Radionuclides measured on water bottle samples during SONNE cruise SO202 (INOPEX)

Boundary scavenging, or the enhanced removal of adsorption-prone elements from the ocean in areas of high particle flux, is an often cited, though not well-quantified, concept used to understand the oceanic distribution of many trace metals. Because 230Th and 231Pa are produced uniformly from uranium decay and removed differentially by scavenging, the process of boundary scavenging can be elucidated by a more detailed knowledge of their water column distributions. To this end, filtered seawater was collected across the gradients in particle flux which span the subarctic Pacific: in the west during the Innovative North Pacific Experiment (INOPEX) and in the east along Line P. Lateral concentration gradients of dissolved 230Th are small throughout the subarctic Pacific at 12 sites of variable particle flux. This contradicts the prediction of the traditional boundary scavenging model. A compilation of water column data from throughout the North Pacific reveals much larger lateral concentration gradients for 230Th between the subarctic North Pacific and subtropical gyre, over lateral gradients in scavenging intensity similar to those found within the subarctic. This reflects a biogeochemical-province aspect to scavenging. Upper water column distributions of 231Pa and 231Pa/230Th ratio are consistent with the influence of scavenging by biogenic opal, while deep waters (>2.5 km) reveal an additional 231Pa sink possibly related to manganese oxides produced at continental margins or ridge crests.

Geochemistry of pore water and sediments from ODP Leg 136 sites

During Leg 136 drilling was conducted at two sites in pelagic sediments of the north central Pacific Ocean. In this report, pore-water analyses for major seawater constituents, alkalinity, ammonia, nitrate, phosphate, silica, Ba, Fe, Li, Mn, and Sr are presented. Although concentration gradients are generally weak, resulting from slow sedimentation and concomitant diffusive communication with overlying water, there is evidence of sediment/pore-water interactions, associated sediment diagenesis, and formation of authigenic minerals. Bulk major and trace element compositions of the sediments are consistent with reactions inferred to occur within the sediments and with the lithology and mineralogy. Elemental compositions of the sediments are not strongly affected by diagenesis and are primarily related to the dominant mineralogy. Sediments are typical of deep ocean pelagic settings with a significant contribution from the alteration of volcanic ash and the formation of zeolites. Sedimentary rare earth element patterns also provide evidence of active scavenging processes by Mn and Fe oxide phases in the deeper sediments at Site 842.

Plutonium and americium concentrations in sea water and in sinking particles

Vertical fluxes of 239+240Pu and 241Am and temporal changes in their inventories in the northwestern Mediterranean Sea have been examined through high-resolution water column sampling coupled with direct measurements of the vertical flux of particle-bound transuranics using time-series sediment traps. Water column profiles of both radionuclides showed well-defined sub-surface maxima (2391240Pu between 100-400 m; 241Am at 100-200 m and 800 m), the depths of which are a result of the different biogeochemical scavenging behavior of the two radionuclides. Comparison of deep water column (0-2,000 m) transuranic inventories with those derived from earlier measurements demonstrate that the total 2391240Pu inventory had not substantially changed between 1976-1990 whereas 241Am had decreased by approximately 24%. Enhanced scavenging of 241Am and a resultant, more rapid removal from the water column relative to 239+240Pu was also supported by the observation of elevated Am/Pu activity ratios in sinking particles collected in sediment traps at depth. Direct measurements of the downward flux of particulate 239+240Pu and 241Am compared with transuranic removal rates derived from observed total water column inventory differences over time, show that particles sinking out of deep waters (1,000-2,000 m) could account for 26-72% of the computed total annual 239+240Pu loss and virtually all of the 241Am removal from the water column. Upper water column (0-200 m) residence times based on direct flux measurements ranged from 20-30 yr for 239+240Pu and 5-10 yr for 241Am. The observation that 241Am/239+240Pu activity ratios in unfiltered Mediterranean seawater are six times lower than those in the north Pacific suggests the existence of a specific mechanism for enhanced scavenging and removal of 241Am from the generally oligotrophic waters of the open Mediterranean. It is proposed that atmospheric inputs of aluminosilicate particles transported by Saharan dust events which frequently occur in the Mediterranean region could enhance the geochemical scavenging and resultant removal of 241Am to the sediments.

