Primary producers are essential organisms for marine ecosystems because they form the basis of food webs, produce half of atmospheric oxygen and are involved in various biogeochemical cycles. At the end of a bloom event, phytoplankton cells are known to produce organic compounds that act as a 'cement', allowing the cells to stick together and form large sinking structures called aggregates. These aggregates are microenvironments with chemical properties that are very different from the surrounding water. The main objective of this study was to determine how the temporal variations in cell assemblages over time and the formation of aggregates following a bloom affect the concentrations of molybdenum (Mo) and barium (Ba) in the water column, which are elements typically measured within accretionary hard tissues (e.g., mollusc shells) to track phytoplankton dynamics in the environment. To do so, we performed an environmental monitoring from March to October 2021 at Lanveoc in the Bay of Brest (France) during which several biological (e.g., variations in phytoplankton assemblages) and chemical (e.g., chemical properties of the water column) parameters were measured once to twice per week. Our results show that spring and summer blooms of Gymnodinium, known to be enriched in Mo, could be one of the reasons explaining the particulate Mo enrichments in the water column. In addition, large phytoplankton aggregates transported a significant amount of Mo to the seafloor and associated suspension feeders. In contrast, the temporal variations in dissolved and particulate Ba concentration were strongly influenced by the formation of diatom blooms. Interestingly, there was a significant shift in Ba from the dissolved to the particulate fraction during the largest diatom bloom in late spring, associated with a significant Ba transport to the seafloor, which may be explained by the adsorption of this element onto diatom frustules. This study therefore highlights the impacts of phytoplankton on the dynamics of these elements in coastal ecosystems.

As part of the HIPPO (HIgh-resolution Primary Production multi-prOxy archives) project, environmental monitoring was carried out between March and October 2021 in the Bay of Brest. The aim of this survey was to better understand the processes which drive the incorporation of chemical elements into scallop shells and their links with phytoplankton dynamics. For this purpose, biological samples (scallops and phytoplankton) as well as water samples were collected in order to analyze various environmental parameters (element chemical properties, nutrients, chlorophyll a, etc.). Given the large number of parameters that were measured, only the major results are presented and discussed here. However, the whole dataset, which has been made available, is much larger and can potentially be very useful for other scientists performing sclerochronological investigations, studying biogeochemical cycles or conducting various ecological research projects. The dataset is available at https://doi.org/10.17882/92043 (Siebert et al., 2023).

Ba/Cashell, Mo/Cashell, and Li/Cashell chronologies of Pecten maximus can provide information on past phytoplankton dynamics. Distinct Ba, Mo, and Li peaks in the shells are associated with algal blooms. This study evaluated the underlying hypothesis that respective element profiles reliably record variations in phytoplankton dynamics occurring within the water column. Therefore, the chemical content of scallops from the Bay of Brest, France, that lived on the sediment surface was compared to conspecific specimens living in a cage above the seafloor and compared with the phytoplankton abundance and the physicochemical properties of the water column. As demonstrated, Ba/Cashell and Mo/Cashell peaks occurred contemporaneously in specimens within the cage and on the sediment, but were higher in the latter. Furthermore, element/Ca peaks agreed with the timing of particulate Ba and Mo enrichments in the seawater. These data support the assumption of a dietary uptake of both elements. Differences in peak heights between shells living in a cage and on the seafloor were controlled by rates of filtration and biomineralization. While the timing and magnitude of Ba/Cashell peaks were linked to Ba-containing diatoms, Mo/Cashell peaks were related to blooms of Mo-enriched dinoflagellate and diatom aggregation events. Two episodes of slight Li enrichment occurred synchronously in cage and sediment shells. Although the exact mechanism causing such Li increases remains unresolved, the findings suggest a link to large diatom blooms or the presence of a specific diatom taxon. This study refines previously hypothesized relationships between trace element enrichments in scallop shells and phytoplankton dynamics.

