(137)Cs baseline levels in the Mediterranean and Black Sea: a cross-basin survey of the CIESM Mediterranean Mussel Watch programme

The common mussel Mytilus galloprovincialis was selected as unique biomonitor species to implement a regional monitoring programme, the CIESM Mediterranean Mussel Watch (MMW), in the Mediterranean and Black Seas. As of today, and upon standardization of the methodological approach, the MMW Network has been able to quantify (137)Cs levels in mussels from 60 coastal stations and to produce the first distribution map of this artificial radionuclide at the scale of the entire Mediterranean and Black Seas. While measured (137)Cs levels were found to be very low (usually < 1 Bq kg(-1) wet wt) (137)Cs activity concentrations in the Black Sea and North Aegean Sea were up to two orders of magnitude higher than those in the western Mediterranean Basin. Such effects, far from representing a threat to human populations or the environment, reflect a persistent signature of the Chernobyl fallout in this area.     

Pigmenting agents in Martian soils: inferences from spectral, Mossbauer, and magnetic properties of nanophase and other iron oxides in Hawaiian palagonitic soil PN-9

We have examined a Hawaiian palagonitic tephra sample (PN-9) that has spectroscopic similarities to Martian bright regions using a number of analytical techniques, including Mossbauer and reflectance spectroscopy, X-ray diffraction, instrumental neutron activation analysis, electron probe microanalysis, transmission electron microscopy, and dithionite-citrate-bicarbonate extraction. Chemically, PN-9 has a Hawaiitic composition with alkali (and presumably silica) loss resulting from leaching by meteoric water during palagonitization; no Ce anomaly is present in the REE pattern. Mineralogically, our results show that nanophase ferric oxide (np-Ox) particles (either nanophase hematite (np-Hm) or a mixture of ferrihydrite and np-Hm) are responsible for the distinctive ferric doublet and visible-wavelength ferric absorption edge observed in Mossbauer and reflectivity spectra, respectively, for this and other spectrally similar palagonitic samples. The np-Ox particles appear to be imbedded in a hydrated aluminosilicate matrix material; no evidence was found for phyllosilicates. Other iron-bearing phases observed are titanomagnetite, which accounts for the magnetic nature of the sample; olivine; pyroxene; and glass. By analogy, np-Ox is likely the primary pigmenting agent of the bright soils and dust of Mars.     

Conduit properties and karstification in the unconfined Floridan aquifer

Exchange of water between conduits and matrix is an important control on regional chemical compositions, karstification, and quality of ground water resources in karst aquifers. A sinking stream (Santa Fe River Sink) and its resurgence (River Rise) in the unconfined portion of the Floridan Aquifer provide the opportunity to monitor conduit inflow and outflow. The use of temperature as a tracer allows determination of residence times and velocities through the conduit system. Based on temperature records from two high water events, flow is reasonably represented as pipe flow with a cross-sectional area of 380 m2, although this model may be complicated by losses of water from the conduit system at higher discharge rates. Over the course of the study year, the River Rise discharged a total of 1.9 x 10(7) m3 more water than entered the River Sink, reflecting net contribution of ground water from the matrix into the conduit system. However, as River Sink discharge rates peaked following three rainfall events during the study period, the conduit system lost water, presumably into the matrix. Surface water in high flow events is typically undersaturated with respect to calcite and thus may lead to dissolution, depending on its residence time in the matrix. A calculation of local denudation is larger than other regional estimates, perhaps reflecting return of water to conduits before calcite equilibrium is reached. The exchange of matrix and conduit water is an important variable in karst hydrology that should be considered in management of these water resources.     

