A quantitative model of water radiolysis and chemical production rates near radionuclide-containing solids

We present a mathematical model that quantifies the rate of water radiolysis near radionuclide-containing solids. Our model incorporates the radioactivity of the solid along with the energies and attenuation properties for alpha (α), beta (β), and gamma (γ) radiation to calculate volume normalized dose rate profiles. In the model, these dose rate profiles are then used to calculate radiolytic hydrogen (H2) and hydrogen peroxide (H2O2) production rates as a function of distance from the solid–water interface. It expands on previous water radiolysis models by incorporating planar or cylindrical solid–water interfaces and by explicitly including γ radiation in dose rate calculations. To illustrate our model\u27s utility, we quantify radiolytic H2 and H2O2 production rates surrounding spent nuclear fuel under different conditions (at 20 years and 1000 years of storage, as well as before and after barrier failure). These examples demonstrate the extent to which α, β and γ radiation contributes to total absorbed dose rate and radiolytic production rates. The different cases also illustrate how H2 and H2O2 yields depend on initial composition, shielding and age of the solid. In this way, the examples demonstrate the importance of including all three types of radiation in a general model of total radiolytic production rates

Radiolytic Hydrogen Production in the Subseafloor Basaltic Aquifer

Hydrogen (H2) is produced in geological settings by dissociation of water due to radiation from radioactive decay of naturally occurring uranium (238U, 235U), thorium (232Th) and potassium (40K). To quantify the potential significance of radiolytic H2 as an electron donor for microbes within the South Pacific subseafloor basaltic aquifer, we use radionuclide concentrations of 43 basalt samples from IODP Expedition 329 to calculate radiolytic H2 production rates in basement fractures. The samples are from three sites with very different basement ages and a wide range of alteration types. U, Th, and K concentrations vary by up to an order of magnitude from sample to sample at each site. Comparison of our samples to each other and to the results of previous studies of unaltered East Pacific Rise basalt suggests that significant variations in radionuclide concentrations are due to differences in initial (unaltered basalt) concentrations (which can vary between eruptive events) and post-emplacement alteration. However, there is no clear relationship between alteration type and calculated radiolytic yields. Local maxima in U, Th, and K produce hotspots of H2production, causing calculated radiolytic rates to differ by up to a factor of 80 from sample to sample. Fracture width also greatly influences H2 production, where microfractures are hotspots for radiolytic H2 production. For example, H2 production rates normalized to water volume are 190 times higher in 1 μm wide fractures than in fractures that are 10 cm wide. To assess the importance of water radiolysis for microbial communities in subseafloor basaltic aquifers, we compare electron transfer rates from radiolysis to rates from iron oxidation in subseafloor basalt. Radiolysis appears likely to be a more important electron donor source than iron oxidation in old (\u3e10 Ma) basement basalt. Radiolytic H2 production in the volume of water adjacent to a square cm of the most radioactive SPG basalt may support as many as 1500 cells

Infant BMI or Weight-for-Length and Obesity Risk in Early Childhood

Weight-for-length (WFL) is currently used to assess adiposity under 2 years. We assessed WFL- versus BMI-based estimates of adiposity in healthy infants in determining risk for early obesity

Inherited susceptibility to bleomycin-induced chromatid breaks in cultured peripheral blood lymphocytes

Background: Susceptibility to bleomycin-induced chromatid breaks in cultured peripheral blood lymphocytes may reflect the way a person deals with carcinogenic challenges. This susceptibility (also referred to as mutagen sensitivity) has been found to be increased in patients with environmentally related cancers, including cancers of the head and neck, lung, and colon, and, in combination with carcinogenic exposure, this susceptibility can greatly influence cancer risk. The purpose of this study was to assess the heritability of mutagen sensitivity. Methods: Heritability was determined by use of a maximum likelihood method that employed the FISHER package of pedigree analysis. Bleomycin-induced breaks per cell values for 135 healthy volunteers without cancer were determined. These individuals were from 53 different pedigrees and included 25 monozygotic twin pairs (n = 50), 14 pairs of dizygotes (twin pairs and siblings, n = 28), and 14 families selected on the basis of a first-degree relative who was successfully treated for head and neck cancer and who had no sign of recurrence for at least 1 year. All data were analyzed simultaneously, and different models of familial resemblance were fitted to the data. All P values are two-sided. Results: Our results showed no evidence for the influence of a shared family environment on bleomycin-induced chromatid breaks. Genetic influences, however, were statistically significant (P = .036) and accounted for 75% of the total variance. Conclusions: The high heritability estimate of the susceptibility to bleomycin-induced chromatid breaks indicates a clear genetic basis. The findings of this study support the notion that a common genetic susceptibility to DNA damage - and thereby a susceptibility to cancer - may exist in the general population

