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Better constraining the ecosystem gross photosynthetic CO2 uptake (GPP) is necessary to reduce the uncertainties on continental vegetation response to climate change. As GPP cannot be directly measured at the ecosystem scale, different proxies of vegetation CO2 uptake have emerged. These proxies are essential for land surface modelers to estimate GPP at large scale. Carbonyl sulfide (COS) shows many similarities with CO2, following the same diffusional pathways through the leaves. However, unlike CO2 that is also emitted by plants during respiration, COS is essentially only taken up by leaves and not re-emitted back to the atmosphere. Therefore, COS is a promising proxy of photosynthetic activity. In previous studies, fixed values of the leaf relative uptake (LRU) ratio of COS to CO2 fluxes normalized by their respective concentration have typically been used to infer GPP for the different biomes. However, it has been shown that LRU ratio changes with varying Photosynthetically Active Radiation (PAR), which limits its accuracy to constrain photosynthetic activity. Therefore, we redefined the COS-based GPP estimation approach to better capture GPP response to changing environmental conditions, by implementing a mechanistic model of COS exchange by continental vegetation in the ORCHIDEE land surface model. We compared the modelled fluxes against field measurements at two sites and studied the model behavior and environmental drivers. Then, we ran global simulations and computed the annual COS vegetation uptake that was found in the middle range values of previous reported budgets (-490 to -1335 Gg S yr-1), with -756 Gg S yr-1. The simulated fluxes were transported, and COS concentrations were evaluated against measurements from the NOAA atmospheric stations. Our results show that the mechanistic approach is more appropriate when studying photosynthetic activity at high temporal resolution, but similar results in concentrations are obtained between the mechanistic and LRU approaches at the global scale. Accurate evaluation of the continental vegetation COS uptake is necessary as it is the main COS sink. However, COS can also be absorbed or emitted by soils, a flux that complicates the use of eddy covariance COS flux measurements or atmospheric COS measurements to derive information on GPP estimates. Therefore, the soil COS exchange should also be represented in land surface models. We implemented two soil COS exchange models in ORCHIDEE, a mechanistic model (based on Ogée et al. 2016) and a second model based on an empirical relationship with soil respiration (following Berry et al., 2013). We evaluated the two models at several sites against field measurements. We also performed global simulations to evaluate the spatial distribution of soil COS fluxes and their seasonal variations. Finally, we estimated the contributions of the combined impact of soil COS exchange and leaf COS uptake (both from the ORCHIDEE model) to the global COS budget and on the COS atmospheric concentration latitudinal gradient.

Soil respiration (i.e. from soils and roots) provides one of the largest global fluxes of carbon dioxide (CO2) to the atmosphere and is likely to increase with warming, yet the magnitude of soil respiration from rapidly thawing Arctic-boreal regions is not well understood. To address this knowledge gap, we first compiled a new CO2 flux database for permafrost-affected tundra and boreal ecosystems in Alaska and Northwest Canada. We then used the CO2 database, multi-sensor satellite imagery, and random forest models to assess the regional magnitude of soil respiration. The flux database includes a new Soil Respiration Station network of chamber-based fluxes, and fluxes from eddy covariance towers. Our site-level data, spanning September 2016 to August 2017, revealed that the largest soil respiration emissions occurred during the summer (June–August) and that summer fluxes were higher in boreal sites (1.87 ± 0.67 g CO2–C m−2 d−1) relative to tundra (0.94 ± 0.4 g CO2–C m−2 d−1). We also observed considerable emissions (boreal: 0.24 ± 0.2 g CO2–C m−2 d−1; tundra: 0.18 ± 0.16 g CO2–C m−2 d−1) from soils during the winter (November–March) despite frozen surface conditions. Our model estimates indicated an annual region-wide loss from soil respiration of 591 ± 120 Tg CO2–C during the 2016–2017 period. Summer months contributed to 58% of the regional soil respiration, winter months contributed to 15%, and the shoulder months contributed to 27%. In total, soil respiration offset 54% of annual gross primary productivity (GPP) across the study domain. We also found that in tundra environments, transitional tundra/boreal ecotones, and in landscapes recently affected by fire, soil respiration often exceeded GPP, resulting in a net annual source of CO2 to the atmosphere. As this region continues to warm, soil respiration may increasingly offset GPP, further amplifying global climate change.

