首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 937 毫秒
1.
A multi-method approach was applied to study changes in dissolved organic matter (DOM) at three estuarine sites with varying salinity, as well as changes resulting from experimental photodegradation. Following measurement of ultraviolet and visible absorption spectra of bulk samples, DOM was isolated using C18 solid phase extraction. The extract was characterized using high performance size exclusion chromatography (HP-SEC) and molecular level characterization was conducted via direct temperature-resolved mass spectrometry (DT-MS) and electrospray ionization mass spectrometry (ESI-MS). The molecular weight distribution of DOM as determined from HP-SEC and ESI-MS varied between techniques, but generally decreased down estuary and with photodegradation for both approaches. Relative differences in molecular weight were significantly correlated with the ratio of absorption coefficients at 254/365 nm. Additionally, photobleaching was significantly correlated with mass spectral characteristics from both DT-MS and ESI-MS. Principal component analysis of DT-MS spectra showed that photoexposure removed different mass spectral characteristics depending on sampling site; however, upon photodegradation, the mass spectral characteristics of both marine DOM and terrestrially dominated DOM approached a common spectrum. We interpret this spectrum, characterized by fragments from aromatic and carbohydrate-like precursors, as photochemically refractory DOM. Our results show that multiple approaches that characterize different aspects of DOM can provide complementary information about its sources and transformation. More specifically, photobleaching results in decreased light absorbance, decreased molecular weight and shifts in the relative abundance of classes of compounds (and broad shifts in m/z values); moreover, these transformations result in photodegraded samples from a low-salinity site which are compositionally similar to samples collected from a mid-salinity site further downstream.  相似文献   

2.
The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.  相似文献   

3.
Aureococcus anophagefferens, the pelagophyte responsible for brown tide blooms, occurs in coastal bays along the northeast coast of the United States. This species was identified in Chincoteague Bay, Maryland, in 1997 and has bloomed there since at least 1998. Time series of dissolved organic matter (DOM) concentrations and characteristics are presented for two sites in Chincoteague Bay: one that experienced a brown tide bloom in 2002 and one that did not. Characteristics of the bulk DOM pool were obtained using dissolved organic carbon (DOC) and ultraviolet-visible (UV-Vis) measurements (spectral slope and specific UV absorbance). High molecular weight DOM (HMW-DOM) was characterized in terms of DOC concentration, carbon: nitrogen (C:N) ratio, isotopic signature, and molecular-level characteristics as determined by direct temperature resolved mass spectrometry (DT-MS). Compositional changes in the DOM pool are associated with brown tide blooms, although a direct relationship between DOM characteristics and bloom development could not be confirmed. DOC measurements suggest that during the brown tide bloom, HMW-DOM was released into the surface water. UV-Vis analysis on the bulk DOM and molecular-level characterization of the HMW-DOM using DT-MS show that this material was optically active and more aromatic in nature. Based upon C:N ratio and HMW-DOC measurements, it appears that this HMW-DOM was more nitrogen enriched. Whether this material was released as exudates or was due to lysis ofA. anophagefferens could not be determined.  相似文献   

4.
In this work, we use Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (13C NMR) data to quantify the changes of major chemical compound classes (carboxylic acid, amide, ester, aliphatic, aromatic and carbohydrate) in high molecular weight (HMW, >1 kDa) dissolved organic matter (DOM) isolated along a transect through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that carboxylic acids and aromatic compounds are lost along the transect, while HMW DOC becomes enriched in carbohydrate moieties that could have a mid-transect source, perhaps the intensive red tide bloom (Choclodinium polykrikoides) which occurred during our sampling period. Taking the second derivative of the FTIR spectra resolved three pools of de-protonated carboxylic acids at our Dismal Swamp site (used to represent terrestrial organic matter in this area): one carboxylic acid pool, complexed with iron, seems to be lost between the Dismal Swamp and river sites; the second appears biogeochemically active throughout the riverine transect, disappearing in the coastal ocean sample; the third seems refractory, with the potential to be transported to and to accumulate within the open ocean. Five-member ring esters (γ-lactones) were the major ester form in the Dismal Swamp; aliphatic and acetate esters were the dominant esters in the estuary/marine DOM. No amide groups were detectable in Dismal Swamp DOM; secondary amides were present at the estuarine/marine sites. Coupling FTIR with 13C NMR provides new insights into the biogeochemical roles of carboxylic acid, amide and ester compounds in aquatic ecosystems.  相似文献   

