Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: C/C and O/O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO₂ were evaluated in combination with measured values and published estimates of δ¹⁸O of coalbed paleowaters that had been present at the time of mineralization. δ¹⁸O_mineral and δ¹⁸O_water values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272 Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600 m at  78 ± 5 °C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between  500 to  1300 m at a lower temperature of 43 ± 6 °C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a δ¹⁸O_water  − 1.25‰ versus VSMOW. Inoculation of coalbeds with methanogenic CO₂-reducing microbes occurred at an even later time, because modern microbially influenced ¹³C-enriched coalbed CO₂ (i.e., the isotopically fractionated residue of microbial CO₂ reduction) is out of isotopic equilibrium with ¹³C-depleted calcite in cleats.     

Oxygen and carbon isotope analysis of the Mooreville Chalk and late Santonian-early Campanian sea level and sea surface temperature changes, northeastern Gulf of Mexico, U.S.A.

Oxygen and carbon isotope profiles for strata of the Mooreville Chalk (upper Santonian-lower Campanian) of the eastern Gulf Coastal Plain, U.S.A., show correlations with published curves for these isotopes. The δ¹⁸O curve exhibits a strong similarity to the Exmouth Plateau δ¹⁸O curve from ODP drilling sites offshore northwestern Australia, and the δ¹³C curve can be correlated with the δ¹³C curve from the English Chalk Trunch section.A thermal maximum probably occurred in the northeastern Gulf of Mexico during the latest Santonian (83.8 Ma), as evidenced by the minimum δ¹⁸O values in the lower Mooreville beds. A δ¹³C positive excursion occurs at the same stratigraphic level, which has been recognized as the “Santonian/Campanian boundary event” worldwide. After this event, ocean surface water temperature decreased throughout the early Campanian. This carbon isotope excursion is followed by a plateau in δ¹³C values with a peak value occurring in a condensed section (80 Ma), which has been correlated to a downlap or maximum flooding surface on seismic data from offshore Alabama. The section characterized by increasing δ¹³C values corresponds to a marine transgression. The interval characterized by decreasing δ¹³C values corresponds to regression and progradation. The maximum flooding event occurred 0.8 Ma later than the thermal maximum event.The Mooreville chalk/marl cycles are most likely a product of fluctuations in siliciclastic sediment influx into the northeastern Gulf of Mexico modulated by the precession band of the Earth's orbital cycles. Higher carbon isotope values occur in the marl beds indicating that these beds were formed in a more anoxic/dysoxic environment characterized by higher clay, silt input and higher organic carbon accumulation.     

12,000-Year, preliminary results of the stable nitrogen and carbon isotope record from the Empakai Crater lake sediments, Northern Tanzania

The stable isotope compositions of organic carbon and nitrogen, the contents of organic carbon and nitrogen and C/N ratios for two cores recovered from the Empakai Crater at water depths of 11 and 20 m are used to document climatic changes in northern Tanzania. Eight ¹⁴C AMS dates determined on total organic matter (OM) indicate that the sedimentation rate in this lake is about 30 cm/ka for the late Pleistocene to early Holocene period. There are differences in the δ¹³C values of organic carbon between the two cores, which may be a result of differences in location from the present shoreline and of different water depths. In the deeper-water core the δ¹³C values show a general downcore decrease to the base of the core with a sharp change to lower values of about 4‰ at a depth of 100 cm (8.7 ka). The general trend of downcore decrease in ¹³C values can be attributed either to a systematic decrease in the relative proportion of C₄ type of OM, owing to an increase in precipitation and change in vegetation cover from grassland to forest, or to utilization of isotopically enriched carbon during photosynthesis. The δ¹⁵N values show a general downcore increase with again a sharp change of about 5‰ to lower values at about 8.7 ka. A sharp change of about 5‰ and 4‰ to more depleted values at a depth of 100 cm of both ¹⁵N and ¹³C, respectively, suggests either hiatus or abrupt change in climatic condition from wetter conditions to drier conditions. There is enhanced preservation of OM in the lake as depicted by high mean values of organic carbon and nitrogen at both sites.     