Beryllium, thorium and protactinium isotope ratios in sediments from the Galapagos microplate

Biogenic particle fluxes from highly productive surface waters, boundary scavenging, and hydrothermal activity are the main factors influencing the deposition of radionuclides in the area of the Galapagos microplate, eastern Equatorial Pacific. In order to evaluate the importance of these three processes throughout the last 100 kyr, concentrations of the radionuclides 10Be, 230Th, and 231Pa, and of Mn and Fe were measured at high resolution in sediment samples from two gravity cores KLH 068 and KLH 093. High biological productivity in the surface waters overlying the investigated area has led to 10Be and 231Pa fluxes exceeding production during at least the last 30 kyr and probably the last 100 kyr. However, during periods of high productivity at the up welling centers off Peru and extension of the equatorial high-productivity zone, a relative loss of 10Be and 231Pa may have occurred in these sediment cores because of boundary scavenging. The effects of hydrothermal activity were investigated by comparing the 230Thex concentrations to the Mn/Fe ratios and by comparing the fluxes of 230Th and 10Be which exceed production. The results suggest an enhanced hydrothermal influence during isotope stages 4 and 5 and to a lesser extent during isotope stage 1 in core KLH 093. During isotope stages 2 and 3, the hydrothermal supply of Mn was deposited elsewhere, probably because of changes in current regime or deep water oxygenation. A strong increase of the Mn/Fe ratio at the beginning of climatic stage 1 which is not accompanied by an increase of the 230Thex concentration is interpreted to be an effect of Mn remobilization and reprecipitation in the sediment.

Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.

Dissolved iron and Fe(II) in an iron induced Southern Ocean phytoplankton bloom measured during TANGAROA cruise SOIREE

During the 13 day Southern Ocean Iron RE-lease Experiment (SOIREE), dissolved iron concentrations decreased rapidly following each of three iron-enrichments, but remained high (>1 nM, up to 80% as FeII) after the fourth and final enrichment on day 8. The former trend was mainly due to dilution (spreading of iron-fertilized waters) and particle scavenging. The latter may only be explained by a joint production-maintenance mechanism; photoreduction is the only candidate process able to produce sufficiently high FeII, but as such levels persisted overnight (8 hr dark period) -ten times the half-life for this species- a maintenance mechanism (complexation of FeII) is required, and is supported by evidence of increased ligand concentrations on day 12. The source of these ligands and their affinity for FeII is not known. This retention of iron probably permitted the longevity of this bloom raising fundamental questions about iron cycling in HNLC (High Nitrate Low Chlorophyll) Polar waters.

Dust flux in the Arabian Sea

Eolian grain size and flux were measured on samples from 11 Arabian Sea sediment traps deployed 200-1250 km offshore. The timing of increased grain size is coincident with the onset of strong summer monsoon winds and dust storm activity over the Arabian Peninsula and Middle East. Data spanning a full annual cycle show that eolian grain size is highly correlated with barometric pressure (r=-0.91) and wind speed (r=0.84), enabling calibration of the downcore record in terms of these primary meteorological variables. Eolian flux is highly correlated with organic carbon flux (r=0.80); both increase 6-8 weeks after the grain size increase and summer monsoon onset. This lag, and the low correlation between eolian grain size and eolian flux (r=0.36), likely result from the differential sinking rates of large and small dust particles in the surface waters as well as biological scavenging associated with monsoon-induced productivity.

(Table 2) Annual mass fluxes, 230Th composition and organic geochemistry of sediment trap samples in the South Altantic

The scavenging of 231Pa and 230Th was investigated in the Atlantic Sector of the Southern Ocean by combining results from sediment trap and in situ filtration studies. We present the first high-resolution profile of dissolved 230Th and 231Pa in surface waters across the ACC, showing a dramatic southward increase of both radionuclides around the southern ACC Front at 533S. High dissolved 231Pa/230Th ratios combined with low 230Th/231Pa fractionation factors (F) in these surface waters result in extremely high 231Pa94/230Th94 ratios of material collected in the shallow traps. Particulate 231Pa94/230Th94 ratios in a shallow trap near Bouvet Island increase continuously during the productive period in austral summer, and drop back in the low flux period. This behavior, following the Rayleigh fractionation principle, is interpreted to be due to an increase in the dissolved 231Pa/230Th ratio in the euphotic zone resulting from preferential scavenging of 230Th relative to 231Pa, even in opal-dominated regions. In the post-bloom stage, the depleted radionuclide concentrations are replenished by upwelling of Circumpolar Deep Water. The high particulate 231Pa94/230Th94 signal is weakened during downward transport of the bloom particles in the water column by incorporation of deep suspended particles, which have a lower 231Pa94/230Th94 ratio. It is shown that under the special hydrographic conditions in the Southern Ocean scavenging from the upper water column significantly influences the budgets of 230Th and 231Pa in the sediment. Nevertheless, the budgets are still made up primarily by scavenging from the large standing stock of deep suspended particles.