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The FLUXNET2015 dataset provides ecosystem-scale data on CO2, water, and energy exchange between the biosphere and the atmosphere, and other meteorological and biological measurements, from 212 sites around the globe (over 1500 site-years, up to and including year 2014). These sites, independently managed and operated, voluntarily contributed their data to create global datasets. Data were quality controlled and processed using uniform methods, to improve consistency and intercomparability across sites. The dataset is already being used in a number of applications, including ecophysiology studies, remote sensing studies, and development of ecosystem and Earth system models. FLUXNET2015 includes derived-data products, such as gap-flled time series, ecosystem respiration and photosynthetic uptake estimates, estimation of uncertainties, and metadata about the measurements, presented for the frst time in this paper. In addition, 206 of these sites are for the frst time distributed under a Creative Commons (CC-BY 4.0) license. This paper details this enhanced dataset and the processing methods, now made available as open-source codes, making the dataset more accessible, transparent, and reproducible., European Union (EU), United States Department of Energy (DOE)

The performance of an open-loop wake steering controller is investigated with a new unique set of wind tunnel experiments. A cluster of three scaled wind turbines, placed on a large turntable, is exposed to a turbulent inflow and dynamically changing wind directions, resulting in dynamically varying wake interactions. The changes in wind direction were sourced and scaled from a field-measured time history and mirrored on to the movement of the turntable. Exploiting the known, repeatable and controllable conditions of the wind tunnel, this study investigates the following effects: fidelity of the model used for synthesizing the controller, assumption of steady state vs. dynamic plant behavior, wind direction uncertainty, the robustness of the formulation in regard to this uncertainty, and a finite yaw rate. The results were analyzed for power production of the cluster, fatigue loads and yaw actuator duty cycle. The study highlights the importance of using a robust formulation and plant flow models of appropriate fidelity, and the existence of possible margins for improvement by the use of dynamic controllers.

As wind turbines in a wind farm interact with each other, a control problem arises that has been extensively studied in the literature: how can we optimize the power production of a wind farm as a whole? A traditional approach to this problem is called induction control, in which the power capture of an upstream turbine is lowered for the benefit of downstream machines. In recent simulation studies, an alternative approach, where the induction factor is varied over time, has shown promising results. In this paper, the potential of this dynamic induction control (DIC) approach is further investigated. Only periodic variations, where the input is a sinusoid, are studied. A proof of concept for this periodic DIC approach will be given by the execution of scaled wind tunnel experiments, showing for the first time that this approach can yield power gains in real-world wind farms. Furthermore, the effects on the damage equivalent loads (DEL) of the turbine are evaluated in a simulation environment. These indicate that the increase in DEL on the excited turbine is limited.

Proton-transfer-reaction mass spectrometry (PTR-MS) is a technique that is widely used to detect volatile organic compounds (VOCs) with proton affinities higher than water. However, n-alkanes generally have a lower proton affinity than water and therefore proton transfer (PT) by reaction with H3O+ is not an effective mechanism for their detection. In this study, we developed a method using a conventional PTR-MS to detect n-alkanes by optimizing ion source and drift tube conditions to vary the relative amounts of different primary ions (H3O+, O2+, NO+) in the reaction chamber (drift tube). There are very few studies on O2+ detection of alkanes and the mixed mode has never been proposed before. We determined the optimum conditions and the resulting reaction mechanisms, allowing detection of n-alkanes from n-pentane to n-tridecane. These compounds are mostly emitted by evaporative/combustion process from fossil fuel use. The charge transfer (CT) mechanism observed with O2+ was the main reaction channel for n-heptane and longer n-alkanes, while for n-pentane and n-hexane the main reaction channel was hydride abstraction (HA). Maximum sensitivities were obtained at low E ∕ N ratios (83 Td), low water flow (2 sccm) and high O2+ ∕ NO+ ratios (Uso = 180 V). Isotopic 13C contribution was taken into account by subtracting fractions of the preceding 12C ion signal based on the number of carbon atoms and the natural abundance of 13C (i.e., 5.6 % for n-pentane and 14.5 % for n-tridecane). After accounting for isotopic distributions, we found that PT cannot be observed for n-alkanes smaller than n-decane. Instead, protonated water clusters of n-alkanes (M ⋅ H3O+) species were observed with higher abundance using lower O2+ and higher water cluster fractions. M ⋅ H3O+ species are probably the source for the M + H+ species observed from n-decane to n-tridecane. Normalized sensitivities to O2+ or to the sum of O2++ NO+ were determined to be a good metric with which to compare sensitivities for n-alkane detection between experiments. Double hydride abstraction was observed from the reaction with O2+. Sensitivity to CT increased with carbon chain length from n-pentane to n-dodecane, sensitivity to HA increased from n-heptane to n-dodecane and sensitivity to PT increased from n-decane to n-tridecane. Sensitivity to CT exponentially decreased with molecular ionization energy, which is inversely related to the carbon chain length. We introduce a calibrated fragmentation algorithm as a method to determine the concentrations of n-alkanes and demonstrate its effectiveness using a custom n-alkane mixture and a much more complex oil example representing perhaps the most difficult mixture available for application of the method. We define optimum conditions for using the mixed ionization mode to measure n-alkanes in conventional PTR-MS instruments regardless of whether they are equipped with switchable reagent ion (SRI) capabilities.

