Michael T. Murrell

A high-resolution record of holocene climate change in speleothem calcite from cold water cave, northeast iowa.

High-precision uranium-thorium mass spectrometric chronology and 18O-13C isotopic analysis of speleothem calcite from Cold Water Cave in northeast Iowa have been used to chart mid-Holocene climate change. Significant shifts in †18O and †13C isotopic values coincide with well-documented Holocene vegetation changes. Temperature estimates based on 18O/16O ratios suggest that the climate warmed rapidly by about 3�C at 5900 years before present and then cooled by 4�C at 3600 years before present. Initiation of a gradual increase in †13C at 5900 years before present suggests that turnover of the forest soil biomass was slow and that equilibrium with prairie vegetation was not attained by 3600 years before present.

Chemical and isotopic constraints on the generation and transport of magma beneath the East Pacific Rise

Abstract Interpretation of U-series disequilibria in midocean ridge basalts is highly dependent on the bulk partition coefficients for U and Th and therefore the mineralogy of the mantle source. Distinguishing between the effect of melting processes and variable source compositions on measured disequilibria (238U-230Th-226Ra and 235U-231Pa) requires measurement of the radiogenic isotopes Hf, Nd, Sr, and Pb. Here, we report measurements of 238U-230Th-226Ra and 235U-231Pa disequilibria; Hf, Nd, Sr, and Pb isotopic; and major and trace element compositions for a suite of 20 young midocean ridge basalts from the East Pacific Rise axis between 9°28′ and 9°52′N. All of the samples were collected within the axial summit trough using the submersible Alvin. The geological setting and observational data collected during sampling operations indicate that all the rocks are likely to have been erupted from 1991 to 1992 or within a few decades of that time. In these samples, 230Th excesses and 226Ra excesses are variable and inversely correlated. Because the eruption ages of the samples are much less than the half-life of 226Ra, this inverse correlation between 230Th and 226Ra excesses can be considered a primary feature of these lavas. For the lava suite analyzed in this study, 226Ra and 230Th excesses also vary with lava composition: 226Ra excesses are negatively correlated with Na8 and La/Yb and positively correlated with Mg#. Conversely, 230Th excesses are positively correlated with Na8 and La/Yb and negatively correlated with Mg#. Th/U, 230Th/232Th, and 230Th excesses are also variable and correlated to one another. 231Pa excesses are large but relatively constant and independent of Mg#, La/Yb, Th/U, and Na8. The isotope ratios 143Nd/144Nd, 176Hf/177Hf, 87Sr/86Sr, and 208Pb/206Pb are constant within analytical uncertainty, indicating that they were derived from a common source. The source is homogeneous with respect to parent/daughter ratios Lu/Hf, Sm/Nd, Rb/Sr, and Th/U; therefore, the measured variations of Th/U, 230Th, and 226Ra excesses and major and trace element compositions in these samples are best explained by polybaric melting of a homogeneous source, not by mixing of compositionally distinct sources.

Porosity of the melting zone and variations in the solid mantle upwelling rate beneath Hawaii: inferences from 238U-230Th-226Ra and 235U-231Pa disequilibria

Abstract Measurements of 238U-230Th-226Ra and 235U-231Pa disequilibria in a suite of tholeiitic-to-basanitic lavas provide estimates of porosity, solid mantle upwelling rate and melt transport times beneath Hawaii. The observation that (230Th/238U) > 1 indicates that garnet is required as a residual phase in the magma sources for all of the lavas. Both chromatographic porous flow and dynamic melting of a garnet peridotite source can adequately explain the combined U-Th-Ra and U-Pa data for these Hawaiian basalts. For chromatographic porous flow, the calculated maximum porosity in the melting zone ranges from 0.3–3% for tholeiites and 0.1–1% for alkali basalts and basanites, and solid mantle upwelling rates range from 40 to 100 cm yr−1 for tholeiites and from 1 to 3 cm yr−1 for basanites. For dynamic melting, the escape or threshold porosity is 0.5–2% for tholeiites and 0.1–0.8% for alkali basalts and basanites, and solid mantle upwelling rates range from 10 to 30 cm yr−1 for tholeiites and from 0.1 to 1 cm yr−1 for basanites. Assuming a constant melt productivity, calculated total melt fractions range from 15% for the tholeiitic basalts to 3% for alkali basalts and basanites.

