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.     

Optical water type discrimination and tuning remote sensing band-ratio algorithms: Application to retrieval of chlorophyll and Kd(490) in the Irish and Celtic Seas

This paper assesses the feasibility of applying remote sensing algorithms based on blue/green reflectance ratios to Case 2 waters. Two algorithms from the SeaDAS (NASA) image processing package, OC4v4 for surface chlorophyll concentration, Chl, and K(490) for the attenuation coefficient for downward irradiance at 490 nm, K_d(490), were investigated using an extensive set of observations from the Irish and Celtic Seas. In situ data from a profiling radiometer were used as inputs for the algorithms to avoid uncertainties in atmospheric correction procedures, and direct measurements of Chl and K_d490 and were used for validation purposes. The standard versions of the algorithms performed poorly: OC4v4 generally overestimated Chl (with a very low coefficient of determination), and K(490) progressively underestimated K_d490 for values greater than 0.3 m⁻¹. A two-step procedure for level 2 product generation was therefore devised in which the numerical coefficients of OC4v4 and K(490) were tuned for the two optical water types known to occur most frequently in this region (McKee, D., Cunningham, A., 2006. Identification and characterisation of two optical water types in the Irish Sea from in situ inherent optical properties and seawater constituents. Estuarine, Coastal and Shelf Science 68, 305–316) by statistical regression on a data set of 102 stations from the Irish and Celtic Seas. The water types were distinguished by the magnitude of their normalised water leaving radiance signals at 665 nm, nL_w(665), and appropriate versions of the tuned algorithms applied to each water type. When this procedure was tested on an independent data set of 19 stations from the Bristol Channel, Chl values were recovered with an RMS error of 0.36 mg m⁻³ and K_d(490) values with an RMS error of 0.095 m⁻¹. The identification of water types from water-leaving radiance signals, and the application of band-ratio algorithms tuned for specific water types, may therefore provide a simple means of improving the quality of remote sensing products in optically complex shelf seas.     

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.     

Petrology,isotope characteristics,and K-Ar ages of the Maranhão,northern Brazil,Mesozoic basalt province

Northern Brazil contains remnants of Mesozoic flood basalts and hypabyssal rocks that were apparently emplaced during tectonism related to opening of the Atlantic Ocean. Analyses and new K-Ar ages reveal that this 700x250 km Maranhão province (5°–8°S) has low-Ti basalts (1.1 wt% TiO₂) in the western part that range about 160 to 190 Ma, and high-Ti basalts (3.4–4.4 wt% TiO₂) in the eastern part about 115–122 Ma. Low-Ti basalt compositions are less evolved and have a smaller range, Mg# 62-56, than the high-Ti basalts, Mg# 44–33. General characteristics of the least evolved members of low- and high-Ti groups include, respectively, Zr 100 and 250 ppm, Sr 225 and 475 ppm, Ba 200 and 500 ppm, Nb 10 and 26 ppm, Y 29 and 36 ppm, La/Yb_(n) 4.2 and 8.8, where La_(n) is 30 and 90. Overall compositions resemble the low- and high-Ti basaltic rocks of the Mesozoic Serra Geral (Paraná) province in southern Brazil. The Maranhão low-Ti basalts have more radiogenic Sr and Pb and higher ¹⁸O than the high-Ti basalts. Respectively, low- vs high-Ti: _Sr26–54 vs 15–18; ²⁰⁶Pb/²⁰⁴Pb=18.25–.78 vs 18.22–.24; and ¹⁸O 8.9–12.6 vs 6.5–8.6. Nd isotopes overlap: _Nd–1.6 to –3.8 vs –2.1 to –3. Ages, compositions, and isotopes indicate that the low- and high-Ti groups had independent parentages from enriched subcontinental mantle. However, both groups can be modeled from one source composition if low-Ti basalt isotopes reflect crustal contamination, and if the parentages for each group were picritic liquids that represent either higher (for low-Ti) or lower (for high-Ti) percentages of melting of that single source. When comparing Pb isotopes of Maranhão and Serra Geral high-Ti basalts (uncontaminated) to evaluate the DUPAL anomaly, Maranhão has Pb 7/4=4.6–11, and Pb 8/4=72–87; Serra Geral has Pb 7/4=10–13, and Pb 8/4=95–125. The small difference is not enough to conform to DUPAL contours, and is inconsistent with large-scale isotopic heterogeneity of mantle beneath Brazil prior to rifting of South America from Africa. Maranhão low-Ti magmas probably relate to the opening of central North Atlantic, and high-Ti magmas to the opening of equatorial Atlantic. The proposed greater percentage of source melting for low-Ti basalts may reflect a Triassic-Jurassic hotspot, while lesser melting for high-Ti magmas may relate to Cretaceous decompressional (rifting) melting.     

