Bulk calcite minor element composition of ODP Leg 130 samples

We investigated minor element ratios (Sr/Ca and Mg/Ca) in bulk sediment samples from Sites 803-807 using a recently optimized sample treatment protocol for calcium-carbonate-rich sediments consisting of sequential reductive and ion exchange treatments. We evaluated this protocol relative to bulk sediment leaching using samples from Sites 804 and 806, the two end-member sites in the depth transect, reporting as well Mn/Ca and Fe/Ca ratios for sediments from these two sites processed by means of both methods. The Sr/Ca ratios were only slightly affected by the sample treatment, with an average reduction of 6%-7% caused primarily by the ion exchange step. The reductive sample treatment, designed to be effective at removing Mn-rich oxyhydroxides, has a major effect on Mg/Ca ratios, with up to 50% reduction, whereas little effect occurred in ion exchange alone on Mg/Ca ratios. The Mn/Ca and Fe/Ca ratios were not consistently offset by the sample treatment, and these ratios do not appear to be representative of calcite geochemistry reflecting either ocean history or diagenetic overprinting. Celestite solubility appears to be an important control on interstitial water Sr concentrations in these sites, and it must be considered when constructing Sr mass balance models of calcite recrystallization. Calcite Sr/Ca ratios (range 1-2 mmol/mol) are similar from site to site when plotted vs. age, with a pattern comparable to that for well-preserved foraminifer tests over the past 40 Ma. Interstitial water Mg and Ca gradients appear to reflect basement character and the intensity of alteration; they can vary substantially over a small area. Calcite Mg/Ca ratios (range 1.5-4.5 mmol/mol) differ from site to site, with generally higher ratios for sites at a shallower water depth. Increasing calcite Mg/Ca ratios correlate with decreasing Sr/Ca ratios in the treated samples. No consistent pattern exists for calcite Mg/Ca ratios vs. age or depth, nor is any direct correlation to interstitial water Mg/Ca ratios present.

Geochemistry and Mg-isotopes of carbonate sediments and porefluids of ODP Site 130-807

Deep-sea pore fluids are potential archives of ancient seawater chemistry. However, the primary signal recorded in pore fluids is often overprinted by diagenetic processes. Recent studies have suggested that depth profiles of Mg concentration in deep-sea carbonate pore fluids are best explained by a rapid rise in seawater Mg over the last 10-20 Myr. To explore this possibility we measured the Mg isotopic composition of pore fluids and carbonate sediments from Ocean Drilling Program (ODP) site 807. Whereas the concentration of Mg in the pore fluid declines with depth, the isotopic composition of Mg in the pore fluid increases from -0.78 per mil near the sediment-water interface to -0.15 per mil at 778 mbsf. The Mg isotopic composition of the sediment, with few important exceptions, does not change with depth and has an average d26Mg value of -4.72 per mil. We reproduce the observed changes in sediment and pore-fluid Mg isotope values using a numerical model that incorporates Mg, Ca and Sr cycling and satisfies existing pore-fluid Ca isotope and Sr data. Our model shows that the observed trends in magnesium concentrations and isotopes are best explained as a combination of two processes: a secular rise in the seawater Mg over the Neogene and the recrystallization of low-Mg biogenic carbonate to a higher-Mg diagenetic calcite. These results indicate that burial recrystallization will add Mg to pelagic carbonate sediments, leading to an overestimation of paleo-temperatures from measured Mg/Ca ratios. The Mg isotopic composition of foraminiferal calcite appears to be only slightly altered by recrystallization making it possible to reconstruct the Mg isotopic composition of seawater through time.