Carbon biogeochemistry of the Betsiboka estuary (north-western Madagascar)

Madagascar’s largest estuary (Betsiboka) was sampled along the salinity gradient during the dry season to document the distribution and sources of particulate and dissolved organic carbon (POC, DOC) as well as dissolved inorganic carbon (DIC). The Betsiboka was characterized by a relatively high suspended matter load, and in line with this, low DOC/POC ratios (0.4–2.5). The partial pressure of CO₂ (pCO₂) was generally above atmospheric equilibrium (270–1530 ppm), but relatively low in comparison to other tropical and subtropical estuaries, resulting in low average CO₂ emission to the atmosphere (9.1 ± 14.2 mmol m⁻² d⁻¹). Despite the fact that C4 vegetation is reported to cover >80% of the catchment area, stable isotope data on DOC and POC suggest that C4 derived material comprises only 30% of both pools in the freshwater zone, increasing to 60–70% and 50–60%, respectively, in the oligohaline zone due to additional lateral inputs. Sediments from intertidal mangroves in the estuary showed low organic carbon concentrations (<1%) and δ¹³C values (average −19.8‰) consistent with important inputs of riverine imported C4 material. This contribution was reflected in δ¹³C signatures of bacterial phospholipid derived fatty acids (i + a15:0), suggesting the potential importance of terrestrial organic matter sources for mineralization and secondary production in coastal ecosystems.     

Stable isotopes of a subfossil Tamarix tree from the Dead Sea region, Israel, and their implications for the Intermediate Bronze Age environmental crisis

Trees growing on the Mt. Sedom salt diapir, at the southern Dead Sea shore, were swept by runoff into salt caves and subsequently deposited therein, sheltered from surface weathering. A subfossil Tamarix tree trunk, found in a remote section of Sedom Cave is radiocarbon dated to between  2265 and 1930 BCE. It was sampled in 109 points across the tree rings for carbon and nitrogen isotopes. The Sedom Tamarix demonstrates a few hundred years of ¹³C and ¹⁵N isotopic enrichment, culminating in extremely high δ¹³C and δ¹⁵N values. Calibration using modern Tamarix stable isotopes in various climatic settings in Israel shows direct relationship between isotopic enrichment and climate deterioration, particularly rainfall decrease. The subfossil Tamarix probably reflects an environmental crisis during the Intermediate Bronze Age, which subsequently killed the tree  1930 BCE. This period coincides with the largest historic fall of the Dead Sea level, as well as the demise of the large regional urban center of the 3rd millennium BCE. The environmental crisis may thus explain the archaeological evidence of a shift from urban to pastoral culture during the Intermediate Bronze Age. This was apparently the most severe long-term historical drought that affected the region in the mid-late Holocene.     

Isotopic evidence for temporal variation in proportion of seasonal precipitation since the last glacial time in the inland Pacific Northwest of the USA

Large-scale atmospheric circulation patterns determine the quantity and seasonality of precipitation, the major source of water in most terrestrial ecosystems. Oxygen isotope (δ¹⁸O) dynamics of the present-day hydrologic system in the Palouse region of the northwestern U.S.A. indicate a seasonal correlation between the δ¹⁸O values of precipitation and temperature, but no seasonal trends of δ¹⁸O records in soil water and shallow groundwater. Their isotope values are close to those of winter precipitation because the Palouse receives  75% of its precipitation during winter. Palouse Loess deposits contain late Pleistocene pedogenic carbonate having ca. 2 to 3‰ higher δ¹⁸O values and up to 5‰ higher carbon isotope (δ¹³C) values than Holocene and modern carbonates. The late Pleistocene δ¹⁸O values are best explained by a decrease in isotopically light winter precipitation relative to the modern winter-dominated infiltration. The δ¹³C values are attributed to a proportional increase of atmospheric CO₂ in soil CO₂ due to a decrease in soil respiration rate and ¹³C discrimination in plants under much drier paleoclimate conditions than today. The regional climate difference was likely related to anticyclonic circulation over the Pleistocene Laurentide and Ice Sheet.     