Th and U isotopic systematics of basalts from the Juan de Fuca and Gorda Ridges by mass spectrometry

We have developed a mass spectrometric technique for the measurement of 230Th/232Th ratios in young volcanic rocks. We show that we can measure 230Th/232Th ratios on MORB samples of ∼- 1 gram with an accuracy and reproducibility of 0.5–1.0%. This represents an improvement of at least a factor of 5–10 in sample size and precision over conventional alpha spectrometry methods. Using this technique, we have measured distinct excesses of230Th activity relative to238U activity for axial samples from the Juan de Fuca (JDF) and Gorda Ridges. These enrichments are 13–15% but range up to 40% in one sample. Low boron concentrations and 234U/238U ratios corresponding to secular equilibrium verify the absence of detectable seawater contamination. From this we infer that primary magmatic processes are the source of the measured230Th activity excesses, and that Th is indeed more incompatible than U during partial melting of MORB sources. 230Th/232Th activity ratios for the axial samples from JDF appear to be relatively high for uncontaminated MORB, ranging from 1.35 to 1.41. From this we infer that the JDF basalts formed from a uniform source highly depleted in Th relative to U (Th/Uwt= 2.15–2.25). One Gorda axial sample has a somewhat lower 230Th/232Th activity ratio of 1.31, suggesting formation from a source only slightly less depleted (Th/U= 2.32 ± 0.02). Based on the small range in 30Th/232Th ratios for axial basalts from JDF, dating off-axis JDF basalts may be feasible.

Mechanisms of Magma Generation Beneath Hawaii and Mid-Ocean Ridges: Uranium/Thorium and Samarium/Neodymium Isotopic Evidence

Measurements of uranium/thorium and samarium/neodymium isotopes and concentrations in a suite of Hawaiian basalts show that uranium/thorium fractionation varies systematically with samarium/neodymium fractionation and major-element composition; these correlations can be understood in terms of simple batch melting models with a garnet-bearing peridotite magma source and melt fractions of 0.25 to 6.5 percent. Midocean ridge basalts shows a systematic but much different relation between uranium/thorium fractionation and samarium/neodymium fractionation, which, although broadly consistent with melting of a garnet-bearing peridotite source, requires a more complex melting model.

Uranium series and beryllium isotope evidence for an extended history of subduction modification of the mantle below Nicaragua

U-series nuclides, beryllium, and lead isotopes have been measured on historic lavas from eight volcanoes in Nicaragua. Low-Ti samples from northern Nicaragua have (230Th)(232Th) ratios from 2.23 to 2.56 and are enriched in 238U and 234U over 230Th by 1–16%. Those from southern Nicaragua have (230Th)(232Th) ≈ 2.1 and have (238U)(230Th) = 1.0–0.9. High-Ti samples have intermediate (230Th)(232Th) ratios and are strongly enriched in 230Th. Lead isotopic data for all samples plot in the mantle array with 206Pb204Pb = 18.50–18.63. Th isotopic ratios for all samples imply source U/Th ratios that are significantly higher than those implied by lead isotopic ratios. All historic samples have (210Po)(230Th) and thus (226Ra)(230Th) > 1, suggesting that lavas erupt less than 8,000 y after generation. Thorium isotopic ratios for all volcanic samples correlate well with 10Be9Be and B/Be as well as with 87Sr86Sr and Ba/La ratios from the literature. (238U)(230Th) ratios do not correlate well with any of these ratios but rather anti-correlate with Th concentrations and published LaYb ratios. These observations, and inferences therefrom, lead to the following preferred, although not completely unique, interpretations. Comparison of thorium, beryllium, and strontium isotopic ratios of the Cocos plate sediments at DSDP 495 with the low-Ti volcanic regression trends shows that the subducted component transferred to the mantle has isotopic compositions similar to the bulk sediments. B/Be and Ba/La ratios of the volcanic samples are well correlated with the isotopes, but the inferred ratios in the subduction component are at least 10 and 5 times higher, respectively, than values in the bulk sediment. These relationships suggest that the subduction component combines the element-transport properties of both a melt and a hydrous fluid. The (230Th)(232Th) and 87Sr86Sr ratios corresponding to a 10Be9Be ratio of zero are about 2.0 and 0.704, significantly higher than expected in the postulated MORB source for the lavas. We attribute these characteristics to subduction related addition of strontium, uranium, plus or minus thorium, and related tracers to the mantle prior to about 4.5 Ma, such that the 10Be signal of this event has decayed away. The observed good correlations are generated primarily by addition of 10Be, U >Th, B and Ba between 4.5 Ma. and ca. 200–300 ka. The most recent event occurred since 200–300 ka and perhaps more recently than 8 ka. It transported only a fraction of the total slab-derived flux of 10Be, B, Ba, and probably thorium stored within the mantle, but added U >Th and may have raised the partition coefficient of uranium over thorium. The magnitude of the uranium excess thus relates to the extent of partial melting of the mantle source during this event. The U-series and beryllium isotope systematics of the high-Ti lavas are consistent with their derivation from the mantle residue after extraction of low-Ti melts.

