Environmental and biological controls on the geochemistry (δ18O, δ13C, Mg/Ca, and Sr/Ca) of living ostracods from Lake Geneva

ABSTRACT : Ostracods are benthic microcrustaceans enclosed in low-Mg calcite bivalves. Stable isotope compositions, Mg/Ca, and Sr/Ca ratios of ostracod fossil valves have proven useful to reconstruct past environmental conditions. Yet, several discrepancies persist and the influence of many factors remains unclear. It is the aim of this study to improve the use of ostracod valve geochemistry as palaeoenvironmental proxies by examining the extent of isotope fractionation and trace element partitioning during valve calcification. To achieve this, the environmental parameters (pH, temperature) and chemical composition of water (C-and O-isotope composition and calcium, magnesium, and strontium content) were measured at sites where living ostracods were sampled. The sampling was on a monthly basis over the course of one year at five different water depths (2, 5, 13, 33, and 70 m) in Lake Geneva, Switzerland. The one-year sampling enabled collection of environmental data for bottom and interstitial pore water. In littoral to sublittoral zones, C-isotope composition of DIC and the Mg/Ca and Sr/Ca ratios of water are found to vary concomitantly with water temperature. This is due to the precipitation of calcite, which is induced by higher photosynthetic activity as temperature and/or solar radiation intensify in summer. In deeper zones, environmental parameters remain largely constant throughout the year. Variations of pH, DIC concentrations and C-isotope compositions in interstitial water result from aerobic as well as anaerobic respiration, calcite dissolution and methanogenesis. Bathymetric distribution, life cycles, and habitats were derived for 15 ostracod species and are predominantly related to water temperature and sediment texture. O-isotope compositions of ostracod valves in Lake Geneva reflect that of water and temperature. However, offsets of up to 3 permil are observed in comparison with proposed inorganic calcite precipitation equilibrium composition. Deprotonation of HCO3- and/or salt effect at crystallisation sites may explain the disequilibrium observed for O-isotopic compositions. C-isotope compositions of ostracod valves are not as well constrained and appear to be controlled by a complex interaction between habitat preferences and seasonal as well as spatial variations of the DIC isotope composition. For infaunal forms, C-isotope compositions reflect mainly the variation of DIC isotope composition in interstitial pore waters. For epifaunal forms, C-isotope compositions reflect the seasonal variation of DIC isotope compositions. C-isotope compositions of ostracod valves is at equilibrium with DIC except for a small number of species (L. inopinata, L. sanctipatricii and possibly C. ophtalmica, and I. beauchampi). Trace element uptake differs considerably from species to species. For most epifaunal forms, trace element content follows the seasonal cycle, recording temperature increases and/or variations of Mg/Ca and Sr/Ca ratios of water. In contrast, infaunal forms are predominantly related to sediment pore water chemistry. RÉSUMÉ EN FRANÇAIS : Les ostracodes sont de petits crustacés benthiques qui possèdent une coquille faite de calcite à faible teneur en magnésium. La composition isotopique et les rapports Mg/Ca et Sr/Ca d'ostracodes fossiles ont été utilisés maintes fois avec succès pour effectuer des reconstructions paléoenvironnementales. Néanmoins, certains désaccords persistent sur l'interprétation de ces données. De plus, l'influence de certains facteurs pouvant biaiser le signal reste encore inconnue. Ainsi, le but de cette étude est de rendre plus performant l'emploi de la composition géochimique des ostracodes comme indicateur paléoenvironnemental. Pour réaliser cela, cinq sites situés dans le Léman à 2, 5, 13, 33 et 70 m de profondeur ont été choisis pour effectuer les