Sediment Trap Material Research Articles

Stable nitrogen isotopic ratios of sinking particles and sediments from the northern Indian Ocean

δ 15N values in modern sediments of the northern Indian Ocean range from < 4‰ in the northern Bay of Bengal to > 11‰ in the central Arabian Sea due to the strong spatial variability of processes influencing nitrogen cycling in the region. Suboxic conditions in Arabian Sea intermediate water lead to denitrification and accumulation of isotopically enriched nitrate in the water column. Upwelling of this enriched nitrate into the euphotic zone results in high δ 15N values in Arabian Sea particulate matter and surface sediments. δ 15N minima in the northern Bay of Bengal are caused by input of terrestrial organic matter as well as depleted nitrate from rivers. δ 15N is about 8‰ in the equatorial Indian Ocean as the influence of oxygen deficiency and river input ceases. δ 15N of recent sediments correlates with the weighed mean δ 15N of sediment trap material caught 500–1000 m above the sea floor, but with an enrichment of 2–3‰ between deep traps and underlying sediments. Only at two locations characterised by high sedimentation rates, there is no significant offset of δ 15N values between traps and sediments. δ 15N of sediments and trap samples from the Arabian Sea are correlated to the Degradation Index (DI) [Dauwe, B., Middelburg, J.J., Hermann, P.M.J., Heip, C.H.R., 1999. Linking diagenetic alteration of amino acids and bulk organic matter reactivity. Limnology and Oceanography, 44, 1809–1814], an indicator of amino acid degradation intensity, confirming the sensitivity of the δ 15N to degradation. These results have to be considered for the interpretation of the δ 15N record in sediment cores with large variations of diagenetic intensities.

Controversy over the relationship between major components of sediment-trap materials and the bulk distribution coefficients of 230Th, 231Pa, and 10Be

A four-end-member mixing model is introduced to estimate the distribution coefficients of 230Th, 231Pa, and 10Be for pure end members (lithogenic clays, organic carbon, carbonates, and opal) in sediment-trap materials from three oceanic regions. Four pure end members contribute differently to the fractionation of nuclides in three regions. Contribution of organic matter to the bulk distribution coefficients cannot be ignored.

The influence of particle size distribution and composition on seasonal sedimentation rates in a temperate lake

To evaluate the effect of particle size and composition on seasonal changes in the sedimentation rate, suspended and sedimenting particles were collected from Trout Lake, Wisconsin, USA during the 2002 ice-free season. Particles were characterized with regard to particulate biogenic silicon (PBSi) concentration and distribution between four size classes. The concentration of particulate chlorophyll and chlorophyll degradation products was also measured in water column particles and sediment trap material collected during the first half of the sampling period. The highest rates of mass sedimentation during the stratified period were measured in spring and early summer. Seasonal increases in sedimentation are related to the presence of large colonial diatoms in the water column as indicated by elevated PBSi concentrations. The majority of particulate matter in the water column was found in the smallest ( 20 μm). Smaller cells appear to carry out most of the photosynthesis in Trout Lake but larger cells are responsible for seasonal trends in sedimentation. These results may explain how pelagic photosynthesis and sedimentation rates can be quantitatively decoupled across a range of trophic conditions but appear correlated when based on mid-summer measurements.

Interannual variability of deep water particle flux in relation to production and lateral sources in the northeast Atlantic

Results of particle flux studies using sediment traps in the northeast Atlantic Ocean at 33oN, 22oW, a time-series station (L1/K276) operated within the German contribution to the international Joint Global Ocean Flux Study (JGOFS) between summer 1993 and summer 2001, are presented. The particle flux at 2000m depth is highly seasonal with only one main peak in February and March and is characterized by strong interannual variability. The comparison of the particle flux time series with the measurements of chlorophyll and phaeopigments in the sediment trap material, and chlorophyll-a concentrations at surface from SeaWiFS together with the similarity of the pattern observed in the alkenone flux, particulate organic carbon (POC) and calcium carbonate (CaCO3) leads to the conclusion that the particle flux at this position is fast and directly coupled to the phytoplankton development and decay in the overlying euphotic zone. SeaWiFS chlorophyll-a data (1997–2001) and characteristics of the upper water column (mixed layer depth, depth of nitracline, primary production) as predicted by an eddy-permitting model of the North Atlantic coupled with a simple nitrate–phytoplankton–zooplankton–detritus (NPZD) pelagic-ecosystem model are used to understand the observed interannual differences in particle flux at 2000m. Our results suggest that the interannual differences in the observed particle flux are a direct consequence of the variability of phytoplankton biomass and primary production in the euphotic zone in this region.

