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1.
Studies of the δ13C of pore water dissolved inorganic carbon (δ13C-DIC) were carried out in shallow water carbonate sediments of the Great Bahamas Bank (GBB) to further examine sediment-seagrass relationships and to more quantitatively describe the couplings between organic matter remineralization and sediment carbonate diagenesis. At all sites studied δ13C-DIC provided evidence for the dissolution of sediment carbonate mediated by metabolic CO2 (i.e., CO2 produced during sediment organic matter remineralization); these observations are also consistent with pore water profiles of alkalinity, total DIC and Ca2+ at these sites. In bare oolitic sands, isotope mass balance further indicates that the sediment organic matter undergoing remineralization is a mixture of water column detritus and seagrass material; in sediments with intermediate seagrass densities, seagrass derived material appears to be the predominant source of organic matter undergoing remineralization. However, in sediments with high seagrass densities, the pore water δ13C-DIC data cannot be simply explained by dissolution of sediment carbonate mediated by metabolic CO2, regardless of the organic matter type. Rather, these results suggest that dissolution of metastable carbonate phases occurs in conjunction with reprecipitation of more stable carbonate phases. Simple closed system calculations support this suggestion, and are broadly consistent with results from more eutrophic Florida Bay sediments, where evidence of this type of carbonate dissolution/reprecipitation has also been observed. In conjunction with our previous work in the Bahamas, these observations provide further evidence for the important role that seagrasses play in mediating early diagenetic processes in tropical shallow water carbonate sediments. At the same time, when these results are compared with results from other terrigenous coastal sediments, as well as supralysoclinal carbonate-rich deep-sea sediments, they suggest that carbonate dissolution/reprecipitation may be more important than previously thought, in general, in the early diagenesis of marine sediments.  相似文献   

2.
Numerous studies of marine environments show that dissolved organic carbon (DOC) concentrations in sediments are typically tenfold higher than in the overlying water. Large concentration gradients near the sediment–water interface suggest that there may be a significant flux of organic carbon from sediments to the water column. Furthermore, accumulation of DOC in the porewater may influence the burial and preservation of organic matter by promoting geopolymerization and/or adsorption reactions. We measured DOC concentration profiles (for porewater collected by centrifugation and “sipping”) and benthic fluxes (with in situ and shipboard chambers) at two sites on the North Carolina continental slope to better understand the controls on porewater DOC concentrations and quantify sediment–water exchange rates. We also measured a suite of sediment properties (e.g., sediment accumulation and bioturbation rates, organic carbon content, and mineral surface area) that allow us to examine the relationship between porewater DOC concentrations and organic carbon preservation. Sediment depth-distributions of DOC from a downslope transect (300–1000 m water depth) follow a trend consistent with other porewater constituents (ΣCO2 and SO42−) and a tracer of modern, fine-grained sediment (fallout Pu), suggesting that DOC levels are regulated by organic matter remineralization. However, remineralization rates appear to be relatively uniform across the sediment transect. A simple diagenetic model illustrates that variations in DOC profiles at this site may be due to differences in the depth of the active remineralization zone, which in turn is largely controlled by the intensity of bioturbation. Comparison of porewater DOC concentrations, organic carbon burial efficiency, and organic matter sorption suggest that DOC levels are not a major factor in promoting organic matter preservation or loading on grain surfaces. The DOC benthic fluxes are difficult to detect, but suggest that only 2% of the dissolved organic carbon escapes remineralization in the sediments by transport across the sediment-water interface.  相似文献   

3.
The terrestrial carbon cycle and the role of atmospheric CO2 concentrations in controlling global temperatures can be inferred from the study of ancient soils (paleosols). Soil-formed goethite and calcite have been the primary minerals used as a geochemical proxy for reconstructing atmospheric pCO2 from ancient terrestrial records. In the case of goethite, optimum sampling strategies for reconstructing pCO2 focus on the portion of the soil profile that displays steep gradients in both soil CO2 concentration and δ13C values of soil CO2 such that a keeling plot can be developed for a given soil and atmospheric pCO2 can be calculated from it. We report data from a Carboniferous paleosol that depart from the expected linear trends. The results indicate that pedogenic goethite is sensitive to variations in the isotopic composition of soil CO2, over a range of timescales, and can record these variations in the carbon isotope composition and mole fraction of Fe(CO3)OH in solid solution with goethite. We explore possible environmental conditions that can drive these changes as a function of either moisture controlled variations in soil respired CO2 or in the residence time of carbon in soils. The implications of this result are overestimation of paleoatmospheric pCO2 from pedogenic goethite.  相似文献   

