Carbon isotopic composition of methane in Florida Everglades soils and fractionation during its transport to the troposphere

The δ13C stable carbon isotopic composition of methane collected in bubbles from the submerged soils of specific environments within the Everglades wetland in southern Florida, United States, varied from −70‰ to −63‰ across the system while organic carbon in the soils and dominant plants varied from −28‰ to −25‰. A methane isotopic budget based upon the soil bubble isotope data and published methane flux measurements predicted a flux of isotopic composition −65‰, a value 5‐10‰ more depleted in 13C than the isotopic composition of methane emanating to the atmosphere. Emergent aquatic plants, which are known to be active methane transporters between soil and atmosphere in this ecosystem, were found to transport methane of δ13C content up to 12‰ different from the δ13C content of the soil methane bubble reservoir. Methane 14C content at one site was determined to be 108.6% modern (Δ14C = 83 ± 10‰)

The analysis of dimethylsulfide and dimethylsulfoniopropionate in sea ice: dry-crushing and melting using stable isotope additions

Sea ice is thought to be an important source of the climate-active gas dimethylsulfide (DMS), since extremely high concentrations of its precursor dimethylsulfoniopropionate (DMSP) have been found associated with high algal biomass. Accurate measurements of DMS and associated compounds in sea ice were until now not possible due to difficulties associated with the unavoidable melting process before analysis. Here we present and evaluate two methods to analyze DMS and DMSP in sea-ice cores accurately. The first, describes the dry-crushing method, which has its focus on the volatile compound DMS. A sub-sample of deeply frozen (<-30 °C) ice is crushed in a stainless steel vessel and the released gas phase is analyzed directly for DMS. The remaining ice is subsequently analyzed for its total DMSP content. With this method, DMS and DMSP profiles can be resolved even in ice cores stored deeply frozen for two years. The second method, involves a melting procedure, during which the conversion of compounds is monitored by adding differently deuterated isotopes of DMS and DMSP. Natural concentrations and stable isotopes of DMS and DMSP are simultaneously analyzed on a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS). Loss and conversion rates of the artificial isotopes are used to reconstruct the original concentrations of DMS and DMSP in ice and give important information on potential dynamical processes in sea-ice communities. It is concluded that in stored cores, the dry-crushing method provides the best results when the aim of the study is to differentiate between DMS and DMSP. When direct processing and analysis of the samples is possible, the isotope-addition method has the potential of providing concentrations of all S-compounds, including dissolved and particulate fractions. Moreover, it is suitable for the determination of process rates within the S-cycle

Simultaneous use of relaxed eddy accumulation and gradient flux techniques for the measurement of sea-to-air exchange of dimethyl sulphide

The sea-to-air flux of the biogenic volatile sulphur compound dimethyl sulphide was assessed with the relaxed eddy accumulation (REA) and the gradient flux (GF) techniques from a stationary platform in the coastal Atlantic Ocean. Fluxes varied between 2 and 16 µmol m-2 d-1. Fluxes derived from REA were on average 7.1±5.03 µmol m-2 d-1, not significantly different from the average flux of 5.3±2.3 µmol m-2 d-1 derived from GF measurements. Gas transfer velocities were calculated from the fluxes and seawater DMS concentrations. They were within the range of gas transfer rates derived from the commonly used parameterizations that relate gas transfer to wind speed.

Factors determining the vertical profile of dimethylsulfide in the Sargasso Sea during summer

