Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis

Pore water profiles of total-CO₂, pH, PO^3?₄, NO^?₃ plus NO^?₂, SO^2?₄, S^2?, Fe²⁺ and Mn²⁺ have been obtained in cores from pelagic sediments of the eastern equatorial Atlantic under waters of moderate to high productivity. These profiles reveal that oxidants are consumed in order of decreasing energy production per mole of organic carbon oxidized (O₂ > manganese oxides ~ nitrate > iron oxides > sulfate). Total CO₂ concentrations reflect organic regeneration and calcite dissolution. Phosphate profiles are consistent with organic regeneration and with the effects of release and uptake during inorganic reactions. Nitrate profiles reflect organic regeneration and nitrate reduction, while dissolved iron and manganese profiles suggest reduction of the solid oxide phases, upward fluxes of dissolved metals and subsequent entrapment in the sediment column. Sulfate values are constant and sulfide is absent, reflecting the absence of strongly anoxic conditions.     

Benthic fluxes and the cycling of biogenic silica and carbon in two southern California borderland basins

Benthic fluxes in two southern California borderland basins have been estimated by modeling water column property gradients, by modeling pore water gradients and by measuring changes in concentration in a benthic chamber. Results have been used to compare the different methods, to establish budgets for biogenic silica and carbon and to estimate rate constants for models of CaCO₃ dissolution. In San Pedro Basin, a low oxygen, high sedimentation rate area, fluxes of radon-222 (86 ± 8 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.9 ± 0.3 mmol m⁻² d⁻¹) and nitrate (−0.8 ± 0.1 mmol m⁻² d⁻¹) measured in a benthic chamber agree within the measurement uncertainty with fluxes estimated from modeling profiles of nutrients and radon obtained in the water column. The diffusive fluxes of radon, SiO₂ and TCO₂ determined from modeling the sediment and pore water also agree with the other approaches. Approximately 33 ± 13% of the organic carbon and 37 ± 47% of the CaCO₃ arriving at the sea floor are recycled. In San Nicolas Basin, which has larger oxygen concentrations and lower sedimentation rates than San Pedro, the fluxes of radon (490 ± 16 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.7 ± 0.2 mmol m⁻² d⁻¹), oxygen (−0.7 ± 0.1 mmol m⁻² d⁻¹) and nitrate (-0.4 ± 0.1 mmol m⁻² d⁻¹) determined from chamber measurements agree with the water column estimates given the uncertainty of the measurements and model estimates. Diffusion from the sediments matches the lander-measured SiO₂ and PO₄³⁻ (0.017 ± 0.002 mmol m⁻² d⁻¹) fluxes, but is not sufficient to supply the radon or TCO₂ fluxes observed with the lander. In San Nicolas Basin 38 ± 9% of the organic carbon and 43 ± 22% of the CaCO₃ are recycled. Approximately 90% of the biogenic silica arriving at the sea floor in each basin is recycled. The rates of CaCO₃ dissolution determined from chamber flux measurements and material balances for protons and electrons are compared to those predicted by previously published models of CaCO₃ dissolution and this comparison indicates that in situ rates are comparable to those observed in laboratory studies of bulk sediments, but orders of magnitude less than those observed in experiments done with suspended sediments.     

Calcium carbonate dissolution in deep sea sediments: reconciling microelectrode, pore water and benthic flux chamber results

We report the benthic fluxes of O₂, titration alkalinity (TA), Ca²⁺, NO₃⁻, PO₄³⁻, and Si(OH)₄ from in situ benthic flux chamber incubations on the Ceara Rise and Cape Verde Plateau and compare them to previously published results. We find within analytical uncertainty that the TA flux is twice the calcium flux, suggesting that dissolution/precipitation of CaCO₃ is the principal mechanism controlling benthic TA and Ca²⁺ fluxes. At sites where the sediments contain significant (>35%) CaCO₃ and the overlying waters are supersaturated with respect to CaCO₃, the ratios of the total dissolution rate to the remineralization rate are significantly less than at all other study sites. We propose that these observations can be explained by precipitation of fresh CaCO₃ at the supersaturated sediment surface followed by redissolution deeper in the sediments because of metabolically-produced CO₂. A numerical simulation is presented to demonstrate the feasibility of this explanation. In addition, surface exchange reactions in high-CaCO₃ sediments coupled with high rates of particle mixing may also impact rates of metabolic dissolution and depress chamber-derived estimates of carbonate alkalinity and calcium benthic fluxes. These results suggest that at supersaturated, high CaCO₃ locations, previous models of sediment diagenesis may have overestimated the impact of metabolic dissolution on the preservation of CaCO₃ deposited on the sea floor.     

