Justina M. Burns

Methods for reactive oxygen species (ROS) detection in aqueous environments

This review summarizes direct and indirect analytical methods for the detection and quantification of the reactive oxygen species (ROS): 1O2, O2·−/HOO·, H2O2, HO·, and CO3·− in aqueous solution. Each section briefly describes the chemical properties of a specific ROS followed by a table (organized alphabetically by detection method, i.e., absorbance, chemiluminescence, etc.) summarizing the nature of the observable (associated analytical signal) for each method, limit of detection, application notes, and reaction of the probe molecule with the particular ROS.

Multivariate Examination of Fe(II)/Fe(III) Cycling and Consequent Hydroxyl Radical Generation

The introduction of Fe(II)(aq) into aerated solutions resulted in net Fe(II) oxidation with concomitant, rapid Fe(II)/Fe(IIII) cycling and concurrent generation of reactive oxygen species. The effect of mixtures of naturally occurring solutes on Fe(II)/Fe(III) cycling and the concurrent oxidation of dissolved organics is reported. The experimental strategy was based on a multivariate, microscale, high-throughput approach for evaluating the effect of covarying concentrations of bromide, iodide, Suwannee River natural organic matter (SRNOM), chloride, and total carbonate species. Superoxide and HO• were evaluated at the center point condition of the experimental design with selective scavengers (superoxide dismutase and benzoic acid). The rate of Fe(II) oxidation decreased in the presence of these scavengers, indicating it is a function of oxygen, superoxide, and HO•. HO• generated during Fe(II)/Fe(III) cycling was quantified with the selective probe 1,3-dicyanotetrachlorobenzene (DCTCB). Through the range of experimental conditions of this design, the ratio of the number of moles of HO• produced to the number of moles of Fe(II) consumed varied from 3 to 750, corresponding to approximately 10 to 2200 Fe(II)/Fe(III) cycles, respectively. The implications of these findings with respect to organic oxidation during the aeration of anoxic Fe(II) rich groundwaters are discussed.

The adsorption of saxitoxin to clays and sediments in fresh and saline waters

The adsorption of saxitoxin to Na- and Ca-montmorillonite, kaolin (crystalline and amorphous), kaolinite, Bread and Butter Creek sediment (an estuarine tidal creek), Gulf of Mexico sediment, and Santa Barbara Basin sediment in deionized water and 32 per thousand salinity simulated seawater (Instant Ocean) is reported. Adsorption was partially reversible for all cases and best described using a Freundlich isotherm. The corresponding Freundlich constants (K(F)) ranged from 8.83 x 10(3)micromol/kg to 6.76 x 10(4)micromol/kg for freshwater and 4.73 x 10(3)micromol/kg-1.11 x 10(4)micromol/kg for seawater. There is a positive linear correlation seen between the K(F) values and the cation-exchange capacity of the adsorbents. The release of saxitoxin from previously equilibrated adsorbents was determined in freshwater (0-18%) and seawater (4-53%).

Surface Charge Controls the Fate of Au Nanorods in Saline Estuaries

This work reports the distribution of negatively charged, gold core nanoparticles in a model marine estuary as a function of time. A single dose of purified polystyrene sulfonate (PSS)-coated gold nanorods was added to a series of three replicate estuarine mesocosms to emulate an abrupt nanoparticle release event to a tidal creek of a Spartina -dominated estuary. The mesocosms contained several phases that were monitored: seawater, natural sediments, mature cordgrass, juvenile northern quahog clam, mud snails, and grass shrimp. Aqueous nanorod concentrations rose rapidly upon initial dosing and then fell to stable levels over the course of approximately 50 h, after which they remained stable for the remainder of the experiment (41 days total). The concentration of nanorods rose in all other phases during the initial phase of the experiment; however, some organisms demonstrated depuration over extended periods of time (100+ h) before removal from the dosed tanks. Clams and biofilm samples were also removed from the contaminated tanks post-exposure to monitor their depuration in pristine seawater. The highest net uptake of gold (mass normalized) occurred in the biofilm phase during the first 24 h, after which it was stable (to the 95% level of confidence) throughout the remainder of the exposure experiment. The results are compared against a previous study of positively charged nanoparticles of the same size to parameterize the role of surface charge in determining nanoparticle fate in complex aquatic environments.

