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The Rim Fire was one of the largest wildfires in California history, burning over 250,000 acres during August and September 2013 affecting air quality locally and regionally in the western U.S. Routine surface monitors, remotely sensed data, and aircraft based measurements were used to assess how well the Community Multiscale Air Quality (CMAQ) photochemical grid model applied at 4 and 12 km resolution represented regional plume transport and chemical evolution during this extreme wildland fire episode. Impacts were generally similar at both grid resolutions although notable differences were seen in some secondary pollutants (e.g., formaldehyde and peroxyacyl nitrate) near the Rim fire. The modeling system does well at capturing near-fire to regional scale smoke plume transport compared to remotely sensed aerosol optical depth (AOD) and aircraft transect measurements. Plume rise for the Rim fire was well characterized as the modeled plume top was consistent with remotely sensed data and the altitude of aircraft measurements, which were typically made at the top edge of the plume. Aircraft-based lidar suggests O 3 downwind in the Rim fire plume was vertically stratified and tended to be higher at the plume top, while CMAQ estimated a more uniformly mixed column of O 3 . Predicted wildfire ozone (O 3 ) was overestimated both at the plume top and at nearby rural and urban surface monitors. Photolysis rates were well characterized by the model compared with aircraft measurements meaning aerosol attenuation was reasonably estimated and unlikely contributing to O 3 overestimates at the top of the plume. Organic carbon was underestimated close to the Rim fire compared to aircraft data, but was consistent with nearby surface measurements. Periods of elevated surface PM 2.5 at rural monitors near the Rim fire were not usually coincident with elevated O 3 ., (Published by Elsevier B.V.)

The proposed revision of the United States (US) air quality standard for ozone will result in violations in sparsely populated remote rural areas in the Western US. Replicating air quality as measured at surface monitoring sites by modeling is particularly difficult in this region due to complex terrain, poorly represented in regional and global models, and uncertainties in emission rates and timing at all scales (locally as well as hundreds to thousands of km upwind). As an alternative method, a fully empirical, receptor-based scheme using in situ aerosol composition and simple meteorological variables to simulate ozone (O3) measurements was tested and found to produce O3 simulation results comparable in uncertainty to regional modeling, and supporting trajectory-based identification of O3 source regions. This approach was tested using two widely-separated (650 km) high altitude (approx. 2 km above sea level) monitoring sites, Lassen Volcanic National Park, in northern California (LAVO) and Great Basin National Park in eastern Nevada (GRBA). Comparing correlations between observed O3 and aerosols, and examining back-trajectories associated with peak concentrations for the two sites permitted distinguishing among local, distant North American, and Asian sources of particulate matter (PM2.5) and O3. This analysis indicates that anthropogenic enhancement of O3 at LAVO is primarily due to transport from Asia. Asia is also the dominant source of anthropogenic O3 at GRBA in spring, but regional North American sources of O3 appear to drive additional ozone peaks in late summer and fall at this more interior site., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The purpose of this study is to investigate the impact of using an ensemble Kalman filter (EnKF) on air quality simulations in the California-Mexico border region on two days (May 30 and June 04, 2010) during Cal-Mex 2010. The uncertainties in ozone (O3) and aerosol simulations in the border area due to the meteorological initial uncertainties were examined through ensemble simulations. The ensemble spread of surface O3 averaged over the coastal region was less than 10ppb. The spreads in the nitrate and ammonium aerosols are substantial on both days, mostly caused by the large uncertainties in the surface temperature and humidity simulations. In general, the forecast initialized with the EnKF analysis (EnKF) improved the simulation of meteorological fields to some degree in the border region compared to the reference forecast initialized with NCEP analysis data (FCST) and the simulation with observation nudging (FDDA), which in turn leading to reasonable air quality simulations. The simulated surface O3 distributions by EnKF were consistently better than FCST and FDDA on both days. EnKF usually produced more reasonable simulations of nitrate and ammonium aerosols compared to the observations, but still have difficulties in improving the simulations of organic and sulfate aerosols. However, discrepancies between the EnKF simulations and the measurements were still considerably large, particularly for sulfate and organic aerosols, indicating that there are still ample rooms for improvement in the present data assimilation and/or the modeling systems., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Unlabelled: Consumer products and building materials emit a number of semivolatile organic compounds (SVOCs) in the indoor environment. Because indoor SVOCs accumulate in dust, we explore the use of dust to determine source strength and report here on analysis of dust samples collected in 30 US homes for six phthalates, four personal care product ingredients, and five flame retardants. We then use a fugacity-based indoor mass balance model to estimate the whole-house emission rates of SVOCs that would account for the measured dust concentrations. Di-2-ethylhexyl phthalate (DEHP) and di-iso-nonyl phthalate (DiNP) were the most abundant compounds in these dust samples. On the other hand, the estimated emission rate of diethyl phthalate is the largest among phthalates, although its dust concentration is over two orders of magnitude smaller than DEHP and DiNP. The magnitude of the estimated emission rate that corresponds to the measured dust concentration is found to be inversely correlated with the vapor pressure of the compound, indicating that dust concentrations alone cannot be used to determine which compounds have the greatest emission rates. The combined dust-assay modeling approach shows promise for estimating indoor emission rates for SVOCs., Practical Implications: The combined dust-assay modeling approach in this study can be used to predict the source strength of indoor released compounds, integrating emissions from consumer products, building materials, and other home furnishings. Our findings show that estimated emission rates are closely related to not only the level of compounds on dust, but also the vapor pressure of the compound. Thus, a fugacity-based indoor mass balance model and measured dust concentrations can be used to estimate the whole-house emission rates from all sources in actual indoor settings, when individual sources of emissions are unknown., (© 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

