Dolomite-rich coralline algae in reefs resist dissolution in acidified conditions

Coral reef ecosystems develop best in high-flow environments but their fragile frameworks are also vulnerable to high wave energy. Wave-resistant algal rims, predominantly made up of the crustose coralline algae (CCA) Porolithon onkodes and P. pachydermum, are therefore critical structural elements for the survival of many shallow coral reefs. Concerns are growing about the susceptibility of CCA to ocean acidification because CCA Mg-calcite skeletons are more susceptible to dissolution under low pH conditions than coral aragonite skeletons. However, the recent discovery of dolomite (Mg0.5Ca0.5(CO3)), a stable carbonate, in P. onkodes cells necessitates a reappraisal of the impacts of ocean acidification on these CCA. Here we show, using a dissolution experiment, that dried dolomite-rich CCA have 6-10 times lower rates of dissolution than predominantly Mg-calcite CCA in both high-CO2 (~ 700 ppm) and control (~ 380 ppm) environments, respectively. We reveal this stabilizing mechanism to be a combination of reduced porosity due to dolomite infilling and selective dissolution of other carbonate minerals. Physical break-up proceeds by dissolution of Mg-calcite walls until the dolomitized cell eventually drops out intact. Dolomite-rich CCA frameworks are common in shallow coral reefs globally and our results suggest that it is likely that they will continue to provide protection and stability for coral reef frameworks as CO2 rises.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Geochemistry and mineralogy of coal samples from Dingji Mine, Huainan Coalfield, China

To investigate the geochemistry of trace elements in coals from the Dingji Mine of the Huainan Coalfield, Anhui province, China, 416 borehole samples of coal, one parting, two floor and two roof mudstones were collected from 9 minable coal seams in 24 boreholes drilled during exploration. The abundances of 47 elements in each sample were determined by various instruments. The boron concentration in the coals suggests that marine influence decreased from coal seam 1 to 13-1. The geometric means of the elements Sn, Bi, Sb, and B are higher than the average for the corresponding elements in the coals from China, the U.S., and world. The enrichment of certain elements in the Shanxi or Upper Shihezi Formations is related to their depositional environment. The roof, floor and parting samples have higher contents of some elements than coal seams. The mineral matters in the coals from the Dingji Mine were found to consist mainly of granular quartz, clay minerals, and carbonate minerals. The elements are classified into two groups based on their stratigraphic distribution from coal seam 1 to 13-1, and the characteristics of each group are discussed. Based on the correlation coefficients of elemental concentrations with ash yield, four groups of elements with different affinities were identified.

Sedimentology of surface sediments from the continental shelf and slope off West Africa (Table 1)

Samples from sutface sediments of the shell, continental slope, and adjacent deep sea regions off West Africa between 27° N and 15° N were investigated with respect to grain size distribution of the total samples, sand contents of the acid insoluble residues, carbonate content of the total samples, and the separate grain size fractions, specific surfaces, colours and mineralogical composition of the clay fractions. The grain size distributions of the total samples of the sediments of the shelf and the continental slope off Spanish-Sahara are controlled mainly by biogenic components. The supply of terrigeneous material in this area is very low. At deeper parts of the continental slope and in the deep sea areas, the relative amounts of carbonate minerals in the sediments are considerably reduced. The prevailing sand contents of the upper slope changes into clay dominance. On the shelf of Mauritania - represented by profiles extending down to 200 m water depth - the grain size is also controlled mainly by biogenic carbonates. Nevertheless, the admixture of fossil silicate components is important, too. The southern parts of the area is investigated are located in a region influenced by sediments of the Senegal River, which especially control the contents of silt and clay. The silicate sands, predominately of quartz, are fossil and form a mixed sediment with younger deposits. The carbonate contents of the different grain size fractions are formed either by sedimentation of carbonate and silicate particles of the respective grain size or by autochtonous disintegration of coarser sediment particles, as shown by the occurence of Mg-rich calcite and especially aragonite in the clay sized fraction. In the northern parts of the area investigated, which have very minute terrigeneous supply, the latter mechanism is the dominant factor, controlling the carbonate contents of the fine grain sized fractions. In the vicinity of the mouth of the Senegal the carbonate contents are influenced by extremely high dilution with terrigencous silicates. Mg-rich calcite and aragonite are produced preferentially in shallow slope and shelf areas up to 500 m of water depth. The specific surfaces of the carbonate-free clay fractions indicate that the clay fractions of the shelfareas with little terrigenous supply consits of relatively coarser particles. Very fine particles are removed and transported towards the deep sea. Lateral differentiation of this kind was not observed in the area off Senegal. The high surface areas, characterizing the clay fractions of this region, are thought to be due to high montmorillonite contents as was found for deep seas sediments. The mineralogical composition of the clay fraction from the southern parts of the area is characterized by high kaolinite and montmorillonite contents, while in the northern illite is predominating. At least two types of montmorillionites are present: in areas influenced by the Senegal mostly one type was found, which could swell to 17; on the shelves and slopes of the other regions the montmorillonite-group is represented by a montmorillonite-mica-type mixed-layer mineral. A "glauconite", found in the sand fraction, which had very similar properties to those of the montmorillonite-mica mixed-layer, is believed to be the source of this mixed-layer-type mineral. Palygorskite is present in all samples out of range of the Senegal supply. It may be an indicator of eolian transported material. The occurence of rich palygorskit deposits in the arid hinterlands emphasizes the terrestrial origin.

