Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay

A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.     

Voltammetric estimation of iron(III) thermodynamic stability constants for catecholate siderophores isolated from marine bacteria and cyanobacteria

Thermodynamic stability constants have been estimated for the complexation of iron(III) with catecholate-type siderophores isolated from the marine bacterium Alteromonas luteoviolacea and from the marine cyanobacterium Synechococcus sp. PCC 7002. Stability constants were determined utilizing the “chelate scale” of Taylor et al. (1994). The scale is based upon a linear relationship between the reduction potentials and the pH-independent thermodynamic stability constants for known iron(III) complexes. Log K values for the alterobactin B ferric iron complex are 43.6 ± 1.5 at pH 8.2 and 37.6 ± 1.2 at pH 6, consistent with a shift from bis-catecholate to monosalicylate/monocatecholate iron coordination with decreasing pH. Synechococcus isolates PCC 7002 Nos. 1 and 3 formed iron(III) complexes with stability constants of approximately 38.1 ± 1.2 and 42.3 ± 1.5, respectively. The binding strengths of the iron(III) complexes examined in this study are quite high, suggesting that catecholate siderophores may play a role in the solubilization and biological uptake of iron in the marine environment.     

In situ estimation of the effective chemical diffusion coefficient of a rock matrix in a fractured aquifer

An in situ method of estimating the effective diffusion coefficient for a chemical constituent that diffuses into the primary porosity of a rock is developed by abruptly changing the concentration of the dissolved constituent in a borehole in contact with the rock matrix and monitoring the time-varying concentration. The experiment was conducted in a borehole completed in mudstone on the campus of the University of the Free State in Bloemfontein, South Africa. Numerous tracer tests were conducted at this site, which left a residual concentration of sodium chloride in boreholes that diffused into the rock matrix over a period of years. Fresh water was introduced into a borehole in contact with the mudstone, and the time-varying increase of chloride was observed by monitoring the electrical conductivity (EC) at various depths in the borehole. Estimates of the effective diffusion coefficient were obtained by interpreting measurements of EC over 34 d. The effective diffusion coefficient at a depth of 36 m was approximately 7.8×10^?6 m²/d, but was sensitive to the assumed matrix porosity. The formation factor and mass flux for the mudstone were also estimated from the experiment.     

Comparison of structural and least-squares lines for estimating geologic relations

Two different goals in fitting straight lines to data are to estimate a true linear relation (physical law) and to predict values of the dependent variable with the smallest possible error. Regarding the first goal, a Monte Carlo study indicated that the structural-analysis (SA) method of fitting straight lines to data is superior to the ordinary least-squares (OLS) method for estimating true straight-line relations. Number of data points, slope and intercept of the true relation, and variances of the errors associated with the independent (X) and dependent (Y) variables influence the degree of agreement. For example, differences between the two line-fitting methods decrease as error in X becomes small relative to error in Y. Regarding the second goal—predicting the dependent variable—OLS is better than SA. Again, the difference diminishes as X takes on less error relative to Y. With respect to estimation of slope and intercept and prediction of Y, agreement between Monte Carlo results and large-sample theory was very good for sample sizes of 100, and fair to good for sample sizes of 20. The procedures and error measures are illustrated with two geologic examples.     

Mantle plumes from top to bottom

Hotspots include midplate features like Hawaii and on-axis features like Iceland. Mantle plumes are a well-posed hypothesis for their formation. Starting plume heads provide an explanation of brief episodes of flood basalts, mafic intrusions, and radial dike swarms. Yet the essence of the hypothesis hides deep in the mantle. Tests independent of surface geology and geochemistry to date have been at best tantalizing. It is productive to bare the current ignorance, rather than to dump the plume hypothesis. One finds potentially fruitful lines of inquiry using simple dynamics and observations. Ancient lithospheric xenoliths may reveal heating by plumes and subsequent thermal equilibration in the past. The effect at the base of the chemical layer is modest 50-100 K for transient heating by plume heads. Thinning of nonbuoyant platform lithosphere is readily observed but not directly attributable to plumes. The plume history in Antarctica is ill constrained because of poor geological exposure. This locality provides a worst case on what is known about surface evidence of hotspots. Direct detection of plume tail conduits in the mid-mantle is now at the edge of seismic resolution. Seismology does not provide adequate resolution of the deep mantle. We do not know the extent of a chemically dense dregs layer or whether superplume regions are cooler or hotter than an adiabat in equilibrium with the asthenosphere. Overall, mid-mantle seismology is most likely to give definitive results as plume conduits are the guts of the dynamic hypothesis. Finding them would bring unresolved deep and shallow processes into place.     