The Western Airborne Contaminants Assessment Project showed that USA National Parks had fish mercury (Hg) concentrations above threshold concentrations set for wildlife. Since significant areas of the Western USA are arid, we hypothesized that dry deposition would be important. The primary question was whether sources of Hg were local and thus, easily addressed, or regional (from within the United States), or global (long range transport), and more difficult to address. To investigate this, surrogate surfaces and passive samplers for the measurement of GOM deposition and concentration, respectively, were deployed from the coast of California to the eastern edge of Nevada. Meteorological data, back trajectory modeling, and ozone concentrations were applied to better understand potential sources of Hg. Lowest seasonal mean Hg deposition (0.2 to 0.4 ng m(-2)h(-1)) was observed at low elevation (<100 m) Pacific Coast sites. Highest values were recorded at Lick Observatory, a high elevation coastal site (1,279 m), and Great Basin National Park (2,062 m) in rural eastern Nevada (1.5 to 2.4 ng m(-2)h(-1)). Intermediate values were recorded in Yosemite and Sequoia National Parks (0.9 to 1.2 ng m(-2)h(-1)). Results indicate that local, regional and global sources of air pollution, specifically oxidants, are contributing to observed deposition. At Great Basin National Park air chemistry was influenced by regional urban and agricultural emissions and free troposphere inputs. Dry deposition contributed ~2 times less Hg than wet deposition at the coastal locations, but 3 to 4 times more at the higher elevation sites. Based on the spatial trends, oxidation in the marine boundary layer or ocean sources contributed ~0.4 ng m(-2)h(-1) at the coastal locations. Regional pollution and long range transport contributed 1 to 2 ng m(-2)h(-1) to other locations, and the source of Hg is global and as such, all sources are important to consider., (© 2013.)

The interrelationships between hydrologically driven evolution of legacy landscapes downstream of major mining districts and the contamination of lowland ecosystems are poorly understood over centennial time scales. Here, we demonstrate within piedmont valleys of California's Sierra Nevada, through new and historical data supported by modeling, that anthropogenic fans produced by 19th century gold mining comprise an episodically persistent source of sediment-adsorbed Hg to lowlands. Within the enormous, iconic Yuba Fan, we highlight (i) an apparent shift in the relative processes of fan evolution from gradual vertical channel entrenchment to punctuated lateral erosion of fan terraces, thus enabling entrainment of large volumes of Hg-laden sediment during individual floods, and (ii) systematic intrafan redistribution and downstream progradation of fan sediment into the Central Valley, triggered by terrace erosion during increasingly long, 10-y flood events. Each major flood apparently erodes stored sediment and delivers to sensitive lowlands the equivalent of ~10-30% of the entire postmining Sierran Hg mass so far conveyed to the San Francisco Bay-Delta (SFBD). This process of protracted but episodic erosion of legacy sediment and associated Hg is likely to persist for >10(4) y. It creates, within an immense swath of river corridor well upstream of the SFBD, new contaminated floodplain surfaces primed for Hg methylation and augments/replenishes potential Hg sources to the SFBD. Anticipation, prediction, and management of toxic sediment delivery, and corresponding risks to lowland ecology and human society globally, depend on the morphodynamic stage of anthropogenic fan evolution, synergistically coupled to changing frequency of and duration extreme floods.

