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The Ecosystem Demography model version 2.2 (ED-2.2) is a terrestrial biosphere model that simulates the biophysical, ecological, and biogeochemical dynamics of vertically and horizontally heterogeneous terrestrial ecosystems. In a companion paper (Longo et al., 2019a), we described how the model solves the energy, water, and carbon cycles, and verified the high degree of conservation of these properties in long-term simulations that include long-term (multi-decadal) vegetation dynamics. Here, we present a detailed assessment of the model's ability to represent multiple processes associated with the biophysical and biogeochemical cycles in Amazon forests. We use multiple measurements from eddy covariance towers, forest inventory plots, and regional remote-sensing products to assess the model's ability to represent biophysical, physiological, and ecological processes at multiple timescales, ranging from subdaily to century long. The ED-2.2 model accurately describes the vertical distribution of light, water fluxes, and the storage of water, energy, and carbon in the canopy air space, the regional distribution of biomass in tropical South America, and the variability of biomass as a function of environmental drivers. In addition, ED-2.2 qualitatively captures several emergent properties of the ecosystem found in observations, specifically observed relationships between aboveground biomass, mortality rates, and wood density; however, the slopes of these relationships were not accurately captured. We also identified several limitations, including the model's tendency to overestimate the magnitude and seasonality of heterotrophic respiration and to overestimate growth rates in a nutrient-poor tropical site. The evaluation presented here highlights the potential of incorporating structural and functional heterogeneity within biomes in Earth system models (ESMs) and to realistically represent their impacts on energy, water, and carbon cycles. We also identify several priorities for further model development.

Earth system models (ESMs) have been developed to represent the role of terrestrial ecosystems on the energy, water, and carbon cycles. However, many ESMs still lack representation of within-ecosystem heterogeneity and diversity. In this paper, we present the Ecosystem Demography model version 2.2 (ED-2.2). In ED-2.2, the biophysical and physiological processes account for the horizontal and vertical heterogeneity of the ecosystem: The energy, water, and carbon cycles are solved separately for a series of vegetation cohorts (groups of individual plants of similar size and plant functional type) distributed across a series of spatially implicit patches (representing collections of microenvironments that have a similar disturbance history).We define the equations that describe the energy, water, and carbon cycles in terms of total energy, water, and carbon, which simplifies the differential equations and guarantees excellent conservation of these quantities in long-term simulation (

In Amazon forests, the relative contributions of climate, phenology, and disturbance to net ecosystem exchange of carbon (NEE) are not well understood. To partition influences across various timescales, we use a statistical model to represent eddy-covariance-derived NEE in an evergreen eastern Amazon forest as a constant response to changing meteorology and phenology throughout a decade. Our best fit model represented hourly NEE variations as changes due to sunlight, while seasonal variations arose from phenology influencing photosynthesis and from rainfall influencing ecosystem respiration, where phenology was asynchronous with dry-season onset. We compared annual model residuals with biometric forest surveys to estimate impacts of drought disturbance. We found that our simple model represented hourly and monthly variations in NEE well (R 2 Combining double low line 0.81 and 0.59, respectively). Modeled phenology explained 1 % of hourly and 26 % of monthly variations in observed NEE, whereas the remaining modeled variability was due to changes in meteorology. We did not find evidence to support the common assumption that the forest phenology was seasonally light- or water-triggered. Our model simulated annual NEE well, with the exception of 2002, the first year of our data record, which contained 1.2 MgC ha'1 of residual net emissions, because photosynthesis was anomalously low. Because a severe drought occurred in 1998, we hypothesized that this drought caused a persistent, multi-year depression of photosynthesis. Our results suggest drought can have lasting impacts on photosynthesis, possibly via partial damage to still-living trees.