Geochronology and petrogenesis of MORB from the Juan de Fuca and Gorda ridges by 238U– 230Th disequilibrium

A highly precise mass spectrometric method of analysis was used to determine238U—234U—230Th—232Th in axial and off-axis basalt glasses from Juan de Fuca (JDF) and Gorda ridges. Initial230Th activity excesses in the axial samples range from 3 to 38%, but generally lie within a narrow range of 12 to 15%. Secondary alteration effects were evaluated usingδ234U and appear to be negligible; hence the230Th excesses are magmatic in origin. Direct dating of MORB was accomplished by measuring the decrease in excess230Th in off-axis samples.238U—230Th ages progressively increase with distance from axis. Uncertainties in age range from 10 to 25 ka for U—Th ages of 50 to 200 ka. The full spreading rate based on U—Th ages for Endeavour segment of JDF is 5.9 ± 1/2 cm/yr, with asymmetry in spreading between the Pacific (4.0 ± 0.6 cm/yr) and JDF (1.9 ± 0.6 cm/yr) plates. For northern Gorda ridge, the half spreading rate for the JDF plate is found to be 3.0 ± 0.4 cm/yr. These rates are in agreement with paleomagnetic spreading rates and topographic constraints. This suggests that assumptions used to determine ages, including constancy of initial 230Th/232Th ratio over time, are generally valid for the areas studied. Samples located near the axis of spreading are typically younger than predicted by these spreading rates, which most likely reflects recent volcanism within a 1–3 km wide zone of crustal accretion. Initial230Th/232Th ratios and230Th activity were also used to examine the recent Th/U evolution and extent of melting of mantle sources beneath these ridges. A negative anomaly in 230Th/232Th for Axial seamount lavas provides the first geochemical evidence of a mantle plume source for Axial seamount and the Cobb-Eickelberg seamount chain and indicates recent depletion of other JDF segment sources. Large230Th activity excesses for lavas from northern Gorda ridge and Endeavour segment indicate formation from a lower degree of partial melting than other segments. An inverse correlation between230Th excess and 230Th/232Th for each ridge indicates that these lower degree melts formed from slightly less depleted sources than higher degree melts. Uniformity in230Th excess for other segments suggests similarity in processes of melt formation and mixing beneath most of the JDF-Gorda ridge area. The average initial230Th/232Th activity ratio of 1.31 for the JDF-Gorda ridge area is in agreement with the predicted value of 1.32 from the Th—Sr isotope mantle array.

Geochemistry of Quaternary travertines in the region north of Rome (Italy): structural, hydrologic and paleoclimatic implications

In the Tyrrhenian region of central Italy, late Quaternary fossil travertines are widespread along two major regional structures: the Tiber Valley and the Ancona–Anzio line. The origin and transport of spring waters from which travertines precipitate are elucidated by chemical and isotopic studies of the travertines and associated thermal springs and gas vents. There are consistent differences in the geochemical and isotopic signatures of thermal spring waters, gas vents and present and fossil travertines between east and west of the Tiber Valley. West of the Tiber Valley, δ13C of CO2 discharged from gas vents and δ13C of fossil travertines are higher than those to the east. To the west the travertines have higher strontium contents, and gases emitted from vents have higher 3He/4He ratios and lower N2 contents, than to the east. Fossil travertines to the west have characteristics typical of thermogene (thermal spring) origin, whereas those to the east have meteogene (low-temperature) characteristics (including abundant plant casts and organic impurities). The regional geochemical differences in travertines and fluid compositions across the Tiber Valley are interpreted with a model of regional fluid flow. The regional Mesozoic limestone aquifer is recharged in the main axis of the Apennine chain, and the groundwater flows westward and is discharged at springs. The travertine-precipitating waters east of the Tiber Valley have shallower flow paths than those to the west. Because of the comparatively short fluid flow paths and low (normal) heat flow, the groundwaters to the east of the Tiber Valley are cold and have CO2 isotopic signatures, indicating a significant biogenic contribution acquired from soils in the recharge area and limited deeply derived CO2. In contrast, spring waters west of the Tiber Valley have been conductively heated during transit in these high heat-flow areas and have incorporated a comparatively large quantity of CO2 derived from decarbonation of limestone. The elevated strontium content of the thermal spring water west of the Tiber Valley is attributed to deep circulation and dissolution of a Triassic evaporite unit that is stratigraphically beneath the Mesozoic limestone. U-series age dates of fossil travertines indicate three main periods of travertine formation (ka): 220–240, 120–140 and 60–70. Based on the regional flow model correlating travertine deposition at thermal springs and precipitation in the recharge area, we suggest that pluvial activity was enhanced during these periods. Our study suggests that travertines preserve a valuable record of paleofluid composition and paleoprecipitation and are thus useful for reconstructing paleohydrology and paleoclimate.

