Stable and clumped isotopes in desert carbonate spring and lake deposits reveal palaeohydrology: A case study of the Lower Jurassic Navajo Sandstone,south‐western USA

Carbon, oxygen and clumped isotope (Δ₄₇) values were measured from lacustrine and tufa (spring)‐mound carbonate deposits in the Lower Jurassic Navajo Sandstone of southern Utah and northern Arizona in order to understand the palaeohydrology. These carbonate deposits are enriched in both ¹⁸O and ¹³C across the basin from east to west; neither isotope is strongly sensitive to the carbonate facies. However, ¹⁸O is enriched in lake carbonate deposits compared to the associated spring mounds. This is consistent with evaporation of the spring waters as they exited the mounds and were retained in interdune lakes. Clumped isotopes (Δ₄₇) exhibit minor systematic differences between lake and tufa‐mound temperatures, suggesting that the rate of carbonate formation under ambient conditions was moderate. These clumped isotope values imply palaeotemperature elevated beyond reasonable surface temperatures (54 to 86°C), which indicates limited bond reordering at estimated burial depths of ca 4 to 5 km, consistent with independent estimates of sediment thickness and burial depth gradients across the basin. Although clumped isotopes do not provide surface temperature information in this case, they still provide useful burial information and support interpretations of the evolution of groundwater locally. The findings of this study significantly extend the utility of combining stable isotope and clumped isotope methods into aeolian environments.     

Origin and evolution of tufa mounds related to artesian karstic springs in Isona area (Pyrenees,NE Spain)

This work analyses a suite of relict tufa mounds generated by artesian karstic springs in Isona area (Spanish Pyrenees). Geological and geophysical data (seismics and vertical electrical resistivity soundings) indicate that the location of the discharge area in which the spring mounds formed was controlled by (1) a bulge in the axial zone of the anticline that affects the Areny-Montsec aquifer, with the consequent thinning of the overlying confining unit and (2) N-S and E-W trending extensional faults. These uncommon meteogene mounds occur in two stepped morphostratigraphic units that constitute the caprock of a mesa 9 km2 in area. The upper tufa complex is 47 m thick and has yielded several U/Th dates of >350 ka. The obtained U/Th ages for the mounds of lower tufa complex, 10 m thick, range from >350 to 214 ± 11 ka. The sedimentological analysis of the scarce exposures and electrical resistivity profiles show the same morphological and depositional components as those described in geothermal springs: (1) Cylindrical vents; (2) Pools fed by the vents and dammed by annular tufa barriers; (3) Tufa barriers (rimstones) constructed by overflowing waters through vertical accretion and progradation. These rimstones may have overhanging upflow sides. (4) Slope tufa facies with terracettes and microgours.     

Sedimentological and palaeohydrological characterization of Late Pleistocene and Holocene tufa mound palaeolakes using trenching methods in the Spanish Pyrenees

Lakes developed in the inner depressions of tufa mounds are rare geomorphic features and still poorly understood. Sedimentation in this unusual type of endorheic lake with a very restricted catchment area is highly sensitive to environmental and hydrological changes. The Isona tufa mound complex, north‐eastern Iberian Peninsula, is associated with the discharge zone of a confined artesian aquifer and comprises 11 tufa mounds consisting of an annular rimstone enclosing a central depression filled with lake deposits. Data gathered from trenches excavated in four palaeolakes located within three different morphostratigraphic units permitted a precise analysis of the geometrical characteristics and stratigraphic relationships of the deposits and provided a sedimentation model for the Late Quaternary infilling of the spring‐fed lakes. The work illustrates that trenches allow a precise characterization of the stratigraphic arrangements, lateral facies changes and deformation structures, which are not apparent in studies relying solely on borehole records, and facilitate sampling for dating and geochemical analyses. The five sedimentary facies described represent different evolutionary stages of the lakes, including: (i) carbonate‐rich palustrine deposits probably related to periods with strong hydrological seasonality; (ii) massive highly bioturbated organic ooze; (iii) banded organic carbonate‐rich facies associated with an increase in the regional effective moisture; (iv) fine‐grained quartz‐rich aeolian/slope‐wash sediments; and (v) colluvial facies deposited following the desiccation of the lakes located at higher altitudes. Geochemical and sedimentological analyses of the lacustrine sequences provided information on the palaeohydrological evolution of the Isona tufa mound complex and the palaeoenvironmental conditions of the area over the last 28 ka. Radiometric dating suggests that deposition occurred simultaneously at ca 22 ka in palaeolakes situated at different elevations. A drop in the piezometric level prompted by the opening of springs at lower altitudes probably caused the deactivation of the upper springs and the desiccation of the lakes. Arid conditions prevailed in the area during the Late Glacial and the early Holocene (28·0 to 8·5 ka bp ). More humid conditions recorded from 8·5 to 4·2 ka and again since 1·7 ka are in accordance with palaeoenvironmental reconstructions available in the Western Mediterranean since the Last Glacial Maximum.     

