Calcium carbonate dissolution in deep sea sediments: reconciling microelectrode, pore water and benthic flux chamber results

We report the benthic fluxes of O₂, titration alkalinity (TA), Ca²⁺, NO₃⁻, PO₄³⁻, and Si(OH)₄ from in situ benthic flux chamber incubations on the Ceara Rise and Cape Verde Plateau and compare them to previously published results. We find within analytical uncertainty that the TA flux is twice the calcium flux, suggesting that dissolution/precipitation of CaCO₃ is the principal mechanism controlling benthic TA and Ca²⁺ fluxes. At sites where the sediments contain significant (>35%) CaCO₃ and the overlying waters are supersaturated with respect to CaCO₃, the ratios of the total dissolution rate to the remineralization rate are significantly less than at all other study sites. We propose that these observations can be explained by precipitation of fresh CaCO₃ at the supersaturated sediment surface followed by redissolution deeper in the sediments because of metabolically-produced CO₂. A numerical simulation is presented to demonstrate the feasibility of this explanation. In addition, surface exchange reactions in high-CaCO₃ sediments coupled with high rates of particle mixing may also impact rates of metabolic dissolution and depress chamber-derived estimates of carbonate alkalinity and calcium benthic fluxes. These results suggest that at supersaturated, high CaCO₃ locations, previous models of sediment diagenesis may have overestimated the impact of metabolic dissolution on the preservation of CaCO₃ deposited on the sea floor.     

6: Classification of VMS deposits: Lessons from the South Uralides

VMS deposits of the South Urals developed within the evolving Urals palaeo-ocean between Silurian and Late Devonian times. Arc-continent collision between Baltica and the Magnitogorsk Zone (arc) in the south-western Urals effectively terminated submarine volcanism in the Magnitogorsk Zone with which the bulk of the VMS deposits are associated. The majority of the Urals VMS deposits formed within volcanic-dominated sequences in deep seawater settings. Preservation of macro and micro vent fauna in the sulphide bodies is both testament to the seafloor setting for much of the sulphides but also the exceptional degree of preservation and lack of metamorphic overprint of the deposits and host rocks. The deposits in the Urals have previously been classified in terms of tectonic setting, host rock associations and metal ratios in line with recent tectono-stratigraphic classifications. In addition to these broad classes, it is clear that in a number of the Urals settings, an evolution of the host volcanic stratigraphy is accompanied by an associated change in the metal ratios of the VMS deposits, a situation previously discussed, for example, in the Noranda district of Canada.Two key structural settings are implicated in the South Urals. The first is seen in a preserved marginal allochthon west of the Main Urals Fault where early arc tholeiites host Cu–Zn mineralization in deposits including Yaman Kasy, which is host to the oldest macro vent fauna assembly known to science. The second tectonic setting for the South Urals VMS is the Magnitogorsk arc where study has highlighted the presence of a preserved early forearc assemblage, arc tholeiite to calc-alkaline sequences and rifted arc bimodal tholeiite sequences. The boninitc rocks of the forearc host Cu–(Zn) and Cu–Co VMS deposits, the latter hosted in fragments within the Main Urals Fault Zone (MUFZ) which marks the line of arc-continent collision in Late Devonian times. The arc tholeiites host Cu–Zn deposits with an evolution to more calc-alkaline felsic volcanic sequences matched with a change to Zn–Pb–Cu polymetallic deposits, often gold-rich. Large rifts in the arc sequence are filled by thick bimodal tholeiite sequences, themselves often showing an evolution to a more calc-alkaline nature. These thick bimodal sequences are host to the largest of the Cu–Zn VMS deposits.The exceptional degree of preservation in the Urals has permitted the identification of early seafloor clastic and hydrolytic modification (here termed halmyrolysis sensu lato) to the sulphide assemblages prior to diagenesis and this results in large-scale modification to the primary VMS body, resulting in distinctive morphological and mineralogical sub-types of sulphide body superimposed upon the tectonic association classification.It is proposed that a better classification of seafloor VMS systems is thus achievable using a three stage classification based on (a) tectonic (hence bulk volcanic chemistry) association, (b) local volcanic chemical evolution within a single edifice and (c) seafloor reworking and halmyrolysis.     

