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Geology topics

J. N. Ryan

Publications and source records attributed to J. N. Ryan.

14 recordsLinked to original sources
USGS2012

A new method of calculating electrical conductivity with applications to natural waters

A new method is presented for calculating the electrical conductivity of natural waters that is accurate over a large range of effective ionic strength (0.0004–0.7 mol kg −1 ), temperature (0–95 °C), pH (1–10), and conductivity (30–70,000 μS cm −1 ). The method incorporates a reliable set of equations to calculate the ionic molal conductivities of cations and anions (H + , Li + , Na + , K + , Cs + , NH 4 + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , F − , Cl − , Br − , SO 4 2- , HCO 3 - , CO 3 2- , NO 3 - , and OH − ), environmentally important trace metals (Al 3+ , Cu 2+ , Fe 2+ , Fe 3+ , Mn 2+ , and Zn 2+ ), and ion pairs (HSO 4 - , NaSO 4 - , NaCO 3 - , and ). These equations are based on new electrical conductivity measurements for electrolytes found in a wide range of natural waters. In addition, the method is coupled to a geochemical speciation model that is used to calculate the speciated concentrations required for accurate conductivity calculations. The method was thoroughly tested by calculating the conductivities of 1593 natural water samples and the mean difference between the calculated and measured conductivities was −0.7 ± 5%. Many of the samples tested were selected to determine the limits of the method and include acid mine waters, geothermal waters, seawater, dilute mountain waters, and river water impacted by municipal waste water. Transport numbers were calculated and H + , Na + , Ca 2+ , Mg 2+ , NH 4 + , K + , Cl − , SO 4 2- , HCO 3 - , CP 3 2- , F − , Al 3+ , Fe 2+ , NO 3 - , and substantially contributed (>10%) to the conductivity of at least one of the samples. Conductivity imbalance in conjunction with charge imbalance can be used to identify whether a cation or an anion measurement is likely in error, thereby providing an additional quality assurance/quality control constraint on water analyses.

Geochimica et Cosmochimica Acta↗
USGS2011

Metallothionein-like multinuclear clusters of mercury(II) and sulfur in peat

Strong mercury(II)–sulfur (Hg-SR) bonds in natural organic matter, which influence mercury bioavailability, are difficult to characterize. We report evidence for two new Hg-SR structures using X-ray absorption spectroscopy in peats from the Florida Everglades with added Hg. The first, observed at a mole ratio of organic reduced S to Hg (S red /Hg) between 220 and 1140, is a Hg 4 S x type of cluster with each Hg atom bonded to two S atoms at 2.34 Å and one S at 2.53 Å, and all Hg atoms 4.12 Å apart. This model structure matches those of metal–thiolate clusters in metallothioneins, but not those of HgS minerals. The second, with one S atom at 2.34 Å and about six C atoms at 2.97 to 3.28 Å, occurred at S red /Hg between 0.80 and 4.3 and suggests Hg binding to a thiolated aromatic unit. The multinuclear Hg cluster indicates a strong binding environment to cysteinyl sulfur that might impede methylation. Along with a linear Hg(SR) 2 unit with Hg—S bond lengths of 2.34 Å at S red /Hg of about 10 to 20, the new structures support a continuum in Hg-SR binding strength in natural organic matter.

Environmental Science & Technology↗
USGS2010

Influence of organic matter on the transport of Cryptosporidium parvum oocysts in a ferric oxyhydroxide-coated quartz sand saturated porous medium

To assess the effect of organic matter on the transport of Cryptosporidium parvum oocysts in a geochemically heterogeneous saturated porous medium, we measured the breakthrough and collision efficiencies of oocysts as a function of dissolved organic matter concentration in a flow-through column containing ferric oxyhydroxide-coated sand. We characterized the surface properties of the oocysts and ferric oxyhydroxide-coated sand using microelectrophoresis and streaming potential, respectively, and the amount of organic matter adsorbed on the ferric oxyhydroxide-coated sand as a function of the concentration of dissolved organic matter (a fulvic acid isolated from Florida Everglades water). The dissolved organic matter had no significant effect on the zeta potential of the oocysts. Low concentrations of dissolved organic matter were responsible for reversing the charge of the ferric oxyhydroxide-coated sand surface from positive to negative. The charge reversal and accumulation of negative charge on the ferric oxyhydroxide-coated sand led to increases in oocyst breakthrough and decreases in oocyst collision efficiency with increasing dissolved organic matter concentration. The increase in dissolved organic matter concentration from 0 to 20 mg L -1 resulted in a two-fold decrease in the collision efficiency.