210Po and 210Pb distributions and residence times in the nearshore region of Lake Superior

The naturally occurring radionuclide, 210Pb, and its decay daughter, 210Po, were measured in the Keweenaw Peninsula region of Lake Superior. Water, suspended particles, sediment trap material (settling particles), and sediment cores and grab samples were collected along three transects that stretched from 1 to 20 km from shore. Departures from secular equilibrium (activity ratio of 210Po:210Pb = 1) were observed for most samples. 210Po‐deficiency was observed in both suspended particles (TSP) with a ratio of 0.43 ± 0.05 (±95% confidence interval (CI)) and settling particles with a ratio of 0.57 ± 0.04; higher ratios in the settling particles resulted from an admixture of resuspended sediments. Ratios in the dissolved phase were 0.45 ± 0.12. Approximately 83% and 85% of total 210Po and 210Pb in the water column was in the particulate phase. No evidence of biological uptake of Po was found. Seasonal and spatial variability in activities and ratios was small. Using steady state solutions to the mass balance equations for both isotopes, similar residence times in the water column were calculated for 210Po and 210Pb (55 ∼ 75 days in a 150‐m‐deep water column). It was possible to calibrate a one‐box model for the paired isotopes so that the model output closely matched rates of sediment and isotope resuspension estimated from sediment traps. However, this calibration required a fractionation of the isotopes during resuspension. The particle settling velocity was estimated to be 2.3 m d−1, which also is in agreement with the estimate (2.4 ± 2.2 m d−1) from sediment traps. These results indicate rapid fluxes of radioisotopes and sediments through the water column largely driven by resuspension of sediments in nearshore areas.

Reconstructing export production at the NE Atlantic margin: potential and limits of the Ba proxy

Barium (Ba), aluminium (Al), and zirconium (Zr) were measured in sediment trap material deployed at two margin settings of the NE Atlantic: the Bay of Biscaye at Goban Spur and the NW Iberian Margin. The Particulate Organic Carbon (POC)/Ba ratios of the trapped material in both margin environments are clearly higher compared to the open ocean. Although lateral advection of POC may partly explain these higher POC/Ba ratios for margin systems, it is clear that the yield of authigenic particulate Ba during organic matter degradation in the water column is lower in margin environments. In order to assess export production in margin settings we optimised transfer functions based on trapped Ba fluxes that were originally elaborated for open ocean settings. Calculations of export production based on trapped Ba flux and POC/Ba ratio were compared with calculations based on trapped POC flux only. Export production based on Ba flux show greater internal consistency amongst traps along the same mooring, suggesting that this approach has advantages over the one based on POC flux only. Estimated export productions are of the same order of magnitude as estimates of new production, but systematically fall short of the latter. This systematic discrepancy needs further investigation.

Sediment Trap Studies in Lake Superior: Insights into Resuspension, Cross-margin Transport, and Carbon Cycling

As part of the Keweenaw Interdisciplinary Transport Experiment in Lake Superior (KITES) project, sediment traps were deployed at multiple locations along the northern coast of the Keweenaw Peninsula in Lake Superior. Traps were deployed at multiple depths (25 m below water surface to 5 m above sediments) at varying distances from shore (0.5–21 km) during the months May-October over a 3-year period. Material captured in the sediment traps was analyzed for total carbon (C), total nitrogen (N), total phosphorus (P), total copper (Cu), 210Pb, and stable isotope ratios of C and N. Copper in sediment trap material, a tracer for mine residues, indicated transport of material in both directions along the peninsula. Cross-margin transport of material occurred at all trap locations along the coast and in all seasons. The most significant finding was that sediment traps suspended just below the thermocline collected large amounts of resuspended sediments even when the trap was moored in 120–220 m of water (9–21 km from shore). Estimates of the contribution to settling fluxes of organic carbon from resuspended sediments ranged from 10–30% in offshore traps; estimates based on 210Pb agreed well with estimates based on a carbon mixing model. Element ratios suggest that resuspended material in offshore traps originated in near-shore regions. Despite the strong influence of resuspension on the composition of sedimenting material, stable isotope ratios were controlled by processes occurring in the water column. Seasonal variations in isotope ratios may reflect seasonal shifts between predominance by autotrophic and heterotrophic processes in the water column.

