Carbon biogeochemistry of the Betsiboka estuary (north-western Madagascar)

Madagascar’s largest estuary (Betsiboka) was sampled along the salinity gradient during the dry season to document the distribution and sources of particulate and dissolved organic carbon (POC, DOC) as well as dissolved inorganic carbon (DIC). The Betsiboka was characterized by a relatively high suspended matter load, and in line with this, low DOC/POC ratios (0.4–2.5). The partial pressure of CO₂ (pCO₂) was generally above atmospheric equilibrium (270–1530 ppm), but relatively low in comparison to other tropical and subtropical estuaries, resulting in low average CO₂ emission to the atmosphere (9.1 ± 14.2 mmol m⁻² d⁻¹). Despite the fact that C4 vegetation is reported to cover >80% of the catchment area, stable isotope data on DOC and POC suggest that C4 derived material comprises only 30% of both pools in the freshwater zone, increasing to 60–70% and 50–60%, respectively, in the oligohaline zone due to additional lateral inputs. Sediments from intertidal mangroves in the estuary showed low organic carbon concentrations (<1%) and δ¹³C values (average −19.8‰) consistent with important inputs of riverine imported C4 material. This contribution was reflected in δ¹³C signatures of bacterial phospholipid derived fatty acids (i + a15:0), suggesting the potential importance of terrestrial organic matter sources for mineralization and secondary production in coastal ecosystems.     

Dissolved organic nitrogen dynamics in the North Sea: A time series analysis (1995–2005)

Dissolved organic nitrogen (DON) dynamics in the North Sea was explored by means of long-term time series of nitrogen parameters from the Dutch national monitoring program. Generally, the data quality was good with little missing data points. Different imputation methods were used to verify the robustness of the patterns against these missing data. No long-term trends in DON concentrations were found over the sampling period (1995–2005). Inter-annual variability in the different time series showed both common and station-specific behavior. The stations could be divided into two regions, based on absolute concentrations and the dominant times scales of variability. Average DON concentrations were 11 μmol l⁻¹ in the coastal region and 5 μmol l⁻¹ in the open sea. Organic fractions of total dissolved nitrogen (TDN) averaged 38 and 71% in the coastal zone and open sea, respectively, but increased over time due to decreasing dissolved inorganic nitrogen (DIN) concentrations. In both regions intra-annual variability dominated over inter-annual variability, but DON variation in the open sea was markedly shifted towards shorter time scales relative to coastal stations. In the coastal zone a consistent seasonal DON cycle existed with high values in spring–summer and low values in autumn–winter. In the open sea seasonality was weak. A marked shift in the seasonality was found at the Dogger Bank, with DON accumulation towards summer and low values in winter prior to 1999, and accumulation in spring and decline throughout summer after 1999. This study clearly shows that DON is a dynamic actor in the North Sea and should be monitored systematically to enable us to understand fully the functioning of this ecosystem.     

Possible diagenetic mobilization of barium in sapropelic sediment from the eastern Mediterranean

In the last few years it has frequently been suggested that Ba is a useful indicator of paleoproductivity. The formation of some sapropels in the Eastern Mediterranean is considered to be related to, or to coincide with, periods of enhanced productivity. A high-resolution sampling study has been undertaken in order to investigate whether the Ba distribution in sapropels reflects a primary input signal or whether it has been altered by diagenetic processes.

On the basis of our results we suggest that three diagenetic stages determine the distribution of Ba. During deposition of the sapropel (stage 1) Ba is mobilized as anoxic conditions prograde. After deposition of the sapropel (stage 2), a progressive oxidation front develops. This front induces the formation of Mn and Fe enrichments and barite precipitation at the oxic/anoxic boundary. Barite precipitation is believed to be caused mainly by a rise in the porewater sulphate concentration after sulphides have been oxidized by the front.

Upon burial (stage 3), suboxic conditions develop as the oxygen becomes exhausted again. In contrast to Fe- and Mn-oxyhydroxides which dissolve and reprecipitate at higher levels, barite is preserved because dissolved sulphate is not depleted.

The interpretation of the Ba distribution in organic-rich sediment is not straightforward. Diagenetic reallocation of a primary Ba signal will possibly disturb the relationship between Ba and organic production. Consequently, one must be very cautious when invoking Ba as a paleoproductivity indicator.     

Geochemistry of eastern Mediterranean sediments: Primary sediment composition and diagenetic alterations

Two cores recovered in the eastern Mediterranean were analysed for major, minor and trace elements. The primary chemical composition of the sediment is different at each location, probably because the lithological sources and the relative biogenic contributions differ.

