Phosphorus components, trace metals and Ba excess of ODP Site 202-1237 sediments

We determined the sedimentary concentrations of phosphorus (P), barium (Ba), manganese (Mn), titanium (Ti), aluminum (Al), and uranium (U) for sediment samples from the southeast Pacific Nazca Ridge, Ocean Drilling Program Site 1237. This unique record extends to 31 Ma over 360 meters composite depth (mcd), recording depositional history as the site progressed eastward over its paleohistory. We sampled with a temporal resolution of ~0.2 m.y. throughout the sequence, equivalent to an average spacing of 1.63 m/sample. Concentrations of sequentially extracted components of P (oxide-associated, authigenic, organic, and detrital) increase toward the modern. Al/Ti ratios indicate that the background detrital source material is consistent with upper continental crust. U enrichment factors (U EFs) generally exceed crustal values and indicate slightly reducing environments. However, authigenic U precipitation can also be influenced by the organic carbon rain rate and may not be solely an indicator of redox conditions. Dramatic changes in Mn EFs at ~162 mcd, from values between 12 and 93 to values <12 after this depth, and a sharp color contact boundary lead us to believe that a paleoredox boundary from an oxygenated to a more reducing depositional environment occurred near this depth. Estimates of biogenic barite concentrations from a total sediment digestion technique (Ba excess) are greater than those from a barite extraction (Ba barite) for selected samples across the entire depth range. Applying a range of Ba/Ti ratios from different source materials to correct for detrital inputs does not change the lack of agreement with Ba barite concentrations. Reactive P (P reactive) concentrations (the sum of oxide-associated, authigenic, and organic P concentrations) increase toward the modern with values typically <12 µmol P/g from the base of our record through ~100 mcd, with a gradual increase to concentrations >15 µmol P/g. Ba excess follows the same general trends as Preactive, with concentrations <14 µmol Ba/g in the lower portion of the record to values >15 µmol Ba/g. Accumulation rate records of these proxies will be needed to infer paleoproductivity. P reactive/Ba excess ratios, an indicator of the relative burial of the nutrient P to organic carbon export, exhibit higher values, similar to modern, from the base of our record through ~180 mcd. The remainder of the record exhibits values lower than modern, indicating that organic carbon export to the sediments was higher relative to nutrient burial.

Extractions and analyses of reactive phosphorus in the Bering Sea from IODP Holes 323-U1341A and 323-U1341B

To reconstruct the cycling of reactive phosphorus (P) in the Bering Sea, a P speciation record covering the last ~ 4 Ma was generated from sediments recovered during Integrated Ocean Drilling Program (IODP) Expedition 323 at Site U1341 (Bowers Ridge). A chemical extraction procedure distinguishing between different operationally defined P fractions provides new insight into reactive P input, burial and diagenetic transformations. Reactive P mass accumulation rates (MARs) are ~ 20-110 µmol/cm2/ka, which is comparable to other open ocean locations but orders of magnitude lower than most upwelling settings. We find that authigenic carbonate fluorapatite (CFA) and opal-bound P are the dominant P fractions at Site U1341. An overall increasing contribution of CFA to total P with sediment depth is consistent with a gradual "sink switching" from more labile P fractions (fish remains, Fe oxides, organic matter) to stable authigenic CFA. However, the positive correlation of CFA with Al content implies that a significant portion of the supposedly reactive CFA is non-reactive "detrital contamination" by eolian and/or riverine CFA. In contrast to CFA, opal-bound P has rarely been studied in marine sediments. We find for the first time that opal-bound P directly correlates with excess silica contents. This P fraction was apparently available to biosiliceous phytoplankton at the time of sediment deposition and is a long-term sink for reactive P in the ocean, despite the likelihood for diagenetic re-mobilisation of this P at depth (indicated by increasing ratios of excess silica to opal-bound P). Average reactive P MARs at Site U1341 increase by ~ 25% if opal-bound P is accounted for, but decrease by ~ 25% if 50% of the extracted CFA fraction (based on the lowest CFA value at Site U1341) is assumed to be detrital. Combining our results with literature data, we present a qualitative perspective of terrestrial CFA and opal-bound P deposition in the modern ocean. Riverine CFA input has mostly been reported from continental shelves and margins draining P-rich lithologies, while eolian CFA input is found across wide ocean regions underlying the Northern Hemispheric "dust belt". Opal-bound P burial is important in the Southern Ocean, North Pacific, and likely in upwelling areas. Shifts in detrital CFA and opal-bound P deposition across ocean basins likely occurred over time, responding to changing weathering patterns, sea level, and biogenic opal deposition.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Permian manganese nodules near Dillon, Montana

Concentrically ringed manganese nodules, similar in form to many found on modern ocean and sea floors, occur in a very fine grained argillaceous sandstone bed of the Permian Park City Formation near Dillon, Montana. They are enriched in many rare elements and contain us much as 2.5 percent zinc, l.3 percent nickel, and 0.22 percent cobalt. The manganese minerals are chalcophanite and todorokite. The nodules probably formed in a shallow marine oxidizing environment on the western side of the Permian sedimentary basin. The occurrence of an appreciable amount of fluorite in the bed suggests that the water was saline.

