Measurements of reactive chlorocarbons over the Surinam tropical rain forest: indications for strong biogenic emissions

International audienceContrary to the understanding of the emissions and chemical behavior of halocarbons from anthropogenic sources (e.g. CFCs and HCFCs), the biogeochemistry of naturally emitted halocarbons is still poorly understood. We present measurements of chloromethane (methyl chloride, CH3Cl), trichloromethane (chloroform, CHCl3), dichloromethane (CH2Cl2), and tetrachloroethylene (C2Cl4) from air samples taken over the Surinam rainforest during the 1998 LBA/CLAIRE campaign. The samples were collected in stainless steel canisters on-board a Cessna Citation jet aircraft and analyzed in the laboratory using a gas chromatograph equipped with FID and ECD. The chlorocarbons we studied have atmospheric lifetimes of ~1 year or less, and appear to have significant emissions from natural sources including oceans, soils and vegetations, as well as biomass burning. These sources are primarily concentrated in the tropics (30º N-30º S). We detected an increase as a function of latitude of methyl chloride, chloroform, and tetrachloroethylene mixing ratios, in pristine air masses advected from the Atlantic Ocean toward the central Amazon. In the absence of significant biomass burning sources, we attribute this increase to biogenic emissions from the Surinam rainforest. From our measurements, we deduce fluxes from the Surinam rainforest of 7.6±1.8 ?g CH3Cl m?2 h?1, 1.11±0.08g CHCl3 ?m?2 h?1, and 0.36±0.07 ?g C2Cl4 m?2 h?1. Extrapolated to a global scale, our emission estimates suggest a large potential source of 2 Tg CH3Cl yr?1 from tropical forests, which could account for the net budget discrepancy (underestimation of sources), as indicated previously. In addition, our estimates suggest a potential emission of 57±17\,Gg C2C4 yr?1 from tropical forest soils, equal to half of the currently missing C2Cl4 sources. We hypothesize that the extensive deforestation over the last two decades relates to the observed global downward trend of atmospheric methyl chloride

Towards understanding the variability in biospheric CO2 fluxes:Using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world

Low temperatures enhance organic nitrate formation: evidence from observations in the 2012 Uintah Basin Winter Ozone Study

Nitrogen dioxide (NO2) and total alkyl nitrates (ΣANs) were measured using thermal dissociation laser-induced fluorescence during the 2012 Uintah Basin Winter Ozone Study (UBWOS) in Utah, USA. The observed NO2 concentration was highest before sunrise and lowest in the late afternoon, suggestive of a persistent local source of NO2 coupled with turbulent mixing out of the boundary layer. In contrast, ΣANs co-varied with solar radiation with a noontime maximum, indicating that local photochemical production combined with rapid mixing and/or deposition was the dominant factor in determining the ΣAN concentrations. We calculate that ΣANs were a large fraction (~60%) of the HOx free radical chain termination and show that the temperature dependence of the alkyl nitrate yields enhances the role of ΣANs in local chemistry during winter by comparison to what would occur in the warmer temperatures of summer

Remote sensing of CO2 and CH4 using solar absorption spectrometry with a low resolution spectrometer

Throughout the last few years solar absorption Fourier Transform Spectrometry (FTS) has been further developed to measure the total columns of CO2 and CH4. The observations are performed at high spectral resolution, typically at 0.02 cm(-1). The precision currently achieved is generally better than 0.25%. However, these high resolution instruments are quite large and need a dedicated room or container for installation. We performed these observations using a smaller commercial interferometer at its maximum possible resolution of 0.11 cm(-1). The measurements have been performed at Bremen and have been compared to observations using our high resolution instrument also situated at the same location. The high resolution instrument has been successfully operated as part of the Total Carbon Column Observing Network (TCCON). The precision of the low resolution instrument is 0.32% for XCO2 and 0.46% for XCH4. A comparison of the measurements of both instruments yields an average deviation in the retrieved daily means of 0.2% for CO2. For CH4 an average bias between the instruments of 0.47% was observed. For test cases, spectra recorded by the high resolution instrument have been truncated to the resolution of 0.11 cm(-1). This study gives an offset of 0.03% for CO2 and 0.26% for CH4. These results indicate that for CH4 more than 50% of the difference between the instruments results from the resolution dependent retrieval. We tentatively assign the offset to an incorrect a-priori concentration profile or the effect of interfering gases, which may not be treated correctly

Atmospheric greenhouse gases retrieved from SCIAMACHY: comparison to ground-based FTS measurements and model results