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.     

A field comparison of indicators of sublethal stress in the salt-marsh grassSpartina patens

There is a need for research into bioindicators of stress in threatened plant communities such as coastal wetlands. Land subsidence, diversion of sediment, and salt-water intrusion produce stresses associated with waterlogging, elevated salinity, and nutrient depletion. Temporal and spatial environmental variation (soil redox potential, interstitial water salinity, pH, ammonium and phosphorus, and cation and trace metal concentrations) was analyzed near Lake de Cade, Louisiana, in a brackish marsh which is a mosaic of healthy plant communities interspersed with areas where wetland loss is occurring. Environmental variation was related to indicators of stress inSpartina patens, which included variables derived from the adenine nucleotide levels in plants, leaf spectral reflectance, leaf proline concentrations, and shoot elongation. In a comparison of burned and unburned sites, streamside and inland marsh, and along a salinity gradient, among-site differences were found in spectral reflectance and adenine-nucleotide-related indicators. Although it was difficult to relate a single causal environmental variable to the response of a specific indicator, spectral reflectance in the visible light range responded to salinity or to elements borne in seawater, and adenine-nucleotide indices were sensitive to nutrient availability. The ability of indicators to detect plant responses changed during the growing season, suggesting that they were responding to the changing importance of different environmental factors. In addition, some reflectance indicator responses occurred along salinity gradients when salinity differences were less than those that were found to have ecologically meaningful effects in greenhouse experiments. A multivariate numerical approach was used to relate environmental variation with indicator responses. We concluded that factors which in combination cause the degradation and loss of Louisiana wetlands produce environmental conditions that are only subtly different from those in vigorously growing marsh communities.     

The age and thermal history of Cerro Rico de Potosi, Bolivia

 Cerro Rico de Potosi, Bolivia, is the world’s largest silver deposit and has been mined since the sixteenth century for silver, and for tin and zinc during the twentieth century, together with by-product copper and lead. The deposit consists primarily of veins that cut an altered igneous body that we interpret to be a dacitic volcanic dome and its underlying tuff ring and explosion breccia. The deposit is compositionally and thermally zoned, having a core of cassiterite, wolframite, bismuthinite, and arsenopyrite surrounded by a peripheral, lower-temperature mineral assemblage consisting principally of sphalerite, galena, lead sulfosalt, and silver minerals. The low-temperature assemblage also was superimposed on the high-temperature assemblage in response to cooling of the main hydrothermal system. Both the dacite dome and the ore fluids were derived from a larger magmatic/hydrothermal source at depth. The dome was repeatedly fractured by recurrent movement on the fault system that guided its initial emplacement. The dome was extruded at 13.8±0.2 Ma (2σ), based on U-Th-Pb dating of zircon. Mineralization and alteration occurred within about 0.3 my of dome emplacement, as indicated by a ⁴⁰Ar/³⁹Ar date of 13.76±0.10 Ma (1σ) for sericite from the pervasive quartz-sericite-pyrite alteration associated with the main-stage, high-temperature, mineralization. The last thermal event able to reset zircon fission tracks occurred no later than 12.5±1.1 Ma (1σ), as indicated by fission-tract dating. Minor sericite, and magmatic-steam alunite veins, were episodically formed around 11 Ma and between 8.3 and 5.7 Ma; the younger episodes occurring at the time of extensional fracturing at Cerro Rico and widespread volcanism in the adjacent Los Frailes volcanic field. None of these younger events appear to be significant thermal/mineralizing events; the exceptionally flat thermal release pattern of ³⁹Ar from sericite and the results of the fission-tract dating of zircon show that none of the younger events was hot enough, and lasted long enough, to cause significant loss of Ar or annealing of zircon fission tracks. U-Th-Pb dating of zircon cores indicates a Precambrian progenitor for some zircons, and REE analyses of dated samples of hydrothermally altered dacite show the presence of a prominent positive Eu anomaly, which constrains interpretations of the origin and evolution of the magmatic/hydrothermal system. Received: 14 October 1995/Accepted: 29 January 1996