Biochemical characteristics of settling particulate organic matter at two north-western Mediterranean sites: a seasonal comparison

Gross sedimentation rates (GSR) and the main biochemical characteristics of settling particulate matter were monitored at two NW Mediterranean sites (the Bay of Banyuls-sur-Mer, France, and the Medes Islands, Spain) throughout a year to assess possible differences in particulate organic matter (POM) availability to the benthic community. A similar seasonal pattern was observed at both sites with higher organic contents and lower GSR during the spring–summer than during the autumn–winter period. At both sites, there was a negative correlation between GSR and sediment trap organic contents, which is indicative of the importance of resuspension in driving GSR. Along the same line, GSR in Medes correlated positively with wave height. The principal component analysis based on GSR and biochemical characteristics of sediment trap material always segregated samples from the two studied sites mostly due to the occurrence of higher lipid and lower carbohydrate contents in Medes. These differences were indicative of the presence of more labile settling POM in the Medes Islands. They were more pronounced during the spring–summer than during the autumn–winter period. Such a pattern may reflect differences in the sensitivity of the two studied sites to resuspension. According to this interpretation, between-sites differences would be high when resuspension is low (i.e. during the spring–summer period when resuspension would mainly affect Banyuls) and become low when resuspension is high (autumn–winter period when resuspension would affect both sites).

Does 234Th/238U disequilibrium provide an accurate record of the export flux of particulate organic carbon from the upper ocean?

The magnitude of the flux of biogenic particulate organic carbon (POC) exported from the surface waters of the world ocean and remineralized at depth is critical to constraining models of the global carbon cycle, yet remains controversial. The use of upper ocean sediment traps is still one of the primary tools for determining this export flux, although trap fluxes have been shown to vary significantly because of hydrodynamic and sample collection biases. Over the past decade, 234Th increasingly has been used as a tracer to estimate POC export from the euphotic zone by multiplying the depth‐integrated 234Th flux by the POC/234Th ratio of sinking particles. The accuracy of this technique is highly dependent on the natural variability in the POC/234Th ratio and 234Th flux, yet the significance of this variability to estimates of POC export remains uncertain. Based on an analysis of new 234Th and POC data from the Labrador Sea and a review of 25 previous independent field studies, we report that POC export fluxes can vary 2–10 times or more solely because of variability in the POC/234Th ratio and procedures used to estimate the 234Th flux. Recommended improvements include studies of the biological, chemical, and physical mechanisms controlling 234Th‐organic matter interactions in seawater; detailed comparisons of POC/234Th ratios in size‐fractionated and sediment trap material; increased spatial and temporal sampling density of234Th; and more standardized procedures to calculate the 234Th export flux.

Dissolved and particulate 231Pa and 230Th in the Atlantic Ocean: constraints on intermediate/deep water age, boundary scavenging, and 231Pa/230Th fractionation

231Pa and 230Th concentrations were determined in filtered seawater and suspended particulate matter collected from the Labrador Sea and the Equatorial and South Atlantic to constrain their application as tracers of intermediate/deep water age and Atlantic thermohaline circulation. Distributions of total 231Pa and 230Th indicate the influence of recently formed North Atlantic Deep Water, as evidenced by nearly invariant concentrations below ∼1000 m in the Labrador Sea and increasing 231Pa and 230Th concentrations as deep waters progress southward from northern source regions. Application of a scavenging–mixing model to both tracer distributions indicates an intermediate/deep water age of 12 yr in the Labrador Sea and a ∼30–140 yr transit time to the low-latitude stations. We attribute a striking increase in total 230Th in the Labrador Sea from 1993 to 1999 to aging of intermediate waters as a consequence of the cessation of deep convection in the Labrador Sea since 1993. The temporal change in the 230Th age of these waters is consistent with the 6 yr time interval between the observations. The average particulate 231Pa/230Th activity ratio in the Labrador Sea and low-latitude deep waters is 0.057±0.003, significantly below the 231Pa/230Th production ratio (0.093) and in agreement with excess 231Pa/230Th ratios in Holocene sediments (0.060±0.004) and sediment trap material (0.034±0.012) from the Atlantic and model simulations. This observation is consistent with the southward transport of deep water strongly attenuating boundary scavenging in the Atlantic. A latitudinal dependence in particle fractionation of these tracers is also evident, with elevated fractionation factors (FTh/Pa) observed near the Equator and South Atlantic gyre (∼11) compared to low values in the Labrador Sea (∼3) and Southern Ocean (∼2). There also exists a depth dependence in FTh/Pa, characterized by low values in surface waters, a broad mid-depth maximum, and decreasing values towards the sea-floor. The latitudinal and depth variations in FTh/Pa are suggested to reflect differences in the chemical composition of marine particles.

