Discharge measurements and storm event chemistry at the San Francisco River station (Planta) in 2007-2008

To improve our knowledge of the influence of land-use on solute behaviour and export rates in neotropical montane catchments we investigated total organic carbon (TOC), Ca, Mg, Na, K, NO3 and SO4 concentrations during April 2007-May 2008 at different flow conditions and over time in six forested and pasture-dominated headwaters (0.7-76 km2) in Ecuador. NO3 and SO4 concentrations decreased during the study period, with a continual decrease in NO3 and an abrupt decrease in February 2008 for SO4. We attribute this to changing weather regimes connected to a weakening La Niña event. Stream Na concentration decreased in all catchments, and Mg and Ca concentration decreased in all but the forested catchments during storm flow. Under all land-uses TOC increased at high flows. The differences in solute behaviour during storm flow might be attributed to largely shallow subsurface and surface flow paths in pasture streams on the one hand, and a predominant origin of storm flow from the organic layer in the forested streams on the other hand. Nutrient export rates in the forested streams were comparable to the values found in literature for tropical streams. They amounted to 6-8 kg/ha/y for Ca, 7-8 kg/ha/y for K, 4-5 kg/ha/y for Mg, 11-14 kg/ha/y for Na, 19-22 kg/ha/y for NO3 (i.e. 4.3-5.0 kg/ha/y NO3-N) and 17 kg/ha/y for SO4. Our data contradict the assumption that nutrient export increases with the loss of forest cover. For NO3 we observed a positive correlation of export value and percentage forest cover.

Pore water and solid-phase data from site Scharendijke (Lake Grevelingen, NL)

Will be submitted by the author

Modes of sapropel formation in the eastern Mediterranean: some constraints based on pyrite properties

Pyrite formation within and directly below sapropels in the eastern Mediterranean was governed by the relative rates of sulphide production and Fe liberation and supply to the organic-rich layers. At times of relatively high [SO4]2- reduction, sulphide could diffuse downward from the sapropel and formed pyrite in underlying sediments. The sources of Fe for pyrite formation comprised detrital Fe and diagenetically liberated Fe(II) from sapropel-underlying sediments. In organic-rich sapropels, input of Fe from the water column via Fe sulphide formation in the water may have been important as well. Rapid pyrite formation at high saturation levels resulted in the formation of framboidal pyrite within the sapropels, whereas below the sapropels slow euhedral pyrite formation at low saturation levels occurred. d34S values of pyrite are -33 per mil to -50 per mil. Below the sapropels d34S is lower than within the sapropels, as a result of increased sulphide re-oxidation at times of relatively high sulphide production and concentration when sulphide could escape from the sediment. The percentage of initially formed sulphide that was re-oxidized was estimated from organic carbon fluxes and burial efficiencies in the sediment. It ranges from 34% to 80%, varying significantly between sapropels. Increased palaeoproductivity as well as enhanced preservation contributed to magnified accumulation of organic matter in sapropels.

Time series of air chemistry measurements at Georg-von-Neumayer station, Dronning Maud Land, Antarctica in the years 1982 to 1991