Molar barium-to-calcium ratios in bivalve shells (Ba/Ca-shell) have been proposed in a variety of studies to serve as a potential proxy for the reconstruction of phytoplankton dynamics. However, the link between phytoplankton and Ba/Ca-shell profiles remains unclear and needs to be deciphered more accurately. In this study, we analyzed the relationship between Ba/Ca-shell peaks and specific phytoplankton species, and assessed the applicability of Ba/Ca-shell ratios as a species-specific phytoplankton proxy. The timing of peaks in highly resolved Ba/Ca-shell time-series in Pecten maximus shells (Bay of Brest, France) from two years (2011, 2012) were compared to the chlorophyll a concentration and the occurrence of individual diatom and dinoflagellate species. In addition, Monte Carlo simulations were used to approximate a species-specific contribution to the measured Ba/Ca-shell peaks. The results clearly demonstrated that the Ba/Ca-shell profiles cannot be explained either by the chlorophyll a concentration nor by the total diatom or dinoflagellate abundance. Instead, time-series of specific phytoplankton, especially diatoms, revealed a high degree of synchronicity with Ba/Ca-shell peaks when temporally lagged by 8 to 13 days (depending on species). The Monte Carlo simulations suggested that the Ba/Ca-shell peak heights cannot be fully explained by the observed phytoplankton cell concentration, but rather by individually weighted phytoplankton time-series, most likely caused by inter-species differences such as cell size and chemical ability to adsorb Ba. Moreover, the approximated species-specific weighting factors agreed well between the studied years. According to our findings, Ba/Ca-shell peaks are likely associated with blooms of specific phytoplankton taxa, with a time lag of ca. one to two weeks, and the amount of cell-associated Ba varies between phytoplankton species. These conclusions provide further insights into the formation of Ba enrichments in bivalve shells and improves the applicability of Ba/Ca-shell profiles as a species-specific proxy of past phytoplankton dynamics.

Phytoplankton dynamics in coastal ecosystems is increasingly altered by land‐based human activities. Yet, this global vision conceals major disparities, among sites and through time. As conventional monitoring time series are quite sparse and relatively short, biological records of environmental variability appear as relevant tools to gain insights into phytoplankton dynamics over larger temporal and spatial scales. Here, we present results of an interdisciplinary project dealing with chemical information archived in shells of Pecten maximus (Bivalvia; Pectinidae), known to form daily growth striae on its shell surface. Several individuals were collected in the Bay of Brest (France) in 2011 and 2012, and analyzed for the molybdenum and lithium concentrations in their soft tissues and the element‐to‐calcium ratios (Mo : Ca and Li : Ca) in their calcitic striae. All shells revealed high synchrony and reproducibility in their Mo : Ca and Li : Ca profiles, characterized with a major peak at the end of May and in mid‐June 2011, respectively. Detailed analysis of physical, chemical, and biological variables measured in seawater during an extensive 9‐month environmental survey enabled a meticulous description of phytoplankton dynamics in 2011 and its impact on shell geochemistry. Main findings strongly suggest that (1) the timing of Mo : Ca peaks reflects the occurrence of silicon limitation and diatom aggregation periods, (2) the height of these peaks relates to the amplitude of the first spring diatom bloom, and (3) Li : Ca serves as a proxy for the temporal dynamics of diatom biovolume and of biogenic silica recycling at the sediment–water interface.

Shells of the fast-growing bivalve Pecten maximus serve as a geochemical archive for the reconstruction of past phytoplankton dynamics. Specifically, high-resolution, temporally accurately aligned molar barium-to-calcium (Ba/Cashell), molybdenum-to-calcium (Mo/Cashell) and lithium-to-calcium ratios (Li/Cashell) of the shell calcite revealed distinct peaks which are closely linked to phytoplankton dynamics. Yet, the development and applicability of these geochemical proxies is still at an early stage and needs further calibration. In this study, we examined the relationship between the timing and magnitude of Ba/Cashell, Mo/Cashell and Li/Cashell peaks of P. maximus and the occurrence of various phytoplankton species (diatoms and dinoflagellates) from a statistical perspective. Studied shell samples (three specimens per calendar year) as well as detailed phytoplankton observation data were derived from the well-studied costal ecosystem of the Bay of Brest (France) over three years (2011, 2012 and 2019). An algorithm-based pseudo-random sampling simulation technique was established that analyzed the complex phytoplankton datasets with respect to the profiles of Ba/Cashell, Mo/Cashell and Li/Cashell to identify potential patterns between phytoplankton and trace element time-series. The simulation results indicate that the timing and magnitude of Ba/Cashell, Mo/Cashell and Li/Cashell peaks agreed best with the occurrence of specific phytoplankton blooms that developed ca. one to two weeks earlier. The data suggest that the formation of transient Ba/Cashell peaks had a plurispecific origin, i.e., potentially linked to blooms of ingestible diatom, dinoflagellate and flagellate species enriched in Ba that occurred 8 to 12 days earlier. Observed peaks in Mo/Cashell profiles demonstrably followed the timing and intensity of blooms of the dominant dinoflagellate genus Gymnodinium spp. after a short time lag of around 8 days, potentially linked to an enhanced enzyme activity of nitrate reductase that requires the presence of Mo in the dinoflagellate cells. In addition, Mo/Cashell peaks agreed with periods of diatom aggregate formation which were hypothesized to induce the formation of Mo/Cashell peaks in scallop shells. Li/Cashell profiles revealed similar patterns as large blooms of the diatom Chaetoceros spp. as well as to neurotoxin producing diatoms of the genus Pseudo-nitzschia when considering a short time lag of 8 to 12 days. These findings highlight the great potential of using Ba/Cashell, Mo/Cashell and Li/Cashell chronologies in P. maximus shells as proxies of past phytoplankton dynamics.

