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Abiotic/biotic coupling in the rhizosphere: a reactive transport modeling analysis

A new generation of models is needed to adequately simulate patterns of soil biogeochemical cycling in response changing global environmental drivers. For example, predicting the influence of climate change on soil organic matter storage and stability requires models capable of addressing complex biotic/abiotic interactions of rhizosphere and weathering processes. Reactive transport modeling provides a powerful framework simulating these interactions and the resulting influence on soil physical and chemical characteristics. Incorporation of organic reactions in an existing reactive transport model framework has yielded novel insights into soil weathering and development but much more work is required to adequately capture root and microbial dynamics in the rhizosphere. This endeavor provides many advantages over traditional soil biogeochemical models but also many challenges.

Procedia Earth and Planetary Science↗

Isotopic insights into biological regulation of zinc in contaminated systems

Aquatic organisms use a variety of biogeochemical reactions to regulate essential and non-essential trace metals. Many of these mechanisms can lead to isotopic fractionation, thus measurement of metal isotopes may yield insights into the processes by which organisms respond to metal exposure. We illustrate these concepts with two case studies, one involving an intra- and the other an extra-cellular mechanism of Zn sequestration. In the first study, the mayfly Neocloeon triangulifer was grown in the laboratory, and fed a diet of Zn-doped diatoms at Zn levels exceeding the requirements for normal mayfly life functions. The N. triangulifer larvae consumed the diatoms and retained their Zn isotopic signature. Upon metamorphosis, the subimago life stage lost Zn mass either in the exuvia or by excretion, and the Zn retained was isotopically enriched. Thus, Zn uptake is nonfractionating, but Zn regulation favors the lighter isotope. Thus the Zn remaining in the subimago was isotopically heavier. In the second study, Zn was adsorbed on the cell walls and exopolysaccharide secretions of cyanobacteria, which favored the heavier Zn isotope. Continued adsorption eventually resulted in nucleation and biomineralization of hydrozincite {Zn5(CO3)2(OH)6}. These case studies demonstrate the utility of Zn isotopes to provide insights into how aquatic insects respond to metal exposure.

Procedia Earth and Planetary Science↗

Isotopic geochemistry of Panama rivers

River water samples collected from 78 watersheds rivers along a 500-km transect across a Late Cretaceous-Tertiary andesitic volcanic arc terrane in west-central Panama provide a synoptic overview of riverine geochemistry, chemical denudation, and CO 2 consumption in the tropics. D/H and 18 O/ 16 O relationships indicate that bedrock dissolution of andesitic arc crust in Panama is driven by water-rock interaction with meteoric precipitation as it passes through the critical zone, with no evidence of a geothermal or hydrothermal input. Sr-isotope relationships suggest a geochemical evolution for Panama riverine waters that involves mixing of bedrock pore water with water having 87 Sr/ 86 Sr ratios between 0.7037-0.7043 and relatively high Sr-contents with waters of low Sr content that enriched in radiogenic Sr that are diluted by infiltrating rainfall to variable extents.

Procedia Earth and Planetary Science↗

Measurement of in situ sulfur isotopes by laser ablation multi-collector ICPMS: opening Pandora’s Box

Laser ablation multi-collector ICPMS is a modern tool for in situ measurement of S isotopes. Advantages of the technique are speed of analysis and relatively minor matrix effects combined with spatial resolution sufficient for many applications. The main disadvantage is a more destructive sampling mechanism relative to the ion microprobe technique. Recent advances in instrumentation allow precise measurement with spatial resolutions down to 25 microns. We describe specific examples from economic geology where increased spatial resolution has greatly expanded insights into the sources and evolution of fluids that cause mineralization and illuminated genetic relations between individual deposits in single mineral districts.

Procedia Earth and Planetary Science↗

Changes in the Chemistry of Groundwater Reacted with CO 2 : Comparison of Laboratory Results with the ZERT Field Pilot

As part of the ZERT program, sediments from two wells at the ZERT site, located in Bozeman, Montana, USA were reacted with a solution having the composition of local groundwater. A total of 50 water samples were collected from 7 containers placed for 15 days in a glove box with one atmosphere of CO 2 to investigate detailed changes in the concentrations of major, minor and trace inorganic compounds, and to compare these with changes observed in groundwater at the ZERT site following CO 2 injection. Laboratory results included rapid changes in pH (8.6 to 5.7), alkalinity (243 to 1295 mg/L as HCO 3 ), electrical conductance (539 to 1822 μS/cm), Ca (28 to 297 mg/L), Mg (18 to 63 mg/L), Fe (5 to 43 μg/L) and Mn (2 to 837 μg/L) following CO 2 injection. These chemical changes, which are in general agreement with those obtained from sampling the ZERT monitoring wells, could provide early detection of CO 2 leakage into shallow groundwater. Dissolution of calcite, some dolomite and minor Mn-oxides, and desorption/ion exchange are likely the main geochemical processes responsible for the observed changes.