Carbonates are important for the concentration of Ca, Mg and Sr, whereas aluminosilicates determine the concentration of Si, Al, K, Li, Y and Be, and to a lesser extent that of Fe, Cr, Ti, Mg, Zn and Zr. In sapropels, organic carbon and sulphur seem to be closely related. Bromine, Mo, P, Fe, V, Cu, Zn, Co, Ni and Cr are closely associated with organic and sulphidic compounds. The concentration versus depth profile for organic carbon in two sapropels points to a rapid establishment of conditions that gave rise to sapropel formation, followed by a gradual transition back to “normal” conditions.

The primary composition is overprinted by diagenetic processes. Sulphate-reducing conditions occurred during and just after sapropel deposition. A progressive oxidation front mechanism, which became active after sapropel deposition, is responsible for additional major geochemical changes. This diagenetic phenomenon has strong implications for the chemistry of Fe, Mn, Ni, Co, Zn, Cu, Cr, V, U, As and Sb.     

Sulphate-related equilibria in the hypersaline brines of the Tyro and Bannock Basins, eastern Mediterranean

The Tyro and Bannock Basins, which are depressions in the eastern Mediterranean, contain hypersaline anoxic brines. These brines are of different composition: Tyro brine is primarily an early-stage halite (NaCl) brine, whereas Bannock brine includes the more soluble ions of late-stage evaporite minerals. Accordingly, the Bannock brine contains a much greater sulphate concentration than the Tyro Brine. This difference in sulphate concentration is reflected in the concentrations of ions such as Ca, Sr and Ba, which form sparingly soluble sulphate minerals.Equilibrium calculations using the Pitzer specific ion interaction model indicate that the brines in both basins are saturated with respect to gypsum (CaSO₄-2H₂O) and supersaturated to saturated with respect to dolomite (CaMg(CO₃)₂). The degree of saturation with respect to dolomite is greater in the Bannock Basin than it is in the Tyro Basin. Correspondingly, recent gypsum crystals and dolomite hardgrounds have been found in the Bannock Basin but not in the Tyro Basin.The Tyro brine is homogeneous in composition, whereas the Bannock brine demonstrates a clear two-layer brine structure. At the interface of the upper and the lower brine distinct positive anomalies occur in the total alkalinity and the concentration of phosphate, and negative anomalies occur in the concentrations of Mn²⁺ and the rare earth elements (REE). These anomalies and the observed association of gypsum/dolomite in the sediments are all consistent with a recent precipitation of dolomite and gypsum in the Bannock Basin. The brines in both basins are also saturated with respect to barite (BaSO₄).The ⁸⁷Sr/⁸⁶Sr and δ³⁴S ratios of the Bannock brines are amazingly consistent but differ dramatically from the values for modern or Messinian-age seawater. The Sr concentration and Sr and S isotope ratios in the gypsum crystals indicate that most of these crystals have resulted from precipitation/recrystallization from the brine and not from seawater. The observed variations between crystals are thought to reflect the recrystallization of (sub-) outcropping Messinian gypsum with a low ⁸⁷Sr/⁸⁶Sr ratio in the presence of seawater or brine fluids and with different extents of diagenesis.     

AquaEnv: An Aquatic Acid–Base Modelling Environment in R

AquaEnv is an integrated software package for aquatic chemical model generation focused on ocean acidification and antropogenic CO₂ uptake. However, the package is not restricted to the carbon cycle or the oceans: it calculates, converts, and visualizes information necessary to describe pH, related CO₂ air–water exchange, as well as aquatic acid–base chemistry in general for marine, estuarine or freshwater systems. Due to the fact that it includes the relevant acid–base systems, it can also be applied to pore water systems and anoxic waters. AquaEnv is implemented in the open source programming language R , which allows for a flexible and versatile application: AquaEnv ’s functionality can be used stand-alone as well as seamlessly integrated into reactive-transport models in the R modelling environment. Additionally, AquaEnv provides a routine to simulate and investigate titrations of water samples with a strong acid or base, as well as a routine that allows for a determination of total alkalinity and total carbonate values from recorded titration curves using non-linear curve-fitting.     

Effects of climate change and nutrient concentrations on carbon sources for zooplankton in a Tibetan Plateau lake over the past millennium

Journal of Paleolimnology - Autochthonous and allochthonous organic carbon (OC) are important carbon sources for zooplankton in lakes, and changes in the abundance and proportions of those sources...     