Recent observations suggest a large and unknown daytime source of nitrous acid (HONO) to the atmosphere. Multiple mechanisms have been proposed, many of which involve chemistry that reduces nitrogen dioxide (NO2) on some time scale. To examine the NO2 dependence of the daytime HONO source, we compare weekday and weekend measurements of NO2 and HONO in two U.S. cities. We find that daytime HONO does not increase proportionally to increases in same-day NO2, i.e., the local NO2 concentration at that time and several hours earlier. We discuss various published HONO formation pathways in the context of this constraint.

The San Joaquin Valley (SJV) experiences some of the worst ozone air quality in the US, frequently exceeding the California 8 h standard of 70.4 ppb. To improve our understanding of trends in the number of ozone violations in the SJV, we analyze observed relationships between organic reactivity, nitrogen oxides (NO[subscript x]), and daily maximum temperature in the southern SJV using measurements made as part of California at the Nexus of Air Quality and Climate Change in 2010 (CalNex-SJV). We find the daytime speciated organic reactivity with respect to OH during CalNex-SJV has a temperature-independent portion with molecules typically associated with motor vehicles being the major component. At high temperatures, characteristic of days with high ozone, the largest portion of the total organic reactivity increases exponentially with temperature and is dominated by small, oxygenated organics and molecules that are unidentified. We use this simple temperature classification to consider changes in organic emissions over the last and next decade. With the CalNex-SJV observations as constraints, we examine the sensitivity of ozone production (PO[subscript 3]) to future NO[subscript x] and organic reactivity controls. We find that PO[subscript 3] is NO[subscript x]-limited at all temperatures on weekends and on weekdays when daily maximum temperatures are greater than 29 °C. As a consequence, NO[subscript x] reductions are the most effective control option for reducing the frequency of future ozone violations in the southern SJV., California Environmental Protection Agency. Air Resources Board (Contract CARB 08-316), United States. National Aeronautics and Space Administration (Grant NNX10AR36G)

Atmospheric photooxidation of isoprene is an important source of secondary organic aerosol (SOA) and there is increasing evidence that anthropogenic oxidant emissions can enhance this SOA formation. In this work, we use ambient observations of organosulfates formed from isoprene epoxydiols (IEPOX) and methacrylic acid epoxide (MAE) and a broad suite of chemical measurements to investigate the relative importance of nitrogen oxide (NO/NO_2) and hydroperoxyl (HO_2) SOA formation pathways from isoprene at a forested site in California. In contrast to IEPOX, the calculated production rate of MAE was observed to be independent of temperature. This is the result of the very fast thermolysis of MPAN at high temperatures that affects the distribution of the MPAN reservoir (MPAN / MPA radical) reducing the fraction that can react with OH to form MAE and subsequently SOA (F_(MAE formation)). The strong temperature dependence of F_(MAE formation) helps to explain our observations of similar concentrations of IEPOX-derived organosulfates (IEPOX-OS;~1 ng m^(–3)) and MAE-derived organosulfates (MAE-OS;~1 ng m^(–3)) under cooler conditions (lower isoprene concentrations) and much higher IEPOX-OS (~20 ng m^(–3)) relative to MAE-OS (