Water Research↗
USGS2005

Dissolution of cinnabar (HgS) in the presence of natural organic matter

Cinnabar (HgS) dissolution rates were measured in the presence of 12 different natural dissolved organic matter (DOM) isolates including humic, fulvic, and hydrophobic acid fractions. Initial dissolution rates varied by 1.3 orders of magnitude, from 2.31 × 10 −13 to 7.16 × 10 −12 mol Hg (mg C) −1 m −2 s −1 . Rates correlate positively with three DOM characteristics: specific ultraviolet absorbance (R 2 = 0.88), aromaticity (R 2 = 0.80), and molecular weight (R 2 = 0.76). Three experimental observations demonstrate that dissolution was controlled by the interaction of DOM with the cinnabar surface: (1) linear rates of Hg release with time, (2) significantly reduced rates when DOM was physically separated from the surface by dialysis membranes, and (3) rates that approached constant values at a specific ratio of DOM concentration to cinnabar surface area, suggesting a maximum surface coverage by dissolution-reactive DOM. Dissolution rates for the hydrophobic acid fractions correlate negatively with sorbed DOM concentrations, indicating the presence of a DOM component that reduced the surface area of cinnabar that can be dissolved. When two hydrophobic acid isolates that enhanced dissolution to different extents were mixed equally, a 20% reduction in rate occurred compared to the rate with the more dissolution-enhancing isolate alone. Rates in the presence of the more dissolution-enhancing isolate were reduced by as much as 60% when cinnabar was prereacted with the isolate that enhanced dissolution to a lesser extent. The data, taken together, imply that the property of DOM that enhances cinnabar dissolution is distinct from the property that causes it to sorb irreversibly to the cinnabar surface.

Geochimica et Cosmochimica Acta↗
USGS2004

Transport of Cryptosporidium oocysts in porous media: Role of straining and physicochemical filtration

The transport and filtration behavior of Cryptosporidium parvum oocysts in columns packed with quartz sand was systematically examined under repulsive electrostatic conditions. An increase in solution ionic strength resulted in greater oocyst deposition rates despite theoretical predictions of a significant electrostatic energy barrier to deposition. Relatively high deposition rates obtained with both oocysts and polystyrene latex particles of comparable size at low ionic strength (1 mM) suggest that a physical mechanism may play a key role in oocyst removal. Supporting experiments conducted with latex particles of varying sizes, under very low ionic strength conditions where physicochemical filtration is negligible, clearly indicated that physical straining is an important capture mechanism. The results of this study indicate that irregularity of sand grain shape (verified by SEM imaging) contributes considerably to the straining potential of the porous medium. Hence, both straining and physicochemical filtration are expected to control the removal of C. parvum oocysts in settings typical of riverbank filtration, soil infiltration, and slow sand filtration. Because classic colloid filtration theory does not account for removal by straining, these observations have important implications with respect to predictions of oocyst transport.

Environmental Science & Technology↗
USGS2004

Fate of volatile organic compounds in constructed wastewater treatment wetlands

The fate of volatile organic compounds was evaluated in a wastewater-dependent constructed wetland near Phoenix, AZ, using field measurements and solute transport modeling. Numerically based volatilization rates were determined using inverse modeling techniques and hydraulic parameters established by sodium bromide tracer experiments. Theoretical volatilization rates were calculated from the two-film method incorporating physicochemical properties and environmental conditions. Additional analyses were conducted using graphically determined volatilization rates based on field measurements. Transport (with first-order removal) simulations were performed using a range of volatilization rates and were evaluated with respect to field concentrations. The inverse and two-film reactive transport simulations demonstrated excellent agreement with measured concentrations for 1,4-dichlorobenzene, tetrachloroethene, dichloromethane, and trichloromethane and fair agreement for dibromochloromethane, bromodichloromethane, and toluene. Wetland removal efficiencies from inlet to outlet ranged from 63% to 87% for target compounds.

Environmental Science & Technology↗
USGS2003

Binding of mercury(II) to aquatic humic substances: Influence of pH and source of humic substances

Conditional distribution coefficients ( K DOM ‘) for Hg(II) binding to seven dissolved organic matter (DOM) isolates were measured at environmentally relevant ratios of Hg(II) to DOM. The results show that K DOM ‘ values for different types of samples (humic acids, fulvic acids, hydrophobic acids) isolated from diverse aquatic environments were all within 1 order of magnitude (10 22.5 ± 1.0 −10 23.5 ± 1.0 L kg - 1 ), suggesting similar Hg(II) binding environments, presumably involving thiol groups, for the different isolates. K DOM ‘ values decreased at low pHs (4) compared to values at pH 7, indicating proton competition for the strong Hg(II) binding sites. Chemical modeling of Hg(II)−DOM binding at different pH values was consistent with bidentate binding of Hg(II) by one thiol group (p K a = 10.3) and one other group (p K a = 6.3) in the DOM, which is in agreement with recent results on the structure of Hg(II)−DOM bonds obtained by extended X-ray absorption fine structure spectroscopy (EXAFS).