14 pages,11 figuresThe major source of reduced sulfur in the remote marine atmosphere is the biogenic compound dimethylsulfide (DMS), which is ubiquitous in the world’s oceans and released through food web interactions. Relevant fluxes and concentrations of DMS, its phytoplankton-produced precursor, dimethylsulfoniopropionate (DMSP) and related parameters were measured during an intensive Lagrangian field study in two mesoscale eddies in the Sargasso Sea during July–August 2004, a period characterized by high mixed-layer DMS and low chlorophyll—the so-called ‘DMS summer paradox’. We used a 1-D vertically variable DMS production model forced with output from a 1-D vertical mixing model to evaluate the extent to which the simulated vertical structure in DMS and DMSP was consistent with changes expected from field-determined rate measurements of individual processes, such as photolysis, microbial DMS and dissolved DMSP turnover, and air–sea gas exchange. Model numerical experiments and related parametric sensitivity analyses suggested that the vertical structure of the DMS profile in the upper 60 m was determined mainly by the interplay of the two depth variable processes—vertical mixing and photolysis—and less by biological consumption of DMS. A key finding from the model calibration was the need to increase the DMS(P) algal exudation rate constant, which includes the effects of cell rupture due to grazing and cell lysis, to significantly higher values than previously used in other regions. This was consistent with the small algal cell size and therefore high surface area-to-volume ratio of the dominant DMSP-producing group—the picoeukaryotes.We gratefully acknowledge the financial assistance provided through NSF Biocomplexity funding (OPP-0083078) and an Australian Research Council Discovery Grant. We are grateful to the comments by D.J. Kieber. We recognize the participation and help of K. Bailey, J. Bisgrove, B. Blomquist, I. Forn, H. Harada, B. Huebert, D. Jones, L. Maroney, A. Neely, S. Riseman, C. Smith, J. Stefels, K. Tinklepaugh, M. Vila-Costa, G. Westby, H. Zemmelink and the R/V Seward Johnson crew. DiTullio et al., 2001; Simo ́ and Dachs, 2002; Simon and Azam, 1989; Zemmelink et al., 2005Peer reviewe

Diagnostic modeling of dimethylsulfide production in coastal water west of the Antarctic Peninsula

14 pages, 10 figures, 3 tablesThe rate of gross biological dimethylsulfide (DMS) production at two coastal sites west of the Antarctic Peninsula, off Anvers Island, near Palmer Station, was estimated using a diagnostic approach that combined field measurements from 1 January 2006 through 1 March 2006 and a one-dimensional physical model of ocean mixing. The average DMS production rate in the upper water column (0–60 m) was estimated to be 3.1±0.6 nM d−1 at station B (closer to shore) and 2.7±0.6 nM d−1 at station E (further from shore). The estimated DMS replacement time was on the order of 1 d at both stations. DMS production was greater in the mixed layer than it was below the mixed layer. The average DMS production normalized to chlorophyll was 0.5±0.1 (nM d−1)/(mg m−3) at station B and 0.7±0.2 (nM d−1)/(mg m−3) at station E. When the diagnosed production rates were normalized to the observed concentrations of total dimethylsulfoniopropionate (DMSPt, the biogenic precursor of DMS), we found a remarkable similarity between our estimates at stations B and E (0.06±0.02 and 0.04±0.01 (nM DMS d−1)/(nM DMSP), respectively) and the results obtained in a previous study from a contrasting biogeochemical environment in the North Atlantic subtropical gyre (0.047±0.006 and 0.087±0.014 (nM DMS d−1)/(nM DMSP) in a cyclonic and anticyclonic eddy, respectively). We propose that gross biological DMS production normalized to DMSPt might be relatively independent of the biogeochemical environment, and place our average estimate at 0.06±0.01 (nM DMS d−1)/(nM DMSPt). The significance of this finding is that it can provide a means to use DMSPt measurements to extrapolate gross biological DMS production, which is extremely difficult to measure experimentally under realistic in situ conditions.This research was supported by the National Science Foundation (NSF) Office of Polar Programs (OPP) under Grant OPP-0083078 to P.A. Matrai. Data from the Palmer LTER data archive were supported by NSF Grant OPP-0217282. Meteorological data were supported by NSF Grants OPP-0537827, OPP-0338147, and OPP-0230028. Surface solar radiation data were provided by the NSF UV Monitoring Network, operated by Biospherical Instruments Inc. under a contract from the NSF OPP via Raytheon Polar Services Company.Peer reviewe