Agriculturally impacted ecosystems can be a source of the greenhouse gas, nitrous oxide (N(2)O); yet in situ measurements of N(2)O fluxes are sparse, particularly in streams and rivers. Dissolved N(2)O was measured from 9 sites over a 13-month period and a gas exchange model was used to predict N(2)O fluxes. N(2)O fluxes were measured at 4 sites on 7 sampling dates using floating chambers. In addition, dissolved N(2)O in porewaters was measured at 4 sites at various depths from 2 to 30 cm. Dissolved N(2)O-N concentrations in surface waters (0.31-1.60 μg L(-1)) varied seasonally with highest concentrations in late fall and early summer and lowest in winter. Estimated N(2)O-N fluxes (26.2-207 μg m(-2) hr(-1)) were in relative agreement with measured N(2)O fluxes using floating chambers (9.5-372 μg m(-2) hr(-1)) and correlated strongly with temperature and nitrate concentrations (R(2) = 0.86). Maximum dissolved N(2)O-N:NO(3)(-)-N ratios were higher in sediment-porewaters at 0.16, compared to surface waters (0.010). The calculated EF5-r value (mean = 0.0028; range = 0.0012-0.0069) was up to 3 times greater than the current IPCC EF5-r emissions factor (0.0025 kg N(2)O-N emitted per kg of NO(3)(-)-N leached). The highest EF5-r values were found in the high-flow sampling events when dissolved N(2)O and NO(3)(-) concentrations were low, highlighting potential constraints in the IPCC methodology for large rivers.

As a result of extensive gold and silver mining in the Mojave Desert, southern California, mine wastes and tailings containing highly elevated arsenic (As) concentrations remain exposed at a number of former mining sites. Decades of weathering and erosion have contributed to the mobilization of As-enriched tailings, which now contaminate surrounding communities. Fluvial transport plays an intermittent yet important and relatively undocumented role in the migration and dispersal of As-contaminated mine wastes in semi-arid climates. Assessing the contribution of fluvial systems to tailings mobilization is critical in order to assess the distribution and long-term exposure potential of tailings in a mining-impacted environment. Extensive sampling, chemical analysis, and geospatial mapping of dry streambed (wash) sediments, tailings piles, alluvial fans, and rainwater runoff at multiple mine sites have aided the development of a conceptual model to explain the fluvial migration of mine wastes in semi-arid climates. Intense and episodic precipitation events mobilize mine wastes downstream and downslope as a series of discrete pulses, causing dispersion both down and lateral to washes with exponential decay behavior as distance from the source increases. Accordingly a quantitative model of arsenic concentrations in wash sediments, represented as a series of overlapping exponential power-law decay curves, results in the acceptable reproducibility of observed arsenic concentration patterns. Such a model can be transferable to other abandoned mine lands as a predictive tool for monitoring the fate and transport of arsenic and related contaminants in similar settings. Effective remediation of contaminated mine wastes in a semi-arid environment requires addressing concurrent changes in the amounts of potential tailings released through fluvial processes and the transport capacity of a wash.

Unlabelled: The effects of storage conditions on the lipid deterioration in California almond nuts and sliced were studied. Natural whole almonds with or without polyethylene (PE) packaging and blanched whole almonds and sliced with PE packaging were stored in 10 different storage conditions which were combinations of different temperatures and relative humidity levels. The peroxide values (PVs), iodine values (IVs), and free fatty acids (FFAs) were monitored during the storage. The PVs in the natural samples did not change noticeably whereas the blanched samples changed greatly, indicating that skins may have played a significant role. The IVs decreased slightly in the 1st 150 d of storage and then leveled off. The slightly faster changes in IVs in the blanched samples coincided with the greater changes in PVs in the blanched samples. The natural samples exhibited much higher FFA levels than the blanched samples after storage. In general, FFA increased with increasing storage time, temperature, and humidity. Highest levels of FFA were observed in the samples stored at high temperature and high humidity., Practical Application: The results reported in this article provide useful information that almond producers and processors could use to develop their storage and transport processes., (© 2012 Institute of Food Technologists®)

