Production and removal of aerosol in a polluted fog layer: model evaluation and fog effect on PM

A radiation fog physics, gas- and aqueous-phase chemistry model is evaluated against measurements in three sites in the San Joaquin Valley of California (SJV) during the winter of 1995. The measurements include for the first time vertically resolved fog chemical composition measurements. Overall the model is successful in reproducing the fog dynamics as well as the temporal and spatial variability of the fog composition (pH, sulfate, nitrate, and ammonium concentrations) in the area. Sulfate production in the fog layer is relatively slow (1–4 μg m⁻³ per fog episode) compared to the episodes in the early 1980s because of the low SO₂ concentrations in the area and the lack of oxidants inside the fog layer. Sulfate production inside the fog layer is limited by the availability of oxidants in the urban areas of the valley and by SO₂ in the more remote areas. Nitrate is produced in the rural areas of the valley by the heterogeneous reaction of N₂O₅ on fog droplets, but this reaction is of secondary importance for the more polluted urban areas. The gas-phase production of HNO₃ during the daytime is sufficient to balance the nitrate removed during the nighttime fog episodes. Entrainment of air from the layer above the fog provides another source of reactants for the fog layer. Wet removal is one of most important processes inside the fog layer in SJV. We estimate based on the three episodes investigated during IMS95 that a typical fog episode removes 500–2000 μg m⁻² of sulfate, 2500–6500 μg m⁻² of nitrate, and 2000–3500 μg m⁻² of ammonium. For the winter SJV valley the net fog effect corresponds to reductions in ground ambient concentrations of 0.05–0.2 μg m⁻³ for sulfate, 3–6 μg m⁻³ for total nitrate, and 1–3 μg m⁻³ for total ammonium.     

Chemistry of fog waters in California's Central Valley—Part 3: concentrations and speciation of organic and inorganic nitrogen

Although organic nitrogen (ON) has been found to be a ubiquitous and significant component in wet and dry deposition, almost nothing is known about its concentration or composition in fog waters. To address this gap, we have investigated the concentration and composition of ON in fog waters collected in Davis, in California's Central Valley. Significant quantities of dissolved organic nitrogen (DON) were found in these samples, with a median concentration of 303 μM N (range=120–1630 μM N). DON typically represented approximately 16% of the total dissolved nitrogen (inorganic+organic) in Davis fog waters. The median concentration of nitrogen in free amino acids and alkyl amines was 16 μM N (range=3.8–120 μM N), which accounted for 3.4% of the DON in Davis fogs. Thus, although the absolute concentrations of free amino compounds were significant, they were only a minor component of the DON pool. Combined amino nitrogen (e.g., proteins and peptides) was present at higher concentrations and accounted for 6.1–29% (median=16%) of DON. Overall, free and combined amino compounds typically accounted for a median value of 22% of DON in the fog waters.The high concentrations of DON found, and the fact that amino and other N-containing organic compounds can serve as nitrogen sources for microorganisms and plants, indicate that atmospheric ON compounds likely play an important role in nitrogen cycling in the Central Valley. In addition, due to the basicity of some N functional groups, ON compounds likely contribute to the previously observed acid buffering capacity of Central Valley fog waters. Finally, a comparison of fog waters with fine particles (PM_2.5) collected from the same site during the same period of time indicated that the median concentrations (mol N m⁻³-air) of total water-soluble ON, free amino nitrogen and total amino nitrogen were very similar in the fog water and PM_2.5. Given the high water solubility of many organic N compounds, this result suggests that ON might contribute to the hygroscopic properties of atmospheric particles.     