Environmental Science & Technology↗
USGS2003

Interactions between dissolved organic matter and mercury in the Florida Everglades

Experiments were conducted using organic matter isolated from various surface waters in the Florida Everglades to study the interactions between dissolved organic matter (DOM) and Hg (II). Conditional distribution coefficients ( ), obtained using an equilibriurn dialysis ligand exchange method, were strongly affected by the Hg/DOM concentration ratio. Very strong interactions ( = 10 L kg -1 ), indicative of Hg-thiol bonds, were observed at Hg/DOM ratios below approximately 1 g Hg per mg DOM. Above approximately 10 g Hg per mg DOM much lower values ( L kg -1 ) were obtained. DOM-Hg interactions were also studied by HgS (log K ) dissolution and precipitation experiments. In the dissolution experiments, a significant amount of Hg was released from cinnabar in the presence of DOM, suggesting strong interactions. Conversely, precipitation of HgS was strongly inhibited in the presence of low concentrations ( 3 mg C/L) of DOM. In both the dissolution and precipitation experiments, organic matter rich in aromatic moities was more reactive with HgS than less aromatic fractions and sulfur-containing model compounds. These results suggest that DOM can influence the geochemistry of inorganic complexes of Hg in the Everglades, especially HgS, by strong Hg-DOM binding and colloidal stabilization.

Florida↗
USGS2002

Binding of mercury(II) to dissolved organic matter: The role of the mercury-to-DOM concentration ratio

The binding of Hg(II) to dissolved organic matter (DOM; hydrophobic acids isolated from the Florida Everglades by XAD-8 resin) was measured at a wide range of Hg-to-DOM concentration ratios using an equilibrium dialysis ligand exchange method. Conditional distribution coefficients ( K DOM ‘) determined by this method were strongly affected by the Hg/DOM concentration ratio. At Hg/DOM ratios below approximately 1 μg of Hg/mg of DOM, we observed very strong interactions ( K DOM ‘ = 10 23.2 ± 1.0 L kg - 1 at pH = 7.0 and I = 0.1), indicative of mercury−thiol bonds. Hg/DOM ratios above approximately 10 μg of Hg/mg of DOM, as used in most studies that have determined Hg−DOM binding constants, gave much lower K DOM ‘ values (10 10.7 ± 1.0 L kg - 1 at pH = 4.9−5.6 and I = 0.1), consistent with Hg binding mainly to oxygen functional groups. These results suggest that the binding of Hg to DOM under natural conditions (very low Hg/DOM ratios) is controlled by a small fraction of DOM molecules containing a reactive thiol functional group. Therefore, Hg/DOM distribution coefficients used for modeling the biogeochemical behavior of Hg in natural systems need to be determined at low Hg/DOM ratios.

Environmental Science & Technology↗
USGS2001

Effect of basin physical characteristics on solute fluxes in nine alpine/subalpine basins, Colorado, USA

Alpine/subalpine basins may exhibit substantial variability in solute fluxes despite many apparent similarities in basin characteristics. An evaluation of controls on spatial patterns in solute fluxes may allow development of predictive tools for assessing basin sensitivity to outside perturbations such as climate change or deposition of atmospheric pollutants. Relationships between basin physical characteristics, determined from geographical information system (GIS) tools, and solute fluxes and mineral weathering rates were explored for nine alpine/subalpine basins in Rocky Mountain National Park, Colorado, using correlation analyses for 1993 and 1994 data. Stream-water nitrate fluxes were correlated positively with basin characteristics associated with the talus environment; i.e., the fractional amounts of steep slopes (??? 30??), unvegetated terrain and young debris (primarily Holocene till) in the basins, and were correlated negatively with fractional amounts of subalpine meadow terrain. Correlations with nitrate indicate the importance of the talus environment in promoting nitrate flux and the mitigating effect of areas with established vegetation, such as subalpine meadows. Total mineral weathering rates for the basins ranged from about 300 to 600 mol ha-1 year -1. Oligoclase weathering accounted for 30 to 73% of the total mineral weathering flux, and was positively correlated with the amount of old debris (primarily Pleistocene glacial till) in the basins. Although calcite is found in trace amounts in bedrock, calcite weathering accounted for up to 44% of the total mineral weathering flux. Calcite was strongly correlated with steep slope, unvegetated terrain, and young debris-probably because physical weathering in steep-gradient areas exposes fresh mineral surfaces that contain calcite for chemical weathering. Oligoclase and calcite weathering are the dominant sources of alkalinity in the basins. However, atmospherically deposited acids consume much of the alkalinity generated by weathering of calcite and other minerals in the talus environment. Published in 2001 by John Wiley and Sons, Ltd.