Calibration of sediment traps and particulate organic carbon export using 234 Th in the Barents Sea

Profiles of particulate and dissolved 234Th (t1/2=24.1 days) in seawater and particulate 234Th collected in drifting traps were analyzed in the Barents Sea at five stations during the ALV3 cruise (from June 28 to July 12, 1999) along a transect from 78°15′N–34°09′E to 73°49′N–31°43′E. 234Th/238U disequilibrium was observed at all locations. 234Th data measured in suspended and trapped particles were used to calibrate the catchment efficiency of the sediment traps. Model-derived 234Th fluxes were similar to 234Th fluxes measured in sediment traps based on a steady-state 234Th model. This suggests that the sediment traps were not subject to large trapping efficiency problems (collection efficiency ranges from 70% to 100% for four traps). The export flux of particulate organic carbon (POC) can be calculated from the model-derived export flux of 234Th and the POC/234Th ratio. POC/234Th ratios measured in suspended and trapped particles were very different (52.0±9.9 and 5.3±2.2 μmol dpm−1, respectively). The agreement between calculated and measured POC fluxes when the POC/234Th ratio of trapped particles was used confirms that the POC/234Th ratio in trap particles is representative of sinking particles. Large discrepancies were observed between calculated and measured POC fluxes when the POC/234Th ratio of suspended particles was used. In the Barents Sea, vertical POC fluxes are higher than POC fluxes estimated in the central Arctic Ocean and the Beaufort Sea and lower than those calculated in the Northeast Water Polynya and the Chukchi Sea. We suggest that the latter fluxes may have been strongly overestimated, because they were based on high POC/234Th ratios measured on suspended particles. It seems that POC fluxes cannot be reliably derived from thorium budgets without measuring the POC/234Th ratio of sediment trap material or of large filtered particles.

The importance of water column processes on the dissolution properties of biogenic silica in deep-sea sediments I. Solubility

Flow-through experiments have been performed to study the thermodynamics of biogenic silica (opal) dissolution in deep-sea sediments. They were applied for the first time on sediment from the Southern Ocean (Van Cappellen and Qiu, 1997a,b). We have extended the use of these experiments to other deep-sea settings, thereby covering a wide range of in situ silicic acid asymptotic concentrations (C asympt; 200 to 900 μmol/L) and biogenic opal content (BSi; 0.5 to 80%). Performing these experiments under in situ bottom temperatures allows for the comparison between experimental apparent solubilities and C asympt concentrations. Low values of BSi apparent solubilities have been measured in the deepest sections of the multicores collected in the northeast Atlantic (229 μmol/L) and in the equatorial Pacific (505 μmol/L). They are only 10 to 20% higher than the in situ C asympt concentrations. This demonstrates a clear control of pore water silicic acid concentrations by the in situ apparent solubility of the BSi, i.e., the solubility of BSi within a complex sedimentary matrix that includes important quantities of silicate minerals. In regions where the percentage detrital/percentage biogenic ratio is low, the apparent solubility of the biogenic silica is close to that of in situ biogenic silica. In the opposite case, when the percentage detrital/percentage biogenic ratio is high, reprecipitation reactions induce strong interference on the dissolution properties of the opal, both in situ and in flow-through experiments. In such a sedimentary matrix, it is important to determine the appropriate opal solubility to be used in early diagenetic models, i.e., the solubility of the biogenic silica just before deposition on the seabed. This has been achieved by performing flow-through experiments on sediment trap material from the north Atlantic site. Comparison of apparent biogenic silica solubility measured by flow-through experiments and the silicic acid concentrations measured in the cups of the sediment traps suggested that the solubility of biogenic silica that reaches the sediment-water interface is not unique and varies spatially and temporally. In fact, it is the degree of coupling between surface waters and the sediment-water interface that will control the aging of biogenic silica in the water column and hence the dissolution properties of the biogenic silica deposited at the sediment-water interface. All these results call for a strong improvement of biogenic silica early diagenetic models that should include not only a reprecipitation term that takes into account interaction with silicate minerals but also the existence of several phases of biogenic silica and thus that should operate in a non-steady-state mode to account for seasonal variations in the quality of deposited biogenic silica.

