Isoprene and monoterpene fluxes from central amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget

We estimated the isoprene and monoterpene source strengths of a pristine tropical forest north of Manaus in the central Amazon Basin using three different micrometeorological flux measurement approaches. During the early dry season campaign of the Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001), a tower-based surface layer gradient (SLG) technique was applied simultaneously with a relaxed eddy accumulation (REA) system. Airborne measurements of vertical profiles within and above the convective boundary layer (CBL) were used to estimate fluxes on a landscape scale by application of the mixed layer gradient (MLG) technique. The mean daytime fluxes of organic carbon measured by REA were 2.1 mg C m^−2 h^−1 for isoprene, 0.20 mg C m^−2 h^−1 for α-pinene, and 0.39 mg C m^−2 h^−1 for the sum of monoterpenes. These values are in reasonable agreement with fluxes determined with the SLG approach, which exhibited a higher scatter, as expected for the complex terrain investigated. The observed VOC fluxes are in good agreement with simulations using a single-column chemistry and climate model (SCM).\ud \ud In contrast, the model-derived mixing ratios of VOCs were by far higher than observed, indicating that chemical processes may not be adequately represented in the model. The observed vertical gradients of isoprene and its primary degradation products methyl vinyl ketone (MVK) and methacrolein (MACR) suggest that the oxidation capacity in the tropical CBL is much higher than previously assumed. A simple chemical kinetics model was used to infer OH radical concentrations from the vertical gradients of (MVK+MACR)/isoprene. The estimated range of OH concentrations during the daytime was 3–8×10^6 molecules cm^−3, i.e., an order of magnitude higher than is estimated for the tropical CBL by current state-of-the-art atmospheric chemistry and transport models. The remarkably high OH concentrations were also supported by results of a simple budget analysis, based on the flux-to-lifetime relationship of isoprene within the CBL. Furthermore, VOC fluxes determined with the airborne MLG approach were only in reasonable agreement with those of the tower-based REA and SLG approaches after correction for chemical decay by OH radicals, applying a best estimate OH concentration of 5.5×10^6 molecules cm^−3. The SCM model calculations support relatively high OH concentration estimates after specifically being constrained by the mixing ratios of chemical constituents observed during the campaign.\ud \ud The relevance of the VOC fluxes for the local carbon budget of the tropical rainforest site during the measurements campaign was assessed by comparison with the concurrent CO2 fluxes, estimated by three different methods (eddy correlation, Lagrangian dispersion, and mass budget approach). Depending on the CO2 flux estimate, 1–6% or more of the carbon gained by net ecosystem productivity appeared to be re-emitted through VOC emissions

Gravimetric calibration of standard gases

Permeation rates of specific gases (e.g. SO2, NO2) in the range of 10 E-9g min E-1 were directly measured using a high performance microbalance. The gases were trapped in small permeation tubes with total weights of about 2.5 g. By controlling the microbalance's temperature the measurements were done at set temperatures between 25 degrees C and 60 degrees C to obtain a reference graph (permeation rate vs. temperature) for each gas. The microbalance was connected to a metered flow of a clean-air device. With adjustable flow rates up to 50l min E-1 the permeating gas could be diluted down to volume mixing ratios in the 10 E-9 and even the 10 E-12 range. (IFU

Field measurements and their interpretation

Some aspects of biosphere-atmosphere exchange of NO, NO2, and HNO3 are discussed. While present data indicate that HNO3 is always deposited to terrestrial ecosystems, vertical fluxes of NO and NO2 are obvious of NO and NO2 by soils and plants are briefly discussed

Coupled carbon-water exchange of the Amazon rain forest. I. Model description, parameterization and sensitivity analysis

Detailed one-dimensional multilayer biosphere-atmosphere models, also referred to as CANVEG models, are used for more than a decade to describe coupled water-carbon exchange between the terrestrial vegetation and the lower atmosphere. Within the present study, a modified CANVEG scheme is described. A generic parameterization and characterization of biophysical properties of Amazon rain forest canopies is inferred using available field measurements of canopy structure, in-canopy profiles of horizontal wind speed and radiation, canopy albedo, soil heat flux and soil respiration, photosynthetic capacity and leaf nitrogen as well as leaf level enclosure measurements made on sunlit and shaded branches of several Amazonian tree species during the wet and dry season. The sensitivity of calculated canopy energy and CO2 fluxes to the uncertainty of individual parameter values is assessed. In the companion paper, the predicted seasonal exchange of energy, CO2, ozone and isoprene is compared to observations. A bi-modal distribution of leaf area density with a total leaf area index of 6 is inferred from several observations in Amazonia. Predicted light attenuation within the canopy agrees reasonably well with observations made at different field sites. A comparison of predicted and observed canopy albedo shows a high model sensitivity to the leaf optical parameters for near-infrared short-wave radiation (NIR). The predictions agree much better with observations when the leaf reflectance and transmission coefficients for NIR are reduced by 25¿40%. Available vertical distributions of photosynthetic capacity and leaf nitrogen concentration suggest a low but significant light acclimation of the rain forest canopy that scales nearly linearly with accumulated leaf area. Evaluation of the biochemical leaf model, using the enclosure measurements, showed that recommended parameter values describing the photosynthetic light response, have to be optimized. Otherwise, predicted net assimilation is overestimated by 30¿50%. Two stomatal models have been tested, which apply a well established semi-empirical relationship between stomatal conductance and net assimilation. Both models differ in the way they describe the influence of humidity on stomatal response. However, they show a very similar performance within the range of observed environmental conditions. The agreement between predicted and observed stomatal conductance rates is reasonable. In general, the leaf level data suggests seasonal physiological changes, which can be reproduced reasonably well by assuming increased stomatal conductance rates during the wet season, and decreased assimilation rates during the dry season. The sensitivity of the predicted canopy fluxes of energy and CO2 to the parameterization of canopy structure, the leaf optical parameters, and the scaling of photosynthetic parameters is relatively low (1¿12%), with respect to parameter uncertainty. In contrast, modifying leaf model parameters within their uncertainty range results in much larger changes of the predicted canopy net fluxes (5¿35%

