Instrument to collect fogwater for chemical analysis

An instrument is presented which collects large samples of ambient fogwater by impaction of droplets on a screen. The collection efficiency of the instrument is determined as a function of droplet size, and it is shown that fog droplets in the range 3–100-µm diameter are efficiently collected. No significant evaporation or condensation occurs at any stage of the collection process. Field testing indicates that samples collected are representative of the ambient fogwater. The instrument may easily be automated, and is suitable for use in routine air quality monitoring programs

The H_2SO_4-HNO_3-NH_3 System at High Humidities and in Fogs: 1. Spatial and Temporal Patterns in the San Joaquin Valley of California

A systematic characterization of the atmospheric H_2SO_4-HNO_3-NH_3 system was conducted in the fog water, the aerosol, and the gas phase at a network of sites in the San Joaquin Valley of California. Spatial patterns of concentrations were established that reflect the distribution of SO_2, NO_x, and NH_3 emissions within the valley. The concept of atmospheric alkalinity was introduced to interpret these concentrations in terms of the buffering capacity of the atmosphere with respect to inputs of strong acids. Regions of predominantly acidic and alkaline fog water were identified. Fog water was found to be alkaline in most of the valley, but small changes in emission budgets could lead to widespread acid fog. An extended stagnation episode was studied in detail: progressive accumulation of H_2SO_4-HNO_3-NH_3 species was documented over the course of the episode and interpreted in terms of production and removal mechanisms. Secondary production of strong acids H_2SO_4 and HNO_3 under stagnant conditions resulted in a complete titration of available alkalinity at the sites farthest from NH_3 sources. A steady SO_2 conversion rate of 0.4–1.1% h^(−1) was estimated in the stagnant mixed layer under overcast conditions and was attributed to nonphotochemical heterogeneous processes. Removal of SO_2 was enhanced in fog, compared to nonfoggy conditions. Conversion of NO_x to HNO_3 slowed down during the stagnation episode because of reduced photochemical activity; fog did not appear to enhance conversion of NO_x. Decreases in total HNO_3 concentrations were observed upon acidification of the atmosphere and were attributed to displacement of NO_3− by H_2SO_4 in the aerosol, followed by rapid deposition of HNO_3(g). The occurrence of fog was associated with general decreases of aerosol concentrations due to enhanced removal by deposition

Fogwater chemistry in an urban atmosphere

Analyses of fogwater collected by inertial impaction in the Los Angeles basin and the San Joaquin Valley indicated unusually high concentrations of major and minor ions. The dominant ions measured were NO_3^−, SO_4^(2−), NH_4^+, and H^+. Nitrate exceeded sulfate on an equivalent basis by a factor of 2.5 in the central and coastal regions of the Los Angeles basin but was approximately equal in the eastern Los Angeles basin and the San Joaquin Valley. Maximum observed values for NH_4^+, NO_3^−, and SO_4^(2−) were 10.0, 12.0, and 5.0, meq 1^(−1), while the lowest p;H observed was 2.2. Iron and lead concentrations of over 0.1 mM and 0.01 mM, respectively, were observed. High concentrations of chemical components in fog appeared to correlate well with the occurrence of smog events. Concentrations in fogwater were also affected by the physical processes of condensation and evaporation. Light, dissipating fogs routinely showed the highest concentrations

The H_2SO_4-HNO_3-NH_3 System at High Humidities and in Fogs: 2. Comparison of Field Data With Thermodynamic Calculations

Concentrations of HNO_3(g) and NH_3(g) determined in the field were compared to predictions from aerosol equilibrium models. The products of HNO_3(g) and NH_3(g) concentrations measured under cool and humid nonfoggy conditions agreed in magnitude with predictions from a comprehensive thermodynamic model for the atmospheric H_2SO_4-HNO_3-NH_3-H_2O system. Observed concentrations of NH_3(g) in fogs were generally consistent with those predicted at equilibrium with fog water, but important discrepancies were noted in some cases. These discrepancies may be due to fluctuations in fog water composition over the course of sample collection or to the sampling of nonfoggy pockets of air present within the fog. Detectable concentrations of HNO_3(g) (up to 23 neq m^(−3)) were often found in fogs with pH 5 were below the detection limit of 4–8 neq m^(−3)

