USGS ScienceSearch

Geology topics

Joseph N. Ryan

Publications and source records attributed to Joseph N. Ryan.

29 records · Page 2Linked to original sources

Effects of humic substances on precipitation and aggregation of zinc sulfide nanoparticles

Nanoparticulate metal sulfides such as ZnS can influence the transport and bioavailability of pollutant metals in anaerobic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences the stability of zinc sulfide nanoparticles as they nucleate and aggregate in water with dissolved NOM. We compared NOM fractions that were isolated from several surface waters and represented a range of characteristics including molecular weight, type of carbon, and ligand density. Dynamic light scattering was employed to monitor the growth and aggregation of Zn−S−NOM nanoparticles in supersaturated solutions containing dissolved aquatic humic substances. The NOM was observed to reduce particle growth rates, depending on solution variables such as type and concentration of NOM, monovalent electrolyte concentration, and pH. The rates of growth increased with increasing ionic strength, indicating that observed growth rates primarily represented aggregation of charged Zn−S−NOM particles. Furthermore, the observed rates decreased with increasing molecular weight and aromatic content of the NOM fractions, while carboxylate and reduced sulfur content had little effect. Differences between NOM were likely due to properties that increased electrosteric hindrances for aggregation. Overall, results of this study suggest that the composition and source of NOM are key factors that contribute to the stabilization and persistence of zinc sulfide nanoparticles in the aquatic environment.

Environmental Science & Technology

Methods for evaluating in-stream attenuation of trace organic compounds

Wastewater treatment plants are often the most substantial contributor of trace organic compounds including pharmaceuticals, steroidal hormones, and surfactants to surface waters. Studying stream reaches below wastewater treatment plants provide valuable information on the environmental persistence of these compounds. Three methods for conducting field investigations to evaluate in-stream attenuation of trace organic compounds are presented: (1) using intrinsic tracers in wastewater, (2) environmental sampling coupled with dye studies to assess travel times between sample locations, and (3) Lagrangian sampling. Advantages and limitations of each method are discussed, along with key findings from several investigations.

Applied Geochemistry

Pathogen and chemical transport in the karst limestone of the Biscayne aquifer: 3. Use of microspheres to estimate the transport potential of Cryptosporidium parvum oocysts

The vulnerability of a municipal well in the Northwest well field in southeastern Florida to potential contamination by Cryptosporidium parvum oocysts was assessed in a large‐scale, forced‐gradient (convergent) injection and recovery test. The field study involved a simultaneous pulse introduction of a nonreactive tracer (SF 6 , an inert gas) and oocyst‐sized (1.6, 2.9, and 4.9 μ m diameter) carboxylated polystyrene microspheres into karst limestone of the Biscayne aquifer characterized by a complex triple (matrix, touching‐vug, and conduit) porosity. Fractional recoveries 97 m down gradient were inversely related to diameter and ranged from 2.9% for the 4.9 μ m microspheres to 5.8% for 1.6 μ m microspheres. Their centers of mass arrived at the pumping well approximately threefold earlier than that of the nonreactive tracer SF 6 (gas), underscoring the need for use of colloid tracers and field‐scale tracer tests for these kinds of evaluations. In a modified triaxial cell using near in situ chemical conditions, 2.9 and 4.9 μ m microspheres underestimated by fourfold to sixfold the attachment potential of the less electronegative 2.9–4.1 μ m oocysts in the matrix porosity of limestone core samples. The field and laboratory results collectively suggested that it may take 200–300 m of transport to ensure even a 1‐log unit removal of oocysts, even though the limestone surfaces exhibited a substantive capability for their sorptive removal. The study further demonstrated the utility of microspheres as oocyst surrogates in field‐scale assessments of well vulnerability in limestone, provided that differences in attachment behaviors between oocysts and microspheres are taken into account.

