Effects of diffusional modification of garnet growth zoning on P-T path calculations

The effect of intragranular diffusion on chemical zoning in garnet and on P-T paths calculated from that zoning was evaluated using a numerical model of multicomponent diffusion in combination with simulations of garnet growth. Syn-and post-growth diffusion of Mg–Fe–Mn–Ca species in garnet was calculated for a model pelitic assemblage over a range of temperatures from 485 to 635°C. Compositions from zoned garnet, as modified by diffusion, hypothetical inclusions of plagioclase within garnet and matrix phases were used to reconstruct pressure-temperature (P-T) paths from isobaric and polybaric model histories. P-T path calculations, based on numerical simulations conducted over an input isobaric heating path that reached peak temperatures between 585 and 635°C, show that relaxation of garnet compositional gradients by diffusion can induce modest to appreciable curvature in the inferred paths. Retrieved paths also indicated somewhat smaller overall temperature changes relative to the actual temperature difference of the input path. The magnitude of these distortions is shown to depend upon the heating and cooling rate and garnet crystal size as well as the actual peak temperature condition. The effect of diffusion on path trajectories in simulations with thermal histories that also included cooling were comparable to heating-only models that reached peak temperatures approximately 15–30°C higher. Compositions of garnets with radii less than 1 mm, that reached actual peak temperatures of 605°C along temperature-time histories characteristic of regional metamorphism, experienced sufficient diffusional relaxation to introduce errors of hundreds of bars to in excess of one kilobar in path trajectories. Path distortions were significant at heating/cooling rates less than 10°C/Ma, but rapidly diminished for rates faster than this. In polybaric simulations diffusion effects were least noticeable when the actual pressure-temperature conditions changed in a clockwise sense (i.e., convex to higher P and higher T), but apprecciable modification was seen in path models that underwent counterclockwise changes in P and T. Reequilibration of garnet rim compositions occurred during cooling on all paths, and temperature maxima obtained from garnet-biotite geothermometry underestimated actual peak conditions by 40 to 70°C. Calculations suggest that P-T path trajectories calculated from garnets of at least 1 mm size, and that experienced actual thermal maxima below 585°C, are not likely to be distorted by diffusional effects during regional metamorphism. However, P-T path reconstructions based on garnet zonation with smaller grains or higher temperatures may lead to misinterpretation of crystallization history. The partitioning record of peak metamorphic temperatures may be destroyed by diffusional reequilibration of garnet rim compositions during cooling, seriously complicating the task of quantitatively estimating diffusion effects on path calculations.     

Calibration of cyclic constitutive models by oscillating functions

Most structures are subjected to more cyclic loads during their life time than static loads. These cyclic action could be a result of either natural or man-made activities and may lead to soil failure. In order to understand the response of the foundation and its interaction with these complex cyclic loadings, various researchers have over the years developed different constitutive models. Although a lot of research is being carried out on these relatively new models, little or no details exist in literature about the model-based identification of the cyclic constitutive parameters which to a large extent govern the quality of the model output. This could be attributed to the difficulties and complexities of the inverse modeling of such complex phenomena. A variety of optimisation strategies are available for the solution of the sum of least-squares problems as usually done in the field of model calibration. However, for the back analysis (calibration) of the soil response to oscillatory load functions, this article gives insight into the model calibration challenges and also puts forward a method for the inverse modeling of cyclic loaded foundation response such that high-quality solutions are obtained with minimum computational effort.     

Monitoring In Situ Biodegradation of MTBE Using Multiple Rounds of Compound‐Specific Stable Carbon Isotope Analysis

At a large industrial facility, methyl tert‐butyl ether (MTBE) was released to the subsurface and dispersed into the light, non‐aqueous phase liquids (LNAPL), in the first aquifer, with the LNAPL serving as a continuous source of MTBE in groundwater. Compound‐specific isotope analysis was conducted on both MTBE and tert‐butyl alcohol (TBA) in groundwater samples collected in 2008, 2011, and 2013 from wells located along and off the center line of the MTBE plume. The study demonstrated the onset and progress of biodegradation of MTBE between 2008 and 2013. The TBA observed in 2008 appears to be derived only in part from MTBE transformation while a significant portion of TBA might be contributed directly from LNAPL sources. In 2011 to 2013, the dominant source of TBA in the mid‐gradient plume was MTBE transformation. A contribution of an offsite LNAPL source, in particular to the down‐gradient area of the plume, is possible but could not be unequivocally confirmed. The time series provided direct evidence for MTBE biodegradation, but also a valuable insight on the sources of TBA.     

Palaeolimnological studies of the eutrophication of volcanic Lake Albano (Central Italy)

We use palaeolimnological techniques to reconstruct the eutrophication history of a volcanic lake (Lake Albano, central Italy) over the past three centuries. The presence of annual varves down to the bottom of the core (c. 1700 A.D.) indicated the lack of bioturbation and likely long-term meromixis. Sedimentation rates were estimated by varve counts (calcite/diatom couplets), indicating a mean rate of 0.15 cm yr^–1. The reconstruction of eutrophication was traced using past populations of algal and photosynthetic bacteria (through their fossil pigment), and geochemistry, as well as fossil remains of chironomids. Phaeophorbidea and the red carotenoid astaxanthin were used to detect past zooplankton development.The first sign of trophic change related to human activities is datedc. 1870 A.D. From that period onward a sharp increase of authigenic CaCO₃, nitrogen, N:P ratio, and dinoxanthin, a characteristic carotenoid of Chrysophyceae and Dinophyceae, is observed.Chironomid analyses showed the near absence of a deep water fauna throughout the core length. The populations of chironomid larvae are restricted to oxygenated littoral zones. In fact, the few fossil remains found are primarily of littoral origin, representing shallow water midges that were transported to profundal waters. The reduction of total chironomid in the uppermost layers of the core is to be related to human land uses.     