A three-dimensional air quality model with 8 km horizontal resolution was applied to estimate the summertime ozone (O(3)) production from mobile sources and fermented livestock feed in California's San Joaquin Valley (SJV) during years 2000, 2005, 2010, 2015, and 2020. Previous studies have estimated that animal feed emissions of volatile organic compounds (VOCs) have greater O(3) formation potential than mobile-source VOC emissions when averaging across the entire SJV. The higher spatial resolution in the current study shows that the proximity of oxides of nitrogen (NO(x)) and VOC emissions from mobile sources enhances their O(3) formation potential. Livestock feed VOC emissions contributed 3-4 ppb of peak O(3) (8-h average) in Tulare County and 1-2 ppb throughout the remainder of the SJV during the CCOS 2000 July-August episode. In total, livestock feed contributed ~3.5 tons of the ground level peak O(3) (8 h average) in the SJV region, and mobile VOC contributed ~12 tons in this episode. O(3) production from mobile sources is declining over time in response to emissions control plans that call for cleaner fuels and engines with advanced emissions controls. Projecting forward to the year 2020, mobile-source VOC emissions are predicted to produce ~3 tons of the ground level peak O(3)(8-h average) and livestock feed VOC emissions are predicted to contribute ~2.5 tons making these sources nearly equivalent.

Background: Previous studies reported adverse impacts of traffic-related air pollution exposure on pregnancy outcomes. Yet, little information exists on how effect estimates are impacted by the different exposure assessment methods employed in these studies., Objectives: To compare effect estimates for traffic-related air pollution exposure and preeclampsia, preterm birth (gestational age less than 37 weeks), and very preterm birth (gestational age less than 30 weeks) based on four commonly used exposure assessment methods., Methods: We identified 81,186 singleton births during 1997-2006 at four hospitals in Los Angeles and Orange Counties, California. Exposures were assigned to individual subjects based on residential address at delivery using the nearest ambient monitoring station data [carbon monoxide (CO), nitrogen dioxide (NO(2)), nitric oxide (NO), nitrogen oxides (NO(x)), ozone (O(3)), and particulate matter less than 2.5 (PM(2.5)) or less than 10 (PM(10))μm in aerodynamic diameter], both unadjusted and temporally adjusted land-use regression (LUR) model estimates (NO, NO(2), and NO(x)), CALINE4 line-source air dispersion model estimates (NO(x) and PM(2.5)), and a simple traffic-density measure. We employed unconditional logistic regression to analyze preeclampsia in our birth cohort, while for gestational age-matched risk sets with preterm and very preterm birth we employed conditional logistic regression., Results: We observed elevated risks for preeclampsia, preterm birth, and very preterm birth from maternal exposures to traffic air pollutants measured at ambient stations (CO, NO, NO(2), and NO(x)) and modeled through CALINE4 (NO(x) and PM(2.5)) and LUR (NO(2) and NO(x)). Increased risk of preterm birth and very preterm birth were also positively associated with PM(10) and PM(2.5) air pollution measured at ambient stations. For LUR-modeled NO(2) and NO(x) exposures, elevated risks for all the outcomes were observed in Los Angeles only--the region for which the LUR models were initially developed. Unadjusted LUR models often produced odds ratios somewhat larger in size than temporally adjusted models. The size of effect estimates was smaller for exposures based on simpler traffic density measures than the other exposure assessment methods., Conclusion: We generally confirmed that traffic-related air pollution was associated with adverse reproductive outcomes regardless of the exposure assessment method employed, yet the size of the estimated effect depended on how both temporal and spatial variations were incorporated into exposure assessment. The LUR model was not transferable even between two contiguous areas within the same large metropolitan area in Southern California., (Copyright © 2011 Elsevier Inc. All rights reserved.)

An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment. Therefore, additional study is required to evaluate the full regulatory implications of upgrading air quality models to SAPRC07.