Sediment community metabolism associated with continental shelf hypoxia, Northern Gulf of Mexico

Net fluxes of respiratory metabolites (O₂, dissolved inorganic carbon (DIC), NH₄ ⁺, NO₃ ^?, and NO₂ ^?) across the sediment-water interface were measured using in-situ benthic incubation chambers in the area of intermittent seasonal hypoxia associated with the Mississippi River plume. Sulfate reduction was measured in sediments incubated with trace levels of³⁵S-labeled sulfate. Heterotrophic remineralization, measured as nutrient regeneration, sediment community oxygen consumption (SOC), sulfate reduction, or DIC production, varied positively as a function of temperature. SOC was inversely related to oxygen concentration of the bottom water. The DIC fluxes were more than 2 times higher than SOC alone, under hypoxic conditions, suggesting that oxygen uptake alone cannot be used to estimate total community remineralization under conditions of low oxygen concentration in the water column. A carbon budget is constructed that compares sources, stocks, transformations, and sinks of carbon in the top meter of sediment. A comparison of remineralization processes within the sediments implicates sulfate reduction as most important, followed by aerobic respiration and denitrification. Bacteria accounted for more than 90% of the total community biomass, compared to the metazoan invertebrates, due presumably to hypoxic stress.     

Biogeochemical cycling in an organic-rich coastal marine basin 4. An organic carbon budget for sediments dominated by sulfate reduction and methanogenesis

In situ carbon flux measurements and calculated burial rates are utilized to construct an organic carbon budget for the upper meter of sediment at a single station in Cape Lookout Bight, a small marine basin located on the Outer Banks of North Carolina, U.S.A. (34°37′N, 76°33′W). Of 149 ± 20 mole · m^?2 · yr^?1 of total organic carbon deposited, 35.6 ± 5.2 mole · m^?2 · yr^?1 is recycled to overlying waters, 84 ± 18% as ∑CO₂ and 16 ± 8% as CH₄. Approximately 68 ± 20% of the upward carbon flux is supported by sulfate reduction while 32 ± 16% takes place as the result of underlying methanogenesis. Measured ∑CO₂ and CH₄ sediment-water fluxes range seasonally from 1900–6300 and 50–2500 μmole · m^?2 · hr^?1 respectively.The mean residence time of metabolizable organic carbon in the upper 80 cm of sediment is approximately four months with greater than 98% of the calculated total remineralization taking place within three years. In spite of large upward fluxes of methane, larger molecules derived from metabolizable sedimentary organic carbon appear to be the dominant reductants for dissolved sulfate.     

Quantifying solute distributions in the bioturbated zone of marine sediments by defining an average microenvironment

The bioturbated zone of marine sediments is a region having a complex, time-dependent geometry of diffusion and chemical reactions. It is possible to simplify this geometry by postulating an average sediment microenvironment and modelling it as representative of the sediment body as a whole. The microenvironment is assumed to correspond to a single, tube-dwelling animal together with its surrounding sediment and can be represented by a finite hollow cylinder. A transport-reaction model derived from this postulate produces good agreement between observed and predicted pore water profiles using realistic physical constants. The average vertical distributions of pore water solutes and their sediment-water fluxes are influenced by the presence of irrigated burrows to varying degrees depending on the kind of reactions governing their behavior. Pore water profiles of solutes, such as NH⁺₄, subject to zero order reaction rates are highly sensitive to the abundance and sizes of burrows while the net flux of the constituent across the sediment-water interface is not. In contrast, profiles of solutes such as Si that are subject to first order reaction rates are less sensitive to the presence of irrigated burrows but net fluxes are greatly affected. Average pore water concentrations, fluxes of solutes like Si and the apparent one-dimensional diffusion coefficients required to match vertical gradients with measured solute fluxes, are influenced by both the size and spacing of burrows. Because of the range of solute concentrations within the microenvironment at any given depth it is not strictly valid to make detailed solubility calculations on the basis of average pore water concentrations within the bioturbated zone.     

