Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ³⁴S_SO4 and δ¹⁸O_SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ¹⁸O_H2O and initial δ¹⁸O_SO4, all strains show ³⁴S enrichment, whereas only six strains show significant ¹⁸O enrichment. The remaining six show no (or minimal) change in δ¹⁸O_SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO₃²⁻), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.     

Footwall mineralization during Late Miocene extension along the West Cycladic Detachment System,Lavrion, Greece

The West Cycladic Detachment System (WCDS) has been mapped from the western Cycladic islands to Lavrion (mainland Greece), where several top‐to‐SSW low‐angle normal faults at different structural levels are observed. Near the detachment horizon, hydrothermal fluid flow originating from Miocene intrusions lead to high‐temperature carbonate strata‐bound Pb–Ag–Zn ore deposits. Zircon (U–Th)/He cooling ages from the mineralized footwall are 7.1 ± 0.6 to 7.9 ± 0.6 Ma. Carbon‐ and O‐isotope analyses of the carbonate host indicate high water‐to‐rock ratios during brittle deformation‐induced metasomatism, and that this interaction, unrelated to proximity of the intrusions, plays the dominant role in the mineralization. The Late Miocene geology of Lavrion is strikingly similar to Serifos island on the SE termination of the WCDS, both characterized by strong localization of detachment faulting and the interaction of brittle deformation with the injection of fluids related to granitoid intrusions.     

Horizontal spatial and temporal distribution patterns of nearshore larval fish assemblages at a temperate rocky shore

There have been no previous studies of the composition of nearshore larval fish assemblages along the coast of Portugal. We aimed to describe the composition and horizontal distribution patterns of larval fish assemblages and their temporal dynamics near a rocky reef at depths shallower than 13 m (inshore) and at two miles (3.70 km) from shore (offshore), as well as along transects perpendicular to the shoreline, from the reef to 10 miles offshore (18.52 km). Samples were taken using 5 min sub-surface trawls at the rocky shore of the Arrábida Marine Park (W Portugal). A total of 1021 larvae were collected, belonging to 61 taxa inshore and to 29 taxa offshore. Along transects, 626 larvae of 52 taxa were collected. Most larvae belonged to coastal species associated with rocky reefs. Total larval abundance and diversity were higher from May to July, which is consistent with the spawning activity of adults. Diversity and total larval abundance decreased significantly with increasing distance from shore, both in the inshore/offshore comparison and in the transects, where this decrease was evident at a very small spatial scale (within the first mile from the reef). Species assemblages differed in the pattern of distribution, with most species clearly associated to the extreme nearshore. The distribution patterns obtained were independent of the spawning mode of species. Results are discussed in the light of the possible physical mechanisms that can potentially act at the Arrábida Marine Park to facilitate larvae retention and the role of larval behaviour.     

Temporal Evolution of a Rapidly-Moving Umbral Dot

We performed two-dimensional spectroscopic observations of the preceding sunspot of NOAA 10905 located off disk center (S8 E36, μ≈0.81) by using the Interferometric BI-dimensional Spectrometer (IBIS) operated at the Dunn Solar Telescope (DST) of the National Solar Observatory, New Mexico. The magnetically insensitive Fe I line at 709.04 nm was scanned in wavelength repetitively at an interval of 37 s to calculate sequences of maps of the line-wing and line-core intensity, and the line-of-sight Doppler velocity at different line depths (3% to 80%). Visual inspection of movies based on speckle reconstructions computed from simultaneous broadband data and the local continuum intensity at 709.04 nm revealed an umbral dot (UD) intruding rapidly from the umbral boundary to the center of the umbra. The apparent motion of this object was particularly fast (1.3 km s⁻¹) when compared to typical UDs. The lifetime and size of the UD was 8.7 min and 240 km, respectively. The rapid UD was visible even in the line-core intensity map of Fe I 709.04 nm and was accompanied by a persistent blueshift of about 0.06 km s⁻¹.     

Factors affecting the distribution of potentially toxic elements in surface soils around an industrialized area of northwestern Greece