Sedimentology of Quaternary perched springline and paludal tufas: criteria for recognition, with examples from Guadalajara Province, Spain

Outcrop‐scale geometries and bed relationships of ambient temperature freshwater carbonates are poorly understood because many described tufas have been dismantled by erosion and present only part of a particular depositional model. At the field scale, four end‐member models encompass the tufa continuum: (1) perched springline; (2) paludal; (3) fluvial; and (4) lacustrine tufas. Individual bed types can occur with variable dominance within several of these models, but one or more beds are characteristically dominant only within a single tufa model, so it can be differentiated from relatively isolated outcrop fragments. Two models (perched springline tufas and paludal tufas) are known in outline only in the literature despite being present within the Quaternary deposits of most karstic regions. Perched springline tufas generally form lobate, fan‐shaped mound morphologies on hillslopes and develop from single or multiple spring resurgences. Mature deposits show a subhorizontal top and a steep face on the downflow side. The steep outer zones of tufa mounds may be developed into cascades with moss curtains or can be dominated by shallow rimstone pools according to face angle. Tufa deposits lying downslope of the mounds are usually detrital in nature, especially if some dismantling of the mound has occurred. The relatively thin subhorizontal lobe‐top deposits commonly contain organic‐rich deposits. Paludal tufas develop predominantly in waterlogged valley bottom situations, where line‐sourced waters emerge from valley side and bottom aquifers. Lime mud precipitation predominates in these sites. Mud is deposited as subhorizontal laminites that thin towards the valley axis and downstream of resurgences. Tufa spring‐mounds may form where lesser volumes of water are involved. Individual tussocks (phytoherm cushions) of grasses and rushes are the most diagnostic feature of the model, but sapropels and peats may be intercalated. Diagenesis in both models is rapid. Lithification of individual beds is virtually instantaneous and always occurs before the decay of the associated living vegetation. The resulting highly porous and permeable fabrics remain fresh in Holocene tufas, but aggrading neomorphism and partial spar infill of vegetation moulds is common in older deposits. Dissolution in many perched springline tufas is small scale. Many large cavities are primary, but with later coatings of speleothems. Early removal of organics from paludal tufas is responsible for autobrecciation and differential compaction.     

Petrography and textural development of inorganic and biogenic lithotypes in a relict barite tufa deposit at Flybye Springs, NT, Canada

