Aaron J. Beck

Effect of diagenesis on the Sr, O, and C isotope composition of late Cretaceous mollusks from the Western Interior Seaway of North America

Evaluating the effects of diagenesis on the isotopic compositions of Sr, O, and C in marine carbonates is critical to their use as proxies in reconstructing information on the salinity, temperature and dissolved inorganic carbon of ancient oceans. We have analyzed a series of samples of mollusk shells from the Baculites compressus zone (late Campanian) of the Pierre Shale of South Dakota. Samples included outer shell material and septa of cephalopods collected inside and outside concretions. Preservation was evaluated using light microscopy, scanning electron microscopy (SEM), trace element analysis and X-ray diffraction. All of the material consists of aragonite based on X-ray diffraction. An SEM preservation index (PI) was established based on comparison of the microstructure of the fossil material with that of modern Nautilus. Excellent preservation (PI = 5) was characterized by well-defined nacreous plates with discrete, angular boundaries. In contrast, samples showing fused nacreous plates with indistinct boundaries were rated poor (PI = 1). 87Sr/86Sr ratios vary with preservation and average 0.707648 ± .000021 (n = 10) for excellent preservation (PI ≈ 5), 0.707615 ± .000028 (n = 5) for good preservation (PI ≈ 3), 0.707404 ± .000074 (n=7) for fair preservation (PI ≈ 2), and 0.707261 ± .000053 (n=8) for poor preservation (PI ≈ 1). These data suggest that as the quality of the preservation declines, the mean 87Sr/86Sr ratio decreases and the standard error of the mean increases. Oxygen and carbon isotope analyses of the same specimens also show decreases with preservation, and δ18O, δ13C and 87Sr/86Sr are well correlated, suggesting that these tracers are all altered as the PI decreases. The Sr/Ca ratio increases as preservation decreases, indicating that Sr is added to the shell material during diagenesis. In contrast, Mg/Ca shows no trend with preservation. If the increasing Sr concentration (and decreasing 87Sr/86Sr) of the shell material with decreasing preservation represents the addition of Sr to the shell during diagenesis, we calculate that the added Sr had 87Sr/86Sr ranging from 0.707582 to 0.707032. Potential sources of the added Sr include older marine carbonates and weathering of volcanic ash layers present in the shale. The mechanisms of alteration likely include epitaxial growth of strontianite on the original shell aragonite and isotopic exchange of C and O between alteration fluids and shell carbonate. We conclude that SEM preservation criteria are effective in screening shell material that records original isotopic values and that variations in Sr, O and C isotope composition in well-preserved material can be used to assess paleoenvironmental parameters, such as salinity and temperature. Our results also indicate that assessing preservation is a critical prerequisite to the determination of numerical ages of shell material using strontium isotope stratigraphy.

Potential cobalt limitation of vitamin B12 synthesis in the North Atlantic Ocean

While recent studies have confirmed the ecological importance of vitamin B12, it is unclear whether the production of this vitamin could be limited by dissolved Co, a trace metal required for B12 biosynthesis, but found at only subnanomolar concentrations in the open ocean. Herein, we demonstrate that the spatial distribution of dissolved B12 (range: 0.13-5 pmol L−1) in the North Atlantic Ocean follows the abundance of total dissolved Co (range: 15-81 pmol L−1). Similar patterns were observed for bacterial productivity (range: 20-103 pmol 3H leucine L−1 hr−1) and algal biomass (range: 0.4-3.9 μg L−1). In contrast, vitamin B1 concentrations (range: 0.7-30 pM) were decoupled from both Co and B12 concentrations. Cobalt amendment experiments carried out in low-dissolved Co waters (∼20 pmol L−1) enhanced B12 production two-fold over unamended controls. This study provides evidence that B12 synthesis could be limited by the availability of Co in some regions of the world ocean.

Isotopic, geophysical and biogeochemical investigation of submarine groundwater discharge: IAEA-UNESCO intercomparison exercise at Mauritius Island

Submarine groundwater discharge (SGD) into a shallow lagoon on the west coast of Mauritius Island (Flic-en-Flac) was investigated using radioactive ((3)H, (222)Rn, (223)Ra, (224)Ra, (226)Ra, (228)Ra) and stable ((2)H, (18)O) isotopes and nutrients. SGD intercomparison exercises were carried out to validate the various approaches used to measure SGD including radium and radon measurements, seepage rate measurements using manual and automated meters, sediment bulk conductivity and salinity surveys. SGD measurements using benthic chambers placed on the floor of the Flic-en-Flac Lagoon showed discharge rates up to 500 cm/day. Large variability in SGD was observed over distances of a few meters, which were attributed to different geomorphological features. Deployments of automated seepage meters captured the spatial and temporal variability of SGD with a mean seepage rate of 10 cm/day. The stable isotopic composition of submarine waters was characterized by significant variability and heavy isotope enrichment and was used to predict the contribution of fresh terrestrially derived groundwater to SGD (range from a few % to almost 100%). The integrated SGD flux, estimated from seepage meters placed parallel to the shoreline, was 35 m(3)/m day, which was in reasonable agreement with results obtained from a hydrologic water balance calculation (26 m(3)/m day). SGD calculated from the radon inventory method using in situ radon measurements were between 5 and 56 m(3)/m per day. Low concentrations of radium isotopes observed in the lagoon water reflected the low abundance of U and Th in the basalt that makes up the island. High SGD rates contribute to high nutrients loading to the lagoon, potentially leading to eutrophication. Each of the applied methods yielded unique information about the character and magnitude of SGD. The results of the intercomparison studies have resulted a better understanding of groundwater-seawater interactions in coastal regions. Such information is an important pre-requisite for the protection and management of coastal freshwater resources.