Systematic biases in eddy covariance measurements of net ecosystem-atmosphere carbon dioxide exchange (NEE) are ubiquitous in forests when turbulence is low at night. We propose an alternative to the conventional bias correction, the friction velocity (u*) filter, by hypothesizing that these biases have two separate, concurrent causes: (1) a subcanopy CO2 storage pool that eludes typical storage measurements, creating a turbulence-dependent bias, and (2) advective divergence loss of CO2, creating a turbulence-independent bias. We correct for (1) using a simple parametric model of missing storage (MS). Prior experiments have inferred (2) directly from atmospheric measurements (DRAINO). For sites at which DRAINO experiments have not been performed or are infeasible, we estimate (2) empirically using a PAR-extrapolated advective respiration loss (PEARL) approach. We compare u* filter estimates of advection and NEE to MS-PEARL estimates at one temperate forest and two tropical forest sites. We find that for tropical forests, u* filters can produce a range of extreme NEE estimates, from long-term forest carbon emission to sequestration, that diverge from independent assessments and are not physically sustainable. Our MS model eliminates the dependence of nighttime NEE on u*, consistent with findings from DRAINO studies that nighttime advective losses of CO2 are often not dependent on the strength of turbulence. Our PEARL estimates of mean advective loss agree with available DRAINO measurements. The MS-PEARL correction to long-term NEE produces better agreement with forest inventories at all three sites. Moreover, the correction retains all nighttime eddy covariance data and is therefore more widely applicable than the u* filter approach, which rejects substantial nighttime data—up to 93% at one of the tropical sites. The full MS-PEARL NEE correction is therefore an equally defensible and more practical alternative to the u* filter, but leads to different conclusions about the resulting carbon balance. Our results therefore highlight the need to investigate which approach's underlying hypotheses are more physically realistic.

The East Asian Summer Monsoon driven by temperature and moisture gradients between the Asian continent and the Pacific Ocean, leads to approximately 50% of the annual rainfall in the region across 20-40°N. Due to its increasing scientific and social importance, there have been several previous studies on identification of moisture sources for summer monsoon rainfall over East Asia mainly using Lagrangian or Eulerian atmospheric water vapor models. The major source regions for EASM previously proposed include the North Indian Ocean, South China Sea and North western Pacific. Based on high-precision and high-frequency 6-year measurement records of hydrofluorocarbons (HFCs), here we report a direct evidence of rapid intrusion of warm and moist tropical air mass from the Southern Hemisphere (SH) reaching within a couple of days up to 33°N into East Asia. We further suggest that the combination of direct chemical tracer record and a back-trajectory model with physical meteorological variables helps pave the way to identify moisture sources for monsoon rainfall. A case study for Gosan station (33.25°N, 126.19°E) indicates that the meridional transport of precipitable water from the SH accompanying the southerly/southwesterly flow contributes most significantly to its summer rainfall.

An approach for analysis and modeling of global atmospheric chemistry is developed for application to measurements that provide a tropospheric climatology of those heterogeneously distributed, reactive species that control the loss of methane and the production and loss of ozone. We identify key species (e.g., O3, NOx, HNO3, HNO4, C2H3NO5, H2O, HOOH, CH3OOH, HCHO, CO, CH4, C2H6, acetaldehyde, acetone) and presume that they can be measured simultaneously in air parcels on the scale of a few km horizontally and a few tenths of a km vertically. As a first step, six global models have prepared such climatologies sampled at the modeled resolution for August with emphasis on the vast central Pacific Ocean basin. Objectives of this paper are to identify and characterize differences in model-generated reactivities as well as species covariances that could readily be discriminated with an unbiased climatology. A primary tool is comparison of multidimensional probability densities of key species weighted by the mass of such parcels or frequency of occurrence as well as by the reactivity of the parcels with respect to methane and ozone. The reactivity-weighted probabilities tell us which parcels matter in this case, and this method shows skill in differentiating among the models' chemistry. Testing 100km scale models with 2km measurements using these tools also addresses a core question about model resolution and whether fine-scale atmospheric structures matter to the overall ozone and methane budget. A new method enabling these six global chemistry-climate models to ingest an externally sourced climatology and then compute air parcel reactivity is demonstrated. Such an objective climatology containing these key species is anticipated from the NASA Atmospheric Tomography (ATom) aircraft mission (2015-2020), executing profiles over the Pacific and Atlantic Ocean basins. This modeling study addresses a core part of the design of ATom.

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 siteto 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 sitelevel 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, coldseason CH4 production and CH4 transport processes. We recommend more cold-season experimental studies in highlatitude 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.

The global burden of atmospheric methane has been increasing over the past decade, but the causes are not well understood. National inventory estimates from the U.S. Environmental Protection Agency indicate no significant trend in U.S. anthropogenic methane emissions from 2002 to present. Here we use satellite retrievals and surface observations of atmospheric methane to suggest that U.S. methane emissions have increased by more than 30% over the 2002-2014 period. The trend is largest in the central part of the country, but we cannot readily attribute it to any specific source type. This large increase in U.S. methane emissions could account for 30-60% of the global growth of atmospheric methane seen in the past decade.

