The chemistry of atmospheric bromine

Bromine may act as a catalyst for recombination of ozone and could be more efficient than either nitric oxide or chlorine. The lower atmosphere contains small concentrations of gaseous bromine produced in part by marine activity, in part by volatilization of particulate material released during the combustion of leaded gasoline, with an additional contribution due to the use of methyl bromide as an agricultural fumigant. Observations by Lazrus et. al. (1975) indicate small concentrations of bromine, ∼ 10^(−11) (v/v) in the contemporary stratosphere and appear to imply a reduction of approximately 0.3% in the global budget of O_3. Estimates are given for future reductions in O_3 which might occur if the use of CH_3Br as an agricultural fumigant were to continue to grow at present rates

Interannual, seasonal, and diel variation in soil respiration relative to ecosystem respiration at a wetland to upland slope at Harvard Forest

Soil carbon dioxide efflux (soil respiration, SR) was measured with eight autochambers at two locations along a wetland to upland slope at Harvard Forest over a 4 year period, 2003–2007. SR was consistently higher in the upland plots than at the wetland margin during the late summer/early fall. Seasonal and diel hystereses with respect to soil temperatures were of sufficient magnitude to prevent quantification of the influence of soil moisture, although apparent short‐term responses of SR to precipitation occurred. Calculations of annual cumulative SR illustrated a decreasing trend in SR over the 5 year period, which were correlated with decreasing springtime mean soil temperatures. Spring soil temperatures decreased despite rising air temperatures over the same period, possibly as an effect of earlier leaf expansion and shading. The synchronous decrease in spring soil temperatures and SR during regional warming of air temperatures may represent a negative feedback on a warming climate by reducing CO2 production from soils. SR reached a maximum later in the year than total ecosystem respiration (ER) measured at a nearby eddy covariance flux tower, and the seasonality of their temperature response patterns were roughly opposite. SR, particularly in the upland, exceeded ER in the late summer/early fall in each year, suggesting that areas of lower efflux such as the wetland may be significant in the flux tower footprint or that long‐term bias in either estimate may create a mismatch. Annual estimates of ER decreased over the same period and were highly correlated with SR

Oxidation and reduction rates for organic carbon in the Amazon mainstream tributary and floodplain, inferred from distributions of dissolved gases

Concentrations of CO2, O2, CH4, and N2O in the Amazon River system reflect an oxidation-reduction sequence in combination with physical mixing between the floodplain and the mainstem. Concentrations of CO2 ranged from 150 microM in the Amazon mainstem to 200 to 300 microM in aerobic waters of the floodplain, and up to 1000 microM in oxygen-depleted environments. Apparent oxygen utilization (AOU) ranged from 80 to 250 microM. Methane was highly supersaturated, with concentrations ranging from 0.06 microM in the mainstem to 100 microM on the floodplain. Concentrations of N2O were slightly supersaturated in the mainstem, but were undersaturated on the floodplain. Fluxes calculated from these concentrations indicated decomposition of 1600 g C sq m y(-1) of organic carbon in Amazon floodplain waters. Analysis of relationships between CH4, O2, and CO2 concentrations indicated that approximately 50 percent of carbon mineralization on the floodplain is anaerobic, with 20 percent lost to the atmoshphere as CH4. The predominance of anaerobic metabolism leads to consumption of N2O on the flood plane. Elevated concentrations of CH4 in the mainstem probably reflect imput from the floodplain, while high levels of CO2 in the mainstem are derived from a combination of varzea drainage and in situ respiration

Sources and sinks for atmospheric N2O

Observations of the temporal and spatial distribution of N2O in solution are not yet sufficient to permit quantitative assessment of the role of the ocean in the budget of atmospheric N2O. Consideration of the global nitrogen cycle suggests that the land should be the primary source of N2O. The gas is removed in the atmosphere by photolysis and by reaction with O(1D), and there may be additional sinks in the ocean

Sources and sinks for atmospheric N_2O

Observations of the temporal and spatial distribution of N_2O in solution are not yet sufficient to permit quantitative assessment of the role of the ocean in the budget of atmospheric N_2O. Consideration of the global nitrogen cycle suggests that the land should be the primary source of N_2O. The gas is removed in the atmosphere by photolysis and by reaction with O(¹D), and there may be additional sinks in the ocean

Atmospheric halocarbons: A discussion with emphasis on chloroform

Bleaching of paper pulp represents a major industrial use of chlorine and could provide an environmentally significant source of atmospheric halocarbons. The related global production of chloroform is estimated at 3 × 10^5 ton yr^(−1) and there could be additional production associated with atmospheric decomposition of perchloroethylene. Estimates are given for the production of methyl chloride, methyl bromide and methyl iodide, 5.2 × 10^6, 7.7 × 10^4, and 7.4 × 10^5 ton yr^(−1) respectively. The relative yields of CH_3Cl, CH_3Br and CH_3I are consistent with the hypothesis of a marine biological source for these compounds. Concentrations of other halocarbons observed in the atmosphere appear to indicate industrial sources

Mass fluxes and isofluxes of methane (CH4) at a New Hampshire fen measured by a continuous wave quantum cascade laser spectrometer

