Gas seepage from Tokamachi mud volcanoes, onshore Niigata Basin (Japan): Origin, post-genetic alterations and CH4-CO2 fluxes

Methane and CO₂ emissions from the two most active mud volcanoes in central Japan, Murono and Kamou (Tokamachi City, Niigata Basin), were measured in from both craters or vents (macro-seepage) and invisible exhalation from the soil (mini- and microseepage). Molecular and isotopic compositions of the released gases were also determined. Gas is thermogenic (δ¹³C_CH4 from −32.9‰ to −36.2‰), likely associated with oil, and enrichments of ¹³C in CO₂ (δ¹³C_CO2 up to +28.3‰) and propane (δ¹³C_C3H8 up to −8.6‰) suggest subsurface petroleum biodegradation. Gas source and post-genetic alteration processes did not change from 2004 to 2010. Methane flux ranged within the orders of magnitude of 10¹-10⁴ g m⁻² d⁻¹ in macro-seeps, and up to 446 g m⁻² d⁻¹ from diffuse seepage. Positive CH₄ fluxes from dry soil were widespread throughout the investigated areas. Total CH₄ emission from Murono and Kamou were estimated to be at least 20 and 3.7 ton a⁻¹, respectively, of which more than half was from invisible seepage surrounding the mud volcano vents. At the macro-seeps, CO₂ fluxes were directly proportional to CH₄ fluxes, and the volumetric ratios between CH₄ flux and CO₂ flux were similar to the compositional CH₄/CO₂ volume ratio. Macro-seep flux data, in addition to those of other 13 mud volcanoes, supported the hypothesis that molecular fractionation (increase of the “Bernard ratio” C₁/(C₂ + C₃)) is inversely proportional to gas migration fluxes. The CH₄ “emission factor” (total measured output divided by investigated seepage area) was similar to that derived in other mud volcanoes of the same size and activity. The updated global “emission-factor” data-set, now including 27 mud volcanoes from different countries, suggests that previous estimates of global CH₄ emission from mud volcanoes may be significantly underestimated.     

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field,Taupo Volcanic Zone,New Zealand

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW_e). Soil CO₂ degassing was quantified with 2663 CO₂ flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m⁻²) using published soil temperature heat flow functions. Both CO₂ flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO₂ gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO₂ emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO₂ emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO₂ emissions due to the loss of >99% of the original CO₂ content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO₂ release to the atmosphere from the high temperature reservoir at Ohaaki. The CO₂ flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO₂ flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m⁻² d⁻¹) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO₂ diffuses through porous media of the soil zone. For high-flux sites (>300 g m⁻² d⁻¹), the δ¹³CO₂ signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO₂ source for each respective upflow. Flux thresholds of <30 g m⁻² d⁻¹ for purely diffusive gas transport, between 30 and 300 g m⁻² d⁻¹ for combined diffusive–advective transport, and ?300 g m⁻² d⁻¹ for purely advective gas transport at Ohaaki were assigned. δ¹³CO₂ values and cumulative probability plots of CO₂ flux data both identified a threshold of ∼15 g m⁻² d⁻¹ by which background (atmospheric and soil respired) CO₂ may be differentiated from hydrothermal CO₂.     

Diffuse gas emissions at the Ukinrek Maars,Alaska: Implications for magmatic degassing and volcanic monitoring

Diffuse CO₂ efflux near the Ukinrek Maars, two small volcanic craters that formed in 1977 in a remote part of the Alaska Peninsula, was investigated using accumulation chamber measurements. High CO₂ efflux, in many places exceeding 1000 g m⁻² d⁻¹, was found in conspicuous zones of plant damage or kill that cover 30,000–50,000 m² in area. Total diffuse CO₂ emission was estimated at 21–44 t d⁻¹. Gas vents 3-km away at The Gas Rocks produce 0.5 t d⁻¹ of CO₂ that probably derives from the Ukinrek Maars basalt based on similar δ¹³C values (∼−6‰), ³He/⁴He ratios (5.9–7.2 R_A), and CO₂/³He ratios (1–2 × 10⁹) in the two areas. A lower ³He/⁴He ratio (2.7 R_A) and much higher CO₂/³He ratio (9 × 10¹⁰) in gas from the nearest arc-front volcanic center (Mount Peulik/Ugashik) provide a useful comparison. The large diffuse CO₂ emission at Ukinrek has important implications for magmatic degassing, subsurface gas transport, and local toxicity hazards. Gas–water–rock interactions play a major role in the location, magnitude and chemistry of the emissions.     