highlights g rap hical a bstract < We characterize the chemical composition of aerosols collected during CalNex 2010. < We observe changes in the compo- sition of the oligomeric fraction throughout the day. < There were increased numbers of nitrogen-containing compounds at night. < Reactions with ammonia to form imines are possible formation pathways. < Increased numbers of CHO compounds during the day, likely a result of photochemistry. abstract Aerosol samples from the CalNex 2010 field study were analyzed using high-resolution mass spectrometry (HR-MS) coupled toananospraydesorption/electrosprayionization (nano-DESI)source.The sampleswere collected in Bakersfield, CA on June 22-23, 2010. The chemical formulas of over 850 unique molecular species were detected in the mass range of 50e400 m/z using positive mode ESI of aerosol samples in the 0.18e0.32mmsizerange.Ouranalysisfocusedonidentificationoftwomaingroups:compoundscontaining only carbon, hydrogen, and oxygen (CHO), and nitrogen-containing organic compounds (NOC). The NOC accounted for 40% (by number) of the compounds observed in the afternoon, and for 52% in the early morning samples. Bycomparing plausible reactanteproduct pairs, we propose that over 50% of the NOC in each sample could have been formed through reactions transforming carbonyls into imines. The CHO only compounds were dominant in the afternoon suggesting a photochemical source. The average O/C ratios of

Proton transfer reaction mass spectrometry (PTR-MS) is a technique that is widely used to detect volatile organic compounds (VOCs) with proton affinities higher than water. However, n-alkanes generally have a lower proton affinity than water and therefore proton transfer (PT) by reaction with H3O+ is not an effective mechanism for their detection. In this study, we developed a method using a conventional PTR-MS to detect n-alkanes by optimizing ion source and drift tube conditions to vary the relative amounts of different primary ions (H3O+, O2+, NO+) in the reaction chamber (drift tube). We determined the optimum conditions and the resulting reaction mechanisms allowing detection of n-alkanes from n-pentane to n-tridecane. These compounds are mostly emitted by evaporative/combustion process from fossil fuel use. The charge transfer (CT) mechanism observed with O2+, was the main reaction channel for n-heptane and longer n-alkanes, while for n-pentane and n-hexane, the main reaction channel was hydride abstraction (HA). Maximum sensitivities were obtained at low E/N ratios (83 Td), low water flow (2 sccm) and high O2+/NO+ ratios (Uso = 180 V). Isotopic 13C contribution was taken into account by subtracting fractions of the preceding 12C ion signal based on number of carbon atoms and the natural abundance of 13C (i.e. 5.6 % for n-pentane and 14.5 % for n-tridecane). After accounting for isotopic distributions, we found that proton transfer cannot be observed for n-alkanes smaller than n-decane. Instead, protonated water clusters of n-alkanes (M·H3O+) species were observed with higher abundance at lower O2+ and higher water clusters amount fractions. M·H3O+ species are probably the source for M+H+ species observed from n-decane to n-tridecane, via a collision dissociation mechanism. Normalized sensitivities to O2+ or to the sum of O2++NO+ were determined to be a good metric with which to compare sensitivities for n-alkane detection between experiments. Double hydride abstraction was observed from the reaction with O2+. Sensitivities to CT and HA both increased with carbon chain length from n-pentane to n-dodecane while PT sensitivity increased from n-decane to n-tridecane. Sensitivity to charge transfer exponentially decreased with molecular ionization energy which is inversely related to the carbon chain length. We define optimum conditions for using mixed ionization mode to measure n-alkanes in conventional PTR-MS instruments that are not equipped with switchable reagent ions (SRI) capabilities.

A relaxed eddy accumulation (REA) system combined with a nitrous acid (HONO) analyzer was developed to measure atmospheric HONO vertical fluxes. The system consists of three major components: (1) a fast-response sonic anemometer measuring both vertical wind velocity and air temperature, (2) a fast-response controlling unit separating air motions into updraft and downdraft samplers by the sign of vertical wind velocity, and (3) a highly sensitive HONO analyzer based on aqueous long path absorption photometry that measures HONO concentrations in the updrafts and downdrafts. A dynamic velocity threshold (±0.5σw, where σw is a standard deviation of the vertical wind velocity) was used for valve switching determined by the running means and standard deviations of the vertical wind velocity. Using measured temperature as a tracer and the average values from two field deployments, the flux proportionality coefficient, β, was determined to be 0.42 ± 0.02, in good agreement with the theoretical estimation. The REA system was deployed in two ground-based field studies. In the California Research at the Nexus of Air Quality and Climate Change (CalNex) study in Bakersfield, California in summer 2010, measured HONO fluxes appeared to be upward during the day and were close to zero at night. The upward HONO flux was highly correlated to the product of NO2 and solar radiation. During the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX 2009) at Blodgett Forest, California in July 2009, the overall HONO fluxes were small in magnitude and were close to zero. Causes for the different HONO fluxes in the two different environments are briefly discussed.