Surface ecophysiology at five sites in tropical South America across vegetation and moisture gradients is investigated. From the moist northwest (Manaus) to the relatively dry southeast (Pé de Gigante, state of São Paulo) simulated seasonal cycles of latent and sensible heat, and carbon flux produced with the Simple Biosphere Model (SiB3) are confronted with observational data. In the northwest, abundant moisture is available, suggesting that the ecosystem is light-limited. In these wettest regions, Bowen ratio is consistently low, with little or no annual cycle. Carbon flux shows little or no annual cycle as well; efflux and uptake are determined by high-frequency variability in light and moisture availability. Moving downgradient in annual precipitation amount, dry season length is more clearly defined. In these regions, a dry season sink of carbon is observed and simulated. This sink is the result of the combination of increased photosynthetic production due to higher light levels, and decreased respiratory efflux due to soil drying. The differential response time of photosynthetic and respiratory processes produce observed annual cycles of net carbon flux. In drier regions, moisture and carbon fluxes are in-phase; there is carbon uptake during seasonal rains and efflux during the dry season. At the driest site, there is also a large annual cycle in latent and sensible heat flux. © 2012.

We investigated the seasonal patterns of Amazonian forest photosynthetic activity, and the effects thereon of variations in climate and land-use, by integrating data from a network of ground-based eddy flux towers in Brazil established as part of the 'Large-Scale Biosphere Atmosphere Experiment in Amazonia' project. We found that degree of water limitation, as indicated by the seasonality of the ratio of sensible to latent heat flux (Bowen ratio) predicts seasonal patterns of photosynthesis. In equatorial Amazonian forests (5° N-5° S), water limitation is absent, and photosynthetic fluxes (or gross ecosystem productivity, GEP) exhibit high or increasing levels of photosynthetic activity as the dry season progresses, likely a consequence of allocation to growth of new leaves. In contrast, forests along the southern flank of the Amazon, pastures converted from forest, and mixed forest-grass savanna, exhibit dry-season declines in GEP, consistent with increasing degrees of water limitation. Although previous work showed tropical ecosystem evapotranspiration (ET) is driven by incoming radiation, GEP observations reported here surprisingly show no or negative relationships with photosynthetically active radiation (PAR). Instead, GEP fluxes largely followed the phenology of canopy photosynthetic capacity (Pc), with only deviations from this primary pattern driven by variations in PAR. Estimates of leaf flush at three non-water limited equatorial forest sites peak in the dry season, in correlation with high dry season light levels. The higher photosynthetic capacity that follows persists into the wet season, driving high GEP that is out of phase with sunlight, explaining the negative observed relationship with sunlight. Overall, these patterns suggest that at sites where water is not limiting, light interacts with adaptive mechanisms to determine photosynthetic capacity indirectly through leaf flush and litterfall seasonality. These mechanisms are poorly represented in ecosystem models, and represent an important challenge to efforts to predict tropical forest responses to climatic variations. © 2013 Elsevier B.V.

Methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), and C2-C5 alkanes were measured throughout the Los Angeles (L.A.) basin in May and June 2010. We use these data to show that the emission ratios of CH4/CO and CH4/CO2 in the L.A. basin are larger than expected from population-apportioned bottom-up state inventories, consistent with previously published work. We use experimentally determined CH4/CO and CH4/CO2 emission ratios in combination with annual State of California CO and CO2 inventories to derive a yearly emission rate of CH4 to the L.A. basin. We further use the airborne measurements to directly derive CH4 emission rates from dairy operations in Chino, and from the two largest landfills in the L.A. basin, and show these sources are accurately represented in the California Air Resources Board greenhouse gas inventory for CH4. We then use measurements of C2-C5 alkanes to quantify the relative contribution of other CH4 sources in the L.A. basin, with results differing from those of previous studies. The atmospheric data are consistent with the majority of CH4 emissions in the region coming from fugitive losses from natural gas in pipelines and urban distribution systems and/or geologic seeps, as well as landfills and dairies. The local oil and gas industry also provides a significant source of CH4 in the area. The addition of CH4 emissions from natural gas pipelines and urban distribution systems and/or geologic seeps and from the local oil and gas industry is sufficient to account for the differences between the top-down and bottom-up CH4 inventories identified in previously published work. Key PointsTop-down estimates of CH4 emissions in L.A. are greater than inventory estimatesEstimates of CH4 emissions from landfills in L.A. agree with CARB inventoryPipeline natural gas and/or seeps, and landfills are main sources of CH4 in L.A. ©2013. American Geophysical Union. All Rights Reserved.