A relict mound of Holocene barite (BaSO₄) tufa underlies the Flybye Springs, a small, barium‐rich, cold sulphur spring system in the Northwest Territories of Canada. The tufa is composed of relatively pure barite with ≤0·34 wt% Ca²⁺ and ≤0·77 wt% Sr²⁺. The mound is made up of coated bubble, raft, undulatory sheet, stromatolitic, coated grain and detrital conglomerate barite tufa. Although previously unreported in barite, these lithotypes are akin to facies found in many carbonate spring deposits. Raft and ooid‐coated grain tufa was formed via ‘inorganic’ barite precipitation in spring water ponds and tributaries where rapid oxidation of sulphide to sulphate established barite supersaturation. Undulatory sheet tufa may have formed by the reaction of dissolved barium with sulphate derived from the oxidation of extracellular polysaccharide‐rich colloidal sulphur films floating in oxygenated, barite‐saturated spring water ponds. Coated bubble, oncoid‐coated grain and stromatolitic tufa with filamentous microfossils was formed in close association with sulphur‐tolerant microbes inhabiting dysoxic and oxygenated spring water tributaries and ponds. Adsorption of dissolved barium to microbial extracellular polysaccharide probably facilitated the development of these ‘biogenic’ lithotypes. Detrital conglomerate tufa was formed by barite cementation of microdetrital tufa, allochthonous lithoclasts and organic detritus, including caribou hair. Biogenic textures, organic artefacts and microfossils in the Flybye barite tufa have survived diagenetic aggradational recrystallization and precipitation of secondary cements, indicating the potential for palaeoecological information to be preserved in barite in the geological record. Similarities between the Flybye barite tufa and carbonate spring deposits demonstrate that analogous textures can develop in chemical sedimentary systems with distinct mineralogy, biology and physiochemistry.     

Evaporative systems and diagenetic patterns in the Calatayud Basin (Miocene,central Spain)

This paper concerns the evaporite units, depositional systems, cyclicity, diagenetic products and anhydritization patterns of the Calatayud Basin (nonmarine, Miocene, central Spain). In outcrop, the sulphate minerals of these shallow lacustrine evaporites consist of primary and secondary gypsum, the latter originating from the replacement of anhydrite and glauberite. In the evaporative systems of this basin, gypsiferous marshes of low salinity can be distinguished from central, saline lakes of higher salinity. In the gypsiferous marsh facies, the dominant, massive, bioturbated gypsum was partly replaced by synsedimentary chert nodules and siliceous crusts. In the saline lake facies, either cycles of gypsiferous lutite‐laminated gypsarenite or irregular alternations of laminated gypsum, nodular and banded glauberite, thenardite and nodular anhydrite precipitated. Early replacement of part of the glauberite by anhydrite also occurred. Episodes of subaerial exposure are represented by: (1) pedogenic carbonates (with nodular magnesite) and gypsiferous crusts composed of poikilitic crystals; and (2) nodular anhydrite, which formed in a sabkha. Additionally, meganodular anhydrite occurs, which presumably precipitated from ascending, highly saline solutions. The timing of anhydritization was mainly controlled by the salinity of the pore solutions, and occurred from the onset of deposition to moderate burial. Locally, a thick (>200 m) sequence of gypsum cycles developed, which was probably controlled by climatic variation. A trend of upward‐decreasing salinity is deduced from the base to the top of the evaporite succession.     

Recurrent spring‐fed rivers in a Middle to Late Pleistocene semi‐arid grassland: Implications for environments of early humans in the Lake Victoria Basin,Kenya

The effect of changing palaeoclimate and palaeoenvironment on human evolution during the Pleistocene is debated, but hampered by few East African records directly associated with archaeological sites prior to the Last Glacial Maximum. Middle to Late Pleistocene deposits on the shoreline of eastern Lake Victoria preserve abundant vertebrate fossils and Middle Stone Age arte‐facts associated with riverine tufas at the base of the deposits, which are ideal for palaeoenvironmental reconstructions. New data from tufas identified on Rusinga Island and on the mainland near Karungu, Kenya are provided from outcrop, thin sections, mineralogical, stable isotopic and U‐series dating analyses. Tufa is identified in four sites: Nyamita (94·0 ± 3·3 and 111·4 ± 4·2 ka); Kisaaka, Aringo (455 ± 45 ka); and Obware. The age ranges of these tufa deposits demonstrate that spring‐fed rivers were a recurrent, variably preserved feature on the Pleistocene landscape for ca 360 kyr. Poor sorting of clastic facies from all sites indicates flashy, ephemeral discharge, but these facies are commonly associated with barrage tufas, paludal environments with δ¹³C values of ca 10‰ indicative of C₃ plants and fossil Hippopotamus, all of which indicate a perennial water source. Other tufa deposits from Nyamita, Obware and Aringo have a mixed C₃/C₄ signature consistent with a semi‐arid C₄ grassland surrounding these spring‐fed rivers. The δ¹⁸O values of tufa from Nyamita are on average ca 1‰ more negative than calcite precipitated from modern rainfall in the region, suggesting greater contribution of depleted monsoonal input, similar to the Last Glacial Maximum. Microdebitage and surface‐collected artefacts indicate that early modern humans were utilizing these spring‐fed rivers. The presence of spring?fed rivers would have afforded animals a reliable water source, sustaining a diverse plant and animal community in an otherwise arid environment.     