Data-driven and hybrid coastal morphological prediction methods for mesoscale forecasting

It is now common for coastal planning to anticipate changes anywhere from 70 to 100 years into the future. The process models developed and used for scheme design or for large-scale oceanography are currently inadequate for this task. This has prompted the development of a plethora of alternative methods. Some, such as reduced complexity or hybrid models simplify the governing equations retaining processes that are considered to govern observed morphological behaviour. The computational cost of these models is low and they have proven effective in exploring morphodynamic trends and improving our understanding of mesoscale behaviour. One drawback is that there is no generally agreed set of principles on which to make the simplifying assumptions and predictions can vary considerably between models. An alternative approach is data-driven techniques that are based entirely on analysis and extrapolation of observations. Here, we discuss the application of some of the better known and emerging methods in this category to argue that with the increasing availability of observations from coastal monitoring programmes and the development of more sophisticated statistical analysis techniques data-driven models provide a valuable addition to the armoury of methods available for mesoscale prediction. The continuation of established monitoring programmes is paramount, and those that provide contemporaneous records of the driving forces and the shoreline response are the most valuable in this regard. In the second part of the paper we discuss some recent research that combining some of the hybrid techniques with data analysis methods in order to synthesise a more consistent means of predicting mesoscale coastal morphological evolution. While encouraging in certain applications a universally applicable approach has yet to be found. The route to linking different model types is highlighted as a major challenge and requires further research to establish its viability. We argue that key elements of a successful solution will need to account for dependencies between driving parameters, (such as wave height and tide level), and be able to predict step changes in the configuration of coastal systems

Boron isotopes in foraminifera : systematics, biomineralisation, and CO2 reconstruction

Funding: Fellowship from University of St Andrews, $100 (pending) from Richard Zeebe, UK NERC grants NE/N003861/1 and NE/N011716/1.The boron isotope composition of foraminifera provides a powerful tracer for CO2 change over geological time. This proxy is based on the equilibrium of boron and its isotopes in seawater, which is a function of pH. However while the chemical principles underlying this proxy are well understood, its reliability has previously been questioned, due to the difficulty of boron isotope (δ11B) analysis on foraminferal samples and questions regarding calibrations between δ11B and pH. This chapter reviews the current state of the δ11B-pH proxy in foraminfera, including the pioneering studies that established this proxy’s potential, and the recent work that has improved understanding of boron isotope systematics in foraminifera and applied this tracer to the geological record. The theoretical background of the δ11B-pH proxy is introduced, including an accurate formulation of the boron isotope mass balance equations. Sample preparation and analysis procedures are then reviewed, with discussion of sample cleaning, the potential influence of diagenesis, and the strengths and weaknesses of boron purification by column chromatography versus microsublimation, and analysis by NTIMS versus MC-ICPMS. The systematics of boron isotopes in foraminifera are discussed in detail, including results from benthic and planktic taxa, and models of boron incorporation, fractionation, and biomineralisation. Benthic taxa from the deep ocean have δ11B within error of borate ion at seawater pH. This is most easily explained by simple incorporation of borate ion at the pH of seawater. Planktic foraminifera have δ11B close to borate ion, but with minor offsets. These may be driven by physiological influences on the foraminiferal microenvironment; a novel explanation is also suggested for the reduced δ11B-pH sensitivities observed in culture, based on variable calcification rates. Biomineralisation influences on boron isotopes are then explored, addressing the apparently contradictory observations that foraminifera manipulate pH during chamber formation yet their δ11B appears to record the pH of ambient seawater. Potential solutions include the influences of magnesium-removal and carbon concentration, and the possibility that pH elevation is most pronounced during initial chamber formation under favourable environmental conditions. The steps required to reconstruct pH and pCO2 from δ11B are then reviewed, including the influence of seawater chemistry on boron equilibrium, the evolution of seawater δ11B, and the influence of second carbonate system parameters on δ11B-based reconstructions of pCO2. Applications of foraminiferal δ11B to the geological record are highlighted, including studies that trace CO2 storage and release during recent ice ages, and reconstructions of pCO2 over the Cenozoic. Relevant computer codes and data associated with this article are made available online.Publisher PDFPeer reviewe

Record of forearc devolatilization in low-T, high-P/T metasedimentary suites: Significance for models of convergent margin chemical cycling