We have developed a mid‐infrared continuous‐wave quantum cascade laser direct‐absorption spectrometer (QCLS) capable of high frequency (≥1 Hz) measurements of 12CH4 and 13CH4 isotopologues of methane (CH4) with in situ 1‐s RMS image precision of 1.5 ‰ and Allan‐minimum precision of 0.2 ‰. We deployed this QCLS in a well‐studied New Hampshire fen to compare measurements of CH4 isoflux by eddy covariance (EC) to Keeling regressions of data from automated flux chamber sampling. Mean CH4 fluxes of 6.5 ± 0.7 mg CH4 m−2 hr−1 over two days of EC sampling in July, 2009 were indistinguishable from mean autochamber CH4 fluxes (6.6 ± 0.8 mgCH4 m−2 hr−1) over the same period. Mean image composition of emitted CH4 calculated using EC isoflux methods was −71 ± 8 ‰ (95% C.I.) while Keeling regressions of 332 chamber closing events over 8 days yielded a corresponding value of −64.5 ± 0.8 ‰. Ebullitive fluxes, representing ∼10% of total CH4 fluxes at this site, were on average 1.2 ‰ enriched in 13C compared to diffusive fluxes. CH4 isoflux time series have the potential to improve process‐based understanding of methanogenesis, fully characterize source isotopic distributions, and serve as additional constraints for both regional and global CH4 modeling analysis

Measurement of HO2 and other trace gases in the stratosphere using a high resolution far-infrared spectrometer at 28 km

This report covers the time period 1 January 1993 to 30 June 1993. During this reporting period we had our third Upper Atmosphere Research Satellite (UARS) correlative balloon flight and submitted the results from this flight to the Central Data Handling Facility (CDHF). We made a number of improvements in our data processing software in preparation for a new analysis of our old balloon data sets. Finally, we continue to analyze the data obtained during the second Airborne Arctic Stratospheric Expedition (AASE 2)

CARBON BALANCE AND VEGETATION DYNAMICS IN AN OLD‐GROWTH AMAZONIAN FOREST

Amazon forests could be globally significant sinks or sources for atmospheric carbon dioxide, but carbon balance of these forests remains poorly quantified. We surveyed 19.75 ha along four 1‐km transects of well‐drained old‐growth upland forest in the Tapajós National Forest near Santarém, Pará, Brazil (2°51′ S, 54°58′ W) in order to assess carbon pool sizes, fluxes, and climatic controls on carbon balance. In 1999 there were, on average, 470 live trees per hectare with diameter at breast height (dbh) ≥10 cm. The mean (and 95% ci) aboveground live biomass was 143.7 ± 5.4 Mg C/ha, with an additional 48.0 ± 5.2 Mg C/ha of coarse woody debris (CWD). The increase of live wood biomass after two years was 1.40 ± 0.62 Mg C·ha−1·yr−1, the net result of growth (3.18 ± 0.20 Mg C·ha−1·yr−1 from mean bole increment of 0.36 cm/yr), recruitment of new trees (0.63 ± 0.09 Mg C·ha−1·yr−1, reflecting a notably high stem recruitment rate of 4.8 ± 0.9%), and mortality (−2.41 ± 0.53 Mg C·ha−1·yr−1 from stem death of 1.7% yr−1). The gain in live wood biomass was exceeded by respiration losses from CWD, resulting in an overall estimated net loss from total aboveground biomass of 1.9 ± 1.0 Mg C·ha−1·yr−1. The presence of large CWD pools, high recruitment rate, and net accumulation of small‐tree biomass, suggest that a period of high mortality preceded the initiation of this study, possibly triggered by the strong El Niño Southern Oscillation events of the 1990s. Transfer of carbon between live and dead biomass pools appears to have led to substantial increases in the pool of CWD, causing the observed net carbon release. The data show that biometric studies of tropical forests neglecting CWD are unlikely to accurately determine carbon balance. Furthermore, the hypothesized sequestration flux from CO2 fertilization (\u3c0.5 Mg C·ha−1·yr−1) would be comparatively small and masked for considerable periods by climate‐driven shifts in forest structure and associated carbon balance in tropical forests

The atmospheric effects of stratospheric aircraft: A fourth program report

This document presents the fourth report from the Atmospheric Effects of Stratospheric Aircraft (AESA) component of NASA's High-Speed Research Program (HSRP). Market and technology considerations continue to provide an impetus for high-speed civil transport research. A recent AESA interim assessment report and a review of that report have shown that considerable uncertainty still exists about the possible impact of aircraft on the atmosphere. The AESA has been designed to develop the body of scientific knowledge necessary for the evaluation of the impact of stratospheric aircraft on the atmosphere. The first Program report presented the basic objectives and plans for AESA. This fourth report comes after the interim assessment and sets forth directions for the 1995 assessment at the end of AESA Phase 1. It also sets forth the goals and directions for AESA Phase 2, as reported at the 1994 Atmospheric Effects of Aviation Project (AEAP) annual meeting held in June. The focus of the Phase 2 effort is to obtain the best possible closure on the outstanding problems identified in the interim assessment and NASA/NRC review. Topics discussed in this report include how high-speed civil transports (HSCT) might affect stratospheric ozone, emissions scenarios and databases to assess potential atmospheric effects from HSCT's, calculated results from 2-D zonal mean models using emissions data, engine trace constituent measurements