Where does the carbon released by burning fossil fuels go? Currently, ocean and land systems remove about half of the CO2 emitted by human activities; the remainder stays in the atmosphere. These removal processes are sensitive to feedbacks in the energy, carbon, and water cycles that will change in the future. Observing how much carbon is taken up on land through photosynthesis is complicated because carbon is simultaneously respired by plants, animals, and microbes. Global observations from satellites and air samples suggest that natural ecosystems take up about as much CO2 as they emit. To match the data, our land models generate imaginary Earths where carbon uptake and respiration are roughly balanced, but the absolute quantities of carbon being exchanged vary widely. Getting the magnitude of the flux is essential to make sure our models are capturing the right pattern for the right reasons. Combining two cutting-edge tools, carbonyl sulfide (OCS) and solar-induced fluorescence (SIF), will help develop an independent answer of how much carbon is being taken up by global ecosystems. Photosynthesis requires CO2, light, and water. OCS provides a spatially and temporally integrated picture of the “front door” of photosynthesis, proportional to CO2 uptake and water loss through plant stomata. SIF provides a high-resolution snapshot of the “side door,” scaling with the light captured by leaves. These two independent pieces of information help us understand plant water and carbon exchange. A coordinated effort to generate SIF and OCS data through satellite, airborne, and ground observations will improve our process-based models to predict how these cycles will change in the future.

Acetone is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere. The oceans impose a strong control on atmospheric acetone, yet the oceanic fluxes of acetone remain poorly constrained. In this work, the global budget of acetone is evaluated using two global models: CAM‐chem and GEOS‐Chem. CAM‐chem uses an online air‐sea exchange framework to calculate the bidirectional oceanic acetone fluxes, which is coupled to a data‐oriented machine‐learning approach. The machine‐learning algorithm is trained using a global suite of seawater acetone measurements. GEOS‐Chem uses a fixed surface seawater concentration of acetone to calculate the oceanic fluxes. Both model simulations are compared to airborne observations from a recent global‐scale, multiseasonal campaign, the NASA Atmospheric Tomography Mission (ATom). We find that both CAM‐chem and GEOS‐Chem capture the measured acetone vertical distributions in the remote atmosphere reasonably well. The combined observational and modeling analysis suggests that (i) the ocean strongly regulates the atmospheric budget of acetone. The tropical and subtropical oceans are mostly a net source of acetone, while the high‐latitude oceans are a net sink. (ii) CMIP6 anthropogenic emission inventory may underestimate acetone and/or its precursors in the Northern Hemisphere. (iii) The MEGAN biogenic emissions model may overestimate acetone and/or its precursors, and/or the biogenic oxidation mechanisms may overestimate the acetone yields. (iv) The models consistently overestimate acetone in the upper troposphere‐lower stratosphere over the Southern Ocean in austral winter. (v) Acetone contributes up to 30–40% of hydroxyl radical production in the tropical upper troposphere/lower stratosphere.

We report airborne measurements of acetaldehyde (CH(3)CHO) during the first and second deployments of the National Aeronautics and Space Administration (NASA) Atmospheric Tomography Mission (ATom). The budget of CH(3)CHO is examined using the Community Atmospheric Model with chemistry (CAM-chem), with a newly-developed online air-sea exchange module. The upper limit of the global ocean net emission of CH(3)CHO is estimated to be 34 Tg a(−1) (42 Tg a(−1) if considering bubble-mediated transfer), and the ocean impacts on tropospheric CH(3)CHO are mostly confined to the marine boundary layer. Our analysis suggests that there is an unaccounted CH(3)CHO source in the remote troposphere and that organic aerosols can only provide a fraction of this missing source. We propose that peroxyacetic acid (PAA) is an ideal indicator of the rapid CH(3)CHO production in the remote troposphere. The higher-than-expected CH(3)CHO measurements represent a missing sink of hydroxyl radicals (and halogen radical) in current chemistry-climate models.

A promising tracer for partitioning the global balance of CO2 is carbonyl sulfide (COS or OCS), a trace gas with leaf-level mechanisms shared with carbon dioxide (CO2) and water (H2O). COS is therefore used to derive insights into photosynthesis and transpiration at ecosystem to global scales. However, it remains unclear whether COS reflects photosynthesis or stomatal conductance most strongly, as its leaf biochemical and physical processes are not perfectly analogous to either CO2 or H2O. There is therefore a need to evaluate the models that encapsulate our current understanding of leaf and soil COS fluxes and predictions of carbon and water cycling against independent constraints in tractable experimental systems.In this study, we measured ecosystem, leaf, and soil fluxes of COS in the model Biosphere 2 (B2) Tropical Rainforest across a controlled whole ecosystem drought manipulation. We simultaneously, measured the stable isotopes of CO2, H2O, and their isotopes (13C-CO2, 18O-CO2, 2H-H2O, 18O-H2O) on atmosphere, leaf, and soil measurement streams connected to atmospheric towers, leaf chambers, and soil flux chambers. During the B2 Water, Atmosphere, and Life Dynamics (B2 WALD) campaign, the enclosed ecosystem received no rain for 66 days and was first rewet at depth (2-4 m) at 54 days. Here, we compare COS fluxes to simultaneous and independent measurements of GPP and transpiration from the leaf to ecosystem scales across ecosystem control, drought, and recovery. We further integrate COS measurements with the aforementioned isotopic tracers of carbon and water cycling into the Simple Biosphere Model (SiB3). Our goal is to explore the strengths and limitations of COS as a tracer of ecosystem processes dynamically responding to severe and controlled ecosystem drought.

