26–27 April and 7–10 November in 1998, and 9–11 April and 19 June in 1999, together with aerosol measurements at the Taean background station in Korea. The overall mean concentrations of SO₂, O₃ and aerosol number in the boundary layer for the observation period ranged 0.1–7.4 ppb 32.1–64.1 ppb and 1.0–143.6 cm⁻³, respectively. It was found that the air mass over the Yellow Sea had a character of both the polluted continental air and clean background air, and the sulfur transport was mainly confined in the atmospheric boundary layer. The median of SO₂ concentration within the boundary layer was about 0.1–2.2 ppb. However, on 8 November, 1998, the mean concentrations of SO₂ and aerosol number increased up to 7.4 ppb and 109.5 cm⁻³, respectively, in the boundary layer, whereas O₃ concentration decreased remarkably. This enhanced SO₂ concentration occurred in low level westerly air stream from China to Korea. Aerosol analyses at the downstream site of Taean in Korea showed 2–3 times higher sulfate concentration than that of other sampling days, indicating a significant amount of SO₂ conversion to non sea-salt sulfate during the long-range transport.     

Field performance of dichotomous sequential PM air samplers

For over one year, the Environmental Protection Commission of Hillsborough County (EPCHC) in Tampa, Florida, operated two dichotomous sequential particulate matter air samplers collocated with a manual Federal Reference Method (FRM) air sampler at a waterfront site on Tampa Bay. The FRM was alternately configured as a PM_2.5, then as a PM₁₀ sampler. For the dichotomous sampler measurements, daily 24-h integrated PM_2.5 and PM_10–2.5 ambient air samples were collected at a total flow rate of 16.7 l min⁻¹. A virtual impactor split the air into flow rates of 1.67 and 15.0 l min⁻¹ onto PM_10–2.5 and PM_2.5 47-mm diameter PTFE^® filters, respectively. Between the two dichotomous air samplers, the average concentration, relative bias and relative precision were 13.3 μg m⁻³, 0.02% and 5.2% for PM_2.5 concentrations (n=282), and 12.3 μg m⁻³, 3.9% and 7.7% for PM_10–2.5 concentrations (n=282). FRM measurements were alternate day 24-h integrated PM_2.5 or PM₁₀ ambient air samples collected onto 47-mm diameter PTFE^® filters at a flow rate of 16.7 l min⁻¹. Between a dichotomous and a PM_2.5 FRM air sampler, the average concentration, relative bias and relative precision were 12.4 μg m⁻³, −5.6% and 8.2% (n=43); and between a dichotomous and a PM₁₀ FRM air sampler, the average concentration, relative bias and relative precision were 25.7 μg m⁻³, −4.0% and 5.8% (n=102). The PM_2.5 concentration measurement standard errors were 0.95, 0.79 and 1.02 μg m⁻³; for PM₁₀ the standard errors were 1.06, 1.59, and 1.70 μg m⁻³ for two dichotomous and one FRM samplers, respectively, which indicate the dichotomous samplers have superior technical merit. These results reveal the potential for the dichotomous sequential air sampler to replace the combination of the PM_2.5 and PM₁₀ FRM air samplers, offering the capability of making simultaneous, self-consistent determinations of these particulate matter fractions in a routine ambient monitoring mode.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

Isoprene and monoterpene fluxes measured above Amazonian rainforest and their dependence on light and temperature

Canopy scale emissions of isoprene and monoterpenes from Amazonian rainforest were measured by eddy covariance and eddy accumulation techniques. The peak mixing ratios at about 10 m above the canopy occurred in the afternoon and were typically about 90 ppt_v of α-pinene and 4–5 ppb_v of isoprene. α-pinene was the most abundant monoterpene in the air above the canopy comprising ≈50% of the total monoterpene mixing ratio. Measured isoprene fluxes were almost 10 times higher than α-pinene fluxes. Normalized conditions of 30°C and 1000 μmol m⁻² s⁻¹ were associated with an isoprene flux of 2.4 mg m⁻² h⁻¹ and a β-pinene flux of 0.26 mg m⁻² h⁻¹. Both fluxes were lower than values that have been specified for Amazon rainforests in global emission models. Isoprene flux correlated with a light- and temperature-dependent emission activity factor, and even better with measured sensible heat flux. The variation in the measured α-pinene fluxes, as well as the diurnal cycle of mixing ratio, suggest emissions that are dependent on both light and temperature. The light and temperature dependence can have a significant effect on the modeled diurnal cycle of monoterpene emission as well as on the total monoterpene emission.     

Extent of H-atom abstraction from OH + p-cymene and upper limits to the formation of cresols from OH + m-xylene and OH + p-cymene

Aromatic hydrocarbons are important constituents of vehicle exhaust and of non-methane volatile organic compounds in ambient air in urban areas. It has recently been proposed that dealkylation is a significant pathway for the OH radical-initiated reactions, leading to the formation of phenolic compounds and/or oxepins (Noda, J., Volkamer, R., Molina, M.J., 2009. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, and p-xylene + OH reaction. Journal of Physical Chemistry A 113, 9658–9666.). We have investigated the formation of cresols from the reactions of OH radicals with m-xylene and p-cymene, and obtain upper limits of <1% for formation of each cresol isomer from OH + m-xylene and <2% for formation of each cresol isomer from OH + p-cymene. In addition, we have measured the formation yield of 4-methylacetophenone (the major product formed subsequent to H-atom abstraction from the CH(CH₃)₂ group) in the OH + p-cymene reaction to be 14.8 ± 3.2%, and estimate that H-atom abstraction from the CH₃ and CH(CH₃)₂ groups in p-cymene accounts for 20 ± 4% of the overall OH radical reaction. We also used a relative rate technique to measure the rate constant for the reaction of OH radicals with 4-methylacetophenone to be (4.50 ± 0.43) × 10^?12 cm³ molecule^?1 s^?1 at 297 ± 2 K.     

