(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Seasonally aggregated values of dissolved inorganic phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2003)

This data set contains measurements of inorganic phosphorus in samples of soil solution collected in 2003 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below) that have been aggregated to seasonal values. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved inorganic P (PO4P). Here volume-weighted mean values are provided as aggregated seasonal values (spring = March to May, summer = June to August, fall = September to November, winter = December to February) for 2003 in spring, fall, and winter. To calculate these values, the sampled volume of soil solution is used as weight for P concentrations of the respective sampling date. Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA SAN++, Skalar [Breda, The Netherlands]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.02 mg P l-1 (CFA, Skalar).

Seasonally aggregated values of dissolved inorganic phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2005)

This data set contains measurements of inorganic phosphorus in samples of soil solution collected in 2005 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below) that have been aggregated to seasonal values. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved inorganic P (PO4P). Here volume-weighted mean values are provided as aggregated seasonal values (spring = March to May, summer = June to August, fall = September to November, winter = December to February) for 2005 in spring, and winter. To calculate these values, the sampled volume of soil solution is used as weight for P concentrations of the respective sampling date. Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA Autoanalyzer [Bran&Luebbe, Norderstedt, Germany]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.04 mg P l-1 (Autoanalyzer, Bran&Luebbe).

Dissolved phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2002)

This data set contains measurements of dissolved phosphorus (total dissolved nitrogen: TDP, dissolved inorganic phosphorus: PO4P and dissolved organic phosphorus: DOP) in samples of soil water collected in 2002 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled bi-weekly, in 2002 at the 23.10.2002; 05.11.2002; 20.11.2002; 05.12.2002; and 28.12.2002, and analyzed for dissolved inorganic P (PO4P) and total dissolved phosphorus (TDP). Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA SAN++, Skalar [Breda, The Netherlands]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. Total dissolved P in soil solution was analyzed by irradiation with UV and oxidation with K2S2O8 followed by reaction with ammonium molybdate (Skalar catnr. 503-553w/r). As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.02 mg P l-1 (CFA, Skalar). Dissolved organic P (DOP) in soil solution was calculated as the difference between TDP and PO4P. In a low number of samples, TDP was equal to or smaller than PO4P; in these cases, DOP was assumed to be zero.

(Table 1, page 146) Iron, manganese and nickel contents of 21 ferromanganese nodules from Combe D'Izame and Mont Peyroux, Montagne Noire

Ferromanganese nodules (equivalent to Recent manganese nodules) are described from the Upper Devonian griotte (red pelagic limestone) of the Montagne Noire (S. France) and the Cephalopodenkalk of the Rheinisches Schiefergebirge, West Germany. They occur as encrustations, commonly exhibiting colloform structures, around skeletal material and limestone clasts. The nodules are associated with encrusting foraminifera and a development in the sublittoral environment is envisaged. Chemically, the ferromanganese nodules are depleted in manganese relative to iron, compared with Recent nodules, a loss which is attributed to diagenetic migration of manganese. Electron probe studies show that manganese covaries positively with calcium, but negatively with iron and silicon. Diagenetic enrichment of hematite occurs in the griotte at hardground horizons where two periods of mineralization can be established. The Devonian ferromanganese nodules show that solution of nodules has not occurred on burial.

Dissolved organic carbon in soil solution of the Jena Experiment (Main Experiment, year 2004)

This data set contains measurements of dissolved organic carbon in samples of soil water collected from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. In April 2002 glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 mm (UMS GmbH, Munich, Germany) were installed in depths of 10, 20, 30 and 60 cm to collect soil solution. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved organic carbon concentration by a high TOC elemental analyzer (Elementar Analysensysteme GmbH, Hanau, Germany). Samples were analyzed as soon as possible and stored at 4°C if necessary. Often in summer, no free soil solution was available for collection, especially in the upper soil layers. Annual mean values of measured biweekly concentrations of dissolved organic carbon are provided.

(Table 1) Nutrient concentrations and carbon isotopes of sea ice segments and brine sampled during Nathaniel B. Palmer cruises NBP98-07 and NBP06-08, Ross Sea

