An ecosystem-scale perspective of the net land methanol flux: synthesis of micrometeorological flux measurements.

Methanol is the second most abundant volatile organic compound in the troposphere and plays a significant role in atmospheric chemistry. While there is consensus about the dominant role of living plants as the major source and the reaction with OH as the major sink of methanol, global methanol budgets diverge considerably in terms of source/sink estimates reflecting uncertainties in the approaches used to model, and the empirical data used to separately constrain these terms. Here we compiled micrometeorological methanol flux data from eight different study sites and reviewed the corresponding literature in order to provide a first cross-site synthesis of the terrestrial ecosystem-scale methanol exchange and present an independent data-driven view of the land-atmosphere methanol exchange. Our study shows that the controls of plant growth on the production, and thus the methanol emission magnitude, and stomatal conductance on the hourly methanol emission variability, established at the leaf level, hold across sites at the ecosystem-level. Unequivocal evidence for bi-directional methanol exchange at the ecosystem scale is presented. Deposition, which at some sites even exceeds methanol emissions, represents an emerging feature of ecosystem-scale measurements and is likely related to environmental factors favouring the formation of surface wetness. Methanol may adsorb to or dissolve in this surface water and eventually be chemically or biologically removed from it. Management activities in agriculture and forestry are shown to increase local methanol emission by orders of magnitude; they are however neglected at present in global budgets. While contemporary net land methanol budgets are overall consistent with the grand mean of the micrometeorological methanol flux measurements, we caution that the present approach of simulating methanol emission and deposition separately is prone to opposing systematic errors and does not allow taking full advantage of the rich information content of micrometeorological flux measurements.

Methane and nitrous oxide exchange over a managed hay meadow.

The methane (CH4) and nitrous oxide (N2O) exchange of a temperate mountain grassland near Neustift, Austria, was measured during 2010-2012 over a time period of 22 months using the eddy covariance method. Exchange rates of both compounds at the site were low, with 97% of all half-hourly CH4 and N2O fluxes ranging between ±200 and ±50 ng m-2 s-1, respectively. The meadow acted as a sink for both compounds during certain time periods, but was a clear source of CH4 and N2O on an annual timescale. Therefore, both gases contributed to an increase of the global warming potential (GWP), effectively reducing the sink strength in terms of CO2 equivalents of the investigated grassland site. In 2011, our best guess estimate showed a net greenhouse gas (GHG) sink of -32 g CO2 equ. m-2 yr-1 for the meadow, whereby 55% of the CO2 sink strength of -71 g CO2m-2 yr-1 was offset by CH4 (N2O) emissions of 7 (32) g CO2 equ. m-2 yr-1. When all data were pooled, the ancillary parameters explained 27 (42)% of observed CH4 (N2O) flux variability, and up to 62 (76)% on shorter timescales in-between management dates. In the case of N2O fluxes, we found the highest emissions at intermediate soil water contents and at soil temperatures close to 0 or above 14 °C. In comparison to CO2, H2O and energy fluxes, the interpretation of CH4 and N2O exchange was challenging due to footprint heterogeneity regarding their sources and sinks, uncertainties regarding post-processing and quality control. Our results emphasize that CH4 and N2O fluxes over supposedly well-aerated and moderately fertilized soils cannot be neglected when evaluating the GHG impact of temperate managed grasslands.

Acetaldehyde exchange above a managed temperate mountain grassland.

An overview of acetaldehyde exchange above a managed temperate mountain grassland in Austria over four growing seasons is presented. The meadow acted as a net source of acetaldehyde in all four years, emitting between 7 and 28 mg C m-2 over the whole growing period. The cutting of the meadow resulted in huge acetaldehyde emission bursts on the day of harvesting or one day later. During undisturbed conditions, both uptake and emission fluxes were recorded. The bidirectional nature of acetaldehyde fluxes was also reflected by clear diurnal cycles during certain time periods, indicating strong deposition processes before the 1st cut and emission towards the end of the growing season. The analysis of acetaldehyde compensation points revealed a complex relationship between ambient acetaldehyde mixing ratios and respective fluxes, significantly influenced by multiple environmental parameters and variable throughout the year. As a major finding of this study, we identified both a positive and negative correlation between concentration and flux on a daily scale, where soil temperature and soil water content were the most significant factors in determining the direction of the slope. In turn, this bidirectional relationship on a daily scale resulted in compensation points between 0.40 ppbv and 0.54 ppbv, which could be well explained by collected ancillary data. We conclude that in order to model acetaldehyde fluxes at the site in Neustift on a daily scale over longer time periods, it is crucial to know the type of relationship, i.e. the direction of the slope, between mixing ratios and fluxes on a given day.