Sources of methane (CH4) and nitrous oxide (N2O) were investigated using measurements from a site in southeast Bakersfield as part of the CalNex (California at the Nexus of Air Quality and Climate Change) experiment from mid-May to the end of June 2010. Typical daily minimum mixing ratios of CH4 and N2O were higher than daily minima that were simultaneously observed at a mid-oceanic background station (NOAA, Mauna Loa) by approximately 70 ppb and 0.5 ppb, respectively. Substantial enhancements of CH4 and N2O (hourly averages > 500 and > 7 ppb, respectively) were routinely observed, suggesting the presence of large regional sources. Collocated measurements of carbon monoxide (CO) and a range of volatile organic compounds (VOCs) (e.g., straight-chain and branched alkanes, cycloalkanes, chlorinated alkanes, aromatics, alcohols, isoprene, terpenes and ketones) were used with a positive matrix factorization (PMF) source apportionment method to estimate the contribution of regional sources to observed enhancements of CH4 and N2O. The PMF technique provided a "top-down" deconstruction of ambient gas-phase observations into broad source categories, yielding a seven-factor solution. We identified these emission source factors as follows: evaporative and fugitive; motor vehicles; livestock and dairy; agricultural and soil management; daytime light and temperature driven; non-vehicular urban; and nighttime terpene biogenics and anthropogenics. The dairy and livestock factor accounted for the majority of the CH4 (70–90 %) enhancements during the duration of experiments. The dairy and livestock factor was also a principal contributor to the daily enhancements of N2O (60–70 %). Agriculture and soil management accounted for ~ 20–25 % of N2O enhancements over a 24 h cycle, which is not surprising given that organic and synthetic fertilizers are known to be a major source of N2O. The N2O attribution to the agriculture and soil management factor had a high uncertainty in the conducted bootstrapping analysis. This is most likely due to an asynchronous pattern of soil-mediated N2O emissions from fertilizer usage and collocated biogenic emissions from crops from the surrounding agricultural operations that is difficult to apportion statistically when using PMF. The evaporative/fugitive source profile, which resembled a mix of petroleum operation and non-tailpipe evaporative gasoline sources, did not include a PMF resolved-CH4 contribution that was significant (< 2 %) compared to the uncertainty in the livestock-associated CH4 emissions. The uncertainty of the CH4 estimates in this source factor, derived from the bootstrapping analysis, is consistent with the ~ 3 % contribution of fugitive oil and gas emissions to the statewide CH4 inventory. The vehicle emission source factor broadly matched VOC profiles of on-road exhaust sources. This source factor had no statistically significant detected contribution to the N2O signals (confidence interval of 3 % of livestock N2O enhancements) and negligible CH4 (confidence interval of 4 % of livestock CH4 enhancements) in the presence of a dominant dairy and livestock factor. The CalNex PMF study provides a measurement-based assessment of the state CH4 and N2O inventories for the southern San Joaquin Valley (SJV). The state inventory attributes ~ 18 % of total N2O emissions to the transportation sector. Our PMF analysis directly contradicts the state inventory and demonstrates there were no discernible N2O emissions from the transportation sector in the southern SJV region.

Biogenic Volatile Organic Compound (BVOC) fluxes were measured onboard the CIRPAS Twin Otter aircraft as part of the California Airborne BVOC Emission Research in Natural Ecosystem Transects (CABERNET) campaign during June 2011. The airborne virtual disjunct eddy covariance (AvDEC) approach used measurements from a PTR-MS and a wind radome probe to directly determine fluxes of isoprene, MVK + MAC, methanol, monoterpenes, and MBO over ∼10 000 km of flight paths focusing on areas of California predicted to have the largest emissions of isoprene. The Fast Fourier Transform (FFT) approach was used to calculate fluxes over long transects of more than 15 km, most commonly between 50 and 150 km. The Continuous Wavelet Transformation (CWT) approach was used over the same transects to also calculate "instantaneous" fluxes with localization of both frequency and time independent of non-stationarities. Vertical flux divergence of isoprene is expected due to its relatively short lifetime and was measured directly using "racetrack" profiles at multiple altitudes. It was found to be linear and in the range 5% to 30% depending on the ratio of aircraft altitude to PBL height (z / zi). Fluxes were generally measured by flying consistently at 400 ± 50 m (a.g.l.) altitude, and extrapolated to the surface according to the determined flux divergence. The wavelet-derived surface fluxes of isoprene averaged to 2 km spatial resolution showed good correspondence to Basal Emission Factor (BEF) landcover datasets used to drive biogenic VOC (BVOC) emission models. The surface flux of isoprene was close to zero over Central Valley crops and desert shrublands, but was very high (up to 15 mg m−2 h−1) above oak woodlands, with clear dependence of emissions on temperature and oak density. Isoprene concentrations of up to 8 ppb were observed at aircraft height on the hottest days and over the dominant source regions. While isoprene emissions from agricultural crop regions, shrublands, and coniferous forests were extremely low, high concentrations of methanol and monoterpenes were found above some of these regions. These observations demonstrate the ability to measure fluxes from specific sources by eddy covariance from an aircraft, and suggest the utility of measurements using fast response chemical sensors to constrain emission inventories and map out source distributions for a much broader array of trace gases than was observed in this study. This paper reports the first regional direct eddy covariance fluxes of isoprene. The emissions of VOCs measured from aircraft with 2 km spatial resolution can quantify the distribution of major sources providing the observations required for testing statewide emission inventories of these important trace gases. These measurements will be used in a future study to assess BVOC emission models and their driving variable datasets.