Time-series sampling of 223Ra and 224Ra at the inlet to Great South Bay (New York): a strategy for characterizing the dominant terms in the Ra budget of the bay.

Ra isotopes are a powerful tool for quantifying the flux of submarine groundwater discharge (SGD) into the sea. Previous studies of 223Ra and 224Ra mass balances in coastal embayments have shown that the Ra balance is dominated by supply via SGD, exchange with the open ocean and radioactive decay. The current study shows that a single time series over a tidal cycle at the principal inlet to Great South Bay (NY, US) is sufficient to determine the net flux of Ra across the inlet, and also can be used to estimate the decay of short-lived Ra in the bay. Estimates of the net Ra flux obtained from a single tidal time-series by using three different approaches agree with those determined from a more time-consuming survey of Ra within the bay, and may represent a first step of estimating SGD in bays and coastal lagoons.

Regression modeling of the North East Atlantic Spring Bloom suggests previously unrecognized biological roles for V and Mo.

In order to identify the biogeochemical parameters controlling pCO2, total chlorophyll a, and dimethyl sulfide (DMS) concentrations during the North East Atlantic Spring Bloom (NASB), we used previously unpublished particulate and dissolved elemental concentrations to construct several linear regression models; first by hypothesis-testing, and then with exhaustive stepwise linear regression followed by leave-one-out cross-validation. The field data was obtained along a latitudinal transect from the Azores Islands to the North Atlantic, and best-fit models (determined by lowest predictive error) of up to three variables are presented. Total chlorophyll a is predicted best by biomass (POC, PON) parameters and by pigments characteristic of picophytoplankton for the southern section of the sampling transect (from the Azores to the Rockhall-Hatton Plateau) and coccolithophores in the northern portion (from the Rockhall-Hatton Plateau to the Denmark Strait). Both the pCO2 and DMS models included variables traditionally associated with the development of the NASB such as mixed-layer depth and with Fe, Si, and P-deplete conditions (dissolved Fe, dissolved and biogenic silica, dissolved PO3−4). However, the regressions for pCO2 and DMS also include intracellular V and Mo concentrations, respectively. Mo is involved in DMS production as a cofactor in dimethylsulfoxide reductase. No significant biological role for V has yet been determined, although intracellular V is significantly correlated (p-value <0.05) with biogenic silica (R2 = 0.72) and total chlorophyll a (R2 = 0.49) while the same is not true for its biogeochemical analogue Mo, suggesting active uptake of V by phytoplankton. Our statistical analysis suggests these two lesser-studied metals may play more important roles in bloom dynamics than previously thought, and highlights a need for studies focused on determining their potential biological requirements and cell quotas.

Journal of Environmental Radioactivity special issue: radium and radon isotopes as environmental tracers.

Radium isotopes (Ra) and radon (Rn) are intermediate nuclides in the U–Th decay series, and have been applied with great success to a wide range of environmental dating and tracing studies. In recent years, advances in measurement instrumentation (RaDeCC, Rad-7, low-background gamma spectrometry) and demonstration of their utility in studying water mixing and submarine groundwater discharge (SGD) have greatly increased interest in Ra and Rn isotopes in the environment. A workshop on the measurement and application of short-lived Ra isotopes held in Monaco in 2006 drew broad international attendance, and covered a range of topics from technical issues of isotope measurement to coastal and open ocean studies of isotope cycling and mass balance (Charette and Scholten, 2008). The success of this first workshop led to the organization of a second, held in Venice, Italy, during 7–11 April 2008. The meeting was attended by 52 scientists representing 14 countries, and covered an even more diverse range of topics related to the use of Ra and Rn isotopes in environmental studies. The scope of presentations included technical aspects of isotope measurements, the use of Ra isotopes as chronometers, and process studies in atmospheric, oceanic, and groundwater systems (Moore, 2008a, b). A number of works presented at the workshop have been elaborated in articles compiled in this special issue. Several working groups also were convened during the workshop to discuss pertinent, emerging topics: analytical standards for short-lived Ra isotopes, identification of appropriate Ra–Rn endmembers for calculating SGD, application of Ra and Rn to freshwater systems, and Ra isotopes in coastal margin processes and the Mediterranean. The standards group recommended methods and tracer solutions for preparing 223Ra and 224Ra standards, and a plan was formulated for the organization of an intercalibration exercise. The SGD endmember group concluded that systems should be characterized initially to identify likely SGD pathways, and that the relationship between Ra and salinity (as well as Fe, Mn, redox, and pH) should be assessed in the subterranean mixing zone between fresh and salt water (the “subterranean estuary”; Moore, 1999). This relationship should be used in conjunction with seepage meter and sediment equilibration samples to guide the endmember choice. The freshwater systems workgroup discussed the site-specific success of Ra isotope application in fresh waters, and N. Dimova presented preliminary experiments on the use of 220Rn as a very short-lived tracer. The group also concluded that Rn would remain only a qualitative tracer of groundwater input to rivers until the emanation (degassing) term could be better constrained. The margins group identified a critical need to quantify the shelf sediment input term for use of Ra isotopes as tracers