Origin of methane in high-arsenic groundwater of Taiwan – Evidence from stable isotope analyses and radiocarbon dating

Groundwaters in the confined aquifers of the Chianan and Ilan coastal plains of Taiwan are rich in dissolved methane (CH₄). Serious endemic “blackfoot disease”, which occurred in the Chianan plain, especially during AD1950-1970, has been demonstrated to have arisen from drinking highly reducing groundwater with abnormal arsenic and humic substance levels. In order to explore the origin of CH₄ and its hydrological implications, stable carbon isotope ratios (δ¹³C) and radiocarbon (¹⁴C) ages of exsolved CH₄, dissolved inorganic carbon (DIC), and sedimentary biogenic sediments from a total of 34 newly completed water wells at 16 sites were determined. The main results obtained are as follows: (1) The δ¹³C_CH4 (−65‰ to −75‰) values indicate that, except for one thermogenic sample (δ¹³C_CH4=38.2‰) from the Ilan plain, all CH₄ samples analyzed were produced via microbially mediated CO₂ reduction. Many δ¹³C_DIC values are considerably greater than −10‰ and even up to 10‰ due to Rayleigh enrichment during CO₂ reduction. (2) Almost all the ¹⁴C ages of CH₄ samples from the shallow aquifer (I) (<60 m depth) are greater than the ¹⁴C ages of coexisting DIC and sediments, suggesting the presence of CH₄ from underlying aquifers. (3) The ¹⁴C ages of coexisting CH₄, DIC and sediments from aquifer (II) of the Chianan plain are essentially equal, reflecting in-situ generation of CH₄ and DIC from decomposition of sedimentary organic matter and sluggishness of the groundwater flow. On the other hand, both CH₄ and DIC from each individual well of the relatively deep aquifers (III) and (IV) in the Chianan plain are remarkably younger than the deposition of their coexisting sediments, indicating that current groundwaters entered these two aquifers much later than the deposition of aquifer sediments. (4) Each CH₄ sample collected from the Ilan plain is older than coexisting DIC, which in turn is distinctly older than the deposition of respective aquifer sediments, demonstrating the presence of much older CO₂ and CH₄ from underlying strata.     

Geochemical relation between gas hydrates and water venting in the seismic blanking zone on the northern Cascadia continental margin offshore Vancouver Island, Canada

The isotopic composition (δD and δ¹⁸O) and chloride concentration (Cl⁻) of pore waters from the northern Cascadia continental margin offshore Vancouver Island were measured to characterize the relations between the water flow regime and the distribution, formation and dissociation of gas hydrates. The δD values of pore waters in gas hydrate-bearing sediments are slightly higher ( 1‰) than those of seawater as the result of gas hydrate dissociation during core recovery and handling. Within the seismic blanking zone, the δD values were slightly lower (− 1‰) than values measured from sites outside the blanking area (0‰). We attribute these differences to 1) distillation of D-rich water during hydrate formation in the center of the blanking zone and 2) limited migration of pore water between inside and outside of the blanking zone due to different fluid fluxes. In contrast, the δ¹⁸O values and Cl⁻ concentrations do not show significant spatial variation due to decreased isotopic fractionation of oxygen and small fraction of chloride relative to hydrogen isotope during gas hydrate formation. The δD value of pore water, therefore, appears to be a sensitive indicator of gas hydrate occurrence. We estimate that gas hydrate occupied at least 2.0 to 6.3% of sediment pore space using δD distribution in this area.     