Airborne measurements of methane (CH4) and carbon dioxide (CO2) were taken over the rice growing region of California's Sacramento Valley in the late spring of 2010 and 2011. From these and ancillary measurements, we show that CH4 mixing ratios were higher in the planetary boundary layer above the Sacramento Valley during the rice growing season than they were before it, which we attribute to emissions from rice paddies. We derive daytime emission fluxes of CH4 between 0.6 and 2.0% of the CO2 taken up by photosynthesis on a per carbon, or mole to mole, basis. We also use a mixing model to determine an average CH 4/CO2 flux ratio of -0.6% for one day early in the growing season of 2010. We conclude the CH4/CO2 flux ratio estimates from a single rice field in a previous study are representative of rice fields in the Sacramento Valley. If generally true, the California Air Resources Board (CARB) greenhouse gas inventory emission rate of 2.7×1010g CH4/yr is approximately three times lower than the range of probable CH4 emissions (7.8-9.3×10 10g CH4/yr) from rice cultivation derived in this study. We attribute this difference to decreased burning of the residual rice crop since 1991, which leads to an increase in CH4 emissions from rice paddies in succeeding years, but which is not accounted for in the CARB inventory. © 2012. American Geophysical Union. All Rights Reserved.

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/NOx ratio 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-NOx oxidation 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. Copyright 2012 by the American Geophysical Union.

We analyze the North American budget for carbon monoxide using data for CO and formaldehyde concentrations from tall towers and aircraft in a model-data assimilation framework. The Stochastic Time-Inverted Lagrangian Transport model for CO (STILT-CO) determines local to regional-scale CO contributions associated with production from fossil fuel combustion, biomass burning, and oxidation of volatile organic compounds (VOCs) using an ensemble of Lagrangian particles driven by high resolution assimilated meteorology. In many cases, the model demonstrates high fidelity simulations of hourly surface data from tall towers and point measurements from aircraft, with somewhat less satisfactory performance in coastal regions and when CO from large biomass fires in Alaska and the Yukon Territory influence the continental US. Inversions of STILT-CO simulations for CO and formaldehyde show that current inventories of CO emissions from fossil fuel combustion are significantly too high, by almost a factor of three in summer and a factor two in early spring, consistent with recent analyses of data from the INTEX-A aircraft program. Formaldehyde data help to show that sources of CO from oxidation of CH4 and other VOCs represent the dominant sources of CO over North America in summer. © Author(s) 2008.

We present a decadal (1994-2004) record of carbon dioxide flux in a 160-year-old black spruce forest/veneer bog complex in central Manitoba, Canada. The ecosystem shifted from a source (+41 g Cm-2, 1995) to a sink (-21 g C m-2, 2004) of CO2 over the decade, with an average net carbon balance near zero. Annual mean temperatures increased 1-2° during the period, consistent with the decadal trend across the North American boreal biome. We found that ecosystem carbon exchange responded strongly to air temperature, moisture status, potential evapotranspiration, and summertime solar radiation. The seasonal cycle of ecosystem respiration significantly lagged that of photosynthesis, limited by the rate of soil thaw and the slow drainage of the soil column. Factors acting over long time scales, especially water table depth, strongly influenced the carbon budget on annual time scales. Net uptake was enhanced and respiration inhibited by multiple years of rainfall in excess of evaporative demand. Contrary to expectations, we observed no correlation between longer growing seasons and net uptake, possibly because of offsetting increases in ecosystem respiration. The results indicate that the interactions between soil thaw and water table depth provide critical controls on carbon exchange in boreal forests underlain by peat, on seasonal to decadal time scales, and these factors must be simulated in terrestrial biosphere models to predict response of these regions to future climate. © 2007 Blackwell Publishing Ltd.