The San Joaquin Valley (SJV) in California currently experiences some of the highest surface ozone (O(3)) concentrations in the United States even though it has a population density that is an order of magnitude lower than many urban areas with similar ozone problems. Previously unrecognized agricultural emissions may explain why O(3) concentrations in the SJV have not responded to traditional emissions control programs. In the present study, the ozone formation potentials (OFP) of livestock feed emissions were measured on representative field samples using a transportable smog chamber. Seven feeds were considered: cereal silage (wheat grain and oat grain), alfalfa silage, corn silage, high moisture ground corn (HMGC), almond shells, almond hulls, and total mixed ration (TMR = 55% corn silage, 16% corn grain, 8% almond hulls, 7% hay, 7% bran + seeds, and 5% protein + vitamins + minerals). The measured short-term OFP for each gram of reactive organic gas (ROG) emissions from all livestock feed was 0.17-0.41 g-O(3) per g-ROG. For reference, OFP of exhaust from light duty gasoline powered cars under the same conditions is 0.69 +/- 0.15 g-O(3) per g-ROG. Model calculations were able to reproduce the ozone formation from animal feeds indicating that the measured ROG compounds account for the observed ozone formation (i.e., ozone closure was achieved). Ethanol and other alcohol species accounted for more than 50% of the ozone formation for most types of feed. Aldehydes were also significant contributors for cereal silage, high moisture ground corn, and total mixed ration. Ozone production calculations based on feed consumption rates, ROG emissions rates, and OFP predict that animal feed emissions dominate the ROG contributions to ozone formation in the SJV with total production of 25 +/- 10 t O(3) day(-1). The next most significant ROG source of ozone production in the SJV is estimated to be light duty vehicles with total production of 14.3 +/- 1.4 t O(3) day(-1). The majority of the animal feed ozone formation is attributed to corn silage. Future work should be conducted to reduce the uncertainty of ROG emissions from animal feeds in the SJV and to include this significant source of ozone formation in regional airshed models.

A quasi-two-dimensional model is presented for simulating transport and transformation of contaminant species in river waters and sediments, taking into account the effect of both biotic and abiotic geochemical reactions on the contaminant fate and mobility. The model considers the downstream transport of dissolved and sediment-associated species, and the mass transfer with bed sediments due to erosion and resuspension, using linked advection-dispersion-reaction equations. The model also couples both equations to the reactive transport within bed sediment phases. This is done by the use of a set of vertical one-dimensional columns representing sediment layers that take into account the reactive transport of chemicals, burial, sorption/desorption to/from the solid phase, and the diffusive transport of aqueous species. Kinetically-controlled reversible solid-water mass exchange models are adopted to simulate interactions between suspended sediments and bulk water, as well as the mass exchange between bed sediments and pore water. An innovative multi-time step approach is used to model the fully kinetic nonlinear reaction terms using a non-iterative explicit method. This approach enables the model to handle fast and near-equilibrium reactions without a significant increase in computational burden. At the end, two demonstration cases are simulated using the model, including transport of a sorbing, non-reactive trace metal and nitrogen cycling, both in the Colusa Basin Drain in the Central Valley of California., (Copyright 2009 Elsevier B.V. All rights reserved.)

Exposure to lead in paint or lead residues in house dust and soil is one of the leading environmental risks to the health of children in the United States. Components of photochemical smog can increase the degradation of binders in lead paint, leading to increased release of lead pigment granules to hands in surface contact or for deposition in house dust and soil. This study uses photochemical air quality modeling to map areas susceptible to increased lead paint degradation as a result of photochemical atmospheric pollutants to prioritize areas of concern. Typical air quality episodes in the South Coast Air Basin of California (SoCAB) are modeled for the 1970s, 1980s, and 1990s. Results indicate that large areas of the SoCAB were susceptible to atmospheric-driven accelerated lead paint degradation. Inner city urban areas from central Los Angeles to Azusa and most of Orange County had the highest susceptibility to accelerated lead paint degradation, followed by inland locations near the San Bernardino Mountains. This study identifies photochemical oxidant gases as contributors to greater lead release from indoor painted surfaces in urban areas.

Emission factors for black carbon (BC) and particle number (PN) were measured from 226 individual heavy-duty (HD) diesel trucks driving through a 1-km-long California highway tunnel in August 2006. Emission factors were based on concurrent increases in BC, PN, and CO2 concentrations (measured at 1 Hz) that corresponded to the passage of individual HD trucks. The distributions of BC and PN emission factors from individual HD trucks are skewed, meaning that a large fraction of pollution comes from a small fraction of the in-use vehicle fleet. The highest-emitting 10% of trucks were responsible for approximately 40% of total BC and PN emissions from all HD trucks. BC emissions were log-normally distributed with a mean emission factor of 1.7 g kg(-1) and maximum values of approximately 10 g kg(-1). Corresponding values for PN emission factors were 4.7 x 10(15) and 4 x 10(16) # kg(-1). There was minimal overlap among high-emitters of these two pollutants: only 1 of the 226 HD trucks measured was found to be among the highest 10% for both BC and PN. Monte Carlo resampling of the distribution of BC emission factors observed in this study revealed that uncertainties (1sigma) in extrapolating from a random sample of n HD trucks to a population mean emission factor ranged from +/- 43% for n=10 to +/- 8% for n=300, illustrating the importance of vehicle sample sizes in emissions studies. When n=10, sample means are more likely to be biased due to misrepresentation of high-emitters. As vehicles become cleaner on average in the future, skewness of the emissions distributions will increase, and thus sample sizes needed to extrapolate reliably from a subset of vehicles to the entire in-use vehicle fleet will become more of a challenge.

