Chemistry of sediment profile GeoB4906

Mineralization of organic matter and the subsequent dissolution of calcite were simulated for surface sediments of the upper continental slope off Gabon by using microsensors to measure O2, pH, pCO2 and Ca2+ (in situ), pore-water concentration profiles of NO3-, NH4+, Fe2+, and Mn2+ and SO42- (ex situ), as well as sulfate reduction rates derived from incubation experiments. The transport and reaction model CoTReM was used to simulate the degradation of organic matter by O2, [NO3]-, Fe(OH)3 and [SO4]2-, reoxidation reactions involving Fe2+ and Mn2+, and precipitation of FeS. Model application revealed an overall rate of organic matter mineralization amounting to 50 µmol C cm**-2 yr**-1, of which 77% were due to O2, 17% to [NO3]- and 3% to Fe(OH)3 and 3% to [SO4]2-. The best fit for the pH profile was achieved by adapting three different dissolution rate constants of calcite ranging between 0.01 and 0.5% d-1 and accounting for different calcite phases in the sediment. A reaction order of 4.5 was assumed in the kinetic rate law. A CaCO3 flux to the sediment was estimated to occur at a rate of 42 g m**-2 yr**-1 in the area of equatorial upwelling. The model predicts a redissolution flux of calcite amounting to 36 g m**-2 yr**-1, thus indicating that ~90% of the calcite flux to the sediment is redissolved.

Interstitial water and sediment chemistry at DSDP Sites 87-582 and 87-584

Two trenches off Japan were explored during DSDP Leg 87. One is the Nankai Trough and the other is the Japan Trench; Site 582 is located on the floor of the former and Site 584 is situated on the deep-sea terrace of the latter. Cores from Site 582 and 584 consist mainly of hemipelagic sediments and diatomaceous silts and mudstone, respectively. In this report we analyze the chemistry of the interstitial water and sediments, as well as the sediment mineralogy. Sulfate reduction is accompanied by the production of secondary pyrite, which is rich in the sediment at both sites. Dissolved Ca concentration is relatively low and changes only slightly at both sites, probably because of the formation of carbonate with high alkalinity. Concentrations of dissolved Mg decrease with depth at Site 584. The dissolved Mg depletion probably results from the formation of Mg-rich carbonate and/or ion exchange and reaction between interstitial water and clay minerals. Higher Si/Al values are due to biogenic opal in the sediments and roughly correlate with higher values of interstitial water SiO2. Increases in dissolved Li concentrations may be related to its release from clay minerals, to advection that results from dewatering, and/or to fluid transport.

Chemistry of interstitial waters and sediments at DSDP Leg 64 Holes

Studies of interstitial waters obtained from DSDP Leg 64 drill sites in the Gulf of California have revealed information both on early diagenetic processes in the sediments resulting from the breakdown of organic matter and on hydrothermal interactions between sediments and hot doleritic sill intrusions into the sediments. In all the sites drilled sulfate reduction occurred as a result of rapid sediment accumulation rates and of relatively high organic carbon contents; in most sites methane production occurred after sulfate depletion. Associated with this methane production are high values of alkalinity and high concentrations of dissolved ammonia, which causes ion exchange processes with the solid phases leading to intermediate maxima in Mg++, K+, Rb+, and Sr++(?). Though this phenomenon is common in Leg 64 drill sites, these concentration reversals had been noticed previously only in Site 262 (Timor Trough) and Site 440 (Japan Trench). Penetrating, hot dolerite sills have led to substantial hydrothermal alteration in sediments at sites drilled in the Guaymas Basin. Site 477 is an active hydrothermal system in which the pore-water chemistry typically shows depletions in sulfate and magnesium and large increases in lithium, potassium, rubidium, calcium, strontium, and chloride. Strontium isotope data also indicate large contributions of volcanic matter and basalt to the pore-water strontium concentrations. At Sites 478 and 481 dolerite sill intrusions have cooled to ambient temperatures but interstitial water concentrations of Li+, Rb+, Sr++ , and Cl- show the gradual decay of a hydrothermal signal that must have been similar to the interstitial water chemistry at Site 477 at the time of sill intrusion. Studies of oxygen isotopes of the interstitial waters at Site 481 indicate positive values of d18O (SMOW) as a result of high-temperature alteration reactions occurring in the sills and the surrounding sediments. A minimum in dissolved chloride at about 100-125 meters sub-bottom at Sites 478, 481, and particularly Site 479 records a possible paleosalinity signal, associated with an event that substantially lowered salinities in the inner parts of the Gulf of California during Quaternary time.