The evolution of a tropical rainforest/grassland mosaic in southeastern Brazil since 28,000 C yr BP based on carbon isotopes and pollen records

The lack of paleoecological records from the montane Atlantic Rainforest of coastal Brazil, a hotspot of biological diversity, has been a major obstacle to our understanding of the vegetational changes since the last glacial cycle. We present carbon isotope and pollen records to assess the impact of the glaciation on the native vegetation of the Serra do Mar rainforest in São Paulo, Brazil. From ca. 28,000 to  22,000 ¹⁴C yr BP, a subtropical forest with conifer trees is indicative of cool and humid conditions. In agreement carbon isotopic data on soil organic matter suggest the presence of C₃ plants and perhaps C₄ plants from  28,000 to  19,000 ¹⁴C yr BP. The significant increase in the sedimentation rate and algal spores from  19,450 to  19,000 ¹⁴C yr BP indicates increasing humidity, associated to an erosion process between  19,000 and  15,600 ¹⁴C yr BP. From  15,600 ¹⁴C yr BP to present there is a substantial increase in arboreal elements and herbs, indicating more humid and warmer climate. From  19,000 to  1000 ¹⁴C yr BP, δ¹³C values indicated the predominance of C₃ plants. These results are in agreement with studies in speleothems of caves, which suggest humid conditions during the last glacial maximum.     

Glide systems of hematite single crystals in deformation experiments

The critical resolved shear stresses (CRSSs) of hematite crystals were determined in compression tests for r-twinning, c-twinning and {a}<m>-slip in the temperature range 25 °C to 400 °C, at 400 MPa confining pressure, and a strain rate of 10^− 5 s^− 1 by Hennig-Michaeli, Ch., Siemes, H., 1982. Experimental deformation of hematile crstals betwen 25 °C and 400 °C at 400 MPa confining pressure. In: Schreyer, W. (Ed.) High Pressure Research in Geoscience, Schweizerbart'sche Verlagsbuchhandlung, Stuttgart, p. 133–150. In the present contribution newly performed experiments on hematite single crystals at temperatures up to 800 °C at strain rates of 10^− 5 s^− 1 and 300 MPa confining pressure extends the knowledge about the CRSS of twin and slip modes. Optical observations, neutron diffraction goniometry, SEM forescatter electron images and electron backscatter diffraction are applied in order to identify the glide modes. Both twinning systems and {a}<m>-slip were confirmed by these methods. Besides the known glide systems the existence of the (c)<a>-slip system could be stated. Mechanical data establish that the CRSS of r-twinning decreases from 140 MPa at 25 °C to  5 MPa at 800 °C and for {a}<m>-slip from > 560 MPa at 25 °C to  40 MPa at 700 °C. At room temperature the CRSS for c-twinning is around 90 MPa and at 600 °C  60 MPa. The data indicate that the CRSSs above 200 °C seem to be between the values for r-twinning and {a}<m>-slip. For (c)<a>-slip only the CRSS at 600 °C could be evaluated to  60 MPa. Exact values are difficult to determine because other glide systems are always simultaneously activated.     

Low-density CO2-rich fluid inclusions from charnockites of southwestern Madurai Granulite Block, southern India; implications on graphite mineralization

Characterization of fluid inclusions in graphite-bearing charnockites from the southwestern part of the Madurai Granulite Block in southern India reveals a probable relation with the formation and break down of graphite during the high-grade metamorphism. The first-generation monophase pure CO₂ inclusions, the composition of which is confirmed by laser Raman spectroscopy, recorded moderate density (0.77–0.87 g/cc) corresponding to low tapping pressure (around 2 kb) than that of the peak granulite-facies metamorphism. The precipitation of graphite, as inferred from graphite inclusions and δ¹³C values of the graphite from the outcrops, is interpreted as the cause of this lowering of fluid density. An intermediate generation of pseudosecondary inclusions resulted from the re-equilibration or modification of the first-generation fluids and the CO₂ formed is interpreted to be the oxidation product from graphite. The youngest generation of fluids which caused widespread retrogression of the granulites is a low-temperature (350 °C) high-saline (32.4–52.0 wt% NaCl equivalent) brine. Carbon isotope data on the graphite from the charnockites show δ¹³C values ranging from −11.3 to −19.9‰, suggesting a possibility of mixing of carbon sources, relating to earlier biogenic and later CO₂ fluid influx. Combining the information gathered from petrologic, fluid inclusion and carbon stable isotope data, we model the fluid evolution in the massive charnockites of the southwestern Madurai Granulite Block.     