We used a 10-year record of the CO2 flux by an old growth boreal forest in central Manitoba (the Northern Old Black Spruce Site (NOBS)), a ∼150-year-old Picea mariana [Mill.] stand) to determine whether and how whole-forest CO2 flux is related to tree ring width. We compared a 37-year ring width chronology collected at NOBS to a second chronology that was collected at a nearby Black Spruce stand with a different disturbance history, and also to three measures of annual whole-forest photosynthesis [gross ecosystem production (GEP)], two measures of annual respiration (R), and one measure of annual carbon balance [net ecosystem production (NEP)]. The year-to-year ring width fluctuations were well correlated between the two sites; increasing our confidence in the NOBS chronology and implying that ring width variation is driven and synchronized by the physical environment. Both chronologies exhibited serial correlation, with a fluctuation in ring width that had an apparent periodicity of ∼7 years. Neither chronology was correlated with variation in annual precipitation or temperature. Ring width and NEP increased, while R decreased from 1995 to 2004. GEP either remained constant or decreased from 1995 to 2004, depending on which measure was considered. The lack of relationship between ring width and GEP may indicate that ring growth is controlled almost entirely by something other than carbon uptake. Alternative explanations for the ring width chronologies include the possibility that wood production varies as a result of shifts in respiration, or that an unidentified aspect of the environment, rather than the balance between GEP and respiration, controls wood production. The serial correlation in ring width may be related to increases and decreases in carbohydrate pools, or to gradual changes in nutrient availability, pathogens, herbivores, soil frost or soil water table. The cause or causes of serial correlation, and the controls on the allocation of photosynthate to wood production, emerge as critical uncertainties for efforts in predicting the carbon balance of boreal ecosystems and inferring past climate from tree rings. © 2006 Blackwell Publishing Ltd.

The Orbiting Carbon Observatory (OCO) mission will make the first global, space-based measurements of atmospheric carbon dioxide (CO 2 ) with the precision, resolution, and coverage needed to characterize CO 2 sources and sinks on regional scales. The measurement approach and instrument specifications were determined through an analysis of existing carbon cycle data and a series of observing system simulation experiments. During its 2-year mission, OCO will fly in a 1:15 PM sun-synchronous orbit with a 16-day ground-track repeat time, just ahead of the EOS Aqua platform. It will carry a single instrument that incorporates three bore-sighted high-resolution spectrometers designed to measure reflected sunlight in the 0.76-μm O 2 A-band and in the CO 2 bands at 1.61 and 2.06 μm. Soundings recorded in these three bands will be used to retrieve the column-averaged CO 2 dry air mole fraction (X CO2 ). A comprehensive validation program was included in the mission to ensure that the space-based X CO2 measurements have precisions of ∼0.3% (1 ppm) on regional scales. OCO measurements will be used in global synthesis inversion and data assimilation models to quantify CO 2 sources and sinks. While OCO will have a nominal lifetime of only 2 years, it will serve as a pathfinder for future long-term CO 2 monitoring missions. © 2004 COSPAR. Published by Elsevier Ltd. All rights reserved.

A model of the daily carbon balance of a black spruce/feathermoss boreal forest ecosystem was developed and results compared to preliminary data from the 1994 BOREAS field campaign in northern Manitoba, Canada. The model, driven by daily weather conditions, simulated daily soil climate status (temperature and moisture profiles), spruce photosynthesis and respiration, moss photosynthesis and respiration, and litter decomposition. Model agreement with preliminary field data was good for net ecosystem exchange (NEE), capturing both the asymmetrical seasonality and short-term variability. During the growing season simulated daily NEE ranged from -4 g C m-2 d-1 (carbon uptake by ecosystem) to + 2 g C m-2 d-1 (carbon flux to atmosphere), with fluctuations from day to day. In the early winter simulated NEE values were + 0.5 g C m-2 d-1, dropping to + 0.2 g C m-2 d-1 in mid-winter. Simulated soil respiration during the growing season (+ 1 to + 5 g C m-2 d-1) was dominated by metabolic respiration of the live moss, with litter decomposition usually contributing less than 30% and live spruce root respiration less than 10% of the total. Both spruce and moss net primary productivity (NPP) rates were higher in early summer than late summer. Simulated annual NEE for 1994 was -51 g C m-2 y-1, with 83% going into tree growth and 17% into the soil carbon accumulation. Moss NPP (58 g C m-2 y-1) was considered to be litter (i.e. soil carbon input; no net increase in live moss biomass). Ecosystem respiration during the snow-covered season (84 g C m-2) was 58% of the growing season net carbon uptake. A simulation of the same site for 1968-1989 showed ≈ 10-20% year-to-year variability in heterotrophic respiration (mean of + 113 g C m-2 y-1). Moss NPP ranged from 19 to 114 g C m-2 y-1; spruce NPP from 81 to 150 g C m-2 y-1; spruce growth (NPP minus litterfall) from 34 to 103 g C m-2 y-1; NEE ranged from +37 to -142 g C m-2 y-1. Values for these carbon balance terms in 1994 were slightly smaller than the 1969-89 means. Higher ecosystem productivity years (more negative NEE) generally had early springs and relatively wet summers; lower productivity years had late springs and relatively dry summers. © 1996 Blackwell Science Ltd.