Geochemistry of planktonic foraminifera of sediment core MD97-2121

In situ measurements of Mg/Ca, Zn/Ca, Mn/Ca, and Ba/Ca in Globigerinoides bulloides and Globigerina ruber from southwest Pacific core top sites and plankton tow are reported and their potential as paleoproxies is explored. The modern samples cover 20° of latitude from 34°S to 54°S, 7-19°C water temperature, and variable influence of subantarctic (SAW) and subtropical (STW) surface waters. Trace element signatures recorded in core top and plankton tow planktic foraminifera are examined in the context of the chemistry and nutrient profiles of their modern water masses. Our observations suggest that Zn/Ca and Mn/Ca may have the potential to trace SAW and STW. Intraspecies and interspecies offsets identified by in situ measurements of Mg/Ca and Zn/Ca indicate that these ratios may also record changes in thermal and nutrient stratification in the upper ocean. We apply these potential proxies to fossilized foraminifera from the high-resolution core MD97 2121. At the Last Glacial Maximum, surface water Mg/Ca temperature estimates indicate that temperatures were approximately 6-7°C lower than those of the present, accompanied by low levels of Mn/Ca and Zn/Ca and minimal thermal and nutrient stratification. This is consistent with regional dominance of SAW and reduced STW inflow associated with a reduced South Pacific Gyre (SPG). Upper ocean thermal and nutrient stratification collapsed during the Antarctic Cold Reversal, before poleward migration of the zonal winds and ocean fronts invigorated the SPG and increased STW inflow in the early Holocene. Together with reduced winds, this favored a stratified upper ocean from circa 10 ka to the present.

Stable isotopes and element concentrations of samples from the Wadi Bih, United Arab Emirates

Ocean acidification triggered by Siberian Trap volcanism was a possible kill mechanism for the Permo-Triassic Boundary mass extinction, but direct evidence for an acidification event is lacking. We present a high-resolution seawater pH record across this interval, using boron isotope data combined with a quantitative modeling approach. In the latest Permian, increased ocean alkalinity primed the Earth system with a low level of atmospheric CO2 and a high ocean buffering capacity. The first phase of extinction was coincident with a slow injection of carbon into the atmosphere, and ocean pH remained stable. During the second extinction pulse, however, a rapid and large injection of carbon caused an abrupt acidification event that drove the preferential loss of heavily calcified marine biota.

Element ratios and stable isotopes of foraminifers from ODP Site 202-1237

Downcore records of magnesium/calcium, strontium/calcium, manganese/calcium, and oxygen and carbon isotopes of planktonic and benthic foraminifers from Ocean Drilling Program (ODP) Site 1237 on the Peru-Chile margin provide critical information regarding the history of climate in the region over the past 6 m.y. Specifically, these records can be used to infer the sea-surface temperature (SST) and sea-surface salinity (SSS) history of a region that today is associated with substantial wind stress curl-driven upwelling (Shipboard Scientific Party, 2003, doi:10.2973/odp.proc.ir.202.108.2003). This report provides data tables and other supporting information for measurements made on planktonic and benthic foraminifers from Site 1237. Items included in this report are (1) oxygen and carbon isotopic measurements of planktonic and benthic foraminifers and (2) Mg/Ca, Sr/Ca, and Mn/Ca ratio measurements of planktonic foraminifers from Holes 1237B, 1237C, and 1237D.

Stable isotope record and trace element ratios of Eocene and Oligocene foraminifers from ODP Site 120-748