Production of calcareous dinoflagellate cysts in response to monsoon forcing off Somalia: a sediment trap study

To study the ecology of calcareous dinoflagellates we examined the impact of the SW and NE monsoons on cyst formation using sediment trap material, collected at 1032 m water depth, off Somalia from June 1992 to February 1993. The results do not confirm the relationship between cyst production and lower nutrient concentrations, as highest cyst fluxes were recorded during late SW monsoon under the relatively nutrient-rich and less agitated conditions of mature upwelled water. Lowest cyst fluxes were found under strongly stratified, nutrient-depleted surface waters during the inter-monsoon. Although all of the studied species seem to prefer a stratified water column, an elevated concentration of nutrients appears to be necessary to maintain high cyst production. Comparison of the mean cyst flux to the sediment trap with that into the underlying surface sediments reveals a loss of 81–96%, which can be attributed to calcite dissolution. The relatively small spheres of Thoracosphaera heimii are affected more than the cysts of the other species.

Distribution of Fe, Mn, Cu and Cd in Upper Sediments and Sediment-Trap Material of Ria Formosa (Portugal)

In shallow highly productive coastal environments intense biogeochemical activity is concentrated in the upper sediment layers. However, pore water composition of permeable inter-tidal sediments change as water flows over the areas during ebb and flood tides. In order to examine metal post-mobilisation, inter-tidal sediment cores of 4 cm length and particles settled in sediment-trap s over several periods during 10 months were collected in Ria Formosa (SW Iberian Peninsula). Concentrations of Al, Fe, Mn, Cu and Cd, loss on ignition and the proportion of fine fraction were determined in sediment layers of 0.5 cm thickness and in sediment-trap material. Levels of Mn in sediments were similar to those in sediment-trap material, although enrichment in the topmost sediment layer (0.1 mm) was observed as MnO 2 is formed. Although Fe in sediments and sediment-trap material ranged within similar intervals, two relationships with Al were found showing that sediment-trap material are impoverished in Fe in comparison to sediments. This suggests that Fe is mainly cycled inside the sediment. Copper and Cd exhibited different patterns. Levels in sediment-trap material were not correlated to Al or LOI, probably due to local contamination or uptake by plankton. These values were lower than levels in the topmost sediment layer , suggesting that Cu and Cd that reach the sediment surface are rapidly released to the water column. Concentrations in sediments, including the topmost layer, exhibited two relationships to Al, for both Cu and Cd. One corresponding to background values and the other found in stations closer to the anthropogenic sources. In these cases Cu and Cd are incorporated into the sediments that is facilitated by AVS values close to the sediment surface. ADDITIONALINDEXWORDS: Surface sediments, heavy metals, geochemistr y, coastal lagoon, Portugal.

Transport and sedimentation of Cu in a microtidal estuary, SE Norway

The transport and sedimentation of copper in the Glomma estuary, SE Norway during a period of 90% reduction in the industrial input of Cu, was studied from sediment trap material and compared to samples of the bottom sediments. Traps were deployed at four stations for several monthly periods during 1990, 1994 and 1995. Trapped material was analysed for suspended particulate matter (SPM), total organic carbon (TOC) and nitrogen (TN), Cu, and Al. Only about 10% of the Cu from the river is trapped in the estuary. Still there was a moderate but significant reduction in Cu concentration in the trap SPM from 1990 to 1994, reflecting the industrial reductions, but only if excluding summer samples apparently influenced by antifouling Cu from boat paint. Settling matter therefore seems appropriate and sensitive for monitoring changes in the Cu load. The results supported the view that TOC is the main carrier of Cu to the sediments.