4.
We examined δ13C values of shallow and deep-water scallop shells as well as δ13C of dissolved inorganic carbon (DIC) from the Bay of Brest in western Brittany. Time series of shell calcite δ13C do not reflect seasonal variation in seawater δ13C, but rather show a consistent pattern of decreasing δ13C with age, suggesting a metabolic effect rather than direct environmental control. This δ13C trend reflects an increasing contribution of metabolic CO2 to skeletal carbonate throughout ontogeny, although this respired CO2 does not seem to be the major source of skeletal carbon (contribution of only 10% over the first year of life). We propose a model of this effect that depends on the availability of metabolic carbon relative to the carbon requirements for calcification. A ratio of “respired to precipitated carbon” is calculated, and represents the amount of metabolic carbon available for calcification. Interestingly, this ratio increases throughout ontogeny suggesting a real increase of metabolic carbon utilization into the skeleton relative to carbon from seawater DIC. This ratio allows us to separate two different populations of Pecten maximus of different water depth. It is therefore suggested that shell δ13C might be used to track differences in the metabolic activity of scallops from different populations.  相似文献   

5.
《Applied Geochemistry》1997,12(3):291-303
The geochemical effects of microbially mediated degradation of aromatic hydrocarbons were observed as changes in solution composition of an artificial groundwater in packed-sand laboratory columns. Benzene, toluene, and xylene, both individually and in a combined fashion, were used as substrates in biodegradation experiments conducted under oxygenated and anoxic conditions in columns filled with quartz, calcite, or Fe3+-coated quartz sand. Typically, column effluent had increased concentrations of dissolved inorganic C, decreased pH, and decreased concentrations of NO3 and dissolved O2 relative to column influent. Efficiency of CO2 generation was similar for the three different substrates, ranging from 22.5 to 26.6% organic C converted to CO2. When all three substrates were combined, the percentage of CO2 produced fell within the range observed in the single substrate experiments. Nitrate disappearance was more varied as a function of substrate identity, with greatest amounts lost when toluene was the substrate. Calcite dissolved as a result of CO2 generated during the biodegradation reactions, and empirically calculated dissolution rates varied between 1.9 and 4.0 x 10−9 mmol cm−2 s−1. The calcite dissolution rate was slower than the biodegradation rate, as evidenced by excess generation of CO2 relative to Ca2+ production. The decrease in pH was less in experiments with calcite present than in those with quartz sand present due to buffering by calcite dissolution. Dissolution of Fe oxyhydroxides was not observed under any experimental conditions.  相似文献   

6.
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.  相似文献   

7.
Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen Methanosarcina barkeri to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H2/CO2, methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H2/CO2 and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7-13% with H2/CO2 as substrate, depending on nontronite concentration (5-10 g/L). The extent was higher when methanol was used as a substrate, reaching 25-33%. Methanogenesis was inhibited by Fe(III) reduction in the H2/CO2 culture, but enhanced when methanol was used. High charge smectite and biogenic silica formed as a result of bioreduction. Our results suggest that methanogens may play an important role in biogeochemical cycling of iron in clay minerals and may have important implications for the global methane budget.  相似文献   

8.
In many anoxic environments propionate is, after acetate, the second most important fermentation product, being degraded further to finally result in CH4 production. In principle, isotope discrimination can be used to assess the path of organic matter degradation to acetate, CO2 and CH4. However, nothing is known about the isotope fractionation in primary and secondary fermentation steps involving propionate, although it is an important precursor of acetate. We therefore studied the degradation of propionate with a syntrophic coculture of Syntrophobacter fumaroxidans and Methanobacterium formicicum. The isotope enrichment factor for propionate degradation to acetate, CO2 and CH4 was almost negligible (εprop 0.9‰). The fermentative production of propionate was studied in cultures with Opitutus terrae growing on pectin, xylan and starch. These polysaccharides were fermented to acetate, succinate, propionate, H2 and CO2. While the δ13C value of the initially produced propionate was similar to that of the organic substrates (ca. −28 to −25‰), the δ13C value of the other fermentation products was higher. The δ13C values of all products generally decreased during the course of fermentation. Finally, a small depletion in 13C (ca. 6‰) with respect to the organic substrate was observed for propionate, while the other fermentation products where slightly enriched. Overall, stable carbon isotope discrimination was small during both fermentative production and consumption of propionate in the anaerobic microbial cultures, so that propionate turnover probably only marginally affects isotope fractionation during anaerobic degradation of organic matter.  相似文献   