Paleoclimate reconstruction in the Levant region from the geochemistry of a Holocene stalagmite from the Jeita cave, Lebanon

Dated oxygen and carbon isotopic profiles from a Holocene stalagmite (11.9–1.1 ka) from the Jeita cave, Lebanon, are compared to variations in crystallographic habit, stalagmite diameter and growth rate. The profiles show generally high δ¹⁸O and δ¹³C values during the late-glacial period, low values during the early Holocene, and again high values after 5.8 ka. On the basis of the good correlation between the morphological and crystallographic aspect of the stalagmite and its isotopic records, as well as the isotopic response of speleothems from central and northern Israel, we relate high δ¹⁸O and δ¹³C values to drier conditions. Between 6.5 and 5.8 ka an increase in isotopic values, a decrease in growth rate and stalagmite diameter suggest a transition from wet conditions in the early Holocene towards drier conditions in the mid-Holocene. The transition occurred in two steps, first a progressive change to drier conditions started at 6.5 ka but was interrupted by a short ( 100 years) return to wetter conditions, followed by an equally rapid (< 200 years) change to drier conditions.     

Polar and neutral isopranyl glycerol ether lipids as biomarkers of archaea in near-surface sediments from the Nankai Trough

The molecular and carbon isotopic compositions of polar isopranyl glycerol ether lipids, which are direct indicators of viable archaea, and neutral isopranyl glycerol ether lipids, which are derived from polar lipids via hydrolysis, in near-surface sediments from a methane seep in the Nankai Trough (off central Japan) were investigated. Procedures for extracting, separating and derivatizing polar and neutral ether lipids for detection using gas chromatography were first examined with one sediment sample and a cultivated methanogen. For all sediment samples, archaeol and hydroxyarchaeol were detected in both the polar and neutral ether lipid fractions. Acyclic and cyclic biphytanes were also detected in both types of lipid fractions after treatment with HI/LiAlH₄ for ether cleavage and alkylation. The δ¹³C values of archaeol, sn-2-hydroxyarchaeol, and sn-3-hydroxyarchaeol in the sample from 0.82 m below the seafloor were lower than −100‰ relative to PDB, indicating that diverse living methanotrophic archaea are present in the seep sediments. Biphytanes released from polar ether lipids in the same sample were less depleted in δ¹³C (−71‰ to −36‰). The wide range of δ¹³C values suggests that the biphytanes were derived not only from methanotrophic but also from non-methanotrophic archaea, and that the relative contributions of the methanotrophic and non-methanotrophic archaea differed, depending on the biphytane compound. The vertical profiles and δ¹³C values of the neutral ether lipids were similar to those of the intact polar ether lipids, suggesting that neutral ether lipids derived from fossil archaea in the samples had mainly been lost by the time of sampling.     

Feldspathic clasts in Yamato-86032: Remnants of the lunar crust with implications for its formation and impact history