échantillonnages. Chaque site a été visité une fois par mois durant une année. Les différents paramètres environnementaux (pH, température) ainsi que la composition géochimique de l'eau (composition isotopique de l'oxygène et du carbone ainsi que teneur en calcium, magnésium et strontium) ont été déterminés pour chaque campagne. Des ostracodes vivants ont été récoltés au cinq sites en même temps que les échantillons d'eau. Ce travail de terrain a permis de caractériser la géochimie de l'eau se trouvant juste au-dessus des sédiments ainsi que celle de l'eau se trouvant dans les interstices du sédiment. Dans les zones littorales à sublittorales, la composition isotopique du carbone inorganique dissout (CID) ainsi que les rapports Mg/Ca et Sr/Ca de l'eau varient linéairement avec la température. Ceci peut être expliqué par la précipitation de calcite qui est contrôlée par l'activité photosynthétique, variant elle même linéairement avec la température. Dans les zones plus profondes, les paramètres environnementaux restent relativement constants tout au long de l'année. Les variations du pH, de la concentration et de la composition isotopique du CID dans les sédiments résultent de la libération de carbone engendrée par la dégradation de la matière organique avec présence d'oxygène ou via réduction de nitrates et de sulfates, par la dissolution de carbonates, ainsi que par la méthanogenèse. La distribution bathymétrique, le cycle de vie ainsi que l'habitat de 15 espèces ont été déterminés. Ceux-ci sont principalement reliés à la température de l'eau et à la texture des sédiments. La composition isotopique de l'oxygène des valves d'ostracodes reflète celle de l'eau et la température qui régnait lors de la calcification. Néanmoins, des écarts pouvant aller jusqu'à 3 0/00 par rapport à l'équilibre théorique ont été obtenus. La déprotonation de HCO3 ou un 'effet de sel' pourrait être à l'origine du déséquilibre observé. La composition isotopique du carbone des valves d'ostracodes n'est pas aussi bien cernée. Celle-ci semble être principalement contrôlée par une interaction complexe entre l'habitat des ostracodes et les variations saisonnières et spatiales de la composition isotopique du CID. Pour les espèces endofaunes, la composition isotopique du carbone reflète principalement la variation de la composition isotopique du CID à l'intérieur des sédiments. Pour les formes épifaunes, c'est la variation saisonnière de la composition du CID qui contrôle celle de la coquille des ostracodes. En général, la composition isotopique du carbone des valves d'ostracodes est en équilibre avec celle de CID, hormis pour quelques rares espèces (L. inopinata, L. sanctipatricii et peut-être C. ophtalmica et I. beauchampi). L'incorporation des éléments traces diffère passablement d'une espèce à l'autre. Pour la plupart des espèces épifaunes, la teneur en éléments traces des coquilles reflète les variations saisonnières. Ces espèces semblent enregistrer les variations soit de la température soit des rapports Mg/Ca et Sr/Ca de l'eau. La teneur en élément traces des formes infaunales, au contraire, est principalement reliée à la chimie de l'eau interstitielle. RÉSUMÉ GRAND-PUBLIC : La connaissance de l'évolution du climat dans le futur est primordiale pour notre société, car elle permet de développer différentes stratégies pour faire face aux problèmes engendrés pas le changement climatique : stratégies environnementale, humanitaire, ou encore économique. Cette problématique est actuellement, à juste titre, sujet d'une vive préoccupation. La géologie peut-elle contribuer à l'effort communautaire entrepris? Naturellement, ce sont les climatologues qui sont sur le devant de la scène. Il n'empêche que ces derniers, pour pouvoir prédire l'avenir, doivent s'appuyer sur le passé. La géologie est alors d'un grand intérêt car c'est effectivement la seule science qui permette d'estimer les variations climatiques à grande échelle sur de longues périodes. Ainsi, voulant moi-même