Records of ocean/atmosphere dynamics over the past centuries are essential to understand processes driving climate variability. This is particularly true for the Northwest Atlantic which is a key region with an essential role in global climate regulation. Over the past two decades, coralline red algae have been increasingly used as environmental and climatic archives for the marine realm and hold the potential to extend long-term instrumental measurements. Here, we investigate the possibility to extract climate and environmental information from annual growth patterns and geochemical composition of the coralline red algae, Clathromorphum compactum, from Saint-Pierre & Miquelon (SPM), a French archipelago southwest of Newfoundland. However, measurements of C. compactum growth trends is challenging due to difficulties in identifying annual growth lines directly. So far, growth pattern investigations were commonly performed based on geochemical data of coralline calcite matrix. Nonetheless, this method is expensive and therefore prevents from analyzing a large number of specimens that would be representative of the population. For this reason, we enhanced the growth line readability by staining polished sections with Mutvei's solution and performed growth analysis based on direct increment width measurements. Geochemical analyses were also carried out in order to validate the assumption that growth lines observed after staining were formed on an annual basis. Moreover, growth pattern and trace element composition were measured on multiple axes of several individuals in order to assess the intra- and interspecimen variability and validate their use for paleoenvironmental reconstructions. Finally, relationships between the C. compactum sclerochronological records from SPM and environmental datasets covering different geographical areas allow a better knowledge of flow dynamics in the Northwest Atlantic and confirm the findings related to Arctica islandica from the same location.

The Northwest Atlantic is a key region with an essential role in global climate regulation, redistributing heat and influencing the carbon cycle. However, little is known about its evolution before 1950, mainly because of the lack of long-term instrumental measurements. The hard parts of long-lived marine biota hold the potential to extend instrumentally derived observation by several decades or centuries and enhance our understanding of global climate processes. Here, we investigate the effects of local, regional, and large-scale climate variability on the marine bivalve, Arctica islandica (Linnaeus, 1767) from Saint-Pierre and Miquelon (SPM). This archipelago lies at the boundary zone between the cold Labrador Current in the north and the warm Gulf Stream waters to the south, an excellent site to capture changes in North Atlantic climate and oceanography. This study presents the northernmost, statistically robust A. islandica growth chronology (1850-2015) from the Western North Atlantic and its potential as an environmental proxy record for past climatic and hydrographic variabilities at different time and geographical scales. In view of our results, it seems that A. islandica shell growth anomalies in SPM are mostly controlled by local primary production. Since long term instrumental records of this environmental variable are not available; we investigate the influence of global and regional environmental phenomena on A. islandica growth and indirectly on primary productivity of archipelago waters. The chronology correlates significantly and positively with the Atlantic Multidecadal Oscillation (AMO) and negatively with the North Atlantic Oscillation, two global climatic indices. The North Atlantic spatial pattern of correlation shows significant and positive correlations of 0-100 m temperatures from 1950 with A. islandica growth in SPM encompassing the subpolar gyre area. These global-scale relationships are refined and the mechanisms leading to them explained by comparing A. islandica growth chronology to regional environmental datasets. These relationships existing between the A. islandica shell growth record at SPM and environmental datasets covering different geographical scales could yield details about past North Atlantic basin and regional environmental conditions through their influence on SPM coastal environment.