Pathways and regulation of carbon, sulfur and energy transfer in marine sediments overlying methane gas hydrates on the Opouawe Bank (New Zealand)

This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr⁻¹. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m⁻² d⁻¹, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m⁻² d⁻¹ of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m⁻² d⁻¹ of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m⁻² d⁻¹ to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m⁻² d⁻¹ of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100-200 nmol cm⁻³ d⁻¹). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m⁻² d⁻¹ or 96 mW m⁻² of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide oxidation and anaerobic oxidation of methane (AOM) produce 95% and 2% of this energy flux, respectively. The low power output by AOM is due to strong bioenergetic constraints imposed on the reaction rate by the composition of the chemical environment. These constraints provide a high potential for dissolved methane efflux from the sediment (12.0 mmol m⁻² d⁻¹) and indicates a much lower efficiency of (dissolved) methane sequestration by AOM at seeps than considered previously. Nonetheless, AOM is able to consume a third of the ascending methane flux (5.9 mmol m⁻² d⁻¹ of CH₄) with a high efficiency of energy expenditure (35 mmol CH₄ kJ⁻¹). It is further proposed that bioenergetic limitation of AOM provides an explanation for the non-zero sulfate concentrations below the AOM zone observed here and in other active and passive margin sediments.     

Can pelagic net heterotrophy account for carbon fluxes from eastern Canadian lakes?

Lakes worldwide are commonly oversaturated with CO₂, however the source of this CO₂ oversaturation is not well understood. To examine the magnitude of the C flux to the atmosphere and determine if an excess of respiration (R) over gross primary production (GPP) is sufficient to account for this C flux, metabolic parameters and stable isotopes of dissolved O₂ and C were measured in 23 Québec lakes. All of the lakes sampled were oversaturated with CO₂ over the sampling period, on average 221 ± 25%. However, little evidence was found to conclude that this CO₂ oversaturation was the result of an excess of pelagic R over GPP. In lakes Croche and à l’Ours, where CO₂ flux, R and GPP were measured weekly, the annual difference between pelagic GPP and R, or net primary production (NPP), was not sufficient to account for the size of the CO₂ flux to the atmosphere. In Lac Croche average annual NPP was 14.4 mg C m⁻² d⁻¹ while the average annual flux of CO₂ to the atmosphere was 34 mg C m⁻² d⁻¹. In Lac à l’Ours average annual NPP was −9.1 mg C m⁻² d⁻¹ while the average annual flux of CO₂ to the atmosphere was 55 mg C m⁻² d⁻¹. In all of the lakes sampled, O₂ saturation averaged 104.0 ± 1.7% during the ice-free season and the isotopic composition of dissolved O₂ (δ¹⁸O_DO) was 22.9 ± 0.3‰, lower than atmospheric values and indicative of net autotrophy. Carbon evasion was not a function of R, nor did the isotopic signature of dissolved CO₂ in the lakes present evidence of excess R over GPP. External inputs of C must therefore subsidize the lake to explain the continued CO₂ oversaturation. The isotopic composition of dissolved inorganic C (δ¹³C_DIC) indicates that the CO₂ oversaturation cannot be attributed to in situ aerobic respiration. δ¹³C_DIC reveals a source of excess C enriched in ¹³C, which may be accounted for by anaerobic sediment respiration or groundwater inputs followed by kinetic isotope fractionation during degassing under open system conditions.     