Drop size-dependent S(IV) oxidation in chemically heterogeneous radiation fogs

Six radiation fog episodes were sampled in the Central Valley of California during winter 1998/1999. Drop size-resolved fog samples were sampled using a size-fractionating Caltech active strand cloudwater collector (sf-CASCC). The sf-CASCC collects a large fog drop sample, comprised mainly of drops larger than 17 μm diameter, and a small fog drop sample, comprised mainly of drops with diameters between 4 and 17 μm. The fog pH was found to vary between approximately pH 5.3 and 6.8, with the pH of the large fog drop sample typically several tenths of a pH unit higher than the simultaneously collected small fog drop sample. At these high pH values, dissolved sulfur dioxide can be rapidly oxidized by a variety of chemical pathways and also can react quickly with dissolved formaldehyde to form hydroxymethanesulfonate. The amount of sulfate produced by aqueous-phase oxidation during each fog episode was determined by application of a tracer technique. The ratio of large : small drop S(IV) oxidation was compared with theoretically predicted ratios of large : small drop S(IV) oxidation rates. Although the higher pH of the large fog drops should promote more rapid S(IV) oxidation by ozone, finite rates of mass transport into the large drops and an increasing rate of complexation of S(IV) by formaldehyde at high pH combine to depress theoretically predicted rates of aqueous sulfate production in large fog drops below rates expected for small fog drops. This prediction is supported by the tracer results that indicate the concentration of sulfate resulting from aqueous-phase S(IV) oxidation in small drops generally exceeded the concentration formed in large drops. These findings stand in sharp contrast to observations in acidic clouds at Whiteface Mountain, New York, where hydrogen peroxide was determined to be the dominant S(IV) oxidant and the rate of S(IV) oxidation was found to be independent of drop size.     

Drop size-dependent chemical composition of clouds and fogs. Part II: Relevance to interpreting the aerosol/trace gas/fog system

Size-resolved fog drop chemical composition measurements were obtained during a radiation fog campaign near Davis, California in December 1998/January 1999 (reported in Reilly et al., Atmos. Environ. 35(33) (2001) 5717; Moore et al., Atmos. Environ. this issue). Here we explore how knowledge of this size-dependent drop composition—particularly from the newly developed Colorado State University 5-Stage cloud water collector—helps to explain additional observations in the fog environment. Size-resolved aerosol measurements before and after fog events indicate relative depletion of large (>2 μm in diameter) particles during fog accompanied by a relative increase in smaller aerosol particle concentrations. Fog equivalent air concentrations suggest that entrainment of additional particles and in-fog sedimentation contributed to observed changes in the aerosol size distribution. Calculated deposition velocities indicate that sedimentation was an important atmospheric removal mechanism for some species. For example, nitrite typically has a larger net deposition velocity than water and its mass is found preferentially in the largest drops most likely to sediment rapidly. Gas–liquid equilibria in fog for NO₃⁻/HNO₃, NH₄⁺/NH₃, and NO₂⁻/HONO were examined. While these systems appear to be close to equilibrium or relative equilibrium during many time periods, divergences are observed, particularly for low liquid water content (<0.1 g m⁻³) fogs and in different drop sizes. Knowledge of the drop size-dependent composition provided additional data useful to the interpretation of these deviations. The results suggest that data from multi-stage cloud water collectors are useful to understanding fog processes as many depend upon drop size.     

Evaluation of secondary organic aerosol formation in winter

Three different methods are used to predict secondary organic aerosol (SOA) concentrations in the San Joaquin Valley of California during the winter of 1995–1996 [Integrated Monitoring Study, (IMS95)]. The first of these methods estimates SOA by using elemental carbon as a tracer of primary organic carbon. The second method relies on a Lagrangian trajectory model that simulates the formation, transport, and deposition of secondary organic aerosol. The model includes a recently developed gas–particle partitioning mechanism. Results from both methods are in good agreement with the chemical speciation of organic aerosol during IMS95 and suggest that most of the OC measured during IMS95 is of primary origin. Under suitable conditions (clear skies, low winds, low mixing heights) as much as 15–20 μg C m⁻³ of SOA can be produced, mainly due to oxidation of aromatics. The low mixing heights observed during the winter in the area allow accumulation of SOA precursors and the acceleration of SOA formation. Clouds and fog slow down the production of secondary compounds, reducing their concentrations by a factor of two or three from the above maximum levels. In addition, it appears that there is significant diurnal variation of SOA concentration. A strong dependence of SOA concentrations on temperature is observed, along with the existence of an optimal temperature for SOA formation.     