contribuer aux recherches menées dans ce domaine, je me suis tourné à la fin de mes études vers la paléoclimatologie, science qui a pour but de reconstruire le climat des temps anciens. Nous nous sommes rendu compte que l'évolution climatique de la région où nous habitons n'avait pas encore fait le sujet d'études approfondies. Il est pourtant important de connaître la variation locale des changements climatiques pour obtenir des modèles climatiques fiables. En conséquence, un vaste projet a vu le jour : reconstruire, à l'aide des sédiments du lac Léman, les variations paléoclimatiques et paléo-environnementales depuis le retrait du Glacier de Rhône, il y a environ 15'000 ans, jusqu'à nos jours. Pour ce genre de travail, la géochimie, qui est une forme de chimie, utilisée en science de la terre regroupant la chimie classique et la chimie isotopique, est une alliée particulièrement efficace. Elle permet en effet, via différentes mesures faites sur des archives géologiques (par exemple des fossiles ou des sédiments) d'obtenir des informations, souvent quantitatives, sur les conditions (le climat, la flore ou encore la bio productivité, etc...) qui régnaient il y a fort longtemps. Les coquilles d'ostracodes, qui sont de petits animaux vivant au fond des lacs, sont une des archives les plus prometteuses. Ces animaux sont des petits crustacés s'entourant d'une coquille calcaire qu'ils sécrètent eux-mêmes. A la mort de l'animal, la coquille est intégrée dans les sédiments et reste intacte à travers les âges. Des études ont montré qu'en analysant la géochimie de ces coquilles fossiles, il est possible de reconstruire les conditions environnementales qui régnaient à l'époque de vie de ces fossiles. Cette démarche nécessite qu'une condition bien précise soit remplie: la composition géochimique de la coquille doit enregistrer de manière fidèle la chimie de l'eau et/ou la température de l'eau présentes au moment de la sécrétion de la coquille. Le but spécifique de notre recherche a précisément été d'étudier la façon dont la chimie de l'eau ainsi que sa température sont enregistrées dans la coquillé des ostracodes. Une fois les relations entre ces divers paramètres dans l'étant actuel du système établies, il sera alors possible de les utiliser pour interpréter des données issues de coquilles fossiles. Pour ce faire, nous avons mesuré la température de l'eau de manière continue et récolté mensuellement des échantillons d'eau et des ostracodes vivants pendant une année. Cinq sites situés à 2, 5, 13, 33 et 70 mètres de profondeur ont été choisis pour effectuer ces échantillonnages dans le Léman. Le travail de terrain nous a amené à étudier la biologie de 15 espèces. Nous avons pu établir la profondeur à laquelle vivent ces animaux, leur période de développement ainsi que leur habitat respectifs. Ces résultats ont permis de mieux cerner la relation qu'il existe entre la chimie de l'eau, sa température et la composition géochimique des coquilles d'ostracodes. Nous avons ainsi pu confirmer que les coquilles d'ostracodes enregistrent de manière fidèle la composition chimique et isotopique de l'eau. De même, nous avons pu établir de manière plus précise l'effet de la température sur la géochimie des coquilles. Néanmoins, les relations trouvées entre ces trois éléments sont plus complexes pour certaines espèces, cette complexité étant souvent liée à un caractère spécifique de leur écologie. Nous avons mis en lumière certains effets qui biaisent les résultats et défini précisément les conditions dans lesquelles on peut s'attendre à avoir des difficultés dans leur interprétation. Maintenant que nous avons établi les relations entre le climat actuel et la composition géochimique des coquilles d'ostracodes actuels, nous pouvons, sur la base de ce modèle, reconstruire le climat depuis le retrait du Glacier du Rhône jusqu'à nos jours à l'aide d'ostracodes fossiles. Mais cela est une autre histoire et fera, je l'espère, le sujet de nos futures recherches.