Stable carbon and oxygen isotope analyses were conducted on well-preserved planktonic and benthic foraminifers from a continuous middle Eocene to Oligocene sequence at Ocean Drilling Program (ODP) Site 748 on the Kerguelen Plateau. Benthic foraminifer d18O values show a 1.0 per mil increase through the middle and upper Eocene, followed by a rapid 1.2 per mil increase in the lowermost Oligocene (35.5 Ma). Surface-dwelling planktonic foraminifer d18O values increase in the lowermost Oligocene, but only by 0.6 per mil whereas intermediate-depth planktonic foraminifers show an increase of about l.0 per mil. Benthic foraminifer d13C values increase by 0.9 per mil in the lowermost Oligocene at precisely the same time as the large d18O increase, whereas planktonic foraminifer d13C values show little or no change. Site 748 oxygen isotope and paleontological records suggest that southern Indian Ocean surface and intermediate waters underwent significant cooling from the early to late Eocene. The rapid 1.2 per mil oxygen isotope increase recorded by benthic foraminifers just above the Eocene/Oligocene boundary represents the ubiquitous early Oligocene d18O event. The shift here is unique, however, as it coincided with the sudden appearance of ice-rafted debris (IRD), providing the first direct link between Antarctic glacial activity and the earliest Oligocene d18O increase. The d18O increase caused by the ice-volume change in the early Oligocene is constrained by (1) related changes in the planktonic to benthic foraminifer d18O gradient at Site 748 and (2) comparisons of late Eocene and early Oligocene planktonic foraminifer d18Ovalues from various latitudes. Both of these records indicate that 0.3 per mil to 0.4 per mil of the early Oligocene d18O increase was ice-volume related.

Impact of fire and post-fire management techniques on soil chemical properties

The effects of fire ( Control burned soil) and two emergency stabilisation techniques (grass Seeding and straw Mulching ) on 20 chemical characteristics were evaluated on 0 – 5 cm top-soils sampled 1, 90, 180 and 365 days after an experimental fi re in a steep shrubland of a temperate-humid region (NW Spain). Most part of pH (in H 2 O and KCl) variance was explained by the sampling date. No clear temporal trends were identi fi able for total soil C and N content, likely due to the large SOM pool in these soils; however, changes on soil δ 13 C were explained by the deposition of 13 C-depleted ashes, followed by its progressive erosion, while those on soil δ 15 N were a consequence of fi re induced N outputs. After the fi re, NH 4 + – N, P, Na, K, Mg, Ca, Mn, Cu, Zn and B concentrations increased, while those of NO 3 − – N, Al, Fe and Co did not vary significantly. Despite a significant decline with time, concentrations of Mg, Ca and Mn at the end of the study were still higher than in unburned soil, while those of K, Cu, Zn and B were similar to the pre-fire levels and those of NH 4 + – N, P and Na were below pre-fire values. Mulching and Seeding treatments for burned soil emergency stabilisation had significant effects on soil δ 15 N and extractable K, Mg and Ca, while data were inconclusive for their possible effects on the extractable Al, Fe and Co

Geochemistry of sediments and interstitial waters of ODP Sites 128-798 and128-799

Interstitial waters in sediments below 400 (Site 798) and 435 meters below seafloor (Site 799) have chloride concentrations of 516-527 and 501-515 mM, respectively, lower than the 540 mM of the modern-day Japan Sea. The chemical composition of interstitial waters, bulk sediments, clay-size sediment fraction, and carbonate nodules from Oki Ridge (Site 798) and Kita-Yamato Trough (Site 799), Japan Sea, reflect in-situ diagenetic processes superimposed on geochemical signals that may indicate freshening of Miocene local marginal basin waters. Interstitial waters at both sites exhibit changes in chemical composition which coincide with the occurrence of low-porosity and high-bulk density layers composed of dolomite and opal-CT, which impede diffusive communication with the overlying interstitial waters. Based on interstitial water stable isotope evidence and mass-balance calculations of chloride dilution, diagenetic reactions that involve the release of structural bound water from opal-A and/or clay minerals contribute to the observed geochemical signals, but cannot account for all the measured chloride dilution.

Are metal ions accumulated by saxicolous lichens growing in a rural environment?