Laboratory measurements of nitric oxide release from forest soil with a thick organic layer under different understory types.

Nitric oxide (NO) plays an important role in the photochemistry of the troposphere. NO from soil contributes up to 40% to the global budget of atmospheric NO. Soil NO emissions are primarily caused by biological activity (nitrification and denitrification), that occurs in the uppermost centimeter of the soil, a soil region often characterized by high contents of organic material. Most studies of NO emission potentials to date have investigated mineral soil layers. In our study we sampled soil organic matter under different understories (moss, grass, spruce and blueberries) in a humid mountainous Norway spruce forest plantation in the Fichtelgebirge (Germany). We performed laboratory incubation and flushing experiments using a customized chamber technique to determine the response of net potential NO flux to physical and chemical soil conditions (water content and temperature, bulk density, particle density, pH, C/N ratio, organic C, soil ammonium, soil nitrate). Net potential NO fluxes (in terms of mass of N) from soil samples taken under different understories ranged from 1.7-9.8 ng m(-2) s(-1) (soil sampled under grass and moss cover), 55.4-59.3 ng m(-2) s(-1) (soil sampled under spruce cover), and 43.7-114.6 ng m(-2) s(-1) (soil sampled under blueberry cover) at optimum water content and a soil temperature of 10 degrees C. The water content for optimum net potential NO flux ranged between 0.76 and 0.8 gravimetric soil moisture for moss covered soils, between 1.0 and 1.1 for grass covered soils, 1.1 and 1.2 for spruce covered soils, and 1.3 and 1.9 for blueberry covered soils. Effects of soil physical and chemical characteristics on net potential NO flux were statistically significant (0.01 probability level) only for NH4+. Therefore, as an alternative explanation for the differences in soil biogenic NO emission we consider more biological factors like understory vegetation type, amount of roots, and degree of mycorrhization; they have the potential to explain the observed differences of net potential NO fluxes

Coupled carbon-water exchange of the Amazon rain forest. II. Comparison of predicted and observed seasonal exchange of energy, CO2, isoprene and ozone at a remote site in Rondônia

A one-dimensional multi-layer scheme describing the coupled exchange of energy and CO2, the emission of isoprene and the dry deposition of ozone is applied to a rain forest canopy in southwest Amazonia. The model was constrained using mean diel cycles of micrometeorological quantities observed during two periods in the wet and dry season 1999. Calculated net fluxes and concentration profiles for both seasonal periods are compared to observations made at two nearby towers. The modeled day- and nighttime thermal stratification of the canopy layer is consistent with observations in dense canopies. The observed and modeled net fluxes above and H2O and CO2 concentration profiles within the canopy show a good agreement. The predicted net carbon sink decreases from 2.5 t C ha-1 yr-1 for wet season conditions to 1 t C ha-1 yr-1 for dry season conditions, whereas observed and modeled midday Bowen ratio increases from 0.5 to 0.8. The evaluation results confirmed a seasonal variability of leaf physiological parameters, as already suggested in a companion study. The calculated midday canopy net flux of isoprene increased from 7.1 mg C m-2 h-1 during the wet season to 11.4 mg C m-2 h-1 during the late dry season. Applying a constant emission capacity in all canopy layers, resulted in a disagreement between observed and simulated profiles of isoprene concentrations, suggesting a smaller emission capacity of shade adapted leaves and deposition to the soil or leaf surfaces. Assuming a strong light acclimation of emission capacity, equivalent to a 66% reduction of the standard emission factor for leaves in the lower canopy, resulted in a better agreement of observed and modeled concentration profiles and a 30% reduction of the canopy net flux compared to model calculations with a constant emission factor. The mean calculated ozone flux for dry season conditions at noontime was ˜12 n mol m-2 s-1, agreeing well with observed values. The corresponding deposition velocity increased from 0.8 cm s-1 to >1.6 cm s-1 in the wet season, which can not be explained by increased stomatal uptake. Considering reasonable physiological changes in stomatal regulation, the modeled value was not larger than 1.05 cm s-1. Instead, the observed fluxes could be explained with the model by decreasing the cuticular resistance to ozone deposition from 5000 to 1000 s m-