The Port Mouton Shear Zone: intersection of a regional fault with a crystallizing granitoid pluton

The peraluminous tonalite–monzogranite Port Mouton Pluton is a petrological, geochemical, structural, and geochronological anomaly among the many Late Devonian granitoid intrusions of the Meguma Lithotectonic Zone of southern Nova Scotia. The most remarkable structural feature of this pluton is a 4-km-wide zone of strongly foliated (040/subvertical) monzogranites culminating in a narrow (10–30 m), straight, zone of compositionally banded rocks that extends for at least 3 km along strike. The banded monzogranites consist of alternating melanocratic and leucocratic compositions that are complementary to the overall composition of that part of the pluton, suggesting an origin by mineral–melt and mineral–mineral sorting. Biotite and feldspar are strongly foliated in the plane of the compositional bands. These compositional variations and foliations originated by a process of segregation flow during shearing of the main magma with a crystallinity of 55–75%. Subsequent minor brittle fracturing of feldspars, twinning of microcline, development of blocky sub-grains in quartz, and kinking of micas demonstrate overprinting by a high-temperature deformation straddling the monzogranite solidus. Small folds and late sigmoidal dykes indicate dextral movement on the shear zone. This Port Mouton Shear Zone (PMSZ) is approximately co-linear with the only outcrops of Late Devonian mafic intrusions in the area, two of which are syn-plutonic with well-developed mingling textures in the marginal tonalite of the Port Mouton Pluton. Also closely co-linear with the mafic intrusions are a granitoid dyke that extends well beyond the outer contact of the Port Mouton Pluton, a swarm of large aligned angular xenolithic slabs, a zone of thin wispy schlieren banding, a large Be-bearing pegmatite, and a breccia pipe with abundant garnetiferous metapelitic xenoliths. In various ways, the shear zone may control all of these features. The Port Mouton Shear Zone is parallel to many other NE-trending faults and shear zones in the northern Appalachians, probably related to the docking of the Meguma Zone along the Cobequid–Chedabucto Fault system.     

Viscosity of peridotite liquid up to 13 GPa: Implications for magma ocean viscosities

The viscosity of synthetic peridotite liquid has been investigated at high pressures using in-situ falling sphere viscometry by combining a multi-anvil technique with synchrotron radiation. We used a newly designed capsule containing a small recessed reservoir outside of the hot spot of the heater, in which a viscosity marker sphere is embedded in a forsterite + enstatite mixture having a higher solidus temperature than the peridotite. This experimental setup prevents spheres from falling before a stable temperature above the liquidus is established and thus avoids difficulties in evaluating viscosities from velocities of spheres falling through a partially molten sample.

Experiments have been performed between 2.8 and 13 GPa at temperatures ranging from 2043 to 2523 K. Measured viscosities range from 0.019 (± 0.004) to 0.13 (± 0.02) Pa s. At constant temperature, viscosity increases with increasing pressure up to  8.5 GPa but then decreases between  8.5 and 13 GPa. The change in the pressure dependence of viscosity is likely associated with structural changes of the liquid that occur upon compression. By combining our results with recently published 0.1 MPa peridotite liquid viscosities [D.B. Dingwell, C. Courtial, D. Giordano, A. Nichols, Viscosity of peridotite liquid, Earth Planet. Sci. Lett. 226 (2004) 127–138.], the experimental data can be described by a non-Arrhenian, empirical Vogel-Fulcher-Tamman equation, which has been modified by adding a term to account for the observed pressure dependence of viscosity. This equation reproduces measured viscosities to within 0.08 log₁₀-units on average. We use this model to calculate viscosities of a peridotitic magma ocean along a liquid adiabat to a depth of  400 km and discuss possible effects on viscosity at greater pressures and temperatures than experimentally investigated.     