Carbon and nitrogen stable isotopes in suspended matter and sediments from the Schelde Estuary

The C/N and stable C and N isotope ratios (δ¹³C, δ¹⁵N) of sedimentary and suspended particulate matter were determined in the Schelde Estuary. Suspended matter was divided into 2 to 5 size fractions by centrifugation. Four major pools of organic matter were recognized: riverine, estuarine, marine and terrestrial materials. Terrestrial organic matter (δ¹³C≈−26‰, δ¹⁵N≈3.5‰, C/N≈21) is important for the sedimentary pool, but suspended matter is dominated by the marine (δ¹³C≈−18‰, δ¹⁵N≈9‰, C/N≈8), riverine (δ¹³C≈−30‰, δ¹⁵N≈9‰, C/N≈7.5) and estuarine (δ¹³C≈−29‰, δ¹⁵N≈15‰, C/N≈8) end-members. In the upper estuary, the suspended matter size fractions vary systematically in their carbon and nitrogen biogeochemistry, with the small particles having low C/N ratios, depleted δ¹³C and enriched δ¹⁵N values relative to large particles. Moreover, sedimentary and suspended matter differ significantly in terms of C/N ratios (17 vs. 8.9), δ¹³C (−26.3 vs. −28.9‰) and δ¹⁵N (+6.9 vs. 12.0‰). In the lower estuary, suspended matter fractions are similar and sedimentary and suspended organic matter differ only in terms of δ¹³C (−23.5 vs. −20.1‰). Our data indicate that autochthonous organic matter contributes significantly to the total suspended matter and that the suspended organic matter composition cannot be explained in terms of conservative mixing of riverine and terrestrial sources on the one hand and marine sources on the other hand.     

Planktonic and whole system metabolism in a nutrient-rich estuary (the Scheldt estuary)

Planktonic gross primary production (GPP), community respiration (CR), and nitrification (NIT) were measured monthly in the Scheldt estuary by the oxygen incubation method in 2003. No significant evolution of planktonic GPP was observed since the 1990s with high rates in the freshwater area (salinity 0; 97±65 mmol C m⁻² d⁻¹) decreasing seaward (22–37 mmol C m⁻² d⁻¹). A significant decrease of NIT was observed with regard to previous investigations although this process still represents up to 20% of total organic matter production in the inner estuary. Planktonic CR was highest in the inner estuary and seemed to be mainly controlled by external organic matter inputs. Planktonic net community production was negative most of the time in the estuary with values ranging from −300 to 165 mmol C m⁻² d⁻¹. Whole estuary net ecosystem production (NEP) was investigated on an annual scale using the results mentioned above and published benthic metabolic rates. A NEP of −39±8 mmol C m⁻² d⁻¹ was estimated, which confirms the strong heterotrophic status of this highly nutrified estuary. NEP rates were computed from June to December 2003 to compare with results derived from the Land-Ocean Interaction in the Coastal Zone budgeting procedure applied to dissolved inorganic phosphorus and carbon (DIP and DIC). DIP budgets failed to provide realistic estimates in the inner estuary where abiotic processes account for more than 50% of the nonconservative DIP flux. DIC budgets predicted a much lower NEP than in situ incubations (−109±31 versus −42±9 mmol C m⁻² d⁻¹) although, as each approach is associated with several critical assumptions, the source of this discrepancy remains unclear.     

Selective preservation of soil organic matter in oxidized marine sediments (Madeira Abyssal Plain)

In ocean margin sediments both marine and terrestrial organic matter (OM) are buried but the factors governing their relative preservation and degradation are not well understood. In this study, we analysed the degree of preservation of marine isoprenoidal and soil-derived branched glycerol dialkyl glycerol tetraethers (GDGTs) upon long-term oxygen exposure in OM-rich turbidites from the Madeira Abyssal Plain by analyzing GDGT concentrations across oxidation fronts. Relative to the anoxic part of the turbidites ca. 7-20% of the soil-derived branched GDGTs were preserved in the oxidized part while only 0.2-3% of the marine isoprenoid GDGT crenarchaeol was preserved. Due to these different preservation factors the Branched Isoprenoid Tetraether (BIT) index, a ratio between crenarchaeol and the major branched GDGTs that is used as a tracer for soil-derived organic matter, substantially increases from 0.02 to 0.4. Split Flow Thin Cell (SPLITT) separation of turbidite sediments showed that the enhanced preservation of soil-derived carbon was a general phenomenon across the fine particle size ranges (<38 μm). Calculations reveal that, despite their relatively similar chemical structures, degradation rates of crenarchaeol are 2-fold higher than those of soil-derived branched GDGTs, suggesting preferential soil OM preservation possibly due to matrix protection.