Selecting between two transition states by which water oxidation intermediates on an oxide surface decay

While catalytic mechanisms on electrode surfaces have been proposed for decades, the pathways by which the product's chemical bonds evolve from the initial charge-trapping intermediates have not been resolved in time. Here, we discover a reactive population of charge-trapping intermediates with states in the middle of a semiconductor's band-gap to reveal the dynamics of two parallel transition state pathways for their decay. Upon photo-triggering the water oxidation reaction from the n-SrTiO3 surface with band-gap, pulsed excitation, the intermediates' microsecond decay reflects transition state theory (TST) through: (1) two distinct and reaction dependent (pH, T, Ionic Strength, and H/D exchange) time constants, (2) a primary kinetic salt effect on each activation barrier and an H/D kinetic isotope effect on one, and (3) realistic activation barrier heights (0.4 - 0.5 eV) and TST pre-factors (10^11 - 10^12 Hz). A photoluminescence from midgap states in n-SrTiO3 reveals the reaction dependent decay; the same spectrum was previously assigned by us to hole-trapping at parallel Ti-O(dot)-Ti (bridge) and perpendicular Ti-O(dot) (oxyl) O-sites using in situ ultrafast vibrational and optical spectroscopy. Therefore, the two transition states are naturally associated with the decay of these respective intermediates. Furthermore, we show that reaction conditions select between the two pathways, one of which reflects a labile intermediate facing the electrolyte (the oxyl) and the other a lattice oxygen (the bridge). Altogether, we experimentally isolate an important activation barrier for water oxidation, which is necessary for designing water oxidation catalysts with high O2 turn over. Moreover, in isolating it, we identify competing mechanisms for O2 evolution at surfaces and show how to use reaction conditions to select between them

Natural variability in Caribbean coral physiology and implications for coral bleaching resilience

Coral reefs are among the most diverse and complex ecosystems in the world that provide important ecological and economical services. Increases in sea surface temperature linked to global climate change threatens these ecosystems by inducing coral bleaching. However, it is not fully known if natural intra- or inter-annual physiological variability is linked to bleaching resilience or recovery capacity of corals. Here, we monitored the coral physiology of three common Caribbean species (Porites divaricata, Porites astreoides, Orbicella faveolata) at six time points over 2 years by measuring the following traits: calcification, biomass, lipids, proteins, carbohydrates, chlorophyll a, algal endosymbiont density, stable carbon isotopes of the host and endosymbiotic algae, and the stable carbon and oxygen isotopes of the skeleton. The overall physiological profile of all three species varied over time and that of P. divaricata was consistently different from the two other coral species. Porites divaricata had higher energy reserves coupled with higher contributions of heterotrophically derived carbon to host tissues than both P. astreoides and O. faveolata. Consistently higher overall energy reserves and heterotrophic contributions to tissues appear to buffer against environmental stress, including bleaching events. Thus, natural physiological variability among coral species appears to be a stronger predictor of coral bleaching resilience than intra- or inter-annual physiological variability within a coral species

Can heterotrophic uptake of dissolved organic carbon and zooplankton mitigate carbon budget deficits in annually bleached corals?

Annual coral bleaching events due to increasing sea surface temperatures are predicted to occur globally by the mid-century and as early as 2025 in the Caribbean, and severely impact coral reefs. We hypothesize that heterotrophic carbon (C) in the form of zooplankton and dissolved organic carbon (DOC) is a significant source of C to bleached corals. Thus, the ability to utilize multiple pools of fixed carbon and/or increase the amount of fixed carbon acquired from one or more pools of fixed carbon (defined here as heterotrophic plasticity) could underlie coral acclimatization and persistence under future ocean-warming scenarios. Here, three species of Caribbean coral—Porites divaricata, P. astreoides, and Orbicella faveolata—were experimentally bleached for 2.5 weeks in two successive years and allowed to recover in the field. Zooplankton feeding was assessed after single and repeat bleaching, while DOC fluxes and the contribution of DOC to the total C budget were determined after single bleaching, 11 months on the reef, and repeat bleaching. Zooplankton was a large C source for P. astreoides, but only following single bleaching. DOC was a source of C for single-bleached corals and accounted for 11–36 % of daily metabolic demand (CHARDOC), but represented a net loss of C in repeat-bleached corals. In repeat-bleached corals, DOC loss exacerbated the negative C budgets in all three species. Thus, the capacity for heterotrophic plasticity in corals is compromised under annual bleaching, and heterotrophic uptake of DOC and zooplankton does not mitigate C budget deficits in annually bleached corals. Overall, these findings suggest that some Caribbean corals may be more susceptible to repeat bleaching than to single bleaching due to a lack of heterotrophic plasticity, and coral persistence under increasing bleaching frequency may ultimately depend on other factors such as energy reserves and symbiont shuffling