Chemical and isotopic tracers of the contribution of microbial gas in Devonian organic-rich shales and reservoir sandstones,northern Appalachian Basin

In this study, the geochemistry and origin of natural gas and formation waters in Devonian age organic-rich shales and reservoir sandstones across the northern Appalachian Basin margin (western New York, eastern Ohio, northwestern Pennsylvania, and eastern Kentucky) were investigated. Additional samples were collected from Mississippian Berea Sandstone, Silurian Medina Sandstone and Ordovician Trenton/Black River Group oil and gas wells for comparison. Dissolved gases in shallow groundwaters in Devonian organic-rich shales along Lake Erie contain detectable CH₄ (0.01–50.55 mol%) with low δ¹³C–CH₄ values (−74.68 to −57.86‰) and no higher chain hydrocarbons, characteristics typical of microbial gas. Nevertheless, these groundwaters have only moderate alkalinity (1.14–8.72 meq/kg) and relatively low δ¹³C values of dissolved inorganic C (DIC) (−24.8 to −0.6‰), suggesting that microbial methanogenesis is limited. The majority of natural gases in Devonian organic-rich shales and sandstones at depth (>168 m) in the northern Appalachian Basin have a low CH₄ to ethane and propane ratios (3–35 mol%; C₁/C₂ + C₃) and high δ¹³C and δD values of CH₄ (−53.35 to −40.24‰, and −315.0 to −174.6‰, respectively), which increase in depth, reservoir age and thermal maturity; the molecular and isotopic signature of these gases show that CH₄ was generated via thermogenic processes. Despite this, the geochemistry of co-produced brines shows evidence for microbial activity. High δ¹³C values of DIC (>+10‰), slightly elevated alkalinity (up to 12.01 meq/kg) and low SO₄ values (<1 mmole/L) in select Devonian organic-rich shale and sandstone formation water samples suggest the presence of methanogenesis, while low δ¹³C–DIC values (<−22‰) and relatively high SO₄ concentrations (up to 12.31 mmole/L) in many brine samples point to SO₄ reduction, which likely limits microbial CH₄ generation in the Appalachian Basin. Together the formation water and gas results suggest that the vast majority of CH₄ in the Devonian organic-rich shales and sandstones across the northern Appalachian Basin margin is thermogenic in origin. Small accumulations of microbial CH₄ are present at shallow depths along Lake Erie and in western NY.     

Stable carbon isotope behaviour of natural seepage of deep underground C-rich methane detected along a fault zone and adsorbed in mudstone: Tokyo Bay area,Japan

Gas was sampled regionally, including by drilling into faults, in the South Kanto gas-field around Tokyo Bay, Japan. Gas samples were collected from cores in a gas sampling container immediately after drilling. A value of δ¹³C₁ = −44.3‰ was obtained for gas in the container and δ¹³C₁ = −36.3‰ for seeping gas in a fault zone. However, typical CH₄ in this dissolved-in-water gas-field is mainly depleted in ¹³C, and δ¹³C₁ values range from −66‰ to −68‰ owing to microbial degradation of organic material. ¹³C-rich CH₄ is so far uncommon in the South Kanto gas-field. Seepages were observed from the surface along the north–south fault zone. The natural gas is stored below the sandstone layer by impermeable mudstone underlying the boundary at a depth of 30 m. Gas seepages were not observed below a depth of 40 m. Gas rises along the fault zone dissolved-in-groundwater up to the shallow region and then separates from the groundwater. ¹³C-rich CH₄ (adsorbed CH₄) was found to have desorbed from drilled mudstone core samples taken at depths of 1400–1900 m in the main gas-production strata. Similarly, ¹³C-rich CH₄ was found in black shale overlying the oceanic crust forming part of a sedimentary accretionary prism underling the Tokyo region. It also appears in the spring-water of spa wells, originating at a depth of 1200–1500 m along a tectonic line. Methane generated by microbial degradation of organic material through CO₂ reduction in the South Kanto gas-field mainly originates as biogenic gas mixed with a small amount of ¹³C-rich CH₄, derived from thermogenic gas without oil components in strata. It is assumed that ¹²C-rich CH₄ is easily detached from core or pore water through gas production, whereas ¹³C-rich CH₄ is strongly adsorbed on the surfaces of particles. The ¹³C-rich CH₄ rises along the major tectonic line or up the 50 m wide normal fault zone from relatively deep sources in the Kanto region.     