Low concentrations of Th and Fe in the Yamato (Y)-86032 bulk meteorite support earlier suggestions that Y-86032 comes from a region of the moon far distant from the Procellarum KREEP Terrain (PKT), probably from the lunar farside. ³⁹Ar–⁴⁰Ar, Rb–Sr, Sm–Nd, and Sm-isotopic studies characterize the chronology of Y-86032 and its precursors in the mega regolith. One of the rock types present in a light gray breccia lithology is an anorthosite characterized by plagioclase with An 93, i.e., more sodic than lunar FANs, but with very low ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr similar to those of FANs. (FAN stands for Ferroan Anorthosite). This “An93 anorthosite” has Nd-isotopic systematics similar to those of nearside norites. A FAN-like “An97 anorthosite” is present in a second light-colored feldspathic breccia clast and has a more negative ε_Nd value consistent with residence in a LREE-enriched environment as would be provided by an early plagioclase flotation crust on the Lunar Magma Ocean (LMO). This result contrasts with generally positive values of ε_Nd for Apollo 16 FANs suggesting the possibility of assymetric development of the LMO. Other possible explanations for the dichotomy in ε_Nd values are advanced in the text. The Y-86032 protolith formed at least 4.43 ± 0.03 Ga ago as determined from a Sm–Nd isochron for mineral fragments from the breccia clast composed predominantly of An93 anorthosite and a second clast of more varied composition. We interpret the mineral fragments as being predominatly from a cogenetic rock suite. An ³⁹Ar–⁴⁰Ar age of 4.36–4.41 ± 0.035 Ga for a third clast composed predominantly of An97 anorthosite supports an old age for the protolith. Initial ¹⁴³Nd/¹⁴⁴Nd in that clast was −0.64 ± 0.13 ε-units below ¹⁴³Nd/¹⁴⁴Nd in reservoirs having chondritic Sm/Nd ratios, consistent with prior fractionation of mafic cumulates from the LMO. A maximum in the ³⁹Ar–⁴⁰Ar age spectrum of 4.23 ± 0.03 Ga for a second sample of the same feldspathic breccia clast probably reflects some diffusive ⁴⁰Ar loss. Lack of solar wind and lunar atmosphere implanted Ar in the light gray breccia clast allows determination of an ³⁹Ar/⁴⁰Ar age of 4.10 ± 0.02 Ga, which is interpreted as the time of initial brecciation of this litholgy. After correction for implanted lunar atmosphere ⁴⁰Ar, impact melt and dark regolith clasts give Ar ages of 3.8 ± 0.1 Ga implying melt formation and final breccia assembly 3.8 Ga ago. Some breccia lithologies were exposed to thermal neutron fluences of 2 × 10¹⁵ n/cm², only about 1% of the fluence experienced by some other lunar highlands meteorites. Other lithologies experienced neutron fluences of 1 × 10¹⁵ n/cm². Thus, Y-86032 spent most of the time following final brecciation deeply buried in the megaregolith. The neutron fluence data are consistent with cosmogenic ³⁸Ar_cos cosmic ray exposure ages of 10 Ma. Variations among differing lithologies in the amount of several regolith exposure indicators, including cosmogenic noble gas abundances, neutron capture induced variations in Sm isotopic abundances, and Ir contents, are consistent with a period of early (>3.8 Ga ago) lunar regolith exposure, subsequent deep burial at >5 m depth, and ejection from the moon 7–10 Ma ago.     

Shear wave velocity and attenuation structure for the shallow crust of the southern Korean peninsula from short period Rayleigh waves

We analyzed the short period Rayleigh waves from the first crustal-scale seismic refraction experiment in the Korean peninsula, KCRUST2002, to determine the shear wave velocity and attenuation structure of the uppermost 1 km of the crust in different tectonic zones of the Korean peninsula and to examine if this can be related to the surface geology of the study area. The experiment was conducted with two large explosive sources along a 300-km long profile in 2002. The seismic traces, recorded on 170 vertical-component, 2-Hz portable seismometers, show distinct Rayleigh waves in the period range between 0.2 s and 1.2 s, which are easily recognizable up to 30–60 km from the sources. The seismic profiles, which traverse three tectonic regions (Gyeonggi massif, Okcheon fold belt and Yeongnam massif), were divided into five subsections based on tectonic boundaries as well as lithology. Group and phase velocities for the five subsections obtained by a continuous wavelet transform method and a slant stack method, respectively, were inverted for the shear wave models. We obtained shear wave velocity models up to a depth of 1.0 km. Overall, the shear wave velocity of the Okcheon fold belt is lower than that of the Gyeonggi and Yeongnam massifs by  0.4 km/s in the shallowmost 0.2 km and by 0.2 km/s at depths below 0.2 km. Attenuation coefficients, determined from the decay of the fundamental mode Rayleigh waves, were used to obtain the shear wave attenuation structures for three subsections (one for each of the three different tectonic regions). We obtained an average value of Q_β^− 1 in the upper 0.5 km for each subsection. Q_β^− 1 for the Okcheon fold belt ( 0.026) is approximately three times larger than Q_β^− 1 for the massif areas ( 0.008). The low shear wave velocity in the Okcheon fold belt is consistent with the high attenuation in this region.     

