Trace metal-binding proteins in marine molluscs and crustaceans

Some marine invertebrates, such as the American oyster, Crassostrea virginica, the blue crab, callinectes sapidus and the American lobster, Homarusamericanus, concentrate trace metals in their tissues. The occurrence of metallothionein, a low molecular weight, sulfur-containing metal-binding protein, has been correlated with elevated levels of trace metals in these organisms. It is our hypothesis that, whilst metallothioneins are involved in the sequestration of elevated levels of trace metals, they primarily function in regulating normal metal metabolism. In this paper we describe recent field and laboratory experiments designed to examine how oysters, blue crabs and lobsters manage accumulated cadmium, copper and zinc. The possible rôles of metallothionein, as well as the tissue distribution of metals, are emphasized. Metallothioneins were found in all animals we examined; concentrations of metallothioneins and the the amount of bound trace metals are related to time of exposure. We have also demonstrated that the laboratory developed metallothionein models for blue crabs and lobsters may be useful in predicting the partitioning of trace metals in animals living in environments polluted with trace metals.     

Cadmium accumulation by the blue crab, callinectes sapidus: Involvement of hemocyanin and characterization of cadmium-binding proteins

The accumulation of cadmium from seawater by the blue crab, Callinectes sapidus, was studied as a function of metal concentration and exposure time, with special emphasis on cadmium-binding proteins. Cadmium was found, in decreasing order of magnitude, in gills, digestive gland and hemolymph. When exposed to 0·5 ppm cadmium for 2–24h, virtually all of the cadmium in the cytosolic fraction of the gill was associated with a low molecular weight (LMW) cadmium-binding protein (MW 8000). However, after 48h of exposure only 50% of the cadmium in the cytosol was bound to this protein. The rest wasfound to be associated with proteins of a molecular weight of 300 000 and 60 000. This pattern of cadmium distribution did not change over a 12-day depuration period. Similar results were obtained upon exposure to 0·1 ppm cadmium. The pattern of cadmium accumulation in the cytosolic fraction of the digestive gland was in marked contrast to that observed for the gill. Initially, the cadmium was distributed over three low molecular weight fractions. During depuration the distribution of cadmium changed and all of the metal became bound to a low molecular weight protein (MW 9000). The cadmium concentrations in the gill and digestive gland remained essentially constant during depuration (12 days). The LMW cadmium-binding proteins were purified by a combination of gelpermeation and ion-exchange chromatography. Their molecular weight, spectral properties and amino acid composition are characteristic of the vertebrate metallothioneins. During exposure to cadmium the metal rapidly appeared in the hemolymph, mainly associated with hemocyanin. During depuration cadmium was transferred from the hemolymph to the digestive gland, demonstrating that hemocyanin acts as a carrier in trace metal transport.     

Kinetics of peptide hydrolysis and amino acid decomposition at high temperature

Dipeptide hydrolysis and amino acid decomposition appear to follow a first-order rate law. The hydrolysis rate increases exponentially with increasing temperature in aqueous solution at both 265 atm and water steam pressures over the temperature range of 100 to 220 degrees C. Dipeptide hydrolysis has a lower apparent activation energy at 265 atm (44.1 KJ/mol) than at water steam pressure (98.9 KJ/mol). At lower temperatures (<200-220 degrees C), the rate of peptide bond hydrolysis is faster at 265 atm than at water steam pressure. At higher temperatures (>200-220 degrees C), however, peptide bond hydrolysis is slower at 265 atm than at water steam pressure. In aqueous solution, amino acid decomposition rates also increase exponentially with increasing temperature. Amino acid decomposition rates are much higher at 265 atm than at water steam pressure over the entire temperature range investigated.     