Earth's atmosphere oxidizes the greenhouse gas methane and other gases, thus determining their lifetimes and oxidation products. Much of this oxidation occurs in the remote, relatively clean free troposphere above the planetary boundary layer, where the oxidation chemistry is thought to be much simpler and better understood than it is in urban regions or forests. The NASA airborne Atmospheric Tomography study (ATom) was designed to produce cross sections of the detailed atmospheric composition in the remote atmosphere over the Pacific and Atlantic Oceans during four seasons. As part of the extensive ATom data set, measurements of the atmosphere's primary oxidant, hydroxyl (OH), and hydroperoxyl (HO₂) are compared to a photochemical box model to test the oxidation chemistry. Generally, observed and modeled median OH and HO₂ agree to with combined uncertainties at the 2σ confidence level, which is ~±40%. For some seasons, this agreement is within ~±20% below 6 km altitude. While this test finds no significant differences, OH observations increasingly exceeded modeled values at altitudes above 8 km, becoming ~35% greater, which is near the combined uncertainties. Measurement uncertainty and possible unknown measurement errors complicate tests for unknown chemistry or incorrect reaction rate coefficients that would substantially affect the OH and HO₂ abundances. Future analysis of detailed comparisons may yield additional discrepancies that are masked in the median values.

Recent warming in the Arctic, which has been amplified during the winter1–3, greatly enhances microbial decomposition of soil organic matter and subsequent release of carbon dioxide (CO2)4. However, the amount of CO2 released in winter is not known and has not been well represented by ecosystem models or empirically based estimates5,6. Here we synthesize regional in situ observations of CO2 flux from Arctic and boreal soils to assess current and future winter carbon losses from the northern permafrost domain. We estimate a contemporary loss of 1,662 TgC per year from the permafrost region during the winter season (October–April). This loss is greater than the average growing season carbon uptake for this region estimated from process models (−1,032 TgC per year). Extending model predictions to warmer conditions up to 2100 indicates that winter CO2 emissions will increase 17% under a moderate mitigation scenario—Representative Concentration Pathway 4.5—and 41% under business-as-usual emissions scenario—Representative Concentration Pathway 8.5. Our results provide a baseline for winter CO2 emissions from northern terrestrial regions and indicate that enhanced soil CO2 loss due to winter warming may offset growing season carbon uptake under future climatic conditions. Winter warming in the Arctic will increase the CO2 flux from soils. A pan-Arctic analysis shows a current loss of 1,662 TgC per year over the winter, exceeding estimated carbon uptake in the growing season; projections suggest a 17% increase under RCP 4.5 and a 41% increase under RCP 8.5 by 2100.

Author(s): Campbell, JE; Whelan, ME; Berry, JA; Hilton, TW; Zumkehr, A; Stinecipher, J; Lu, Y; Kornfeld, A; Seibt, U; Dawson, TE; Montzka, SA; Baker, IT; Kulkarni, S; Wang, Y; Herndon, SC; Zahniser, MS; Commane, R; Loik, ME | Abstract: The future resilience of coast redwoods (Sequoia sempervirens) is now of critical concern due to the detection of a 33% decline in California coastal fog over the 20th century. However, ecosystem-scale measurements of photosynthesis and stomatal conductance are challenging in coast redwood forests, making it difficult to anticipate the impacts of future changes in fog. To address this methodological problem, we explore coastal variations in atmospheric carbonyl sulfide (COS or OCS), which could potentially be used as a tracer of these ecosystem processes. We conducted atmospheric flask campaigns in coast redwood sites, sampling at surface heights and in the canopy (~70nm), at the University of California Landels-Hill Big Creek Reserve and Big Basin State Park. We simulated COS atmosphere-biosphere exchange with a high-resolution 3-D model to interpret these data. Flask measurements indicated a persistent daytime drawdown between the coast and the downwind forest (45n±n6nppt COS) that is consistent with the expected relationship between COS plant uptake, stomatal conductance, and gross primary production. Other sources and sinks of COS that could introduce noise to the COS tracer technique (soils, anthropogenic activity, nocturnal plant uptake, and surface hydrolysis on leaves) are likely to be small relative to daytime COS plant uptake. These results suggest that COS measurements may be useful for making ecosystem-scale estimates of carbon, water, and energy exchange in coast redwood forests.