Size distributions and formation of dicarboxylic acids in atmospheric particles

The PM2.5 concentrations and the size distributions of dicarboxylic acids in Hong Kong were studied. Eleven sets of daily PM2.5 samples were obtained at a downtown sampling site during the period of 5–16 December 2000 using an R&P speciation PM2.5 sampler. About 6–12% of the total oxalic acid was found in the gas phase in some samples. A good correlation between succinate and sulfate (R²=0.88) and a moderate correlation between oxalate and sulfate (R²=0.74) were found. Sampling artifacts of oxalate, malonate and succinate were found to be negligible. A total of 18 sets of 48–96 h size distribution data on dicarboxylic acids, sulfate, nitrate and sodium at an urban site and a rural site from June 2000 to May 2001 were obtained using a Micro-Orifice Uniform Deposit Impactor. Data from both sites show similar size distribution characteristics of the dicarboxylic acids. The condensation mode of oxalate was usually observed at 0.177–0.32 μm. The location of the peak of the droplet mode of oxalate was associated with that of sulfate. When the peak of sulfate in the droplet mode appeared at 0.32–0.54 μm, the peak of oxalate sometimes appeared at 0.32–0.54 μm and sometimes shifted to 0.54–1.0 μm. When the peak of sulfate in the droplet mode appeared at 0.54–1.0 μm, the peak of oxalate sometimes appeared at 0.54–1.0 μm and sometimes shifted to 1.0–1.8 μm. Oxalate, succinate and sulfate found in the droplet mode were attributed to in-cloud formation. The slight shift of the oxalate peak from 0.32–0.54 to 0.54–1.0 μm or from 0.54–1.0 to 1.0–1.8 μm was ascribed to minor oxalate evaporation after in-cloud formation. The maximum peak of malonate sometimes appeared in the droplet mode and sometimes appeared at 3.1–6.2 μm. The formation of malonate is associated to the reactions between sea salt and malonic acid.     

Drop size-dependent chemical composition in clouds and fogs. Part I. Observations

The first observations of size-dependent cloud and fog drop inorganic ion and trace metal concentrations obtained using the Colorado State University 5-Stage cloud water collector (CSU 5-Stage) during field studies of orographic clouds (Whiteface Mountain, NY, July 1998) and radiation fogs (Davis, CA, January 1999) are reported. Although some mixing between drop sizes occurs, the CSU 5-Stage effectively separates the largest drops (>≈30 μm in diameter) from the smallest ones (<≈10 μm in diameter) permitting the discernment of size-dependent drop composition not possible with previous two- or three-stage collectors. At Whiteface, pH and the concentrations of the “major” ions −NH₄⁺, NO₃⁻, and SO₄²⁻—appeared largely independent of drop size as measured by a two-stage collector. The same major ion concentrations differed in Davis fogs by up to a factor of approximately 10 in the two-stage collector with consistently higher small drop concentrations. In both locations, CSU 5-Stage data generally indicate a greater range of concentrations is present across the drop size spectrum. CSU 5-Stage data show “U”- shaped profiles of major ion concentration vs. drop size at Whiteface and “L”- shaped profiles at Davis and the maximum/minimum concentration differences between fractions increased up to a factor of 2 (Whiteface) and 30 (Davis). Lower concentration species at both locations showed multiple concentration vs. drop size profiles with CSU 5-Stage data again exhibiting more variability than observed with the two-stage collector. While rarely reported, significant nitrite concentrations—relatively higher in the larger drops—were observed, and copper concentrations merit further investigation in the Davis fogs. The findings presented here are consistent with other studies. The implications and benefits of the increased resolution of size-dependent drop composition provided by the CSU 5-Stage are explored for the Davis fogs in a companion paper (Moore et al., Atmos. Environ. (2004), this issue).     