Dissolution kinetics of biogenic silica from the water column to the sediments

Stirred flow-through experiments were conducted for the first time with planktonic biogenic silica (BSi). We investigated the dissolution kinetics of uncleaned and chemically cleaned BSi collected in ocean surface water, sediment traps, and sediments from the Norwegian Sea, the Southern Ocean, and the Arabian Sea. The solubility at 2°C is rather constant (1000 to 1200 μM). The dissolution rates are, however, highly variable, declining with water depth, and phytoplankton reactivity is two to three orders of magnitude higher than pure siliceous oozes. The reactivity decrease correlates well with an increase in the integrated peak intensity ratios of Si-O-Si/Si-OH measured by Fourier transform infrared (FTIR) spectroscopy. The removal of organic or inorganic coatings enhance the reactivity by at least an order of magnitude. Atomic Al/Si ratios of 0.03 to 0.08 in sedimentary diatom frustules decrease significantly to 0.02 as a result of removal of inorganic coatings and detritals present. Near equilibrium, the dissolution rates exhibit a linear dependence on the degree of undersaturation. At higher degrees of undersaturation—that is, at low concentrations of dissolved silica—the dissolution rates of uncleaned samples define a nonlinear trend.The nonlinear kinetics imply that the dissolution of natural BSi is strongly accelerated in silica-depleted surface waters. The FTIR results suggest that internal condensation reactions reduce the amount of surface reaction sites and are partly responsible for the reactivity decrease with depth. The high content of Al in sedimentary BSi is likely caused by precipitation of dissolved silica with Al dissolved from minerals in sediment. Nonbiogenic silica as coatings or detritals are partly responsible for the solubility and reactivity decrease of BSi in sediments. One order of magnitude different rate constants measured in Norwegian Sea and Southern Ocean sediment trap material support the so-called opal paradox—that is, high BSi accumulation rates in sediments in spite of low BSi production rates in surface waters of the Southern Ocean.

The Effect of a Large Resuspension Event in Southern Lake Michigan on the Short-term Cycling of Organic Contaminants

In January and March, 1998, a series of intense, northerly wind-driven storms suspended sediment over the entire coastline of the southern basin of Lake Michigan. The effect of large scale resuspension on organic contaminant cycling was investigated using a two-pronged sample collection strategy that included analysis of settling sediment trap material and discrete air and water samples collected before and after a major resuspension event. It was found that major resuspension events result in a large flux of contaminants. For example, 6.2 ng/cm 2 ΣPCB (sum of 89 congener peaks) and 175 ng/cm 2 ΣPAHs (sum of 31 compounds) fell through the water column in the southern basin between November and May but almost half of that occurred in the month of March after a series of intense storms induced a largescale resuspension event in that month. Assuming the concentration of contaminants in settling sediments is similar throughout the basin, the March event brought ∼400 kg of ΣPCBs and ∼13,000 kg ΣPAHs into the water column. Furthermore, the data indicate that concentrations of dissolved phase ΣPCB and ΣPAHs declined significantly (α = 0.05) after the event and after resuspended sediment had settled from the surface waters. As a result of the depressed dissolved concentrations at the surface, the potential for gas-phase input to the lake increases on the southwestern coastal region near Chicago, IL and Gary, IN. The potential input of gas-phase contaminants was 8 kg for ΣPCBs and 2,200 kg for ΣPAHs over the 40-day lifetime of the near-shore event.