Developing oxygen isotope proxies from archaeological sources for the study of Late Holocene human–climate interactions in coastal southwest Florida

Oxygen isotopes (δ¹⁸O) derived from archaeological Mercenaria campechiensis shells and Ariopsis felis otoliths potentially provide low-latitude paleoclimate data for studying Late Holocene human–climate interactions in coastal southwest Florida. Specimens analyzed come from the Pineland site complex. Deposits record abrupt and subtle environmental changes appearing to have been climate-related and to have impacted the sedentary human residents. One archaeological shell-otolith set dates to 2nd/3rd century A.D. within the Roman Optimum (RO) climatic episode. A second set dates to 13th/14th century A.D. within the Little Ice Age (LIA). A modern shell-otolith set was analyzed for comparison. δ¹⁸O_ARAGONITE of modern and LIA shells suggest similar seasonal conditions. RO shell is 1‰ more positive during summer, suggesting higher estuarine salinity than in modern and LIA times. Modern and LIA otoliths also have similar δ¹⁸O_ARAGONITE. Estimated Winter temperatures are within measured instrument records. Summer temperatures are overestimated reflecting Summer migration into less-saline water. Estimated Summer temperatures for RO otolith are similar to today's, suggesting elevated estuarine salinity and diminished rainy season, consistent with similar aged zooarchaeological assemblages. Comparisons of two taxa aid in interpreting archaeological δ¹⁸O data; however, early results are mixed with expected profiles for RO specimens and unexpected profiles for LIA specimens.     

Paleohydrology of the upper Laurentian Great Lakes from the late glacial to early Holocene

Between 10,500 and 9000 cal yr BP, δ¹⁸O values of benthic ostracodes within glaciolacustrine varves from Lake Superior range from − 18 to − 22‰ PDB. In contrast, coeval ostracode and bivalve records from the Lake Huron and Lake Michigan basins are characterized by extreme δ¹⁸O variations, ranging from values that reflect a source that is primarily glacial ( − 20‰ PDB) to much higher values characteristic of a regional meteoric source ( − 5‰ PDB). Re-evaluated age models for the Huron and Michigan records yield a more consistent δ¹⁸O stratigraphy. The striking feature of these records is a sharp drop in δ¹⁸O values between 9400 and 9000 cal yr BP. In the Huron basin, this low δ¹⁸O excursion was ascribed to the late Stanley lowstand, and in the Lake Michigan basin to Lake Agassiz flooding. Catastrophic flooding from Lake Agassiz is likely, but a second possibility is that the low δ¹⁸O excursion records the switching of overflow from the Lake Superior basin from an undocumented northern outlet back into the Great Lakes basin. Quantifying freshwater fluxes for this system remains difficult because the benthic ostracodes in the glaciolacustrine varves of Lake Superior and Lake Agassiz may not record the average δ¹⁸O value of surface water.     

Hydrologic and climatic implications of stable isotope and minor element analyses of authigenic calcite silts and gastropod shells from a mid-Pleistocene pluvial lake, Western Desert, Egypt

Authigenic calcite silts at Wadi Midauwara in Kharga Oasis, Egypt, indicate the prolonged presence of surface water during the Marine Isotope Stage 5e pluvial phase recognized across North Africa. Exposed over an area of  4.25 km², these silts record the ponding of water derived from springs along the Libyan Plateau escarpment and from surface drainage. The δ¹⁸O values of these lacustrine carbonates (− 11.3‰ to − 8.0‰ PDB), are too high to reflect equilibrium precipitation with Nubian aquifer water or water of an exclusively Atlantic origin. Mg/Ca and Sr/Ca of the silts have a modest negative covariance with silt δ¹⁸O values, suggesting that the water may have experienced the shortest residence time in local aquifers when the water δ¹⁸O values were highest. Furthermore, intra-shell δ¹⁸O, Sr/Ca, and Ba/Ca analyses of the freshwater gastropod Melanoides tuberculata are consistent with a perennially fresh water source, suggesting that strong evaporative effects expected in a monsoonal climate did not occur, or that dry season spring flow was of sufficient magnitude to mute the effects of evaporation. The input of a second, isotopically heavier water source to aquifers, possibly Indian Ocean monsoonal rain, could explain the observed trends in δ¹⁸O and minor element ratios.     