Agriculture comprises a substantial, and increasing, fraction of land use in many regions of the world. Emissions from agricultural vegetation and other biogenic and anthropogenic sources react in the atmosphere to produce ozone and secondary organic aerosol, which comprises a substantial fraction of particulate matter (PM2.5). Using data from three measurement campaigns, we examine the magnitude and composition of reactive gas-phase organic carbon emissions from agricultural crops and their potential to impact regional air quality relative to anthropogenic emissions from motor vehicles in California's San Joaquin Valley, which is out of compliance with state and federal standards for tropospheric ozone PM2.5. Emission rates for a suite of terpenoid compounds were measured in a greenhouse for 25 representative crops from California in 2008. Ambient measurements of terpenoids and other biogenic compounds in the volatile and intermediate-volatility organic compound ranges were made in the urban area of Bakersfield and over an orange orchard in a rural area of the San Joaquin Valley during two 2010 seasons: summer and spring flowering. We combined measurements from the orchard site with ozone modeling methods to assess the net effect of the orange trees on regional ozone. When accounting for both emissions of reactive precursors and the deposition of ozone to the orchard, the orange trees are a net source of ozone in the springtime during flowering, and relatively neutral for most of the summer until the fall, when it becomes a sink. Flowering was a major emission event and caused a large increase in emissions including a suite of compounds that had not been measured in the atmosphere before. Such biogenic emission events need to be better parameterized in models as they have significant potential to impact regional air quality since emissions increase by several factors to over an order of magnitude. In regions like the San Joaquin Valley, the mass of biogenic emissions from agricultural crops during the summer (without flowering) and the potential ozone and secondary organic aerosol formation from these emissions are on the same order as anthropogenic emissions from motor vehicles and must be considered in air quality models and secondary pollution control strategies.

© Author(s) 2014. CC Attribution 3.0 License. Biogenic isoprene fluxes were measured onboard the CIRPAS Twin Otter aircraft as part of the California Airborne Biogenic volatile organic compound (BVOC) Emission Research in Natural Ecosystem Transects (CABERNET) campaign during June 2011. The airborne virtual disjunct eddy covariance (AvDEC) approach used measurements from a proton transfer reaction mass spectrometer (PTR-MS) and a wind radome probe to directly determine fluxes of isoprene over 7400 km of flight paths focusing on areas of California predicted to have the largest emissions. The fast Fourier transform (FFT) approach was used to calculate fluxes of isoprene over long transects of more than 15 km, most commonly between 50 and 150 km. The continuous wavelet transformation (CWT) approach was used over the same transects to also calculate instantaneous isoprene fluxes with localization of both frequency and time independent of non-stationarities. Fluxes were generally measured by flying consistently at 400 m ± 50 m (a.g.l.) altitude, and extrapolated to the surface according to the determined flux divergence determined in the racetrack-stacked profiles. The wavelet-derived surface fluxes of isoprene averaged to 2 km spatial resolution showed good correspondence to basal emission factor (BEF) land-cover data sets used to drive BVOC emission models. The surface flux of isoprene was close to zero over Central Valley crops and desert shrublands, but was very high (up to 15 mg '2 h−1) above oak woodlands, with clear dependence of emissions on temperature and oak density. Isoprene concentrations of up to 8 ppb were observed at aircraft height on the hottest days and over the dominant source regions. Even though the isoprene emissions from agricultural crop regions, shrublands, and coniferous forests were extremely low, observations at the Walnut Grove tower south of Sacramento demonstrate that isoprene oxidation products from the high emitting regions in the surrounding oak woodlands accumulate at night in the residual layer above the valley and mix down into the valley in the morning. Thus, the isoprene emissions surrounding the valley have relevance for the regional photochemistry that is not immediately apparent solely from the direct emission flux distribution. This paper reports the first regional observations of fluxes from specific sources by eddy covariance from an aircraft which can finally constrain statewide isoprene emission inventories used for ozone simulations by state agencies. While previously there was no available means to constrain the biogenic models, our results provide a good understanding of what the major sources of isoprene are in California, their magnitude, and how they are distributed. This data set on isoprene fluxes will be particularly useful for evaluating potential model alternatives which will be dealt with in a separate paper to assess isoprene emission models and their driving variable data sets.