Fire suppression in Sierran ecosystems creates a substantial wildfire hazard and may exacerbate nutrient inputs into Lake Tahoe by allowing the buildup of O horizon material, which serves as a source for high N and P concentrations in runoff water. The purpose of this study was to evaluate the effects of biomass reduction using cut-to-length mechanical harvest followed by chipping and controlled burning on surface runoff volume and water quality. Based on previous findings regarding N and P leaching flux and soil solution concentrations, we hypothesized that controlled burning and/or mechanical harvest with residue chipping does not increase inorganic N, P, and S concentrations in overland flow. Runoff, snowmelt, and rainfall were collected, volume measurements were taken, and samples were analyzed for NO(3)-N, NH(4)-N, PO(4)-P, and SO(4). Runoff volume, season, and year were identified as important parameters influencing overland flow nutrient concentrations and loads. Higher nutrient concentrations were commonly associated with summer rather than winter runoff, but the opposite was true for nutrient loads due to the higher runoff volumes. Treatment (unharvested, harvested, unburned, burned) effect was a strong predictor for discharge loads of NO(3)-N and SO(4) but was a weak predictor for PO(4)-P. Discharge loads of NO(3)-N and SO(4) were greater for the unburned harvested and the burned unharvested treatments than for the unburned, unharvested control sites or the burned and harvested combined treatment. Although mechanical harvest and/or controlled burning had a small initial impact on increased nutrient loading, the effects were minimal compared with background levels. Hence, these management practices may have the potential to improve forest health without the danger of large-magnitude nutrient mobilization and degradation of runoff water quality found with wildfire.

Tracer studies are combined with a three-dimensional (3-D) numerical modeling study to provide a robust description of hydrodynamic and particle transport in Clear Lake, a multi-basin, polymictic lake in northern California, USA. The focus is on the mechanisms of transport of contaminants away from the vicinity of the Sulphur Bank Mercury Mine and out of the Oaks Arm to the rest of the lake and the hydraulic connection existing among the sub-basins of the lake. Under stratified conditions, the rate of spreading of the tracer was found to be large. In less than a week the tracer spread from the eastern end of the Oaks Arm to the other basins. Under non-stratified conditions, the tracer spread more slowly and had a concentration that gradually diminished with distance from the injection location. The numerical results showed that the mechanisms accounting for these observed patterns occur in pulses, with maximum rates coinciding with the stratified periods. Stratification acts first to enhance the currents by inhibiting vertical momentum mixing and decoupling the surface currents from bottom friction. The diversity of the flow structures that results from the interaction of the wind and the density fields in the lake is responsible for the high dispersion rates. Contaminants originating in the Oaks Arm are shown to be transported into the Lower Arm following the surface currents and into the Upper Arm mainly through the bottom currents. It was also shown that, under stratified conditions, both the baroclinic (density driven) gradients and the wind forcing act jointly to exacerbate the interbasin exchange.

Two thermodynamic equilibrium models were applied to estimate changes in mean airborne fine particle (PM2.5) mass concentrations that could result from changes in ambient concentrations of sulfate, nitric acid, or ammonia in the southeastern United States, the midwestern United States, and central California. Pronounced regional differences were found. Southeastern sites exhibited the lowest current mean concentrations of nitrate, and the smallest predicted responses of PM2.5 nitrate and mass concentrations to reductions of nitric acid, which is the principal reaction product of the oxidation of nitrogen dioxide (NO2) and the primary gas-phase precursor of fine particulate nitrate. Weak responses of PM2.5 nitrate and mass concentrations to changes in nitric acid levels occurred even if sulfate concentrations were half of current levels. The midwestern sites showed higher levels of fine particulate nitrate, characterized by cold-season maxima, and were projected to show decreases in overall PM levels following decreases of either sulfate or nitric acid. For some midwestern sites, predicted PM2.5 nitrate concentrations increased as modeled sulfate levels declined, but sulfate reductions always reduced the predicted fine PM mass concentrations; PM2.5 nitrate concentrations became more sensitive to reductions of nitric acid as modeled sulfate concentrations were decreased. The California sites currently have the highest mean concentrations of fine PM nitrate and the lowest mean concentrations of fine PM sulfate. Both the estimated PM2.5 nitrate and fine mass concentrations decreased in response to modeled reductions of nitric acid at all California sites. The results indicate important regional differences in expected PM2.5 mass concentration responses to changes in sulfate and nitrate precursors. Analyses of ambient data, such as described here, can be a key part of weight of evidence (WOE) demonstrations for PM2.5 attainment plans. Acquisition of the data may require special sampling efforts, especially for PM2.5 precursor concentration data.