In order to investigate the factors influencing the distribution of 32 potentially toxic elements in the Ptolemais–Kozani basin, northwestern Greece, 38 soil samples were collected and analyzed. Concentrations of Al, Ca, Fe, K, Mg, Mn, Na, P, Ti, Ba, Co, Cr, Cu, La, Li, Ni, Pb, Sc, Sr, V, Y, and Zn were determined by ICP-AES and concentrations of As, Bi, Cd, Cs, Mo, Rb, Sb, Th, Tl, and U by ICP-MS. Bivariate analysis, principal component analysis, and geostatistical analysis were employed to investigate the factors influencing the distribution of the elements determined in the study area. The results indicate that the distribution of the majority of elements determined, especially for Cr, Ni, and associated elements, is greatly influenced by the geology and geomorphology of the study area. Principal component analysis has yielded four factors that explain over 77% of the total variance in the data. These factors are as follows: lithophilic elements that are associated with Al silicates minerals of K (factor I: 29.4%), ultramafic rocks (factor II: 20.5%), elements that are coprecipitated with Fe and Mn oxides (factor III: 18.0%), and anthropogenic activities (factor IV: 9.3%). The anthropogenic activities that influence the distribution of several potentially toxic elements (i.e., Cd, Cu, Pb, Zn) are agricultural practices and the deposition of fly ash in the vicinity of the local power stations.     

The role of boundary organizations in climate change adaptation from the perspective of municipal practitioners

In climate change impact research it is crucial to carefully select the meteorological input for impact models. We present a method for model selection that enables the user to shrink the ensemble to a few representative members, conserving the model spread and accounting for model similarity. This is done in three steps: First, using principal component analysis for a multitude of meteorological parameters, to find common patterns of climate change within the multi-model ensemble. Second, detecting model similarities with regard to these multivariate patterns using cluster analysis. And third, sampling models from each cluster, to generate a subset of representative simulations. We present an application based on the ENSEMBLES regional multi-model ensemble with the aim to provide input for a variety of climate impact studies. We find that the two most dominant patterns of climate change relate to temperature and humidity patterns. The ensemble can be reduced from 25 to 5 simulations while still maintaining its essential characteristics. Having such a representative subset of simulations reduces computational costs for climate impact modeling and enhances the quality of the ensemble at the same time, as it prevents double-counting of dependent simulations that would lead to biased statistics.     

Non-glacial paleoenvironments and the extent of Weichselian ice sheets on Severnaya Zemlya, Russian High Arctic

The extent of the Barents-Kara Sea ice sheet (northern Europe and Russia) during the Last Glacial Maximum (LGM), in Marine Isotope Stage (MIS) 2 is controversial, especially along the southern and northeastern (Russian High Arctic) margins. We conducted a multi-disciplinary study of various organic and mineral fractions, obtaining chronologies with ¹⁴C and luminescence dating methods on a 10.5 m long core from Changeable Lake (4 km from the Vavilov Ice Cap) on Severnaya Zemlya. The numeric ages indicate that the last glaciation at this site occurred during or prior to MIS 5d-4 (Early Middle Weichselian). Deglaciation was followed by a marine transgression which affected the Changeable Lake basin. After the regression the basin dried up. In late Middle Weichselian time (ca 25–40 ka), reworked marine sediments were deposited in a saline water body. During the Late Weichselian (MIS 2), the basin was not affected by glaciation, and lacustrine sediments were formed which reflect cold and arid climate conditions. During the termination of the Pleistocene and into the Holocene, warmer and wetter climate conditions than before led to a higher sediment input. Thus, our chronology demonstrates that the northeastern margin of the LGM Barents-Kara Sea ice sheet did not reach the Changeable Lake basin. This result supports a modest model of the LGM ice sheet in northern Europe determined from numeric ice sheet modelling and geological investigations.     

Ontogenic shifts in predatory roles involving two invasive species

The red swamp crayfish, Procambarus clarkii, and the eastern mosquitofish, Gambusia holbrooki have been introduced worldwide, but the interactions between these invasive species are not well known. The effects of crayfish presence, crayfish size and water depth on the consumption of G. holbrooki by P. clarkii were analyzed, as were the effects of mosquitofish presence and water depth on the consumption of recently hatched crayfish (RHC) by mosquitofish. To better understand this subject we conducted aquaria and open air mesocosm experiments simulating a rice field section. Aquarium experiments showed that P. clarkii consumes G. holbrooki and that G. holbrooki consumes RHC. Adult crayfish size did not significantly affect the consumption of mosquitofish and water depth had no effect on the consumption of G. holbrooki by P. clarkii and vice versa. In the outdoor mesocosm experiments P. clarkii caused no statistically significant effect on G. holbrooki numbers or biomass when compared with controls without crayfish. In spite of this, the analysis of crayfish stomach contents clearly demonstrated that several G. holbrooki individuals were consumed, indicating that crayfish can profit from the presence of G. holbrooki. Results from our study suggest that in shallow pools there are strong interactions between the two invasive species since adult crayfish predate mosquitofish and mosquitofish predate recently hatched crayfish. Therefore, there are bidirectional trophic interactions between these invasive species which change depending on their relative size. We believe that these interactions should become more relevant in confined areas such as small shallow pools formed during the late summer and autumn.