Our objective is to describe a multi-layer model of C3-canopy processes that effectively simulates hourly CO2 and latent energy (LE) fluxes in a mixed deciduous Quercus-Acer (oak-maple) stand in central Massachusetts, USA. The key hypothesis governing the biological component of the model is that stomatal conductance (g(s)) is varied so that daily carbon uptake per unit of foliar nitrogen is maximized within the limitations of canopy water availability. The hydraulic system is modelled as an analogue to simple electrical circuits in parallel, including a separate soil hydraulic resistance, plant resistance and plant capacitance for each canopy layer. Stomatal opening is initially controlled to conserve plant water stores and delay the onset of water stress. Stomatal closure at a threshold minimum leaf water potential prevents xylem cavitation and controls the maximum rate of water flux through the hydraulic system. We show a strong correlation between predicted hourly CO2 exchange rate (r2 = 0.86) and LE (r2 = 0.87) with independent whole-forest measurements made by the eddy correlation method during the summer of 1992. Our theoretical derivation shows that observed relationships between CO2 assimilation and LE flux can be explained on the basis of stomatal behaviour optimizing carbon gain, and provides an explicit link between canopy structure, soil properties, atmospheric conditions and stomatal conductance.

The turbulent exchanges of CO2 and water vapour between an aggrading deciduous forest in the north-eastern United States (Harvard Forest) and the atmosphere were measured from 1990 to 1994 using the eddy covariance technique. We present a detailed description of the methods used and a rigorous evaluation of the precision and accuracy of these measurements. We partition the sources of error into three categories: (1) uniform systematic errors are constant and independent of measurement conditions (2) selective systematic errors result when the accuracy of the exchange measurement varies as a function of the physical environment, and (3) sampling uncertainty results when summing an incomplete data set to calculate long-term exchange. Analysis of the surface energy budget indicates a uniform systematic error in the turbulent exchange measurements of -20 to 0%. A comparison of nocturnal eddy flux with chamber measurements indicates a selective systematic underestimation during calm (friction velocity < 0.17 m s-1) nocturnal periods. We describe an approach to correct for this error. The integrated carbon sequestration in 1994 was 2.1 t C ha-1 y-1 with a 90% confidence interval due to sampling uncertainty of ±0.3 t C ha-1 y-1 determined by Monte Carlo simulation. Sampling uncertainty may be reduced by estimating the flux as a function of the physical environment during periods when direct observations are unavailable, and by minimizing the length of intervals without flux data. These analyses lead us to place an overall uncertainty on the annual carbon sequestration in 1994 of -0.3 to +0.8 t C ha-1 y-1. © 1996 Blackwell Science Ltd.

Two independent methods of estimating gross ecosystem production (GEP) were compared over a period of 2 years at monthly integrals for a mixed forest of conifers and deciduous hardwoods at Harvard Forest in central Massachusetts. Continuous eddy flux measurements of net ecosystem exchange (NEE) provided one estimate of GEP by taking day to night temperature differences into account to estimate autotrophic and heterotrophic respiration. GEP was also estimated with a quantum efficiency model based on measurements of maximum quantum efficiency (Qmax), seasonal variation in canopy phenology and chlorophyll content, incident PAR, and the constraints of freezing temperatures and vapour pressure deficits on stomatal conductance. Quantum efficiency model estimates of GEP and those derived from eddy flux measurements compared well at monthly integrals over two consecutive years (R2= 0–98). Remotely sensed data were acquired seasonally with an ultralight aircraft to provide a means of scaling the leaf area and leaf pigmentation changes that affected the light absorption of photosynthetically active radiation to larger areas. A linear correlation between chlorophyll concentrations in the upper canopy leaves of four hardwood species and their quantum efficiencies (R2= 0–99) suggested that seasonal changes in quantum efficiency for the entire canopy can be quantified with remotely sensed indices of chlorophyll. Analysis of video data collected from the ultralight aircraft indicated that the fraction of conifer cover varied from < 7% near the instrument tower to about 25% for a larger sized area. At 25% conifer cover, the quantum efficiency model predicted an increase in the estimate of annual GEP of < 5% because unfavourable environmental conditions limited conifer photosynthesis in much of the non‐growing season when hardwoods lacked leaves. Copyright © 1995, Wiley Blackwell. All rights reserved

