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Oceanic dissolved organic carbon (DOC) is an important carbon pool, similar in magnitude to atmospheric CO2, but the fate of its oldest forms is not well understood1, 2. Hot hydrothermal circulation may facilitate the degradation of otherwise un-reactive dissolved organic matter, playing an important role in the long-term global carbon cycle. The oldest, most recalcitrant forms of DOC, which make up most of oceanic DOC, can be recovered by solid-phase extraction. Here we present measurements of solid-phase extractable DOC from samples collected between 2009 and 2013 at seven vent sites in the Atlantic, Pacific and Southern oceans, along with magnesium concentrations, a conservative tracer of water circulation through hydrothermal systems. We find that magnesium and solid-phase extractable DOC concentrations are correlated, suggesting that solid-phase extractable DOC is almost entirely lost from solution through mineralization or deposition during circulation through hydrothermal vents with fluid temperatures of 212–401 °C. In laboratory experiments, where we heated samples to 380 °C for four days, we found a similar removal efficiency. We conclude that thermal degradation alone can account for the loss of solid-phase extractable DOC in natural hydrothermal systems, and that its maximum lifetime is constrained by the timescale of hydrothermal cycling, at about 40 million years3.

The rewetting of drained peatlands alters peat geochemistry and often leads to sustained elevated methane emission. Although this methane is produced entirely by microbial activity, the distribution and abundance of methane-cycling microbes in rewetted peatlands, especially in fens, is rarely described. In this study, we compare the community composition and abundance of methane-cycling microbes in relation to peat porewater geochemistry in two rewetted fens in northeastern Germany, a coastal brackish fen and a freshwater riparian fen, with known high methane fluxes. We utilized 16S rRNA high-throughput sequencing and quantitative polymerase chain reaction (qPCR) on 16S rRNA, mcrA, and pmoA genes to determine microbial community composition and the abundance of total bacteria, methanogens, and methanotrophs. Electrical conductivity (EC) was more than 3 times higher in the coastal fen than in the riparian fen, averaging 5.3 and 1.5 mS cm−1, respectively. Porewater concentrations of terminal electron acceptors (TEAs) varied within and among the fens. This was also reflected in similarly high intra- and inter-site variations of microbial community composition. Despite these differences in environmental conditions and electron acceptor availability, we found a low abundance of methanotrophs and a high abundance of methanogens, represented in particular by Methanosaetaceae, in both fens. This suggests that rapid (re)establishment of methanogens and slow (re)establishment of methanotrophs contributes to prolonged increased methane emissions following rewetting.

The common process of low energy geothermal exploitation is the doublet of production- and reinjection borehole. The quality of water reinjected into a elastic reservoir is essential for the reliability of an injection well. In order to estimate precipitation reactions it is necessary to obtain extensive reliable analysis data of the water for the use of thermodynamic modelling. For thermal anoxic brines, the analysis of major and especially minor ion content is difficult because of matrix effects and possible iron precipitation. A selection of analysing methods were applied to two anoxic thermal brines of deep sandstone aquifers of Northern Germany. Detection limits and measured data of the major constituents are presented of Na+, K+, NH4+, Ca2+, Mg2+, Ba2+, Sr2+, Fe-total, Mn2+, SiO44-, B(OH)(3), Zn2+, Pb2+, Cd2+, F-, Cl-, Br-, I-, SO42-, SO32-, S2-, PO43-, NO3-, NO2- and DOC. The measurements were done with ICP-OES, ionselective electrodes, photometry, polarography, titration methods, ion chromatography and TOC-analyzer. Except for SO(4)(2-)and Cl-, the anion analysis was done on-site, since the high iron content in the anoxic water requires acidification in order to prevent iron hydroxide precipitation. The minor constituents Zn2+, Pb2+, Cu2+, Cd2+, Cr3+, Sc3+, Co2+, Y3+, La3+, Ce3+, Al3+, were enriched by trace matrix separation using the cation exchange resin Chelex((R))100. The element concentrations in the acidic eluates of the Chelex((R))100 columns were measured using ICP-MS. The pH dependency of the exchange equilibrium at pH values of 4, 5 and 6 (buffered and unbuffered) as well as the relation to the salt content between 35 and 250 gl(-1) total dissolved solids of Na-K-Ca-Mg-Cl-SO4 were evaluated by sensitivity analysis.

Abstract Arid Central Asia represents a key region for understanding climate variability and interactions in the Northern Hemisphere. Patterns and mechanisms of Holocene climate change in arid Central Asia are, however, only partially understood. Multi-proxy data combining diatom, ostracod, sedimentological, geochemical and stable isotope analyses from a ca. 6000-year-old lake sediment core from Son Kol (Central Kyrgyzstan) show distinct and repeated changes in species assemblages. Diatom- and ostracod-inferred conductivity shifts between meso-euhaline and freshwater conditions suggest water balance and regime shifts. Organism-derived data are corroborated by stable isotope, mineralogical and geochemical records, underlining that Son Kol was affected by strong lake level fluctuations of several meters. The δ13Ccarb/δ18Ocarb correlation shows repeated switchovers from a closed to an open lake system. From 6000 to 3800 and 3250 to 1950 cal. yr BP, Son Kol was a closed basin lake with higher conductivities, increased nutrient availability and a water level located below the modern outflow. Son Kol became again a hydrologically open lake at 3800 and 1950 cal. yr BP. Comparisons to other local and regional paleoclimate records indicate that these regime shifts were largely controlled by changing intensity and position of the Westerlies and the Siberian Anticyclone that triggered changes in the amount of winter precipitation. A strong influence of the Westerlies ca. 5000–4400, 3800–3250 and since 1950 cal. yr BP enhanced the amount of precipitation during spring, autumn and winter, whereas cold and dry winters prevailed during phases with a strong Siberian Anticyclone and southward shifted Westerlies at ca. 6000–5000, 4400–3800 and 3250–1950 cal. yr BP. Similarities between variations in winter precipitation at Son Kol and records of the predominant NAO-mode further suggest a teleconnection between wet (dry) winter climate in Central Asia and a positive (negative) NAO-mode. Thus, this study identifies climate fluctuations as the main driver for hydrological regime shifts in Son Kol controlling physicochemical conditions and consequently causing abrupt species assemblage changes. This emphasizes the importance of multi-proxy approaches to identify triggers, thresholds and cascades of aquatic ecosystem transformations.