Transport and thermodynamics constrain belowground carbon turnover in a northern peatland

Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH₄) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH₄ was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH₄ with depth (5500 μmol L⁻¹ DIC, 500 μmol L⁻¹ CH₄). Highest DIC and CH₄ production rates occurred close to the water table (decomposition constant k_d ∼ 10⁻³-10⁻⁴ a⁻¹) or in some distinct zones at depth (k_d ∼ 10⁻⁴ a⁻¹). Deeper into the peat, decomposition proceeded very slowly at about k_d = 10⁻⁷ a⁻¹. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (−20 to −25 kJ mol⁻¹ CH₄). The methanogenic precursor acetate also accumulated (150 μmol L⁻¹). In line with these findings, CH₄ was formed by hydrogenotrophic methanogenesis at Gibbs free energies of −35 to −40 kJ mol⁻¹ CH₄. This was indicated by an isotopic fractionation α_CO2-CH4 of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol⁻¹ substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH₄ may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.     

Particulate-associated potentially harmful elements in urban road dusts in Xi’an,China

Sixty five urban road dust samples were collected from different land use areas of ∼240 km² in Xi’an, China. The concentrations of Ag, As, Cr, Cu, Hg, Pb, Sb and Zn were determined to investigate potentially harmful element (PHE) contamination, distribution and possible sources. In addition, the concentrations in different size fractions were measured to assess their potential impact on human health. The highest concentrations were found in the fraction with particle diameters between 80 μm and 101 μm, the finest particles (<63 μm) were not the most important carriers for Ag, As, Cd, Cr, Cu, Hg, Pb and Zn. The percentages of these elements in particles with diameters less than 63 μm (PM₆₃) and less than 101 μm (PM₁₀₁) were in the range of 7–15%, and 30–55%, respectively. Three main factors influencing element distributions have been identified: (a) industrial activities; (b) prior agricultural land use; and (c) other activities commonly found in urban areas, such as traffic, coal combustion, waste dumping, and building construction/renovation. The highest concentrations were found in industrial areas for As (20 mg kg⁻¹), Cr (853 mg kg⁻¹), Cu (1071 mg kg⁻¹), Pb (3060 mg kg⁻¹) and Zn (2112 mg kg⁻¹), and in previous agricultural areas for Ag and Hg, indicating significant contributions from industrial activities and prior agricultural activities.     

Environmental geochemistry of an active Hg mine in Xunyang,Shaanxi Province,China

The Xunyang Hg mine (XMM) situated in Shaanxi Province is an active Hg mine in China. Gaseous elemental Hg (GEM) concentrations in ambient air were determined to evaluate its distribution pattern as a consequence of the active mining and retorting in the region. Total Hg (HgT) and methylmercury (MeHg) concentrations in riparian soil, sediment and rice grain samples (polished) as well as Hg speciation in surface water samples were measured to show local dispersion of Hg contamination. As expected, elevated concentrations of GEM were found, ranging from 7.4 to 410 ng m⁻³. High concentrations of HgT and MeHg were also obtained in riparian soils, ranged from 5.4 to 120 mg kg⁻¹ and 1.2 to 11 μg kg⁻¹, respectively. Concentrations of HgT and MeHg in sediment samples varied widely from 0.048 to 1600 mg kg⁻¹ and 1.0 to 39 μg kg⁻¹, respectively. Surface water samples showed elevated HgT concentrations, ranging from 6.2 to 23,500 ng L⁻¹, but low MeHg concentrations, ranging from 0.022 to 3.7 ng L⁻¹. Rice samples exhibited high concentrations of 50–200 μg kg⁻¹ in HgT and of 8.2–80 μg kg⁻¹ in MeHg. The spatial distribution patterns of Hg speciation in the local environmental compartments suggest that the XMM is the source of Hg contaminations in the study area.     