In situ measurements of organic compounds in both gas and particle phases were made with a thermal desorption aerosol gas chromatography (TAG) instrument. The gas/particle partitioning of phthalic acid, pinonaldehyde, and 6,10,14-trimethyl-2-pentadecanone is discussed in detail to explore secondary organic aerosol (SOA) formation mechanisms. Measured fractions in the particle phase (f(part)) of 6,10,14-trimethyl-2-pentadecanone were similar to those expected from the absorptive gas/particle partitioning theory, suggesting that its partitioning is dominated by absorption processes. However, f(part) of phthalic acid and pinonaldehyde were substantially higher than predicted. The formation of low-volatility products from reactions of phthalic acid with ammonia is proposed as one possible mechanism to explain the high f(part) of phthalic acid. The observations of particle-phase pinonaldehyde when inorganic acids were fully neutralized indicate that inorganic acids are not required for the occurrence of reactive uptake of pinonaldehyde on particles. The observed relationship between f(part) of pinonaldehyde and relative humidity suggests that the aerosol water plays a significant role in the formation of particle-phase pinonaldehyde. Our results clearly show it is necessary to include multiple gas/particle partitioning pathways in models to predict SOA and multiple SOA tracers in source apportionment models to reconstruct SOA.

[1] Secondary organic aerosols (SOA), known to form in the atmosphere from oxidation of volatile organic compounds (VOCs) emitted by anthropogenic and biogenic sources, are a poorly understood but substantial component of atmospheric particles. In this study, we examined the chemical and physical properties of SOA at Bakersfield, California, a site influenced by anthropogenic and terrestrial biogenic emissions. Factor analysis was applied to the infrared and mass spectra of fine particles to identify sources and atmospheric processing that contributed to the organic mass (OM). We found that OM accounted for 56% of submicron particle mass, with SOA components contributing 80% to 90% of OM from 15 May to 29 June 2010. SOA formed from alkane and aromatic compounds, the two major classes of vehicle-emitted hydrocarbons, accounted for 65% OM (72% SOA). The alkane and aromatic SOA components were associated with 200 nm to 500 nm accumulation mode particles, likely from condensation of daytime photochemical products of VOCs. In contrast, biogenic SOA likely formed from condensation of secondary organic vapors, produced from NO3radical oxidation reactions during nighttime hours, on 400 nm to 700 nm sized primary particles, and accounted for less than 10% OM. Local petroleum operation emissions contributed 13% to the OM, and the moderate O/C (0.2) of this factor suggested it was largely of secondary origin. Approximately 10% of organic aerosols in submicron particles were identified as either vegetative detritus (10%) or cooking activities (7%), from Fourier transform infrared spectroscopic and aerosol mass spectrometry measurements, respectively. While the mass spectra of several linearly independent SOA components were nearly identical and external source markers were needed to separate them, each component had distinct infrared spectrum, likely associated with the source-specific VOCs from which they formed.

We present simultaneous fast, in-situ measurements of formaldehyde and glyoxal from two rural campaigns, BEARPEX 2009 and BEACHON-ROCS, both located in Pinus Ponderosa forests with emissions dominated by biogenic volatile organic compounds (VOCs). Despite considerable variability in the formaldehyde and glyoxal concentrations, the ratio of glyoxal to formaldehyde, RGF, displayed a very regular diurnal cycle over nearly 2 weeks of measurements. The only deviations in RGF were toward higher values and were the result of a biomass burning event during BEARPEX 2009 and very fresh anthropogenic influence during BEACHON-ROCS. Other rapid changes in glyoxal and formaldehyde concentrations have hardly any affect on RGF and could reflect transitions between low and high NO regimes. The trend of increased RGF from both anthropogenic reactive VOC mixtures and biomass burning compared to biogenic reactive VOC mixtures is robust due to the short timescales over which the observed changes in RGF occurred. Satellite retrievals, which suggest higher RGF for biogenic areas, are in contrast to our observed trends. It remains important to address this discrepancy, especially in view of the importance of satellite retrievals and in situ measurements for model comparison. In addition, we propose that RGF represents a useful metric for biogenic or anthropogenic reactive VOC mixtures and, in combination with absolute concentrations of glyoxal and formaldehyde, furthermore represents a useful metric for the extent of anthropogenic influence on overall reactive VOC processing via NOx. In particular, RGF yields information about not simply the VOCs dominating reactivity in an airmass, but the VOC processing itself that is directly coupled to ozone and secondary organic aerosol production.