Abstract Dolomite is a very common carbonate mineral in ancient sediments, but is rarely found in modern environments. Because of the difficulties in precipitating dolomite in the laboratory at low temperatures, the controls on its formation are still debated after more than two centuries of research. Two important parameters to constrain the environment of dolomitization are the temperature of formation and the oxygen isotope composition of the fluid from which it precipitated. Carbonate clumped isotopes (expressed with the parameter Δ47) are increasingly becoming the method of choice to obtain this information. However, whereas many clumped isotope studies treated dolomites the same way as calcite, some recent studies observed a different phosphoric acid fractionation for Δ47 during acid digestion of dolomite compared to calcite. This causes additional uncertainties in the Δ47 temperature estimates for dolomites analyzed in different laboratories using different acid digestion temperatures. To tackle this problem we present here a (proto-)dolomite-specific Δ47-temperature calibration from 25 to 1100 °C for an acid reaction temperature of 70 °C and anchored to widely available calcite standards. For the temperature range 25 to 220 °C we obtain a linear Δ47-T relationship based on 289 individual measurements with R2 of 0.864: ∆ 47 CDES 70 ° C = 0.0428 ± 0.0020 × 10 6 T 2 + 0.1481 ± 0.0160 T in Kelvin When including two isotopically scrambled dolomites at 1100 °C, the best fit is obtained with a third order polynomial temperature relationship (R2 = 0.924): ∆ 47 CDES 70 ° C ‰ = − 0.0002 × 10 6 T 2 3 + 0.0041 × 10 6 T 2 2 + 0.0115 × 10 6 T 2 + 0.2218 . Applying a calcite Δ47-T relationship produced under identical laboratory conditions results in 3 to 16 °C colder calculated formation temperatures for dolomites (with formation temperature from 0 to 100 °C) than using the (proto-)dolomite specific calibration presented here. For the synthetic samples formed between 70 and 220 °C we also determined the temperature dependence of the oxygen isotope fractionation relative to the water. Based on the similarity between our results and two other recent studies ( Vasconcelos et al., 2005 and Horita, 2014 ) we propose that a combination of the three datasets represents the most robust calibration for (proto-)dolomite formed in a wide temperature range from 25 to 350 °C. 10 3 α CaMg − carbonates − Water = 2.9923 ± 0.0557 × 10 6 T 2 − 2.3592 ± 0.4116 Because of the uncertainties in the phosphoric acid oxygen and clumped isotope fractionation for (proto-)dolomite, we promote the use of three samples that are available in large amounts as possible inter-laboratory reference material for oxygen and clumped isotope measurements. A sample of the middle Triassic San Salvatore dolomite from southern Switzerland, the NIST SRM 88b dolomite standard already reported in other Δ47 studies and a lacustrine Pliocene dolomite from La Roda (Spain). This study demonstrates the necessity to apply (proto-)dolomite specific Δ47-T relationships for accurate temperature estimates of dolomite formation, ideally done at identical acid digestion temperatures to avoid additional uncertainties introduced by acid digestion temperature corrections. In addition, the simultaneous analyses of dolomite reference material will enable a much better comparison of published dolomite clumped and oxygen isotope data amongst different laboratories.

Peatlands store substantial amounts of carbon and are vulnerable to climate change. We present a modified version of the Organising Carbon and Hydrology In Dynamic Ecosystems (ORCHIDEE) land surface model for simulating the hydrology, surface energy, and CO2 fluxes of peatlands on daily to annual timescales. The model includes a separate soil tile in each 0.5° grid cell, defined from a global peatland map and identified with peat-specific soil hydraulic properties. Runoff from non-peat vegetation within a grid cell containing a fraction of peat is routed to this peat soil tile, which maintains shallow water tables. The water table position separates oxic from anoxic decomposition. The model was evaluated against eddy-covariance (EC) observations from 30 northern peatland sites, with the maximum rate of carboxylation (Vcmax) being optimized at each site. Regarding short-term day-to-day variations, the model performance was good for gross primary production (GPP) (r2 = 0.76; Nash–Sutcliffe modeling efficiency, MEF = 0.76) and ecosystem respiration (ER, r2 = 0.78, MEF = 0.75), with lesser accuracy for latent heat fluxes (LE, r2 = 0.42, MEF = 0.14) and and net ecosystem CO2 exchange (NEE, r2 = 0.38, MEF = 0.26). Seasonal variations in GPP, ER, NEE, and energy fluxes on monthly scales showed moderate to high r2 values (0.57–0.86). For spatial across-site gradients of annual mean GPP, ER, NEE, and LE, r2 values of 0.93, 0.89, 0.27, and 0.71 were achieved, respectively. Water table (WT) variation was not well predicted (r2 cmax and latitude (temperature), which better reflects the spatial gradients of annual NEE than using an average Vcmax value. Source at https://doi.org/10.5194/gmd-11-497-2018.