Wetlands are the largest global natural methane (CH4) source, and emissions between 50 and 70° N latitude contribute 10–30 % to this source. Predictive capability of land models for northern wetland CH4 emissions is still low due to limited site measurements, strong spatial and temporal variability in emissions, and complex hydrological and biogeochemical dynamics. To explore this issue, we compare wetland CH4 emission predictions from the Community Land Model 4.5 (CLM4.5-BGC) with site- to regional-scale observations. A comparison of the CH4 fluxes with eddy flux data highlighted needed changes to the model's estimate of aerenchyma area, which we implemented and tested. The model modification substantially reduced biases in CH4 emissions when compared with CarbonTracker CH4 predictions. CLM4.5 CH4 emission predictions agree well with growing season (May–September) CarbonTracker Alaskan regional-level CH4 predictions and site-level observations. However, CLM4.5 underestimated CH4 emissions in the cold season (October–April). The monthly atmospheric CH4 mole fraction enhancements due to wetland emissions are also assessed using the Weather Research and Forecasting-Stochastic Time-Inverted Lagrangian Transport (WRF-STILT) model coupled with daily emissions from CLM4.5 and compared with aircraft CH4 mole fraction measurements from the Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) campaign. Both the tower and aircraft analyses confirm the underestimate of cold-season CH4 emissions by CLM4.5. The greatest uncertainties in predicting the seasonal CH4 cycle are from the wetland extent, cold-season CH4 production and CH4 transport processes. We recommend more cold-season experimental studies in high-latitude systems, which could improve the understanding and parameterization of ecosystem structure and function during this period. Predicted CH4 emissions remain uncertain, but we show here that benchmarking against observations across spatial scales can inform model structural and parameter improvements.

Existing estimates of methane (CH4) fluxes from North American wetlands vary widely in both magnitude and distribution. In light of these differences, this study uses atmospheric CH4 observations from the US and Canada to analyze seven different bottom-up, wetland CH4 estimates reported in a recent model comparison project. We first use synthetic data to explore whether wetland CH4 fluxes are detectable at atmospheric observation sites. We find that the observation network can detect aggregate wetland fluxes from both eastern and western Canada but generally not from the US. Based upon these results, we then use real data and inverse modeling results to analyze the magnitude, seasonality, and spatial distribution of each model estimate. The magnitude of Canadian fluxes in many models is larger than indicated by atmospheric observations. Many models predict a seasonality that is narrower than implied by inverse modeling results, possibly indicating an oversensitivity to air or soil temperatures. The LPJ-Bern and SDGVM models have a geographic distribution that is most consistent with atmospheric observations, depending upon the region and season. These models utilize land cover maps or dynamic modeling to estimate wetland coverage while most other models rely primarily on remote sensing inundation data.

Our understanding of biosphere–atmosphere exchange has been considerably enhanced by eddy covariance measurements. However, there remain many trace gases, such as molecular hydrogen (H[subscript 2]), that lack suitable analytical methods to measure their fluxes by eddy covariance. In such cases, flux-gradient methods can be used to calculate ecosystem-scale fluxes from vertical concentration gradients. The budget of atmospheric H[subscript 2] is poorly constrained by the limited available observations, and thus the ability to quantify and characterize the sources and sinks of H[subscript 2] by flux-gradient methods in various ecosystems is important. We developed an approach to make nonintrusive, automated measurements of ecosystem-scale H2 fluxes both above and below the forest canopy at the Harvard Forest in Petersham, Massachusetts, for over a year. We used three flux-gradient methods to calculate the fluxes: two similarity methods that do not rely on a micrometeorological determination of the eddy diffusivity, K, based on (1) trace gases or (2) sensible heat, and one flux-gradient method that (3) parameterizes K. We quantitatively assessed the flux-gradient methods using CO[subscript 2] and H[subscript 2]O by comparison to their simultaneous independent flux measurements via eddy covariance and soil chambers. All three flux-gradient methods performed well in certain locations, seasons, and times of day, and the best methods were trace gas similarity for above the canopy and K parameterization below it. Sensible heat similarity required several independent measurements, and the results were more variable, in part because those data were only available in the winter, when heat fluxes and temperature gradients were small and difficult to measure. Biases were often observed between flux-gradient methods and the independent flux measurements, and there was at least a 26% difference in nocturnal eddy-derived net ecosystem exchange (NEE) and chamber measurements. H[subscript 2] fluxes calculated in a summer period agreed within their uncertainty and pointed to soil uptake as the main driver of H[subscript 2] exchange at Harvard Forest, with H[subscript 2] deposition velocities ranging from 0.04 to 0.10 cm s[superscript −1]., National Science Foundation (U.S.) (NSF Graduate Research Fellowship), United States. National Aeronautics and Space Administration (Advanced Global Atmospheric Gases Experiment (AGAGE)), Massachusetts Institute of Technology. Joint Program on the Science & Policy of Global Change, Martin Family Society of Fellows for Sustainability, Massachusetts Institute of Technology (Ally of Nature Research Fund), Massachusetts Institute of Technology (William Otis Crosby Lectureship), Massachusetts Institute of Technology (Warren Klein Fund)