Transcriptional Response of Two Core Photosystem Genes in Symbiodinium spp. Exposed to Thermal Stress

Mutualistic symbioses between scleractinian corals and endosymbiotic dinoflagellates (Symbiodinium spp.) are the foundation of coral reef ecosystems. For many coral-algal symbioses, prolonged episodes of thermal stress damage the symbiont\u27s photosynthetic capability, resulting in its expulsion from the host. Despite the link between photosynthetic competency and symbiont expulsion, little is known about the effect of thermal stress on the expression of photosystem genes in Symbiodinium. This study used real-time PCR to monitor the transcript abundance of two important photosynthetic reaction center genes, psbA(encoding the D1 protein of photosystem II) and psaA (encoding the P700 protein of photosystem I), in four cultured isolates (representing ITS2-types A13, A20, B1, and F2) and two in hospite Symbiodinium spp. within the coral Pocillopora spp. (ITS2-types C1b-c and D1). Both cultured and in hospite Symbiodinium samples were exposed to elevated temperatures (32°C) over a 7-day period and examined for changes in photochemistry and transcript abundance. Symbiodinium A13 and C1b-c (both thermally sensitive) demonstrated significant declines in both psbA and psaA during the thermal stress treatment, whereas the transcript levels of the other Symbiodinium types remained stable. The downregulation of both core photosystem genes could be the result of several different physiological mechanisms, but may ultimately limit repair rates of photosynthetic proteins, rendering some Symbiodinium spp. especially susceptible to thermal stress

Annual coral bleaching and the long-term recovery capacity of coral

Mass bleaching events are predicted to occur annually later this century. Nevertheless, it remains unknown whether corals will be able to recover between annual bleaching events. Using a combined tank and field experiment, we simulated annual bleaching by exposing three Caribbean coral species (Porites divaricata, Porites astreoides and Orbicella faveolata) to elevated temperatures for 2.5 weeks in 2 consecutive years. The impact of annual bleaching stress on chlorophyll a, energy reserves, calcification, and tissue C and N isotopes was assessed immediately after the second bleaching and after both short- and long-term recovery on the reef (1.5 and 11 months, respectively). While P. divaricata and O. faveolata were able to recover from repeat bleaching within 1 year, P. astreoides experienced cumulative damage that prevented full recovery within this time frame, suggesting that repeat bleaching had diminished its recovery capacity. Specifically, P. astreoides was not able to recover protein and carbohydrate concentrations. As energy reserves promote bleaching resistance, failure to recover from annual bleaching within 1 year will likely result in the future demise of heat-sensitive coral species

Intra-generational social mobility and educational qualifications

AbstractThe relation between intra-generational social class mobility of parents and their children's subsequent educational qualifications, and the implications of this relation for educational stratification, is explored by fitting statistical models to data from two UK longitudinal datasets: one based on the UK Census (ONS LS) and the 1970 birth cohort study (BCS70). Children whose parents are upwardly mobile gain higher educational qualifications than their peers in their class of origin, but obtain lower qualifications than their peers in their class of destination. The reverse pattern is observed for the downwardly mobile. These results mirror those obtained for the relation between adult intra-generational social mobility and a number of widely used measures of health. The implications of the findings for different explanations of the social class gradient in educational attainment are examined. The findings provide greater support for theoretical explanations of educational inequalities that are based on differences in economic circumstances between social classes than they do for explanations based on social class variations in the levels of cultural capital and aspirations. This conclusion is strengthened by the fact that the overall pattern of results from these analyses is unchanged after statistically controlling for levels of parental education. The findings also have methodological implications for measuring the social class gradient in attainment and qualifications