Biogeochemistry of platelet ice: its influence on particle flux under fast ice in the Weddell Sea, Antarctica

An array of four sediment traps and one current meter was deployed under a well-developed platelet layer for 15 days in the Drescher Inlet in the Riiser Larsen ice shelf, in February 1998. Traps were deployed at 10 m (just under the platelet layer), 112 m (above the thermocline), 230 m (below thermocline) and 360 m (close to sea floor). There was a substantial flux of particulate organic material out of the platelet layer, although higher amounts were collected in the traps either side of the thermocline. Material collected was predominantly composed of faecal pellets containing diatom species growing within the platelet layer. The size classes of these pellets suggest they derive from protists grazing rather than from larger metazoans. Sediment trap material was analysed for particulate organic carbon/nitrogen/phosphorus (POC/PON/POP) and δ 13CPOC (carbon isotopic composition of POC). These were compared with organic matter in the overlying platelet layer and the water column. In turn, the biogeochemistry of the platelet layer and water column was investigated and the organic matter characteristics related to inorganic nutrients (nitrate, nitrite, ammonium, silicate, phosphate), dissolved organic carbon/nitrogen (DOC/DON), pH, dissolved inorganic carbon (DIC), oxygen and δ 13 CDIC (carbon isotopic composition dissolved inorganic carbon).

Demineralization of marine and freshwater sediments for CP/MAS 13C NMR analysis

A method was developed to demineralize sediment trap material and marine sediments containing labile organic matter (OM), in preparation for cross polarization and magic angle spinning (CP/MAS) solid-state 13C NMR analysis. Carbonate and silicate minerals were dissolved with HCl and a mixture of dilute HCl/HF, respectively. Demineralization kinetics were assessed for a range of freshwater and marine sediments, as well as pure mineral and organic samples. For samples with a very low organic carbon (OC) concentration (<1 wt.%) and samples containing a large fraction of acid-soluble OC, the organic molecules solubilized during the dissolution of the mineral fraction were recovered by freeze-drying the supernatants following (i) removal of dissolved calcium and residual HF by CaF 2 precipitation, (ii) removal of the dissolved paramagnetic metals by sulfide precipitation, and (iii) desalting using ion retardation chromatography. When applied to a wide range of freshwater and marine particles, demineralization resulted in OC enrichment factors that varied between 2.2 and 20.8, with losses representing less than 20.5% of the initial OC content. X-ray diffraction and fluorescence analysis of the natural and demineralized samples showed that minerals and paramagnetic metals were effectively removed. While molecular fractionation might be substantial when the mineral constituents were dissolved with HCl and HF, the small changes (<11%) in the (C/N) a and (H/C) a ratios when the acid-soluble organic matter was recovered suggest that the molecular composition of the organic fraction was not appreciably altered. In combination with CP/MAS 13C NMR spectroscopy, this demineralization method allows comprehensive elucidation of the chemical structure of total OC, especially in samples with very low OC concentrations and/or with a significant fraction of chemically labile organic compounds.

Oxygen isotopes of marine diatoms and relations to opal-A maturation

In order to develop the potential tool of diatom oxygen isotopes for paleoenvironmental studies we compared oxygen isotopes of natural marine diatoms sampled from ocean surface water, sediment traps and surface sediments with oxygen isotopic fractionations determined for laboratory diatom cultures. Freshly grown natural diatoms (phytoplankton samples and sediment trap material) and cultured diatoms reveal similar oxygen isotope fractionation factors. The fresh diatoms have 3 to 10‰ lower isotope fractionation factors than fossil (sedimentary) diatoms. A temperature-related oxygen isotope fractionation could not be established for the laboratory cultures (and the natural phytoplankton samples), and there is evidence that diatom growth rate until reaching the stationary growth state also controls the measured silica-water oxygen isotope fractionation factor. It is possible, however, that slow diatom growth in sea surface water may well lead to a temperature-dependent silica-water oxygen isotope fractionation which is the prerequisite for a use of diatom oxygen isotopes in paleo-surface water studies. FTIR-spectroscopic analyses of various diatomaceous materials revealed that the ratio of integrated peak intensities for Si-O-Si/Si-OH correlates with the 3 to 10‰ δ 18O silica increase from fresh to fossil diatoms. Open-system (flow-through) silica dissolution experiments suggest that the diatom frustules are isotopically homogenous and that the increase in 18O is therefore not due to dissolution of isotopically light surficial Si-OH groups. It is concluded that slow internal condensation reactions during silica maturation in surface sediments cause both an increase in the intensity ratio of Si-O-Si/Si-OH and the 18O content of framework oxygen. These findings also indicate that the oxygen isotope compositions of marine sediment diatoms do not indicate sea surface water temperature but rather reflect variable 18O contents of surface sediments.