Evidence for the enhanced lability of dissolved organic matter following permafrost slope disturbance in the Canadian High Arctic

Arctic landscapes are believed to be highly sensitive to climate change and accelerated disturbance of permafrost is expected to significantly impact the rate of carbon cycling. While half the global soil organic matter (SOM) is estimated to reside in Arctic soils, projected warmer temperatures and permafrost disturbance will release much of this SOM into waterways in the form of dissolved organic matter (DOM). The spring thaw and subsequent flushing of soils releases the highest contributions of DOM annually but has historically been undersampled due to the difficulties of sampling during this period. In this study, passive samplers were placed throughout paired High Arctic watersheds during the duration of the 2008 spring flush in Nunavut, Canada. The watersheds are very similar with the exception of widespread active layer detachments (ALDs) that occurred within one of the catchments during a period of elevated temperatures in the summer of 2007. DOM samples were analyzed for structural and spectral characteristics via nuclear magnetic resonance (NMR) and fluorescence spectroscopy as well as vulnerability to degradation with simulated solar exposure. Lignin-derived phenols were further assessed utilizing copper(II) oxide (CuO) oxidation and gas chromatography/mass spectrometry (GC/MS). The samples were found to have very low dissolved lignin phenol content (∼0.07% of DOC) and appear to originate from primarily non-woody angiosperm vegetation. The acid/aldehyde ratios for dissolved vanillyl phenols were found to be high (up to 3.6), indicating the presence of highly oxidized lignin. Differences between DOM released from the ALD vs. the undisturbed watershed suggest that these shallow detachment slides have significantly impacted the quality of Arctic DOM. Although material released from the disturbed catchment was found to be highly oxidized, DOM in the lake into which this catchment drained had chemical characteristics indicating high contributions from microbial and/or primary productivity. The resulting pool of dissolved carbon within the lake appears to be more biologically- and photochemically-labile than material from the undisturbed system. These disturbances may have implications for projected climate warming; sustained elevated temperatures would likely perpetuate widespread ALDs and further affect carbon cycling in this environment.     

Emplacement age and thermal footprint of the diamondiferous Ellendale E9 lamproite pipe, Western Australia

The diamondiferous Ellendale 9 (E9) pipe is a funnel-shaped maar-diatreme volcano consisting of inward-dipping tuff sequences intruded by lamproite plugs and dykes. The host rocks for the E9 pipe are Permian sandstones. The multiple lithological contacts exposed within the mined maar volcano provide a natural laboratory in which to study the effect of volcanic processes on U–Th–Pb–He systematics. Zircon from the regional sandstone and E9 lamproite display a bimodal distribution of ages on (U–Th)/He–U/Pb plots. The zircon U/Pb ages for the E9 pipe (n?=?52) range from 440 to 2,725 Ma, while the cluster of (U–Th)/He ages for the lamproite dyke zircon indicate that dyke emplacement occurred at 20.6?±?2.8 Ma, concordant with a maximum emplacement age of about ≤22 Ma from phlogopite ⁴⁰Ar/³⁹Ar. These ages indicate a xenocrystic origin for the zircon entrained in the E9 dyke. The U/Pb ages of detrital zircon from the regional sandstone host (373–3,248 Ma; n?=?41) are indistinguishable from those of the lamproite zircon xenocrysts, whereas the detrital zircon in the host sandstone yield (U–Th)/He ages from 260 to 1,500 Ma. A thermochronology traverse across the E9 lamproite dyke reveals that the zircon (U–Th)/He ages in the host sandstone have not been significantly thermally reset during dyke emplacement, even at the contact. The capability of the zircon (U–Th)/He method to distinguish deep, mantle source lithologies from upper crustal source lithologies could be used in geochemical exploration for diamonds. Pre-screening of detrital samples using etching and helium assay methods will improve the efficiency and decrease the cost of greenfields exploration.