Hydrological Processes↗
USGS1999

Inhibition of precipitation and aggregation of metacinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

Precipitation and aggregation of metacinnabar (black HgS) was inhibited in the presence of low concentrations (≥3 mg C/L) of humic fractions of dissolved organic matter (DOM) isolated from the Florida Everglades. At low Hg concentrations (≤5 × 10 - 8 M), DOM prevented the precipitation of metacinnabar. At moderate Hg concentrations (5 × 10 - 5 M), DOM inhibited the aggregation of colloidal metacinnabar (Hg passed through a 0.1 μm filter but was removed by centrifugation). At Hg concentrations greater than 5 × 10 - 4 M, mercury formed solid metacinnabar particles that were removed from solution by a 0.1 μm filter. Organic matter rich in aromatic moieties was preferentially removed with the solid. Hydrophobic organic acids (humic and fulvic acids) inhibited aggregation better than hydrophilic organic acids. The presence of chloride, acetate, salicylate, EDTA, and cysteine did not inhibit the precipitation or aggregation of metacinnabar. Calcium enhanced metacinnabar aggregation even in the presence of DOM, but the magnitude of the effect was dependent on the concentrations of DOM, Hg, and Ca. Inhibition of metacinnabar precipitation appears to be a result of strong DOM-Hg binding. Prevention of aggregation of colloidal particles appears to be caused by adsorption of DOM and electrostatic repulsion.

Environmental Science & Technology↗
USGS1997

Transport and recovery of bacteriophage PRD1 in a sand and gravel aquifer: Effect of sewage-derived organic matter

To test the effects of sewage-derived organic matter on virus attachment, 32P-labeled bacteriophage PRD1, linear alkylbenzene sulfonates (LAS), and tracers were injected into sewage-contaminated (suboxic, elevated organic matter) and uncontaminated (oxic, low organic matter) zones of an iron oxide-coated quartz sand and gravel aquifer on Cape Cod, MA. In the uncontaminated zone, 83% of the PRD1 were attenuated over the first meter of transport by attachment to aquifer grains. In the contaminated zone, 42% of the PRD1 were attenuated over the first meter of transport. Sewage-derived organic matter contributed to the difference in PRD1 attenuation by blocking attachment sites in the contaminated zone. At greater distances down gradient (to a total transport distance of 3.6 m), a near-constant amount of PRD1 continued to break through, suggesting that aquifer grain heterogeneities allowed a small amount of reversible attachment. Injection of an LAS mixture (25 mg L-1), a common sewage constituent, remobilized 87% of the attached PRD1 in the contaminated zone, but only 2.2% in the uncontaminated zone. LAS adsorption promoted virus recovery in the contaminated zone by altering the PRD1-surface interactions; however, the amount of LAS adsorbed was not sufficient to promote release of the attached PRD1 in the uncontaminated zone.

Environmental Science & Technology↗
USGS1996

The reversibility of virus attachment to mineral surfaces

Virus transport through groundwater is limited by attachment to mineral surfaces and inactivation. Current virus transport models do not consider the implications of the reversibility of virus attachment to minerals. To explore the reversibility of virus attachment to mineral surfaces, we attached PRD1, a bacteriophage considered to be a good model of enteric viruses, to quartz and ferric oxyhydroxide-coated quartz surfaces over a range of pH values in equilibrium 'static columns'. Following attachment, we detached the viruses by replacing the pore solution with solutions of equal and higher pH. The extent of virus attachment followed an attachment 'edge' that occurred at a pH value about 2.5-3.5 pH units above the pH(IEP) of the mineral surfaces. Viruses attached below this edge were irreversibly attached until the pH of the detachment solution exceeded the pH value of the attachment edge. Viruses attached above this edge were reversibly attached. Derjaguin-Landau-Verwey-Overbeek (DEVO) potential energy calculations showed that the attachment edge occurred at the pH at which the potential energy of the primary minimum was near zero, implying that the position of the primary minimum (attractive or repulsive) controlled the equilibrium distribution of the viruses. The results suggest that the reversibility of virus attachment must be considered in virus transport models for accurate predictions of virus travel time.

Colloids and Surfaces A: Physicochemical and Engin↗