Description: High‐resolution records of opal, carbonate, and terrigenous fluxes have been obtained from a high‐sedimentation rate core (MD84‐527: 43°50′S; 51°19;′E; 3269 m) by normalization to 230Th. This method estimates paleofluxes to the seafloor on a point‐by‐point basis and distinguishes changes in sediment accumulation due to variations in vertical rain rates from those due to changes in syndepositional sediment redistribution by bottom currents. We also measured sediment δ15N to evaluate the changes in nitrate utilization in the overlying surface waters associated with paleoflux variations. Our results show that opal accumulation rates on the seafloor during the Holocene and stage 3, based on 14C dating, were respectively tenfold and fivefold higher than the vertical rain rates, At this particular location, changes in opal accumulation on the seafloor appear to be mainly controlled by sediment redistribution by bottom currents rather than variations in opal fluxes from the overlying water column. Correction for syndepositional sediment redistribution and the improved time resolution that can be achieved by normalization to 230Th disclose important variations in opal rain rates. We found relatively high but variable opal paleoflux during stage 3, with two maxima centered at 36 and 30 kyr B.P., low opal paleoflux during stage 2 and deglaciation and a pronounced maximum during the early Holocene, We interpret this record as reflecting variations in opal production rates associated with climate‐induced latitudinal migration of the southern ocean frontal system. Sediments deposited during periods of high opal paleoflux also have high authigenic U concentrations, suggesting more reducing conditions in the sediment, and high Pa‐231/Th‐230 ratios, suggesting increased scavenging from the water column. Sediment δ15N is circa 1.5 per mil higher during isotopic stage 2 and deglaciation. The low opal rain rates recorded during that period appear to have been associated with increased nitrate depletion. This suggests that opal paleofluxes do not simply reflect latitudinal migration of the frontal system but also changes in the structure of the upper water column. Increased stratification during isotopic stage 2 and deglaciation could have been produced by a meltwater lid, leading to lower nitrate supply rates to surface waters.

Description: Variations in carbonate flux and dissolution, which occurred in the equatorial Atlantic during the last 24,000 years, have been estimated by a new approach that allows the point‐by‐point determination of paleofluxes to the seafloor. An unprecedented time resolution can thus be obtained which allows sequencing of the relatively rapid events occurring during deglaciation. The method is based on observations that the flux of unsupported 230Th into deep‐sea sediments is nearly independent of the total mass flux and is close to the production rate. Thus excess 230Th activity in sediments can be used as a reference against which fluxes of other sedimentary components can be estimated. The study was conducted at two sites (Ceará Rise; western equatorial Atlantic, and Sierra Leone Rise; eastern equatorial Atlantic) in cores raised from three different depths at each site. From measurements of 230Th and CaCO3, changes in carbonate flux with time and depth were obtained. A rapid increase in carbonate production, starting at the onset of deglaciation, was found in both areas. This event may have important implications for the postglacial increase in atmospheric CO2 by increasing the global carbonate carbon to organic carbon rain ratio and decreasing the alkalinity of surface waters (and possibly the North Atlantic Deep Water). Increased carbonate dissolution occurred in the two regions during deglaciation, followed by a minimum during mid‐Holocene and renewed intensification of dissolution in late Holocene. During the last 16,000 years, carbonate dissolution was consistently more pronounced in the western than in the eastern basin, reflecting the influence of Antarctic Bottom Water in the west. This trend was reversed during stage 2, possibly due to the accumulation of metabolic CO2 below the level of the Romanche Fracture Zone in the eastern basin.

Description: Variations in carbonate flux and dissolution, which occurred in the equatorial Atlantic during the last 24,000 years, have been estimated by a new approach that allows the point-by-point determination of paleofluxes to the seafloor. An unprecedented time resolution can thus be obtained which allows sequencing of the relatively rapid events occurring during deglaciation. The method is based on observations that the flux of unsupported 230Th into deep-sea sediments is nearly independent of the total mass flux and is close to the production rate. Thus excess 230Th activity in sediments can be used as a reference against which fluxes of other sedimentary components can be estimated. The study was conducted at two sites (Ceará Rise; western equatorial Atlantic, and Sierra Leone Rise; eastern equatorial Atlantic) in cores raised from three different depths at each site. From measurements of 230Th and CaCO3, changes in carbonate flux with time and depth were obtained. A rapid increase in carbonate production, starting at the onset of deglaciation, was found in both areas. This event may have important implications for the postglacial increase in atmospheric CO2 by increasing the global carbonate carbon to organic carbon rain ratio and decreasing the alkalinity of surface waters (and possibly the North Atlantic Deep Water). Increased carbonate dissolution occurred in the two regions during deglaciation, followed by a minimum during mid-Holocene and renewed intensification of dissolution in late Holocene. During the last 16,000 years, carbonate dissolution was consistently more pronounced in the western than in the eastern basin, reflecting the influence of Antarctic Bottom Water in the west. This trend was reversed during stage 2, possibly due to the accumulation of metabolic CO2 below the level of the Romanche Fracture Zone in the eastern basin.