Characterization of Reactants Reaction Mechanisms and Reaction Products Leading to Extreme Acid Rain and Acid Aerosol Conditions in Southern California

Analyses of fogwater collected by inertial impaction in the Los Angeles basin and the San Joaquin Valley indicated unusually high concentrations of major and minor ions. The dominant ions measured were NO_3^-, SO_4^(2-), NH_4^+ and H^+ Nitrate exceeded sulfate on an equivalent basis by a factor of 2.5 in the central and coastal regions of the Los Angeles basin, but was approximately equal in the eastern Los Angeles basin and the San Joaquin Valley. Maximum observed values for NH_4^+, NO_3^- and SO_4^(2-) were 10., 12., and 5. meq L^(-1), while the lowest pH observed was 2.2. Iron and lead concentrations over 0.1 mM and 0.01 mM, respectively, were observed. High concentrations of chemical components in fog appeared to correlate well with the occurrence of smog events. Concentrations in fogwater were also affected by the physical processes of condensation and evaporation. Light, dissipating fogs routinely showed the highest concentrations. The chemistry of urban fog has been modelled using a hybrid kinetic and equilibrium computer code. Extreme acidity found in Southern California fog may be due either to condensation and growth on acidic condensation nuclei or in situ S(IV) oxidation. Important oxidants of S(IV) were found to be O_2 as catalyzed by Fe(III) and Mn(II), H_2)_2 and 0_3. formation of hydroxymethane sulfonate ion (HMSA) via the nucleophilic addition of HSO_3^-to CH_2 CH_2O(ℓ) significantly increased the droplet capacity for S(IV) but did not slow down the net S(IV) oxidation rate leading to fog acidification. Gas phase nitric acid, ammonia and hydrogen peroxide were scavenged efficiently, although aqueous phase hydrogen peroxide was depleted rapidly by reduction with S(IV). Nitrate production in the aqueous phase was found to be dominated by HNO_3 gas phase scavenging. Major aqueous-phase species concentrations were controlled primarily by condensation, evaporation, and pH

Uric Acid Predicts Long-Term Cardiovascular Risk in Type 2 Diabetes but Does Not Mediate the Benefits of Fenofibrate: the FIELD Study

Aim To explore the relationship between baseline uric acid (UA) levels and long-term cardiovascular events in adults with type 2 diabetes (T2D) and to determine whether the cardioprotective effects of fenofibrate are partly mediated through its UA-lowering effects. Methods Data from the Fenofibrate Intervention and Event Lowering in Diabetes (FIELD) trial were utilized, comprising 9795 adults with T2D randomly allocated to treatment with fenofibrate or matching placebo. Plasma UA was measured before and after a 6-week, active fenofibrate run-in phase in all participants. Cox proportional hazards models were used to explore the relationships between baseline UA, pre-to-post run-in reductions in UA and long-term cardiovascular outcomes. Results Mean baseline plasma UA was 0.33 mmol/L (SD 0.08). Baseline UA was a significant predictor of long-term cardiovascular events, with every 0.1 mmol/L higher UA conferring a 21% increase in event rate (HR 1.21, 95% CI 1.13-1.29, P <.001). This remained significant after adjustment for treatment allocation, cardiovascular risk factors and renal function. The extent of UA reduction during fenofibrate run-in was also a significant predictor of long-term cardiovascular events, with every 0.1 mmol/L greater reduction conferring a 14% lower long-term risk (HR 0.86, 95% CI 0.76-0.97, P = .015). This effect was not modified by treatment allocation (P-interaction = .77). Conclusions UA is a strong independent predictor of long-term cardiovascular risk in adults with T2D. Although greater reduction in UA on fenofibrate is predictive of lower cardiovascular risk, this does not appear to mediate the cardioprotective effects of fenofibrate.Peer reviewe