Carbonate deposition in a fluvial tufa system: processes and products (Corvino Valley – southern Italy)

In a multi‐scale approach to the study of the organic and mineral components in an active barrage‐type tufa system of southern Italy, neo‐formed deposits, in both natural depositional sites and on inorganic substrates placed in the stream for this study, were observed and compared through one year of monitoring. Dams and lobes representing the basic morpho‐facies of the deposits are composed of two depositional facies: vacuolar tufa (a mixture of phytoclastic and framestone tufa) and stromatolitic tufa (phytoherm boundstone tufa). Three petrographic components comprise both facies: micrite and microsparite, often forming peloidal to aphanitc, laminar and dendrolitic fabrics, and sparite, which occurs as isolated to coalescent fan‐shaped crystals forming botryoids or continuous crusts. All fabrics occurring in all depositional facies are organized into layers with a more or less well‐developed cyclicity, which has its best expression in stromatolitic lamination. The precipitation of all types of calcite (with Mg 1·0 to 3·2 mole % and Sr 0·5 to 0·8 mole %) takes place more or less constantly during all seasons, in spite of the low saturation state of the water (the saturation index range is 0·75 to 0·89) within the active depositional zone; the latter extends for a few hundred microns through the external surface of the deposit. The active depositional zone has a particular micro‐morphology composed of porous micro‐columns (50 to 150 μm in size), separated by interstitial channels. Mineral precipitation occurs upon both external surfaces and within internal cavities of the micro‐columns, while further point sites of precipitation occur suspended within the masses of cyanobacterial tufts. Sub‐spherical mineral units, ‘nano‐spheres’ (10 to 20 nm in diameter) are the basic biotic neo‐precipitate; they commonly form by replacing non‐living degrading organic matter and at point sites along the external surface of living cyanobacterial sheaths. Nano‐spheres agglutinate to form first rod‐shaped aggregates (100 to 200 nm) which then evolve into triads of fibres or polyhedral structures. Successively, both triads and polyhedral solids coalesce to form larger calcite crystals (mainly tetrahedrons tens of microns in size) that represent the fundamental bricks for the construction of the micro‐columns in the active depositional zone. Precipitation is attributed to the presence of a widespread biofilm that occurs in the active depositional zone; this is composed of a heterogeneous community comprising epilithic and endolithic filamentous cyanobacteria, green algae, unicellular prokaryotes, actinobacteria and fungi, with a variable amount of extracellular polymeric substances. No precipitation takes place where the biofilm is absent, indicating that the biological activities of the biofilm are crucial, with its living organisms and non‐living organic matter. Basic aggregates of neo‐precipitates do not form in association with any one particular type of organic matter substrate, but appear to be related to the seasonal temperature variation: polyhedral micro‐crystals mainly precipitate in the colder season, short triads in the intermediate seasons, and long triads in the warmest conditions. These three basic crystal aggregates have a petrographic counterpart, respectively, in the spar, microspar and micrite.     

Diagenesis or dire genesis? The origin of columnar spar in tufa stromatolites of central Greece and the role of chironomid larvae

Two Greek Pleistocene tufa stromatolites were examined petrographically and with stable isotope geochemistry to determine whether calcite spar is of primary or diagenetic origin. The younger (ca 100 ka) tufa from Zemeno primarily is micritic, with primary columnar calcite spar restricted to areas immediately above chironomid larval tubes. This relationship suggests that chironomid larval feeding behaviour is responsible for the development of Zemeno tufa columnar calcite, probably involving biological substances smeared onto the tufa surface. Most micritic crystals are not suitably oriented to allow later post‐depositional growth resulting in columnar fabrics. The older (ca 1 Ma) predominantly sparry tufa from Nemea contains some chironomid tubes and organic cyanobacterial filaments preserved in crystal fans but also contains many fabrics found in primary speleothem spar. Columnar spar here is unlikely to be the result of post‐depositional crystal growth. A comparison of stable isotopic trends between the two tufa deposits suggests that both contain interpretable seasonal trends and implies little or minor post‐depositional alteration of either tufa. Consequently, there is no basis for the common assumption that sparry tufa fabrics must be of diagenetic origin.     