Sediment-water oxygen and nutrient fluxes in a river-dominated estuary

Sediment oxygen uptake and net sediment-water fluxes of dissolved inorganic and organic nitrogen and phosphorus were measured at two sites in Fourleague Bay, Louisiana, from August 1981, through May 1982. This estuary is an extension of Atchafalaya Bay which receives high discharge and nutrient loading from the Atchafalaya River. Sediment O₂ uptake averaged 49 mg m^?2 h^?1. On the average, ammonium (NH₄ ⁺) was released from the sediments (mean flux =+129 μmol m^?2 h^?1), and NO₃ ^? was taken up (mean flux =?19 μmol m^?2h^?1). However, very different NO₃ ^? fluxes were observed at the two sites, with sediment uptake at the upper, river-influenced, high NO₃ ^? site (mean flux =?112 μmol m^?2 h^?1) and release at the lower, marine-influenced low NO₃ ^? site (mean flux =+79 μmol m^?2 h^?1). PO₄ ^3? fluxes were low and often negative (mean flux =?8 μmol m^?2 h^?1), while dissolved organic phosphorus fluxes were high and positive (mean flux =+124 μmol m^?2 h^?1). Dissolved organic nitrogen fluxes varied greatly, ranging from a mean of +305 μmol m^?2 h^?1 at the lower bay, to ?710 μmol m^?2 h^?1 at the upper bay. Total dissolved nitrogen and phosphorus fluxes indicated the sediments were a nitrogen (mean flux =+543 μmol m^?2 h^?1) and phosphorus source (mean flux =+30 μmol m^?2 h^?1) at the lower bay, and a nitrogen sink (mean flux =?553 μmol m^?2 h^?1) and phosphorus source (mean flux =+17 μmol m^?2 h^?1) in the upper bay. Mean annual O∶N ration of the positive inorganic sediment fluxes were 27∶1 at the upper bay and 18∶1 at the lower bay. Based on these data we hypothesize that nitrification and denitrification are important sediment processes in the upper bay. We further hypothesize that Atchafalaya River discharge affects sediment-water fluxes through seasonally high nutrient loading which leads to net nutrient uptake by sediments in the upper bay and release in the lower bay, where there is less river influnces.     

Dissolved silicate dynamics of the Rhode River watershed and estuary

We continuously measured dissolved silicate concentrations and fluxes discharged from various Rhode River subwatersheds for a period of 14 yr from 1984 to 1998 and for 15 mo in 1971–1972. We also measured dissolved silicate concentrations along a transect from the head of the tide in Rhode River estuary to Chesapeake Bay. The average concentration of dissolved silicate discharged from the Rhode River watershed was 10.8 mg Si l^?1. There were consistent and significant differences in silicate concentrations discharged over time and space among subwatersheds. Mean annual silicate flux from the watershed was 26.6 kg Si ha^?1 and 93% of this occurred during the winter and spring seasons. There were large interannual variations in silicate flux, due primarily to differences in precipitation and water discharge, rather than silicate concentration. Land use had little or no effect on silicate flux from various subwatersheds. Silicate concentrations discharged from a subset of subwatersheds in 1995–1996 were 25% to 35% lower than in a period with similar precipitation in 1971–1972. Mean annual concentrations of silicate discharged from nine subwatersheds have been declining about 1.5% yr^?1 or by 0.21–0.26 mg Si l^?1 yr^?1 over the last 25 yr. Despite high average silicate fluxes from the watershed, at times the Rhode River estuary developed low dissolved silicate concentrations, which could have been limiting to the growth of diatoms. Examples were in the spring after a winter with low watershed discharge (as low as 0.019 mg Si l^?1 in 1995) and after protracted drought (as low as 0.041 mg Si l^?1 in 1993).     