5.
Microbial decomposition experiments were used to characterize changes in the amino acid and amino sugar yields and compositions of natural marine substrates during early diagenesis in seawater. On average, 63% of added carbon and 68% of added nitrogen were removed within the first 30 days of decomposition. In all cases, amino acid utilization accounted for a substantial fraction of the removed C and N. Carbon-normalized amino acid yields decreased to less than 50% of their starting values and most of this change occurred within the first 10 days of decomposition. Increases in the concentrations of amino sugars and decreases in the GlcN:GalN ratio in particulate organic matter (POM) illustrated the significance of microbial production during the decomposition of added substrates. Changes in the mol % composition of amino acids during early diagenesis were substantial but highly variable with substrate. Previous survey data collected from the same region were used in conjunction with the experimental data to investigate the utility of several established amino acid-based indices of organic matter diagenesis. This comparison showed that a combination of these degradation indexes is most effective for describing the diagenetic state of dissolved organic matter (DOM). Carbon-normalized amino acid yields were found to be the most effective indicator for early diagenesis. Relative abundances of amino acids were effective indicators of intermediate stages of diagenesis and the mol % composition of the non-protein amino acid γ-Aba (γ-aminobutyric acid) was an effective indicator of advanced DOM diagenesis.  相似文献   

6.
The coupled reverse osmosis-electrodialysis (RO/ED) method was used to isolate dissolved organic matter (DOM) from 16 seawater samples. The average yield of organic carbon was 75 ± 12%, which is consistently greater than the yields of organic carbon that have been commonly achieved using XAD resins, C18 adsorbents, and cross-flow ultrafiltration. UV-visible absorbance spectra and molar C/N ratios of isolated samples were consistent with the corresponding properties of DOM in the original seawater samples, indicating that DOM samples can be isolated using the coupled RO/ED method without any bias for/against these two properties. Five of the samples were desalted sufficiently that reliable measurements of their 13C and 1HNMR spectra and their Fourier transform ion cyclotron resonance (FTICR) mass spectra could be obtained. The 13C and 1HNMR spectra of RO/ED samples differed distinctly from those of samples that have been isolated in much lower yields by other methods. In particular, RO/ED samples contained a relatively lower proportion of carbohydrate carbon and a relatively greater proportion of alkyl carbon than samples that have been isolated using cross-flow ultrafiltration. From the FTICR mass spectra of RO/ED samples, samples from the open ocean contained a much lower proportion of unsaturated compounds and a much higher proportion of fatty acids than coastal samples.  相似文献   

7.
Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO2) and m/z 18 (H2O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ13C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.  相似文献   

8.
Forty-nine aragonitic and calcitic shells from 14 species of marine tropical molluscs (Bivalvia, Gastropoda, Polyplacophora) and ambient waters from Martinique have been analyzed for their carbon and oxygen isotope compositions. Mineralogy of shells was systematically determined by Raman spectroscopy that reveals composite shell structures and early processes of diagenetic alteration. In mangrove, brackish waters result from the mixing between 89±1% of seawater and 11±1% of freshwater, a hydrological budget quantified by both oxygen isotope and salinity mass balance calculations. Mollusc shells from the mangrove environment (S=31‰; δ18O=0.5‰) are characterized by mean δ13C values (−1.2‰) lower than those (+2.6‰) living in the open sea (S=35‰; δ18O=1‰). These low carbon isotope compositions result from the oxidation of organic matter into bicarbonate ions used in the building of mollusc shells. The oxygen isotope compositions of the studied mollusc species are mainly controlled by the temperature and composition of seawater whereas the role of the so-called “vital effects” is negligible. Contrasting with carbon isotopes, variability in the δ18O values among and within species of mollusc shells is very low (1σ=0.15) for a given littoral environment. Using ambient temperatures of seawater (28-30 °C), oxygen isotope fractionations between all studied living species and environmental waters match those extrapolated from the fractionation equation established for molluscs by Grossman and Ku [Chem. Geol., Isot. Geosci. Sect. 59 (1986) 59] in the range 3-20 °C. By analyzing calcite and aragonite layers from the same shell or by comparing shells from different species living in the same environment, there is no evidence that oxygen isotope fractionation between aragonite and water differs from that between calcite and water. On the basis of these results, we conclude that the oxygen isotope compositions of shells from most fossil mollusc species are suitable to estimate past seawater temperatures at any paleolatitude.  相似文献   