Strike-slip fault bridge fluid pumping mechanism: insights from field-based palaeostress analysis and numerical modelling

We present a finite-element study of stress perturbation in evolving compressive and extensional strike-slip fault bridges. The results are compared with a fracture study of a compressive bridge at St Donats, UK. Horizontally interbedded calcareous mudstone and bioclastic calcilutite at St Donats have a distinct vertical permeability anisotropy. This sedimentary sequence behaves as a set of horizontal aquifers. The fluid flow in these aquifers is sensitive to mean stress gradients. Paleostress analysis of field fracture data, verified by finite-element modelling, indicates a rotation of σ₁ towards parallelism with boundary faults inside the growing compressive bridge. Boundary faults and bridge faults recorded numerous fluid flow events. The modelled mean stress pattern shows a regional maximum within the bridge and local maxima/minima pairs at boundary fault tips.Finite-element modelling of an extensional bridge indicates that σ₃ rotates towards parallelism with boundary faults. The mean stress pattern is similar to the pattern in compressive bridge but with maxima and minima locations interchanged. The stress patterns are reestablished by each stress build-up preceding the rupturation of the boundary faults throughout the development stages of strike-slip fault bridges. Mean stress gradients developed pre-failure control the fluid flow in fractures of the strike-slip fault system at and after the end of each stress build-up and the fluid flow in boundary faults post-failure. Fracture reactivation and new fracture generation within an evolving bridge is a process consisting of multiple successive events that retain the storage capacity of the bridge. Rupture and sealing of the main bounding-faults is a step-wise process that opens and closes fluid conduits between areas with different pressures.     

Development of a soil moisture‐based distributed hydrologic model for determining hydrologically based critical source areas

A simple grid cell‐based distributed hydrologic model was developed to provide spatial information on hydrologic components for determining hydrologically based critical source areas. The model represents the critical process (soil moisture variation) to run‐off generation accounting for both local and global water balance. In this way, it simulates both infiltration excess run‐off and saturation excess run‐off. The model was tested by multisite and multivariable evaluation on the 50‐km² Little River Experimental Watershed I in Georgia, U.S. and 2 smaller nested subwatersheds. Water balance, hydrograph, and soil moisture were simulated and compared to observed data. For streamflow calibration, the daily Nash‐Sutcliffe coefficient was 0.78 at the watershed outlet and 0.56 and 0.75 at the 2 nested subwatersheds. For the validation period, the Nash‐Sutcliffe coefficients were 0.79 at the watershed outlet and 0.85 and 0.83 at the 2 subwatersheds. The per cent bias was less than 15% for all sites. For soil moisture, the model also predicted the rising and declining trends at 4 of the 5 measurement sites. The spatial distribution of surface run‐off simulated by the model was mainly controlled by local characteristics (precipitation, soil properties, and land cover) on dry days and by global watershed characteristics (relative position within the watershed and hydrologic connectivity) on wet days when saturation excess run‐off was simulated. The spatial details of run‐off generation and travel time along flow paths provided by the model are helpful for watershed managers to further identify critical source areas of non‐point source pollution and develop best management practices.     

Snow model sensitivity analysis to understand spatial and temporal snow dynamics in a high‐elevation catchment

In this paper, we addressed a sensitivity analysis of the snow module of the GEOtop2.0 model at point and catchment scale in a small high‐elevation catchment in the Eastern Italian Alps (catchment size: 61 km²). Simulated snow depth and snow water equivalent at the point scale were compared with measured data at four locations from 2009 to 2013. At the catchment scale, simulated snow‐covered area (SCA) was compared with binary snow cover maps derived from moderate‐resolution imaging spectroradiometer (MODIS) and Landsat satellite imagery. Sensitivity analyses were used to assess the effect of different model parameterizations on model performance at both scales and the effect of different thresholds of simulated snow depth on the agreement with MODIS data. Our results at point scale indicated that modifying only the “snow correction factor” resulted in substantial improvements of the snow model and effectively compensated inaccurate winter precipitation by enhancing snow accumulation. SCA inaccuracies at catchment scale during accumulation and melt period were affected little by different snow depth thresholds when using calibrated winter precipitation from point scale. However, inaccuracies were strongly controlled by topographic characteristics and model parameterizations driving snow albedo (“snow ageing coefficient” and “extinction of snow albedo”) during accumulation and melt period. Although highest accuracies (overall accuracy = 1 in 86% of the catchment area) were observed during winter, lower accuracies (overall accuracy < 0.7) occurred during the early accumulation and melt period (in 29% and 23%, respectively), mostly present in areas with grassland and forest, slopes of 20–40°, areas exposed NW or areas with a topographic roughness index of ?0.25 to 0 m. These findings may give recommendations for defining more effective model parameterization strategies and guide future work, in which simulated and MODIS SCA may be combined to generate improved products for SCA monitoring in Alpine catchments.     