We examined controls on the carbon isotopic composition of sea ice brines and organic matter during cruises to the Ross Sea, Antarctica in November/December 1998 and November/December 2006. Brine samples were analyzed for salinity, nutrients, total dissolved inorganic carbon (sum CO2), and the 13C/12C ratio of Sum CO2 (d13C(sum CO2)). Particulate organic matter from sea ice cores was analyzed for percent particulate organic carbon (POC), percent total particulate nitrogen (TPN), and stable carbon isotopic composition (d13C(POC)). Sum CO2 in sea ice brines ranged from 1368 to 7149 µmol/kg, equivalent to 1483 to 2519 µmol/kg when normalized to 34.5 psu salinity (s sum CO2), the average salinity of Ross Sea surface waters. Sea ice primary producers removed up to 34% of the available sum CO2, an amount much higher than the maximum removal observed in sea ice free water. Carbonate precipitation and CO2 degassing may reduce s sum CO2 by a similar amount (e.g., 30%) in the most hypersaline sea ice environments, although brine volumes are low in very cold ice that supports these brines. Brine d13C(sum CO2) ranged from -2.6 to +8.0 per mil while d13C(POC) ranged from -30.5 to -9.2 per mil. Isotopic enrichment of the sum CO2 pool via net community production accounts for some but not all carbon isotopic enrichment of sea ice POC. Comparisons of s sum CO2, d13C(sum CO2), and d13C(POC) within sea ice suggest that epsilon p (the net photosynthetic fractionation factor) for sea ice algae is ~8 per mil smaller than the epsilon p observed for phytoplankton in open water regions of the Ross Sea. These results have implications for modeling of carbon uptake and transformation in the ice-covered ocean and for reconstruction of past sea ice extent based on stable isotopic composition of organic matter in sediment cores.

Census of calcareous nannofossil taxa expressed as percent of total number of individuals counted, ODP Legs 113, 114, 119, 120

Quantitative analysis of upper Eocene-upper Oligocene calcareous nannofossil assemblages from five Ocean Drilling Program sites in the Atlantic and Indian Ocean sectors of the Southern Ocean reveals an abrupt increase in cool-water taxa at the top of magnetic Subchron C13R ca. 35.9 Ma, coincident with an enrichment of ~1? d18O in the planktonic foraminifers at these sites. The synchrony of the abrupt increase in cool-water taxa in the Southern Ocean renders this event a useful biostratigraphic datum at southern high latitudes. This earliest Oligocene cool-water taxa increase was the sharpest and largest during the late Eocene-late Oligocene interval and indicates a drop in surface-water temperature of more than 3°C in the Southern Ocean. This suggests that the earliest Oligocene d18O shift represents primarily a temperature signal; a small portion (~0.2?) is attributable to a global ice-volume increase.

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station MSM16/2_847-1 (Z2-S2, aged flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Pore water geochemistry of arctic deep sea sediments measured at station MSM16/2_809-1 (REF, Reference)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station MSM16/2_838-1 (Z1-S3, new flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station MSM16/2_855-1 (Z2-S3, aged flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Sulphate reduction rates of arctic deep sea sediments measured at station MSM16/2_809-1 (REF, Reference)

Turnover rates were determined for surface sediment cores obtained in 2009 and 2010. Sulfate reduction (SR) were measured ex situ by the whole core injection method (doi:10.1080/01490457809377722). We incubated the samples at in situ temperature (1.0°C) for 12 hours with carrier-free 35**SO4 (dissolved in water, 50 kBq). Sediment was fixed in 20 ml 20% ZnAc solution for AOM or SR, respectively. Turnover rates were measured as previously described (doi:10.4319/lom.2004.2.171).

Sulphate reduction rates of Håkon Mosby mud volcano sediments measured at station MSM16/2_823-1 (Z3-S3, old flow surface)

Turnover rates were determined for surface sediment cores obtained in 2009 and 2010. Sulfate reduction (SR) were measured ex situ by the whole core injection method (doi:10.1080/01490457809377722). We incubated the samples at in situ temperature (1.0°C) for 12 hours with carrier-free 35**SO4 (dissolved in water, 50 kBq). Sediment was fixed in 20 ml 20% ZnAc solution for AOM or SR, respectively. Turnover rates were measured as previously described (doi:10.4319/lom.2004.2.171).

Sulphate reduction and methane oxidation rates of Håkon Mosby mud volcano sediments measured at station MSM16/2_855-1 (Z2-S3, aged flow surface)

Sulfate reduction (SR) and anaerobic oxidation of methane (AOM) were measured ex situ by the whole core injection method (doi:10.1080/01490457809377722). We incubated the samples at in situ temperature (1.0°C) for 12 hours with either 14** CH4 (dissolved in water, 2.5 kBq) or carrier-free 35** SO4 (dissolved in water, 50 kBq). Sediment was fixed in 25 ml 2.5% sodium hydroxide (NaOH) solution or 20 ml 20% ZnAc solution for AOM or SR, respectively. Turnover rates were measured as previously described (http://edoc.mpg.de/177065; doi:10.4319/lom.2004.2.171).