Chemical characterization of stratus cloudwater and its role as a vector for pollutant deposition in a Los Angeles pine forest

Highly concentrated, acidic stratus cloudwater was monitored as it intercepted a pine forest (Henninger Flats) 25 km northeast of Los Angeles. Observed pH values ranged from 2.06 to 3.87 for over 100 samples collected in 1982 and 1983 with a median value below pH 3. The ratio of nitrate/sulfate in cloudwater samples was between 1.5 and 2: rainwater at the same site had a ratio of approximately 1. The solute deposition accompanying several light. spring rains (summing to ~1 % of annual rainfall) was a disproportionate fraction of the annual total: H^+. NO_3 and SO _4^2 were -20% or more. Based on a reasonable estimate of fog precipitation, deposition of sulfate, nitrate and free acidity due to intercepting stratus clouds may be of comparable magnitude as that due to the incident rainfall at Henninger Flats. Cloudwater that had deposited on local pine needles was collected. It was in general more concentrated than ambient cloudwater but with comparable acidity. Enrichment of K^+ and Ca^(2+) in those samples and in throughfall is believed to be due to leaching from foliar surfaces. Injury to sensitive plant tissue has been noted in the literature when prolonged exposure to this severe kind of micro-environment has been imposed

Characterizing, modelling and understanding the climate variability of the deep water formation in the North-Western Mediterranean Sea

Observing, modelling and understanding the climate-scale variability of the deep water formation (DWF) in the North-Western Mediterranean Sea remains today very challenging. In this study, we first characterize the interannual variability of this phenomenon by a thorough reanalysis of observations in order to establish reference time series. These quantitative indicators include 31 observed years for the yearly maximum mixed layer depth over the period 1980–2013 and a detailed multi-indicator description of the period 2007–2013. Then a 1980–2013 hindcast simulation is performed with a fully-coupled regional climate system model including the high-resolution representation of the regional atmosphere, ocean, land-surface and rivers. The simulation reproduces quantitatively well the mean behaviour and the large interannual variability of the DWF phenomenon. The model shows convection deeper than 1000 m in 2/3 of the modelled winters, a mean DWF rate equal to 0.35 Sv with maximum values of 1.7 (resp. 1.6) Sv in 2013 (resp. 2005). Using the model results, the winter-integrated buoyancy loss over the Gulf of Lions is identified as the primary driving factor of the DWF interannual variability and explains, alone, around 50 % of its variance. It is itself explained by the occurrence of few stormy days during winter. At daily scale, the Atlantic ridge weather regime is identified as favourable to strong buoyancy losses and therefore DWF, whereas the positive phase of the North Atlantic oscillation is unfavourable. The driving role of the vertical stratification in autumn, a measure of the water column inhibition to mixing, has also been analyzed. Combining both driving factors allows to explain more than 70 % of the interannual variance of the phenomenon and in particular the occurrence of the five strongest convective years of the model (1981, 1999, 2005, 2009, 2013). The model simulates qualitatively well the trends in the deep waters (warming, saltening, increase in the dense water volume, increase in the bottom water density) despite an underestimation of the salinity and density trends. These deep trends come from a heat and salt accumulation during the 1980s and the 1990s in the surface and intermediate layers of the Gulf of Lions before being transferred stepwise towards the deep layers when very convective years occur in 1999 and later. The salinity increase in the near Atlantic Ocean surface layers seems to be the external forcing that finally leads to these deep trends. In the future, our results may allow to better understand the behaviour of the DWF phenomenon in Mediterranean Sea simulations in hindcast, forecast, reanalysis or future climate change scenario modes. The robustness of the obtained results must be however confirmed in multi-model studies