Controls on ostracod valve geochemistry: Part 2. Carbon and oxygen isotope compositions

The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in 18O of more than 30/00 relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in 18O for these species of 1.7 to 2.30/00. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens' δ13C values are mainly controlled by seasonal variations in δ13CDIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate growth indicate that different growth rates or low pH within the calcification site cannot be the cause of oxygen isotope 'vital effects' in ostracods. Two mechanisms that might enrich the 18O of ostracod valves are deprotonation of that may also contribute to valve calcification, and effects comparable to salt effects with high concentrations of Ca and/or Mg within the calcification site that may also cause a higher temperature dependency of oxygen isotope fractionation.

Geochemistry and Stable Isotopes of Surface Water and Groundwater in the Continental Pit in Butte, Montana, USA

The Continental porphyry Cu‐Mo mine, located 2 km east of the famous Berkeley Pit lake of Butte, Montana, contains two small lakes that vary in size depending on mining activity. In contrast to the acidic Berkeley Pit lake, the Continental Pit waters have near-neutral pH and relatively low metal concentrations. The main reason is geological: whereas the Berkeley Pit mined highly‐altered granite rich in pyrite with no neutralizing potential, the Continental Pit is mining weakly‐altered granite with lower pyrite concentrations and up to 1‐2% hydrothermal calcite. The purpose of this study was to gather and interpret information that bears on the chemistry of surface water and groundwater in the active Continental Pit. Pre‐existing chemistry data from sampling of the Continental Pit were compiled from the Montana Bureau of Mines and Geology and Montana Department of Environmental Quality records. In addition, in March of 2013, new water samples were collected from the mine’s main dewatering well, the Sarsfield well, and a nearby acidic seep (Pavilion Seep) and analyzed for trace metals and several stable isotopes, including dD and d18O of water, d13C of dissolved inorganic carbon, and d34S of dissolved sulfate. In December 2013, several soil samples were collected from the shore of the frozen pit lake and surrounding area. The soil samples were analyzed using X‐ray diffraction to determine mineral content. Based on Visual Minteq modeling, water in the Continental Pit lake is near equilibrium with a number of carbonate, sulfate, and molybdate minerals, including calcite, dolomite, rhodochrosite (MnCO3), brochantite (CuSO4·3Cu(OH)2), malachite (Cu2CO3(OH)2), hydrozincite (Zn5(CO3)2(OH)6), gypsum, and powellite (CaMoO4). The fact that these minerals are close to equilibrium suggests that they are present on the weathered mine walls and/or in the sediment of the surface water ponds. X‐Ray Diffraction (XRD) analysis of the pond “beach” sample failed to show any discrete metal‐bearing phases. One of the soil samples collected higher in the mine, near an area of active weathering of chalcocite‐rich ore, contained over 50% chalcanthite (CuSO4·5H2O). This water‐soluble copper salt is easily dissolved in water, and is probably a major source of copper to the pond and underlying groundwater system. However, concentrations of copper in the latter are probably controlled by other, less‐soluble minerals, such as brochantite or malachite. Although the acidity of the Pavilion Seep is high (~ 11 meq/L), the flow is much less than the Sarsfield Well at the current time. Thus, the pH, major and minor element chemistry in the Continental Pit lakes are buffered by calcite and other carbonate minerals. For the Continental Pit waters to become acidic, the influx of acidic seepage (e.g., Pavilion Seep) would need to increase substantially over its present volume.

An evaluation of the Cypress Creek watershed for inorganic chemical load as it flows into Lake Houston

Background. The Cypress Creek is one of the main tributaries of Lake Houston, which provides drinking water to 21.4 million customers. Furthermore, the watershed is being utilized for contact and non-contact recreation, such as canoeing, swimming, hiking trail, and picnics. Water along the creek is impacted by numerous wastewater outfalls from both point and non-point sources. As the creek flows into Lake Houston, it carries both organic and inorganic contaminants that may affect the drinking water quality of this important water source reservoir. Objective. This study was carried out to evaluate the inorganic chemical load of the water in Cypress Creek along its entire length, from the headwaters in Waller County and up to the drainage into Lake Houston. The purpose was to determine whether there are hazardous concentrations of metals in the water and what would be the likely sources. Method. Samples were collected at 29 sites along the creek and analyzed for 29 metals, 17 of which were on the Environmental Protection Agency priority pollution list. Public access sites primarily at bridges were used for sample collection. Samples were transported on ice to the University Of Texas School Of Public Health laboratory, spiked with 2 ml HNO3 kept overnight in the refrigerator, and the following day transported to the EPA laboratory for analysis. Analysis was done by EPA Method 200.7-ICP, Method 200.8ICP/MS and Method 245.1-CVAAS. Results. Metals were present above the detection limits at 65% of sites. Concentrations of aluminum, iron, sodium, potassium, magnesium, and calcium, were particularly high at all sites. Aluminum, sodium, and iron concentrations greatly exceeded the EPA secondary drinking water standards at all sites. ^ Conclusion. The recreational water along Cypress Creek is impacted by wastewater from both permitted and non-permitted outfalls, which deposit inorganic substances into the water. Although a number of inorganic contaminants were present in the water, toxic metals regulated by the EPA were mostly below the recommended limits. However, high concentrations of aluminum, sodium, and iron in the Cypress Creek bring forward the issue of unauthorized discharges of salt water from mining, as well as industrial and domestic wastewater.^

Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

Geochemistry on Holocene sediments from the Mediterranean

The enhanced accumulation of organic matter in Eastern Mediterranean sapropels and their unusually low d15N values have been attributed to either enhanced nutrient availability which led to elevated primary production and carbon sequestration or to enhanced organic matter preservation under anoxic conditions. In order to evaluate these two hypothesis we have determined Ba/Al ratios, amino acid composition, N and organic C concentrations and d15N in sinking particles, surface sediments, eight spatially distributed core records of the youngest sapropel S1 (10-6 ka) and older sapropels (S5, S6) from two locations. These data suggest that (i) temporal and spatial variations in d15N of sedimentary N are driven by different degrees of diagenesis at different sites rather than by changes in N-sources or primary productivity and (ii) present day TOC export production would suffice to create a sapropel like S1 under conditions of deep-water anoxia. This implies that both enhanced TOC accumulation and d15N depletion in sapropels were due to the absence of oxygen in deep waters. Thus preservation plays a major role for the accumulation of organic-rich sediments casting doubt on the need of enhanced primary production for sapropel formation.

