SEARCH · Geology Reports

Results for “Interfaces”

Search indexed USGS publications on groundwater, aquifers, geologic maps, mineral resources and earthquakes. Explore source records by subject and place.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6Linked to original sources

USGS2018

Microspatial ecotone dynamics at a shifting range limit: plant–soil variation across salt marsh–mangrove interfaces

Ecotone dynamics and shifting range limits can be used to advance our understanding of the ecological implications of future range expansions in response to climate change. In the northern Gulf of Mexico, the salt marsh–mangrove ecotone is an area where range limits and ecotone dynamics can be studied in tandem as recent decreases in winter temperature extremes have allowed for mangrove expansion at the expense of salt marsh. In this study, we assessed aboveground and belowground plant–soil dynamics across the salt marsh–mangrove ecotone quantifying micro-spatial patterns in horizontal extent. Specifically, we studied vegetation and rooting dynamics of large and small trees, the impact of salt marshes (e.g. species and structure) on mangroves, and the influence of vegetation on soil properties along transects from underneath the mangrove canopy into the surrounding salt marsh. Vegetation and rooting dynamics differed in horizontal reach, and there was a positive relationship between mangrove tree height and rooting extent. We found that the horizontal expansion of mangrove roots into salt marsh extended up to eight meters beyond the aboveground boundary. Variation in vegetation structure and local hydrology appear to control mangrove seedling dynamics. Finally, soil carbon density and organic matter did not differ within locations across the salt marsh-mangrove interface. By studying aboveground and belowground variation across the ecotone, we can better predict the ecological effects of continued range expansion in response to climate change.

Oecologia↗

USGS2015

Climate change and wildfire risk in an expanding wildland–urban interface: a case study from the Colorado Front Range Corridor

Context Wildfire is a particular concern in the wildland–urban interface (WUI) of the western United States where human development occurs close to flammable natural vegetation. Objectives (1) Assess the relative influences of WUI expansion versus climate-driven fire regime change on spatial and temporal patterns of burned WUI, and (2) determine whether WUI developed in the future will have higher or lower wildfire risk than existing WUI. Methods We projected the spatial pattern of the WUI and its associated wildfire risk from 2005 to 2050 at 90-m spatial resolution and 5-year intervals in Colorado Front Range using CHANGE, a landscape change model that simulates land cover and land use change, natural vegetation dynamics, and wildfire in a unified framework. A total of four scenarios from a factorial design with static versus changing WUI and static versus changing fire regimes were simulated to examine the effects of WUI expansion and climate-driven fire regime change on burned area in the WUI. Results Both WUI expansion and fire regime change contributed to the increase of burned WUI, but fire regime change had a stronger influence. The effects of WUI expansion and fire regime change had a combined influence greater than the sum of their individual effects. This interaction was a result of projected WUI expansion into regions of higher wildfire risk than existing WUI. Conclusions The human footprint will continue to expand into wildland areas and must be considered along with climate effects when assessing the impacts of changing fire regimes in future landscapes.

Landscape Ecology↗

USGS2024

Forest fire, thinning, and flood in wildland-urban interface: UAV and lidar-based estimate of natural disaster impacts

Context Wildland-urban interface (WUI) areas are facing increased forest fire risks and extreme precipitation events due to climate change, which can lead to post-fire flood events. The city of Flagstaff in northern Arizona, USA experienced WUI forest thinning, fire, and record rainfall events, which collectively contributed to large floods and damages to the urban neighborhoods and city infrastructure. Objectives We demonstrate multi-temporal, high resolution image applications from an unoccupied aerial vehicle (UAV) and terrestrial lidar in estimating landscape disturbance impacts within the WUI. Changes in forest vegetation and bare ground cover in WUIs are particularly challenging to estimate with coarse-resolution satellite images due to fine-scale landscape processes and changes that often result in mixed pixels. Methods Using Sentinel-2 satellite images, we document forest fire impacts and burn severity. Using 2016 and 2021 UAV multispectral images and Structure-from-Motion data, we estimate post-thinning changes in forest canopy cover, patch sizes, canopy height distribution, and bare ground cover. Using repeat lidar data within a smaller area of the watershed, we quantify geomorphic effects in the WUI associated with the fire and subsequent flooding. Results We document that thinning significantly reduced forest canopy cover, patch size, tree density, and mean canopy height resulting in substantially reduced active crown fire risks in the future. However, the thinning equipment ignited a forest fire, which burned the WUI at varying severity at the top of the watershed that drains into the city. Moderate-high severity burns occurred within 3 km of downtown Flagstaff threatening the WUI neighborhoods and the city. The upstream burned area then experienced 100-year and 200–500-year rainfall events, which resulted in large runoff-driven floods and sedimentation in the city. Conclusion We demonstrate that UAV high resolution images and photogrammetry combined with terrestrial lidar data provide detailed and accurate estimates of forest thinning and post-fire flood impacts, which could not be estimated from coarser-resolution satellite images. Communities around the world may need to prepare their WUIs for catastrophic fires and increase capacity to manage sediment-laden stormwater since both fires and extreme weather events are projected to increase.