Gap-filling strategies for annual VOC flux data sets.

Up to now the limited knowledge about the exchange of volatile organic compounds (VOCs) between the biosphere and the atmosphere is one of the factors which hinders more accurate climate predictions. Complete long-term flux data sets of several VOCs to quantify the annual exchange and validate recent VOC models are basically not available. In combination with long-term VOC flux measurements the application of gap-filling routines is inevitable in order to replace missing data and make an important step towards a better understanding of the VOC ecosystem-atmosphere exchange on longer time scales. We performed VOC flux measurements above a mountain meadow in Austria during two complete growing seasons (from snowmelt in spring to snow reestablishment in late autumn) and used this data set to test the performance of four different gap-filling routines, mean diurnal variation (MDV), mean gliding window (MGW), look up tables (LUT) and linear interpolation (LIP), in terms of their ability to replace missing flux data in order to obtain reliable VOC sums. According to our findings the MDV routine was outstanding with regard to the minimization of the gap-filling error for both years and all quantified VOCs. The other gap-filling routines, which performed gap-filling on 24 h average values, introduced considerably larger uncertainties. The error which was introduced by the application of the different filling routines increased linearly with the number of data gaps. Although average VOC fluxes measured during the winter period (complete snow coverage) were close to zero, these were highly variable and the filling of the winter period resulted in considerably higher uncertainties compared to the application of gap-filling during the measurement period. The annual patterns of the overall cumulative fluxes for the quantified VOCs showed a completely different behavior in 2009, which was an exceptional year due to the occurrence of a severe hailstorm, compared to 2011. Methanol was the compound which contributed with 381.5 mgCm-2 and 449.9 mgCm-2 most to the cumulative VOC carbon emissions in 2009 and 2011, respectively. In contrast to methanol emissions, however, considerable amounts of monoterpenes (-327.3 mgCm-2) were deposited to the mountain meadow in consequence to the hailstorm in 2009. Other quantified VOCs had considerably lower influences on the annual patterns.

Eddy covariance VOC emission and deposition fluxes above grassland using PTR-TOF.

Eddy covariance (EC) is the preferable technique for flux measurements since it is the only direct flux determination method. It requires a continuum of high time resolution measurements (e.g. 5-20 Hz). For volatile organic compounds (VOC) soft ionization via proton transfer reaction has proven to be a quantitative method for real time mass spectrometry; here we use a proton transfer reaction time of flight mass spectrometer (PTR-TOF) for 10 Hz EC measurements of full mass spectra up to m/z 315. The mass resolution of the PTR-TOF enabled the identification of chemical formulas and separation of oxygenated and hydrocarbon species exhibiting the same nominal mass. We determined 481 ion mass peaks from ambient air concentration above a managed, temperate mountain grassland in Neustift, Stubai Valley, Austria. During harvesting we found significant fluxes of 18 compounds distributed over 43 ions, including protonated parent compounds, as well as their isotopes and fragments and VOC-H+ - water clusters. The dominant BVOC fluxes were methanol, acetaldehyde, ethanol, hexenal and other C6 leaf wound compounds, acetone, acetic acid, monoterpenes and sequiterpenes. The smallest reliable fluxes we determined were less than 0.1 nmol m-2 s-1, as in the case of sesquiterpene emissions from freshly cut grass. Terpenoids, including mono- and sesquiterpenes, were also deposited to the grassland before and after the harvesting. During cutting, total VOC emission fluxes up to 200 nmolC m-2 s-1 were measured. Methanol emissions accounted for half of the emissions of oxygenated VOCs and a third of the carbon of all measured VOC emissions during harvesting.

Deposition Fluxes of Terpenes over Grassland.