Procedia Earth and Planetary Science↗

Microbial-sized, carboxylate-modified microspheres as surrogate tracers in a variety of subsurface environments: An overview

Since 1986, fluorescent carboxylate-modified polystyrene/latex microspheres (FCM) have been co-injected into aquifers along with conservative tracers and viruses, bacteria, and (or) protozoa. Use of FCM has resulted in new information about subsurface transport behaviors of microorganisms in fractured crystalline rock, karst limestone, soils, and granular aquifers. FCM have been used as surrogates for oocysts of the pathogenic protist Cryptosporidium parvum in karst limestone and granular drinking-water aquifers. The advantages of FCM in subsurface transport studies are that they are safe in tracer applications, negatively charged, easy to detect, chemically inert, and available in wide range of sizes. The limitations of FCM are that the quantities needed for some field transport studies can be prohibitively expensive and that their surface characteristics may not match the microorganisms of interest. These limitations may be ameliorated, in part by using chemically modified FCM so that their surface characteristics are a better match to that of the organisms. Also, more sensitive methods of detection may allow using smaller quantities of FCM. To assess how the transport behaviors of FCM and pathogens might compare at the field scale, it is helpful to conduct side-by-side comparisons of their transport behaviors using the geologic media and site-specific conditions that characterize the field site.

Procedia Earth and Planetary Science↗

Mobilization of mercury and arsenic from a carbonate-hosted ore deposit, central Idaho, U.S.A.

The Cinnabar and Fern mine sites in central Idaho are primary source areas for elevated mercury and arsenic entering the South Fork of the Salmon River, which provides critical spawning habitat for bull trout and Chinook salmon. Mercury mineralization is hosted by carbonate rocks, which generate waters dominated by Ca2+ and HCO3 - at pH 7 to 9. A synoptic sampling was conducted on headwater tributaries to determine geologic background concentrations and quantify trace metal concentrations in stream water associated with historical mining. Geologic background concentrations in unfiltered Cinnabar Creek water were 8 - 14 ng Hg L-1 and 4.8 - 9.5 µg As L-1. Immediately downstream from the mine site, concentrations increased to 257 ng Hg L-1 and 20.6 µg As L-1. Groundwater inflow diluted these concentrations by approximately half before the confluence of Cinnabar Creek with Sugar Creek. As expected, mercury and arsenic concentrations increased downstream in Sugar Creek below the confluence with Cinnabar Creek. However, the final downstream reach on Sugar Creek showed an increase in unfiltered mercury, methylmercury, and iron concentrations relative to the upstream reach. This increase is associated with historical mining activity in a mineralized area of carbonate rock that intersects the reach.

Idaho↗

Changes in erosion and ocean circulation recorded in the Hf isotopic compositions of North Atlantic and Indian Ocean ferromanganese crusts

High-resolution Hf isotopic records are presented for hydrogenetic Fe–Mn crusts from the North Atlantic and Indian Oceans. BM1969 from the western North Atlantic has previously been shown to record systematically decreasing Nd isotopic compositions from about 60 to ∼4 Ma, at which time both show a rapid decrease to unradiogenic Nd composition, thought to be related to the increasing influence of NADW or glaciation in the northern hemisphere. During the Oligocene, North Atlantic Hf became progressively less radiogenic until in the mid-Miocene (∼15 Ma) it reached +1. It then shifted gradually back to an ϵ Hf value of +3 at 4 Ma, since when it has decreased rapidly to about −1 at the present day. The observed shifts in the Hf isotopic composition were probably caused by variation in intensity of erosion as glaciation progressed in the northern hemisphere. Ferromanganese crusts SS663 and 109D are from about 5500 m depth in the Indian Ocean and are now separated by ∼2300 km across the Mid-Indian Ridge. They display similar trends in Hf isotopic composition from 20 to 5 Ma, with the more northern crust having a composition that is consistently more radiogenic (by ∼2 ϵ Hf units). Paradoxically, during the last 20 Ma the Hf isotopic compositions of the two crusts have converged despite increased separation and subsidence relative to the ridge. A correlatable negative excursion at ∼5 Ma in the two records may reflect a short-term increase in erosion caused by the activation of the Himalayan main central thrust. Changes to unradiogenic Hf in the central Indian Ocean after 5 Ma may alternatively have been caused by the expanding influence of NADW into the Mid-Indian Basin via circum-Antarctic deep water or a reduction of Pacific flow through the Indonesian gateway. In either case, these results illustrate the utility of the Hf isotope system as a tracer of paleoceanographic changes, capable of responding to subtle changes in erosional regime not readily resolved using other isotope systems.