Benthic fluxes of mercury species in a lagoon environment (Grado Lagoon,Northern Adriatic Sea,Italy)

The role of the major biogeochemical processes in Hg cycling at the sediment–water interface was investigated in the Grado Lagoon (Northern Adriatic Sea). This wetland system has been extensively contaminated from the Idrija Hg Mine (Slovenia) through the Isonzo River suspended load carried by tidal fluxes. Three approaches were used to study the sediment–water exchange of total Hg (THg), methylmercury (MeHg), reactive Hg (RHg) and dissolved gaseous Hg (DGHg): (1) estimation of diffusive fluxes from porewater and overlying water concentrations, (2) measurements of benthic fluxes using a deployed light benthic chamber in situ and (3) measurements of benthic fluxes during oxic–anoxic transition with a laboratory incubation experiment. The THg solid phase, ranging between 9.5 and 14.4 μg g⁻¹, showed slight variability with depth and time. Conversely, MeHg contents were highest (up to 21.9 ng g⁻¹) at the surface; they tended to decrease to nearly zero concentration with depth, thus suggesting that MeHg production and accumulation occur predominantly just below the sediment–water interface. Porewater MeHg concentrations (0.9–7.9 ng L⁻¹, 0.15–15% of THg) varied seasonally; higher contents were observed in the warmer period. The MeHg diffusive fluxes (up to 17 ng m⁻² day⁻¹) were similar to those in the nearby Gulf of Trieste [Covelli, S., Horvat, M., Faganeli, J., Brambati, A., 1999. Porewater distribution and benthic flux of mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Estuar. Coast. Shelf Sci. 48, 415–428], although the lagoon sediments contained four-fold higher THg concentrations. Conversely, the THg diffusive fluxes in the lagoon (up to 110 ng m⁻² day⁻¹) were one- to two-fold higher than those previously estimated for the Gulf of Trieste. The diurnal MeHg benthic fluxes were highest in summer at both sites (41,000 and 33,000 ng m⁻² day⁻¹ at the fishfarm and in the open lagoon, respectively), thus indicating the influence of temperature on microbial processes. The diurnal variations of dissolved THg and especially MeHg were positively correlated with O₂ and inversely with DIC, suggesting an important influence of benthic photosynthetic activities on lagoon benthic Hg cycling, possibly through the production of organic matter promptly available for methylation. The results from the dark chamber incubated in the laboratory showed that the regeneration of dissolved THg was slightly affected by the oxic–anoxic transition. Conversely, the benthic flux of MeHg was up to 15-fold higher in sediments overlain by O₂ depleted waters. In the anoxic phase, the MeHg fluxes proceeded in parallel with Fe fluxes and the methylated form reached approximately 100% of dissolved THg. The MeHg is mostly released into overlying water (mean recycling efficiency of 89%) until the occurrence of sulphide inhibition, due to scavenging of the available Hg substrate for methylation. The results suggest that sediments in the Grado Lagoon, especially during anoxic events, should be considered as a primary source of MeHg for the water column.     

Estimating specific surface area of fine stream bed sediments from geochemistry

Specific surface area (SSA) of headwater stream bed sediments is a fundamental property which determines the nature of sediment surface reactions and influences ecosystem-level, biological processes. Measurements of SSA – commonly undertaken by BET nitrogen adsorption – are relatively costly in terms of instrumentation and operator time. A novel approach is presented for estimating fine (<150 μm) stream bed sediment SSA from their geochemistry – after removal of organic matter – for agricultural headwater catchments across 15,400 km² of central England, UK. From a regional set of 1972 stream bed sediment sites with common characteristics for which geochemical data were available, 60 samples were selected – based on maximising their variation in Al concentrations – and their BET SSA measured by N₂ adsorption. After careful selection of potential regression predictors following a principal component analysis and removal of a subset of samples with the largest Mo concentrations (>2.5 mg kg⁻¹), four elements were identified as significant predictors of SSA (ordered by decreasing predictive power): V > Ca > Al > Rb. The optimum model from these four elements accounted for 73% of the variation in bed sediment SSA (range 6–46 m² g⁻¹) with a root mean squared error of prediction – based on leave-one-out cross-validation – of 6.3 m² g⁻¹. It is believed that V is the most significant predictor because its concentration is strongly correlated both with the quantity of Fe-oxides and clay minerals in the stream bed sediments, which dominate sediment SSA. Sample heterogeneity in SSA – based on triplicate measurements of sub-samples – was a substantial source of variation (standard error = 2.2 m² g⁻¹) which cannot be accounted for in the regression model.     