Isotope characterization and estimated temperature of formation of calcite veins in ODP Sites 124-768 and 124-770 (Table 1)

Secondary carbonate minerals were recovered within the basalts at both ODP Sites 768 and 770 in the Sulu and Celebes seas. Petrographic and X-ray diffraction analyses indicate that the carbonates are calcites. Other alteration products recognized in the thin sections are smectites, iron oxides, and gypsum. The 13C values of carbonates from both sites range from 1.6 per mil to 2.3 per mil, which are indicative of inorganic carbonate formation with no contributions from 13C-depleted sources such as oxidized organic carbon or methane. The oxygen isotopes at Site 770 range from 30.8 per mil to 31.6 per mil, which indicates a pervasive circulation of cold seawater (9° to 12°C) during alteration of the Celebes Sea basalts. In contrast, carbonates associated with Site 768 basalts have less positive d18O values (21.0 per mil to 27.3 per mil). A lighter 18O isotopic signature indicates the formation of secondary calcite at either higher temperatures or in a system closed to seawater. The rapidly deposited pyroclastic flows at Site 768 would have limited water access to the crust very soon after its formation, which leads us to speculate that the carbonates in the Sulu Sea basalts were formed by isotopically modified fluids resulting from basalt alteration in a closed system.

Isotopes content, mineralogical composition, Uranium and Thorium contents and determined activity ratios from METEOR cruise M74/3 in 2007

Authigenic carbonate deposits have been sampled with the remotely operated vehicle 'MARUM-QUEST 4000 m' from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea). Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent, sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The delta18O carbonate values range from 1.3 to 4.2 per mil V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low delta13Ccarbonate values (as low - 54.6per mil V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by delta13C methane values ranging from - 70.3 to - 66.7per mil V-PDB, and also by back-calculations considering delta 13C methane values of carbonate and incorporated lipid biomarkers.

(Table 1) Water chemistry of groundwater and snow samples from three sites in Ontario, Canada

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently ''natural'' ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path. Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.

(Table T1) Geochemical composition of tochilinite and related minerals of ODP Hole 173-1068A

Tochilinite (approximately FeS(Mg,Fe)(OH)2) is locally abundant in Hole 1068A serpentinites from Cores 173-1068A-21R and 22R. It occurs in veins, as fillings in void space, and in intergrowths with serpentine and andradite. An apparently related mineral, but with Ca and Al largely replacing Mg, occurs in association with, and possibly as a replacement of, pyrrhotite in serpentinite breccias from the bottom of Core 173-1068A-20R. The transition from Mg-Fe-rich brucite tochilinites to Ca- and S-rich carbonate tochilinites is consistent with increasing sulfur and oxygen activity upsection. Tochilinite has been reported at other sites on the Iberia Abyssal Plain and is abundant to the point of being a rock-forming mineral in several samples from Site 1068. Rather than being a mineralogical curiosity, tochilinite appears to be common and a major sink for sulfur in the upper serpentinites of the Iberia Abyssal Plain.