Water Resources Research

A critical review of three methods used for the measurement of mercury (Hg2+)-dissolved organic matter stability constants

Three experimental techniques - ion exchange, liquid-liquid extraction with competitive ligand exchange, and solid-phase extraction with competitive ligand exchange (CLE-SPE) - were evaluated as methods for determining conditional stability constants (K) for the binding of mercury (Hg2+) to dissolved organic matter (DOM). To determine the utility of a given method to measure stability constants at environmentally relevant experimental conditions, experimental results should meet three criteria: (1) the data must be experimentally valid, in that they were acquired under conditions that meet all the requirements of the experimental method, (2) the Hg:DOM ratio should be determined and it should fall within levels that are consistent with environmental conditions, and (3) the stability constants must fall within the detection window of the method. The ion exchange method was found to be limited by its detection window, which constrains the method to stability constants with log K values less than about 14. The liquid-liquid extraction method was found to be complicated by the ability of Hg-DOM complexes to partition into the organic phase. The CLE-SPE method was found to be the most suitable of these methods for the measurement of Hg-DOM stability constants. Stability constants for DOM isolates measured using the CLE-SPE method at environmentally relevant Hg:DOM ratios were log K = 25-30 (M-1). These values are consistent with the strong Hg2+ binding expected for reduced S-containing binding sites.

Applied Geochemistry

Sampling colloids and colloid-associated contaminants in ground water

It has recently been recognized that mobile colloids may affect the transport of contaminants in ground water. To determine the significance of this process, knowledge of both the total mobile load (dissolved + colloid-associated) and the dissolved concentration of a ground-water contaminant must be obtained. Additional information regarding mobile colloid characteristics and concentrations are required to predict accurately the fate and effects of contaminants at sites where significant quantities of colloids are found. To obtain this information, a sampling scheme has been designed and refined to collect mobile colloids while avoiding the inclusion of normally immobile subsurface and well-derived solids. The effectiveness of this sampling protocol was evaluated at a number of contaminated and pristine sites. The sampling results indicated that slow, prolonged pumping of ground water is much more effective at obtaining ground-water samples that represent in situ colloid populations than bailing. Bailed samples from a coal tar-contaminated site contained 10–100 times greater colloid concentrations and up to 750 times greater polycyclic aromatic hydrocarbon concentrations as were detected in slowly pumped samples. The sampling results also indicated that ground-water colloid concentrations should be monitored in the field to determine the adequacy of purging if colloid and colloid-associated contaminants are of interest. To avoid changes in the natural ground-water colloid population through precipitation or coagulation, in situ ground-water chemistry conditions must be preserved during sampling and storage. Samples collected for determination of the total mobile load of colloids and low-solubility contaminants must not be filtered because some mobile colloids are removed by this process. Finally, suggestions that mobile colloids are present in ground water at any particular site should be corroborated with auxiliary data, such as colloid levels in “background” wells, colloid-size distributions, ground-water geochemistry, and colloid surface characteristics.

Connecticut, Delaware, Massachusetts, Nevada, New

Conservative and reactive solute transport in constructed wetlands

The transport of bromide, a conservative tracer, and rhodamine WT (RWT), a photodegrading tracer, was evaluated in three wastewater‐dependent wetlands near Phoenix, Arizona, using a solute transport model with transient storage. Coupled sodium bromide and RWT tracer tests were performed to establish conservative transport and reactive parameters in constructed wetlands with water losses ranging from (1) relatively impermeable (15%), (2) moderately leaky (45%), and (3) significantly leaky (76%). RWT first‐order photolysis rates and sorption coefficients were determined from independent field and laboratory experiments. Individual wetland hydraulic profiles influenced the extent of transient storage interaction in stagnant water areas and consequently RWT removal. Solute mixing and transient storage interaction occurred in the impermeable wetland, resulting in 21% RWT mass loss from main channel and storage zone photolysis (10%) and sorption (11%) reactions. Advection and dispersion governed solute transport in the leaky wetland, limiting RWT photolysis removal (1.2%) and favoring main channel sorption (3.6%). The moderately leaky wetland contained islands parallel to flow, producing channel flow and minimizing RWT losses (1.6%).