Source apportionment of time and size resolved ambient particulate matter measured with a rotating DRUM impactor

Ambient particulate chemical composition data acquired from samples collected using a three-stage Davis Rotating-drum Universal-size-cut Monitoring (DRUM) impactor in Detroit, MI, between February and April 2002 were analyzed through the application of a three-way factor analysis model. PM_2.5 (particulate matter ⩽2.5 μm in aerodynamic diameter) was collected by a DRUM impactor with 3-h time resolution and three size modes (2.5 μm>D_p>1.15 μm, 1.15 μm>D_p>0.34 μm and 0.34 μm>D_p>0.1 μm). A novel three-way factor analysis model was applied to these data where the source profiles are a three-way array of size, composition and source while the contributions are a matrix of sample by source. Nine factors were identified: road salt, industrial (Fe+Zn), cloud processed sulfate, two types of metal works, road dust, local sulfate source, sulfur with dust, and homogeneously formed sulfate. Road salt had high concentrations of Na and Cl. Mixed industrial emissions are characterized by Fe and Zn. The cloud processed sulfate had a high concentration of S in the intermediate size mode. The first metal works represented by Fe in all three size modes and by Zn, Ti, Cu, and Mn. The second included a high concentration of small size particle sulfur with intermediate size Fe, Zn, Al, Si, and Ca. Road dust contained Na, Al, Si, S, K, and Fe in the large size mode. The local and homogeneous sulfate factors show high concentrations of S in the smallest size mode, but different time series behavior in their contributions. Sulfur with dust is characterized by S and a mix of Na, Mg, Al, Si, K, Ca, Ti, and Fe from the medium and large size modes. This study shows that the utilization of time and size resolved DRUM data can assist in the identification of sources and atmospheric processes leading to the observed ambient concentrations.     

Spatial representativeness and scales of transport during the 1995 integrated monitoring study in California's San Joaquin Valley

Daily measurements of PM₁₀ mass and chemical composition were obtained for the period 1–14 November 1995 from a saturation monitoring network around Corcoran, and for varying portions of the period 9 December 1995–6 January 1996 for three networks around Bakersfield, Fresno, and the Kern Wildlife Refuge, in California's San Joaquin Valley. During the latter period, monitoring locations were also operated along the boundaries and across the width of the Valley. The Corcoran, Bakersfield, and Fresno networks consisted of 12–25 sites, located in areas of about 300–800 km². Each network also included one core site, situated at a pre-existing monitoring location, with more extensive and more temporally resolved measurements. Mean concentrations of PM₁₀ and its constituents varied from core-site concentrations by 20% or more over distances ranging from 4 to 14 km. Local source influences were observed to affect sites over distances of less than 1 km, but primary particulate emissions were also transported over urban or sub-regional scales of approximately 10–30 km during the winter and greater than 30 km in the fall. During winter, gas-phase precursors of secondary aerosol may have been transported over distances of approximately 100 km, but little evidence was found for transport of primary PM on such a scale.     

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.     

PM10 measurements at McMurdo Station,Antarctica

PM₁₀ aerosols at McMurdo Station, Antarctica were sampled continuously during the austral summers of 1995–1996 and 1996–1997. PM₁₀ (particles with aerodynamic diameters less than 10 μm) mass concentrations at Hut Point, located less than 1 km from downtown McMurdo, averaged 3.4 μg m⁻³, more than an order of magnitude lower than the USEPA annual average National Ambient Air Quality Standard (NAAQS) of 50 μg m⁻³. Concentrations of methanesulfonate and nitrate were similar to those measured at other Antarctic coastal sites. Non-sea-salt sulfate (NSS) concentrations on Ross Island were higher than those found at other coastal locations. The average elemental carbon concentration (129 ng m⁻³) downwind of the station was two orders of magnitude higher than those measured at remote coastal and inland Antarctic sites during summer. Average sulfur dioxide concentrations (746 ng m⁻³) were 3–44 times higher than those reported for coastal Antarctica. Concentrations of Pb and Zn were 17 and 46 times higher than those reported for the South Pole. A methanesulfonate to biogenic sulfate ratio (R) of 0.47 was derived that is consistent with the proposed temperature dependence of R.     