Sedimentology and geochemistry of Oxygen Isotope Stage 3 and Holocene sediments from Laguna Potrok Aike, Patagonia

Seismic reflection studies in the maar lake Laguna Potrok Aike (51°58? S, 70°23? W) revealed an erosional unconformity associated with a sub-aquatic lake-level terrace at a water depth of 30m. Radiocarbon-dated, multi-proxy sediment studies of a piston core from this location indicate that the sediment below this discontinuity has an age of 45kyr BP (Oxygen Isotope Stage 3), and was deposited during an interval of high lake level. In comparison to the Holocene section, geochemical indicators of this older part of the record either point towards a different sediment source or to a different transport mechanism for Oxygen Isotope Stage 3 sediments. Holocene sedimentation started again before 6790cal. yr BP, providing a sediment record of hydrological variability until the present. Geochemical and isotopic data indicate a fluctuating lake level until 5310cal. yr BP. During the late Holocene the lake level shows a receding tendency. Nevertheless, the lake level did not drop below the 30m terrace to create another unconformity. The geochemical characterization of volcanic ashes reveals evidence for previously unknown explosive activity of the Reclús and Mt. Burney volcanoes during Oxygen Isotope Stage 3.

Sedimentology and geochemistry of late glacial and Holocene sediments from Laguna Potrok Aike, Patagonia

A high-resolution multiproxy geochemical approach was applied to the sediments of Laguna Potrok Aike in an attempt to reconstruct moist and dry periods during the past 16 000 years in southeastern Patagonia. The age-depth model is inferred from AMS 14C dates and tephrochronology, and suggests moist conditions during the Lateglacial and early Holocene (16 000-8700 cal. BP) interrupted by drier conditions before the beginning of the Holocene (13 200-11 400 cal. BP). Data also imply that this period was a major warm phase in southeastern Patagonia and was approximately contemporaneous with the Younger Dryas chronozone in the Northern Hemisphere (12 700-11 500 cal. BP). After 8650 cal. BP a major drought may have caused the lowest lake level of the record. Since 7300 cal. BP, the lake level rose and was variable until the 'Little Ice Age', which was the dominant humid period after 8650 cal. BP.

Geochemistry at DSDP Leg 74 Holes

Clay mineralogical and inorganic geochemical data from the Campanian to the Pleistocene provide information bearing on the evolution of both continental and marine paleoenvironments in the Walvis Ridge area. (1) Alteration processes of basalts occurred under subaerial conditions during the Campanian and Maestrichtian and were virtually absent in deeper marine environments. (2) Strong tectonic effects were present during the Campanian and persisted until the early Eocene. (3) Subsidence of this part of the Walvis Ridge became important during the late Maestrichtian and continued into the Paleocene and Eocene. (4) The influence of global climatic cooling was evident from the late Eocene on. (5) Modification of oceanic circulation and the increasing influence of surface and deep water masses on the sedimentation characterized the Cenozoic.

Interstitial water d13C and sediment geochemistry of ODP Leg 166 sites

A review of interstitial water samples collected from Sites 1003-1007 of the Bahamas Transect along with a shore-based analysis of oxygen and carbon isotopes, minor and trace elements, and sediment chemistry are presented. Results indicate that the pore-fluid profiles in the upper 100 meters below seafloor (mbsf) are marked by shifts between 20 and 40 mbsf that are thought to be caused by changes in sediment reactivity, sedimentation rates, and the influence of strong bottom currents that have been active since the late Pliocene. Pore-fluid profiles in the lower Pliocene-Miocene sequences are dominated by diffusion and do not show significant evidence of subsurface advective flow. Deeper interstitial waters are believed to be the in situ fluids that have evolved through interaction with sediments and diffusion. Pore-fluid chemistry is strongly influenced by carbonate recrystallization processes. Increases in pore-fluid Cl- and Na+ with depth are interpreted to result mainly from carbonate remineralization reactions that are most active near the platform margin. A lateral gradient in detrital clay content observed along the transect, leads to an overall lower carbonate reactivity, and enhances preservation of metastable aragonite further away from the platform margin. Later stage burial diagenesis occurs at slow rates and is limited by the supply of reactive elements through diffusion.