Sediment geochemistry of ODP Leg 127 sites

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the final preserved chemistry of Japan Sea sediments are evaluated by investigating the rare earth element (REE), major element, and trace element concentrations in 59 squeeze-cake whole-round and 27 physical-property sample residues from Sites 794, 795, and 797, cored during ODP Leg 127. The most important variation in sedimentary chemical composition is the increase in SiO2 concentration through the Pliocene diatomaceous sequences, which dilutes most other major and trace element components by various degrees. This biogenic input is largest at Site 794 (Yamato Basin), moderately developed at Site 797 (Yamato Basin), and of only minor importance at Site 795 (Japan Basin), potentially reflecting basinal contrasts in productivity with the Yamato Basin recording greater biogenic input than the Japan Basin and with the easternmost sequence of Site 794 lying beneath the most productive waters. There are few systematic changes in solid-phase chemistry resulting from the opal-A/opal-CT or opal-CT/quartz silica phase transformations. Most major and trace element concentrations are controlled by the aluminosilicate fraction of the sediment, although the effects of diagenetic silica phases and manganese carbonates are of localized importance. REE total abundances (Sum REE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the upper Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. SumREE at Site 795 also is affiliated strongly with aluminosilicate phases and yet is diluted only slightly by siliceous input. At Site 797, SumREE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. Ce/Ce* profiles at all three sites increase essentially monotonically with depth and record progressive diagenetic LREE fractionation. The observed Ce/Ce* increases are not responding to changes in the paleoceanographic oxygenation state of the overlying water, as there is no independent evidence to suggest the proper oceanographic conditions. Ce/Ce* correlates slightly better with depth than with age at the two Yamato Basin sites. The downhole increase in Ce/Ce* at Sites 794 and 797 is a passive response to the diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and Lan/Ybn suggests that other processes mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column and that an additional ~38% is recycled at or near the seafloor. Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply buried interstitial waters.

Description and chemical composition of ferromanganese deposits from Trout Lake, northern Wisconsin

Sediments were collected with Eckman and Petersen dredges from the bottom of Trout Lake, northern Wisconsin, at 221 stations. Sampling was done with a spud sampler at 32 stations, and core samples were obtained with a Jenkins and Mortimer and a Twenhofel sampler at 17 stations. The shore and offshore deposits of the shores of Trout Lake and the shores of the islands are described. Megascopic descriptions are given of the samples collected with the Eckman and Petersen dredges. Sediments on bottoms of about 10 meters or deeper are mainly gyttja, or crusts composed of mixtures of organic matter, ferric hydroxide, and some form of manganese oxide. The latter deposits are extensive. Detailed descriptions of some of the samples of sands are given, and generalizations respecting size and distribution are made. Tables showing quartiles, medians, and coefficients of sorting and skewness of the coarse sediments collected from the bottom are given in tables. Mechanical analyses of all fine sediments, mainly gyttja, were not made, as previous experience seems to have demonstrated that results have no sedimentational value. Organic matter of the gyttja was determined and also the percentages of lignin in the organic matter. Core samples are composed almost entirely of fine materials, mainly gyttja, and determinations were made on these samples in the same way as on the samples obtained with the Eckman and Petersen dredges. Studies of the core samples show that the fine sediments usually contain in excess of 90 per cent moisture and there is very little change in the moisture content from top to bottom of cores. A map shows the distribution of the iron and manganese deposits. These deposits were found to contain 10 to 20 per cent of organic matter, 11 to 16 per cent of metallic iron, and 12 to 30 per cent of metallic manganese. No stratification of any kind was found in any of the deep-water sediments of Trout Lake except in the iron and manganese crusts. Absence of stratification is considered to be due to the slow rate of deposition and the mixing of sediments by organisms which dwell in them. The data indicate that the rate of deposition in the deep waters of Trout Lake is of the order of 1 foot in 15,000 years.

Protein and organic phosphorus in particulate matter and mesoplankton fraction in waters of the East Pacific

Vertical distribution of organic phosphorus and phosphatase activity was studied in the Southeast Pacific Ocean. The average rate of mineralization of organic phosphorus in the 0-200 m layer was shown to differ by a factor of 5-10 in oligotrophic and eutrophic areas, while residence time of phosphorus in production-destruction cycles differed by a factor of only 2-5, apparently because of both concentration of organic phosphorus and phosphorolysis rate increased simultaneously in the areas.