The levels of Mn, Cu, zn, Mg and Ca were measured in the lichens Xanthoparmelia conspersa (Ach.) Hale and Parmelia glabratula ssp. fuliginosa (Fr. ex Duby): Laund. growing on a steep slate rock surface in south Gwynedd, Wales, UK. The objective was to test the following hypotheses: 1) that foliose lichens growing in a rural environment concentrate metal ions relative to the substratum, 2) that the concentration of metal ions increases significantly with thallus size and 3) that individual ions accumulate preferentially either in the marginal lobes or thallus centre. Mg and Ca were present in rainfall whereas all ions were present in rock surface runoff and in the substratum. Levels of Mn, Mg and Ca were increased in runoff collected from the bottom compared with the top of the rock surface. In P. glabratula ssp. fuliginosa thalli, ions were present as follows, Mg > Ca=Mn=Zn>Cu, and there were no significant differences in thalli collected from the top and bottom of the rock surface. With the exception of Mg and Ca, ion levels in thalli were similar to or less than those in the substratum. The levels of Ca, Cu and Zn were similar in thalli from under 1 to over 4 cm in diameter. However, the level of Mg increased with thallus size in X. conspersa while the level of Mn decreased with thallus size in both species. Ion levels were similar in the marginal lobes and centres of large diameter (over 4 cm) and small diameter (under 2 cm) X. conspersa thalli. With the exception of Mg, there was no evidence for a significant accumulation of ions relative to the substratum or with thallus size. In addition, there was no evidence to suggest preferential accumulation of ions either in the thallus centre or marginal lobes.

Geochemical composition of calcite and aragonite, and characteristics of hydrothermal fluids of ODP Leg 168 sites

During Leg 168 a transect was drilled across the eastern flank of the Juan de Fuca Ridge in an area where the volcanic basement is covered by sediments of variable thickness. Samples of basement volcanic rocks were recovered from nine locations along the transect, where the basement sediment interface is presently heated to temperatures varying from 15° to 64°C. Altered rocks with secondary calcium carbonate were common at four of the sites, where present-day temperatures range from 38° to 64°C. Fluid inclusions in aragonite suggest that the mineral precipitated from an aqueous fluid of seawater salinity at temperatures well below 100°C. The chemical compositions of secondary calcite and aragonite were determined with both an electron microprobe and a laser-ablation inductively coupled plasma-mass spectroscopy (LA-ICP-MS) microprobe. These two techniques yielded consistent analyses of the same minor elements (Mg and Sr) in the same specimens. The combined results show that secondary aragonites contain very little Mg, Mn, Fe, Co, Ni, Cu, Zn, Rb, La, Ce, Pb, or U, yet they contain significant Sr. In contrast, secondary calcites contain significant Mg, Mn, Fe, Ni, Cu, Zn, and Pb, yet very little Co, Rb, Sr, La, Ce, or U. Secondary calcium carbonates provide subseafloor reservoirs for some minor and trace elements. Replacement of aragonite by calcite should result in a release of Sr, Rb, and Zn to solution, and it provides a sink for Mg, Mn, Ni, Cu, Zn, and Pb.

Lake Tiefer See varve microfacies, bulk geochemistry, µ-XRF, vegetation openness and Cladocera record

The Holocene sediment record of Lake Tiefer See exhibits striking alternations between well-varved and non-varved intervals. Here we present a high resolution multi-proxy record for the past ~6000 years and discuss possible causes for the observed sediment variability. This approach comprises of microfacies, geochemical and microfossil analyses as well as of a multiple dating concept including varve counting, tephrochronology and radiocarbon dating. Four periods of predominantly well-varved sediment were identified at 6000-3950 cal. a BP, 3100-2850 cal. a BP, 2100-750 cal. a BP and AD 1924-present. Except of sub-recent varve formation, these periods are considered to reflect reduced lake circulation and consequently, stronger anoxic bottom water conditions. In contrast, intercalated intervals of poor varve preservation or even extensively mixed non-varved sediments indicate strengthened lake circulation. Sub-recent varve formation since AD 1924 is, in addition to natural forcing, influenced by enhanced lake productivity due to modern anthropogenic eutrophication. The general increase in periods of intensified lake circulation in Lake Tiefer See since ~4000 cal. a BP presumably is caused by gradual changes in Northern Hemisphere orbital forcing, leading to cooler and windier conditions in Central Europe. Superimposed decadal to centennial scale variability of the lake circulation regime likely is the result of additional human-induced changes of the catchment vegetation. The coincidence of major non-varved periods at Lake Tiefer See and intervals of bioturbated sediments in the Baltic Sea implies a broader regional significance of our findings.

