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1. Influence of plant ecophysiology on ozone dry deposition: comparing between multiplicative and photosynthesis-based dry deposition schemes and their responses to rising CO₂ level

   https://doi.org/10.5194/bg-19-1753-2022  

   Sun, Shihan ; Tai, Amos P. ; Yung, David H. ; Wong, Anthony Y. ; Ducker, Jason A. ; Holmes, Christopher D. ( January 2022 , Biogeosciences)

   Abstract. Dry deposition is a key process for surface ozone(O3) removal. Stomatal uptake is a major component of O3 drydeposition, which is parameterized differently in current land surfacemodels and chemical transport models. We developed and used a standaloneterrestrial biosphere model, driven by a unified set of prescribedmeteorology, to evaluate two widely used dry deposition modeling frameworks,Wesely (1989) and Zhang et al. (2003), with different configurations ofstomatal resistance: (1) the default multiplicative method in the Weselyscheme (W89) and Zhang et al. (2003) scheme (Z03), (2) the traditionalphotosynthesis-based Farquhar–Ball–Berry (FBB) stomatal algorithm, and (3) theMedlyn stomatal algorithm (MED) based on optimization theory. We found thatusing the FBB stomatal approach that captures ecophysiological responses toenvironmental factors, especially to water stress, can generally improve thesimulated dry deposition velocities compared with multiplicative schemes.The MED stomatal approach produces higher stomatal conductance than FBB andis likely to overestimate dry deposition velocities for major vegetationtypes, but its performance is greatly improved when spatially varying slopeparameters based on annual mean precipitation are used. Large discrepancieswere also found in stomatal responses to rising CO2 levels from 390to 550 ppm: the multiplicative stomatal method with an empirical CO2response function produces reduction (−35 %) in global stomatalconductance on average much larger than that with the photosynthesis-basedstomatal method (−14 %–19 %). Our results show the potential biases inO3 sink caused by errors in model structure especially in the Weselydry deposition scheme and the importance of using photosynthesis-basedrepresentation of stomatal resistance in dry deposition schemes under achanging climate and rising CO2 concentration. 

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2. Autonomous seawater <i>p</i>CO₂ and pH time series from 40 surface buoys and the emergence of anthropogenic trends

   https://doi.org/10.5194/essd-11-421-2019  

   Sutton, Adrienne J. ; Feely, Richard A. ; Maenner-Jones, Stacy ; Musielwicz, Sylvia ; Osborne, John ; Dietrich, Colin ; Monacci, Natalie ; Cross, Jessica ; Bott, Randy ; Kozyr, Alex ; et al ( January 2019 , Earth System Science Data)

   Abstract. Ship-based time series, some now approaching over 3 decades long, are critical climate records that have dramatically improved our ability to characterize natural and anthropogenic drivers of ocean carbon dioxide (CO2) uptake and biogeochemical processes. Advancements in autonomous marine carbon sensors and technologies over the last 2 decades have led to the expansion of observations at fixed time series sites, thereby improving the capability of characterizing sub-seasonal variability in the ocean. Here, we present a data product of 40 individual autonomous moored surface ocean pCO2 (partial pressure of CO2) time series established between 2004 and 2013, 17 also include autonomous pH measurements. These time series characterize a wide range of surface ocean carbonate conditions in different oceanic (17 sites), coastal (13 sites), and coral reef (10 sites) regimes. A time of trend emergence (ToE) methodology applied to the time series that exhibit well-constrained daily to interannual variability and an estimate of decadal variability indicates that the length of sustained observations necessary to detect statistically significant anthropogenic trends varies by marine environment. The ToE estimates for seawater pCO2 and pH range from 8 to 15 years at the open ocean sites, 16 to 41 years at the coastal sites, and 9 to 22 years at the coral reef sites. Only two open ocean pCO2 time series, Woods Hole Oceanographic Institution Hawaii Ocean Time-series Station (WHOTS) in the subtropical North Pacific and Stratus in the South Pacific gyre, have been deployed longer than the estimated trend detection time and, for these, deseasoned monthly means show estimated anthropogenic trends of 1.9±0.3 and 1.6±0.3 µatm yr−1, respectively. In the future, it is possible that updates to this product will allow for the estimation of anthropogenic trends at more sites; however, the product currently provides a valuable tool in an accessible format for evaluating climatology and natural variability of surface ocean carbonate chemistry in a variety of regions. Data are available at https://doi.org/10.7289/V5DB8043 and https://www.nodc.noaa.gov/ocads/oceans/Moorings/ndp097.html (Sutton et al., 2018). 

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3. How can mountaintop CO₂ observations be used to constrain regional carbon fluxes?

   https://doi.org/10.5194/acp-17-5561-2017  

   Lin, John C. ; Mallia, Derek V. ; Wu, Dien ; Stephens, Britton B. ( January 2017 , Atmospheric Chemistry and Physics)

   Despite the need for researchers to understand terrestrial biospheric carbon fluxes to account for carbon cycle feedbacks and predict future CO₂ concentrations, knowledge of these fluxes at the regional scale remains poor. This is particularly true in mountainous areas, where complex meteorology and lack of observations lead to large uncertainties in carbon fluxes. Yet mountainous regions are often where significant forest cover and biomass are found – i.e., areas that have the potential to serve as carbon sinks. As CO₂ observations are carried out in mountainous areas, it is imperative that they are properly interpreted to yield information about carbon fluxes. In this paper, we present CO₂ observations at three sites in the mountains of the western US, along with atmospheric simulations that attempt to extract information about biospheric carbon fluxes from the CO₂ observations, with emphasis on the observed and simulated diurnal cycles of CO₂. We show that atmospheric models can systematically simulate the wrong diurnal cycle and significantly misinterpret the CO₂ observations, due to erroneous atmospheric flows as a result of terrain that is misrepresented in the model. This problem depends on the selected vertical level in the model and is exacerbated as the spatial resolution is degraded, and our results indicate that a fine grid spacing of ∼ 4 km or less may be needed to simulate a realistic diurnal cycle of CO₂ for sites on top of the steep mountains examined here in the American Rockies. In the absence of higher resolution models, we recommend coarse-scale models to focus on assimilating afternoon CO₂ observations on mountaintop sites over the continent to avoid misrepresentations of nocturnal transport and influence. 