In a PICL: The sedimentary deposits and facies of perennially ice‐covered lakes

Perennially ice‐covered lakes can have significantly different facies than open‐water lakes because sediment is transported onto the ice, where it accumulates, and sand grains preferentially melt through to be deposited on the lake floor. To characterize the facies in these lakes, sedimentary deposits from five Antarctic perennially ice‐covered lakes were described using lake‐bottom observations, underwater video and images, and sediment cores. One lake was dominated by laminated microbial mats and mud (derived from an abutting glacier), with disseminated sand and rare gravel. The other four lakes were dominated by laminated microbial mats and moderately well to moderately sorted medium to very coarse sand with sparse granules and pebbles; they contained minor interstitial or laminated mud (derived from streams and abutting glaciers). The sand was disseminated or localized in mounds and 1 m to more than 10 m long elongate ridges. Mounds were centimetres to metres in diameter; conical, elongate or round in shape; and isolated or deposited near or on top of one another. Sand layers in the mounds had normal, inverse, or no grading. Nine mixed mud and sand facies were defined for perennially ice‐covered lakes based on the relative proportion of mud to sand and the style of sand deposition. While perennially ice‐covered lake facies overlap with other ice‐influenced lakes and glaciomarine facies, they are characterized by a paucity of grains coarser than granules, a narrow range in sand grain sizes, and inverse grading in the sand mounds. These facies can be used to infer changes in ice cover through time and to identify perennially ice‐covered lakes in the rock record. Ancient perennially ice‐covered lakes are expected on Earth and Mars, and their characterization will provide new insights into past climatic conditions and habitability.     

The formation and environmental significance of calcite rafts in tropical tufa-depositing rivers of northern Australia

Spring‐fed rivers of the Barkly karst in tropical northern Australia form an array of tufa and related freshwater carbonate deposits. One of these deposits, calcite rafts, is precipitated at the water–air interface principally as a consequence of CO₂ degassing and evaporation. Calcite rafts have been reported in cave environments but have not been described in detail from fluvial systems. Observations using scanning electron microscopy coupled with water chemistry data reveal that they form by a combination of physical, chemical and biological processes. They grow downwards into the water column and form a dentate lower surface, while a flat upper surface occurs at the water–air interface. The rafts are readily inhabited by microorganisms, particularly diatoms, which frequently become entombed by calcite as the rafts develop. The decay of the biological material leaves voids, creating a pock‐marked texture. The rafts are subject to secondary calcite growth along the crystal edges. Once they become submerged in the water column after disturbance of the water surface, they may become completely covered by this overgrowth, creating a homogeneous veneer. The rafts form in quiescent settings, principally behind tufa dams in large, lake‐like water bodies along each river. Therefore, they can be used in conjunction with adjacent exposures of other tufa facies to decipher palaeohydrological conditions. Although the rafts are extremely thin and fragile, they are readily preserved within fossil waterhole facies, and their occurrence has been identified in rocks from the Quaternary to the Tertiary.     

Sedimentology of coexisting travertine and tufa deposits in a mounded geothermal spring carbonate system,Obruktepe, Turkey

