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John A. Fitzpatrick

Publications and source records attributed to John A. Fitzpatrick.

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Geochronologic, isotopic, and geochemical data from pre-Cretaceous plutonic rocks in the Lane Mountain area, San Bernardino County, California

Pre-Cretaceous, predominantly dioritic plutonic rocks in the Lane Mountain area, California, intrude metasedimentary and metavolcanic rocks considered part of the El Paso terrane. New geochronologic (uranium-lead zircon), geochemical, and isotopic data provide a reliable basis for dividing these pre-Cretaceous plutonic rocks into two mappable suites of Permian–Triassic and Late Jurassic ages. The 26 Permian–Triassic samples included in this report have a mean age of ~248 mega-annum (Ma), range in composition from monzodiorite to quartz monzonite and granodiorite, and have a mean initial 87 Sr/ 86 Sr ratio (Sri) of ~0.7045. The 22 Late Jurassic samples have a mean age of ~149 Ma, range in composition from gabbro to granite, and have a mean Sr i of ~0.7055. Accurate mapping of these two plutonic suites and their detailed field relations with the associated metamorphic rocks is essential for resolving the geologic history and regional tectonic significance of the Lane Mountain area. The sub-0.706 Sr i values of both plutonic suites at Lane Mountain are consistent with previous suggestions that the El Paso terrane is allochthonous and did not develop on Precambrian continental lithosphere. Both suites are considered parts of northwest-trending magmatic arcs interpreted to have formed above east-dipping subduction zones along the evolving North American continental margin, and both arcs are interpreted to cross a major east-west-trending boundary between the El Paso terrane and rocks considered part of ancestral North America in the San Bernardino Mountains area to the south. The El Paso terrane thus appears to have been attached to the San Bernardino Mountains area at least since Permian–Triassic time, although the boundary probably has been modified by Cenozoic faulting.

California

Geochronologic, isotopic, and geochemical data from igneous rocks in the Lane Mountain area, San Bernardino County, California

We present new geochronologic, isotopic, and geochemical data for selected igneous rocks in the Lane Mountain area, California. We determined SHRIMP-RG U-Pb zircon ages for the following units: (1) Larrea complex (~253 Ma and ~149–146 Ma); (2) Daisy granodiorite (~151 Ma); (3) Jack Spring quartz monzonite (~85–82 Ma); (4) unnamed porphyritic dikes and stocks (~80–73 Ma); and (5) Lane Mountain volcanics (~22 Ma). These results confirm and refine previous age determinations for the Larrea complex, Jack Spring quartz monzonite, and Lane Mountain volcanics, and provide the first reliable ages for the Daisy granodiorite and the unnamed porphyritic rocks. Sri of the plutonic rocks increases from ~0.704 to ~0.705–0.706 to ~0.708–0.709 for samples dated as ~250, ~150, and ~85–70 Ma, respectively, which indicates progressively greater involvement of Precambrian continental lithosphere in magma generation through time. The Sri and geochemical data suggest that the most significant change in magmatic source occurred between ~150 and 85 Ma.

California

Forest calcium depletion and biotic retention along a soil nitrogen gradient

High nitrogen (N) accumulation in terrestrial ecosystems can shift patterns of nutrient limitation and deficiency beyond N toward other nutrients, most notably phosphorus (P) and base cations (calcium [Ca], magnesium [Mg], and potassium [K]). We examined how naturally high N accumulation from a legacy of symbiotic N fixation shaped P and base cation cycling across a gradient of nine temperate conifer forests in the Oregon Coast Range. We were particularly interested in whether long-term legacies of symbiotic N fixation promoted coupled N and organic P accumulation in soils, and whether biotic demands by non-fixing vegetation could conserve ecosystem base cations as N accumulated. Total soil N (0–100 cm) pools increased nearly threefold across the N gradient, leading to increased nitrate leaching, declines in soil pH from 5.8 to 4.2, 10-fold declines in soil exchangeable Ca, Mg, and K, and increased mobilization of aluminum. These results suggest that long-term N enrichment had acidified soils and depleted much of the readily weatherable base cation pool. Soil organic P increased with both soil N and C across the gradient, but soil inorganic P, biomass P, and P leaching loss did not vary with N, implying that historic symbiotic N fixation promoted soil organic P accumulation and P sufficiency for non-fixers. Even though soil pools of Ca, Mg, and K all declined as soil N increased, only Ca declined in biomass pools, suggesting the emergence of Ca deficiency at high N. Biotic conservation and tight recycling of Ca increased in response to whole-ecosystem Ca depletion, as indicated by preferential accumulation of Ca in biomass and surface soil. Our findings support a hierarchical model of coupled N–Ca cycling under long-term soil N enrichment, whereby ecosystem-level N saturation and nitrate leaching deplete readily available soil Ca, stimulating biotic Ca conservation as overall supply diminishes. We conclude that a legacy of biological N fixation can increase N and P accumulation in soil organic matter to the point that neither nutrient is limiting to subsequent non-fixers, while also resulting in natural N saturation that intensifies base cation depletion and deficiency.

