Environmental controls on the boron and strontium isotopic composition of aragonite shell material of cultured Arctica islandica

Ocean acidification, the decrease in ocean pH associated with increasing atmospheric CO2, is likely to impact marine organisms, particularly those that produce carbonate skeletons or shells. Therefore, it is important to investigate how environmental factors (seawater pH, temperature and salinity) influence the chemical compositions in biogenic carbonates. In this study we report the first high-resolution strontium (Sr-87 / Sr-86 and delta(88) / Sr-86) and boron (delta B-11) isotopic values in the aragonite shell of cultured Arctica islandica (A. islandica). The Sr-87/Sr-86 ratios from both tank water and shell samples show ratios nearly identical to the open ocean, which suggests that the shell material reflects ambient ocean chemistry without terrestrial influence. The Sr-84-Sr-87 double-spike-resolved shell delta(88) / Sr-86 and Sr concentration data show no resolvable change throughout the culture period and reflect no theoretical kinetic mass fractionation throughout the experiment despite a temperature change of more than 15 degrees C. The delta B-11 records from the experiment show at least a 5% increase through the 29-week culture season (January 2010-August 2010), with low values from the beginning to week 19 and higher values thereafter. The larger range in delta B-11 in this experiment compared to predictions based on other carbonate organisms (2-3 %) suggests that a species-specific fractionation factor may be required. A significant correlation between the Delta pH (pH(shell) - pH(sw)) and seawater pH (pH(sw)) was observed (R-2 = 0.35), where the pH(shell) is the calcification pH of the shell calculated from boron isotopic composition. This negative correlation suggests that A. islandica partly regulates the Delta pH of the extrapallial fluid. However, this proposed mechanism only explains approximately 35% of the variance in the delta B-11 data. Instead, a rapid rise in delta B-11 of the shell material after week 19, during the summer, suggests that the boron uptake changes when a thermal threshold of \u3e 13 degrees C is reached

Combined U–Th/He and 40Ar/39Ar geochronology of post-shield lavas from the Mauna Kea and Kohala volcanoes, Hawaii

Late Quaternary, post-shield lavas from the Mauna Kea and Kohala volcanoes on the Big Island of Hawaii have been dated using the 40Ar/39Ar and U–Th/He methods. The objective of the study is to compare the recently demonstrated U–Th/He age method, which uses basaltic olivine phenocrysts, with 40Ar/39Ar ages measured on groundmass from the same samples. As a corollary, the age data also increase the precision of the chronology of volcanism on the Big Island. For the U–Th/He ages, U, Th and He concentrations and isotopes were measured to account for U-series disequilibrium and initial He. Single analyses U–Th/He ages for Hamakua lavas from Mauna Kea are 87 ± 40 to 119 ± 23 ka (2σ uncertainties), which are in general equal to or younger than 40Ar/39Ar ages. Basalt from the Polulu sequence on Kohala gives a U–Th/He age of 354 ± 54 ka and a 40Ar/39Ar age of 450 ± 40 ka. All of the U–Th/He ages, and all but one spurious 40Ar/39Ar ages conform to the previously proposed stratigraphy and published 14C and K–Ar ages.The ages also compare favorably to U–Th whole rock–olivine ages calculated from 238U–230Th disequilibria. The U–Th/He and 40Ar/39Ar results agree best where there is a relatively large amount of radiogenic 40Ar (>10%), and where the 40Ar/36Ar intercept calculated from the Ar isochron diagram is close to the atmospheric value. In two cases, it is not clear why U–Th/He and 40Ar/39Ar ages do not agree within uncertainty. U–Th/He and 40Ar/39Ar results diverge the most on a low-K transitional tholeiitic basalt with abundant olivine. For the most alkalic basalts with negligible olivine phenocrysts, U–Th/He ages were unattainable while 40Ar/39Ar results provide good precision even on ages as low as 19 ± 4 ka. Hence, the strengths and weaknesses of the U–Th/He and 40Ar/39Ar methods are complimentary for basalts with ages of order 100–500 ka