A big-leaf model of C3-canopy mass and energy exchange was used to predict hourly CO2 and O3 uptake by a mixed deciduous Quercus-Acer (oak-maple) stand in central Massachusetts, USA. The model is based on canopy-radiation interactions, leaf mesophyll metabolism (photosynthetic electron transport, carboxylation and oxygenation of ribulose 1,5-bisphosphate [RuP2] by RuP2 carboxylase/oxygenase [Rubisco], and respiration), physical transport conductances of mass and heat above and within the canopy, conductances of mass at the leaf surface and in the mesophyll, and mass and energy exchange at the soil surface (forest floor). Predictions of hourly CO2 and O3 uptake were compared to independent whole-forest CO2 and O3 exchange measurements made by the eddy correlation method during a 68 day period in the summer and early autumn of 1992. Predicted hourly CO2 exchange rate was strongly correlated (r ≈ +0.91) with measured hourly CO2 exchange, but mean day-time predicted whole-forest CO2 uptake was c. 13% (c. 1.13 μmol CO2 m-2 s-1) greater than CO2 uptake measured by eddy correlation. The model tended to overpredict CO2 uptake during late afternoon, but was accurate during the rest of the day. Predicted and measured O3 uptake rates also were positively correlated (r ≈ +0.76). The diurnal patterns of predicted and measured O3 uptake indicated that stomata1 conductance (gs) was accurately predicted during the morning, but in the afternoon the model overpredicted gs. This pattern was consistent with the overprediction of afternoon CO2 uptake, and suggested that a feedback inhibition of photosynthesis occurred in the afternoon. This might have been related to source-sink imbalance following several hours of photosynthesis. On the whole, and in spite of the simplifications inherent in the big-leaf representation of the canopy, the model is useful for predicting forest-environment interactions and for interpreting mass and energy exchange measurements.

Present understanding of global atmospheric chemistry is reviewed. Models are presented and compared with a wide range of atmospheric observations, with emphasis on the stratosphere. In general, excellent agreement is found between the calculated and observed distributions of long lived trace gases. The abundances of many shorter lived species are also satisfactorily reproduced, including NO 2 , HNO 3 , O, O 3 , OH and ClO. Discrepancies between theory and observation are examined and their significance assessed. The influence of human perturbations due to combustion, agriculture and chlorocarbon releases is discussed with emphasis on O 3 . Uncertainties associated with present models are highlighted. Combustion related releases of CO cause a decrease in the abundance of tropospheric OH with consequent increase in the concentrations of CH 4 , H 2 , CH 3 Cl and other halocarbons. CO emissions may become sufficiently large during the next century to induce substantial increases in tropospheric ozone on a global scale. Recombination of nitrogen fixed by agriculture and combustion may lead to an enhanced source of atmospheric N 2 O with a related impact on stratospheric NO x . Chlorocarbon industry provides an important source of stratospheric chlorine, and enhanced levels of stratospheric Cl x and NO x may cause a significant reduction in the abundance of atmospheric O 3 , by as much as 10% during the next century. Perturbations due to various anthropogenic activities interact in a nonlinear fashion and the influence on atmospheric chemistry is correspondingly complex.

An increase in the concentration of inorganic chlorine to levels comparable to that of oxidized reactive nitrogen could cause a significant change in the chemistry of the lower stratosphere leading to a reduction potentially larger than 15% in the column density of ozone. This could occur, for example by the middle of the next century, if emissions of man-made chlorocarbons were to grow at a rate of 3% per year. Ozone could be further depressed by release of industrial bromocarbon.

Oxidation of CS2 and COS initiated by reaction with OH can provide a source of atmospheric SO2 as large as 12 Mtonnes S yr -1 and may represent the dominant source of SO2 in remote regions of the marine troposphere. © 1979 Nature Publishing Group.