Oregon

The impact of biotic/abiotic interfaces in mineral nutrient cycling: A study of soils of the Santa Cruz chronosequence, California

Biotic/abiotic interactions between soil mineral nutrients and annual grassland vegetation are characterized for five soils in a marine terrace chronosequence near Santa Cruz, California. A Mediterranean climate, with wet winters and dry summers, controls the annual cycle of plant growth and litter decomposition, resulting in net above-ground productivities of 280–600 g m −2 yr −1 . The biotic/abiotic (A/B) interface separates seasonally reversible nutrient gradients, reflecting biological cycling in the shallower soils, from downward chemical weathering gradients in the deeper soils. The A/B interface is pedologically defined by argillic clay horizons centered at soil depths of about one meter which intensify with soil age. Below these horizons, elevated solute Na/Ca, Mg/Ca and Sr/Ca ratios reflect plagioclase and smectite weathering along pore water flow paths. Above the A/B interface, lower cation ratios denote temporal variability due to seasonal plant nutrient uptake and litter leaching. Potassium and Ca exhibit no seasonal variability beneath the A/B interface, indicating closed nutrient cycling within the root zone, whereas Mg variability below the A/B interface denotes downward leakage resulting from higher inputs of marine aerosols and lower plant nutrient requirements. The fraction of a mineral nutrient annually cycled through the plants, compared to that lost from pore water discharge, is defined their respective fluxes F j,plants = q j,plants /( q j,plants + q j,discharge ) with average values for K and Ca ( F K,plants = 0.99; F Ca,plants = 0.93) much higher than for Mg and Na ( F Mg,plants 0.64; F Na,plants = 0.28). The discrimination against Rb and Sr by plants is described by fractionation factors ( K Sr/Ca = 0.86; K Rb/K = 0.83) which are used in Rayleigh fractionation-mixing calculations to fit seasonal patterns in solute K and Ca cycling. K Rb/K and K 24 Mg / 22 Mg "> K24Mg/22Mg values (derived from isotope data in the literature) fall within fractionation envelopes bounded by inputs from rainfall and mineral weathering. K Sr/Ca and K 44 Ca / 40 Ca "> K44Ca/40Ca fractionation factors fall outside these envelopes indicating that Ca nutrient cycling is closed to these external inputs. Small net positive K and Ca fluxes (6–14 mol m −2 yr −1 ), based on annual mass balances, indicate that the soils are accumulating mineral nutrients, probably as a result of long-term environmental disequilibrium.

California

Evaluation of ground-water and boron sources by use of boron stable-isotope ratios, tritium, and selected water-chemistry constituents near Beverly Shores, northwestern Indiana, 2004