Nutrient distribution and fluxes from three Mediterranean coastal rivers (NE Algeria) under large damming

Nutrient distribution and fluxes into and from dams and into coastal waters from three rivers (NE Algeria) were assessed during a one-year period in three stations for each river: at the entrance and the exit of dam and at the outlet. The main characteristics of the rivers were the high levels of NH₄ and PO₄, even in dam entrances, contrarily to SiO₄ levels that are still low upstream the dams. From the inorganic nutrient incoming fluxes, the dams trapped annually 42 to 93%, depending on the nutrient, but released in great levels dissolved organic forms at their exits. At catchment scale, dissolved nitrogen loadings reach 338 kg/km²/yr, in which the organic fraction forms up to 34%; while those of dissolved phosphorus reach 172 kg/km²/yr, with a great organic fraction. The Si:N ratios decreased while N:P ratios increased at river outlets, indicating large inputs of N over P in the lower catchments.     

Recycling of Organic Matter in the Sediments of Santa Monica Basin,California Borderland

Geochemical and isotopic data for the uppermost 1.2 m of the sediments of the central Santa Monica Basin plain were examined to better understand organic matter deposition and recycling at this site. Isotopic signatures (Δ¹⁴C and δ¹³C) of methane (CH₄) and dissolved inorganic carbon (DIC) indicate the occurrence of anaerobic oxidation of CH₄ that is fueled by CH₄ supplied from a relict reservoir that is decoupled from local organic carbon (C_org) degradation and methanogenesis. This finding was corroborated by a flux budget of pore-water solutes across the basal horizon of the profile. Together these results provide a plausible explanation for the anomalously low ratio between alkalinity production and sulfate consumption reported for these sediments over two decades ago. Shifts in Δ¹⁴C and δ¹³C signatures of C_org have previously been reported across the 20-cm depth horizon for this site and attributed to a transition from oxic to anoxic bottom water that occurred ~350 years BP. However, we show that this horizon also coincides with a boundary between the base of a hemipelagic mud section and the top of a turbidite interval, complicating the interpretation of organic geochemical data across this boundary. Radiocarbon signatures of DIC diffusing upward into surface sediments indicate that remineralization at depth is supported by relatively ¹⁴C-enriched C_org within the sedimentary matrix. While the exact nature of this C_org is unclear, possible sources are hemipelagic mud sections that were buried rapidly under thick turbidites, and ¹⁴C-rich moieties dispersed within C_org-poor turbidite sections.     

The geochemistry of dissolved inorganic carbon in a surficial groundwater aquifer in North Inlet, South Carolina, and the carbon fluxes to the coastal ocean

We report measurements of pH, total dissolved inorganic carbon (DIC), total or titration alkalinity (TAlk), Ca²⁺, Mg²⁺, sulfate, and sulfide data at the seawater-freshwater interface in a shallow groundwater aquifer in North Inlet, South Carolina. These measurements and a diagenetic modeling analysis indicate that the groundwaters at North Inlet are mixtures of seawater and freshwater end-members and are seriously modified by carbon dioxide inputs from organic carbon degradation via SO₄²⁻ reduction across the entire salinity range and fermentation and CaCO₃ dissolution in the low-salinity region. DIC and TAlk are several times higher than the theoretical dilution line, whereas Ca²⁺ is slightly higher and SO₄²⁻ is somewhat lower than the dilution line. Partial pressure of CO₂ in the groundwater is extremely high (0.05 to 0.12 atm). These deviations are consistent with theoretical predictions from known diagenetic reactions. Estimated groundwater DIC fluxes to the South Atlantic Bight from either the surficial aquifer (via salt marshes) or the Upper Floridan Aquifer (direct input) are significant when compared to riverine flux in this area.     