In-situ radionuclide transport and preferential groundwater flows at INEEL (Idaho): decay-series disequilibrium studies

Uranium and thorium-decay series disequilibria in groundwater occur as a result of water-rock interactions, and they provide site-specific, natural analog information for assessment of in-situ, long-term migration of radionuclides in the far field of a nuclear waste disposal site. In this study, a mass balance model was used to relate the decay-series radionuclide distributions among solution, sorbed and solid phases in an aquifer system to processes of water transport, sorption-desorption, dissolution-precipitation, radioactive ingrowth-decay, and α recoil. Isotopes of U (238U, 234U), Th (232Th, 230Th, 228Th, 234Th), Ra (226Ra, 228Ra, 224Ra), and Rn (222Rn) were measured in 23 groundwater samples collected from a basaltic aquifer at the Idaho National Engineering and Environmental Laboratory (INEEL), Idaho. The results show that groundwater activities of Th and Ra isotopes are 2–4 orders lower than those of their U progenitors which average 1.35 ± 0.40 dpm 238U/L, with 234U/238U ratios of ∼1.6–3.0. 222Rn activities range from 20 to 500 dpm/L. Modeling of the observed disequilibria places the following constraints on the time scale of radionuclide migration and water-rock interaction at INEEL: (1) Time for sorption is minutes for Ra and Th; time for desorption is days for Ra and years for Th; and time for precipitation is days for Th, years for Ra, and centuries for U. (2) Retardation factors due to sorption average >106 for 232Th, ∼104 for 226Ra, and ∼103 for 238U. (3) Dissolution rates of rocks are ∼70 to 800 mg/L/y. (4) Ages of groundwater range from <10 to 100 years. Contours of groundwater age, as well as spatial patterns of radionuclide disequilibria, delineate two north-south preferential flow pathways and two stagnated locales. Relatively high rates of dissolution and precipitation and α-recoil of 222Rn occur near the groundwater recharging sites as well as in the major flow pathways. Decay of the sorbed parent radionuclides (e.g., 226Ra and 228Ra) on micro-fracture surfaces constitutes an important source of their daughter (222Rn and 228Th) activities in groundwater.

231Pa and230Th chronology of mid-ocean ridge basalts

Mass spectrometric measurements of235U231Pa and238U230Th disequilibria are used to further constrain processes producing U-series disequilibria in young mid-ocean ridge basalts (MORB) and to determine eruption ages for samples from 9–10°N East Pacific Rise and Juan de Fuca-Gorda ridges.231Pa/235U activity ratios for axial basalts are large and relatively uniform within ridge segments. The systematically large231Pa/235U,230Th/238U, and226Ra/230Th activity ratios in MORB are inconsistent with simple equilibrium melting models and crustal contamination or seawater alteration processes. More complicated melting processes involving disequilibrium or heterogeneous melting of mantle sources and disequilibrium transport of melts to the crust could produce the large U-series disequilibria in MORB. 231Pa and230Th model ages were determined by estimating initial231Pa/235U and230Th/232Th ratios from axial samples and by assuming constancy of these ratios over time. All231Pa and230Th ages agree to ±0–7 ka for samples with ages of 0–130 ka. These concordant ages validate the model assumptions of the two dating methods and suggest that mantle sources and melt generation processes have been uniform for these areas during the past 130 ka. Consequently,231Pa and230Th age-dates can be used to quantify the temporal and spatial dependence of volcanism at oceanic spreading centers during the past 375 ka.