Using Mg/Ca Ratios from the Limpet Patella depressa Pennant, 1777 Measured by Laser-Induced Breakdown Spectroscopy (LIBS) to Reconstruct Paleoclimate

Measurement of the elemental composition of shells is increasingly emerging as an avenue for obtaining high-resolution insights into paleoclimate and past seasonality. Several studies have shown significant correlations between Mg/Ca ratios measured on shell carbonate and the sea surface temperature (SST) within which this carbonate was precipitated. However, other investigations have reported large variability in this relationship between species. Therefore, further studies, including taxa previously not considered are still required in order to validate these new species as suitable climate proxies. Here, we measured Mg/Ca ratios for limpet Patella depressa Pennant, 1777 samples live-collected in northern Spain for the first time. The elemental ratio was measured using laser-induced breakdown spectroscopy (LIBS), a technique that significantly decreases the time required for sample preparation and increases the number of shells that can be analyzed. In this study, calibration-free LIBS (CF-LIBS) methods were applied to estimate molar concentrations of chemical elements on biogenic calcium carbonate. The Mg/Ca ratio evolution along the shell growth axis was compared with stable oxygen isotope (δ18O) profiles obtained from these same limpets and the SST at the place where the mollusk grew to determine if the sequences obtained correctly reflected environmental conditions during the life-span of the mollusk. The results showed a significant correlation between Mg/Ca ratio series and both δ18O profiles and SST, highlighting the paleoenvironmental and archaeological potential of LIBS analyses on this mollusk species that is frequently found in archaeological contexts in the western Europe.

Taphonomy of a Panopea Ménard de la Groye, 1807 shell bed from the Pisco Formation (Miocene, Peru)

Invertebrate taphonomy can provide significant information about the post-mortem processes that affected the fossil record. In the East Pisco Basin of southern Peru, a Panopea Ménard de la Groye, 1807 shell bed was found in the upper Miocene strata of the Pisco Formation, hinting at a peculiar biostratinomic and diagenetic history. This bed contains abundant invertebrate fossil molds cemented by dolomite. The specimens of the deep infaunal bivalve, Panopea sp., occur together with bivalves representative of shallow infaunal species (Trachycardium sp. and Dosinia ponderosa [Gray, 1838]) and balanid barnacles, which are sessile encrusters. The Panopea specimens host compound molds evidencing an abundant encrusting fauna, including serpulids, ?foraminifera, bryozoans, and barnacles that colonized the inner surfaces of the valves before their final burial. We hypothesize that short-term, storm-related processes exhumed the living bivalves, resulting in a sedimentological concentration of relatively well-preserved shells. After the death of the exhumed bivalves, the inner surfaces of the articulated Panopea shells, representing hard-substratal, sheltered environments on an otherwise unstable sandy seafloor (i.e., “benthic islands”), were colonized by different encrusting organisms. Following the final burial, dolomite precipitated, cementing the sediment infill of the valves. Lastly, a decrease of pH occurred at the sulfate reduction-methanogenesis boundary, inducing the dissolution of the shell carbonate.

Radiocarbon in Marsh Periwinkle (Littorina Irrorata) Conchiolin: Applications for Archaeology

ABSTRACTIn coastal and island archaeology, carbonate mollusk shells are often among the most abundant materials available for radiocarbon (14C) dating. The marsh periwinkle (Littorina irrorata) is one of these such species, ubiquitously found along the Atlantic and Gulf coasts of the United States in both modern and archaeological contexts. This paper presents a novel approach to dating estuarine mollusks where rather than attempting to characterize the size and variability of reservoir effects to “correct” shell carbonate dates, we describe a compound-specific approach that isolates conchiolin, the organic matter bound with the shell matrix of the L. irrorata. Conchiolin typically constitutes <5% of shell weight. In L. irrorata, it is derived from the snail’s terrestrial diet and is thus not strongly influenced by marine, hardwater, or other carbon reservoir effects. We compare the carbon isotopes (δ13C and Δ14C) of L. irrorata shell carbonate, conchiolin, and bulk soft tissue from six modern, live-collected specimens from Apalachicola Bay, Florida, with samples that represent possible sources of carbon within their environment including surface sediments, marsh plant tissues, and dissolved inorganic carbon (DIC) in water. Ultimately, this paper demonstrates that samples obtained from wet chemical oxidation of L. irrorata conchiolin produces accurate 14C dates.

Planktonic foraminiferal spine versus shell carbonate Na incorporation in relation to salinity

Sea surface salinity is one of the most important parameters to reconstruct in paleoclimatology, reflecting amongst other things the hydrological cycle, paleodensity, ice volume, and regional and global circulation of water masses. Recent culture studies and a Red Sea field study revealed a significant positive relation between salinity and Na incorporation within benthic and planktonic foraminiferal shells. However, these studies reported varying partitioning of Na between and within the same species. The latter could be associated with ontogenetic variations, most likely spine loss. Varying Na concentrations were observed in different parts of foraminiferal shells, with spines and regions close to the primary organic sheet being especially enriched in Na. In this study, we unravel the Na composition of different components of the planktonic foraminiferal shell wall using electron probe micro-analysis (EPMA) and solution ICP-MS. A model is presented to interpret EPMA data for spines and spine bases to quantitatively assess differences in composition and contribution to whole-shell Na∕Ca signals. The same model can also be applied to other spatial inhomogeneities observed in foraminiferal shell chemistry, like elemental (e.g., Mg, Na, S) banding and/or hotspots. The relative contribution of shell carbonate, organic linings, spines and spine bases to whole-shell Na chemistry is considered quantitatively. This study shows that whereas the high Na areas may be susceptible to taphonomic alterations, the Na chemistry of the shell itself seems relatively robust. Comparing both shell and spine Na∕Ca values with salinity shows that shell chemistry records salinity, albeit with a very modest slope.