Interstitial water chemistry, Deep Sea Drilling Project, Leg 96

On Leg 96 of the Deep Sea Drilling Project (DSDP), holes were drilled in Orca and Pigmy basins on the northern Gulf of Mexico continental slope and on the Mississippi Fan. The holes on the fan encountered interbedded sand, silt, and mud deposited extremely rapidly, most during late Wisconsin glacial time. Pore-water chemistry in these holes is variable, but does not follow lithologic changes in any simple way. Both Ca and SO4 are enriched in the pore water of many samples from the fan. Two sites drilled in the prominent central channel of the middle fan show rapid SO4 reduction with depth, whereas two nearby sites in overbank deposits show no sulfate reduction for 300 m. Calcium concentration decreases as SO4 is depleted and Li follows the same pattern. Strontium, which like Li, is enriched in samples enriched in Ca, does not decrease with SO4 and Ca. Potassium in the pore water decreases with depth at almost all sites. Sulfate reduction was active at the two basin sites and, as on the fan, this resulted in calcium carbonate precipitation and a lowering of pore water Ca, Mg, and Li. The Orca Basin site was drilled through a brine pool of 258? salinity. Pore-water salinity decreases smoothly with depth to 50 m and remains well above normal seawater values to the bottom of the hole at about 90 m. This suggests constant sedimentation under anoxic hypersaline conditions for at least the last 50,000 yr.

Pore water chemistry of ODP Sites 201-1225, 201-1226 and 201-1231

High-resolution analyses of the oxygen isotope ratio (18O/16O) of dissolved sulfate in pore waters have been made to depths of >400 meters below seafloor (mbsf) at open-ocean and upwelling sites in the eastern equatorial Pacific Ocean. d18O values of dissolved sulfate (d18O-SO4) at the organic-poor open-ocean Site 1231 gave compositions close to modern seawater (+9.5 per mil vs. Vienna-standard mean ocean water, providing no chemical or isotopic evidence for microbial sulfate reduction (MSR). In contrast, the maximum d18O values at Sites 1225 and 1226, which contain higher organic matter contents, are +20 per mil and +28 per mil, respectively. Depth-correlative trends of increasing d18O-SO4, alkalinity, and ammonium and the presence of sulfide indicate significant oxidation of sedimentary organic matter by sulfate-reducing microbial populations at these sites. Although sulfate concentration profiles at Sites 1225 and 1231 both show similarly flat trends without significant net MSR, d18O-SO4 values at Site 1225 reveal the presence of significant microbial sulfur-cycling activity, which contrasts to Site 1231. This activity may include contributions from several processes, including enzyme-catalyzed equilibration between oxygen in sulfate and water superimposed upon bacterial sulfate reduction, which would tend to shift d18O-SO4 toward higher values than MSR alone, and sulfide oxidation, possibly coupled to reduction of Fe and Mn oxides and/or bacterial disproportionation of sulfur intermediates. Large isotope enrichment factors observed at Sites 1225 and 1226 (epsilon values between 42 per mil and 79 per mil) likely reflect concurrent processes of kinetic isotope fractionation, equilibrium fractionation between sulfate and water, and sulfide oxidation at low rates of sulfate reduction. The oxygen isotope ratio of dissolved pore water sulfate is a powerful tool for tracing microbial activity and sulfur cycling by the deep biosphere of deep-sea sediments.

Late Miocene to Pleistocene paleoceanographic records from the Feni and Gardar Drifts: Pliocene reduction in abyssal flow

Magnetic fabric analyses from two North Atlantic drift deposits provide proxies for determining relative variations in the strength of abyssal flow over the last 10 my. The data show a cessation of current-controlled sedimentation at the shallower Feni Drift (2417 m) at the time of onset of Northern Hemisphere glaciation (2.6 Ma). Drift formation ended nearly 2 my earlier (4.2 Ma) at the deeper Gardar Drift (3220 m), implying stepwise reduction in deep-water flow. Relatively light delta18O values at the deeper Gardar Drift indicate a warmer, thus also more salty, water mass site prior to 6 Ma. We interpret this as representing Mediterranean Sea water, which flowed north at depths greater than that of the Feni Drift Site. The supply of Mediterranean Water to the North Atlantic was shut off as the Gibraltar Straits closed, causing the Messinian salinity crisis, and never returned to that position in the water column after the Mediterranean opened again.