Diagenetic processes on metals in hypersaline mudflat sediments from a subtropical saltmarsh (SE Gulf of California): Postdepositional mobility and geochemical fractions

To understand the biogeochemical cycles of trace metals (Cd, Cu, Fe, Mn, Ni and Zn) in a hypersaline subtropical marsh, geochemical studies of both interstitial and solid phases were conducted on sediment cores from Chiricahueto marsh, SE Gulf of California. The sequential extraction procedure proposed by Tessier was used to estimate the percentages of the metals present in each geochemical phase of the sediment. Metal concentrations in the solid phase were found to be enriched in the upper layers and mainly associated with reactive fractions such as organic matter, Fe–Mn oxyhydroxides and carbonates (46–74% of Ni, Mn and Cd, and 11–19% of Cu and Zn). Principal factor analysis (PFA) and Spearman correlation analysis revealed a strong positive association of metals and their reactive phases with OC (the diagenetic component), and a negative or non-association with the mud content, Al, Fe and Li (the lithogenic component). Diagenetically released metals are mainly mobilized within hypersaline sediments by buoyancy transport (>90% of total flux) in response to an extreme salinity gradient by input of fresh groundwater (3–6 psu cm⁻¹). The molecular diffusion due to the gradient of metals in porewater (maximum and higher levels at 5–7 and below 20 cm depth, respectively) is significantly less important to the advective transport. Most of the metals mobilized by diffusion–advection processes are re-precipitated in the sediments by authigenic minerals, only <10% of most metals are extruded out to the overlying water column. Authigenic accumulation rates were estimated as 1.42–7.09 mg m⁻² a⁻¹ for Cd; 58.8–378 for Cu; 6922–17,985 for Fe; 38.2–345 for Mn; 20.8–263 for Ni; and 282–2956 mg m⁻² a⁻¹ for Zn. The Mn–Fe oxyhydroxides (40–85% of reactive metals) in the upper oxic–suboxic layers (<5 cm below surface) and sulfide minerals (75–97%) in anoxic sediment layers (7–18 cm) constitute the main scavengers for metals.     

Methane and carbon dioxide flux from a macrotidal salt marsh,Bay of Fundy,New Brunswick

Fluxes of methane (CH₄) and carbon dioxide (CO₂) to the atmosphere at 52 sites within a salt marsh were measured by a dark static chamber technique from mid July to mid September. Mean CH₄ fluxes ranged from 0.2 mg m^?2 d^?1 to 11.0 mg m^?2 d^?1, with an overall average of 1.6 mg m^?2 d^?1. Flux of CH₄ was inversely correlated (r²=0.23, p = 0.001) with salinity of the upper porewater at the site, suggesting the dominant role of SO₄ ^2? in inhibiting methanogenesis in salt-marsh sediments. The combination of salinity and water table position was able to explain only 29% of the variance in CH₄ emission. Mean soil flux of CO₂ ranged from 0.3 g m^?2 d^?1 to 3.7 g m^?2 d^?1, with an overall average of 2.5 g m^?2 d^?1; it was correlated with aboveground biomass (positive, r²=0.38, p = 0.001) and position of the water table (negative, r² = 0.55, p = 0.001). The combination of biomass and water table position accounted for 63% of the variance in CO₂ flux. There were high variations in gas flux within the six plant communities. The sequences were CH₄: upland edge > panne > pool > middle marsh > low marsh > high marsh, and CO₂: middle marsh > low marsh > upland edge > high marsh > panne > pool. Compared to other salt-marsh systems, this Bay of Fundy marsh emits small amounts of CH₄ and CO₂.     