(Table 1) Composition of clay minerals in DSDP Hole 75-532

An investigation of the quantitative composition of the coarse (> 40 µm) and clay (< 2 µm) fraction of HPC 532, DSDP Leg 75, in 1300 m water depth on the eastern Walvis Ridge off Southwest Africa yielded the following results: (1) The sediments reflect a complete Latest Miocene to Recent depositional history. Sedimentation rates vary between 2.3 and 7.8 cm/ka. (2) Preservation of calcium carbonate is subject to strong variations: short-term (< 100,000 years) and long-term (about 1 m.y.) cycles in carbonate dissolution have been observed, with strongest dissolution occurring during periods of lowered sea level. (3) Upwelling influence from the near-coastal upwelling centre has been detected by means of the opal content: interglacial periods show high opal contents, because the Benguela Current turned westward at about 20°S and carried opal-laden upwelled water to the west. Sediments from glacial periods, however, show opal minima. Besides these short-term cyclic variations in opal content, long-term cycles have been found, with maximum upwelling influence in the latest Pliocene/early Quaternary. (4) Each CaCO3 dissolution minimum (maximum) is correlated with an opal maximum (minimum) throughout the sediment sequence. (5) The oceanographic system off southwest Africa remained essentially unchanged since the latest Miocene: sea level rose and fell periodically on a small and on a large scale, and the Benguela Current flowed southeast-northwest and turned to the west at the latitude of Site 532 during interglacial periods, when sea level was high. (6) The climate in the near-coastal area of southwest Africa in the latitude of Site 532 has probably been arid throughout the investigated period.

Lithofacies, chronostratigraphy, minerals and diagenetic silica facies at DSDP Leg 80 Holes

X-ray powder diffraction and optical and scanning-electron microscope analyses of sediment samples taken from four sites drilled in the Goban Spur area of the northeast Atlantic show variable diagenetic silicification of sediments at several stratigraphic horizons. The results are as follows: 1. The silicified sediments are middle Eocene at Site 548, Paleocene to lower Albian at Site 549, upper to lower Paleocene at Site 550, and lower Turanian at Site 551. 2. There are three types of these silicified sediments: nodular type in carbonate-rich host sediments, bedded type in clayey host sediments, and a type transitional between the other two. 3. Silica diagenesis is considered to progress as follows: dissolution of siliceous fossils; precipitation of opal CT in pore spaces and transformation of biogenic silica (opal A) to opal CT, development of opal CT cement; chalcedonic quartz precipitation in pore spaces and replacement of foraminiferal tests by chalcedonic quartz; and finally, transformation of opal CT to quartz, and cementation. But the strong influence of host-sediment types on diagenetic silica fades is recognized. Bedded-type silicified sediments in a clayey environment indicate a lower grade of silica diagenesis. Only very weak chalcedonic quartz formation is recognized, and there is no opal CT cementation, even in Lower Cretaceous bedded-type clayey silicified sediments. 4. The rf(101) spacing of opal CT shows two distinct trends of ordering or decrease with burial depth; one is a rapid change, in the case of nodular silicified sediments, and the other is a more gentle shift, found in bedded silicified sediments. 5. Diagenetic silica facies of the nodular type develop as irregular concentric zones around some nodule nuclei. Also, quartz-chert nodule formation occurs at rather shallower horizons, and is discordant with the trend of decreasing d(101) spacing in opal CT. 6. Silicified sediments at Site 551 are shallower than at the other sites. The diagenetic silica facies suggest the probable erosion of 300 m or more of sediment at this site. 7. The zeolites clinoptilolite and phillipsite were found in the sediment samples recovered on Leg 80. Clinoptilolite occurs from the shallower levels to the deepest horizons of diagenetically silicified zones, suggesting that clinoptilolite formation is related to diagenesis of biogenic silica. Phillipsite at Site 551 (Section 551-5-2) may originate from volcanogenie material.

(Table 1) Color, Fe-C-S chemistry and carbonate content from ODP Sites 172-1062 and 172-1063

Reflectance spectra collected during ODP Leg 172 were used in concert with solid phase iron chemistry, carbonate content, and organic carbon content measurements to evaluate the agents responsible for setting the color in sediments. Factor analysis has proved a valuable and rapid technique to detect the local and regional primary factors that influence sediment color. On the western North Atlantic drifts, sediment color is the result of primary mineralogy as well as diagenetic changes. Sediment lightness is controlled by the carbonate content while the hue is primarily due to the presence of hematite and Fe2+/Fe3+ changes in clay minerals. Hematite, most likely derived from the Permo-Carboniferous red beds of the Canadian Maritimes, is differentially preserved at various sites due to differences in reductive diagenesis and dilution by other sedimentary components. Various intensities for diagenesis result from changes in organic carbon content, sedimentation rates, and H2S production via anaerobic methane oxidation. Iron monosulfides occur extensively at all high sedimentation sites especially in glacial periods suggesting increased high terrigenous flux and/or increased reactive iron flux in glacials.