Depth, age, strontium isotopic ratios and trace elemental ratios of samples from thirteen DSDP and ODP holes

Large variations exist between published mid-Cretaceous (late Barremian to early Turonian stages) seawater Sr-isotope stratigraphies; this has resulted in disparate interpretations of crustal production rates. We report on a detailed investigation of seawater Sr-isotope stratigraphy based on foraminifers and, where available, on inoceramid bivalves from 12 mid-Cretaceous Deep Sea Drilling Project and Ocean Drilling Program sections. The effects of diagenesis are assessed using scanning electron microscope observations and trace-elemental analyses, but are best distinguished by comparing the 87Sr/86Sr values of similar-age samples from different sites. Strontium-isotope analyses compiled from 9 of 12 sites that have detailed age control define one band of common values. This band is used as a composite curve, which presumably represents seawater 87Sr/86Sr values. The composite curve shows a "trough" of markedly lower 87Sr/86Sr values in the Aptian and early Albian stages, higher but constant values for the middle Albian-Cenomanian stages, followed by a decrease in 87Sr/86Sr values in the early Turonian. Variations between published mid-Cretaceous Sr-isotope records result from diagenetic alteration, analytical problems, and the diverse biostratigraphic approaches and assumptions used to estimate sample ages. When preexisting age data are made consistent, the composite record shows close similarities with data sets derived from measurements of macrofossils in land sections of Europe and North America. The interval of decreased 87Sr/86Sr values in the Aptian-Albian stages overlaps with the pulse of mid-plate volcanic activity that produced the Ontong Java, Manihiki, and Kerguelen Plateaus. The exact age and the shape of the trough, however, are consistent with increased spreading rates at oceanic ridges, given the existing data on the timing of mid-plate volcanic activity.

Geological investigation of a section at Kulyumbe river in Siberia

An integrated, high-resolution chemostratigraphic (C, O and Sr isotopes) and magnetostratigraphic study through the upper Middle Cambrian - lowermost Ordovician shallow-marine carbonates of the northwestern margin of the Siberian Platform is reported. The interval was analysed at the Kulyumbe section, which is exposed along the Kulyumbe River: an eastern tributary of the Enisej River. It comprises the upper Ust'-Brus, Labaz, Orakta, Kulyumbe, Ujgur, and lower Iltyk formations and includes the Steptoean positive carbon isotopic excursion (SPICE) studied here in detail from upper Cambrian carbonates of the Siberian Platform for the first time. The peak of the excursion, showing d13C positive values as high as +4.6? and least-altered 87Sr/86Sr ratios of 0.70909, is reported herein from the Yurakhian Horizon of the Kulyumbe Formation. The stratigraphic position of the SPICE excursion does not support traditional correlation of the boundary between the Orakta and Labaz formations at Kulyumbe River with its supposedly equivalent level in Australia, Laurentia, South China, and Kazakhstan, where the Glyptagnostus stolidotus and G. reticulatus biozones are known to immediately precede the SPICE excursion and span the Middle-Upper Cambrian boundary. The Cambrian-Ordovician boundary is probably situated in the middle Nyajan Horizon of the Iltyk Formation, in which carbon isotope values show a local maximum below a decrease in the upper part of the Nyajan Horizon, attributed herein to the Tremadocian. A refined magnetic polarity sequence shows that the geomagnetic reversal frequency was very high during the Middle Cambrian at 5-10 reversals per Ma, assuming a total duration of ~10 Ma and up to 100 magnetic intervals in the Middle Cambrian. By contrast, the sequence attributed herein to the Upper Cambrian on chemostratigraphic grounds contains only 10-11 magnetic intervals. Preprint in Open Access hdl:10013/epic.30209.d001