High-latitude ecosystems have the capacity to release large amounts of carbon dioxide (CO2) to the atmosphere in response to increasing temperatures, representing a potentially significant positive feedback within the climate system. Here, we combine aircraft and tower observations of atmospheric CO2 with remote sensing data and meteorological products to derive temporally and spatially resolved year-round CO2 fluxes across Alaska during 2012-2014. We find that tundra ecosystems were a net source of CO2 to the atmosphere annually, with especially high rates of respiration during early winter (October through December). Long-term records at Barrow, AK, suggest that CO2 emission rates from North Slope tundra have increased during the October through December period by 73% ± 11% since 1975, and are correlated with rising summer temperatures. Together, these results imply increasing early winter respiration and net annual emission of CO2 in Alaska, in response to climate warming. Our results provide evidence that the decadalscale increase in the amplitude of the CO2 seasonal cycle may be linked with increasing biogenic emissions in the Arctic, following the growing season. Early winter respirationwas not well simulated by the Earth System Models used to forecast future carbon fluxes in recent climate assessments. Therefore, these assessments may underestimate the carbon release from Arctic soils in response to a warming climate.

Accurately quantifying the timing and magnitude of respiration and photosynthesis by high-latitude ecosystems is important for understanding how a warming climate influences global carbon cycling. Data-driven estimates of photosynthesis across Arctic regions often rely on satellite-derived enhanced vegetation index (EVI); we find that satellite observations of solar-induced chlorophyll fluorescence (SIF) provide a more direct proxy for photosynthesis. We model Alaskan tundra CO2 cycling (2012–2014) according to temperature and shortwave radiation, and alternately input EVI or SIF to prescribe the annual seasonal cycle of photosynthesis. We find that EVI-based seasonality indicates spring “green-up” to occur nine days prior to SIF-based estimates, and that SIF-based estimates agree with aircraft and tower measurements of CO_2. Adopting SIF, instead of EVI, for modeling the seasonal cycle of tundra photosynthesis can result in more accurate estimates of growing season duration and net carbon uptake by arctic vegetation.

[1] Measurements of carbonyl sulfide (OCS) have been proposed to provide a unique constraint on carbon assimilation by the biosphere that is independent of the influence of plant and soil respiration of CO2, but this constraint depends on a comprehensive understanding of the processes controlling OCS in the biosphere. We conducted a high-resolution temporal and spatial survey of OCS and CO2 mixing ratios during the California Nexus Experiment research cruise along the coast of California (U.S.) and into the Sacramento River Delta using a newly constructed compact quantum cascade laser spectrometer (precision for OCS of

With rapid changes in climate and the seasonal amplitude of carbon dioxide (CO2) in the Arctic, it is critical that we detect and quantify the underlying processes controlling the changing amplitude of CO2 to better predict carbon cycle feedbacks in the Arctic climate system. We use satellite and airborne observations of atmospheric CO2 with climatically forced CO2 flux simulations to assess the detectability of Alaskan carbon cycle signals as future warming evolves. We find that current satellite remote sensing technologies can detect changing uptake accurately during the growing season but lack sufficient cold season coverage and near-surface sensitivity to constrain annual carbon balance changes at regional scale. Airborne strategies that target regular vertical profile measurements within continental interiors are more sensitive to regional flux deeper into the cold season but currently lack sufficient spatial coverage throughout the entire cold season. Thus, the current CO2 observing network is unlikely to detect potentially large CO2 sources associated with deep permafrost thaw and cold season respiration expected over the next 50 y. Although continuity of current observations is vital, strategies and technologies focused on cold season measurements (active remote sensing, aircraft, and tall towers) and systematic sampling of vertical profiles across continental interiors over the full annual cycle are required to detect the onset of carbon release from thawing permafrost.

Northern high-latitude carbon sources and sinks, including those resulting from degrading permafrost, are thought to be sensitive to the rapidly warming climate. Because the near-surface atmosphere integrates surface fluxes over large ( ∼ 500–1000 km) scales, atmospheric monitoring of carbon dioxide (CO2) and methane (CH4) mole fractions in the daytime mixed layer is a promising method for detecting change in the carbon cycle throughout boreal Alaska. Here we use CO2 and CH4 measurements from a NOAA tower 17 km north of Fairbanks, AK, established as part of NASA's Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE), to investigate regional fluxes of CO2 and CH4 for 2012–2014. CARVE was designed to use aircraft and surface observations to better understand and quantify the sensitivity of Alaskan carbon fluxes to climate variability. We use high-resolution meteorological fields from the Polar Weather Research and Forecasting (WRF) model coupled with the Stochastic Time-Inverted Lagrangian Transport model (hereafter, WRF-STILT), along with the Polar Vegetation Photosynthesis and Respiration Model (PolarVPRM), to investigate fluxes of CO2 in boreal Alaska using the tower observations, which are sensitive to large areas of central Alaska. We show that simulated PolarVPRM–WRF-STILT CO2 mole fractions show remarkably good agreement with tower observations, suggesting that the WRF-STILT model represents the meteorology of the region quite well, and that the PolarVPRM flux magnitudes and spatial distribution are generally consistent with CO2 mole fractions observed at the CARVE tower. One exception to this good agreement is that during the fall of all 3 years, PolarVPRM cannot reproduce the observed CO2 respiration. Using the WRF-STILT model, we find that average CH4 fluxes in boreal Alaska are somewhat lower than flux estimates by Chang et al. (2014) over all of Alaska for May–September 2012; we also find that enhancements appear to persist during some wintertime periods, augmenting those observed during the summer and fall. The possibility of significant fall and winter CO2 and CH4 fluxes underscores the need for year-round in situ observations to quantify changes in boreal Alaskan annual carbon balance.