Description: Over much of the ocean’s surface, productivity and growth are limited by a scarcity of bioavailable nitrogen. Sedimentary δ15N records spanning the last deglaciation suggest marked shifts in the nitrogen cycle during this time, but the quantification of these changes has been hindered by the complexity of nitrogen isotope cycling. Here we present a database of δ15N in sediments throughout the world’s oceans, including 2,329 modern seafloor samples, and 76 timeseries spanning the past 30,000 years. We show that the δ15N values of modern seafloor sediments are consistent with values predicted by our knowledge of nitrogen cycling in the water column. Despite many local deglacial changes, the globally averaged δ15N values of sinking organic matter were similar during the Last Glacial Maximum and Early Holocene. Considering the global isotopic mass balance, we explain these observations with the following deglacial history of nitrogen inventory processes. During the Last Glacial Maximum, the nitrogen cycle was near steady state. During the deglaciation, denitrification in the pelagic water column accelerated. The flooding of continental shelves subsequently increased denitrification at the seafloor, and denitrification reached near steady-state conditions again in the Early Holocene. We use a recent parameterization of seafloor denitrification to estimate a 30–120% increase in benthic denitrification between 15,000 and 8,000 years ago. Based on the similarity of globally averaged δ15N values during the Last Glacial Maximum and Early Holocene, we infer that pelagic denitrification must have increased by a similar amount between the two steady states.

Description: Key Points: Use of sedimentary nitrogen isotopes is examined; On average, sediment 15N/14N increases approx. 2 per mil during early burial; Isotopic alteration scales with water depth Abstract: Nitrogen isotopes are an important tool for evaluating past biogeochemical cycling from the paleoceanographic record. However, bulk sedimentary nitrogen isotope ratios, which can be determined routinely and at minimal cost, may be altered during burial and early sedimentary diagenesis, particularly outside of continental margin settings. The causes and detailed mechanisms of isotopic alteration are still under investigation. Case studies of the Mediterranean and South China Seas underscore the complexities of investigating isotopic alteration. In an effort to evaluate the evidence for alteration of the sedimentary N isotopic signal and try to quantify the net effect, we have compiled and compared data demonstrating alteration from the published literature. A 〉100 point comparison of sediment trap and surface sedimentary nitrogen isotope values demonstrates that, at sites located off of the continental margins, an increase in sediment 15N/14N occurs during early burial, likely at the seafloor. The extent of isotopic alteration appears to be a function of water depth. Depth-related differences in oxygen exposure time at the seafloor are likely the dominant control on the extent of N isotopic alteration. Moreover, the compiled data suggest that the degree of alteration is likely to be uniform through time at most sites so that bulk sedimentary isotope records likely provide a good means for evaluating relative changes in the global N cycle.