The iron isotopic composition of subglacial streams draining the Greenland ice sheet

In this study, we present the first measurements of iron (Fe) stable isotopic composition (δ56Fe) of subglacial streams draining the Greenland Ice Sheet (GIS). We measure the δ56Fe values [(δ56Fe, ‰ = (56Fe/54Fe)sample/(56Fe/54Fe)standard − 1) × 103] of both dissolved and suspended sediment Fe in subglacial outflows from five distinct land-terminating glaciers. Suspended sediments have δ56Fe values that lie within the crustal array (δ56Fe ∼ 0‰). In contrast, the δ56Fe values of dissolved Fe in subglacial outflows are consistently less than 0‰, reaching a minimum of −2.1‰ in the outflow from the Russell Glacier. The δ56Fe values of dissolved Fe vary geographically and on daily time scales. Major element chemistry and mineral saturation state modeling suggest that incongruent silicate weathering and sulfide oxidation are the likely drivers of subglacial stream Fe chemistry, and that the extent of chemical weathering influences the δ56Fe of dissolved Fe. The largest difference in δ56Fe between dissolved and suspended load is −2.1‰, and occurs in the subglacial system from the Russell glacier (southwest GIS). Major element chemistry indicates this outflow to be the least chemically weathered, while more mature subglacial systems (i.e., that exhibit greater extents of subglacial weathering) have dissolved loads with δ56Fe that are indistinguishable from suspended sediments (Δ56Fesuspended-dissolved ∼ 0‰). Ultimately, the dissolved Fe generated in some subglacial systems from the GIS is a previously unrecognized source of isotopically light Fe into the hydrosphere. The data illustrate that the dissolved Fe supplied by subglacial weathering can have variable δ56Fe values depending on the degree of chemical weathering. Thus, Fe isotopes have potential as a proxy for subglacial chemical weathering intensity or mode. Finally, based on our regional Fe concentration measurements from each glacial outflow, we estimate a flux weighted continental scale dissolved iron export of 2.1 Gg Fe yr−1 to the coastal ocean, which is within the range of previous estimates

Toward a radiometric ice clock: uranium ages of the Dome C ice core

Ice sheets and deep ice cores have yielded a wealth of paleoclimate information based on continuous dating methods while independent radiometric ages of ice have remained elusive. Here we demonstrate the application of (234U/238U) measurements to dating the EPICA Dome C ice core based on the accumulation of 234U in the ice matrix from recoil during 238U decay out of dust bound within the ice. Measured (234U/238U) activity ratios within the ice generally increase with depth while the surface areas of the dust grains are relatively constant. Using a newly designed device for measuring surface area for small samples, we were able to estimate reliably the recoil efficiency of nuclides from dust to ice. The resulting calculated radiometric ages range between 80 ka and 870 ka. Measured samples in the upper 3100 m fall on the previously published age-depth profile. Samples in the 3200–3255 m section show a marked change from 723–870 ka to 85 ka indicating homogenization of the deep ice prior to resetting of the (234U/238U) age in the basal layers. The mechanism for homogenization is likely enhanced lateral ice flow due to high basal melting and geothermal heat flux

Decoupling of dissolved and bedrock neodymium isotopes during sedimentary cycling

The radiogenic neodymium isotope ratio143Nd/144Nd (expressed as εNd) has been applied to examine seawater elemental budgets, sedimentary provenance, oceanic water mass source and circulation, large scale geochemical cycling, and continental crust growth rates. These applications are underpinned by the assumption that during sedimentary processing the parent/daughter (samarium/neodymium) ratio is conservative during low temperature fluid related processes. In this study, we report εNd data from two streams draining sedimentary formations in the Arctic archipelago of Svalbard. The εNd value of the dissolved load is offset from stream suspended sediment samples by up to 5.5 epsilon units. We demonstrate that dissolved load εNd values are controlled by the dissolution of labile phases present in the catchment rocks which are isotopically distinct from the silicate residue and account for up to 12 % Nd in the bulk sediment. This study highlights; 1) the potential for incongruent release of Nd isotopes to seawater from rocks and sediments, with implications for the isotopic composition of seawater, and 2) the large scale decoupling between a rapidly exchanging labile reservoir and a silicate-bound reservoir during sediment recycling