Emissions from gasoline and diesel vehicles are predominant anthropogenic sources of reactive gas-phase organic carbon and key precursors to secondary organic aerosol (SOA) in urban areas. Their relative importance for aerosol formation is a controversial issue with implications for air quality control policy and public health. We characterize the chemical composition, mass distribution, and organic aerosol formation potential of emissions from gasoline and diesel vehicles, and find diesel exhaust is seven times more efficient at forming aerosol than gasoline exhaust. However, both sources are important for air quality; depending on a region’s fuel use, diesel is responsible for 65% to 90% of vehicular-derived SOA, with substantial contributions from aromatic and aliphatic hydrocarbons. Including these insights on source characterization and SOA formation will improve regional pollution control policies, fuel regulations, and methodologies for future measurement, laboratory, and modeling studies.

The Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) took place in Blodgett Forest, a Ponderosa pine forest in the Sierra Nevada of California, USA, during summer 2009. We deployed a proton transfer reaction–quadrupole mass spectrometer (PTR-QMS) to measure fluxes and concentrations of biogenic volatile organic compounds (BVOCs). Eighteen ion species, including the major BVOC expected at the site, were measured sequentially at 5 heights to observe their vertical gradient from the forest floor to above the canopy. Fluxes of the 3 dominant BVOCs methanol, 2-Methyl-3-butene-2-ol (MBO), and monoterpenes were measured above the canopy by the disjunct eddy covariance (EC) method. Canopy-scale fluxes were also determined by the flux–gradient similarity method (K-theory). A universal K (Kuniv) was determined as the mean of individual K's calculated from the measured fluxes divided by vertical gradients for methanol, MBO, and monoterpenes. This Kuniv was then multiplied by the gradients of each observed ion species to compute their fluxes. The flux–gradient similarity method showed very good agreement with the disjunct EC method. Fluxes are presented for all measured species and compared to historical measurements from the same site, and used to test emission algorithms used to model fluxes at the regional scale. MBO was the dominant emission observed, followed by methanol, monoterpenes, acetone, and acetaldehyde. The flux–gradient similarity method is shown to be tenable, and we recommend its use, especially in experimental conditions when fast measurement of BVOC species is not available.

carbon (EC) and the AMS tracer C4H9 for hydrocarbon-like organic aerosol (HOA) peaked in the early morning during rush hour, indicative of primary emissions. The fact that the particle number concentration peaked in the afternoon, when EC was at minimum, indicates that the midday increase in number concentration was likely due to new particle formation. The potential importance of solar radiation, the condensation sink of vapor on existing particles, concentrations of OH, O3 ,S O2 ,N H3, and VOCs for both condensational growth and new particle formation is evaluated based on the covariation of these parameters with ultrafine mass. The results suggest that the ultrafine particles are from secondary sources that are co-emitted or co-produced with glyoxal and formaldehyde.

Orange trees are widely cultivated in Mediterranean climatic regions where they are an important agricultural crop. Citrus have been characterized as emitters of volatile organic compounds (VOC) in chamber studies under controlled environmental conditions, but an extensive characterization at field scale has never been performed using modern measurement methods, and is particularly needed considering the complex interactions between the orchards and the polluted atmosphere in which Citrus is often cultivated. For one year, in a Valencia orange orchard in Exeter, California, we measured fluxes using PTRMS (Proton Transfer Reaction Mass Spectrometer) and eddy covariance for the most abundant VOC typically emitted from citrus vegetation: methanol, acetone, and isoprenoids. Concentration gradients of additional oxygenated and aromatic compounds from the ground level to above the canopy were also measured. In order to characterize concentrations of speciated biogenic VOC (BVOC) in leaves, we analyzed leaf content by GC-MS (Gas Chromatography – Mass Spectrometery) regularly throughout the year. We also characterized in more detail concentrations of speciated BVOC in the air above the orchard by in-situ GC-MS during a few weeks in spring flowering and summer periods. Here we report concentrations and fluxes of the main VOC species emitted by the orchard, discuss how fluxes measured in the field relate to previous studies made with plant enclosures, and describe how VOC content in leaves and emissions change during the year in response to phenological and environmental parameters. The orchard was a source of monoterpenes and oxygenated VOC. The highest emissions were observed during the springtime flowering period, with mid-day fluxes above 2 nmol m−2 s−1 for methanol and up to 1 nmol m−2 s−1 for acetone and monoterpenes. During hot summer days emissions were not as high as we expected considering the known dependence of biogenic emissions on temperature. We provide evidence that thickening of leaf cuticle wax content limited gaseous emissions during the summer.