Carbonyl sulfide (OCS), the most abundant sulfur gas in the atmosphere, has a summer minimum associated with uptake by vegetation and soils, closely correlated with CO2. We report the first direct measurements to our knowledge of the ecosystem flux of OCS throughout an annual cycle, at a mixed temperate forest. The forest took up OCS during most of the growing season with an overall uptake of 1.36 ± 0.01 mol OCS per ha (43.5 ± 0.5 g S per ha, 95% confidence intervals) for the year. Daytime fluxes accounted for 72% of total uptake. Both soils and incompletely closed stomata in the canopy contributed to nighttime fluxes. Unexpected net OCS emission occurred during the warmest weeks in summer. Many requirements necessary to use fluxes of OCS as a simple estimate of photosynthesis were not met because OCS fluxes did not have a constant relationship with photosynthesis throughout an entire day or over the entire year. However, OCS fluxes provide a direct measure of ecosystem-scale stomatal conductance and mesophyll function, without relying on measures of soil evaporation or leaf temperature, and reveal previously unseen heterogeneity of forest canopy processes. Observations of OCS flux provide powerful, independent means to test and refine land surface and carbon cycle models at the ecosystem scale.

Forests are the dominant source of volatile organic compounds into the atmosphere, with isoprene being the most significant species. The oxidation chemistry of these compounds is a significant driver of local, regional and global atmospheric composition. Observations made over Borneo during the OP3 project in 2008, together with an observationally constrained box model are used to assess our understanding of this oxidation chemistry. In line with previous work in tropical forests, we find that the standard model based on MCM chemistry significantly underestimates the observed OH concentrations. Geometric mean observed to modelled ratios of OH and HO2 in airmasses impacted with isoprene are 5.32−4.43+3.68 and 1.18−0.30+0.30 respectively, with 68 % of the observations being within the specified variation. We implement a variety of mechanistic changes into the model, including epoxide formation and unimolecular decomposition of isoprene peroxy radicals, and assess their impact on the model success. We conclude that none of the current suggestions can simultaneously remove the bias from both OH and HO2 simulations and believe that detailed laboratory studies are now needed to resolve this issue.

The first in situ point observations of iodine monoxide (IO) at a clean marine site were made using a laser-induced fluorescence instrument deployed at Mace Head, Ireland in August 2007. IO mixing ratios of up to 49.8 pptv (equivalent to pmol mol−1; 1 s average) were observed at day-time low tide, well in excess of previous observed spatially-averaged maxima. A strong anti-correlation of IO mixing ratios with tide height was evident and the high time resolution of the observations showed IO peaked in the hour after low tide. The temporal delay in peak IO compared to low tide has not been observed previously but coincides with the time of peak aerosol number previously observed at Mace Head. A long path-differential optical absorption spectroscopy instrument (with a 2 × 6.8 km folded path across Roundstone Bay) was also based at the site for 3 days during the point measurement observation period. Both instruments show similar temporal trends but the point measurements of IO are a factor of ~6–10 times greater than the spatially averaged IO mixing ratios, providing direct empirical evidence of the presence of inhomogeneities in the IO mixing ratio near the intertidal region.

Aircraft OH and HO2 measurements made over West Africa during the AMMA field campaign in summer 2006 have been investigated using a box model constrained to observations of long-lived species and physical parameters. "Good" agreement was found for HO2 (modelled to observed gradient of 1.23 ± 0.11). However, the model significantly overpredicts OH concentrations. The reasons for this are not clear, but may reflect instrumental instabilities affecting the OH measurements. Within the model, HOx concentrations in West Africa are controlled by relatively simple photochemistry, with production dominated by ozone photolysis and reaction of O(1D) with water vapour, and loss processes dominated by HO2 + HO2 and HO2 + RO2. Isoprene chemistry was found to influence forested regions. In contrast to several recent field studies in very low NOx and high isoprene environments, we do not observe any dependence of model success for HO2 on isoprene and attribute this to efficient recycling of HOx through RO2 + NO reactions under the moderate NOx concentrations (5–300 ppt NO in the boundary layer, median 76 ppt) encountered during AMMA. This suggests that some of the problems with understanding the impact of isoprene on atmospheric composition may be limited to the extreme low range of NOx concentrations.