Water Resources Research

Use of PRD1 bacteriophage in groundwater viral transport, inactivation, and attachment studies

PRD1, an icosahedra-shaped, 62 nm (diameter), double-stranded DNA bacteriophage with an internal membrane, has emerged as an important model virus for studying the manner in which microorganisms are transported through a variety of groundwater environments. The popularity of this phage for use in transport studies involving geologic media is due, in part, to its relative stability over a range of temperatures and low degree of attachment in aquifer sediments. Laboratory and field investigations employing PRD1 are leading to a better understanding of viral attachment and transport behaviors in saturated geologic media and to improved methods for describing mathematically subsurface microbial transport at environmentally significant field scales. Radioisotopic labeling of PRD1 is facilitating additional information about the nature of viral interactions with solid surfaces in geologic media, the importance of iron oxide surfaces, and allowing differentiation between inactivation and attachment in field-scale tracer tests.

FEMS Microbiology Ecology

Mobilization of natural colloids from an iron oxide-coated sand aquifer: Effect of pH and ionic strength

Field and laboratory column experiments were performed to assess the effect of elevated pH and reduced ionic strength on the mobilization of natural colloids in a ferric oxyhydroxide-coated aquifer sediment. The field experiments were conducted as natural gradient injections of groundwater amended by sodium hydroxide additions. The laboratory experiments were conducted in columns of undisturbed, oriented sediments and disturbed, disoriented sediments. In the field, the breakthrough of released colloids coincided with the pH pulse breakthrough and lagged the bromide tracer breakthrough. The breakthrough behavior suggested that the progress of the elevated pH front controlled the transport of the mobilized colloids. In the laboratory, about twice as much colloid release occurred in the disturbed sediments as in the undisturbed sediments. The field and laboratory experiments both showed that the total mass of colloid release increased with increasing pH until the concurrent increase in ionic strength limited release. A decrease in ionic strength did not mobilize significant amounts of colloids in the field. The amount of colloids released normalized to the mass of the sediments was similar for the field and the undisturbed laboratory experiments.

Environmental Science & Technology

Silica-coated titania and zirconia colloids for subsurface transport field experiments

Silica-coated titania (TiO 2 ) and zirconia (ZrO 2 ) colloids were synthesized in two sizes to provide easily traced mineral colloids for subsurface transport experiments. Electrophoretic mobility measurements showed that coating with silica imparted surface properties similar to pure silica to the titania and zirconia colloids. Measurements of steady electrophoretic mobility and size (by dynamic light scattering) over a 90-day period showed that the silica-coated colloids were stable to aggregation and loss of coating. A natural gradient field experiment conducted in an iron oxide-coated sand and gravel aquifer also showed that the surface properties of the silica-coated colloids were similar. Colloid transport was traced at μg L - 1 concentrations by inductively coupled plasma-atomic emission spectroscopy measurement of Ti and Zr in acidified samples.

Environmental Science & Technology

Determination of hydrologic pathways during snowmelt for alpine/subalpine basins, Rocky Mountain National Park, Colorado

Alpine/subalpine ecosystems in Rocky Mountain National Park may be sensitive to atmospherically derived acidic deposition. Two‐ and three‐component hydrograph separation analyses and correlation analyses were performed for six basins to provide insight into streamflow generation during snowmelt and to assess basin sensitivity to acidic deposition. Three‐component hydrograph separation results for five basins showed that streamflow contained from 42 to 57% direct snowmelt runoff, 37 to 54% subsurface water, and 4 to 13% direct rain runoff for the May through October 1994 study period. Subsurface contributions were 89% of total flow for the sixth basin. The reliability of hydrograph separation model assumptions was explored. Subsurface flow was positively correlated with the amount of surficial material in a basin and was negatively correlated with basin slope. Basins with extensive surficial material and shallow slopes are less susceptible to ecosystem changes due to acidic deposition than basins with less surficial material and steeper slopes. This study was initiated to expand the intensive hydrologic research that has been conducted in Loch Vale basin to a more regional scale.

Water Resources Research

Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca 2+ . Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13 C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pH pzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

Florida