Understanding the effects of intensification of Amazon basin hydrological cycling-manifest as increasingly frequent floods and droughts-on water and energy cycles of tropical forests is essential to meeting the challenge of predicting ecosystem responses to climate change, including forest "tipping points". Here, we investigated the impacts of hydrological extremes on forest function using 12+ years of observations (between 2001-2020) of water and energy fluxes from eddy covariance, along with associated ecological dynamics from biometry, at the Tapajós National Forest. Measurements encompass the strong 2015-2016 El Niño drought and La Niña 2008-2009 wet events. We found that the forest responded strongly to El Niño-Southern Oscillation (ENSO): Drought reduced water availability for evapotranspiration (ET) leading to large increases in sensible heat fluxes (H). Partitioning ET by an approach that assumes transpiration (T) is proportional to photosynthesis, we found that water stress-induced reductions in canopy conductance (G s ) drove T declines partly compensated by higher evaporation (E). By contrast, the abnormally wet La Niña period gave higher T and lower E, with little change in seasonal ET. Both El Niño-Southern Oscillation (ENSO) events resulted in changes in forest structure, manifested as lower wet-season leaf area index. However, only during El Niño 2015-2016, we observed a breakdown in the strong meteorological control of transpiration fluxes (via energy availability and atmospheric demand) because of slowing vegetation functions (via shutdown of G s and significant leaf shedding). Drought-reduced T and G s , higher H and E, amplified by feedbacks with higher temperatures and vapor pressure deficits, signaled that forest function had crossed a threshold, from which it recovered slowly, with delay, post-drought. Identifying such tipping point onsets (beyond which future irreversible processes may occur) at local scale is crucial for predicting basin-scale threshold-crossing changes in forest energy and water cycling, leading to slow-down in forest function, potentially resulting in Amazon forests shifting into alternate degraded states., (© 2023 John Wiley & Sons Ltd.)

The hydroxyl radical (OH) fuels atmospheric chemical cycling as the main sink for methane and a driver of the formation and loss of many air pollutants, but direct OH observations are sparse. We develop and evaluate an observation-based proxy for short-term, spatial variations in OH (Proxy OH ) in the remote marine troposphere using comprehensive measurements from the NASA Atmospheric Tomography (ATom) airborne campaign. Proxy OH is a reduced form of the OH steady-state equation representing the dominant OH production and loss pathways in the remote marine troposphere, according to box model simulations of OH constrained with ATom observations. Proxy OH comprises only eight variables that are generally observed by routine ground- or satellite-based instruments. Proxy OH scales linearly with in situ [OH] spatial variations along the ATom flight tracks (median r 2 = 0.90, interquartile range = 0.80 to 0.94 across 2-km altitude by 20° latitudinal regions). We deconstruct spatial variations in Proxy OH as a first-order approximation of the sensitivity of OH variations to individual terms. Two terms modulate within-region Proxy OH variations-water vapor (H 2 O) and, to a lesser extent, nitric oxide (NO). This implies that a limited set of observations could offer an avenue for observation-based mapping of OH spatial variations over much of the remote marine troposphere. Both H 2 O and NO are expected to change with climate, while NO also varies strongly with human activities. We also illustrate the utility of Proxy OH as a process-based approach for evaluating intermodel differences in remote marine tropospheric OH.

Pyrocumulonimbus (pyroCb) are wildfire-generated convective clouds that can inject smoke directly into the stratosphere. PyroCb have been tracked for years, yet their apparent rarity and episodic nature lead to highly uncertain climate impacts. In situ measurements of pyroCb smoke reveal its distinctive and exceptionally stable aerosol properties and define the long-term influence of pyroCb activity on the stratospheric aerosol budget. Analysis of 13 years of airborne observations shows that pyroCb are responsible for 10 to 25% of the black carbon and organic aerosols in the "present-day" lower stratosphere, with similar impacts in both the North and South Hemispheres. These results suggest that, should pyroCb increase in frequency and/or magnitude in future climates, they could generate dominant trends in stratospheric aerosol.

Urban regions emit a large fraction of anthropogenic emissions of greenhouse gases (GHG) such as carbon dioxide (CO 2 ) and methane (CH 4 ) that contribute to modern-day climate change. As such, a growing number of urban policymakers and stakeholders are adopting emission reduction targets and implementing policies to reach those targets. Over the past two decades research teams have established urban GHG monitoring networks to determine how much, where, and why a particular city emits GHGs, and to track changes in emissions over time. Coordination among these efforts has been limited, restricting the scope of analyses and insights. Here we present a harmonized data set synthesizing urban GHG observations from cities with monitoring networks across North America that will facilitate cross-city analyses and address scientific questions that are difficult to address in isolation., (© 2022. The Author(s).)