The first Air Chemistry Observatory at the German Antarctic station Georg von Neumayer (GvN) was operated for 10 years from 1982 to 1991. The focus of the established observational programme was on characterizing the physical properties and chemical composition of the aerosol, as well as on monitoring the changing trace gas composition of the background atmosphere, especially concerning greenhouse gases. The observatory was designed by the Institut für Umweltphysik, University of Heidelberg (UHEIIUP). The experiments were installed inside the bivouac lodge, mounted on a sledge and put upon a snow hill to prevent snow accumulation during blizzards. All experiments were under daily control and daily performance protocols were documented. A ventilated stainless steel inlet stack (total height about 3-4 m above the snow surface) with a 50% aerodynamic cut-off diameter around 7-10 µm at wind velocities between 4-10 m/s supplied all experiments with ambient air. Contamination free sampling was realized by several means: (i) The Air Chemistry Observatory was situated in a clean air area about 1500 m south of GvN. Due to the fact that northern wind directions are very rare, contamination from the base can be excluded for most of the time. (ii) The power supply (20 kW) is provided by a cable from the main station, thus no fuel-driven generator is operated in the very vicinity. (iii) Contamination-free sampling is controlled by the permanently recorded wind velocity, wind direction and by condensation particle concentration. Contamination was indicated if one of the following criteria were given: Wind direction within a 330°-30° sector, wind velocity <2.2 m/s or >17.5 m/s, or condensation particle concentrations >2500/cm**3 during summer, >800/cm**3 during spring/autumn and >400/cm**3 during winter. If one or a definable combination of these criteria were given, high volume aerosol sampling and part of the trace gas sampling were interrupted. Starting at 1982 through 1991-01-14 surface ozone was measured with an electrochemical concentration cell (ECC). Surface ozone mixing ratio are given in ppbv = parts per 10**9 by volume. The averaging time corresponds to the given time intervals in the data sheet. The accuracy of the values are better than ±1 ppbv and the detection limit is around 1.0 ppbv. Aerosols were sampled on two Whatman 541 cellulose filters in series and analyzed by ion chromatography at the UHEI-IUP. Generally, the sampling period was seven days but could be up to two weeks on occasion. The air flow was around 100 m**3/h and typically 10000-20000 m**3 of ambient air was forced through the filters for one sample. Concentration values are given in nanogram (ng) per 1 m**3 air at standard pressure and temperature (1013 mbar, 273.16 K). Uncertainties of the values were approximately ±10% to ±15% for the main components MSA, chloride, nitrate, sulfate and sodium, and between ±20% and ±30% for the minor species bromide, ammonium, potassium, magnesium and calcium.

(Table 1) Ion concentrations in the haemolymph of Apherusa glacialis after incubation at different medium salinities

Amphipods living at the underside of Arctic sea ice are exposed to varying salinities due to freezing and melting, and have to cope with the resulting osmotic stress. Extracellular osmotic and ionic regulation at different salinities, thermal hysteresis, and supercooling points (SCPs) were studied in the under-ice amphipod Apherusa glacialis. The species is euryhaline, capable to regulate hyperosmotically at salinities S(R) < 30 g/kg, and osmoconforms at salinities S(R) >= 30 g/kg. Hyperosmotic regulation is an adaptation to thrive in low-salinity meltwater below the ice. Conforming to the ambient salinity during freezing reduces the risk of internal ice formation. Thermal hysteresis was not observed in the haemolymph of A. glacialis. The SCP of the species was -7.8 ± 1.9°C. Several ions were specifically downregulated ([Mg2+], [SO4]2-), or upregulated ([K+], [Ca2+]) in comparison to the medium. Strong downregulation of [Mg2+], is probably necessary to avoid an anaesthetic effect at low temperatures.

Data on the biogeochemical cycle of methane in the ocean

Geological, mineralogical and microbiological aspects of the methane cycle in water and sediments of different areas in the oceans are under consideration in the monograph. Original and published estimations of formation- and oxidation rates of methane with use of radioisotope and isotopic methods are given. The role of aerobic and anaerobic microbial oxidation of methane in production of organic matter and in formation of authigenic carbonates is considered. Particular attention is paid to processes of methane transformation in areas of its intensive input to the water column from deep-sea hydrothermal sources, mud volcanoes, and cold methane seeps.