Description: We report results from time-series decay and sequential leaching experiments of laboratory cultured and coastal plankton to elucidate the mechanisms controlling barite formation in seawater. Batch-cultured diatoms (Stephanopyxis palmerina) and coccolithophorids (Emiliania huxleyi) were let to decay in the dark for 8–10 weeks, suspended in aerated seawater. The development of barite crystals was monitored by Scanning Electron Microscopy (SEM). A similar experiment was conducted with plankton collected during the spring-bloom in Vineyard Sound (MA). In addition to SEM, suspended particles were sequentially leached for Ba (distilled water rinse; 10% (v/v) HNO3 rinse at room temperature; 30% (v/v) HCl at 80°C overnight; 50% (v/v) HNO3 at 80°C overnight) immediately after collection, and after 10-week decay in seawater, in seawater poisoned with HgCl2, and in seawater spiked with 135Ba. Both experiments showed an increase in the number of barite crystals during decay. The spring-bloom plankton had initially a large pool of labile Ba, soluble in distilled water and cold dilute HNO3 that was lost from the plankton after 10-week decay in both axenic and nonaxenic conditions. In contrast, Ba in the decayed plankton samples was predominantly in forms extracted by hot HCl and hot HNO3 acids, which were attributed to presence of barite Ba and refractory organic Ba respectively. The increase in barite crystal counts under a Scanning Electron Microscope (SEM), the increase in HCl extractable Ba relative to organic carbon, and the loss of a large fraction of Ba during plankton decay suggest that living plankton consists of a relatively large pool of labile Ba, which is rapidly released during plankton decomposition and acts as the main source of Ba for barite formation in supersaturated microenvironments. Since mass balance indicates that only a small proportion (2 to 4%) of the labile-Ba pool is converted to barite, the availability of microenvironments that could locally concentrate Ba released by plankton decay seems to be the main limiting factor in barite precipitation.

Description: The neodymium isotope composition (ɛNd) of authigenic phases in marine sediment is widely used to reconstruct the origin and mixing of water masses of overlying seawater through time. However, at some locations in the modern ocean, the ɛNd of authigenic phases in surface sediment is not consistent with that of local seawater, raising concerns about its current interpretation as a paleotracer of water masses. To further investigate this question, we conducted a laboratory-based incubation experiment with a Mn-oxide phase placed at the sediment–water interface of multicores to assess the extent to which the authigenic phase records seawater ɛNd. Multicores were collected from the Strait of Georgia (SoG), which is a relatively deep coastal waterway with high sedimentation rates, oxygenated surface sediments, and active macrofauna, separating the mainland coast of British Columbia and Vancouver Island. Manganese oxide-coated XAD resin beads were placed at the sediment surface and the cores were incubated for 6 months in a tank filled with SoG seawater spiked with Nd. While the ɛNd of the Mn-oxide coated resin (−4.0) was similar to that of SoG seawater used for the incubation (−3.7), the Nd/Nd of the Mn-oxide phase measured after the incubation indicates that, under our experimental conditions, a minimum of 83% of the Nd associated with the Mn-oxide phase is not sourced from seawater, but from pore water. The Nd/Nd ratio of the Mn-oxide resin is necessary to determine the predominant source of Nd to the resin because the ɛNd of SoG pore water (−3.9) is within analytical error of seawater (−3.7). Using field data and constraints from the Nd mass balance during the incubation, we conclude that the similarity of ɛNd in pore water and seawater in the SoG is fortuitous and not a result of a top-down or bottom-up control. Although the setting of our sediments is not directly comparable to open ocean locations, this study raises concerns about the use of ɛNd in paleocirculation studies, and points to the necessity of elucidating the factors controlling local lithogenic dissolution in pore waters as a prerequisite for the correct interpretation of ɛNd in the authigenic phases of marine sediments.

Description: The first inter-calibration study of the stable silicon isotope composition of dissolved silicic acid in seawater, δ30Si(OH)4, is presented as a contribution to the international GEOTRACES program. Eleven laboratories from seven countries analyzed two seawater samples from the north Pacific subtropical gyre (Station ALOHA) collected at 300 m and at 1000 m water depth. Sampling depths were chosen to obtain samples with a relatively low (9 μmol L-1, 300 m) and a relatively high (113 μmol L-1, 1000 m) silicic acid concentration as sample preparation differs for low- and high- concentration samples. Data for the 1000m water sample were not normally distributed so the median is used to represent the central tendency for the two samples. Median δ30Si(OH)4 values of +1.66 ‰ for the low-concentration sample and +1.25 ‰ for the high-concentration sample were obtained. Agreement among laboratories is overall considered very good; however, small but statistically significant differences among the mean isotope values obtained by different laboratories were detected likely reflecting interlaboratory differences in chemical preparation including pre-concentration and purification methods together with different volumes of seawater volume analyzed, and the use of different mass spectrometers including the Neptune MC-ICP-MS (Thermo Fisher™, Germany), the Nu Plasma MC-ICP-MS (Nu Instruments™, Wrexham, UK), and the Finnigan™ (now Thermo Fisher™, Germany) MAT 252 IRMS. Future studies analyzing δ30Si(OH)4 in seawater should also analyze and report values for these same two reference waters in order to facilitate comparison of data generated among and within laboratories over time.