The effect of pH and ionic strength on proton adsorption by the thermophilic bacterium Anoxybacillus flavithermus

Numerous studies have utilized surface complexation theory to model proton adsorption behaviour onto mesophilic bacteria. However, few experiments, to date, have investigated the effects of pH and ionic strength on proton interactions with thermophilic bacteria. In this study, we characterize proton adsorption by the thermophile Anoxybacillus flavithermus by performing acid-base titrations and electrophoretic mobility measurements in NaNO₃ (0.001-0.1 M). Equilibrium thermodynamics (Donnan model) were applied to describe the specific chemical reactions that occur at the water-bacteria interface. Acid-base titrations were used to determine deprotonation constants and site concentrations for the important cell wall functional groups, while electrophoretic mobility data were used to further constrain the model. We observe that with increasing pH and ionic strength, the buffering capacity increases and the electrophoretic mobility decreases. We develop a single surface complexation model to describe proton interactions with the cells, both as a function of pH and ionic strength. Based on the model, the acid-base properties of the cell wall of A. flavithermus can best be characterized by invoking three distinct types of cell wall functional groups, with pK_a values of 4.94, 6.85, and 7.85, and site concentrations of 5.33, 1.79, and 1.42 × 10⁻⁴ moles per gram of dry bacteria, respectively. A. flavithermus imparts less buffering capacity than pure mesophilic bacteria studied to date because the thermophile possesses a lower total site density (8.54 × 10⁻⁴ moles per dry gram bacteria).     

Reduction in organic contaminant exposure and resultant hepatic hydropic vacuolation in winter flounder (Pseudopleuronectes americanus) following improved effluent quality and relocation of the Boston sewage outfall into Massachusetts Bay, USA: 1987-2003

Effluent upgrades for metropolitan Boston have included toxicant reduction, primary and secondary treatment and outfall extension. Between 1992 and 2003 winter flounder at five stations were surveyed annually for liver and muscle burden and chronic hepatic sub-lethal impacts of polynuclear and halogenated aromatic hydrocarbons, and metals. Trends in flounder availability and fin condition were also examined. In 1988 12% of the adult winter flounder in Boston Harbor exhibited hepatic neoplasms and up to 80% had hepatic hydropic vacuolation (HV). Tumor prevalence fell to 0-2% and HV to <50% by 1996. Since then tumors have been absent, while a steady prevalence of HV has persisted, consistent with lower hydrocarbon loading and tissue levels. Contaminants and HV also fell with distance from the Boston outfall. After the outfall extension was activated in 2000, there has been no significant change in flounder liver health at the new outfall site.     

Detecting Freshwater Inputs via Groundwater Discharge to Marina Lagoon, Mediterranean Coast, Egypt

Much work in recent years has reported on the role of submarine groundwater discharge (SGD) on coastal biogeochemistry, but most of those studies have focused on temperate or tropical climates where year-round rainfall recharges surficial aquifers. The aim of this work, however, was to examine SGD behaviors in an arid setting??Marina Lagoon on the Egyptian Mediterranean coast. SGD was estimated via radon surveys and time-series measurements in lagoon waters during two campaigns (wet season in March 2009 and dry season in July 2010). Relatively higher values of radon were detected in March (maximum >30?dpm/L) compared to July (up to 16?dpm/L), which would indicate either enhanced input rates, or lower mixing/atmospheric losses during the wet season. Lower salinity waters within Marina Lagoon were characterized by higher radon and higher concentrations of dissolved inorganic nitrogen (DIN) and silica (DISi), characteristic of groundwater inputs. Based on lagoon and groundwater radon measurements and an advection-diffusion model, SGD average rates between 0.83 to 2.4?×?10⁸?L/day were estimated for both surveys. Since no seasonal pattern was detected, we suspect that either (1) SGD is derived from a regional aquifer not influenced by recharge from local rainfall or (2) local water use for irrigation and domestic purposes artificially recharges the surficial aquifer in the dry summer (tourist) months, which compensates for the lack of rainfall occurring at that time.     