The recent discoveries of deeply buried Cretaceous reservoir bodies in the Atlantic Ocean revealed that relationships between the distribution of spring carbonate deposits and faults are poorly understood. The well‐exposed Quaternary deposits at Obruktepe (Denizli Basin, Turkey) provide an opportunity to reconstruct the three‐dimensional sedimentary architecture of such a system. Integration of sedimentological, lithofacies and geochemical analyses reveals complexity in the lateral relationships between sedimentary environments, faults and geothermal spring carbonates. Five environmental systems are distinguished based on the lithofacies analysis: (i) vent; (ii) smooth slope; (iii) travertine‐terrace; (iv) tufa‐barrage; and (v) flood systems. Encrusting, baffling and settling sedimentary processes are reflected in data acquired at several scales, from lithofacies observations to the morphology and arrangement of geobodies, together with microfabrics and stable carbon and oxygen isotope data. Mean values of +4·9‰ δ¹³C and −8·74‰ δ¹⁸O Vienna PeeDee Belemnite reflect geothermal circulation of springwaters. The environmental distribution and lithofacies indicate a lateral continuum between travertine and tufa deposits within this hot spring system. This finding supports two depositional models in which water flow variation is the main control on both CaCO₃ precipitation and the resulting formation of travertine and tufa. The proposed models address the factors responsible for the development of these complex mound‐shaped carbonate spring deposits, and how they are related to fluid circulation at depth and in association with faults.     

Using fossil spring deposits in the Death Valley region,USA to evaluate palaeoflowpaths

Spring deposits reveal the timing and environment of past groundwater discharge. Herein, however, the potential for fossil spring deposits to infer water sources and palaeoflowpaths through trace elements and stable and radiogenic isotopes is examined. Past discharge (70 to 285 ka) in the Tecopa Basin in the Death Valley region of southeastern California is represented by tufa deposits, including mounds, pools, cemented ledges and rare calcite feeder veins. δ¹⁸O values indicate that spring discharge was a mixture of far‐travelled (regional) water with a significant, and perhaps dominant contribution of local recharge on a nearby range front and alluvial pediment, rather than simply representing an elevated regional water table. δ¹³C values indicate regional water had a high TDS, whereas solute data imply low overall solute contents, consistent with dilution by a large component of local recharge. Radiogenic isotope data (U‐series, ⁸⁷Sr/⁸⁶Sr) for tufa indicate that siliciclastic rocks (a regional aquitard) interacted with discharging water. To access this aquitard, regional flow was probably partitioned into a permeable north–south damage zone of a north–south range‐bounding fault along the foot of the Resting Spring Range, which ultimately controlled the location of groundwater discharge. Existing models for modern discharge in the Tecopa Basin, by contrast, call upon westward interbasin flow in carbonate rocks from the Spring Mountains through the intervening (and nearly perpendicular) Nopah and Resting Spring Ranges. Understanding the controls on regional groundwater flow is critical in this and other arid regions where water is, by definition, a scarce resource. Thus, although it is a case study, this report highlights a fruitful approach to palaeohydrology that can be widely applied. Copyright © 2007 John Wiley & Sons, Ltd.     

Pleistocene sea‐floor fibrous crusts and spherulites in the Danakil Depression (Afar,Ethiopia)

Pleistocene fibrous aragonite fabrics, including crusts and spherules, occur in the Danakil Depression (Afar, Ethiopia) following the deposition of two distinctive Middle and Late Pleistocene coralgal reef units and pre‐dating the precipitation of evaporites. Crusts on top of the oldest reef unit (Marine Isotope Stage 7) cover and fill cavities within a red algal framework. The younger aragonite crusts directly cover coralgal bioherms (Marine Isotope Stage 5) and associated deposits. Their stratigraphic position between marine and evaporitic deposits, and their association to euryhaline molluscs, suggest that the crusts and spherules formed in restricted semi‐enclosed conditions. The availability of hard substrate controls crust formation with crusts more often found on steep palaeo‐slopes, from sea level up to at least 80 m depth, while spherules mainly occur associated with mobile substrate. Crusts reach up to 30 cm in thickness and can be microdigitate, columnar (branching and non‐branching) or non‐columnar, with laminated and non‐laminated fabrics. Two different lamination types are found within the crystalline fabrics: (i) isopachous lamination; and (ii) irregular lamination. These two types of lamination can be distinguished by the organization of the aragonite fibres, as well as the lateral continuity of the laminae. Scanning electron microscopy with energy dispersive X‐ray spectroscopy analyses on well‐preserved samples revealed the presence of Mg‐silicate laminae intercalated with fibrous aragonite, as well as Mg‐silicate aggregates closely associated with the fibrous aragonite crusts and spherules. The variety of observed fabrics results from a continuum of abiotic and microbial processes and, thus, reflects the tight interaction between microbially mediated and abiotic mineralization mechanisms. These are the youngest known isopachously laminated, digitate and columnar branching fibrous crusts associated with a transition from marine to evaporitic conditions. Understanding the context of formation of these deposits in Afar can help to better interpret the depositional environment of the widespread Precambrian sea‐floor precipitates.     