9.
The high molecular weight fraction of dissolved organic matter in a suite of lakes, rivers, seawater, and marine sediment interstitial water samples was collected by ultrafiltration and characterized by molecular level and spectroscopic techniques. Proton nuclear magnetic resonance spectra of all samples show a high degree of similarity, with major contributions from carbohydrates, bound acetate, and lipids. Molecular level analyses of neutral sugars show seven monosaccharides, rhamnose, fucose, arabinose, xylose, mannose, glucose, and galactose, to be abundant, and to occur in comparable relative amounts in each sample. Previous studies have emphasized the distinctive composition of dissolved humic substances in fresh and marine waters, and have attributed these differences to sources and transformations of organic matter unique to each environment. In contrast we find a large fraction of freshwater high molecular weight dissolved organic matter (HMWDOM; > 1kD) to be indistinguishable from marine HMWDOM in bulk and molecular-level chemical properties. Aquatic HMWDOM is similar in chemical composition to biologically derived acylated heteropolysaccharides isolated from marine algal cultures, suggesting a biological source for some fraction of persistent HMWDOM. High molecular weight DOC contributes 51 ± 26% of the total DOC, and monosaccharides 18 ± 8% of the total HMWDOC in our freshwater samples. These contributions are on average higher and more variable, but not significantly different than for surface seawater (30% and 16% respectively). Biogeochemical processes that produce, accumulate, and recycle DOM may therefore share important similarities and be broadly comparable across a range of environmental settings.  相似文献   

10.
This study presents magnesium stable-isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species, seawater samples collected from the western Dutch Wadden Sea, and reference materials. The aim of this study is to explore the influence of mineralogy, taxonomy and environmental factors (e.g., seawater isotopic composition, temperature, salinity) on magnesium-isotopic (δ26Mg) ratios of skeletal carbonates. Using high-precision multi-collector inductively coupled plasma mass spectrometry, we observed that the magnesium-isotopic composition of seawater from the semi-enclosed Dutch Wadden Sea is identical to that of open marine seawater. We further found that a considerable component of the observed variability in δ26Mg values of marine skeletal carbonates can be attributed to differences in mineralogy. Furthermore, magnesium-isotope fractionation is species-dependent, with all skeletal carbonates being isotopically lighter than seawater. While δ26Mg values of skeletal aragonite and high-magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences, the δ26Mg values of echinoids, brachiopods and bivalves likely result from a taxon-specific level of control on Mg-isotope incorporation during biocalcification. Moreover, no resolvable salinity and temperature effect were observed for coralline red algae and echinoids. In contrast, Mg-isotope data of bivalves yield ambiguous results, which require further validation. The data presented here, point to a limited use of Mg isotopes as temperature proxy, but highlight the method’s potential as tracer of seawater chemistry through Earth’s history.  相似文献   

11.
Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ11B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ11B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ11B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.  相似文献   

12.
Representative samples of crude oils from Cusiana, Cupiagua, Apiay, Castilla and Chichimene fields in the Eastern Llanos Basin of Colombia were analyzed to determine its compound-specific stable carbon isotope composition (CSIA) using gas chromatography–isotopic ratio–mass spectrometry (GC–IRMS). GC–IRMS analyses of n-alkanes allowed differentiating between Cretaceous and Cretaceous/Tertiary oil samples. Cretaceous sourced samples have δ13C-enriched values than Cretaceous/Tertiary sourced samples; the heavier isotope composition of these samples is due to their major terrigenous organic matter input. Their isotope distribution patterns suggest significant algal and/or bacterial contribution (marine origin). The analysis of the n-alkane fractions by GC–IRMS confirms that the organic matter has marine origin in those samples from Cusiana, Cupiagua and Apiay while Castilla and Chichimene have marine origin with terrestrial inputs. The results were confirmed by gas chromatography/FID and gas chromatography/mass spectrometry (GC/MS). Basic geochemical composition show that samples from Cupiagua/Cusiana fields and Apiay/Castilla/Chichimene fields in the Llanos basin, Colombia present different characteristics reflecting a specific for each depositional environment.  相似文献   