Chemistry of the heavily urbanized Bagmati River system in Kathmandu Valley, Nepal: export of organic matter, nutrients, major ions, silica, and metals

Water quality in less-developed countries is often subject to substantial degradation, but is rarely studied in a systematic way. The concentration and flux of major ions, carbon, nitrogen, silicon, and trace metals in the heavily urbanized Bagmati River within Kathmandu Valley, Nepal, are reported. The concentrations of all chemical species increased with distance downstream with the exceptions of protons and nitrate, and showed strong relationships with population density adjacent to the river. Total dissolved nitrogen (TDN), dominated by NH₄, was found in high concentrations along the Bagmati drainage system. The export of dissolved organic carbon (DOC) and TDN were 23 and 33 tons km^?2 year^?1, respectively, at the outlet point of the Kathmandu Valley, much higher than in relatively undeveloped watersheds. The cationic and silica fluxes were 106 and 18 tons km^?2 year^?1 at the outlet of the Bagmati within Kathmandu Valley, and 36 and 32 tons km^?2 year^?1 from the relatively pristine headwater area. The difference between headwaters and the urban site suggests that the apparent weathering flux is three times higher than the actual weathering rate in the heavily urbanized Bagmati basin. Fluxes of cations and silica are above the world average, as well as fluxes from densely populated North American and European watersheds. End-member composition of anthropogenic sources like sewage or agricultural runoff is needed to understand the drivers of this high rate of apparent weathering.     

Benthic metabolism and nutrient cycling along an estuarine salinity gradient

Benthic metabolism and nutrient exchange across the sediment-water interface were examined over an annual cycle at four sites along a freshwater to marine transect in the Parker River-Plum Island Sound estuary in northeastern Massachusetts, U.S. Sediment organic carbon content was highest at the freshwater site (10.3%) and decreased along the salinity gradient to 0.2% in the sandy sediments at the marine end of the estuary. C:N ratios were highest in the mid estuary (23:1) and lowest near the sea (11:1). Chlorophyll a in the surface sediments was high along the entire length of the estuary (39–57 mg chlorophyll a m⁻²) but especially so in the sandy marine sediments (172 mg chlorophyll a m⁻²). Chlorophyll a to phaeophytin ratios suggested most chlorophyll is detrital, except at the sandy marine site. Porewater sulfide values varied seasonally and between sites, reflecting both changes in sulfate availability as overlying water salinity changed and sediment metabolism. Patterns of sediment redox potential followed those of sulfide. Porewater profiles of inorganic N and P reflected strong seasonal patterns in remineralization, accumulation, and release. Highest porewater NH₄ ⁺ values were found in upper and mid estuarine sediments, occasionally exceeding 1 mM N. Porewater nitrate was frequently absent, except in the sandy marine sediments where concentrations of 8 μM were often observed. Annual average respiration was lowest at the marine site (13 mmol O₂ m⁻² d⁻¹ and 21 mmol TCO₂ m⁻² d⁻¹) and highest in the mid estuary (130 mmol O₂ m⁻² d⁻¹ and 170 mmol TCO₂ m⁻² d⁻¹) where clam densities were also high. N₂O and CH₄ fluxes were low at all stations throughout the year: Over the course, of a year, sediments varied from being sources to sinks of dissolved organic C and N, with the overall spatial pattern related closely to sediment organic content. There was little correlation between PO₄ ³⁻ flux and metabolism, which we attribute to geochemical processes. At the two sites having the lowest salinities, PO₄ ³⁻ flux was directed into the sediments. On average, between 22% and 32% of total system metabolism was attributable to the benthos. The mid estuary site was an exception, as benthic metabolism accounted for 95% of the total, which is attributable to high densities of filter-feeding clams. Benthic remineralization supplied from less than 1% to over 190% of the N requirements and 0% to 21% of the P requirements of primary producers in this system. Estimates of denitrification calculated from stoichiometry of C and N fluxes ranged from 0% for the upper and mid estuary site to 35% for the freshwater site to 100% of sediment organic N remineralization at the marine site. We hypothesize that low values in the upper and mid estuary are attributable to enhanced NH₄ ⁺ fluxes during summer due to desorption of exchangeable ammonium from rising porewater salinity. NH₄ ⁺ desorption during summer may be a mechanism that maintains high rates of pelagic primary production at a time of low inorganic N inputs from the watershed.     