Whiting events: biogenic origin due to the photosynthetic activity of cyanobacterial picoplankton

An annual whiting event occurs each year in late May to early June in Fayetteville Green Lake, New York. The initiation of this event correlates with exponential growth of the Synechococcus population within the lake. Synechococcus is the dominant (by approximately 4 orders of magnitude) autotrophic organism owing to the oligotrophic condition of the lake. The delta 13C values of the dissolved inorganic C range seasonally from -9.5% in winter to -6.2% in summer due to photosynthetic activity. Calcite precipitates principally in the microenvironment surrounding Synechococcus because of a photosynthetically driven alkalization process and the availability of the cells as nucleation sites. This calcite has a heavier delta 13C value (>4%) than does the dissolved inorganic C of the lake water owing to the cells' preferential uptake of 12C. A conceptual model suggests that photosynthetic activity and cell surface chemistry, together with the substantial surface area that arises from the great abundance of micron-sized cells, allow Synechococcus to dominate the annual whiting events in Fayetteville Green Lake.     

Radiative heating of interstellar grains falling toward the solar nebula: 1-D diffusion calculations

As the dense molecular cloud that was the precursor of our Solar System was collapsing to form a protosun and the surrounding solar-nebula accretion disk, infalling interstellar grains were heated much more effectively by radiation from the forming protosun than by radiation from the disk's accretion shock. Accordingly, we have estimated the temperatures experienced by these infalling grains using radiative diffusion calculations whose sole energy source is radiation from the protosun. Although the calculations are 1-dimensional, they make use of 2-D, cylindrically symmetric models of the density structure of a collapsing, rotating cloud. The temperature calculations also utilize recent models for the composition and radiative properties of interstellar grains (Pollack et al. 1994. Astrophys. J. 421, 615-639), thereby allowing us to estimate which grain species might have survived, intact, to the disk accretion shock and what accretion rates and molecular-cloud rotation rates aid that survival. Not surprisingly, we find that the large uncertainties in the free parameter values allow a wide range of grain-survival results: (1) For physically plausible high accretion rates or low rotation rates (which produce small accretion disks), all of the infalling grain species, even the refractory silicates and iron, will vaporize in the protosun's radiation field before reaching the disk accretion shock. (2) For equally plausible low accretion rates or high rotation rates (which produce large accretion disks), all non-ice species, even volatile organics, will survive intact to the disk accretion shock. These grain-survival conclusions are subject to several limitations which need to be addressed by future, more sophisticated radiative-transfer models. Nevertheless, our results can serve as useful inputs to models of the processing that interstellar grains undergo at the solar nebula's accretion shock, and thus help address the broader question of interstellar inheritance in the solar nebula and present Solar System. These results may also help constrain the size of the accretion disk: for example, if we require that the calculations produce partial survival of organic grains into the solar nebula, we infer that some material entered the disk intact at distances comparable to or greater than a few AU. Intriguingly, this is comparable to the heliocentric distance that separates the C-rich outer parts of the current Solar System from the C-poor inner regions.     

Long-term biological effects of petroleum residues on fiddler crabs in salt marshes

In September 1969, the Florida barge spilled 700,000L of No. 2 fuel oil into the salt marsh sediments of Wild Harbor (Buzzards Bay, MA). Today the aboveground environment appears unaffected, but a substantial amount of moderately degraded petroleum still remains 8-20cm below the surface. The salt marsh fiddler crabs, Uca pugnax, burrow into the sediments at depths of 5-25cm, and are chronically exposed to the spilled oil. Behavioral studies conducted with U. pugnax from Wild Harbor and a control site, Great Sippewissett marsh, found that crabs exposed to the oil avoided burrowing into oiled layers, suffered delayed escape responses, lowered feeding rates, and achieved lower densities. The oil residues are therefore biologically active and affect U. pugnax populations. Our results add new knowledge about long-term consequences of spilled oil, a dimension that should be included when assessing oil-impacted areas and developing management plans designed to restore, rehabilitate, or replace impacted areas.     

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4+ production during urea hydrolysis were incorporated in the model and captured critical changes in the major metal species. The electrical phase increases were potentially due to ion exchange processes that modified charge structure at mineral/water interfaces. Our study revealed the potential of geophysical monitoring for geochemical changes during urea hydrolysis and the advantages of combining multiple approaches to understand complex biogeochemical processes in the subsurface.