Orange trees are widely cultivated in regions with high concentrations of tropospheric ozone. Citrus absorb ozone through their stomata and emit volatile organic compounds (VOC), which, together with soil emissions of NO, contribute to non-stomatal ozone removal. In a Valencia orange orchard in Exeter, California, we used fast sensors and eddy covariance to characterize water and ozone fluxes. We also measured meteorological parameters necessary to model other important sinks of ozone deposition. We present changes in magnitude of these ozone deposition sinks over the year in response to environmental parameters. Within the plant canopy, the orchard constitutes a sink for ozone, with non-stomatal ozone deposition larger than stomatal uptake. In particular, soil deposition and reactions between ozone, VOC and NO represented the major sinks of ozone. This research aims to help the development of metrics for ozone-risk assessment and advance our understanding of citrus in biosphere-atmosphere exchange.

The Fluxnet synthesis dataset originally compiled for the La Thuile workshop contained approximately 600 site years. Since the workshop, several additional site years have been added and the dataset now contains over 920 site years from over 240 sites. A data refresh update is expected to increase those numbers in the next few months. The ancillary data describing the sites continues to evolve as well. There are on the order of 120 site contacts and 60 proposals have been approved to use the data. These proposals involve around 120 researchers. The size and complexity of the dataset and collaboration has led to a new approach to providing access to the data and collaboration support and the support team attended the workshop and worked closely with the attendees and the Fluxnet project office to define the requirements for the support infrastructure. As a result of this effort, a new website (http://www.fluxdata.org) has been created to provide access to the Fluxnet synthesis dataset. This new web site is based on a scientific data server which enables browsing of the data on-line, data download, and version tracking. We leverage database and data analysis tools such as OLAP data cubes and web reports to enable browser and Excel pivot table access to the data.

During summer 2010, a proton transfer reaction – time of flight – mass spectrometer (PTR-TOF-MS) and a quadrupole proton transfer reaction mass spectrometer (PTR-MS) were deployed simultaneously for one month in an orange orchard in the Central Valley of California to collect continuous data suitable for eddy covariance (EC) flux calculations. The high time resolution (5 Hz) and high mass resolution (up to 5000 m/Δm) data from the PTR-TOF-MS provided the basis for calculating the concentration and flux for a wide range of volatile organic compounds (VOC). Throughout the campaign, 664 mass peaks were detected in mass-to-charge ratios between 10 and 1278. Here we present PTR-TOF-MS EC fluxes of the 27 ion species for which the vertical gradient was simultaneously measured by PTR-MS. These EC flux data were validated through spectral analysis (i.e., co-spectrum, normalized co-spectrum, and ogive). Based on inter-comparison of the two PTR instruments, no significant instrumental biases were found in either mixing ratios or fluxes, and the data showed agreement within 5% on average for methanol and acetone. For the measured biogenic volatile organic compounds (BVOC), the EC fluxes from PTR-TOF-MS were in agreement with the qualitatively inferred flux directions from vertical gradient measurements by PTR-MS. For the 27 selected ion species reported here, the PTR-TOF-MS measured total (24 h) mean net flux of 299 μg C m−2 h−1. The dominant BVOC emissions from this site were monoterpenes (m/z 81.070 + m/z 137.131 + m/z 95.086, 34%, 102 μg C m−2 h−1) and methanol (m/z 33.032, 18%, 72 μg C m−2 h−1). The next largest fluxes were detected at the following masses (attribution in parenthesis): m/z 59.048 (mostly acetone, 12.2%, 36.5 μg C m−2 h−1), m/z 61.027 (mostly acetic acid, 11.9%, 35.7 μg C m−2 h−1), m/z 93.069 (para-cymene + toluene, 4.1%, 12.2 μg C m−2 h−1), m/z 45.033 (acetaldehyde, 3.8%, 11.5 μg C m−2 h−1), m/z 71.048 (methylvinylketone + methacrolein, 2.4%, 7.1 μg C m−2 h−1), and m/z 69.071 (isoprene + 2-methyl-3-butene-2-ol, 1.8%, 5.3 μg C m−2 h−1). Low levels of emission and/or deposition (