Sphaerosiderites as sensitive recorders of non‐marine depositional and diagenetic history: Insights from the Lower Cretaceous Wealden Supergroup

Waterlogged, reducing soils in modern and ancient wetlands feature distinctive syndepositional to early diagenetic spherical iron carbonate concretions, known as sphaerosiderites. Sphaerosiderites are thought to record pore water elemental chemistry and local palaeoenvironmental conditions, and are widely used in palaeohydrological reconstructions throughout the Phanerozoic. The Lower Cretaceous non‐marine Wealden Supergroup of Southern England, deposited in fluvio‐lacustrine settings, contains abundant well‐preserved sphaerosiderites offering an ideal archive for unravelling the geochemistry of ancient non‐marine environments. Sphaerosiderites were characterised via multiple microanalytical techniques (SEM‐EDS, EPMA, XRD, SIMS), and show morphological and compositional heterogeneity (e.g. concentric zones of variably enriched Mn, Ca or Mg, elemental differences between cores and rims) in well‐preserved sphaerosiderites from the Ashdown and Tunbridge Wells Sand formations. The preservation of primary fabrics, lack of post‐burial cements or extensive alteration suggests these sphaerosiderites record primary palaeoenvironmental conditions. By contrast, in the Wadhurst Clay Formation, sphaerosiderites are recrystallised, potentially reflecting wide scale palaeoenvironmental changes (e.g. marine incursions). New experimental constraints on elemental uptake during siderite growth suggests that rather than reflecting pore water elemental chemistry, the elemental heterogeneity in the Wealden sphaerosiderites reflects complex parameters; variations in pH, cation concentrations, DIC, growth rate and siderite saturation state in groundwaters. At a larger scale, morphological and compositional differences between sphaerosiderites from distinct palaeosol horizons record spatial and temporal variability in local hydrogeochemistry. This suggests that the Weald Basin wetlands of the Lower Cretaceous featured a dynamic and periodically fluctuating groundwater table, where sphaerosiderites growing close to the soil surface responded rapidly to variability in physiochemical conditions, consistent with wet and warm conditions suggested by sedimentological evidence and climate model simulations. Similar morphological and compositional variability noted in other Phanerozoic sphaerosiderites suggests analogous processes operated in ancient wetlands, and that sphaerosiderites could provide a crucial tool to understand wetland dynamics in deep time.

[1]  N. Tosca,et al.  Growth kinetics of siderite at 298.15 K and 1 bar , 2020, Geochimica et Cosmochimica Acta.

[2]  N. Tosca,et al.  Geochemical controls on the elemental composition of siderite: Implications for palaeo-environmental reconstructions , 2020, Geochimica et Cosmochimica Acta.

[3]  A. Turchyn,et al.  The microbially driven formation of siderite in salt marsh sediments , 2019, Geobiology.

[4]  M. Lever,et al.  Experimental calibration of clumped isotopes in siderite between 8.5 and 62 °C and its application as paleo-thermometer in paleosols , 2019, Geochimica et Cosmochimica Acta.

[5]  N. Tosca,et al.  The role of microbial sulfate reduction in calcium carbonate polymorph selection , 2018, Geochimica et Cosmochimica Acta.

[6]  A. Boyce,et al.  Groundwater table fluctuations recorded in zonation of microbial siderites from end-Triassic strata , 2016 .

[7]  Kevin McDonough Wetlands (5th edition) , 2016 .

[8]  S. Passey The habit and origin of siderite spherules in the Eocene coal-bearing Prestfjall Formation, Faroe Islands , 2014 .

[9]  Jianwu Tang,et al.  Siderite ‘clumped’ isotope thermometry: A new paleoclimate proxy for humid continental environments , 2014 .

[10]  P. Allen,et al.  The non-marine Lower Cretaceous Wealden strata of southern England , 2012 .

[11]  C. Rollion-Bard,et al.  Determination of SIMS matrix effects on oxygen isotopic compositions in carbonates , 2011 .

[12]  V. Vulava,et al.  Micromorphology and Stable-Isotope Geochemistry of Historical Pedogenic Siderite Formed in PAH-Contaminated Alluvial Clay Soils, Tennessee, U.S.A. , 2010 .

[13]  Li Zhang,et al.  Tropical wetlands: seasonal hydrologic pulsing, carbon sequestration, and methane emissions , 2010, Wetlands Ecology and Management.

[14]  G. Ludvigson,et al.  Estimating the Oxygen Isotopic Composition of Equatorial Precipitation During the Mid-Cretaceous , 2010 .

[15]  T. Atkinson,et al.  Constraints on palaeoenvironments in the Lower Cretaceous Wealden of southern England, from the geochemistry of sphaerosiderites , 2010, Journal of the Geological Society.

[16]  M. Coleman,et al.  Inorganic synthesis of Fe--Ca--Mg carbonates at low temperature , 2009 .

[17]  Kyungsik Choi,et al.  Late Quaternary evolution of macrotidal Kimpo tidal flat, Kyonggi Bay, west coast of Korea , 2006 .

[18]  J. Radley A Wealden guide II: the Wessex Sub‐basin , 2006 .

[19]  J. Radley A Wealden guide I: the Weald Sub‐basin , 2006 .

[20]  G. Ludvigson,et al.  Evidence for increased latent heat transport during the Cretaceous (Albian) greenhouse warming , 2004 .

[21]  Paul J. Valdes,et al.  Cretaceous (Wealden) climates: a modelling perspective , 2004 .

[22]  G. Ludvigson,et al.  Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved? , 2004 .

