J.M. McArthur

Arsenic poisoning of Bangladesh groundwater

In Bangladesh and West Bengal, alluvial Ganges aquifers used for public water supply are polluted with naturally occurring arsenic, which adversely affects the health of millions of people. Here we show that the arsenic derives from the reductive dissolution of arsenic-rich iron oxyhydroxides, which in turn are derived from weathering of base-metal sulphides. This finding means it should now be possible, by sedimentological study of the Ganges alluvial sediments, to guide the placement of new water wells so they will be free of arsenic.

Mechanism of arsenic release to groundwater, Bangladesh and West Bengal

In some areas of Bangladesh and West Bengal, concentrations of As in groundwater exceed guide concentrations, set internationally and nationally at 10 to 50 m gl ˇ1 and may reach levels in the mg l ˇ1 range. The As derives from reductive dissolution of Fe oxyhydroxide and release of its sorbed As. The Fe oxyhydroxide exists in the aquifer as dispersed phases, such as coatings on sedimentary grains. Recalculated to pure FeOOH, As concentrations in this phase reach 517 ppm. Reduction of the Fe is driven by microbial metabolism of sedimentary organic matter, which is present in concentrations as high as 6% C. Arsenic released by oxidation of pyrite, as water levels are drawn down and air enters the aquifer, contributes negligibly to the problem of As pollution. Identification of the mechanism of As release to groundwater helps to provide a framework to guide the placement of new water wells so that they will have acceptable concentrations of As. # 2000 Elsevier Science Ltd. All rights reserved.

Strontium Isotope Stratigraphy: LOWESS Version 3: Best Fit to the Marine Sr‐Isotope Curve for 0–509 Ma and Accompanying Look‐up Table for Deriving Numerical Age

An improved and updated version of the statistical LOWESS fit to the marine 87Sr/86Sr record and a revised look‐up table (V3:10/99; available from j.mcarthur@ucl.ac.uk) based upon it enables straightforward conversion of 87Sr/86Sr to numerical age, and vice versa, for use in strontium isotope stratigraphy (SIS). The table includes 95% confidence intervals on predictions of numerical age from 87Sr/86Sr. This version includes the Triassic and Paleozoic record (0–509 Ma) omitted from previous versions because of the paucity of adequate data at the time of preparation. We highlight differences between the previous versions of the table and the current version and discuss some aspects of the 87Sr/86Sr record that may have geological significance. We give examples of how the table can be used and where it has proven useful.

Arsenic in groundwater: Testing pollution mechanisms for sedimentary aquifers in Bangladesh

In the deltaic plain of the Ganges-Meghna-Brahmaputra Rivers, arsenic concentrations in groundwater commonly exceed regulatory limits (.50 m gL 21 ) because FeOOH is microbially reduced and releases its sorbed load of arsenic to groundwater. Neither pyrite oxidation nor competitive exchange with fertilizer phosphate contribute to arsenic pollution. The most intense reduction and so severest pollution is driven by microbial degradation of buried deposits of peat. Concentrations of ammonium up to 23 mg L 21 come from microbial fermentation of buried peat and organic waste in latrines. Concentrations of phosphorus of up to 5 mg L 21 come from the release of sorbed phosphorus when FeOOH is reductively dissolved and from degradation of peat and organic waste from latrines. Calcium and barium in groundwater come from dissolution of detrital (and possibly pedogenic) carbonate, while magnesium is supplied by both carbonate dissolution and weathering of mica. The 87 Sr/ 86 Sr values of dissolved strontium define a two-component mixing trend between monsoonal rainfall (0.711 6 0.001) and detrital carbonate (,0.735).

Strontium isotope profile of the early Toarcian (Jurassic) oceanic anoxic event, the duration of ammonite biozones, and belemnite palaeotemperatures

We profile 87Sr/86Sr, δ13C, δ18O, Sr/Ca, Mg/Ca, and Na/Ca in belemnites through Pliensbachian and Toarcian strata on the Yorkshire coast, UK, which include the early Jurassic oceanic anoxic event. The 87Sr/86Sr profile shows that the relative duration of ammonite subzones differ by a factor of up to 30: the Lower Jurassic exaratum subzone is 30 times longer than the clevelandicum subzone because the exaratum subzone in Yorkshire, which contains the anoxic event, is condensed by a factor of between 6.5 and 12.2 times, relative to adjacent strata. Using our 87Sr/86Sr profile, the resolution in correlation and dating attainable in the interval is between ±1.5 m and ±15 m of section, and better than 0.25 Myr. In parts of the sequence, this stratigraphic resolution equals that attainable with ammonites. A new age model is provided for late Pliensbachian and early Toarcian time that is based on the 87Sr/86Sr profile. Through the sequence, the Sr/Ca, Mg/Ca, Na/Ca and δ18O of belemnite carbonate covary, suggesting that elemental ratios may be useful for palaeotemperature measurement. Our δ13Cbelemnite data splits into three the previously reported positive isotope excursion (to +6.5‰) in the early Toarcian. We speculate that the excursion(s) resulted from addition to surface waters of isotopically heavy CO2 via ebullition of methanogenic CO2 from the sediment during early burial of organic rich (>10% TOC) sediments

