Geochemistry of Early Toarcian carbonates

The Early Toarcian was characterized by two large perturbations to the carbon cycle: a positive trend associated with increased organic matter burial and ocean anoxia, and a pronounced negative carbon isotope excursion (CIE). We contrast the geochemical evolution in the carbonate phases of two successions: one from the Paris Basin (Sancerre core, comprising black shales), the other from the Lusitanian Basin (Peniche section with very minor lithological expression of bottom water anoxia). Our aim was to identify whether these carbon cycle perturbations were related, and differentiate between the common (global) versus regional expressions of the biogeochemical response and ocean chemistry. Our results highlight contrasts in timing of different phases of anoxia in both locations through the widely documented negative CIE. Widespread anoxic conditions were not a necessary prerequisite for generating a pronounced CIE, as required by the recycling (so-called "Küspert") model. The production of carbonate simultaneously dropped during the d13C negative shift in both locations, likely in response to lowered seawater saturation rate induced by substantial absorption of CO2 from the atmosphere. The recovery interval was accompanied by a rapid reestablishment of seawater alkalinity, and primary and carbonate productivity in epicontinental seas, as evidenced by high d13C and Sr/Ca, in contrast with the more open ocean regime in the Lusitanian Basin. Our results confirm that parallels can be draw between the ocean productivity response and feedback during the Toarcian CIE and the PETM. Both events are characterized by ocean acidification and reduced pelagic calcification followed by a peak in nearshore coccolith productivity, which could have helped the recovery from the perturbation.

The influence of calcium and magnesium on the growth of the lichens Parmelia saxatilis and Xanthoria parietina on slate substrates

In South Gwynedd, Wales, U.K., the calcicole lichen Xanthoria parietina occurs not only on alkaline substrates at inland sites but also on siliceous rock at coastal martimie sites while the calcifuge species Parmelia saxatilis occurs only at inland sites and on slate rocks. Samples of maritime and inland slate did not differ significantly in their calcium or magnesium content. Thalli of X. parietina on pieces of slate did not survive when transplanted from maritime rocks to a site inland. Thalli of maritime X. parietina and P. saxatilis on slate were then transplanted to a site inland and were treated at intervals during 1 year either with calcium carbonate applied as a thick paste or a 0.25 mM solution of calcium chloride. Treatment of X. parietina with calcium carbonate enabled the thalli to survive and grow. However, addition of calcium carbonate to P. saxatilis resulted in low growth rates and fragmentation of the centres of the thalli. The calcium chloride solution had no statistically significant effects on the growth of either species. In addition, thalli of both species were treated with calcium or magnesium carbonates or wetted with an alkaline buffer at intervals over 12-14 months. Thalli of X. parietina survived and grew rapidly when treated with either carbonate but the growth of the buffer-treated thalli gradually declined over the experimental period. Thalli of P. saxatilis fragmented and disappeared after 8-10 months after treatment with either carbonate but normal growth occurred in the buffer treatment. Xanthoria parietina may occur on siliceous maritime rocks at the site because of the presence of calcium or magnesium in sea spray combined with the spray’s alkaline pH. By contrast, P. saxatilis may be confined to siliceous rocks inland because the thalli grow poorly in the presence of calcium and magnesium.

Chemical composition of hydrothermal carbonates and barites from the Deryugin Basin, Sea of Okhotsk

Data on hydrothermal activity in the Deryugin Basin (Sea of Okhotsk) are reviewed. Barites and carbonates found in sediment cores sampled at feet of hydrothermal mounds were subdivided into recycled and authigenic types. Recycled minerals were represented by crystals and aggregations of travertine-like barite and fragments of barite and carbonate tubes. Authigenic formations included: (1) carbonate nodules; (2) barite micronodules; (3) transparent colorless barite that generated numerous small nests and filled cavities in sediments; (4) yellow barite formed thin (0.5 mm) veins; and (5) white barite cemented small aggregations of coarse-grained sediments. A detailed examination of formation processes of authigenic minerals in the bottom sediment cores allowed to conclude that, there, hydrothermal activity is still going on today. This was confirmed by high methane concentration in near-bottom water above a field of hydrothermal barite minerals.

Table 2: Isotopic and elemental compositions of Mesoproterozoic carbonates from Yanshan, North China

In Yanshan, located in the northern part of North China, Mesoproterozoic carbonate sequences (1.6-1.4 Ga) form a 10, 000m thick succession in an aulacogen basin. Carbon and oxygen isotope (d13O and d18O, resp.) data were obtained from 110 carbonate samples across three sections of these Mesoproterozoic deposits. From the early to late Mesoproterozoic, low negative values of d13O appear, followed by low positive variation and then a stable increase. An abrupt decrease in d13O values, with subsequent rapid increase, is found at the end of the Mesoproterozoic. During the whole Mesoproterozoic, d18O shows a mainly negative trend and occasional highly negative isotopic shifts (from lower to upper deposits). Whole-rock carbon and oxygen isotopic compositions and profilesmust be studied to provide a paleogeochemical record that can be associated with paleocean sedimentary environments, temperature, biological productivity, and sea-level fluctuations. Results of the present study correlate well with other international carbon and oxygen isotope profiles, suggesting that a global marine geochemical system existed during the interval of 1.6-1.4 Ga under a globally united tectonic, sedimentary, and geochemical background.