Streamwater chemistry in three contrasting monolithologic Czech catchments

Hydrochemical patterns resulting from differing bedrock geochemistry were ascertained by concurrent streamwater sampling in three small catchments, each underlain by geochemically contrasting silicate rock types in the western Czech Republic, Central Europe in 2001–2010. The catchments are situated 5–7 km apart in the Slavkov Forest and are occupied by Norway spruce (Picea abies) plantations. They have similar altitude, area, topography, mean annual air temperature, and atmospheric deposition fluxes. The amount of base cations oxides (Ca + Mg + Na + K) is markedly different among the three studied rocks (leucogranite 8%, amphibolite 22%, serpentinite 36%). The leucogranite contains a very small amount of MgO, while the serpentinite contains extremely large amounts of MgO. The amphibolite contains an intermediate amount of MgO and elevated CaO. The Lysina, on leucogranite, exhibited very small concentrations of Mg (median 0.4 mg L⁻¹) in streamwater; Pluh?v Bor, on serpentinite, contained extremely high concentrations of streamwater Mg (18 mg L⁻¹). Streamwater in the Na Zeleném catchment, on amphibolite, contained an intermediate amount of Mg and an elevated Ca. Very low pH (4.2), negative alkalinity (−60 μeq L⁻¹) and high inorganic monomeric Al concentrations (0.3 mg L⁻¹) were found in the stream draining leucogranite. Serpentinite streamwater exhibited the highest pH (7.6), alkalinity (+940 μeq L⁻¹) and Ni concentrations (100 μg L⁻¹). Aquatic chemistry reflected the composition of the underlying rocks within the studied catchments. Contrasting streamwater compositions of the studied catchments were generated according to the MAGIC model simulations mainly by differences in chemical weathering rates of base cations (65 meq m⁻² a⁻¹ at Lysina, 198 meq m⁻² a⁻¹ at Na Zeleném, and 241 meq m⁻² a⁻¹ at Pluh?v Bor).     

An iodine mass-balance for Lake Constance, Germany: Insights into iodine speciation changes and fluxes

Lake Constance is one of Europe’s largest oligotrophic lakes and provides a water source for more than 4.5 million people in Germany and Switzerland. We present here a 12 month study on iodine concentrations, speciation and fluxes to and from the lake to gain a quantitative understanding of the limnic iodine cycle. Monthly water samples were obtained from all major tributaries (14) and the outflow to construct a mass-balance model. Sediment traps were also deployed in the lake for two years at two different stations. Total soluble iodine (TSI) in aqueous samples were analysed by ICP-MS and speciation (iodide, iodate and soluble organically bound iodine, SOI) by ion chromatography-ICP-MS. Iodine concentrations in the Alpine tributaries (1-2 μg l⁻¹) decreased over the summer months due to increasing proportions of snow and glacial melt water from the Alps, while iodine levels in the lowland rivers (∼2-10 μg l⁻¹) increased over the summer. Deposition of TSI to the catchment (16,340 kg I yr⁻¹) was similar to the TSI out-flux by rivers (16,000 kg I yr⁻¹). By also including the particulate riverine iodine flux out of the catchment (∼12,350 kg I yr⁻¹) it is shown that the catchment is a net source of iodine, with the highest particulate fluxes coming from the Alpine rivers. The total TSI flux to the lake was 16,770 kg I yr⁻¹, the largest proportion coming from the Alpenrhein (43%), followed by the Schussen (8%) and Bregenzer Ach (7.7%). Overall the mass-balance for TSI in the lake was negative, with more iodine flowing out of the lake than in (−2050 kg I yr⁻¹; 12% of TSI in-flux). To maintain mass-balance, 8.8 μg I m⁻² d⁻¹ from the Obersee and 23 μg I m⁻² d⁻¹ from the Untersee must be released from the sediments into the water column. Thus, in comparison with the total iodine flux to the sediments measured by the sediment traps (4762-8075 kg I yr⁻¹), up to 39% of the deposited iodine may be mobilised back into the lake. SOI was the dominant iodine fraction entering the lake, with a total flux of 10,290 kg I yr⁻¹ (64% of TSI input), followed by iodate (3120 kg I yr⁻¹) and iodide (2760 kg I yr⁻¹). Net formation of SOI from iodide and iodate was also noted within the lake, with an estimated production of 6560 kg I yr⁻¹, suggesting a strong role for biology in iodine cycling. In conclusion, organically bound iodine was the dominant iodine species in aqueous and solid phases in Lake Constance, despite low DOC concentrations (<2 mg l⁻¹), and thus is expected to play an important role in iodine cycling in most freshwater environments.     