13.
The calcium-isotope composition (δ44/42Ca) was analyzed in modern, Cretaceous and Carboniferous marine skeletal carbonates as well as in bioclasts, non-skeletal components, and diagenetic cements of Cretaceous and Carboniferous limestones. In order to gain insight in Ca2+aq-CaCO3-isotope fractionation mechanisms in marine carbonates, splits of samples were analyzed for Sr, Mg, Fe, and Mn concentrations and for their oxygen and carbon isotopic composition. Biological carbonates generally have lower δ44/42Ca values than inorganic marine cements, and there appears to be no fractionation between seawater and marine inorganic calcite. A kinetic isotope effect related to precipitation rate is considered to control the overall discrimination against 44Ca in biological carbonates when compared to inorganic precipitates. This is supported by a well-defined correlation of the δ44/42Ca values with Sr concentrations in Cretaceous limestones that contain biological carbonates at various stages of marine diagenetic alteration. No significant temperature dependence of Ca-isotope fractionation was found in shells of Cretaceous rudist bivalves that have recorded large seasonal temperature variations as derived from δ18O values and Mg concentrations. The reconstruction of secular variations in the δ44/42Ca value of seawater from well preserved skeletal calcite is compromised by a broad range of variation found in both modern and Cretaceous biological carbonates, independent of chemical composition or mineralogy. Despite these variations that may be due to still unidentified biological fractionation mechanisms, the δ44/42Ca values of Cretaceous skeletal calcite suggest that the δ44/42Ca value of Cretaceous seawater was 0.3-0.4‰ lower than that of the modern ocean.  相似文献   

14.
In recent decades, tangential-flow ultrafiltration (UF) technology has become a primary tool for isolating large amounts of “ultrafiltered” marine dissolved organic carbon (UDOC; 0.1 μm to ∼1 nm) for the detailed characterization of DOC chemical composition and radiocarbon (Δ14C) signatures. However, while total DOC Δ14C values are generally thought to be quite similar in the world ocean, previous studies have reported widely different Δ14C values for UDOC, even from very similar ocean regions, raising questions about the relative “reactivity” of high molecular weight (HMW) DOC. Specifically, to what degree do variations in DOM molecular weight (MW) vs. composition alter its relative persistence, and therefore HMW DOC Δ14C values?In this study we evaluate the effects of varying proportions of HMW vs. low molecular weight (LMW) DOC on UDOC Δ14C values. Using concentration factor (CF) as a proxy for MW distributions, we modeled the retention of both OC and Δ14C in several very large CF experiments (CF >3000), from three depths (20, 670, and 915 m) in the North Pacific Subtropical Gyre (NPSG). The resulting DOC and Δ14C UF permeation coefficients generally increase with depth, consistent with mass balance trends, indicating very significant permeation of LMW, 14C-depleted DOC at depth, and higher recoveries of Δ14C-enriched, HMW DOC in the surface. In addition, changes in CF during sample concentration and ionic strength during sample diafiltration had very large and predictable impacts on UDOC Δ14C values.Together these results suggest that previously reported disparities in UDOC Δ14C values are reconciled by linked trends of Δ14C content vs. MW. At low CFs, UDOC samples have similar Δ14C values to total DOC. In contrast, UDOC samples collected at extremely high CFs (and after diafiltration) have more positive Δ14C values. We demonstrate that the observed relationships between UDOC Δ14C and CF derived from our data can directly explain offsets in all previously published UDOC Δ14C values for the NPSG. While CF is not traditionally considered in UF studies, our results indicate it can substantially influence the interpretation of UDOC 14C “age”, and thus reactivity, in the marine environment. In addition, our results indicate that CF can in fact be used as a proxy for average MW. We suggest that a variable-CF-UF approach, coupled with molecular-level Δ14C analyses, presents a new tool for studying relationships between molecular size, age, and “labile” DOC distributions in the ocean.  相似文献   