[23]  C. Romanek,et al.  Precipitation kinetics and carbon isotope partitioning of inorganic siderite at 25°C and 1 atm , 2004 .

[24]  Kyungsik Choi,et al.  Spherulitic siderites in the Holocene coastal deposits of Korea (eastern Yellow Sea): elemental and isotopic composition and depositional environment , 2003 .

[25]  J. Andrews,et al.  Atmospheric pCO2 and depositional environment from stable-isotope geochemistry of calcrete nodules (Barremian, Lower Cretaceous, Wealden Beds, England) , 2002, Journal of the Geological Society.

[26]  K. Taylor,et al.  The Paleohydrology of Lower Cretaceous Seasonal Wetlands, Isle of Wight, Southern England , 2000 .

[27]  Kyungsik Choi,et al.  Occurrence of authigenic siderites in the Early Holocene coastal deposit in the west coast of Korea: an indicator of depositional environment , 1999 .

[28]  T. White,et al.  Meteoric sphaerosiderite lines and their use for paleohydrology and paleoclimatology , 1998 .

[29]  Q. Fisher,et al.  Siderite concretions from nonmarine shales (Westphalian A) of the Pennines, England; controls on their growth and composition , 1998 .

[30]  D. Batten Palaeonenvironmental implications of plant, insect and other organic-walled microfossils in the Weald Clay Formation (Lower Cretaceous) of southeast England , 1998 .

[31]  J. Rae,et al.  Effect of bacteria on the elemental composition of early diagenetic siderite: implications for palaeoenvironmental interpretations , 1997 .

[32]  W. Shotyk,et al.  Chemical composition, pH, and redox state of sulfur and iron in complete vertical porewater profiles from two Sphagnum peat bogs, Jura Mountains, Switzerland , 1997 .

[33]  K. Alvin,et al.  An English Wealden floral list, with comments on possible environmental indicators , 1996 .

[34]  D. Horne A revised ostracod biostratigraphy for the Purbeck-Wealden of England , 1995 .

[35]  M. Coleman Microbial processes: Controls on the shape and composition of carbonate concretions , 1993 .

[36]  Derek R. Lovley,et al.  Reduction of Fe(III) in sediments by sulphate-reducing bacteria , 1993, Nature.

[37]  P. Wersin,et al.  Isotopic composition of siderite as an indicator of depositional environment , 1992 .

[38]  W. Carothers,et al.  Elemental and Isotopic Composition of Siderite in the Kuparuk Formation, Alaska: Effect of Microbial Activity and Water/Sediment Interaction on Early Pore-Water Chemistry , 1992 .

[39]  P. Aharon,et al.  Diagenetic Siderite and Other Ferroan Carbonates in a Modern Subsiding Marsh Sequence , 1992 .

[40]  W. Wimbledon,et al.  Correlation of NW European Purbeck-Wealden (nonmarine Lower Cretaceous) as seen from the English type-areas , 1991 .

[41]  Max Coleman,et al.  Formation of siderite‐Mg‐calcite‐iron sulphide concretions in intertidal marsh and sandflat sediments, north Norfolk, England , 1990 .

[42]  P. Mozley Relation between depositional environment and the elemental composition of early diagenetic siderite , 1989 .

[43]  R. Rosenbauer,et al.  Experimental oxygen isotope fractionation between siderite-water and phosphoric acid liberated CO2-siderite , 1988 .

[44]  D. Batten,et al.  Evidence of freshwater dinoflagellates and other algae in the English Wealden (Early Cretaceous) , 1988 .

[45]  J. Kantorowicz The Petrology and Diagenesis of Middle Jurassic Clastic Sediments, Ravenscar Group, Yorkshire , 1985 .

[46]  K. Pye,et al.  SEM analysis of siderite cements in intertidal marsh sediments, Norfolk, England , 1984 .

[47]  P. Allen Pursuit of Wealden models , 1981, Journal of the Geological Society.

[48]  L. Marynowski,et al.  Pedogenic siderites fossilizing Ediacaran soil microorganisms on the Baltica paleocontinent , 2019, Geology.

[49]  Nicole Bauer,et al.  Principles Of Chemical Sedimentology , 2016 .

[50]  D. Fowle,et al.  Paleoclimatic applications and modern process studies of pedogenic siderite , 2013 .

[51]  B. Khim,et al.  Elemental composition of siderite grains in early-Holocene deposits of Youngjong Island (west coast of Korea), and its palaeoenvironmental implications , 2000 .

[52]  C. Hunt,et al.  Purbeck–Wealden (early Cretaceous) climates , 1998 .

[53]  J. Radley Stratigraphy, palaeontology and palaeoenvironment of the Wessex Formation (Wealden Group, Lower Cretaceous) at Yaverland, Isle of Wight, southern England , 1994 .

[54]  P. Allen Wealden research—ways ahead , 1989 .

[55]  A. A. Morter Purbeck-Wealden Beds Mollusca and their relationship to ostracod biostratigraphy, stratigraphical correlation and palaeoecology in the Weald and adjacent areas , 1984 .

[56]  D. Batten Palynofacies and salinity in the Purbeck and Wealden of southern England , 1982 .

[57]  D. Postma Formation of siderite and vivianite and the pore-water composition of a Recent bog sediment in Denmark , 1980 .

[58]  E. Nickel,et al.  Supergene alteration of sulphides. III. The composition of associated carbonates , 1976 .

[59]  P. Allen Wealden of the Weald: a new model , 1975 .

[60]  R. Berner Sedimentary pyrite formation , 1970 .