Earth and Planetary Science Letters↗

Lower crustal flow and the role of shear in basin subsidence: An example from the Dead Sea basin

We interpret large-scale subsidence (5–6 km depth) with little attendant brittle deformation in the southern Dead Sea basin, a large pull-apart basin along the Dead Sea transform plate boundary, to indicate lower crustal thinning due to lower crustal flow. Along-axis flow within the lower crust could be induced by the reduction of overburden pressure in the central Dead Sea basin, where brittle extensional deformation is observed. Using a channel flow approximation, we estimate that lower crustal flow would occur within the time frame of basin subsidence if the viscosity is ≤7×10 19 –1×10 21 Pa s, a value compatible with the normal heat flow in the region. Lower crustal viscosity due to the strain rate associated with basin extension is estimated to be similar to or smaller than the viscosity required for a channel flow. However, the viscosity under the basin may be reduced to 5×10 17 –5×10 19 Pa s by the enhanced strain rate due to lateral shear along the transform plate boundary. Thus, lower crustal flow facilitated by shear may be a viable mechanism to enlarge basins and modify other topographic features even in the absence of underlying thermal anomalies.

Dead Sea basin↗

Cordilleran-margin quartzites in Baja California – implications for tectonic transport

One of the current controversies in Cordilleran tectonics concerns the position of Baja California prior to ∼300 km of opening of the Gulf of California. Geologic arguments, together with paleomagnetic results from Lower Cretaceous volcanic rocks, suggest that the rocks of the Baja Peninsula formed and evolved along the coast of northwestern Mexico prior to opening of the Gulf. In contrast, paleomagnetic data from Cretaceous–early Tertiary plutonic rocks and clastic strata have been interpreted by some workers to suggest that Baja was located near southern Mexico at approximately 80 Ma. The presence of similar detrital zircon ages in lower Paleozoic quartzites of northeast Baja and in lower Paleozoic strata east of the Gulf, in northwestern Mexico and southwestern US, provides strong support for the northern paleoposition, suggesting that Baja has been transported northward by only ∼300 km

Earth and Planetary Science Letters↗

Osmium isotope constraints on lower crustal recycling and pluton preservation at Lassen Volcanic Center, CA

Osmium isotope compositions of intermediate- to silicic-composition calc-alkaline volcanic rocks from the Lassen volcanic region of the Cascade arc are significantly more radiogenic ( γ Os =+23 to +224) than typical mantle. These evolved arc rocks in the Lassen region have unradiogenic Sr, Nd, and Pb isotope compositions which overlap with those of contemporaneous mafic lavas. Crystal fractionation of mafic- to intermediate-composition magmas produces Re/Os ratios that are high enough to evolve to very radiogenic Os isotope compositions in only a few million years, providing a potential fingerprint for detecting the involvement of such young, relatively mafic crust in magmatic systems. However, the Sr, Nd, and Pb isotope compositions will remain constant over such short time intervals due to relatively low parent/daughter enrichment during magmatic evolution. The radiogenic Os isotope compositions in typically evolved Lassen rocks are interpreted to reflect significant interaction with lower crustal material that has radiogenic Os isotope compositions. Beneath this section of the Cascade arc, large amounts of such high- γ Os lower crust may have formed and been isolated from MASH zone mixing and homogenization processes during the Pliocene or Late Miocene. The results from this study indicate that Os isotopes may provide a unique glimpse into lower crustal processes, such as recycling, in primitive orogenic arcs.