9.
Rates of sulfate reduction were measured over a 3 year period in the anoxic nearshore sediments of Cape Lookout Bight, North Carolina, using both a tube incubation method and a 35S-sulfate direct injection technique. The methods yielded similar depth-integrated rates over the upper 30 cm ranging from less than 10 mol SO=4 · m−2 · y−1 in winter to greater than 50 mol SO=4 · m−2 · y−1 in summer. There were also seasonal changes in the Arrhenius activation energies for the sulfate reduction rates indicating that the assumption that Ea is constant with temperature is not always valid. The time averaged annual turnover rate for all three years was 20.4 (±11.4) mol SO=4 · m−2 · y−1. Surface rates ranged seasonally from less than 0.01 to over 3 mM SO=4 · d−1 between winter and summer, respectively. A subsurface rate maximum was observed to develop during the summer months which accounted for 28 percent of the annual depth integrated sulfate reduction rate. Subsurface rate maxima are the result of changes in the chemistry (substrate type and/or concentration) and the microbiology in the sediments. The possibility of the subsurface maximum being an artifact of the 35S method is also discussed. However, the sulfate reduction rates compare well with previous measurements of the carbon sediment-water plus burial fluxes and with a depth integrated CO2 production rate modelled from a ΣCO2 concentration profile from the same site.  相似文献   

10.
Highly negative δC13 values, ?18 to ? 40%., for carbonate cements found in Recent barrier and beach sands of the Mississippi River Delta complex strongly suggest that considerable carbon is furnished to the CaCO3 cements by either chemical or biological oxidation of CH4. These cemented sands are commonly found on beaches of the Chandeleur barrier island chain and other sites along the Louisiana coast where Holocene sands are rapidly transgressing over highly organic marsh deposits. Generation of CH4 from underlying anoxic marsh sediments, followed by vertical migration and oxidation to CO2 in the porous overlying sand, appears to be the unique set of conditions regulating this process of carbonate cementation.  相似文献   

11.
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.  相似文献   

12.
Carbonate-rich sediments at shoal to shelf depths (<200 m) represent a major CaCO3 reservoir that can rapidly react to the decreasing saturation state of seawater with respect to carbonate minerals, produced by the increasing partial pressure of atmospheric carbon dioxide (pCO2) and “acidification” of ocean waters. Aragonite is usually the most abundant carbonate mineral in these sediments. However, the second most abundant (typically ∼24 wt%) carbonate mineral is high Mg-calcite (Mg-calcite) whose solubility can exceed that of aragonite making it the “first responder” to the decreasing saturation state of seawater. For the naturally occurring biogenic Mg-calcites, dissolution experiments have been used to predict their “stoichiometric solubilities” as a function of mol% MgCO3. The only valid relationship that one can provisionally use for the metastable stabilities for Mg-calcite based on composition is that for the synthetically produced phases where metastable equilibrium has been achieved from both under- and over-saturation. Biogenic Mg-calcites exhibit a large offset in solubility from that of abiotic Mg-calcite and can also exhibit a wide range of solubilities for biogenic Mg-calcites of similar Mg content. This indicates that factors other than the Mg content can influence the solubility of these mineral phases. Thus, it is necessary to turn to observations of natural sediments where changes in the saturation state of surrounding waters occur in order to determine their likely responses to the changing saturation state in upper oceanic waters brought on by increasing pCO2. In the present study, we investigate the responses of Mg-calcites to rising pCO2 and “ocean acidification” by means of a simple numerical model based on the experimental range of biogenic Mg-calcite solubilities as a function of Mg content in order to bracket the behavior of the most abundant Mg-calcite phases in the natural environment. In addition, observational data from Bermuda and the Great Bahama Bank are also presented in order to project future responses of these minerals. The numerical simulations suggest that Mg-calcite minerals will respond to rising pCO2 by sequential dissolution according to mineral stability, progressively leading to removal of the more soluble phases until the least soluble phases remain. These results are confirmed by laboratory experiments and observations from Bermuda. As a consequence of continuous increases in atmospheric CO2 from burning of fossil fuels, the average composition of contemporary carbonate sediments could change, i.e., the average Mg content in the sediments may slowly decrease. Furthermore, evidence from the Great Bahama Bank indicates that the amount of abiotic carbonate production is likely to decline as pCO2 continues to rise.  相似文献   