Eddy covariance flux measurements were carried out for two subsequent vegetation periods above a temperate mountain grassland in an alpine valley using a proton-transfer-reaction - mass spectrometer (PTR-MS) and a PTR-time of flight - mass spectrometer (PTR-TOF). In 2008 and during the first half of the vegetation period 2009 the volume mixing ratios (VMRs) for the sum of monoterpenes (MTs) were typically well below 1 ppbv and neither MT emission nor deposition was observed. After a hailstorm in July 2009 an order of magnitude higher amount of terpenes was transported to the site from nearby coniferous forests causing elevated VMRs. As a consequence, deposition fluxes of terpenes to the grassland, which continued over a time period of several weeks without significant re-emission, were observed. For days without precipitation the deposition occurred at velocities close to the aerodynamic limit. In addition to monoterpene uptake, deposition fluxes of the sum of sesquiterpenes (SQTs) and the sum of oxygenated terpenes (OTs) were detected. Considering an entire growing season for the grassland (i.e., 1st of April to 1st of November), the cumulative carbon deposition of monoterpenes reached 276 mg C m-2. This is comparable to the net carbon emission of methanol (329 mg C m-2), which is the dominant non methane volatile organic compound (VOC) emitted from this site, during the same time period. It is suggested that deposition of monoterpenes to terrestrial ecosystems could play a more significant role in the reactive carbon budget than previously assumed.

Estimating carbon dioxide fluxes from temperate mountain grasslands using broad-band vegetation indices.

The broad-band normalised difference vegetation index (NDVI) and the simple ratio (SR) were calculated from measurements of reflectance of photosynthetically active and short-wave radiation at two temperate mountain grasslands in Austria and related to the net ecosystem CO2 exchange (NEE) measured concurrently by means of the eddy covariance method. There was no significant statistical difference between the relationships of midday mean NEE with narrow- and broad-band NDVI and SR, measured during and calculated for that same time window, respectively. The skill of broad-band NDVI and SR in predicting CO2 fluxes was higher for metrics dominated by gross photosynthesis and lowest for ecosystem respiration, with NEE in between. A method based on a simple light response model whose parameters were parameterised based on broad-band NDVI allowed to improve predictions of daily NEE and is suggested to hold promise for filling gaps in the NEE time series. Relationships of CO2 flux metrics with broad-band NDVI and SR however generally differed between the two studied grassland sites indicting an influence of additional factors not yet accounted for.

BVOC fluxes above mountain grassland.

Grasslands comprise natural tropical savannah over managed temperate fields to tundra and cover one quarter of the Earth's land surface. Plant growth, maintenance and decay result in volatile organic compound (VOCs) emissions to the atmosphere. Furthermore, biogenic VOCs (BVOCs) are emitted as a consequence of various environmental stresses including cutting and drying during harvesting. Fluxes of BVOCs were measured with a proton-transfer-reaction-mass-spectrometer (PTR-MS) over temperate mountain grassland in Stubai Valley (Tyrol, Austria) over one growing season (2008). VOC fluxes were calculated from the disjunct PTR-MS data using the virtual disjunct eddy covariance method and the gap filling method. Methanol fluxes obtained with the two independent flux calculation methods were highly correlated (y = 0.95×-0.12, R2 = 0.92). Methanol showed strong daytime emissions throughout the growing season - with maximal values of 9.7 nmol m-2 s-1, methanol fluxes from the growing grassland were considerably higher at the beginning of the growing season in June compared to those measured during October (2.5 nmol m-2 s-1). Methanol was the only component that exhibited consistent fluxes during the entire growing periods of the grass. The cutting and drying of the grass increased the emissions of methanol to up to 78.4 nmol m-2 s-1. In addition, emissions of acetaldehyde (up to 11.0 nmol m-2 s-1), and hexenal (leaf aldehyde, up to 8.6 nmol m-2 s-1) were detected during/after harvesting.

First eddy covariance flux measurements by PTR-TOF.

The recently developed PTR-TOF instrument was evaluated to measure methanol fluxes emitted from grass land using the eddy covariance method. The high time resolution of the PTR-TOF allowed storing full mass spectra up to m/z 315 with a frequency of 10 Hz. Three isobaric ions were found at a nominal mass of m/z 33 due to the high mass resolving power of the PTR-TOF. Only one of the three peaks contributed to eddy covariance fluxes. The exact mass of this peak agrees well with the exact mass of protonated methanol (m/z 33.0335). The eddy covariance methanol fluxes measured with PTR-TOF were compared to virtual disjunct eddy covariance methanol fluxes simultaneously measured with a conventional PTR-MS. The methanol fluxes from both instruments show excellent agreement.