Energy dispersive X-ray analysis of the surface of a deep-sea ferromanganese nodule

In an effort to elucidate the mechanism of formation and accretion of ferromanganese nodules, transverse sections of undisturbed botryoid surfaces of nodules from the abyssal central North Pacific were examined by X-ray analyses both by multiple replicate sample transects and mapping. Surface concentrations of Mn and Fe were found of the size and shape of microorganisms. Abundant microorganism-like objects covering the surface and the apparent absence of Si (i.e. no sediment) with the Mn and Fe concentrations suggests microorganisms may be involved either in the selective accretion or removal of these metals. If metal accretion was simply physicochemical, one would expect a more or less even distribution of Mn and Fe on the botryoid surfaces.The replicate X-ray sample transects showed that Mn and Fe have a distribution corresponding to botryoid zonation. Areas of high Mn X-ray intensity were found associated with the cap and equatorial zones of the botryoid. Most of the valley zone of the botryoid show a more or less even Mn distribution and an increase in Fe X-ray intensity. At the base of the botryoid both metals apparently precipitously decrease.     

Radium Sampling Methods and Residence Times in St. Andrew Bay,Florida

Activity ratios (AR) of radium isotopes have been used with success to constrain estimates of water ages and to approximate residence times in coastal waters. We compared two common radium sampling methods (grab sampling and stationary moorings) to estimate water ages and the residence time of St. Andrew Bay waters in northwest Florida, USA. Both sampling methods utilize manganese dioxide fibers (“Mn fibers”) to adsorb dissolved radium from the water column. Grab samples capture radium activities at a discrete time while moorings integrate radium activities over longer deployments. The two methods yielded similar results in this study and thus both approaches are useful for water age comparisons and residence time approximations. However, since radium often varies as a function of tidal stage, deploying moorings over a complete tidal cycle is the preferred approach. An estimated residence time for North Bay and West Bay of 8–11 days was approximated using ARs for both ex²²⁴Ra/²²³Ra and ex²²⁴Ra/²²⁸Ra. Some complications were introduced as St. Andrew Bay is a tidally dominated, rather than a river-dominated bay system where this method has previously been applied. The largest freshwater source to this bay system is from a man-made reservoir, with an average freshwater flow of only 20 m³ s^?1. The activity concentrations and ARs measured by both sampling methods suggest that while the reservoir is the prominent radium source, it is not the only radium source. Nonetheless, a tidal mixing model applied to the western half of the system yielded an approximate flushing time of 10–12 days, similar to that derived from our radium-based water age approach.     

Definition and global correlation of the Santonian-Campanian boundary

Review of biostratigraphical evidence from different regions shows that criteria used by workers on various marine fossil groups to define the Santonian-Campanian boundary differ considerably in relative age and position. Probably the most widely recognizable of these criteria is the extinction of the distinctive crinoid Marsupites testudinarius (North America, Europe, Asia, north Africa, Australia), which, coincides exactly with two separate definitions of the boundary - appearances of the ammonite Placenticeras bidorsatum and the belemnite Gonioteuthis granulataquadrata - and may also coincide with a third - entry of the planktic foraminiferan Globotruncana elevata. A comparison of evidence from upper Santonian and lower Campanian successions in widely separated regions allows us to place a series of important biostratigraphical markers in correct order. Defining the boundary at the extinction of M. testudinarius corresponds to a ⁸⁷Sr/⁸⁶Sr of 0.707479, and a small positive excursion in δ¹³C. The base of magnetochron 33R, generally considered to coincide with, or fall just above the base of the Campanian, is shown to lie within the upper Santonian Uintacrinus socialis Zone.     