The hydroxyl radical (OH) plays a key role in the oxidation of trace gases in the troposphere. However, observations of OH and the closely related hydroperoxy radical (HO2) have been sparse, especially in the tropics. Based on a low-pressure laser-induced fluorescence technique (FAGE – Fluorescence Assay by Gas Expansion), an instrument has been developed to measure OH and HO2 aboard the Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft. During the African Monsoon Multidisciplinary Analyses (AMMA) campaign, observations of OH and HO2 (HOx) were made in the boundary layer and free troposphere over West Africa on 13 flights during July and August 2006. Mixing ratios of both OH and HO2 were found to be highly variable, but followed a diurnal cycle: OH varied from 1.3 pptv to below the instrumental limit of detection, with a median mixing ratio of 0.17 pptv. HO2 varied from 42.7 pptv to below the limit of detection, with a median mixing ratio of 8.0 pptv. A median HO2/OH ratio of 95 was observed. Daytime OH observations were compared with the primary production rate of OH from ozone photolysis in the presence of water vapour. Daytime HO2 observations were generally reproduced by a simple steady-state HOx calculation, where HOx was assumed to be formed from the primary production of OH and lost through HO2 self-reaction. Deviations between the observations and this simple model were found to be grouped into a number of specific cases: (a) within cloud, (b) in the presence of high levels of isoprene in the boundary layer and (c) within a biomass burning plume. HO2 was sampled in and around cloud, with significant short-lived reductions of HO2 observed. Up to 9 pptv of HO2 was observed at night, with HO2 above 6 pptv observed at altitudes above 6 km. In the forested boundary layer, HO2 was underestimated by a steady state calculation at altitudes below 500 m but overestimated between 500 m and 2 km. In a biomass burning plume, observed HO2 concentrations were significantly below those calculated.

Measurements of NO and NO2 were made at a surface site (55.28 degrees N, 77.77 degrees W) near Kuujjuarapik, Canada during February and March 2008. NOx mixing ratios ranged from near zero to 350 pptv with emission from snow believed to be the dominant source. The amount of NOx was observed to be dependent on the terrain over which the airmass has passed before reaching the measurement site. The 24 h average NOx emission rates necessary to reproduce observations were calculated using a zero-dimensional box model giving rates ranging from 6.9 x 10(8) molecule cm(-2) s(-1) to 1.2 x 10(9) molecule cm(-2) s(-1) for trajectories over land and from 3.8 x 10(8) molecule cm(-2) s(-1) to 6.6 x 10(8) molecule cm(-2) s(-1) for trajectories over sea ice. These emissions are higher than those suggested by previous studies and indicate the importance of lower latitude snowpack emissions. The difference in emission rate for the two types of snow cover shows the importance of snow depth and underlying surface type for the emission potential of snow-covered areas. (C) 2010 Elsevier Ltd. All rights reserved.

A field instrument has been developed for the purpose of measuring gas-phase atmospheric iodine species in the marine boundary layer. Vacuum UV resonance-fluorescence (RF), generated using a microwave discharge lamp, is employed to detect atomic iodine via the (5p46s)–(5p5) transitions around 178–184 nm. The system can be operated in two modes; either to directly measure ambient iodine atoms, or to measure the total photolabile iodine loading of ambient air, through broadband visible photolysis of photolabile iodine-containing species, with subsequent RF detection of the iodine atoms released. In both cases the instrument allows for the in situ measurement of the species detected, which is advantageous for gathering information concerning their local sources and distribution. The instrument is calibrated through generation of a known concentration of iodine atoms from the photolysis of I2 using a mercury pen-ray lamp. The instrument was deployed for the first time in August 2007 at Mace Head on the west coast of Ireland; initial results from this field trial are presented. Ambient iodine atoms were measured at levels up to 22 ± 4.8 ppt during the day, coinciding with the lowest tides, when Laminaria seaweed beds were exposed. The total photolabile iodine loading was also measured during several night-time and day-time periods and was found to correlate inversely with tidal height. Inferred I2 concentrations based on these measurements indicate levels of several hundred ppt at the Mace Head site. These measurements represent the first direct observations of ambient iodine atoms and measurement of total photolabile iodine in the atmosphere.

The design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO2 radicals with the Fluorescence Assay by Gas Expansion (FAGE) technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC) instrument and a GC instrument for formaldehyde detection; NO/NO2, CO, O3, and H2O vapour analysers. Ray tracing simulations and NO2 actinometry have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1) high precision kinetics investigations over a range of atmospheric conditions; (2) detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3) field instrument intercomparison, calibration, development, and investigations of instrument response at a range of atmospheric conditions.