Geochemical analysis of two sediment cores from the southern Mendeleev Ridge

We present results of an inorganic geochemical pore water and sediment study conducted on Quaternary sediments from the western Arctic Ocean. The sediment cores were recovered in 2008 from the southern Mendeleev Ridge during RV Polarstern Expedition ARK-XXIII/3. With respect to sediment sources and depositional processes, peaks in Ca/Al, Mg/Al, Sr/Al and Sr/Mg indicate enhanced input of both ice-rafted (mainly dolomite) and biogenic carbonate during deglacial warming phases. Distinct and repetitive brown layers enriched in Mn (oxyhydr)oxides occur mostly in association with these carbonate-rich intervals. For the first time, we show that the brown layers are also consistently enriched in scavenged trace metals Co, Cu, Mo and Ni. The bioturbation patterns of the brown layers, specifically well-defined brown burrows into the underlying sediments, support formation close to the sediment-water interface. The Mn and trace metal enrichments were probably initiated under warmer climate conditions. Both river runoff and melting sea ice delivered trace metals to the Arctic Ocean, but also enhanced seasonal productivity and organic matter export to the sea floor. As Mn (oxyhydr)oxides and scavenged trace metals were deposited at the sea floor, a co-occurring organic matter "pulse" triggered intense diagenetic Mn cycling at the sediment-water interface. These processes resulted in the formation of Mn and trace metal enrichments, but almost complete organic matter degradation. As warmer conditions ceased, reduced riverine runoff and/or a solid sea ice cover terminated the input of riverine trace metal and fresh organic matter, and greyish-yellowish sediments poor in Mn and trace metals were deposited. Oxygen depletion of Arctic bottom waters as potential cause for the lack of Mn enrichments during glacial intervals is highly improbable. While the original composition and texture of the brown layers resulted from specific climatic conditions (including transient Mn redox cycling at the sediment-water interface), pore water data show that early diagenetic Mn redistribution is still affecting the organic-poor sediments in several meters depth. Given persistent steady state diagenetic conditions, purely authigenic Mn-rich brown layers may form, while others may completely vanish. The degree of diagenetic Mn redistribution largely depends on the depositional environment within the Arctic Ocean, the availability of Mn and organic matter, and seems to be recorded by the Co/Mo ratios of single Mn-rich layers. We conclude that brown Arctic sediment layers are not necessarily synchronous features, and correlating them across different parts of the Arctic Ocean without additional age control is not recommended.

Sediment and pore water data of five cores from the continental slope off Uruguay

Assessing frequency and extent of mass movement at continental margins is crucial to evaluate risks for offshore constructions and coastal areas. A multidisciplinary approach including geophysical, sedimentological, geotechnical, and geochemical methods was applied to investigate multistage mass transport deposits (MTDs) off Uruguay, on top of which no surficial hemipelagic drape was detected based on echosounder data. Nonsteady state pore water conditions are evidenced by a distinct gradient change in the sulfate (SO4**2-) profile at 2.8 m depth. A sharp sedimentological contact at 2.43 m coincides with an abrupt downward increase in shear strength from approx. 10 to >20 kPa. This boundary is interpreted as a paleosurface (and top of an older MTD) that has recently been covered by a sediment package during a younger landslide event. This youngest MTD supposedly originated from an upslope position and carried its initial pore water signature downward. The kink in the SO4**2- profile approx. 35 cm below the sedimentological and geotechnical contact indicates that bioirrigation affected the paleosurface before deposition of the youngest MTD. Based on modeling of the diffusive re-equilibration of SO4**2- the age of the most recent MTD is estimated to be <30 years. The mass movement was possibly related to an earthquake in 1988 (approx. 70 km southwest of the core location). Probabilistic slope stability back analysis of general landslide structures in the study area reveals that slope failure initiation requires additional ground accelerations. Therefore, we consider the earthquake as a reasonable trigger if additional weakening processes (e.g., erosion by previous retrogressive failure events or excess pore pressures) preconditioned the slope for failure. Our study reveals the necessity of multidisciplinary approaches to accurately recognize and date recent slope failures in complex settings such as the investigated area.

Sulfate and methane concentrations measured in pore water of sediment core GeoB13809-1 and GeoB13849-1

Several previous studies have shown that submarine mass-movements can profoundly impact the shape of pore water profiles. Therefore, pore water geochemistry and diffusion models were proposed as tools for identifying and dating recent (max. several thousands of years old) mass-transport deposits (MTDs). In particular, sulfate profiles evidentially indicate transient pore water conditions generated by submarine landslides. After mass-movements that result in the deposition of sediment packages with distinct pore water signatures, the sulfate profiles can be kink-shaped and evolve into the concave and linear shape with time due to molecular diffusion. Here we present data from the RV METEOR cruise M78/3 along the continental margin off Uruguay and Argentina. Sulfate profiles of 15 gravity cores are compared with the respective acoustic facies recorded by a sediment echosounder system. Our results show that in this very dynamic depositional setting, non-steady state profiles occur often, but are not exclusively associated with mass-movements. Three sites that show acoustic indications for recent MTDs are presented in detail. Where recent MTDs are identified, a geochemical transport/reaction model is used to estimate the time that has elapsed since the perturbation of the pore water system and, thus, the timing of the MTD emplacement. We conclude that geochemical analyses are a powerful complementary tool in the identification of recent MTDs and provide a simple and accurate way of dating such deposits.