(Table 1) Peak intensities and stable carbon and oxygen isotope ratios of various diagenetic carbonates of ODP Site 128-799

Abundant and various diagenetic carbonates were recovered from a 1084-m-thick, Quaternary to lower Miocene section at ODP Site 799 in the Japan Sea. Petrographic, XRD, SEM, EDS-chemical, and isotopic analyses revealed wide variations in occurrence and textural relations and complex mineralogy and chemistry. Diagenetic carbonates include calcite, calcium-rich rhodochrosite, iron- and manganese-rich magnesite, iron- and manganese-rich dolomite and ankerite, and iron- and manganeserich lansfordite (hydrous Mg-carbonate). Rhodochrosite commonly occurs as small, solid nodules and semi-indurated, thin layers in bioturbated, mottled sediments of Units I and II (late Miocene to Quaternary). Lansfordite occurs as unindurated nodules and layers in Unit II (late Miocene and Pliocene), whereas magnesite forms indurated beds a few centimeters thick in slightly bioturbated-to-faintly laminated sediments of Unit III (middle and late Miocene). Some rhodochrosite nodules have dark-colored, pyritic cores, and some pyrite-rhodochrosite nodules are overgrown by and included within magnesite beds. Dolomite and ankerite tend to form thick beds (>10 cm) in bedded to laminated sediments of Units III, IV, and V (early to late Miocene). Calcite occurs sporadically throughout the Site 799 sediments. The d18O values of carbonates and the interstitial waters, and the measured geothermal gradient indicate that almost all of the Site 799 carbonates are not in isotopic equilibrium with the ambient waters, but were precipitated in the past when the sediments were at shallower depths. Depths of precipitation obtained from the d18O of carbonates span from 310 to 510 mbsf for magnesite and from 60 to 580 mbsf for dolomite-ankerite. Rhodochrosite and calcite are estimated to have formed within sediments at depths shallower than 80 mbsf. Diagenetic history in the Site 799 sediments have been determined primarily by the environment of deposition; in particular, by the oxidation-reduction state of the bottom waters and the alkalinity level of the interstitial waters. Under the well-oxygenated bottom-water conditions in the late Miocene and Pliocene, manganese initially accumulated on the seafloor as hydrogenous oxides and subsequently was mobilized and reprecipitated as rhodochrosite within the shallow sulfate-reduction, sub-oxic zone. Precipitation of lansfordite occurred in the near-surface sediments with abundant organic carbon and an extremely high alkalinity during the latest Miocene and Pliocene. The lansfordite was transformed to magnesite upon burial in the depth interval 310 to 510 mbsf. Dolomite first precipitated at shallow depths in Mn-poor, anoxic, moderately biocalcareous sediments of early to late Miocene. With increasing temperature and depth, the dolomite recrystallized and reequilibrated with ambient waters at depths below about 400 mbsf.

(Table 1) Calcium carbonate and trace elements at DSDP Leg 80 Holes

The evolution through time of trace element contents (Sr, Mg, Mn, and Fe) of sediments at Sites 549 and 550 is similar to that of previously studied oceanic sites. A comparison with some North Atlantic sites and with outcrops of the Gubbio section (Italy) allowed us to show that 1. A negative correlation between Sr and Mg contents, generally characteristic of pelagic carbonate having undergone diagenesis, is confirmed. 2. Magnesium diagenesis occurs over a relatively short time and is sensitive to the sedimentation rate of each individual time period, whereas Sr diagenesis is a long-term phenomenon and is sensitive to the overall average sedimentation rate at the site. Strontium loss by sediments is related to sediment age (i.e., residence time of sediments in a given diagenetic environment) and could be a rough method of dating individual sediment layers. 3. The nature of the seafloor (oceanic or continental) does not appear to play an important part in the content of Fe and Mn in sediments. Their distribution depends more on mid-oceanic ridge activity, paleodepth (through mediation of CaCO3 dissolution and environment), and distance of the site from the ridge.

Calcium carbonate content in surface sediments and benthic fauna on Antarctic shelves

We analyzed 214 new core-top samples for their CaCO3 content from shelves all around Antarctica in order to understand their distribution and contribution to the marine carbon cycle. The distribution of sedimentary CaCO3 on the Antarctic shelves is connected to environmental parameters where we considered water depth, width of the shelf, sea-ice coverage and primary production. While CaCO3 contents of surface sediments are usually low, high(> 15%) CaCO3 contents occur at shallow water depths (150-200 m) on narrow shelves of the eastern Weddell Sea and at a depth range of 600-900 m on the broader and deeper shelves of the Amundsen, Bellingshausen and western Weddell Seas. Regions with high primary production, such as the Ross Sea and the western Antarctic Peninsula region, have generally low CaCO3 contents in the surface sediments. The predominant mineral phase of CaCO3 on the Antarctic shelves is low-magnesium calcite. With respect to ocean acidification, our findings suggest that dissolution of carbonates in Antarctic shelf sediments may be an important negative feedback only after the onset of calcite undersaturation on the Antarctic shelves. Macrozoobenthic CaCO3 standing stocks do not increase the CaCO3 budget significantly as they are two orders of magnitude lower than the budget of the sediments. This first circumpolar compilation of Antarctic shelf carbonate data does not claim to be complete. Future studies are encouraged and needed to fill data gaps especially in the under-sampled southwest Pacific and Indian Ocean sectors of the Southern Ocean.