Existing estimates of methane fluxes from North American wetlands vary widely in both magnitude and distribution. In light of these disagreements, this study uses atmospheric methane observations from the US and Canada to analyze seven different bottom-up, wetland methane estimates reported in a recent model comparison project. We first use synthetic data to explore how well atmospheric observations can constrain wetland fluxes. We find that observation sites can identify an atmospheric pattern from Canadian wetlands but not reliably from US wetlands. The network can also identify the spatial distribution of fluxes in Canada at multi-province spatial scales. Based upon these results, we then use real data to evaluate the magnitude, temporal distribution, and spatial distribution of each model estimate. Most models overestimate the magnitude of fluxes across Canada. Most predict a seasonality that is too narrow, potentially indicating an over-sensitivity to air or soil temperatures. In addition, the LPJ-Bern model has a spatial distribution that is most consistent with atmospheric observations. Unlike most models, LPJ-Bern utilizes land cover maps, not just remote sensing inundation data, to estimate wetland coverage. A flux model with a constant spatial distribution outperforms most other existing flux estimates across Canada.

[1] Airborne and ground-based measurements during the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May/June 2010 show a weekend effect in ozone in the South Coast Air Basin (SoCAB) consistent with previous observations. The well-known and much-studied weekend ozone effect has been attributed to weekend reductions in nitrogen oxide (NOx = NO + NO2) emissions, which affect ozone levels via two processes: (1) reduced ozone loss by titration and (2) enhanced photochemical production of ozone due to an increased ratio of non-methane volatile organic compounds (VOCs) to NOx. In accord with previous assessments, the 2010 airborne and ground-based data show an average decrease in NOx of 46 ± 11% and 34 ± 4%, respectively, and an average increase in VOC/NOxratio of 48 ± 8% and 43 ± 22%, respectively, on weekends. This work extends current understanding of the weekend ozone effect in the SoCAB by identifying its major causes and quantifying their relative importance from the available CalNex data. Increased weekend production of a VOC-NOxoxidation product, peroxyacetyl nitrate, compared to a radical termination product, nitric acid, indicates a significant contribution from increased photochemical production on weekends. Weekday-to-weekend differences in the products of NOx oxidation show 45 ± 13% and 42 ± 12% more extensive photochemical processing and, when compared with odd oxygen (Ox = O3 + NO2), 51 ± 14% and 22 ± 17% greater ozone production efficiency on weekends in the airborne and ground-based data, respectively, indicating that both contribute to higher weekend ozone levels in the SoCAB.

[1] Measurements of OH and HO2 concentrations were made at the surface of the eastern coast of the Hudson Bay during the COBRA campaign from February 18th to March 8th 2008. Diurnally averaged OH and HO2 concentrations peaked at 1.16 (±1.02) × 106 molecule cm−3 and 1.42 (±0.64) × 108 molecule cm−3 respectively. A box-model, constrained to supporting observations, is used to access the radical budget in this cold, northerly environment. Formaldehyde (HCHO) photolysis is found to be the dominant daytime radical source, providing 74% of the observed HOx. A considerable (>80% of the total source) surface HCHO source is required to reconcile the model and observed HCHO concentrations. Model simulations also suggest significant roles for the heterogeneous loss of HO2 and for halogen chemistry in the cycling of HO2 to OH. The formation of HO2NO2 is identified as an important radical reservoir, reducing HOx concentrations during the day and enhancing them at night. This impacts both local oxidizing capacity and reduces local ozone production by approximately 30%. The sensitivity of the local chemistry to uncertainties in these processes is explored. The majority of these processes are not currently represented in global chemistry models.

We report measurements of atmospheric composition over a tropical rainforest and over a nearby oil palm plantation in Sabah, Borneo. The primary vegetation in each of the two landscapes emits very different amounts and kinds of volatile organic compounds (VOCs), resulting in distinctive VOC fingerprints in the atmospheric boundary layer for both landscapes. VOCs over the Borneo rainforest are dominated by isoprene and its oxidation products, with a significant additional contribution from monoterpenes. Rather than consuming the main atmospheric oxidant, OH, these high concentrations of VOCs appear to maintain OH, as has been observed previously over Amazonia. The boundary-layer characteristics and mixing ratios of VOCs observed over the Borneo rainforest are different to those measured previously over Amazonia. Compared with the Bornean rainforest, air over the oil palm plantation contains much more isoprene, monoterpenes are relatively less important, and the flower scent, estragole, is prominent. Concentrations of nitrogen oxides are greater above the agro-industrial oil palm landscape than over the rainforest, and this leads to changes in some secondary pollutant mixing ratios (but not, currently, differences in ozone). Secondary organic aerosol over both landscapes shows a significant contribution from isoprene. Primary biological aerosol dominates the super-micrometre aerosol over the rainforest and is likely to be sensitive to land-use change, since the fungal source of the bioaerosol is closely linked to above-ground biodiversity.