Abstract-Agricultural activity in California's Central Valley may be an important source of pesticides that are transported in the air to the Sierra Nevada Mountain Range, USA. Pesticides applied to this intensive crop production area may volatilize under warm temperatures typical of the valley and be transported through the atmosphere to be deposited in the cooler, higher elevation regions of the Sierra Nevada Mountains. To determine the extent of summertime atmospheric transport of pesticides to this region, highvolume air, dry deposition, and surface water samples were collected in the Central Valley and at different elevations in California's Sequoia National Park. Results revealed that the highest residue concentrations were those of compounds with heavy summertime agricultural use. A significant drop in pesticide concentrations in both air and water samples was observed within a few 100-m elevation from the valley; however, levels remained relatively constant between ϳ500 and 2,000 m. Water concentrations from two areas above 3,000 m contained levels less than a tenth as high as those at lower elevations. Possible effects of the pesticides were estimated using measured water concentrations to calculate total exposure of three aquatic species to organophosphate insecticides. Aggregate exposure calculations showed concentrations were well below 96-h LC50 values for rainbow trout and stonefly but concentrations may be harmful to amphipods.

[1] Biogenic volatile organic compound (BVOC) emissions, such as isoprene and terpenes, can be oxidized to form less volatile carbonyls, acids, and multifunctional oxygenated products that may condense to form secondary organic aerosols (SOA). This research was designed to assess the contribution of oxidized BVOC emissions to SOA in coniferous forests by collecting high-volume particulate samples for 6 days and 5 nights in the summer of 2003. The samples were analyzed for acids, carbonyls, polyols and alkanes to quantify oxidized BVOCs. Terpene and isoprene oxidation products were among the most abundant chemical species detected with the exception of hexadecanoic acid, octadecanoic acid and two butyl esters of unknown origin. The terpene oxidation products of pinonic acid, pinic acid, nopinone and pinonaldehyde showed clear diurnal cycles with concentrations two-to eight-fold higher at night. These cycles resulted from the diurnal cycles in gaseous terpene concentrations and lower temperatures that enhanced condensation of semivolatile chemicals onto aerosols. The terpene-derived compounds averaged 157 ± 118 ng/m 3 of particulate organic matter while the isoprene oxidation compounds, namely the 2-methyltetrols and 2-methylglyceric acid, accounted for 53 ± 19 ng/m 3 . Together, the terpene and isoprene oxidation products represented 36.9% of the identified organic mass of 490 ± 95 ng/m 3 . PM 10 organic matter loadings in the region were approximately 2.1 ± 1.2 mg/m 3 , so about 23% of the organic matter was identified and at least 8.6% was oxidized BVOCs. The BVOC oxidation products we measured were significant, but not dominant, contributors to the regional SOA only 75 km downwind of the Sacramento urban area.

Aricultural activity in California's Central Valley may be an important source of pesticides that are transported in the air to the Sierra Nevada Mountain Range, USA. Pesticides applied to this intensive crop production area may volatilize under warm temperatures typical of the valley and be transported through the atmosphere to be deposited in the cooler, higher elevation regions of the Sierra Nevada Mountains. To determine the extent of summertime atmospheric transport of pesticides to this region, high‐volume air, dry deposition, and surface water samples were collected in the Central Valley and at different elevations in California's Sequoia National Park. Results revealed that the highest residue concentrations were those of compounds with heavy summertime agricultural use. A significant drop in pesticide concentrations in both air and water samples was observed within a few 100‐m elevation from the valley; however, levels remained relatively constant between ∼500 and 2,000 m. Water concentrations from two areas above 3,000 m contained levels less than a tenth as high as those at lower elevations. Possible effects of the pesticides were estimated using measured water concentrations to calculate total exposure of three aquatic species to organophosphate insecticides. Aggregate exposure calculations showed concentrations were well below 96‐h LC50 values for rainbow trout and stonefly but concentrations may be harmful to amphipods.

Abstract. We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments -a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) -and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light-and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4-68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72-10.2 µgCg −1 h −1 , depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

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Acrolein, a volatile, unsaturated aldehyde, is a known respiratory toxicant and one of the 188 most hazardous air pollutants identified by the U.S. EPA. A newly developed analytical method was used to determine residential indoor air concentrations of acrolein and other volatile aldehydes in nine homes located in three California counties (Los Angeles, Placer, Yolo). Average indoor air concentrations of acrolein were an order of magnitude higher than outdoor concentrations at the same time. All homes showed similar diurnal patterns in indoor air concentrations, with acrolein levels in evening samples up to 2.5 times higherthan morning samples. These increases were strongly correlated with temperature and cooking events, and homes with frequent, regular cooking activity had the highest baseline (morning) acrolein levels. High acrolein concentrations were also found in newly built, uninhabited homes and in emissions from lumber commonly used in home construction, suggesting indoor contributions from off-gassing and/or secondary formation. The results provide strong evidence that human exposure to acrolein is dominated by indoor air with little contribution from ambient outdoor air.

Acrolein, an unsaturated aldehyde found in both indoor and outdoor air, is considered one of the greatest noncancer health risks of all organic air pollutants. Current methods for determining acrolein often employ sorbent-filled cartridges containing a carbonyl derivatizing agent (e.g., dinitrophenylhydrazine). These methods are of limited use for unsaturated compounds due to the formation of unstable derivatives, coelution of similar compounds, long sample collection times, and ozone interferences that result in poor sensitivity, selectivity, and reproducibility. The goal of this research was to develop an analytical method for determining ppt concentrations of acrolein and other carbonyls in air with short sampling times (10 min). The method uses a mist chamber to collect carbonyls by forming water-soluble carbonyl-bisulfite adducts. The carbonyls are then liberated from the bisulfite, derivatized, and quantified by gas chromatography/electron capture negative ionization mass spectrometry. The method was applied to determine atmospheric acrolein concentrations at three sites in northern California reflecting hemispheric background concentrations, biogenic-dominated regions, and urban environments. The resulting acrolein concentrations were 0.056, 0.089, and 0.29 microg/m3, respectively, which are all above the EPA Reference Concentration of 0.02 microg/m3. The minimum detection limit of 0.012 microg/m3 is below that of other published methods. Methacrolein, methyl vinyl ketone, crotonaldehyde, glyoxal, methyl glyoxal, and benzaldehyde were also quantified.

The atmospheric degradation of three chlorofluorocarbon (CFC) replacement compounds, namely HFC-134a, results in the formation of trifluoroacetic acid (TFA). Concentrations of TFA were determined in precipitation and surface water samples collected in California and Nevada during 1996-1997. Terminal lake systems were found to have concentrations 4-13 times higher than their calculated yearly inputs, providing evidence for accumulation. The results support dry deposition as the primary contributor of TFA to surface waters in arid and semiarid environments. Precipitation samples obtained from three different locations contained 20.7-1530 ng/L with significantly higher concentrations in fogwater (median ) 689 ng/L) over rainwater (median ) 63.7 ng/L). Elevated levels of TFA were observed for rainwater collected in Nevada (median ) 136 ng/L) over those collected in California (median ) 49.5 ng/L), indicating continual uptake and concentration as clouds move from a semiarid to arid climate. Thus several mechanisms exist, including evaporative concentration, vapor-liquid phase partitioning, lowered washout volumes of atmospheric deposition water, and dry deposition, which may lead to elevated concentrations of TFA in atmospheric and surface waters above levels expected from usual rainfall washout.