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4. EcH₂O-iso 1.0: Water isotopes and age tracking in a process-based,distributed ecohydrological model

   https://doi.org/10.5194/gmd-2018-25  

   Kuppel, Sylvain ; Tetzlaff, Doerthe ; Maneta, Marco P. ; Soulsby, Chris ( July 2018 , Geoscientific Model Development Discussions)

   We introduce EcH₂O-iso, a new development of the physically-based, fully-distributed ecohydrological model EcH2O where the tracking of water isotopic tracers (²H and ¹⁸O) and age has been incorporated. EcH₂O-iso is evaluated at a montane, low-energy experimental catchment in eastern Scotland using 16 independent isotope time series from various landscape positions and compartments; encompassing soil water, groundwater, stream water, and plant xylem. We find a good model-observation match in most cases, despite having only calibrated the model using hydrometric data and energy fluxes. These results provide further validation of the physical basis of the model for successfully capturing catchment hydrological functioning, both in terms of the celerity in energy propagation (e.g. runoff generation under prevailing hydraulic gradients) and flow velocities of water molecules (e.g., in consistent tracer concentrations at given locations and times). We also show that the spatially-distributed formulation of EcH₂O-iso provides a powerful tool for quantitatively linking water stores and fluxes with spatio-temporal patterns of isotopes ratios and water ages. Finally, our study highlights some model development and benchmarking needs, refined using isotope-based calibration, for hypothesis testing and improved simulations of catchment dynamics that is transferable beyond the catchment landscape studied here. 

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5. OH and HO₂ radical chemistry in a midlatitude forest: measurements and model comparisons

   https://doi.org/10.5194/acp-20-9209-2020  

   Lew, Michelle M. ; Rickly, Pamela S. ; Bottorff, Brandon P. ; Reidy, Emily ; Sklaveniti, Sofia ; Léonardis, Thierry ; Locoge, Nadine ; Dusanter, Sebastien ; Kundu, Shuvashish ; Wood, Ezra ; et al ( January 2020 , Atmospheric Chemistry and Physics)

   null (Ed.)

   Abstract. Reactions of the hydroxyl (OH) and peroxy (HO2 and RO2) radicals playa central role in the chemistry of the atmosphere. In addition to controlling the lifetimes ofmany trace gases important to issues of global climate change, OH radical reactionsinitiate the oxidation of volatile organic compounds (VOCs) which can lead to the production ofozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicalsin forest environments characterized by high mixing ratios of isoprene and low mixing ratios ofnitrogen oxides (NOx) (typically less than 1–2 ppb) have shown seriousdiscrepancies with modeled concentrations. These results bring into question our understanding ofthe atmospheric chemistry of isoprene and other biogenic VOCs under low NOxconditions. During the summer of 2015, OH and HO2 radical concentrations, as well as totalOH reactivity, were measured using laser-induced fluorescence–fluorescence assay by gasexpansion (LIF-FAGE) techniques as part of the Indiana Radical Reactivity and Ozone productioN InterComparison (IRRONIC). This campaign took place in a forested area near Indiana University's Bloomington campus which is characterized by high mixing ratios of isoprene (average daily maximum ofapproximately 4 ppb at 28 ∘C) and low mixing ratios of NO (diurnal averageof approximately 170 ppt). Supporting measurements of photolysis rates, VOCs,NOx, and other species were used to constrain a zero-dimensional box model basedon the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM 3.2),including versions of the Leuven isoprene mechanism (LIM1) for HOx regeneration(RACM2-LIM1 and MCM 3.3.1). Using an OH chemical scavenger technique, the study revealed thepresence of an interference with the LIF-FAGE measurements of OH that increased with bothambient concentrations of ozone and temperature with an average daytime maximum equivalentOH concentration of approximately 5×106 cm−3. Subtraction of theinterference resulted in measured OH concentrations of approximately4×106 cm−3 (average daytime maximum) that were in better agreement with modelpredictions although the models underestimated the measurements in the evening. The addition ofversions of the LIM1 mechanism increased the base RACM2 and MCM 3.2 modeled OH concentrationsby approximately 20 % and 13 %, respectively, with the RACM2-LIM1 mechanism providing thebest agreement with the measured concentrations, predicting maximum daily OH concentrationsto within 30 % of the measured concentrations. Measurements of HO2 concentrationsduring the campaign (approximately a 1×109 cm−3 average daytime maximum)included a fraction of isoprene-based peroxy radicals(HO2*=HO2+αRO2) and were found to agree with modelpredictions to within 10 %–30 %. On average, the measured reactivity was consistent with thatcalculated from measured OH sinks to within 20 %, with modeled oxidation productsaccounting for the missing reactivity, however significant missing reactivity (approximately40 % of the total measured reactivity) was observed on some days. 

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