Sulfate and nitrate firn concentrations on the Greenland ice sheet

Intercomparison of three new chemical ice core records from northern Greenland (covering the time span from approximately 1500 A.D. to present) with previously published records for southern and central Greenland reveals a uniform timing of anthropogenic changes in sulfate and nitrate firn concentrations over the entire ice sheet. The anthropogenic sulfate increase started around 1890, was interrupted by a transient decrease in the 1930s, and has resumed a major increase since 1950. Since the late 1970s though, a significant 30% decline in Greenland sulfate firn levels can be documented. The maximum anthropogenic increase in northern Greenland sulfate firn concentrations (up to 200-230 ppb) is 2-3 times larger than in southern and central Greenland. Nitrate records show an essentially steady increase since 1950 and, documented for the first time, a slight reduction during most recent years. Maximum nitrate firn levels of 100-130 ppb exceed the preindustrial background by 100% all over the Greenland ice sheet. Comparison with anthropogenic SO2 and NO x emission records indicates that the major increase in sulfate firn concentrations since 1950 can be attributed to Eurasian sources, while firn levels during the first half of this century appear to be dominated by North American emissions. A stronger North American source contribution is indicated over the entire 20th century in the case of nitrate. Applying a macroscopic deposition model separate time series for wet and dry deposition were derived which revealed a close correspondence of wet deposited sulfate with the timing of U.S. emissions, while the temporal evolution of Eurasian emissions is mainly reflected in the dry sulfate deposition record. During this century wet sulfate deposition increased by a factor of two while the total dry sulfate deposition flux increased by more than 500%. Wet and dry nitrate deposition both increased by 100% during the same period.

Geochemical parameters of sediments and waters in areas of ocean barrier zones

Geochemical barrier zones play an important role in determining various physical systems and characteristics of oceans, e.g. hydrodynamics, salinity, temperature and light. In the book each of more than 30 barrier zones are illustrated and defined by physical, chemical and biological parameters. Among the topics discussed are processes of inflow, transformation and precipitation of the sedimentary layer of the open oceans and more restricted areas such as the Baltic, Black and Mediterranean Seas.

Geochemical and biogeochemical parameters of Black Sea waters and suspended matter

The monograph focuses on the analysis of data addressing the problem of H2S contamination and oxic-anoxic interface in the Black Sea. Regularities of the fine structure of vertical distribution of oxygen, hydrogen sulfide, biogenic elements, organic substances, suspended matter, and metals of the iron-manganese group in the area of contact of aerobic and anaerobic waters have been revealed. Also effects of biochemical, physico-chemical and dynamic processes on their vertical distribution have been examined. Sulfate reduction in seawater and bottom sediments has been studied. Quantitative estimates of H2S fluxes at the water - bottom sediment and O2-H2S interfaces have been done. Features of H2S oxidation have been studied, its budget in the Black Sea has been calculated. Multiyear spatial-temporal variability of the oxic-anoxic interface has been investigated.

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.

Hydrological and sedimentological investigation of Radok Lake, Amery Oasis, East Antarctica

Radok Lake in Amery Oasis, East Antarctica, has a water depth of ca. 360 m, making it the deepest non-subglacial lake in Antarctica. Limnological analyses revealed that the lake had, despite a 3 m thick ice cover, a completely mixed water column during austral summer 2001/2002. High oxygen contents, low ion concentrations, and lack of planktonic diatoms throughout the water column indicate that Radok Lake is ultra-oligotrophic today.The late glacial and postglacial lake history is documented in a succession of glacial, glaciolimnic, and limnic sediments at different locations in the lake basin. The sediments record regional differences and past changes in allochthonous sediment supply and lake productivity. However, the lack of age control on these changes, due to extensive sediment redeposition and the lack of applicable dating methods, excluded Radok Lake sediments for advanced paleoenvironmental reconstructions.

Pore water and solid-phase measurements on sediment cores from the Black Sea

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe) oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ. Here we combine detailed geochemical analyses of the sediment and pore water with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P) and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. Our results show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g. vivianite) are converted to sulfide phases, leading to an enrichment in solid phase S and the release of phosphate to the pore water. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front. Our model results further demonstrate that downward migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM (~ 1-100 pmol/cm**3/d) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the pore water at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.