Concentrations of boron greater than the U.S. Environmental Protection Agency (USEPA) 900 μg/L removal action level (RAL) standard were detected in water sampled by the USEPA in 2004 from three domestic wells near Beverly Shores, Indiana. The RAL regulates only human-affected concentrations of a constituent. A lack of well logs and screened depth information precluded identification of whether water from sampled wells, and their boron sources, were from human-affected or natural sources in the surficial aquifer, or associated with a previously defined natural, confined aquifer source of boron from the subtill or basal sand aquifers. A geochemically-based classification of the source of boron in ground water could potentially determine the similarity of boron to known sources or mixtures between known sources, or classify whether the relative age of the ground water predated the potential sources of contamination. The U.S. Geological Survey (USGS), in cooperation with the USEPA, investigated the use of a geochemical method that applied boron stable isotopes, and concentrations of boron, tritium, and other constituents to distinguish between natural and human-affected sources of boron in ground water and thereby determine if the RAL was applicable to the situation. Boron stable-isotope ratios and concentrations of boron in 17 ground-water samples and tritium concentrations in 9 ground-water samples collected in 2004 were used to identify geochemical differences between potential sources of boron in ground water near Beverly Shores, Indiana. Boron and δ 11 B analyses for this investigation were made on unacidified samples to assure consistency of the result with unacidified analyses of δ 11 B values from other investigations. Potential sources of boron included surficial-aquifer water affected by coal-combustion products (CCP) or domestic-wastewater, upward discharge of ground water from confined aquifers, and unaffected water from the surficial aquifer that was distant from human-affected boron sources. Boron concentrations in potential ground-water sources of boron were largest (15,700 to 24,400 μg/L) in samples of CCP-affected surficial aquifer water from four wells at a CCP landfill and smallest (27 to 63 μg/L) in three wells in the surficial aquifer that were distant from human-affected boron sources. Boron concentrations in water from the basal sand aquifer ranged from 656 μg/L to 1,800 μg/L. Boron concentrations in water from three domestic-wastewater-affected surficial aquifer wells ranged from 84 to 387 μg/L. Among the representative ground-water samples, boron concentrations from all four samples of CCP-affected surficial aquifer water and four of five samples of water from the basal sand aquifer had concentrations greater than the RAL. A comparison of boron concentrations in acid-preserved and unacidified samples indicated that boron concentrations reported for this investigation may be from about 11 to 16 percent less than would be reported in a standard analysis of an acidified sample. The stable isotope boron-11 was most enriched in comparison to boron-10 in ground water from a confined aquifer, the basal sand aquifer (δ 11 B, 24.6 to 34.0 per mil, five samples); it was most depleted in CCP-affected water from the surficial aquifer (δ 11 B, 0.1 to 6.6 per mil, four samples). Domestic-wastewater-affected water from the surficial aquifer (δ 11 B, 8.7 to 11.7 per mil, four samples) was enriched in boron-11, in comparison to individual samples of a borax detergent additive and a detergent with perborate bleach; it was intermediate in composition between basal sand aquifer water and CCP-affected water from the surficial aquifer. The similarity between a ground-water sample from the surficial aquifer and a hypothetical mixture of unaffected surficial aquifer and basal sand aquifer waters indicates the potential for long-term upward discharge of ground water into the surficial aquifer from one or more confined aquifers. Estimated δ 11 B values for acidified samples were depleted by 1.9 to 2.8 per mil in comparison to unacidified samples from the four wells sampled; those differences were small in comparison to the differences between δ 11 B values of representative sources of boron in ground water. Tritium concentrations ranged from 7.0 to 10.3 tritium units in six samples from the surficial aquifer and were less than 0.8 tritium units in three samples from the basal sand aquifer. Water from wells in the surficial aquifer represents predominantly modern, post-1972 recharge and sources of boron and other constituents. Water from the basal sand aquifer is associated with pre-1952 recharge from sources not affected by local boron inputs. Ground water from six wells (five domestic wells and one public-supply well) where the ground-water source was unknown had boron concentrations, boron isotope ratios, and tritium concentrations similar to water from the basal sand aquifer. Boron concentrations greater than the RAL were found in water from four of these six wells. The boron isotope and tritium data from these four wells indicate a natural source of boron in ground water; therefore, the RAL does not apply to boron concentrations in water from these wells. Water samples from two domestic wells where the ground-water source was unknown had boron concentrations less than the RAL and boron isotope ratios and tritium concentrations that were similar to domestic-wastewater-affected water from the surficial aquifer. The boron isotope ratio for a sample from one domestic well was similar to that of CCP-affected water from the surficial aquifer and detergent compositions; the boron concentration of that sample was less than the RAL. The classifications of differences among representative sources of boron in ground water and water samples from wells where the ground-water source was unknown generally agreed with distinctions based on strontium-87/strontium-86 ratios and concentrations of strontium, chloride, nitrate, and ammonia. This application of boron concentrations, boron isotope ratios, and tritium concentrations to classify differences in relation to potential sources of boron in ground water was able to distinguish between boron from natural sources and from human-affected sources that are subject to regulation.