Aircraft-based volatile organic compounds flux measurements with relaxed eddy accumulation

Regional estimates of fluxes of volatile organic compounds (VOCs) are required to improve our understanding of their role in the chemistry of the atmosphere. Flux measurements on such a scale can best be obtained using aircraft-based systems. These systems usually rely on the eddy covariance technique, which requires fast response gas sensors for flux measurement, but such sensors are not available for most organic compounds, therefore, the relaxed eddy-accumulation (REA) technique was selected. An aircraft-based REA sampling system was developed and used to measure isoprene emission over the boreal forest during the 1996 summer. Over a short period in July at the Boreal Ecosystem/Atmosphere Study (BOREAS) southern study area (SSA), the isoprene fluxes ranged from −0.06 to 1.79 μg m^-2 s^-1, with a mean of 0.59±0.34 μg m^-2 s^-1, while in August at the BOREAS northern study area (NSA) the isoprene fluxes ranged from 0.00 to 0.26 μg m^-2 s^-1, with a mean of 0.14±0.09 μg m^-2 s^-1. In the SSA, the isoprene fluxes over aspen ranged from 0.44 to 1.79 μg m^-2 s^-1, with a mean of 0.92±0.33 μg m^-2 s^-1, whereas over black spruce, isoprene fluxes ranged from −0.06 to 0.54 μg m^-2 s^-1, with a mean of 0.36±0.21 μg m^-2 s^-1. The isoprene fluxes were exponentially correlated with solar radiation and radiative surface temperature. High correlations between isoprene fluxes and the fluxes of CO₂ and latent heat were also observed. Carbon lost through isoprene emissions was about 0.7 and 0.8% of the CO₂ assimilation rate for aspen and black spruce, respectively. The results demonstrate that the aircraft-based relaxed eddy-accumulation technique is a promising approach for quantifying the atmosphere–surface exchange of VOCs on a regional scale.     

SOA from methylglyoxal in clouds and wet aerosols: Measurement and prediction of key products

Aqueous OH radical oxidation of methylglyoxal in clouds and wet aerosols is a potentially important global and regional source of secondary organic aerosol (SOA). We quantify organic acid products of the aqueous reaction of methylglyoxal (30–3000 μM) and OH radical (approx. 4 × 10^?12 M), model their formation in the reaction vessel and investigate how the starting concentrations of precursors and the presence of acidic sulfate (0–840 μM) affect product formation. Predicted products were observed. The predicted temporal evolution of oxalic acid, pyruvic acid and total organic carbon matched observations at cloud relevant concentrations (30 μM), validating this methylglyoxal cloud chemistry, which is currently being implemented in some atmospheric models of SOA formation. The addition of sulfuric acid at cloud relevant concentrations had little effect on oxalic acid yields. At higher concentrations (3000 μM), predictions deviate from observations. Larger carboxylic acids (≥C₄) and other high molecular weight products become increasingly important as concentration increases, suggesting that small carboxylic acids are the major products in clouds while larger carboxylic acids and oligomers are important products in wet aerosols.     

Black carbon (BC) in alpine aerosols and cloud water—concentrations and scavenging efficiencies

During April 1999 and March 2000, intensive field campaigns were performed on a mid-level mountain (Rax, 1644 m a.s.l.) in Central Europe both under out-of-cloud and in-cloud conditions. The black carbon (BC) content of both aerosol and cloud water as well as BC scavenging efficiencies of Rax clouds were measured. As a tracer for the non-carbonaceous aerosol, sulfate was used. Although BC concentrations on Rax were low (April 1999 out-of-cloud average: 0.43 μg/m³, March 2000: 0.72 μg/m³), the BC mass fraction of the aerosol was fairly high (1999: 3.5%, 2000: 6.4%). Average BC concentrations in cloud water were 1.09 μg/ml (1999) and 1.4 μg/ml (2000). These values are far higher than literature values, but comparable to those found in an earlier study (J. Geophys. Res. 105 (D20) (2000) 24637) at a high-level mountain (Sonnblick, 3106 m a.s.l.) some 200 km distant from Rax. The average BC scavenging efficiency of the Rax clouds in March 2000 was 0.54. The increase of scavenging efficiency with increasing liquid water content of the clouds found earlier on Sonnblick for sulfate and aerosol carbon (J. Atmos. Chem 35 (2000) 33), organic carbon (J. Geophys. Res. 105 (2000) 19857), and BC (J. Geophys. Res. 105 (D20) (2000) 24637) was also confirmed on Rax.     