Chemistry of interstitial waters of ODP Site 166-718

Preliminary data are presented on dissolved heavy metals in interstitial water samples collected at Site 718 of Ocean Drilling Program Leg 118. The heavy metals at this site are divided into three groups: Group I (B, K, Mn, Ni, Pb, total Si, total P, V) behaves like Mg, which decrease with depth; Group II (Ba, Cu, Sr, Ti) behaves like Ca, which increases with depth; and Group 111 (Cd, Co, Cr, Fe, Na, Mo, Zn) contains metals that are independent of depth. Mg decreases with depth from 50 mM at the seafloor to 21 mM at 900 mbsf. Mn in the sulfate reduction zone (1.0 to 2.8 ppm) is more highly concentrated than in the methane fermentation zone (0.23 to 0.50 ppm), except for Section 116-718-1H-1. A similar behavior is also observed for V and Pb. Ni, B, and K decrease non-uniformly with depth. Ca and Sr increase with depth at the same rates, indicating the dissolution of inorganic calcium carbonate by anaerobic oxidation of organic matter (Sayles, 1981, doi:10.1016/0016-7037(81)90132-0). The distribution of Ba with depth is very similar to those of Ca and Sr. Cu and Ti profiles trend to increase non-uniformly with depth. Fe is constant with depth. The sharp decrease in total silicate concentration at the seafloor probably indicates a decrease in the decomposition of siliceous biological matter (e.g., diatoms) and production of opal. The constant levels of Group 111, except for Na and Fe, may reveal equal sources of supply from surface seawater and the Himalayas over time.

Organic chemistry of sediments of the Peru margin

Organic-carbon-rich anoxic sediments from the continental shelf (Site 680) and the lower continental slope (Site 688) off Peru were studied to determine factors controlling the accumulation of reduced sulfur. High concentrations of organic matter in diatomaceous muds, its thermal immaturity, and the presence of abundant hydrogen-containing organic compounds lead to the conclusion that organic matter is not limiting for reduced sulfur formation. Rather, high degrees of iron pyritization at Site 680 limit pyrite accumulation in sediments from this shelf site. The low degree of iron pyritization and nearly complete reduction of dissolved sulfate at Site 688 suggest that a lack of interstitial sulfate is limiting pyrite formation there. Although factors that limit the formation of sedimentary iron sulfide are different at each site, the resulting average reduced-sulfur concentrations are remarkably similar (0.85 wt.% at Site 680 and 0.86 wt.% at Site 688). Carbon to sulfur (C/S) ratios are higher in samples containing in excess of 3 wt.% organic carbon than the average of 2.8 in normal marine sediments and have been primarily influenced by variations in organic matter concentrations.

Pore water chemistry of sediment core GeoB15101-7 and water chemistry of CTD casts GeoB15101-1 and GeoB15101-6

Submarine brine lakes feature sharp and persistent concentration gradients between seawater and brine, though these should be smoothed out by free diffusion in open ocean settings. The anoxic Urania basin of the Eastern Mediterranean contains an ultra sulfidic, hypersaline brine of Messinian origin above a thick layer of suspended sediments. With a dual modeling approach we reconstruct its contemporary stratification by geochemical solute transport fundamentals, and show that thermal convection is required to maintain mixing in the brine and mud layer. The origin of the Urania basin stratification was dated to 1650 years before present, which may be linked to a major earthquake in the region. The persistence of the chemoclines may be key to the development of diverse and specialized microbial communities. Ongoing thermal convection in the fluid mud layer may have important, yet unresolved consequences for sedimentological and geochemical processes, also in similar environments.

Sulphur chemistry of the ODP Site 206-1256 volcanic section

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800 m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530 ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155 ppm sulfur and are more oxidized, have high SO4/Sum S ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative d34S[sulfide-S] values (down to -30 per mil) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940 ppm S, and with d34S shifted to -6.0 per mil from the mantle value (0 per mil). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 * 10**10 mol S/yr, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 * 10**-8 mol/cm**-2/yr1 over 15 m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 * 10**11 mol/yr, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

Seawater carbonate chemistry and processes during experiments with crabs Chionoecetes tanneri and Cancer magister, 2007

Rising levels of atmospheric carbon dioxide could be curbed by large-scale sequestration of CO2 in the deep sea. Such a solution requires prior assessment of the impact of hypercapnic, acidic seawater on deep-sea fauna. Laboratory studies were conducted to assess the short-term hypercapnic tolerance of the deep-sea Tanner crab Chionoecetes tanneri, collected from 1000 m depth in Monterey Canyon off the coast of central California, USA. Hemolymph acid- base parameters were monitored over 24 h of exposure to seawater equilibrated with ~1% CO2 (seawater PCO2 ~6 torr or 0.8 kPa, pH 7.1), and compared with those of the shallow-living Dungeness crab Cancer magister. Short-term hypercapnia-induced acidosis in the hemolymph of Chionoecetes tanneri was almost uncompensated, with a net 24 h pH reduction of 0.32 units and a net bicarbonate accumulation of only 3 mM. Under simultaneous hypercapnia and hypoxia, short-term extracellular acidosis in Chionoecetes tanneri was completely uncompensated. In contrast, Cancer magister fully recovered its hemolymph pH over 24 h of hypercapnic exposure by net accumulation of 12 mM bicarbonate from the surrounding medium. The data support the hypothesis that deep-sea animals, which are adapted to a stable environment and exhibit reduced metabolic rates, lack the short-term acid-base regulatory capacity to cope with the acute hypercapnic stress that would accompany large-scale CO2 sequestration. Additionally, the data indicate that sequestration in oxygen-poor areas of the ocean would be even more detrimental to deep-sea fauna.