California↗

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153]

In a recent contribution [1] , Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ; [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH) x(aq) and Fe(II) (aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4] , but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Earth and Planetary Science Letters↗

Density of the continental roots: Compositional and thermal contributions

The origin and evolution of cratonic roots has been debated for many years. Precambrian cratons are underlain by cold lithospheric roots that are chemically depleted. Thermal and petrologic data indicate that Archean roots are colder and more chemically depleted than Proterozoic roots. This observation has led to the hypothesis that the degree of depletion in a lithospheric root depends mostly on its age. Here we test this hypothesis using gravity, thermal, petrologic, and seismic data to quantify differences in the density of cratonic roots globally. In the first step in our analysis we use a global crustal model to remove the crustal contribution to the observed gravity. The result is the mantle gravity anomaly field, which varies over cratonic areas from -100 to +100 mGal. Positive mantle gravity anomalies are observed for cratons in the northern hemisphere: the Baltic shield, East European Platform, and the Siberian Platform. Negative anomalies are observed over cratons in the southern hemisphere: Western Australia, South America, the Indian shield, and Southern Africa. This indicates that there are significant differences in the density of cratonic roots, even for those of similar age. Root density depends on temperature and chemical depletion. In order to separate these effects we apply a lithospheric temperature correction using thermal estimates from a combination of geothermal modeling and global seismic tomography models. Gravity anomalies induced by temperature variations in the uppermost mantle range from -200 to +300 mGal, with the strongest negative anomalies associated with mid-ocean ridges and the strongest positive anomalies associated with cratons. After correcting for thermal effects, we obtain a map of density variations due to lithospheric compositional variations. These maps indicate that the average density decrease due to the chemical depletion within cratonic roots varies from 1.1% to 1.5%, assuming the chemical boundary layer has the same thickness as the thermal boundary layer. The maximal values of the density drop are in the range 1.7-2.5%, and correspond to the Archean portion of each craton. Temperatures within cratonic roots vary strongly, and our analysis indicates that density variations in the roots due to temperature are larger than the variations due to chemical differences.

Earth and Planetary Science Letters↗

Geochronology and eruptive history of the Katmai volcanic cluster, Alaska Peninsula

In the Katmai district of the Alaska Peninsula, K–Ar and 40 Ar/ 39 Ar ages have been determined for a dozen andesite–dacite stratocones on the arc front and for 11 rear-arc volcanoes, 10 of which are monogenetic. Tied to mapping and stratigraphic studies, our dating emphasized proximal basal lavas that rest on basement rocks, in order to estimate ages of inception of each polygenetic cone. Oldest among arc-front cones is Alagogshak Volcano (690–43 ka), succeeded in the Holocene by the active Mount Martin cone. Mount Mageik consists of four overlapping subedifices, basal lavas of which give ages of 93, 71, and 59 ka, and Holocene. The three small prehistoric cones of Trident Volcano yield ages of 143, 101–58, and 44 ka. Falling Mountain and Mount Cerberus, dacite domes near the 1912 Novarupta vent, are related compositionally to the Trident group and give ages of 70 ka and 114 ka. Mount Katmai, which underwent caldera collapse in 1912, consists of two subedifices that overlapped in space and time, and is the only arc-front center here to include basalt and rhyolite; one cone began by 90 ka, the other by 47 ka. Snowy Mountain also consists of two contiguous cones, which started around 200 and 171 ka, respectively, the younger remaining active into the Holocene. Devils Desk, the only mafic cone on the arc front, was short-lived at about 245 ka. In the rear-arc, (1) Mount Griggs produced mafic-to-silicic andesite in several episodes between 292 ka and the Holocene; (2) the Savonoski River cluster includes a Pliocene dacite dome and five small mafic cones (390–88 ka); (3) Gertrude Creek cone (49.8% SiO 2 ) yields an age of 500 ka; and (4) the Saddlehorn Creek cluster includes five Pliocene basalt-to-andesite remnants. Eruptive volumes were reconstructed, permitting estimates of average eruption rates for edifice lifetimes. Since the mid Pleistocene, total volume erupted along the arc front here is 210±47 km 3 and in the rear-arc 39±6 km 3 , of which Mount Griggs alone accounts for 35±5 km 3 . Most productive has been Mount Katmai at 70±18 km 3 , yielding a rate of ∼1 km 3 /kyr, followed by Mount Mageik (0.33 km 3 /kyr) and Mount Griggs (0.3 km 3 /kyr since 50 ka).