Ammonia concentrations and fluxes over a forest in the midwestern USA

We present measurements of ammonia (NH₃) over a deciduous forest in southern Indiana collected during four field campaigns; two in the spring during the transition to leaf-out and two during the winter. Above canopy NH₃ concentrations measured continuously using two Wet Effluent Diffusion Denuders indicate mean concentrations of 0.6–1.2 μg m⁻³ during the spring and 0.3 μg m⁻³ during the winter. Measurements suggest that on average the forest act as a sink of NH₃, with a representative daily deposition flux of 1.8 mg-NH₃ m⁻² during the spring. However, on some days during the spring inverted concentration gradients of NH₃ were observed resulting in an apparent upward flux of nearly 0.2 mg-NH₃ m⁻² h⁻¹. Analyses suggest that this apparent emission flux may be due to canopy emission but evaporation of ammonium nitrate particles may also be partly responsible for the observed inverted concentration gradients.     

Seasonal and shorter-term variations in particulate atmospheric nitrate in Baltimore

Fine particle nitrate concentrations were measured at 10-min intervals for approximately 9.5 months beginning on 14 February 2002, at the Baltimore Supersite Ponca St. location using an R&P 8400N semi-continuous monitor. The measurement results were used to characterize seasonal and shorter-term excursions in nitrate concentrations and determine their influence on PM_2.5 concentrations. Over the 9.5-month study period, nitrate levels of 1.7±1.6 μg m⁻³ accounted for 11.4% of the PM_2.5 mass. Monthly averages ranged from 0.8 μg m⁻³ in August to 2.9 μg m⁻³ in November, and accounted for 4.7–17.3% of monthly PM_2.5 mass. Hourly averages, however, were often larger, especially in the colder months, owing to numerous relatively short-term transients, where hourly nitrate concentrations exceeded 5.0 μg m⁻³. These often occurred along with NO_x and ultrafine particle transients during the morning commute hours.A total of 275 short-term transients (31.7% of the total) exceeding 1.0 μg m⁻³ were identified. These were associated with one of three sets of conditions. The first, most typical (177, i.e. 64.4% of the 275 incidences), is characterized by high NO_x typically between 0500 and 0800EST and is attributed to early morning commute traffic activity. The second type occurred during the afternoon due to photochemical activity. The excursions in the afternoon occurred infrequently (only 9.5% of all the observed transients) during the study period and were characterized by less elevated nitrate concentrations than morning and nighttime transients. The third (72, i.e. 26.2% of the 275 transients) occurred at night, typically between 2000EST and 0200EST.Multiple linear regression analysis between nitrate excursions and volume size distributions indicates that particulate nitrate observed is closely related to the near accumulation (0.1–0.2 μm) and droplet modes (0.5–1.0 μm) in the morning hours, and associated with the droplet (0.5–1.0 μm) and coarse modes (1.0–2.5 μm) for nighttime transients, suggesting that processes governing particulate nitrate formation depend on time-of-day.     

Preliminary data suggest that venlafaxine environmental concentrations could be toxic to plants

Venlafaxine hydrochloride is a structurally novel antidepressant. Its occurrence in surface waters and drinking water has only been reported in recent works. The aim of this work is to assess the acute and chronic sublethal toxicity of venlafaxine in relevant taxa of riparian ecosystems. We used the fern Polystichum setiferum during the critical life stage of development. Reliable biomarkers of cell viability (mitochondrial activity), plant physiology (chlorophyll), and growth (DNA content) were assessed as sensitive endpoints of toxicity. About DNA quantification, our results show that venlafaxine induces acute lethal phytotoxicity at 24 and 48 h (LOECs 1 μg L^?1 and 0.1 μg L^?1, respectively). At 24 h, hormetic effects in spores of P. setiferum mitochondrial activity mask lethality and adverse effects are observed (LOEC 1 μg L^?1). At 48 h a reduction in the mitochondrial activity happens (LOEC 10 μg L^?1). In chronic exposure of 1 week, LOEC for DNA is 0.1 μg L^?1. Mitochondrial activity showed a strong hormetic stimulation of a surviving spore population (LOEC 10 μg L^?1). Changes were not observed in chlorophyll autofluorescence. Environmental concentrations of venlafaxine can be deleterious for the development of significant populations of sensitive individuals in riparian ecosystems.     