Lithium isotopes in the system Qz-Ms-fluid:An experimental study

The fractionation of lithium isotopes among quartz, muscovite, and a chloride-bearing aqueous fluid has been investigated experimentally at 400°-500°C and 50-100 MPa. Experiments were performed for 15-60 days in cold seal vessels with natural mineral specimens. Lithium was introduced primarily through the fluid, which also contained KCl and HCl. In most runs, the fluid was prepared with the L-SVEC standard (δ⁷Li = 0) and was 1 M in total chloride with K/Li/H = 100/10/1. In two experiments, a ⁶Li spike was employed. The experiments demonstrate that quartz and muscovite are susceptible to pronounced, rapid shifts in Li isotopic composition by diffusion through interaction with a Li-bearing fluid, particularly at 500°C. At 500°C, fractionation factors were determined to be Δ_{quartz-aqueous} ≅ +8 to + 12‰ and Δ_{muscovite-aqueous} ≅ +18 to + 20‰. An intermineral fractionation factor is given by Δ_{muscovite-quartz} ≈ +9‰. At 400°C, the results suggest Δ_{quartz-aqueous} ≈ +4 to + 6‰. The study provides evidence of systematic fractionation in lithium isotopes at the temperatures of some magmatic processes, such as those associated with porphyry-type ore systems and pegmatites.     

Isotopic constraints on Columbia River flood basalt genesis and the nature of the subcontinental mantle

Pb, O, Nd, and Sr isotopic data for the Columbia River basalts paint a complex picture for the origin of this flood basalt province. At least 3 distinct mantle sources appear to have been involved, superimposed upon which are the effects of crystal fractionation and mass exchange with evolved crustal wallrocks. To a large degree, the initiation of Columbia River volcanism and the geochemical characteristics of the basalts appear to have been influenced by subduction of the Juan de Fuca plate beneath the North American plate in a manner analogous to the origin of back-arc basins. The physical structure of the crust appears to have influenced the late stage evolution of the magmas by directing the locus of eruption to the border between the ancient continental interior and much younger crust to the south and west. This proximity to the continental interior also allowed old enriched subcontinental mantle to become involved in the very late stages of Columbia River volcanism. An important consequence of the existence of enriched mantle regions beneath continents is that the combination, crust plus enriched mantle, requires more incompatible elements to have been extracted from the remainder of the mantle than would be the case if no enriched mantle existed.     

pp′-DDT adsorption to suspended particulate matter in sea water

A procedure was devised to study pp′-DDT [2,2-bis($\text{p-}\text{chlorophenyl}$)-1,1,1-trichloroethane] adsorption and desorption to suspended particulates in aqueous solutions. DDT adsorption to a marine sediment, sediment fractions, clay and humic acid suspended in sea water was investigated and the humic fraction was found to have a greater adsorbing capacity than the clay or sediment. Removal of the humic fraction from sediment reduced the adsorption capacity to less than 60 per cent of the original sediment sample. It was concluded that suspended humic particulates may be important agents for transporting chlorinated hydrocarbons through the water column and for concentrating them in sediments and in detritus-feeding organisms.     

The effect of annealing on the luminescence decay-time of synthetic calcite:Mn

Calcite was synthesized by four methods, and the luminescence decay-time was measured for nine samples before and after heating hydrothermally in the temperature range 200–400°C. Decay-time data were collected between room temperature and approximately 15 K. The decay time at room temperature is approximately 50 ms, with little difference between a given calcite before and after hydrothermal treatment. The decay time at 15 K is always greater than at room temperature as the effect of thermal quenching diminishes. Differences in decay time before and after heating are more apparent at low temperature owing to this reduction in thermal quenching. The decay time decreased significantly in two samples, and an increase in decay time was observed in the remaining seven samples following heating. Among the latter group, the change in decay time was insignificant in three samples. The results are compared with previous data in which it was shown that the effect of heating is to increase the intensity of luminescence.     

An Anatomy of Adaptation to Climate Change and Variability

Adaptation to climate variability and change is important both for impact assessment (to estimate adaptations which are likely to occur) and for policy development (to advise on or prescribe adaptations). This paper proposes an "anatomy of adaptation" to systematically specify and differentiate adaptations, based upon three questions: (i) adapt to what? (ii) who or what adapts? and (iii) how does adaptation occur? Climatic stimuli include changes in long-term mean conditions and variability about means, both current and future, and including extremes. Adaptation depends fundamentally on the characteristics of the system of interest, including its sensitivities and vulnerabilities. The nature of adaptation processes and forms can be distinguished by numerous attributes including timing, purposefulness, and effect. The paper notes the contribution of conceptual and numerical models and empirical studies to the understanding of adaptation, and outlines approaches to the normative evaluation of adaptation measures and strategies.