Magma evolution beneath Bequia,Lesser Antilles,deduced from petrology of lavas and plutonic xenoliths

Extrusive and intrusive igneous rocks represent different parts of a magmatic system and ultimately provide complementary information about the processes operating beneath volcanoes. To shed light on such processes, we have examined and quantified the textures and mineral compositions of plutonic and cumulate xenoliths and lavas from Bequia, Lesser Antilles arc. Both suites contain assemblages of iddingsitized olivine, plagioclase, clinopyroxene and spinel with rare orthopyroxene and ilmenite. Mineral zoning is widespread, but more protracted in lavas than xenoliths. Plagioclase cores and olivine have high anorthite (An?≤?98) and low forsterite (Fo?≤?84) compositions respectively, implying crystallisation from a hydrous mafic melt that was already fractionated. Xenolith textures range from adcumulate to orthocumulate with variable mineral crystallisation sequences. Textural criteria are used to organize the xenoliths into six groups. Amphibole, notably absent from lavas, is a common feature of xenoliths, together with minor biotite and apatite. Bulk compositions of xenoliths deviate from the liquid line of descent of lavas supporting a cumulate origin with varying degrees of reactive infiltration by evolved hydrous melts, preserved as melt inclusions in xenolith crystals. Volatile saturation pressures in melt inclusions indicate cumulate crystallization over a 162–571 MPa pressure range under conditions of high dissolved water contents (up to 7.8 wt% H₂O), consistent with a variety of other thermobarometric estimates. Phase assemblages of xenoliths are consistent with published experimental data on volatile-saturated low-magnesium and high-alumina basalts and basaltic andesite from the Lesser Antilles at pressures of 200–1000 MPa, temperatures of 950–1050 °C and dissolved H₂O contents of 4–7 wt%. Once extracted from mid-crustal mushes, residual melts ascend to higher levels and undergo H₂O-saturated crystallization in shallow, pre-eruptive reservoirs to form phenocrysts and glomerocrysts. The absence of amphibole from lavas reflects instability at low pressures, whereas its abundance in xenoliths testifies to its importance in mid-crustal differentiation processes. A complex, vertically extensive (6 to at least 21 km depth) magmatic system is inferred beneath Bequia. Xenoliths represent fragments of the mush incorporated into ascending magmas. The widespread occurrence of evolved melts in the mush, but the absence of erupted evolved magmas, in contrast to islands in the northern Lesser Antilles, may reflect the relative immaturity of the Bequia magmatic system.     

MedFlux: Investigations of particle flux in the Twilight Zone

The MedFlux project was devised to determine and model relationships between organic matter and mineral ballasts of sinking particulate matter in the ocean. Specifically we investigated the ballast ratio hypothesis, tested various commonly used sampling and modeling techniques, and developed new technologies that would allow better characterization of particle biogeochemistry. Here we describe the rationale for the project, the biogeochemical provenance of the DYFAMED site, the international support structure, and highlights from the papers published here. Additional MedFlux papers can be accessed at the MedFlux web site (http://msrc.sunysb.edu/MedFlux/).