Interpreting multiple sulfur isotope signals in modern anoxic sediments using a full diagenetic model (California-Mexico margin: Alfonso basin)

Recent studies targeting the metabolic, physiological, and biochemical controls of sulfur isotope fractionation in microbial systems have drawn linkages between results from culture experiments and the sulfur isotope signatures observed in natural environments. Several of those studies have used newer techniques to explore the minor isotope (33S and 36S) variability in those systems, and also have attempted to place them in an ecophysiological context. Sparingly few have incorporated this newfound understanding of minor isotope behavior into natural systems (sediment pore waters, water columns) and none of them have refined existing isotope-dependent reaction-transport models to explicitly include 33S. In this study, we construct a three-isotope (32S, 33S, and 34S) reaction-transport model of pore water sulfate for a well-characterized sedimentary system within the California-Mexico Margin (Alfonso Basin). An additional goal is placing recent laboratory culture work into a natural, physical context. The model first reproduces the measured bulk geochemical characteristics of the pore water profiles of [SO4 2], [CH4], dissolved inorganic carbon ([DIC]), and [Ca2]—and predicts bulk (non-isotope-specific but depth-dependent) rates of sulfate reduction. Next, the model uses those depth-dependent bulk rates, in combination with empirically calibrated fractionation factors, to explain the minor isotope characteristics (34S and 33S values) of the 0 to 40 cm pore water SO4 2. The down core, isotopic evolution of pore water sulfate requires a large fractionation associated with sulfate reduction (34 SR 70 5) that appears to be independent of bulk rate, but in line with low temperature thermodynamic predictions. The minor isotope characteristics (33 SR 0.5130) are also independent of rate and fall within the range expected from microbial calibrations, but differ from minor isotope predictions of thermodynamic equilibrium. The high value of 34 SR raises key questions in relating the physiological state of marine microorganisms relative to their laboratory counterparts, as well as point toward exceedingly low metabolic rates in natural marine sediments

Anthropogenic disturbance keeps the coastal seafloor biogeochemistry in a transient state

Coastal sediments and continental shelves play a crucial role in global biogeochemistry, as they form the prime site of organic carbon burial. Bottom trawling and dredging are known to increasingly impact the coastal seafloor through relocation and homogenisation of sediments, yet little is known about the effects of such anthropogenic sediment reworking on the overall cycling of carbon and other elements within the coastal seafloor. Here, we document the transient recovery of the seafloor biogeochemistry after an in situ disturbance. Evidence from pore-water data and model simulations reveal a short-term increase in the overall carbon mineralisation rate, as well as a longer-term shift in the redox pathways of organic matter mineralisation, favouring organoclastic sulphate reduction over methane formation. This data suggests that anthropogenic sediment reworking could have a sizeable impact on the carbon cycle in cohesive sediments on continental shelves. This imprint will increase in the near future, along with the growing economic exploitation of the coastal ocean

RADIv1: a non-steady-state early diagenetic model for ocean sediments in Julia and MATLAB/GNU Octave

We introduce a time-dependent, one-dimensional model of early diagenesis that we term RADI, an acronym accounting for the main processes included in the model: chemical reactions, advection, molecular and bio-diffusion, and bio-irrigation. RADI is targeted for study of deep-sea sediments, in particular those containing calcium carbonates (CaCO3). RADI combines CaCO3 dissolution driven by organic matter degradation with a diffusive boundary layer and integrates state-of-the-art parameterizations of CaCO3 dissolution kinetics in seawater, thus serving as a link between mechanistic surface reaction modeling and global-scale biogeochemical models. RADI also includes CaCO3 precipitation, providing a continuum between CaCO3 dissolution and precipitation. RADI integrates components rather than individual chemical species for accessibility and is straightforward to compare against measurements. RADI is the first diagenetic model implemented in Julia, a high-performance programming language that is free and open source, and it is also available in MATLAB/GNU Octave. Here, we first describe the scientific background behind RADI and its implementations. Following this, we evaluate its performance in three selected locations and explore other potential applications, such as the influence of tides and seasonality on early diagenesis in the deep ocean. RADI is a powerful tool to study the time-transient and steady-state response of the sedimentary system to environmental perturbation, such as deep-sea mining, deoxygenation, or acidification events

RADIv1: a non-steady-state early diagenetic model for ocean sediments in Julia and MATLAB/GNU Octave

We introduce a time-dependent, one-dimensional model of early diagenesis that we term RADI, an acronym accounting for the main processes included in the model: chemical reactions, advection, molecular and bio-diffusion, and bio-irrigation. RADI is targeted for study of deep-sea sediments, in particular those containing calcium carbonates (CaCO3). RADI combines CaCO3 dissolution driven by organic matter degradation with a diffusive boundary layer and integrates state-of-the-art parameterizations of CaCO3 dissolution kinetics in seawater, thus serving as a link between mechanistic surface reaction modeling and global-scale biogeochemical models. RADI also includes CaCO3 precipitation, providing a continuum between CaCO3 dissolution and precipitation. RADI integrates components rather than individual chemical species for accessibility and is straightforward to compare against measurements. RADI is the first diagenetic model implemented in Julia, a high-performance programming language that is free and open source, and it is also available in MATLAB/GNU Octave. Here, we first describe the scientific background behind RADI and its implementations. Following this, we evaluate its performance in three selected locations and explore other potential applications, such as the influence of tides and seasonality on early diagenesis in the deep ocean. RADI is a powerful tool to study the time-transient and steady-state response of the sedimentary system to environmental perturbation, such as deep-sea mining, deoxygenation, or acidification events

Letting the good times roll: A theory of voter inference and experimental evidence

This paper examines inference and attribution in a simple and ubiquitous strategic situation: a voter is faced with discerning whether a leader worked on his or her behalf after observing an informative, but noisy signal about the leader's performance. We characterize perfect Bayesian equilibria, quantal response equilibria (QRE), and provide a simple model of a heuristic-based approach, referred to as strategic naivete, within a wide class of such environments. We also discuss experiments conducted to examine human behavior within such an environment. While it is clear that the observed behavior is inconsistent with perfect Bayesian equilibrium, distinguishing between QRE and strategic naivete will require further work. We conclude with a discussion of the broader implications of probabilistic and/or heuristic-based attribution processes for electoral politics and political economy. Copyright Springer Science + Business Media B.V. 2007

The dissemination and uptake of competency frameworks

Clinical competencies are increasingly being used to structure career and clinical progression in post-registration nursing. Competency framework documents have been proposed as a way of supporting competence development. One major national initiative in this respect is the NHS Education for Scotland (NES) competency frameworks which have seen development of over 26 such frameworks dealing with a wide range of nursing specialties. Utilising an initial scoping study followed by a stakeholder evaluation the dissemination and uptake of a selected number of competency frameworks was investigated. Participants in the scoping study (n = 18) and in the main stakeholder survey ( n = 24) from a sample of Health Boards and Higher Education Institutions were recruited. Data were collected by telephone and face-to-face interviews. Within the NHS and HEI's the specified framework documents have a variable penetration. Documents are used to support CPD at the individual and organisational levels. They also inform, albeit in a very limited way, curricular developments in HEIs. The success of framework documents is linked to their timeliness in relation to local and national developments such as service redesign and to whether or not documents were `championed' by committed practitioners or professional groups. Competency framework documents are recognised and utilised by clinicians, NHS managers and Education providers. Information providers and users need to co-ordinate their initiatives in order that staff development links with service redesign