15.
The Ca isotope variation of 11 Miocene and Pleistocene, authigenic, marine phosphates is rather small compared to the corresponding variation in δ18O values. The δ44Ca values are not correlated with the δ18O values and, therefore, they are not temperature controlled. It is likely that the δ44Ca values of the phosphorites reflect the variation in the δ44Ca values of paleo-seawater but, in contrast to Sr, not the isotopic composition of seawater itself. Furthermore, Ca and Sr isotopic compositions are decoupled with decreasing stratigraphic age of the phosphate peloids with Sr isotopic compositions changing to more radiogenic values while Ca isotopic compositions remain rather stable. All samples have δ44Ca values below present-day seawater values, suggesting that phosphate formation discriminates against heavy Ca isotopes.Phosphorites and carbonaceous sediments have a similar Ca isotopic variation during the Miocene. A systematic and more or less constant shift between marine carbonates and phosphates is observed: the phosphate samples are slightly less enriched in 40Ca compared to carbonates. This shift has been related to a mineral-dependent kinetic mass fractionation during precipitation from seawater. The rather stable δ44Ca value for the 19 to 9 Ma old phosphorites points to a constant δ44Ca fractionation of about 1.1 between seawater and phosphorites during the past and suggests steady-state conditions for the Mid-Miocene seawater (sedimentation flux equals erosion flux).  相似文献   

16.
The Korneuburg Basin, with mainly upper Lower Miocene (Karpatian) sediment filling, is divided by the Mollmannsdorf–Obergänserndorf Swell into two sub-basins characterised by different environmental settings. Paleoecological data indicate a marine northern part and a mainly estuarine southern part. Nevertheless, short-termed marine ingressions from the north allowed marine faunas (ostracods, molluscs, and echinoids) to temporarily settle the southern part of the basin. The carbon and oxygen isotopic composition of gastropod shells from these different environmental settings were investigated. Highest δ18O and δ13C values are found in Turritella shells from the northern part of the basin, and in Turritella shells from layers interpreted as a marine ingression in the south. Generally, components of the mudflat fauna (Tympanotonos cinctus, Granulolabium bicinctum, Terebralia bidendata, and Ocenebra crassilabiata) have slightly lower isotope values. Considerable freshwater influx in the southern part is documented by abundant freshwater genera such as Melanopsis, which show low carbon and oxygen isotope values. Data of identical taxa, especially Turritella and Granulolabium, reflect a trend from higher isotope values at the marine northern part to slightly lower values in the mainly estuarine southern part of the basin. Differences in δ18O between the marine and the estuarine assemblages are interpreted to be caused by changes in salinity and isotopic composition of ambient water rather than by temperature. Paleotemperature estimates derived from oxygen isotope data are in good agreement with existing paleoclimatic proxies for the Korneuburg Basin. Hence, an annual range of the sea-surface temperature from 13 to 26°C can be predicted within that protected basin.  相似文献   

17.
The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ11B has some limitations such as the knowledge of the fractionation factor (α4-3) between boric acid and the borate ion and the amplitude of “vital effects” on this proxy that are not well constrained. Using secondary ion mass spectrometry (SIMS) we have examined the internal variability of the boron isotope ratio in the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24 ± 0.1 °C) in seawater with pH ranging between 7.90 and 8.45. Intra-shell boron isotopes showed large variability with an upper limit value of ≈30‰. Our results suggest that the fractionation factor α4-3 of 0.97352 (Klochko et al., 2006) is in better agreement with our experiments and with direct pH measurements in seawater vacuoles associated with the biomineralization process in these foraminifera. Despite the large variability of the skeletal pH values in each cultured specimen, it is possible to link the lowest calculated pH values to the experimental culture pH values while the upper pH limit is slightly below 9. This variability can be interpreted as follows: foraminifera variably increase the pH at the biomineralization site to about 9. This increase above ambient seawater pH leads to a range in δ11B (Δ11B) for each seawater pH. This Δ11B is linearly correlated with the culture seawater pH with a slope of −13.1 per pH unit, and is independent of the fractionation factor α4-3, or the δ11Bsw through time. It may also be independent of the pKB (the dissociation constant of boric acid) value. Therefore, Δ11B in foraminifera can potentially reconstruct paleo-pH of seawater.  相似文献   