Modeling CO2 chemistry, δC, and oxidation of organic carbon and methane in sediment porewater: Implications for paleo-proxies in benthic foraminifera

I present a numerical diffusion-advection-reaction model to simulate CO₂ chemistry, δ¹³C, and oxidation of organic carbon and methane in sediment porewater. The model takes into account detailed reaction kinetics of dissolved CO₂ compounds, H₂O, H⁺, OH⁻, boron and sulfide compounds. These reactions are usually assumed to be in local equilibrium, which is shown to be a good approximation in most cases. The model also includes a diffusive boundary layer across which chemical species are transported between bottom water and the sediment-water interface. While chemical concentrations and δ¹³C_TCO2 at these locations are frequently assumed equal, I demonstrate that they can be quite different. In this case, shells of benthic foraminifera do not reflect the desired properties of bottom water, even for species living at the sediment-water interface (z = 0 cm). Environmental conditions recorded in their shells are strongly influenced by processes occurring within the sediment. The model is then applied to settings in the Santa Barbara Basin and at Hydrate Ridge (Cascadia Margin), locations of strong organic carbon and methane oxidation. In contrast to earlier studies, I show that a limited contribution of methane-derived carbon to porewater TCO₂ in the Santa Barbara Basin cannot be ruled out. Simulation of methane venting shows that at oxidation rates greater than , the δ¹³C of porewater TCO₂ at z > 1 cm is depleted by more than 15‰ relative to bottom water. Depletions of this magnitude have not been observed in living benthic foraminifera, even at methane vents with much higher oxidation rates. This suggests that foraminifera at these sites either calcify at very shallow sediment depth or during times when oxidation rates are much lower than ∼50 μmol cm⁻² y⁻¹.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.     

Biogeochemical characteristics of the lower Mississippi River, USA, during June 2003

During June 2003, a period of mid level discharge (17,400 m⁻³ s⁻¹), a parcel of water in the lower Mississippi River was sampled every 2 h during its 4-d transit from river km 362 near Baton Rouge to km 0 at Head of Passes, Louisiana, United States. Properties measured at the surface during each of the 48 stations were temperature, salinity, dissolved organic carbon (DOC), total dissolved nitrogen, dissolved macronutrients (NO₃+NO₂, PO₄, Si(OH)₄), chlorophylla (chla; three size fractions: < 5 μm, 5–20 μm, and > 20 μm) pigment composition by HPLC, total suspended matter (TSM), particulate organic carbon (POC), and particulate nitrogen (PN). Air-water CO₂ flux was calculated from surface water dissolved inorganic carbon and pH. During the 4 d transit, large particles appeared to be settling out of the surface water. Concentrations of chla containing particles > 20 μm declined 37%, TSM declined 43%, POC declined 42% and PN declined 57%. Concentrations of the smaller chla containing particles did not change suggesting only large particulate materials were settling. There was no measurable loss of dissolved NO₃, PO₄, or Si(OH)₄, consistent with the observation that chla did not increase during the 4-d transit. DOC declined slightly (3%). These data indicate there was little autotrophic or heterotrophic activity in the lower Mississippi River at this time, but the system was slightly net heterotrophic.     

Geochemistry,dissolved elemental flux rates,and dissolution kinetics of lithologies of Alaknanda and Bhagirathi rivers in Himalayas,India

Alaknanda and Bhagirathi (AB) river basins in the Himalayan region in India expose lithologies comprising mainly of granites, low–high-grade metamorphics, shales and carbonates which, in conjunction with the monsoon rains and glacial melt, control water chemistry and dissolved elemental flux rates. In the present study, we monitored two locations: (a) Srinagar on the Alaknanda river and (b) Maneri on the Bhagirathi river for daily variations in total suspended sediments, major ions and dissolved silica over one complete year (July 2004–June 2005). Based on long-term discharge data, discharge-weighted composition and dissolved elemental flux rates (with respect to Ca, Mg, HCO₃, Si) of the river were estimated. The information thus obtained has substantially added up to the existing chemical data of these rivers and has refined the flux rates. Our high-frequency samples provide informations such as (a) water chemical compositions that show a large temporal and spatial variation and (b) carbonate lithology that controls water chemistry predominantly. The dissolution kinetics of various lithologies namely leucogranite, gneiss, quartzite, phyllite and shale of the AB river basins were studied through batch experiments at controlled temperature (25 and 5°C) and pH (8.4) condition. In laboratory, these lithologies undergo slow rates of dissolution (10⁻¹³ to 10⁻¹⁵ mol/m² s), while field weathering rates based on dissolved elemental flux rates in the AB rivers are much higher (10⁻⁸ to 10⁻⁹ mol/m² s). Extremely high physical weathering rates in AB rivers, which enhance chemical weathering significantly, mainly attribute this wide discrepancy in laboratory-derived rates of representative basin rocks and dissolved elemental fluxes in the field. However, laboratory-simulated experiments facilitate to quantify elemental release rates, understand the kinetics of the dissolution reactions, and compare their roles at individual level.     