Using the Chu construction for generalizing formal concept analysis

Abstract. The goal of this paper is to show a connection between FCA generalisations and the Chu construction on the category ChuCors, the category of formal contexts and Chu correspondences. All needed categorical properties like categorical product, tensor product and its bifunctor properties are presented and proved. Finally, the second order generalisation of FCA is represented by a category built up in terms of the Chu construction

Soil bacterial and fungal communities across a pH gradient in an arable soil

Soils collected across a long-term liming experiment (pH 4.0-8.3), in which variation in factors other than pH have been minimized, were used to investigate the direct influence of pH on the abundance and composition of the two major soil microbial taxa, fungi and bacteria. We hypothesized that bacterial communities would be more strongly influenced by pH than fungal communities. To determine the relative abundance of bacteria and fungi, we used quantitative PCR (qPCR), and to analyze the composition and diversity of the bacterial and fungal communities, we used a bar-coded pyrosequencing technique. Both the relative abundance and diversity of bacteria were positively related to pH, the latter nearly doubling between pH 4 and 8. In contrast, the relative abundance of fungi was unaffected by pH and fungal diversity was only weakly related with pH. The composition of the bacterial communities was closely defined by soil pH; there was as much variability in bacterial community composition across the 180-m distance of this liming experiment as across soils collected from a wide range of biomes in North and South America, emphasizing the dominance of pH in structuring bacterial communities. The apparent direct influence of pH on bacterial community composition is probably due to the narrow pH ranges for optimal growth of bacteria. Fungal community composition was less strongly affected by pH, which is consistent with pure culture studies, demonstrating that fungi generally exhibit wider pH ranges for optimal growth. The ISME Journal (2010) 4, 1340-1351; doi: 10.1038/ismej.2010.58; published online 6 May 2010&nbsp

High export of dissolved silica from the Greenland Ice Sheet

Silica is an essential element for marine life and plays a key role in the biogeochemistry of the ocean. Glacial activity stimulates rock weathering, generating dissolved silica that is exported to coastal areas along with meltwater. The magnitude of the dissolved silica export from large glacial areas such as the Greenland Ice Sheet is presently poorly quantified and not accounted for in global budgets. Here we present data from two fjord systems adjacent to the Greenland Ice Sheet which reveal a large export of dissolved silica by glacial meltwater relative to other macronutrients. Upscaled to the entire Greenland Ice Sheet, the export of dissolved silica equals 22 ± 10 Gmol Si yr−1. When the silicate-rich meltwater mixes with upwelled deep water, either inside or outside Greenland's fjords, primary production takes place at increased silicate to nitrate ratios. This likely stimulates the growth of diatoms relative to other phytoplankton groups

Ice sheets as a missing source of silica to the polar oceans

Ice sheets play a more important role in the global silicon cycle than previously appreciated. Input of dissolved and amorphous particulate silica into natural waters stimulates the growth of diatoms. Here we measure dissolved and amorphous silica in Greenland Ice Sheet meltwaters and icebergs, demonstrating the potential for high ice sheet export. Our dissolved and amorphous silica flux is 0.20 (0.06-0.79) Tmol year(-1), ∼50% of the input from Arctic rivers. Amorphous silica comprises >95% of this flux and is highly soluble in sea water, as indicated by a significant increase in dissolved silica across a fjord salinity gradient. Retreating palaeo ice sheets were therefore likely responsible for high dissolved and amorphous silica fluxes into the ocean during the last deglaciation, reaching values of ∼5.5 Tmol year(-1), similar to the estimated export from palaeo rivers. These elevated silica fluxes may explain high diatom productivity observed during the last glacial-interglacial period