Statistics For Strontium Isotope Stratigraphy: A Robust Lowess Fit to the Marine Sr‐Isotope Curve For 0 to 206 Ma, With Look‐Up Table For Derivation of Numeric Age

We provide a best‐fit curve to 1849 strontium isotope data for the period 0 to 206 Ma using the LOcally‐WEighted regression Scatterplot Smoother (LOWESS) method. This is a robust, nonparametric modern regression technique. Since it does not yield an explicit mathematical equation relating 87Sr/86Sr to time, a look‐up table to determine numeric age has been generated in steps of 1 × 10−6 in 87Sr/86Sr. The calibration uses the timescales of Shackleton and coworkers for 0‐7 Ma; Cande and Kent for 7‐72 Ma; Obradovich for 72‐95 Ma and Gradstein and coworkers for >95 Ma. The look‐up table includes 95% confidence intervals on the predictions of numeric age. When using this table, the uncertainty on the 87Sr/86Sr of the sample whose age is sought must be added to that inherent in the LOWESS regression. We show how to determine the uncertainty in 87Sr/86, i.e., how best to obtain the 95% confidence bounds on a single measurement of 87Sr/86 for a sample, and on the mean 87Sr/86 value for 2 or more replicate measurements of 87Sr/86 in the sample; these confidence intervals reflect analytical‐system reproducibility for routine samples (as opposed to that of standard control materials, e.g., NIST 987) and are necessary to establish the final upper and lower bounds on predicted numeric age.

Paleoceanographic changes of the Late Pliensbachian–Early Toarcian interval: a possible link to the genesis of an Oceanic Anoxic Event

Abstract Secular records of the elemental and isotopic composition of belemnite calcite were studied in Pliensbachian and Toarcian sections from the Yorkshire coast, UK, and Southern Germany, to investigate oceanographic change during an interval prior to and including the Toarcian Oceanic Anoxic Event (OAE). Records from Southern Germany are correlated to the UK stratigraphy using strontium isotope stratigraphy. The geochemical trends measured from belemnite calcite are consistent between the two sections, and are interpreted in terms of temperature and salinity of the northwest European epi-continental sea. The data suggest that a dramatic environmental change coincided with the Toarcian OAE. Belemnite Mg/Ca, Sr/Ca, and Na/Ca ratios increase by a factor of between 1.7 and 2 coincident with a 3‰ negative shift in δ18O from the mid-tenuicostatum zone until the lower falciferum zone of the UK ammonite biostratigraphy (a period of ∼0.6–0.7 Myr). Taken at face value, the Mg/Ca and δ18O data argue for an abrupt warming of 6–7°C and substantial freshening during this interval. Global warming accompanied by an accelerated hydrological cycle and increased runoff is proposed to explain these changes. Prior to these events, data from lower in the Yorkshire section suggest a possible cooling accompanied by a shift to more saline waters during the period from the upper Pliensbachian margaritatus zone to the Toarcian lower tenuicostatum zone. This earlier event may also have been important in causing density stratification in the northwest European epi-continental sea.

Basinal restriction, black shales, Re‐Os dating, and the Early Toarcian (Jurassic) oceanic anoxic event

[1] Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187 Os/ 188 Os and d 98 Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3% in d 98 Mo and up to 0.6% for 187 Os/ 188 Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d 98 Mo and initial 187 Os/ 188 Os for palaeo-oceanographic interpretation.

Toarcian oceanic anoxic event: An assessment of global causes using belemnite C isotope records

) from black shales markingthe Toarcian oceanic anoxic event (T-OAE). The first explanation envisions recycling of dissolved inorganiccarbon (DIC) with a light isotopic signature into the photic zone from the lower levels of a salinity-stratifiedwater mass, essentially requiring a regional paleoceanographic driver of the carbon cycle. The second involvesthe rapid and massive dissociation of methane from gas hydrates that effectively renders the T-OAE a globalperturbation of the carbon cycle. We present C isotope records from belemnites (d

RARE-EARTH GEOCHEMISTRY OF PHOSPHORITES

Abstract The abundance of rare-earth elements (REEs) in francolite increases with increasing age as a result of post-depositional enrichment. Abundances are higher in pelletal samples than in non-pelletal ones because the higher surface/mass ratio of pelletal francolite promotes enrichment during diagenesis. Onshore francolite has higher REE abundances than that found offshore. Distribution patterns in francolite may be similar to those reported for open-ocean water or shale, depending upon the dominant source of the REEs: different patterns result from weathering and deep-burial diagenetic modification of the original patterns and abundances. Negative Ce anomalies occur in francolites containing structural sulphur that is isotopically indistinguishable from seawater of the same age; zero or positive anomalies occur in francolites which contain sulphur that is isotopically lighter than seawater.