Designation of marine protected areas in Belgium: A legal and ecological success?

In Belgium a long process (1999–2005) led to the designation of several marine protected areas (MPAs). In order to analyse the designation process, the ‘policy arrangement approach’ was used as an analytical tool. Attention was given to four dimensions (actors and coalitions, arguments, rules and resources). Particular attention was paid to the switch from an authoritative to a more deliberated policy style in reaction to conflicts with stakeholders. This switch in policy style contributed to a successful legal designation, but does not guarantee the best protection of marine biodiversity. This case study linked science (setting ecological goals) to policy (analysis of a policy process) and led to some more general conclusions on the designation of MPAs and the role of participation in this process.     

Impact of climate and CO2 on a millennium-long tree-ring carbon isotope record

We present one millennium-long (1171-year), and three 100 year long annually resolved δ¹³C tree-ring chronologies from ecologically varying Juniperus stands in the Karakorum Mountains (northern Pakistan), and evaluate their response to climatic and atmospheric CO₂ changes. All δ¹³C records show a gradual decrease since the beginning of the 19th century, which is commonly associated with a depletion of atmospheric δ¹³C due to fossil fuel burning. Climate calibration of high-frequency δ¹³C variations indicates a pronounced summer temperature signal for all sites. The low-frequency component of the same records, however, deviates from long-term temperature trends, even after correction for changes in anthropogenic CO₂. We hypothesize that these high-elevation trees show a response to both climate and elevated atmospheric CO₂ concentration and the latter might explain the offset with target temperature data. We applied several corrections to tree-ring δ¹³C records, considering a range of potential CO₂ discrimination changes over the past 150 years and calculated the goodness of fit with the target via calibration/verification tests (R², residual trend, and Durbin-Watson statistics). These tests revealed that at our sites, carbon isotope fixation on longer timescales is affected by increasing atmospheric CO₂ concentrations at a discrimination rate of about 0.012‰/ppmv. Although this statistically derived value may be site related, our findings have implications for the interpretation of any long-term trends in climate reconstructions using tree-ring δ¹³C, as we demonstrate with our millennium-long δ¹³C Karakorum record. While we find indications for warmth during the Medieval Warm Period (higher than today’s mean summer temperature), we also show that the low-frequency temperature pattern critically depends on the correction applied. Patterns of long-term climate variation, including the Medieval Warm Period, the Little Ice Age, and 20th century warmth are most similar to existing evidence when a strong influence of increased atmospheric CO₂ on plant physiology is assumed.     

Regional grain size variations in aeolian sediments along the transition between Tibetan highlands and north‐western Chinese deserts – the influence of geomorphological settings on aeolian transport pathways

Sediment distribution is investigated applying grain size analysis to 279 surface samples from the transitional zone between high mountains (Qilian Shan) and their arid forelands (Hexi Corridor) in north‐western China. Six main sediment types were classified. Medium scale (10³ m) geomorphological setting is carefully considered as it may play an important role concerning sediment supply and availability. A tripartite distribution of sedimentological landscape units along the mountain to foreland transition is evident. Aeolian sediments (e.g. loess and dune sands) are widespread. They are used to identify aeolian transport pathways. The mU/fS‐ratio (5–11 µm/48–70 µm) among primary loess opposes the two grain size fractions being most sensitive to varying accumulation conditions. The first fraction is attributed to long‐distance transport in high suspension clouds whereas the latter represents local transport in saltation mode. The ratio shows strong correlation with elevation (R² = 0.77). Thus, it indicates a relatively higher far‐traveled dust supply in mountainous areas (>3000 m above sea level [a.s.l.]) compared to the foreland. The contribution of westerlies to high mountain loess deposits is considered likely. Hereby, the influence of the geomorphological setting on grain size composition of aeolian sediments becomes apparent: the contribution from distant dust sources is ubiquitous in the study area. However, the far‐distance contribution may be reduced by the availability of fine sand provided in low topography settings. Plain foreland areas support fine sand deflation from supplying river beds, allowing the formation of sandy loess in foreland areas and intramontane basins. In contrast, high mountain topography inhibits strong sand deflation into loess deposits. Eastern parts of the Hexi Corridor show higher aeolian sand occurrence. In contrast, the western parts are dominated by gravel gobi surfaces. This is attributed to higher sand supply in eastern parts provided by the Badain Jaran Desert and fluvial storages as sand sources. Copyright © 2014 John Wiley & Sons, Ltd.     

Oxidation of pyrite during extraction of carbonate associated sulfate

The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ³⁴S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ³⁴S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ³⁴S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ³⁴S_pyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe³⁺ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H₂O, not O₂. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.     

Dispersion of the salt-marsh periwinkle Littoraria irrorata: Effects of water level,size, and season

This paper documents horizontal and vertical dispersion patterns of a Texas population of the saltmarsh periwinkle, Littoraria irrorata, over a 15-month period. The study was conducted within a tidal marsh on the Anahuac National Wildlife Refuge in Galveston Bay. Two mark-recapture experiments demonstrated that L. irrorata rarely move more than 2 m from their release point over long periods of time and do not home to individual Spartina plants. Adult L. irrorata forage farther away from the base of Spartina stalks at low tide than do juvenile snails. Remaining near the plant base may decrease both temperature and desiccation stress on juveniles. During warm months, L. irrorata climb grass stalks with tidal inundation and forage on the substratum at low tide. Snails are inactive and aggregate in detrital debris at the base of Spartina clumps during the winter. *** DIRECT SUPPORT *** A01BY058 00016