13.
It is well known that the incorporation of isotopically light metabolic carbon (CM) significantly affects the stable carbon isotope (δ13C) signal recorded in biogenic carbonates. This can obscure the record of δ13C of seawater dissolved inorganic carbon (δ13CDIC) potentially archived in the shell carbonate. To assess the CM contribution to Mercenaria mercenaria shells collected in North Carolina, USA, we sampled seawater δ13CDIC, tissue, hemolymph and shell δ13C. All shells showed an ontogenic decrease in shell δ13C, with as much as a 4‰ decrease over the lifespan of the clam. There was no apparent ontogenic change in food source indicated by soft tissue δ13C values, therefore a change in the respired δ13C value cannot be the cause of this decrease. Hemolymph δ13C, on the other hand, did exhibit a negative relationship with shell height indicating that respired CO2 does influence the δ13C value of internal fluids and that the amount of respired CO2 is related to the size or age of the bivalve. The percent metabolic C incorporated into the shell (%CM) was significantly higher (up to 37%, with a range from 5% to 37%) than has been found in other bivalve shells, which usually contain less than 10%CM. Interestingly, the hemolymph did contain less than 10%CM, suggesting that complex fractionation might occur between hemolymph and calcifying fluids. Simple shell biometrics explained nearly 60% of the observed variability in %CM, however, this is not robust enough to predict %CM for fossil shells. Thus, the metabolic effect on shell δ13C cannot easily be accounted for to allow reliable δ13CDIC reconstructions. However, there does seem to be a common effect of size, as all sites had indistinguishable slopes between the %CM and shell height (+0.19% per mm of shell height).  相似文献   

14.
This study used a mass-balance simulation approach in conjunction with geochemical, mineralogical, thermodynamic and isotopic constraints, to assess the origins of NaSO4(±HCO3) type groundwater and springwater associated with smectitic sulphide-mineral-bearing unconsolidated surficial sediments and the underlying Paskapoo Formation in south-central Alberta. Results indicate that alteration of albite to kaolinite and alteration of kaolinite to Na-smectite are the primary controls on dissolved Na and SiO2 concentrations in groundwater and springwater. Concentrations of dissolved Ca and Mg are controlled by reactions involving carbonate minerals and possibly cation exchange. Dissolved SO4 is generated primarily through oxidation of pyrite. Most H+ generated by oxidation of pyrite is consumed in aluminosilicate alteration reactions. The carbon isotopic composition of CO2 gas required in mass-balance simulations suggests the presence of an isotopically heterogeneous environment with respect to 13C. This apparent isotopic heterogeneity may result from the presence of varying fractions of atmospheric and microbially respired CO2.  相似文献   

15.
Rates of CO2 emission from bare salt-marsh sediments in areas of short and tall formSpartina alterniflora were measured monthly for 1 yr. Maximum emission rates, as high as 325 ml CO2m?2h?1, were observed during summer months, while minimum rates, 10.2 ml CO2 m?2h?1, were observed during the winter. An exponential function of inverse soil temperature explained most of the seasonal variability, but other factors are involved in regulating CO2 emissions as demonstrated by rates that were higher in spring than in late summer at equivalent temperatures. Annual CO2 emissions from bare sediments were 27.3 and 18.6 mol C m?2 yr?1 in communities of short and tallS. alterniflora, respectively. It was estimated that losses of dissolved inorganic carbon from the turnover of pore water, up to 14.6 mol C m?2 yr?1 at the creek bank (tall,S. alterniflora) site, and diffusion of CO2 from the root system ofS. alterniflora through the culms, 12.3 to 16.2 mol C m?2 yr?1, could also be important pathways of carbon loss from marsh sediments. If the internal flux of CO2 from the root system through the culm is refixed within the leaves, then the observed rate of 9.8 μI CO2 min?1 cm?2 of culm cross sectional area appears to make a small but significant contribution to total photosynthesis.  相似文献   