18.
Dissolved organic matter (DOM) in sediment pore water is a complex molecular mixture reflecting various sources and biogeochemical processes. In order to constrain those sources and processes, molecular variations of pore water DOM in surface sediments from the NW Iberian shelf were analyzed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and compared to river and marine water column DOM. Weighted average molecular element ratios of oxygen to carbon ((O/C)wa) and hydrogen to carbon ((H/C)wa) provided general information about DOM sources. DOM in local rivers was more oxygenated ((O/C)wa 0.52) and contained less hydrogen ((H/C)wa 1.15) than marine pore water DOM (mean (O/C)wa 0.50, mean (H/C)wa 1.26). The relative abundance of specific compound groups, such as highly oxygenated aromatic compounds or nitrogen-bearing compounds with low H/C ratios, correspond to a high concentration of lignin phenols (160 μg/g sediment dry weight) and a high TOC/TN ratio (13.3) in the sedimentary organic matter and were therefore assigned to terrestrial sources. The lower degree of unsaturation and a higher relative abundance of nitrogen-bearing compounds in the pore water DOM reflected microbial activity within the sediment. One sampling site on the shelf with a high sediment accumulation, and a humic-rich river sample showed a wide range of sulfur compounds in the DOM, accompanied by a higher abundance of lipid biomarkers for sulfate-reducing bacteria, probably indicating early diagenetic sulfurization of organic matter.  相似文献   

19.
Brachiopod shells are widely used as an archive to reconstruct elemental and isotopic composition of seawater. Studies, focused on oxygen and carbon isotopes over the last decades, are increasingly extending to the emerging calcium isotope system. To date, only little attention has been paid to test the reliability of fossil brachiopods on their modern counterparts.In this context, the present study investigates two modern brachiopods, Terebratulina septentrionalis (eastern Canada, 5–30 m depth, 7.1 °C seasonal temperature variation, two-layer shell) and Gryphus vitreus (northern Mediterranean, 200 m depth, constant all-year round temperature, three-layer shell). Both species were sampled along the ontogenetic growth direction and calcium, oxygen, and carbon isotopes as well as elemental concentration were measured. Calcium isotopes were analyzed on TIMS. The elemental composition was analyzed by LA-ICP-MS and ICP-AES.The results indicate an intra-specimen δ44/40Ca variation ranging from 0.16 to 0.33‰, pointing to a fairly homogenous distribution of calcium isotopes in brachiopod shells. However, in the light of the suggested 0.7‰ increase in calcium isotopes over the Phanerozoic such intra-specimen variations constrain ocean reconstruction. δ44/40Ca values of T. septentrionalis do not seem to be affected by growth rate. Calcium isotopic values of G. vitreus are heavy in the central part of the shell and trend towards lighter values in peripheral areas approaching the maximum isotopic composition of T. septentrionalis. The maximum inter-species δ44/40Ca difference of 0.62‰ between T. septentrionalis and G. vitreus indicates that care should be taken when using different taxa, species with different strontium content or brachiopods with specialized shell structure, such as G. vitreus, for ocean water reconstruction in terms of Ca isotopic composition. T. septentrionalis may record Ca isotopic fractionation related to seasonal seawater temperature variations in its shell but this is difficult to resolve at the current analytical precision. Average δ18O-derived temperatures of the two investigated species are close to on-site measured temperatures.  相似文献   

20.
《Chemical Geology》2006,225(1-2):61-76
The boron geochemical cycle has been simulated using a time-dependent geochemical box model that was coupled to a one-dimension model of seawater–oceanic crust interactions. Boron elemental and isotopic compositions of oceanic rocks as a function of depth were calculated by mass balance, using the temperature and porosity profiles of the crust as well as the available experimental and empirical distribution coefficients and fractionation factors between mineral and water. Ranges of boron elemental and isotopic variations of seawater were calculated for crust–seawater interactions that take place from the ridge-axis to the off-axis closure of the hydrothermal system. The present-day δ11B of seawater (40‰) could represent a steady-state value. However, depending on crustal permeability, lifetime of water–rock interactions, and expansion rate of the oceanic ridge, the δ11B of seawater may vary from 30‰ to 50‰ at the 10 million year scale.Some boron isotope compositions of Cretaceous biogenic carbonates and ophiolitic serpentinites from Oman are comparable to modern rock samples, suggesting that the δ11B of Cretaceous seawater was close to the present-day value. Low δ11B values of some biogenic carbonates cannot be attributed to low pH values of past seawater, but more probably to δ11B variations of seawater or diagenetic alteration by crustal aqueous fluids. Boron isotope composition of hydrothermally altered serpentines could be considered as a promising proxy of the seawater composition.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号