Rj Howarth

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.

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.

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.

Strontium isotope profiles across K/T boundary sequences in Denmark and Antarctica

Strontium isotope profiles, derived from minimally altered samples, across marine K/T boundary sequences exposed at Kjolby Gaard and Nye Klov, Denmark, and on Seymour Island, Antarctica, show neither the boundary excursions, nor the boundary spikes, in 87Sr/86Sr that have been reported for K/T boundary sequences from elsewhere. Nor do our data conform to modelled predictions of the Sr isotopic response of the oceans to a positive spike in 87Sr/86Sr at the terminal Cretaceous. Boundary values for 87Sr/86Sr (with 95% confidence intervals) are 0.707828±3 in Denmark and 0.707832±7 in Antarctica. Our data suggest that 87Sr/86Sr stopped increasing and started decreasing at least 90 ka before the K/T boundary.

Comment on "limited temporal variability of arsenic concentrations in 20 wells monitored for 3 years in Araihazar, Bangladesh".

Millions of people in Bangladesh have probably switched their water consumption to wells that meet the local standard for As in drinking water of 50 μg/L as a result of blanket field testing throughout the country. It is therefore important to know if As concentrations in those wells could change over time. To address this issue, we report here precise groundwater As analyses for time-series samples collected from a suite of 20 tube wells containing e50 μg/L As and ranging from 8 to 142 m in depth. For 17 out of 20 wells, the standard deviation of groundwater As concentrations was <10 μg/L over the 3-year monitoring period (n ) 24-44 per well). Six of the 17 wells are community wells, each of which serves the needs of several hundred people in particularly affected villages. Of the three wells showing larger fluctuations in chemical composition including As, two are very shallow (8 and 10 m). Variations in As concentrations for one of these wells (50 ( 32 μg/L, n ) 36), as well as another shallow well showing smaller variations (48 ( 5 μg/L, n ) 36), appear to be coupled to seasonal precipitation and recharge linked to the monsoon. The other shallow well showing larger variations in composition indicates a worrisome and steady increase in As concentrations from 50 to 70 μg/L (n ) 36) over 3 years. The time series of As (30 ( 11 μg/L, n ) 24) and other constituents in one deep community well (59 m) show large fluctuations that suggest entrainment of shallow groundwater through a broken PVC pipe. Even though the majority of wells that were initially safe remained so for 3 years, our results indicate that tube wells should be tested periodically.