Seawater carbonate chemistry and processes during experiments with cyanobacterium Nodularia spumigena, 2009

The surface ocean absorbs large quantities of the CO2 emitted to the atmosphere from human activities. As this CO2 dissolves in seawater, it reacts to form carbonic acid. While this phenomenon, called ocean acidification, has been found to adversely affect many calcifying organisms, some photosynthetic organisms appear to benefit from increasing [CO2]. Among these is the cyanobacterium Trichodesmium, a predominant diazotroph (nitrogen-fixing) in large parts of the oligotrophic oceans, which responded with increased carbon and nitrogen fixation at elevated pCO2. With the mechanism underlying this CO2 stimulation still unknown, the question arises whether this is a common response of diazotrophic cyanobacteria. In this study we therefore investigate the physiological response of Nodularia spumigena, a heterocystous bloom-forming diazotroph of the Baltic Sea, to CO2-induced changes in seawater carbonate chemistry. N. spumigena reacted to seawater acidification/carbonation with reduced cell division rates and nitrogen fixation rates, accompanied by significant changes in carbon and phosphorus quota and elemental composition of the formed biomass. Possible explanations for the contrasting physiological responses of Nodularia compared to Trichodesmium may be found in the different ecological strategies of non-heterocystous (Trichodesmium) and heterocystous (Nodularia) cyanobacteria.

Seawater carbonate chemistry and dark respiration and photosynthetic capacity during experiments with coral Acropora formosa, 2010

Ocean acidification is expected to lower the net accretion of coral reefs yet little is known about its effect on coral photophysiology. This study investigated the effect of increasing CO2 on photosynthetic capacity and photoprotection in Acropora formosa. The photoprotective role of photorespiration within dinoflagellates (genus Symbiodinium) has largely been overlooked due to focus on the presence of a carbon-concentrating mechanism despite the evolutionary persistence of a Form II Rubisco. The photorespiratory fixation of oxygen produces phosphoglycolate that would otherwise inhibit carbon fixation though the Calvin cycle if it were not converted to glycolate by phosphoglycolate phosphatase (PGPase). Glycolate is then either excreted or dealt with by enzymes in the photorespiratory glycolate and/or glycerate pathways adding to the pool of carbon fixed in photosynthesis. We found that CO2 enrichment led to enhanced photoacclimation (increased chlorophyll a per cell) to the subsaturating light levels. Light-enhanced dark respiration per cell and xanthophyll de-epoxidation increased, with resultant decreases in photosynthetic capacity (Pnmax) per chlorophyll. The conservative CO2 emission scenario (A1B; 600-790 ppm) led to a 38% increase in the Pnmax per cell whereas the 'business-as-usual' scenario (A1F1; 1160-1500 ppm) led to a 45% reduction in PGPase expression and no change in Pnmax per cell. These findings support an important functional role for PGPase in dinoflagellates that is potentially compromised under CO2 enrichment.

Seawater carbonate chemistry, gross photosynthesis and metabolically induced rate of pH change during experiments with macroalgae, 2012

Ocean acidification (OA) is a reduction in oceanic pH due to increased absorption of anthropogenically produced CO2. This change alters the seawater concentrations of inorganic carbon species that are utilized by macroalgae for photosynthesis and calcification: CO2 and HCO3 increase; CO32 decreases. Two common methods of experimentally reducing seawater pH differentially alter other aspects of carbonate chemistry: the addition of CO2 gas mimics changes predicted due to OA, while the addition of HCl results in a comparatively lower [HCO3]. We measured the short-term photosynthetic responses of five macroalgal species with various carbon-use strategies in one of three seawater pH treatments: pH 7.5 lowered by bubbling CO2 gas, pH 7.5 lowered by HCl, and ambient pH 7.9. There was no difference in photosynthetic rates between the CO2, HCl, or pH 7.9 treatments for any of the species examined. However, the ability of macroalgae to raise the pH of the surrounding seawater through carbon uptake was greatest in the pH 7.5 treatments. Modeling of pH change due to carbon assimilation indicated that macroalgal species that could utilize HCO3 increased their use of CO2 in the pH 7.5 treatments compared to pH 7.9 treatments. Species only capable of using CO2 did so exclusively in all treatments. Although CO2 is not likely to be limiting for photosynthesis for the macroalgal species examined, the diffusive uptake of CO2 is less energetically expensive than active HCO3 uptake, and so HCO3-using macroalgae may benefit in future seawater with elevated CO2.