An adjoint method was used to investigate the sensitivity of peak ozone at selected sites in Southern California to nearly 900 model inputs including surface emissions, reaction rate coefficients, dry deposition velocities, boundary conditions, and initial conditions. Simulations showed large changes in ozone and ozone sensitivities at three sites investigated between summers 1987 and 1997 due to emission reductions. However, only small changes in ozone and ozone sensitivities were predicted between 1997 and 2010. Sensitivities of the differences in ozone between simulations with different emission scenarios were calculated and compared to sensitivities of ozone in each simulation. In some cases, the sensitivities of ozone differences were smaller than those of ozone itself, but in other cases, such as when the sensitivityto NOx emissions changed sign, sensitivities of differences were larger. The adjoint method was most useful for determining when and where model inputs affect, or have the potential to affect, an ozone response. For example, the method was used to plot the spatial distribution of important emission source regions to 1-hour versus 8-hour peak ozone. Changes in the distribution and sign of the adjoint function for emitted species revealed changes in the area of influence of pollutant emissions on peak ozone due to emission controls. The adjoint method provides useful information complementary to that obtained from forward sensitivity analysis methods.

The sorption kinetics and concentration of polychlorinated biphenyls (PCBs) in historically polluted sediment is modeled to assess a remediation strategy based on in situ PCB sequestration by mixing with activated carbon (AC). We extend our evaluation of a model based on intraparticle diffusion by including a biomimetic semipermeable membrane device (SPMD) and a first-order degradation rate for the aqueous phase. The model predictions are compared with the previously reported experimental PCB concentrations in the bulk water phase and in SPMDs. The simulated scenarios comprise a marine and a freshwater sediment, four PCB congeners, two AC grain sizes, four doses of AC, and comparison with laboratory experiments for up to 540 days of AC amendment slowly mixed with sediment. The model qualitatively reproduces the observed shifts in the PCB distribution during repartitioning after AC amendment but systematically overestimates the overall effect of the treatment in reducing aqueous and SPMD concentrations of PCBs by a factor of 2-6. For our AC application in sediment, competitive sorption of the various solutes apparently requires a reduction by a factor of 16 of the literature values for the AC-water partitioning coefficient measured in pure aqueous systems. With this correction, model results and measurements agree within a factor of 3. We also discuss the impact of the nonlinearity of the AC sorption isotherm and first-order degradation in the aqueous phase. Regular mixing of the sediment accelerates the benefit of the proposed amendment substantially. But according to our scenario, after AC amendment is homogeneously mixed into the sediment and then left undisturbed, aqueous PCB concentrations tend toward the same reduction after approximately 5 or more years.

Chlorine maintenance in distribution systems is an issue for water suppliers. The complex pipe geometry in distribution systems, the dynamic flow conditions experienced within them, and the varied nature of chlorine's reactivity make it difficult to predict chlorine levels throughout a water system. Computer-based mathematical models of water quality transport and fate within distribution systems offer a promising tool for predicting chlorine in a cost-effective manner. Nevertheless, the use of water quality models can only be effective and reliable when both hydraulics and the mechanisms of chlorine dissipation within the water system are properly defined. Bulk water decay can be measured experimentally. However, wall reaction rates are more complex to determine and must be deduced from field measurement by comparison with simulation results. The simulation-optimization model presented in this paper provides an effective tool to simplify the chlorine decay model calibration process that is often tedious. The optimization tool is based on the weighted-least-squares method solved by Gauss-Newton technique. Application of the model onto a real-life system shows that quantity, quality and location of measurement nodes play an important role in estimation of parameters.

Evaporative loss of particulate matter (with aerodynamic diameter < 2.5 microm, [PM2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from < 10% during cold months to > 80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM2.5 acquired on Teflon-membrane filters, measured PM2.5 mass was 8-16% lower than actual PM2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM2.5 was as much as 32-44% lower than actual PM2.5 at three California Central Valley locations.