SCIAMACHY onboard ENVISAT (launched in 2002) enables the retrieval of global long-term column-averaged dry air mole fractions of the two most important anthropogenic greenhouse gases carbon dioxide and methane (denoted XCO_2 and XCH_4). In order to assess the quality of the greenhouse gas data obtained with the recently introduced v2 of the scientific retrieval algorithm WFM-DOAS, we present validations with ground-based Fourier Transform Spectrometer (FTS) measurements and comparisons with model results at eight Total Carbon Column Observing Network (TCCON) sites providing realistic error estimates of the satellite data. Such validation is a prerequisite to assess the suitability of data sets for their use in inverse modelling. It is shown that there are generally no significant differences between the carbon dioxide annual increases of SCIAMACHY and the assimilation system CarbonTracker (2.00 ± 0.16 ppm yr^(−1) compared to 1.94 ± 0.03 ppm yr−1 on global average). The XCO_2 seasonal cycle amplitudes derived from SCIAMACHY are typically larger than those from TCCON which are in turn larger than those from CarbonTracker. The absolute values of the northern hemispheric TCCON seasonal cycle amplitudes are closer to SCIAMACHY than to CarbonTracker and the corresponding differences are not significant when compared with SCIAMACHY, whereas they can be significant for a subset of the analysed TCCON sites when compared with CarbonTracker. At Darwin we find discrepancies of the seasonal cycle derived from SCIAMACHY compared to the other data sets which can probably be ascribed to occurrences of undetected thin clouds. Based on the comparison with the reference data, we conclude that the carbon dioxide data set can be characterised by a regional relative precision (mean standard deviation of the differences) of about 2.2 ppm and a relative accuracy (standard deviation of the mean differences) of 1.1–1.2 ppm for monthly average composites within a radius of 500 km. For methane, prior to November 2005, the regional relative precision amounts to 12 ppb and the relative accuracy is about 3 ppb for monthly composite averages within the same radius. The loss of some spectral detector pixels results in a degradation of performance thereafter in the spectral range currently used for the methane column retrieval. This leads to larger scatter and lower XCH_4 values are retrieved in the tropics for the subsequent time period degrading the relative accuracy. As a result, the overall relative precision is estimated to be 17 ppb and the relative accuracy is in the range of about 10–20 ppb for monthly averages within a radius of 500 km. The derived estimates show that the SCIAMACHY XCH_4 data set before November 2005 is suitable for regional source/sink determination and regional-scale flux uncertainty reduction via inverse modelling worldwide. In addition, the XCO2 monthly data potentially provide valuable information in continental regions, where there is sparse sampling by surface flask measurements

Mummy berry pseudosclerotia survive for several years

Organic blueberry production in the PNW has many challenges, including diseases like mummy berry caused by the fungus Monilinia vaccinii-corymbosi (Reade) Honey. Management recommendations focus on reducing overwintering pseudosclerotia, however, it is unknown how long they survive. Based on qualitative observations pseudosclerotia are hypothesized to survive multiple years after contact with the soil surface. The development of apothecia from M. vaccinii-corymbosi pseudosclerotia was evaluated over multiple years at a location without a history of blueberry production. A total of 1,000 pseudosclerotia were placed on field soil plots in 2018 and replicated eight times. Another 100 pseudosclerotia were placed in wire corrals on field soil and replicated fifteen times. Plots and corrals were regularly examined each spring for the emergence of apothecia. The pseudosclerotia were able to survive, germinate, and produce apothecia for up to five years after their placement. Very few pseudosclerotia produced apothecia in any year, varying from 0 to 18 at any observed time. Pieces of partial or whole pseudosclerotia were observed for up to three years after placement. Our study shows that a pseudosclerotial “seed bank” exists under blueberry bushes, necessitating a long-term implementation of mummy berry cultural management tactics

Toward accurate CO_2 and CH_4 observations from GOSAT

The column-average dry air mole fractions of atmospheric carbon dioxide and methane (X_(CO_2) and X_(CH_4)) are inferred from observations of backscattered sunlight conducted by the Greenhouse gases Observing SATellite (GOSAT). Comparing the first year of GOSAT retrievals over land with colocated ground-based observations of the Total Carbon Column Observing Network (TCCON), we find an average difference (bias) of −0.05% and −0.30% for X_(CO_2) and X_(CH_4) with a station-to-station variability (standard deviation of the bias) of 0.37% and 0.26% among the 6 considered TCCON sites. The root-mean square deviation of the bias-corrected satellite retrievals from colocated TCCON observations amounts to 2.8 ppm for X_(CO_2) and 0.015 ppm for X_(CH_4). Without any data averaging, the GOSAT records reproduce general source/sink patterns such as the seasonal cycle of X_(CO_2) suggesting the use of the satellite retrievals for constraining surface fluxes

Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations

We construct a global atmospheric budget for acetaldehyde using a 3-D model of atmospheric chemistry (GEOS-Chem), and use an ensemble of observations to evaluate present understanding of its sources and sinks. Hydrocarbon oxidation provides the largest acetaldehyde source in the model (128 Tg a<sup>−1</sup>, a factor of 4 greater than the previous estimate), with alkanes, alkenes, and ethanol the main precursors. There is also a minor source from isoprene oxidation. We use an updated chemical mechanism for GEOS-Chem, and photochemical acetaldehyde yields are consistent with the Master Chemical Mechanism. We present a new approach to quantifying the acetaldehyde air-sea flux based on the global distribution of light absorption due to colored dissolved organic matter (CDOM) derived from satellite ocean color observations. The resulting net ocean emission is 57 Tg a<sup>−1</sup>, the second largest global source of acetaldehyde. A key uncertainty is the acetaldehyde turnover time in the ocean mixed layer, with quantitative model evaluation over the ocean complicated by known measurement artifacts in clean air. Simulated concentrations in surface air over the ocean generally agree well with aircraft measurements, though the model tends to overestimate the vertical gradient. PAN:NO<sub>x</sub> ratios are well-simulated in the marine boundary layer, providing some support for the modeled ocean source. We introduce the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) for acetaldehyde and ethanol and use it to quantify their net flux from living terrestrial plants. Including emissions from decaying plants the total direct acetaldehyde source from the land biosphere is 23 Tg a<sup>−1</sup>. Other terrestrial acetaldehyde sources include biomass burning (3 Tg a<sup>−1</sup>) and anthropogenic emissions (2 Tg a<sup>−1</sup>). Simulated concentrations in the continental boundary layer are generally unbiased and capture the spatial gradients seen in observations over North America, Europe, and tropical South America. However, the model underestimates acetaldehyde levels in urban outflow, suggesting a missing source in polluted air. Ubiquitous high measured concentrations in the free troposphere are not captured by the model, and based on present understanding are not consistent with concurrent measurements of PAN and NO<sub>x</sub>: we find no compelling evidence for a widespread missing acetaldehyde source in the free troposphere. We estimate the current US source of ethanol and acetaldehyde (primary + secondary) at 1.3 Tg a<sup>−1</sup> and 7.8 Tg a<sup>−1</sup>, approximately 60{%} and 480% of the corresponding increases expected for a national transition from gasoline to ethanol fuel

The arctic seasonal cycle of total column CO2 and CH4 from ground-based solar and lunar FTIR absorption spectrometry

Solar absorption spectroscopy in the near infrared has been performed in Ny-Ålesund (78.9° N, 11.9° E) since 2002; however, due to the high latitude of the site, the sun is below the horizon from October to March (polar night) and no solar absorption measurements are possible. Here we present a novel method of retrieving the total column dry-air mole fractions (DMFs) of CO2 and CH4 using moonlight in winter. Measurements have been taken during the polar nights from 2012 to 2016 and are validated with TCCON (Total Carbon Column Observing Network) measurements by solar and lunar absorption measurements on consecutive days and nights during spring and autumn. The complete seasonal cycle of the DMFs of CO2 and CH4 is presented and a precision of up to 0.5 % is achieved. A comparison of solar and lunar measurements on consecutive days during day and night in March 2013 yields non-significant biases of 0. 66 ± 4. 56 ppm for xCO2 and −1. 94 ± 20. 63 ppb for xCH4. Additionally a model comparison has been performed with data from various reanalysis models

Measurements of Gas‐Phase Inorganic and Organic Acids from Biomass Fires by Negative‐Ion Proton‐Transfer Chemical‐Ionization Mass Spectrometry

[1] Emissions from 34 laboratory biomass fires were investigated at the combustion facility of the U.S. Department of Agriculture Fire Sciences Laboratory in Missoula, Montana. Gas-phase organic and inorganic acids were quantified using negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), open-path Fourier transform infrared spectroscopy (OP-FTIR), and proton-transfer-reaction mass spectrometry (PTR-MS). NI-PT-CIMS is a novel technique that measures the mass-to-charge ratio (m/z) of ions generated from reactions of acetate (CH3C(O)O−) ions with inorganic and organic acids. The emission ratios for various important reactive acids with respect to CO were determined. Emission ratios for isocyanic acid (HNCO), 1,2 and 1,3-benzenediols (catechol, resorcinol), nitrous acid (HONO), acrylic acid, methacrylic acid, propionic acid, formic acid, pyruvic acid, and glycolic acid were measured from biomass burning. Our measurements show that there is a significant amount of HONO in fresh smoke. The NI-PT-CIMS measurements were validated by comparison with OP-FTIR measurements of HONO and formic acid (HCOOH) and with PTR-MS measurements of HCOOH