Lowland rainforest response to hydrological changes during the last 1500 years in Gabon, Western Equatorial Africa

Pollen and δ¹³C_TOM data obtained from two contrasting lake sequences (Lakes Kamalété and Nguène), located 200 km apart in the lowland rainforest of Gabon, provide complementary local and regional 1500-yr records of high resolution (15–30 yr) vegetation change. A combination of aquatic, semi-aquatic and terrestrial pollen showed in both records that the tropical rainforest increased during periods of high rainfall and decreased during drought intervals. The strong fluctuations of water balance at decadal scale during the “Medieval Warm Period” ( 1100–800 cal yr BP) coincided with a noticeable increase in shade-intolerant taxa, indicating recurring rainforest canopy disturbance. The δ¹³C_TOM signal showed high-amplitude variations in both records, which positively correlates with the rainforest dynamics and local vegetation changes. The similar trends in both the pollen and the δ¹³C_TOM signals between these sites demonstrate the regional broadly synchronous timing of shifting hydrological conditions. The largely positive co-variation between strong fluctuations of hydrological conditions and changes in rainforest structure and composition indicate that regional climatic change is probably the driving force for major rainforest dynamics in Gabon. Any significant anthropogenic impact on vegetation has not been clearly identified, and this issue still needs to be resolved independently by obtaining detailed archeological records across the interval 1400–800 BP, which currently seem to be extremely rare or not easily available.     

Postorogenic carbonatites at Eden Lake, Trans-Hudson Orogen (northern Manitoba, Canada): Geological setting, mineralogy and geochemistry

The Eden Lake pluton in the Trans-Hudson Orogen is the first known occurrence of carbonatites in Manitoba. The pluton is largely made up of modally and geochemically diverse syenitic rocks derived from postorogenic magma(s) of shoshonitic affinity. Their diversity can be accounted for by a combination of crystal fractionation and fluid release in the final evolutionary stage (crystallization of quartz alkali-feldspar syenite). At Eden Lake, carbonatites, represented predominantly by coarse-grained massive to foliated sövite, occur as branching veins and lenticular bodies up to 4 m in thickness showing crosscutting relations with respect to all of the syenitic units. The host rocks are intensely fenitized at the contact, and there is also abundant mineralogical and textural evidence for assimilation of silicate material by carbonatitic magma through wallrock reaction and xenolith fragmentation and digestion. The bulk of the carbonatites are composed of (in order of crystallization): Sr–REE-rich fluorapatite, aegirine–augite, and coarse calcite crystals surrounded by fine-grained calcite (on average,  90 vol.% of the rock). Noteworthy accessory constituents are celestine, bastnäsite-(Ce) (both as primary inclusions in calcite), Nb–Zr–rich titanite, low-Hf zircon, allanite-(Ce) and andradite. The calcite is chemically uniform (Sr-rich, Mg–Mn–Fe-poor and low in ¹³C), but shows clear evidence of ductile deformation and syndeformational cataclasis. Geochemically, the carbonatites are enriched in Sr, Ba, light rare-earth elements, Th and U, but depleted in high-field-strength elements (particularly, Ti, Nb and Ta). The stable-isotope composition of coarse- and fine-grained calcite from the carbonatites and interstitial calcite from syenites is remarkably uniform: ca. − 8.16 ± 0.27‰ δ¹³C (PDB) and + 8.04 ± 0.19‰ δ¹⁸O (SMOW). The available textural and geochemical evidence indicates that the Eden Lake carbonatites are not consanguineous with the associated syenites and may have been derived from a Nb–Ti-retentive and ¹³C-depleted source such as the subducted crustal material underlying the Eden Lake deformation corridor.