Adsorption of domoic acid to marine sediments and clays

Conditional solid-water distribution coefficients (K(d)) for the adsorption of domoic acid (DA) to a series of complex sediments and clays were determined in artificial seawater. K(d) ranged from 5.11 L g(-1) to 0.97 L g(-1), with a corresponding ranking of: kaolinite > Gulf of Mexico sediment > Santa Barbara Basin sediment > Bread and Butter Creek sediment > poorly crystallized kaolin > Ca-montmorillonite > Na-montmorillonite > well crystallized kaolin > diatomaceous earth. Adsorption correlated with the anion exchange capacity of the clays tested (R(2) = 0.98), but not the more structurally complex sediments. The effect of added transition metals (Fe(iii), Cu(ii), Al(iii)) and terrestrially derived dissolved organic matter (Suwannee River DOM, SRDOM) on DA adsorption to Na-montmorillonite, well crystallized kaolin, and Gulf of Mexico sediment, was also tested. The addition of transition metals led to increased adsorption to all surfaces by a factor of 2-7, presumably by enabling the adsorption of DA-metal complexes. SRDOM enhanced DA adsorption by a factor of approximately 2.5. The release of adsorbed DA from sediments was also examined. Under our conditions, adsorbed DA equilibrated with the overlying aqueous phase within minutes with approximately 50% release.

Short-Term Fe Cycling during Fe(II) Oxidation: Exploring Joint Oxidation and Precipitation with a Combinatorial System

The net oxidation of Fe(II)aq by dioxygen initiates a suite of reactions including the oxidation of multiple Fe(II) complexes, generation of secondary oxidants, Fe(III) reduction, and precipitation of insoluble products. This work reports application of a multifactorial strategy to describe the oxidation of Fe(II) under conditions that correspond to those found where Fe(II)-rich groundwaters mix rapidly with overlying oxygenated waters. Response surfaces were constructed describing the relationship of the net oxidation process with mixtures of the common ligands chloride (Cl-), bromide (Br-), total carbonate (CO3(2-)), Fe(II), and Suwannee River natural organic matter (SRNOM) at pH 8.00. Response surfaces were generated in the presence and absence of added phosphate, representing conditional end members corresponding to geographical locations where Fe(III) precipitation is respectively forced and unconstrained. Comparison of net Fe(II) oxidation rates in the presence and absence of phosphate then enabled resolution of the relative contributions of Fe(II) oxidation and Fe(III) reduction to the overall process. The differences between the two surfaces demonstrated the importance of Fe(II) regeneration on the rapid (min) time scale during net oxidation. The minimum Fe(II) concentration necessary to initiate measurable cycling is reported. The presence of reactive oxygen species was evaluated through the use of probes added to the center point condition of the experimental matrix. Analysis of the statistical significance of the Fe(II)-factor relationships demonstrated that over the conditional scale of the experiments complexation of Fe(II) by the selected ligands did not correlate to the experimental outcome.

Combinatorial Parameter Space As an Empirical Tool for Predicting Water Chemistry: Fe(II) Oxidation Across a Watershed.

Fe(II) oxidation kinetics in surface waters are a complex function of the concentration of several dissolved species that vary geographically and temporally across watersheds. This work reports an empirical, combinatorial investigation of Fe(II) oxidation that simultaneously evaluated these variations across the pH, Fe(II), PO₄³⁻, Cl⁻, Br(-), CO₃²⁻, and natural organic matter (NOM) axes. The work assayed the effects of independent and dependent variables through application of a novel experimental design that varied Fe(II), PO₄³⁻, Cl⁻, Br⁻, and CO₃²⁻ along the pH axis. Each factor was varied across concentration ranges corresponding to the natural variation between typical fresh and salt water. The system was designed to describe the oxidation of Fe(II) that occurs when Fe(II)-rich groundwaters are mixed rapidly with oxic overlaying waters as a result of tidal movement, bioturbation, dredging, and other mixing/resuspension events. Factors and interfactor interactions were statistically evaluated to determine their importance to Fe(II) oxidation at the 95% level of confidence. Significant factors were retained and used to construct predictive numerical models of Fe(II) oxidation rates. Two models (M1 and M2) were constructed to represent the conditional endmembers of unrestricted Fe cycling (M1) and restricted Fe cycling (due to forced precipitation of Fe(III), M2). The models were challenged to predict net Fe(II) oxidation rates across a watershed (the Congaree/Santee rivers, sampled at ten different locations in South Carolina). The models were generally capable of predicting Fe(II) oxidation rates to within the 95% confidence interval, although M2 consistently overpredicted the rate relative to M1. The minimum initial Fe(II) concentration needed to observe Fe cycling is estimated based on the model output.