Indiana

Use of 87 Sr/ 86 Sr and δ 11 B to Identify Slag-Affected Sediment in Southern Lake Michigan

Slag is a ubiquitous byproduct of the iron-smelting industry and influences geochemistry and water quality in adjacent geologic units, ground and surface water. Despite extensive slag deposition along the Indiana shoreline of Lake Michigan, definitive evidence that slag has affected lakebed sediments has not been established. Concerns for the protection of water and ecosystem resources in the Great Lakes motivated this study to determine if strontium and boron isotopes could be used to identify and delineate slag-affected bed sediment in Lake Michigan. Sixty-five samples of bed sediment were acquired from the southern lobe of Lake Michigan and analyzed for 87Sr/86Sr and ??11B. Samples immediately offshore from Indiana steel mills and slag-disposal sites contained higher median 87Sr/86Sr values (0.70881) than shoreline sediments collected elsewhere in the basin (0.70847) and uniquely decreased with increasing distance from the shoreline. The highest ??11B values occurred in sediments from the Indiana shoreline (+12.9 to 16.4???) but were also elevated in sediments collected offshore from three Lake Michigan cities (+11.7 to 12.7???). Contoured isotope data indicated that 82-154 km2 of bed sediment along the Indiana shoreline had elevated 87Sr/86Sr and ??11B values relative to shoreline sediments elsewhere in southern Lake Michigan.

Environmental Science & Technology

Responses of sediment geochemistry to climate change in Owens Lake sediment: An 800-k.y. record of saline/fresh cycles in core OL-92

Geochemical parameters of sediments from drill hole OL-92 indicate that Owens Lake was saline, alkaline, and highly productive during interglacial periods, and was hydrologically open and relatively unproductive during glacial periods. Abundance of CaCO 3 , organic carbon, and cation-exchange capacity of the clay fraction show cyclic variation down the core. Six minima in these components during the past 500 k.y. are interpreted as caused by intensive overflow that occurred during Sierran glacial advances. Maxima in these components indicate closed-lake conditions, reflecting warmer and more arid interglacial climates. The pattern of CaCO 3 abundance suggests that closed lake conditions predominated over the past 500 k.y. The absence of gaylussite and gypsum in the sediments, however, indicates lake salinity never exceeded about 15 wt %, a limit which requires flushing of accumulated salts every 10 k.y. Oscillations of CaCO 3 generally indicate a 100-k.y. dominant cycle, a characteristic of the marine δ 18 O record. Four of the last five marine isotope terminations are clearly shown in the Owens Lake record. The last interglacial at Owens Lake appears to have occurred between 120 ka and 50 ka. The roughly 10-k.y. offset between this interval and marine oxygen-isotope stage 5 reflects either error in the age-depth model, or alternatively, a time lag between changes in Northern Hemisphere ice volumes and the manifestation of local climate change in lake geochemistry and sedimentology.

California

The Solubility and Stabilization of Ikaite (CaCO3·6H2O) from 0° to 25°C: Environmental and Paleoclimatic Implications for Thinolite Tufa

We determined the solubility of ikaite from 0° to 25°C to model its saturation state in natural waters and test the hypothesis that it is the precursor of the calcite pseudomorphs in thinolite tufa of Quaternary Lake Lahontan. Reversible solubility at buffered $P_{CO_{2}}$ yields the following expression for the dissolution constant of ikaite: $log K_{ikaite} = 0.15981 - 2011.1/T$. Where $T = ^{\circ}K$, and $0^{\circ}C \leq t \leq 25^{\circ}C$. Derived standard state properties are $\Delta G_{ikaite}^{\circ} = -2541.9 kJmol^{-1} \pm 0.66; \Delta H_{ikaite}^{\circ} = -2973.4 kJmol^{-1} \pm 1.02; S_{ikaite}^{\circ} = 306.6 JT^{-1}mol^{-1} \pm 1.2$. Modeling shows that ikaite is undersaturated at all temperatures in seawater and in alkaline lakes, but that it rapidly approaches saturation near 0°C. Its precipitation in near-freezing marine sediments requires large additions of $HCO_{3}$ to pore fluids from the diagenetic decomposition of organic matter. Its crystallization in tufas of alkaline lakes, however, requires only small additions of Ca from springs. Simple kinetic experiments show that ikaite is stabilized in natural environments by orthophosphate, which prevents the crystallization of the more stable anhydrous forms of $CaCO_{3}$ but does not interact with the ikaite. Therefore, the presence of ikaite or its pseudomorphs is an indicator of near-freezing conditions in environments with high concentrations of orthophosphate. If ikaite is the precursor of thinolite tufa, then the thinolite likely grew below the sediment-water interface at the site of sublacustrine springs during prolonged cold periods.

Journal of Geology