Methods were developed to estimate the potential impacts and natural resource damages resulting from oil spills using probabilistic modeling techniques. The oil fates model uses wind data, current data, and transport and weathering algorithms to calculate mass balance of fuel components in various environmental compartments (water surface, shoreline, water column, atmosphere, sediments, etc.), oil pathway over time (trajectory), surface distribution, shoreline oiling, and concentrations of the fuel components in water and sediments. Exposure of aquatic habitats and organisms to whole oil and toxic components is estimated in the biological model, followed by estimation of resulting acute mortality and ecological losses. Natural resource damages are based on estimated costs to restore equivalent resources and/or ecological services, using Habitat Equivalency Analysis (HEA) and Resource Equivalency Analysis (REA) methods. Oil spill modeling was performed for two spill sites in central San Francisco Bay, three spill sizes (20th, 50th, and 95th percentile volumes from tankers and larger freight vessels, based on an analysis of likely spill volumes given a spill has occurred) and four oil types (gasoline, diesel, heavy fuel oil, and crude oil). The scenarios were run in stochastic mode to determine the frequency distribution, mean and standard deviation of fates, impacts, and damages. This work is significant as it demonstrates a statistically quantifiable method for estimating potential impacts and financial consequences that may be used in ecological risk assessment and cost-benefit analyses. The statistically-defined spill volumes and consequences provide an objective measure of the magnitude, range and variability of impacts to wildlife, aquatic organisms and shorelines for potential spills of four oil/fuel types, each having distinct environmental fates and effects.

Secondary airborne particulate matter formed from gas-phase pollutants contributes significantly to the most severe particulate air quality events that occur in the United States each year. In this study, a mechanistic air quality model is demonstrated that can predict source contributions to the size distribution of secondary airborne particulate matter. Calculations performed for a typical air quality episode in Southern California show that NOx released from diesel engines and catalyst-equipped gasoline engines account for the majority of the secondary particulate nitrate aerosol measured at inland locations. NH3 released from catalyst-equipped gasoline engines, farm animals, and residential sources account for the majority of the secondary particulate ammonium ion at inland locations in the region. When both tailpipe and road dust emissions are considered, transportation sources dominate the size distribution of total (primary plus secondary) airborne particulate matter in the South Coast Air Basin during the episode studied. These findings suggest that the public health risk associated with air pollution released from transportation sources is significant relative to other public health threats such as traffic accidents.

A mass balance for lead for the year 1989 in the South Coast Air Basin has inputs to the atmosphere of 600 +/- 190 kg/day and outputs of 580 +/- 160 kg/day, showing rough agreement. Stationary sources are responsible for only about 5% of the total lead emissions. The bulk of the lead is emitted from vehicles using leaded gasoline (37%) and unleaded gasoline (15%), as well as from resuspension of previously deposited lead on roads (43%). Over half of the total emitted lead deposits on roads and nearby soil, while about one-third is carried out the basin by wind. A small amount, less than 10%, is deposited on surfaces throughout the basin. These percentages are approximately the same as those in a mass balance for the same region calculated for 1972, when lead emissions from leaded gasoline were about a factor of 70 greater than leaded gas emissions in 1989. When the lead emissions are used as inputs to a simple continuously stirred flow reactor model for the basin, reasonable agreement is obtained between calculated and measured concentrations.

The volatilization of volatile organic chemicals during domestic water usage can result in significant indoor air concentrations, and the subsequent inhalation of these contaminants is an important route of exposure. The magnitude of these exposures is highly dependent on the activities undertaken by the exposed individual, as well as the activities of other occupants of the home. The indoor air quality-exposure Model for the Analysis of Volatiles and Residential Indoor Air Quality (MARVIQ) was used to ascertain the impact of water-use activities on the potential contaminant dose to household members. Human time-activity patterns of various population groups were sampled from the California Air Resources Board database, applying distributions of water-use occurrence and water-use duration to each activity based on survey results. Indoor air concentrations in a sample house and the resulting potential inhalation dose to the occupants were computed for different individuals and pairs of individuals to test for exposure and coexposure effects. The simulated daily exposure is well described by a simplified equation that is a function of the amount of time the individual spends in the shower, the bath, and the bathroom; the total water usage in the home; and the fraction of time the individual is at home. These results can be used to identify high-risk populations, individuals, and households. The study also demonstrates the importance of further research on joint time-activity patterns in multiperson households for assessment of exposure and coexposure effects.