Laminated tufa sediments formed from overflow karst springs: Controls on their deposition and carbon–oxygen isotope records

Tufa sediments are freshwater carbonates that precipitate in karst regions after degassing of carbon dioxide from groundwater in contact with the atmosphere. When laminated, these carbonates can provide high‐resolution records for the study of climate, hydrological and environmental conditions at the time of their precipitation. The formation of these carbonates directly depends on the hydrological regime, and in karst regions discontinuous discharges are often recorded. This study investigates the record of recent laminated tufa sediments precipitated downstream overflow springs in Trabaque Canyon (central Spain). The hydrological dynamics of the karst system were monitored for over three years and a stable isotope record was obtained from laminated tufa carbonates precipitated from an overflow spring. Additionally, a hydrological model of overflow springs was generated and a tufa δ¹⁸O record under constrained parameters was simulated. Temperature is the dominant control of the variation in tufa δ¹³C and δ¹⁸O values within each lamina, although when comparing different laminae, δ¹³C_DIC and δ¹⁸O of river water are also major controls. The positive correlation between tufa δ¹³C values and water temperature is caused by the fractionation occurred by carbon dioxide degassing due to the thermal dependence of carbon dioxide solubility. Additionally, the system recorded a temperature‐independent degassing process caused by the large gradient between groundwater and atmospheric carbon dioxide that is limited to the proximity of the spring. This study cautions on the risk of assuming continuous deposition when studying laminated tufa sediments and highlights the potential of their stable isotope records to provide hydrological information of their aquifers during the past.     

Exceptional silica speleothems in a volcanic cave: A unique example of silicification and sub‐aquatic opaline stromatolite formation (Terceira,Azores)

Silica stromatolites occur in a number of modern hydrothermal environments, but their formation in caves is very rare. The silica stromatolitic speleothems of the Branca Opala cave (Terceira Island, Azores), however, provide an excellent opportunity for their study. These formations may be analogous to ancient silica stromatolites seen around the world. Petrographic, mineralogical and geochemical analyses were undertaken on the silica speleothems of the above cave, and on the silica‐tufa deposits outside it, with the aim of understanding their genesis. The possible hydrothermal origin of their silica is discussed. X‐ray diffraction analyses showed opal‐A to be the sole silica phase. Negligible ordering of this opal‐A showed ageing to be insignificant, as expected for recent silica deposits. Most of the silica speleothems examined were definable as sub‐aquatic opaline stromatolites that are not currently growing. Optical microscopy clearly revealed a lower microlaminated, an intermediate and an upper microlaminated zone within the stromatolites. Stromatolite types (I, II and III) were classified with respect to their internal structure and distribution throughout the cave. Scanning electron microscopy showed silicified bacterial filaments within the stromatolites, the silicified plant remains and the silica‐tufa deposits. Bacteria therefore played a major role in the precipitation of the opal‐A. Plasma emission/mass spectrometry showed major, minor and rare earth elements to be present in only small quantities. The rare earth elements were mainly hosted within volcanic grains. Rapid silica precipitation from highly super‐saturated water would explain the intense silicification of the plant remains found inside and outside the cave. The opaline stromatolites, the silica‐tufa deposits and the above‐mentioned intense general silicification suggest a local hydrothermal source for the silica. Indeed, these deposits strongly resemble plant‐rich silica sinter associated with low‐temperature hot spring deposits that include bacterial filaments. However, no geochemical signals that might indicate a hydrothermal origin could be found.     