The post-depositional reactivity of iron and managanese in the sediments of a macrotidal estuarine system

Four cores of anoxic sediments were collected from the Seine estuary to assess the early diagenesis pathways leading to the formation of previously reactive phase. Pore waters were analyzed for dissolved iron (Fe) and manganese (Mn) and different ligands (e.g., sulfate, chloride, total inorganic carbon). The anoxic zone is present up to the first centimeter depth, in these conditions the reduction of Mn and Fe oxides and SO₄ ²⁻ was verified. The sulfate reduction was well established with a subsequent carbon mineralization in the NORMAI94 core. The chemical speciation of Mn and Fe in the dissolved and solid phases was determined. For the dissolved phase, thermodynamic calculations were used to characterize and illustrate the importance of carbonate and phosphate phases as sinks for Fe and Mn. The ion activity product (IAP) of Fe and Mn species was compared to the solubility products (Ks) of these species. In the solid phase, the presence of higher concentration of calcium carbonate in the Seine sediments is an important factor controlling Mn cycle. The carbonate-bound Mn can reach more than 75% of the total concentration. This result is confirmed by the use of electron spin resonance (ESR) spectroscopy. The reduction of Fe is closely coupled to the sulfate reduction by the formation of new solid phases such as FeS and FeS₂, which can be regarded as temporal sinks for sulfides. These forms were quantified in all cores as acid volatile sulfide (AVS: FeS+ free sulfide) and chromium reducible sulfide (CRS: FeS₂+elemental sulfur S⁰).     

Volcanic and anthropogenic contributions to global weathering budgets

We evaluate whether the global weathering budget is near steady state for the pre-anthropogenic modern environment by assessing the magnitude of acidity-generating volcanic exhalations. The weathering rate induced by volcanic acid fluxes, of which the CO₂ flux is the most important, can be expressed as an average release rate of dissolved silica, based on a model feldspar-weathering scheme, and the ratio of carbonate-to-silicate rock weathering. The theoretically predicted flux of silica from chemical weathering is slightly smaller than the estimated global riverine silica flux. After adjustment for carbonate weathering, the riverine dissolved bicarbonate flux is larger than the volcanic carbon degassing rate by a factor of about three. There are substantial uncertainties associated with the calculated and observed flux values, but the modern system may either not be in steady state, or additional, “unknown” carbon sources may exist. The closure errors in the predicted budgets and observed riverine fluxes suggest that continental weathering rates might have had an impact on atmospheric CO₂ levels at a time scale of 10³-10⁴ years, and that enhanced weathering rates during glacial periods might have been a factor in the reduced glacial atmospheric CO₂ levels. Recent anthropogenic emissions of carbon and sulfur have a much larger acid-generating capacity than the natural fluxes. Estimated potential weathering budgets to neutralize these fluxes are far in excess of observed values. A theoretical scenario for a return to steady state at the current anthropogenic acidity emissions (disregarding the temporary buffering action of the ocean reservoir) requires either significantly lower pH values in continental surface waters as a result of storage of strong acids, and/or higher temperatures as a result of enhanced atmospheric CO₂ levels in order to create weathering rates that can neutralize the total flux of anthropogenic and natural background acidity.     

Nutrient pore water chemistry,Great Bay,New Hampshire: Benthic fluxes

Benthic fluxes of C, N, P and Si have been measured at two sites in Great Bay Estuary, New Hampshire. Higher fluxes of reactive phosphate, nitrate and reactive silicate were observed at the site where bioturbation is known to occur and the fluxes of NH₄ ⁺, PO₄ ^?3 and reactive silicate at this location were from 3 to 6 times higher than that calculated by simple pore water diffusion models. *** DIRECT SUPPORT *** A01BY019 00010