16.
The natural abundance of radiocarbon (14C) provides unique insight into the source and cycling of sedimentary organic matter. Radiocarbon analysis of bacterial phospholipid lipid fatty acids (PLFAs) in salt-marsh sediments of southeast Georgia (USA)—one heavily contaminated by petroleum residues—was used to assess the fate of petroleum-derived carbon in sediments and incorporation of fossil carbon into microbial biomass. PLFAs that are common components of eubacterial cell membranes (e.g., branched C15 and C17, 10-methyl-C16) were depleted in 14C in the contaminated sediment (mean Δ14C value of +25 ± 19‰ for bacterial PLFAs) relative to PLFAs in uncontaminated “control” sediment (Δ14C = +101 ± 12‰). We suggest that the 14C-depletion in bacterial PLFAs at the contaminated site results from microbial metabolism of petroleum and subsequent incorporation of petroleum-derived carbon into bacterial membrane lipids. A mass balance calculation indicates that 6-10% of the carbon in bacterial PLFAs at the oiled site could derive from petroleum residues. These results demonstrate that even weathered petroleum may contain components of sufficient lability to be a carbon source for biomass production by marsh sediment microorganisms. Furthermore, a small but significant fraction of fossil carbon is assimilated even in the presence of a much larger pool of presumably more-labile and faster-cycling carbon substrates.  相似文献   

17.
Late Devonian (Famennian) marine successions globally are typified by organic-rich black shales deposited in anoxic and euxinic waters and the cessation of shelf carbonate sedimentation. This global ‘carbonate crisis’, known as the Hangenberg Event, coincides with a major extinction of reef-building metazoans and perturbations to the global carbon cycle, evidenced by positive carbon-isotope excursions of up to 4‰. It has been suggested that authigenic carbonate, formed as cements in sedimentary pore spaces during early burial diagenesis, is a significant mass fraction of the total global carbon burial flux, particularly during periods of low oxygen concentration. Because some authigenic carbonate could have originated from remineralization of organic carbon in sediments, it is possible for this reservoir to be isotopically depleted and thereby drive changes in the carbon isotopic composition of seawater. This study presents bulk isotopic and elemental analyses from fine-grained siliciclastics of the Late Devonian–Early Mississippian Bakken Formation (Williston Basin, USA) to assess the volume and isotopic composition of carbonates in these sediments. Carbonate in the Bakken black shales occurs primarily as microscopic disseminated dolomite rhombs and calcite cements that, together, comprise a significant mass-fraction (ca 9%). The elemental composition of the shales is indicative of a dynamic anoxic to sulphidic palaeoenvironment, likely supported by a fluctuating chemocline. Despite forming in an environment favourable to remineralization of organic matter and the precipitation of isotopically depleted authigenic carbonates, the majority of carbon isotope measurements of disseminated carbonate fall between −3‰ and +3‰, with systematically more depleted carbonates in the deeper-water portions of the basin. Thus, although there is evidence for a significant total mass-fraction of carbonate with contribution from remineralized organic matter, Bakken authigenic carbonates suggest that Famennian black shales are unlikely to be sufficiently 13C-depleted relative to water column dissolved inorganic carbon to serve as a major lever on seawater isotopic composition.  相似文献   