Importance of wet precipitation as a removal and transport process for atmospheric water soluble carbonyls

Carbonyl compounds exist in the atmosphere as either gases or aerosols. Some of them are water soluble and known as oxidation products of biogenic and/or anthropogenic hydrocarbons. Five carbonyl compounds, glyoxal (GO), 4-oxopentanal (4-OPA), glycolaldehyde (GA), hydroxyacetone (HA) and methylglyoxal (MG) have been identified in a temporal series of 12 rain samples. The concentrations of the compounds in the samples were high at the beginning of the rain event and decreased with time to relatively low and fairly constant levels, indicating that the compounds were washed out from the atmosphere at the start of the rain event. Possibly, these compounds also existed in the cloud condensation nuclei (CCN). Wet deposition rates of the carbonyl compounds were calculated for nine samples collected during a 20 h period. The deposition rates ranged from 0 (4-OPA) to 1.2×10⁻¹ mg C m⁻² h⁻¹ (MG) with the average of 2.9×10⁻² mg C m⁻² h⁻¹. Production rates of isoprene oxidation products (GA, HA and MG) in the area surrounding the sampling site were estimated with a chemical box model. The deposition rates exceeded the production rates in most samples. This indicates that the rainfall causes a large net flux of the water soluble compounds from the atmosphere to the ground. Insoluble carbonyl compounds such as n-nonanal and n-decanal were expected to be present in the atmosphere, but were not detected in the rain during the sampling period, suggesting that an aerosol containing these insoluble compounds does not effectively act as a CCN.     

Methane emissions from an anaerobic swine lagoon

Gaseous methane (CH₄) emissions from a swine waste holding lagoon were determined periodically during the year. Micrometeorological techniques were used in order that emission rates from the lagoon were measured under ambient conditions with little disturbance to the natural environment. During the cold winter measurement period, CH₄ fluxes were linearly related to lagoon water temperature below 22°C (r=0.87). During warmer measurement periods, both water and air temperatures and windspeed affected emissions rates. In general, flux rates followed a diurnal pattern with greater fluxes during the day when both temperature and windspeed were greatest. Mathematical models using air and water temperature and windspeed factors could explain 47 to 75% of the variation in fluxes. Daily emission rates ranged from 1 to 500 kg CH₄ ha⁻¹ d⁻¹. The average flux for the year was 52.3 kg CH₄ ha⁻¹ d⁻¹ which corresponded to about 5.6 kg CH₄ animal⁻¹ yr⁻¹ from the primary lagoon.     

Solubilities of selected organic electronic materials in pressurized hot water and estimations of aqueous solubilities at 298.15 K

Increasing production and disposal of organic light-emitting diode (OLED) displays for smartphones and tablets may have impact on the environment depending on the aqueous solubility of the pertinent chemicals. Here, aqueous solubilities are presented for several compounds, mostly aromatic amines, used as hole transport materials in the OLED displays. Solute selection includes 1,4-bis(diphenylamino)benzene, tetra-N-phenylbenzidine, 4,4′-bis(N-carbazolyl)-1,1′-biphenyl, 1,3,5-tris(diphenylamino)benzene, and 9,10-bis(phenylethynyl)anthracene. The solubilities are those in pressurized hot water (PHW), i.e., measured at elevated temperature (up to 260 °C) and pressure. The semi-quantitative estimates of room-temperature solubilities of the solutes have been obtained from extrapolations of the solubilities in PHW. For the compounds studied, the estimated aqueous solubilities at room temperature do not exceed 2 × 10^?11 g of the solute per 1 kg of water. Aqueous solubilities of triphenylamine have also been measured and used to upgrade a recent group-contribution model of aqueous solubilities of organic nonelectrolytes with the parameters for the nitrogen atom in aromatic amines.     

Concentration-dependent NH3 deposition processes for moorland plant species with and without stomata

Currently, in operational modelling of NH₃ deposition a fixed value of canopy resistance (R_c) is generally applied, irrespective of the plant species and NH₃ concentration. This study determined the effect of NH₃ concentration on deposition processes to individual moorland species. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to Deschampsia cespitosa (L.) Beauv., Calluna vulgaris (L.) Hull, Eriophorum vaginatum L., Cladonia spp., Sphagnum spp., and Pleurozium schreberi (Brid.) Mitt. Measurements were conducted across a wide range of NH₃ concentrations (1–140 μg m⁻³).NH₃ concentration directly affects the deposition processes to the vegetation canopy, with R_c, and cuticular resistance (R_w) increasing with increasing NH₃ concentration, for all the species and vegetation communities tested. For example, the R_c for C. vulgaris increased from 14 s m⁻¹ at 2 μg m⁻³ to 112 s m⁻¹ at 80 μg m⁻³. Diurnal variations in NH₃ uptake were observed for higher plants, due to stomatal uptake; however, no diurnal variations were shown for non-stomatal plants. R_c for C. vulgaris at 80 μg m⁻³ was 66 and 112 s m⁻¹ during day and night, respectively. Differences were found in NH₃ deposition between plant species and vegetation communities: Sphagnum had the lowest R_c (3 s m⁻¹ at 2 μg m⁻³ to 23 at 80 μg m⁻³), and D. cespitosa had the highest nighttime value (18 s m⁻¹ at 2 μg m⁻³ to 197 s m⁻¹ at 80 μg m⁻³).