Evaluating groundwater discharge to tidal rivers based on a Rn-222 time-series approach

The natural flux of groundwater into coastal water bodies has recently been shown to contribute significant quantities of nutrients and trace metals to the coastal ocean. Groundwater discharge and hyporheic exchange to estuaries and rivers, however, is frequently overlooked though it often carries a distinctly different chemical signature than surface waters. Most studies that attempt to quantify this input to rivers use multiple geochemical tracers. However, these studies are often limited in their spatial and temporal extents because of the labor-intensive nature of integrating multiple measurement techniques. We describe here a method of using a single tracer, ²²²Rn, to rapidly characterize groundwater discharge into tidally-influenced rivers and streams. In less than one week of fieldwork, we determined that of six streams that empty into the Indian River Lagoon (IRL), Florida, three (Eau Gallie River, Turkey Creek, and Main Canal) did not receive substantial groundwater inputs, one canal (C-25 Canal) was dominated by groundwater exchange, and the remaining two (Sebastian River system and Crane Creek) fell somewhere in between. For more detailed discharge assessments, we focused on the Sebastian River system, a stratified tidal river estuary, during a relatively dry period (June) and a wet period (July) in 2008. Using time-series ²²²Rn and current velocity measurements we found that groundwater discharge into all three branches of the Sebastian River increased by 1–2 orders of magnitude during the wetter period. The estimated groundwater flow rates were higher than those reported into the adjacent IRL, suggesting that discharge into these rivers can be more important than direct discharge into the IRL. The techniques employed here should work equally well in other river/stream systems that experience significant groundwater discharge. Such assessments would allow area managers to quickly assess the distribution and magnitude of groundwater discharge nature into rivers over large spatial ranges.     

Electron Microprobe/SIMS Determinations of Al in Olivine: Applications to Solar Wind,Pallasites and Trace Element Measurements

Electron probe microanalyser measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~ 100 µg g^?1 level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimise electron beam current density, a rastered 50 × 100 µm electron beam was adequate and minimised sensitivity to small Al‐rich contaminants. Reproducible analyses of eleven SIMS‐cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 µg g^?1. The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: Imilac, Eagle Station and Springwater. Our focus was on Al in olivine, but our technique could be refined to give accurate electron probe measurements for other contamination‐sensitive trace elements. For solar wind, it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio.     

Radon and radium isotopes as tracers of submarine groundwater discharge – Results from the Ubatuba,Brazil SGD assessment intercomparison

We determined groundwater flow rates shortly after the wet season into an embayment near Ubatuba, Brazil as part of an international intercomparison experiment for submarine groundwater discharge (SGD) assessment techniques. Our estimated rates were determined by the combined use of continuous radon measurements and assessment of radium isotope patterns. The spatial distribution of the short-lived radium isotopes (²²³Ra and ²²⁴Ra) provided the means for independent evaluations of radon losses by mixing and atmospheric evasion. We were thus able to construct a well-constrained mass balance for radon that included a groundwater flux term. Our results showed that the groundwater discharge into this embayment from the fractured crystalline rock aquifer is not steady-state but varies with tidal modulation and rain-induced forcing. Tidally modulated and rain-induced flow rates were comparable during this period. The SGD rates estimated from radon ranged from 1 cm/day to 29 cm/day (cm³/cm² day) with a mean and standard deviation of 13 ± 6 cm/day. These estimates were mostly similar to a dye-dilution automatic seepage meter (15 ± 19 cm/day) and were within the broad ranges estimated by manual and continuous heat seepage meters but lower than indicated by an artificial tracer test performed nearshore.     

Enhanced production of stratospheric OH from methane oxidation at elevated reactive chlorine levels in northern midlatitudes

Examination of odd-hydrogen production and loss processes in the lower stratosphere reveals that the large abundances of midlatitude ClO recently measured requires a reassessment of the OH yield from methane oxidation due to a more rapid initiation of the methane oxidation sequence by atomic chlorine. Using a steady state calculation for OH and an iterative procedure for evaluating odd-hydrogen production from the methane oxidation sequence, we demonstrate that both OH and reactive chlorine are amplified below 25 km. The amplified values of OH and ClO are found to be consistent with recent measurements of ClO concentrations and of OH column abundances.