18.
Release of CO2 from surface ocean water owing to precipitation of CaCO3 and the imbalance between biological production of organic matter and its respiration, and their net removal from surface water to sedimentary storage was studied by means of a quotient θ = (CO2 flux to the atmosphere)/(CaCO3 precipitated). θ depends not only on water temperature and atmospheric CO2 concentration but also on the CaCO3 and organic carbon masses formed. In CO2 generation by CaCO3 precipitation, θ varies from a fraction of 0.44 to 0.79, increasing with decreasing temperature (25 to 5°C), increasing atmospheric CO2 concentration (195–375 ppmv), and increasing CaCO3 precipitated mass (up to 45% of the initial DIC concentration in surface water). Primary production and net storage of organic carbon counteracts the CO2 production by carbonate precipitation and it results in lower CO2 emissions from the surface layer. When atmospheric CO2 increases due to the ocean-to-atmosphere flux rather than remaining constant, the amount of CO2 transferred is a non-linear function of the surface layer thickness because of the back-pressure of the rising atmospheric CO2. For a surface ocean layer approximated by a 50-m-thick euphotic zone that receives input of inorganic and organic carbon from land, the calculated CO2 flux to the atmosphere is a function of the CaCO3 and Corg net storage rates. In general, the carbonate storage rate has been greater than that of organic carbon. The CO2 flux near the Last Glacial Maximum is 17 to 7×1012 mol/yr (0.2–0.08 Gt C/yr), reflecting the range of organic carbon storage rates in sediments, and for pre-industrial time it is 38–42×1012 mol/yr (0.46–0.50 Gt C/yr). Within the imbalanced global carbon cycle, our estimates indicate that prior to anthropogenic emissions of CO2 to the atmosphere the land organic reservoir was gaining carbon and the surface ocean was losing carbon, calcium, and total alkalinity owing to the CaCO3 storage and consequent emission of CO2. These results are in agreement with the conclusions of a number of other investigators. As the CO2 uptake in mineral weathering is a major flux in the global carbon cycle, the CO2 weathering pathway that originates in the CO2 produced by remineralization of soil humus rather than by direct uptake from the atmosphere may reduce the relatively large imbalances of the atmosphere and land organic reservoir at 102–104-year time scales.  相似文献   

19.
Microbial decomposition of organic matter in recent sediments of the Landsort Deep—an anoxic basin of the central Baltic Sea—resulted in the formation of a characteristic assemblage of authigenic mineral precipitates of carbonates, sulfides. phosphates and amorphous silica, The dominant crystalline phases are a mixed Mn-carbonate [(Mn0.85Ca0.10Mg0.05)CO3]. Mn-sulfide [MnS] and Fecarbonate [FeCO3]. Amorphous Fe-sulfide [FeS]. Mn-phosphate [Mn3(PO4)2] and a mixed Fe-Ca-phosphate [(Fe0.86Ca0.14)3(PO4)2] were identified by their chemical compositions only. The variability in composition of these solid phases and their mode of occurrence as a co-existing assemblage constrains the conditions and solution composition from which they precipitated. Estimates of activities for dissolved Fe. Mn. PO4, CO3 and S in equilibrium with such an assemblage are close to those found in recent anoxic interstitial water-sediment systems. It is important to have detailed knowledge of the composition and stability conditions of these solid precipitates in order to refine stoichiometric models of interstitial nutrient regeneration in anoxic sediments.  相似文献   

20.
Muddy carbonate deposits near the Dry Tortugas, Florida, are characterized by high organic carbon remineralization rates. However, approximately half of the total sedimentary organic matter potentially supporting remineralization is occluded in CaCO3 minerals (intracrystalline). While a portion of nonintracrystalline organic matter appears to cycle rapidly, intracrystalline organic matter has an approximately constant concentration with depth, suggesting that as long as its protective mineral matrix is intact, it is not readily remineralized. Organic matter in excess of intracrystalline organic matter that is preserved may have a variety of mineral associations (e.g., intercrystalline, adsorbed or detrital). In surface sediment, aspartic acid contributed ∼22 mole % and ∼50 mole % to nonintracrystalline and intracrystalline pools, respectively. In deeper sediment (1.6-1.7m), the composition of hydrolyzable amino acids in both pools was similar (aspartic acid ∼40 mole %). Like amino acids, intracrystalline and nonintracrystalline fatty acids have different compositions in surface sediments, but are indistinguishable at depth. These data suggest that preserved organic matter in the nonintracrystalline pool is stabilized by its interactions with CaCO3. Neutral lipids are present in very low abundances in the intracrystalline pool and are extensively degraded in both the intracrystalline and nonintracrystalline pools, suggesting that mineral interactions do not protect these compounds from degradation. The presence of chlorophyll-a, but absence of phytol, in the intracrystalline lipid pool demonstrates that chloropigments are present only in the nonintracrystalline pool. Sedimentary chloropigments decrease with depth at similar rates in Dry Tortugas sediments as found in alumino-silicate sediments from the Long Island Sound, suggesting that chloropigment degradation is largely unaffected by mineral interactions. Overall, however, inclusion and protection of organic matter by biominerals is a major pathway for organic matter preservation in this low-organic carbon, biomineral-rich regime.  相似文献   

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