[1] The Franciscan Complex (Coast Ranges and Diablo Range, California) and the Western Baja Terrane (WBT; Baja California, Mexico) were metamorphosed along high-P/T paths like those experienced in many active subduction zones, recording peak conditions up to ∼1 GPa and 300°C. Franciscan and WBT metasedimentary rocks are similar in lithology and geochemistry to clastic sediments outboard of many subduction zones. These metamorphic suites provide evidence regarding devolatilization history experienced by subducting sediments, information that is needed to mass-balance the inputs of materials into subduction zones with their respective outputs. Analyzed samples have lower total volatile contents than their likely protoliths. Little variation in LOI among similar lithologies at differing metamorphic grades, suggests that loss of structurally bound water occurred during early clay-mineral transformations. Finely disseminated carbonate is present in the lowest-grade rocks, but absent in all higher-grade rocks. δ13CVPDB of reduced-C is uniform in the lower-grade Franciscan samples (mean = −25.1‰, 1σ = 0.4‰), but varies in higher-grade rocks (−28.8 to −21.9‰). This likely reflects a combination of devolatilization and C-isotope exchange, between organic and carbonate reservoirs. Nitrogen concentration ranges from 102 to 891 ppm, with δ15Nair of +0.1 to +3.0‰ (n = 35); this organic-like δ15N probably represents an efficient transfer of N from decaying organic matter to reacting clay minerals. The lowest-grade rocks in the Coastal Belt have elevated carbonate contents and correlated N-δ15N variations, and exhibit the most uniform δ13C and C/N, all consistent with these rocks having experienced less devolatilization. Most fluid-mobile trace elements are present at concentrations indistinguishable from protoliths. Suggesting that, despite apparent loss of much clay-bound H2O and CO2 from diagenetic cements (combined, <5–10 wt. %), most fluid-mobile trace elements are retained to depths of up to ∼40 km. Organic-like δ15N, lower than that of many seafloor sediments, is consistent with some loss of adsorbed N (perhaps as NO3−) during early stages of diagenesis. The efficient entrainment of fluid-mobile elements to depths of at least 40 km in these relatively cool subduction zone settings lends credence to models invoking transfer of these elements to the subarc mantle

Boron isotope sensitivity to seawater pH change in a species of Neogoniolithon coralline red alga

The increase in atmospheric carbon dioxide (CO2) observed since the industrial revolution has reduced surface ocean pH by ∼0.1 pH units, with further change in the oceanic system predicted in the coming decades. Calcareous organisms can be negatively affected by extreme changes in seawater pH (pHsw) such as this due to the associated changes in the oceanic carbonate system. The boron isotopic composition (δ11B) of biogenic carbonates has been previously used to monitor pH at the calcification site (pHcf) in scleractinian corals, providing mechanistic insights into coral biomineralisation and the impact of variable pHsw on this process. Motivated by these investigations, this study examines the δ11B of the high-Mg calcite skeleton of the coralline red alga Neogoniolithon sp. to constrain pHcf, and investigates how this taxon’s pHcf is impacted by ocean acidification. δ11B was measured in multiple algal replicates (n = 4–5) cultured at four different pCO2 scenarios – averaging (±1σ) 409 (±6), 606 (±7), 903 (±12) and 2856 (±54) μatm, corresponding to average pHsw (±1σ) of 8.19 (±0.03), 8.05 (±0.06), 7.91 (±0.03) and 7.49 (±0.02) respectively. Results show that skeletal δ11B is elevated relative to the δ11B of seawater borate at all pHsw treatments by up to 18‰. Although substantial variability in δ11B exists between replicate samples cultured at a given pHsw (smallest range = 2.32‰ at pHsw 8.19, largest range = 6.08‰ at pHsw 7.91), strong correlations are identified between δ11B and pHsw (R2 = 0.72, p < 0.0001, n = 16) and between δ11B and B/Ca (R2 = 0.72, p < 0.0001, n = 16). Assuming that skeletal δ11B reflects pHcf as previously observed for scleractinian corals, the average pHcf across all experiments was 1.20 pH units (0.79 to 1.56) higher than pHsw, with the magnitude of this offset varying parabolically with decreasing pHsw, with a maximum difference between pHsw and pHcf at a pHsw of 7.91. Observed relationships between pHsw and calcification rate, and between pHsw and pHcf, suggest that coralline algae exhibit some resilience to moderate ocean acidification via increase of pHcf relative to pHsw in a similar manner to scleractinian corals. However, these results also indicate that pHcf cannot be sufficiently increased by algae exposed to a larger reduction in pHsw, adversely impacting calcification rates of coralline red algae