Alaska↗

Transient rheology of the uppermost mantle beneath the Mojave Desert, California

Geodetic data indicate that the M7.1 Hector Mine, California, earthquake was followed by a brief period (a few weeks) of rapid deformation preceding a prolonged phase of slower deformation. We find that the signal contained in continuous and campaign global positioning system data for 2.5 years after the earthquake may be explained with a transient rheology. Quantitative modeling of these data with allowance for transient (linear biviscous) rheology in the lower crust and upper mantle demonstrates that transient rheology in the upper mantle is dominant, its material properties being typified by two characteristic relaxation times ???0.07 and ???2 years. The inferred mantle rheology is a Jeffreys solid in which the transient and steady-state shear moduli are equal. Consideration of a simpler viscoelastic model with a linear univiscous rheology (2 fewer parameters than a biviscous model) shows that it consistently underpredicts the amplitude of the first ???3 months signal, and allowance for a biviscous rheology is significant at the 99.0% confidence level. Another alternative model - deep postseismic afterslip beneath the coseismic rupture - predicts a vertical velocity pattern opposite to the observed pattern at all time periods considered. Despite its plausibility, the advocated biviscous rheology model is non-unique and should be regarded as a viable alternative to the non-linear mantle rheology model for governing postseismic flow beneath the Mojave Desert. Published by Elsevier B.V.

Earth and Planetary Science Letters↗

Slowing extrusion tectonics: Lowered estimate of post-Early Miocene slip rate for the Altyn Tagh fault

Determination of long-term slip rate for the Altyn Tagh fault is essential for testing whether Asian tectonics is dominated by lateral extrusion or distributed crustal shortening. Previous slip-history studies focused on either Quaternary slip-rate measurements or pre-Early Miocene total-offset estimates and do not allow a clear distinction between rates based on the two. The magmatic and metamorphic history revealed by SHRIMP zircon dating of clasts from Miocene conglomerate in the Xorkol basin north of the Altyn Tagh fault strikingly matches that of basement in the southern Qilian Shan and northern Qaidam regions south of the fault. This match requires that the post-Early Miocene long-term slip rate along the Altyn Tagh fault cannot exceed 10 mm/year, supporting the hypothesis of distributed crustal thickening for post-Early Miocene times. This low long-term slip rate and recently documented large pre-Early Miocene cumulative offset across the fault support a two-stage evolution, wherein Asian tectonics was dominated by lateral extrusion before the end of Early Miocene, and since then has been dominated by distributed crustal thickening and rapid plateau uplift. ?? 2003 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters↗

Ultra-high chlorine in submarine Kı̄lauea glasses: Evidence for direct assimilation of brine by magma

Basaltic glass grains from the submarine south flank of Kı̄lauea, Hawai′i, have Cl concentrations of 0.01–1.68 wt%, the latter being the highest Cl content yet recorded for a Hawaiian glass. The high-Cl glass grains are products of brine assimilation by tholeiite magma. The glasses are grains in a sandstone clast from bedded breccias draping the southwestern margin of Kı̄lauea’s submarine midslope bench. The clast contains two distinct suites of glass grains: abundant degassed tholeiites, perhaps derived from subaerial lavas of Mauna Loa that shattered upon ocean entry, and a smaller population of Kea-type tholeiite ( n =17 analyzed) that erupted subaqueously, based on elevated S (780–1050 ppm), H 2 O (0.42–1.27 wt%), and CO 2 (<30–120 ppm), probably early in Kı̄lauea’s shield-building stage. Ten grains in this group have Cl>1000 ppm, six >5000 ppm, and two grains have >10 000 ppm dissolved Cl. Abundances of H 2 O, Na 2 O, K 2 O, and several trace elements increase regularly with Cl concentration, and we estimate that Cl enrichment was due to up to 13 wt% addition of a brine consisting of 78% H 2 O (wt), 13% Cl, 4.4% Na, 2.6% K, 2.6% Ca, 620 ppm Ba, 360 ppm Sr, 65 ppm Rb, and 7 ppm Pb. The large amounts of brine addition argue against bulk assimilation of low-porosity brine-bearing rock. The brine’s composition is appropriate for a seawater-derived hydrothermal fluid that reacted with basaltic wall rocks at T >100°C, losing Mg and S and gaining K, Ca, Rb, Ba, Sr, and Pb, followed by phase separation near 500°C and ∼50 MPa (5 km below sea level at hydrostatic pressure). Brine was assimilated at or near the depth it formed, as estimated on petrologic grounds, but under lithostatic conditions. The highest extents of assimilation either forced volatile saturation of the magma or enriched already coexisting magmatic vapor in H 2 O. Possible mechanisms for assimilation are: (1) forcible injection of brine into magma during bursting of overpressured pockets heated by new dikes, or (2) intrusion of magma into lenses or sills occupied by trapped brine.

Hawaii↗