Source apportionment of wintertime secondary organic aerosol during the California regional PM10/PM2.5 air quality study

The UCD/CIT air quality model with the Caltech Atmospheric Chemistry Mechanism (CACM) was used to predict source contributions to secondary organic aerosol (SOA) formation in the San Joaquin Valley (SJV) from December 15, 2000 to January 7, 2001. The predicted 24-day average SOA concentration had a maximum value of 4.26 μg m^?3 50 km southwest of Fresno. Predicted SOA concentrations at Fresno, Angiola, and Bakersfield were 2.46 μg m^?3, 1.68 μg m^?3, and 2.28 μg m^?3, respectively, accounting for 6%, 37%, and 4% of the total predicted organic aerosol. The average SOA concentration across the entire SJV was 1.35 μg m^?3, which accounts for approximately 20% of the total predicted organic aerosol. Averaged over the entire SJV, the major SOA sources were solvent use (28% of SOA), catalyst gasoline engines (25% of SOA), wood smoke (16% of SOA), non-catalyst gasoline engines (13% of SOA), and other anthropogenic sources (11% of SOA). Diesel engines were predicted to only account for approximately 2% of the total SOA formation in the SJV because they emit a small amount of volatile organic compounds relative to other sources. In terms of SOA precursors within the SJV, long-chain alkanes were predicted to be the largest SOA contributor, followed by aromatic compounds. The current study identifies the major known contributors to the SOA burden during a winter pollution episode in the SJV, with further enhancements possible as additional formation pathways are discovered.     

Density of foliage mass and area in the boreal forest cover in Finland,with applications to the estimation of monoterpene and isoprene emissions

The distribution of the density of foliage mass and area in forest canopies throughout Finland (60–70°N) were determined on the basis of the permanent sample plots used in the Finnish National Forest Inventory. These parameters were linked to the long-term monthly mean air temperatures for 1961–1990, which had been converted to hourly temperature and radiation values with the help of a weather simulator in order to calculate the spatial distribution of mean yearly emissions of monoterpene and isoprene over Finland. The mean total density of foliage mass in southern Finland (60°⩽latitude<65°N) was around 500 g m⁻², equivalent to 4–5 m² of total foliage area per m² of land area. In northern Finland (65°⩽latitude<70°N), the maximum values remained below 200–300 g m⁻², or 2–3 m² m⁻². The highest values were achieved in forests dominated by mature Norway spruces. The higher temperatures and longer growing season in southern Finland led to greater emissions than in the rest of the country. Total annual emissions of monoterpene were 1070 kg km⁻² yr⁻¹ in southern Finland and 460 kg km⁻² yr⁻¹ in the north, and those of isoprene from Norway spruce canopies 150 and 40 kg km⁻² yr⁻¹, respectively.     

Five years of formaldehyde and acetaldehyde monitoring in the Rio de Janeiro downtown area – Brazil

The fuel matrix used in Brazil is unique around the world. The intensive use of hydrated ethanol, gasohol (gasoline with 25% v/v of ethanol), compressed natural gas (CNG), and biodiesel leads to a peculiar composition of the urban atmosphere. From 1998 to 2002 an increase in formaldehyde levels was observed and since then, a reduction. This work presents a monitoring campaign that was executed from March 2004 to February 2009 by sampling at early morning on every sunny Wednesday for a total of 183 samples. The results indicate a strong reduction in formaldehyde levels from 2004 (average of 135.8 μg m^?3 with SD 28.4 μg m^?3) to 2009 (average of 49.3 μg m^?3 with SD 27.4 μg m^?3). The levels of acetaldehyde showed a slight reduction from 2004 (average of 34.9 μg m^?3 with SD 8.0 μg m^?3) to 2009 (average of 26.8 μg m^?3 with SD 11.5 μg m^?3). Comparing the results with the concurrent evolution of the fleet and of fuel composition indicates that the observed formaldehyde levels could be associated with the increase in ethanol use and in CNG use by engines with improved technology over the first converted CNG engines. Modelling studies using the OZIPR trajectory model and the SAPRC chemical mechanism indicate that formaldehyde is the main ozone precursor in Rio de Janeiro and acetaldehyde is the forth one.