Palaeo-hydrogeological control on groundwater As levels in Red River delta,Vietnam

To study the geological control on groundwater As concentrations in Red River delta, depth-specific groundwater sampling and geophysical logging in 11 monitoring wells was conducted along a 45 km transect across the southern and central part of the delta, and the literature on the Red River delta’s Quaternary geological development was reviewed. The water samples (n = 30) were analyzed for As, major ions, Fe²⁺, H₂S, NH₄, CH₄, δ¹⁸O and δD, and the geophysical log suite included natural gamma-ray, formation and fluid electrical conductivity. The SW part of the transect intersects deposits of grey estuarine clays and deltaic sands in a 15–20 km wide and 50–60 m deep Holocene incised valley. The NE part of the transect consists of 60–120 m of Pleistocene yellowish alluvial deposits underneath 10–30 m of estuarine clay overlain by a 10–20 m veneer of Holocene sediments. The distribution of δ¹⁸O-values (range −12.2‰ to −6.3‰) and hydraulic head in the sample wells indicate that the estuarine clay units divide the flow system into an upper Holocene aquifer and a lower Pleistocene aquifer. The groundwater samples were all anoxic, and contained Fe²⁺ (0.03–2.0 mM), Mn (0.7–320 μM), SO₄ (<2.1 μM–0.75 mM), H₂S (<0.1–7.0 μM), NH₄ (0.03–4.4 mM), and CH₄ (0.08–14.5 mM). Generally, higher concentrations of NH₄ and CH₄ and low concentrations of SO₄ were found in the SW part of the transect, dominated by Holocene deposits, while the opposite was the case for the NE part of the transect. The distribution of the groundwater As concentration (<0.013–11.7 μM; median 0.12 μM (9 μg/L)) is related to the distribution of NH₄, CH₄ and SO₄. Low concentrations of As (?0.32 μM) were found in the Pleistocene aquifer, while the highest As concentrations were found in the Holocene aquifer. PHREEQC-2 speciation calculations indicated that Fe²⁺ and H₂S concentrations are controlled by equilibrium for disordered mackinawite and precipitation of siderite. An elevated groundwater salinity (Cl range 0.19–65.1 mM) was observed in both aquifers, and dominated in the deep aquifer. A negative correlation between aqueous As and an estimate of reduced SO₄ was observed, indicating that Fe sulphide precipitation poses a secondary control on the groundwater As concentration.     

Methane and sulfide fluxes in permanent anoxia: In situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m⁻² d⁻¹. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m⁻² d⁻¹) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 10⁷ mol yr⁻¹. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m⁻² d⁻¹. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.     

Arsenic speciation and turnover in intact organic soil mesocosms during experimental drought and rewetting

Wetlands are significant sources and sinks for arsenic (As), yet the geochemical conditions and processes causing a release of dissolved arsenic and its association with the solid phase of wetland soils are poorly known. Here we present experiments in which arsenic speciation was determined in peatland mesocosms in high spatiotemporal resolution over 10 months. The experiment included a drought/rewetting treatment, a permanently wet, and a defoliated treatment. Soil water content was determined by the TDR technique, and arsenic, iron and sulfate turnover from mass balancing stocks and fluxes in the peat, and solid phase contents by sequential extractions. Arsenic content ranged from 5 to 25 mg kg⁻¹ and dissolved concentrations from 10 to 300 μg L⁻¹, mainly in form of As(III), and secondarily of As(V) and dimethylated arsenic (DMA). Total arsenic was mainly associated with amorphous iron hydroxides (R² > 0.95, α < 0.01) and deeper into the peat with an unidentified residual fraction. Arsenic release was linked to ferrous iron release and primarily occurred in the intensely rooted uppermost soil. Volumetric air contents of 2-13 % during drought eliminated DMA from the porewater and suppressed its release after rewetting for >30 d. Dissolved As(III) was oxidized and immobilized as As(V) at rates of up to 0.015 mmol m⁻³ d⁻¹. Rewetting mobilized As(III) at rates of up to 0.018 mmol m⁻³ d⁻¹ within days. Concurrently, Fe(II) was released at depth integrated rates of up 20 mmol m⁻³ d⁻¹. The redox half systems of arsenic, iron, and sulfur were in persistent disequilibrium, with H₂S being a thermodynamically viable reductant for As(V) to As(III). The study suggests that rewetting can lead to a rapid release of arsenic in iron-rich peatlands and that methylation is of lesser importance than co-release with iron reduction, which was largely driven by root activity.