Can 234U–230Th dating be used to date large semi‐arid tufas? Challenges from a study in the Naukluft Mountains,Namibia

The large, extensive tufa deposits of the semi‐arid Naukluft Mountains, Namibia are potentially important palaeoenvironmental indicators in an area with few proxy records. Tufas are reliable indicators of increased moisture availability, and have been shown to be amenable to ²³⁴U–²³⁰Th dating, although two challenges are detrital contamination and open‐system behaviour. Densely cemented tufa facies are good candidates for dating, minimising these problems. We report attempts to date five densely‐cemented units, which are only found rarely within the Naukluft deposits. We applied a detailed methodology using multiple subsample analysis, measurement of insoluble residues, application of ‘isochron’ mixing lines, and attempted open‐systems modelling, alongside observations of micromorphology and cathodoluminescence in order to assess the validity of any obtained dates. Surprisingly, densely cemented tufas were found not always to be suitable for dating. Two units contained detrital contamination, which could not be corrected for using a single leachate correction or ‘isochron’ methods. Two units contained ‘excess ²³⁰Th’. This could result under a closed‐system if initial (²³⁴U/²³⁸U) was sufficiently high. Alternatively this may be the result of open‐system behaviour, and loss of uranium, or incorporation of initial unsupported ²³⁰Th, which render samples unsuitable for ²³⁴U–²³⁰Th dating. Micromorphological appearance and cathodoluminescence behaviour are used to explore these possibilities. This study exemplifies the need for careful sample selection, and highlights the importance of analysing multiple subsamples from any tufa sample. The detailed methodology applied proves to be a powerful tool for identifying the range of problems that can be encountered when selecting suitable candidate samples for successful dating. It also shows that semi‐arid tufa sequences may contain very little material suitable for dating. A reliable age of c 80 ka was obtained for a banded unit within a large fluvial barrage, with less reliable dates suggesting tufa deposition during times since >350 ka through to the late Holocene. Copyright © 2010 John Wiley & Sons, Ltd.     

Confirmation of an interglacial age for the Condat tufa (Dordogne,France) from biostratigraphic and isotopic data

The Condat tufa is a localised deposit, reaching 8.2m in thickness, composed of freshwater carbonates deposited in a complex series of environments which include marsh, spring and stream facies. Five radiocarbon determinations had previously been obtained from different stratigraphic levels within the tufa and had given a consistent series, ranging from 12320 ± 175 BP to 31050 ± 1500BP. Although the youngest two dates, from near the surface of the tufa, had been rejected as being anomalously young, the older dates were regarded as indicating tufa formation during the last cold stage. Biostratigraphic analyses of the molluscan and ostracod faunas, presented here, demonstrate that the tufa formed under fully temperate conditions throughout. The occurrence of certain snails that are either locally extinct (e.g. Belgrandia marginata) or unknown living in western France (e.g. Daudebardia brevipes), together with the geomorphological setting, suggest that the tufa is of interglacial age. New radiocarbon determinations of the Condat tufa all proved to be >33 Ka BP and support this conclusion.     

Petrographic and trace element analysis of uranium-rich tufa calcite, middle Miocene Barstow Formation, California, USA

An integrated petrographic and spectroscopic (X‐ray diffraction, phosphor imaging and synchrotron X‐ray absorption spectroscopy) study of tufas from the Miocene Barstow Formation, California, relates sample morphology, mineralogy and geochemical composition. The tufas, composed mainly of calcite that formed at the interface between an ancient alkaline lake and ground or spring waters, have textures similar to those of microbially mediated terrestrial stromatolites and travertines. The tufas have elevated concentrations of a number of trace elements including Mn, Fe, Sr and U. Synchrotron X‐ray fluorescence analyses show that U concentrations can exceed 500 p.p.m. X‐ray absorption spectroscopy indicates that the U in these samples is incorporated as U(IV). It is suggested here that alkaline lake waters had a high U/Ca ratio and tufa calcite formed where groundwater or (possibly epithermal) springs brought in Ca and trace elements such as Sr. The rapid, and possibly microbially mediated, precipitation of calcite allowed for incorporation of high concentrations of trace metals as either structural substitutes or extremely fine‐scale inclusions.