Arizona↗

USGS1978

Possible fossil H2O liquid-ice interfaces in the Martian crust

Throughout the northern equatorial region of Mars, extensive areas have been uniformly stripped, roughly to a constant depth. These terrains vary widely in their relative ages. A model is described here to explain this phenomenon as reflecting the vertical distribution of H 2 O liquid and ice in the crust. Under present conditions the Martian equatorial regions are stratified in terms of the stability of water ice and liquid water. This arises because the temperature of the upper 1 or 2 km is below the melting point of ice and liquid is stable only at greater depth. It is suggested here that during planetary outgassing earlier in Martian history H 2 O was injected into the upper few kilometers of the crust by subsurface and surface volcanic eruption and lateral migration of the liquid and vapor. As a result, a discontinuity in the physical state of materials developed in the Martian crust coincident with the depth of H 2 O liquid-ice phase boundary. Material above the boundary remained pristine; material below underwent diagenetic alteration and cementation. Subsequently, sections of the ice-laden zone were erosionally stripped by processes including eolian deflation, gravitational slump and collapse, and fluvial transport due to geothermal heating and melting of the ice. The youngest plains which display this uniform stripping may provide a minimum stratigraphic age for the major period of outgassing of the planet. Viking results suggest that the total amount of H 2 O outgassed is less than half that required to fill the ice layer, hence any residual liquid eventually found itself in the upper permafrost zone or stored in the polar regions. Erosion stopped at the old liquid-ice interface due to increased resistance of subjacent material and/or because melting of ice was required to mobilize the debris. Water ice may remain in uneroded regions, the overburden of debris preventing its escape to the atmosphere. Numerous morphological examples shown in Viking and Mariner 9 images suggest interaction of impact, volcanic, and gravitational processes with the ice-laden layer. Finally, volcanic eruptions into ice produces a highly oxidized friable amorphous rock, palagonite. Based on spectral reflectance properties, these materials may provide the best analog to Martian surface materials. They are easily eroded, providing vast amounts of eolian debris, and have been suggested (Toulmin et al. , 1977) as possible source rocks for the materials observed at the Viking landing sites.

Icarus↗

USGS1986

A comparison of the coupled fresh water-salt water flow and the Ghyben-Herzberg sharp interface approaches to modeling of transient behavior in coastal aquifer systems

A quasi-three dimensional finite difference model which simulates coupled, fresh water and salt water flow, separated by a sharp interface, is used to investigate the effects of storage characteristics, transmissivity, boundary conditions and anisotropy on the transient responses of such flow systems. The magnitude and duration of the departure of aquifer response from the behavior predicted using the Ghyben-Herzberg, one-fluid approach is a function of the ease with which flow can be induced in the salt water region. In many common hydrogeologic settings short-term fresh water head responses, and transitional responses between short-term and long-term, can only be realistically reproduced by including the effects of salt water flow on the dynamics of coastal flow systems. The coupled fresh water-salt water flow modeling approach is able to reproduce the observed annual fresh water head response of the Waialae aquifer of southeastern Oahu, Hawaii.

Hawaii↗

USGS2018

Respiratory hazard assessment of combined exposure to complete gasoline exhaust and respirable volcanic ash in a multicellular human lung model at the air-liquid interface

Communities resident in urban areas located near active volcanoes can experience volcanic ash exposures during, and following, an eruption, in addition to sustained exposures to high concentrations of anthropogenic air pollutants ( e.g., vehicle exhaust emissions). Inhalation of anthropogenic pollution is known to cause the onset of, or exacerbate, respiratory and cardiovascular diseases. It is further postulated similar exposure to volcanic ash can also affect such disease states. Understanding of the impact of combined exposure of volcanic ash and anthropogenic pollution to human health, however, remains limited. The aim of this study was to assess the biological impact of combined exposure to respirable volcanic ash (from Soufrière Hills volcano (SHV), Montserrat and Chaitén volcano (ChV), Chile; representing different magmatic compositions and eruption styles) and freshly-generated complete exhaust from a gasoline vehicle. A multicellular human lung model (an epithelial cell-layer composed of A549 alveolar type II-like cells complemented with human blood monocyte-derived macrophages and dendritic cells cultured at the air-liquid interface) was exposed to diluted exhaust (1:10) continuously for 6 h, followed by immediate exposure to the ash as a dry powder (0.54 ± 0.19 μg/cm 2 and 0.39 ± 0.09 μg/cm 2 for SHV and ChV ash, respectively). After an 18 h incubation, cells were exposed again for 6 h to diluted exhaust, and a final 18 h incubation (at 37 °C and 5% CO 2 ). Cell cultures were then assessed for cytotoxic, oxidative stress and (pro-)inflammatory responses. Results indicate that, at all tested (sub-lethal) concentrations, co-exposures with both ash samples induced no significant expression of genes associated with oxidative stress ( HMOX1, NQO1 ) or production of (pro-)inflammatory markers (IL-1β, IL-8, TNF-α) at the gene and protein levels. In summary, considering the employed experimental conditions, combined exposure of volcanic ash and gasoline vehicle exhaust has a limited short-term biological impact to an advanced lung cell in vitro model.

Environmental Pollution↗

USGS2013

Parallelization of a hydrological model using the message passing interface

With the increasing knowledge about the natural processes, hydrological models such as the Soil and Water Assessment Tool (SWAT) are becoming larger and more complex with increasing computation time. Additionally, other procedures such as model calibration, which may require thousands of model iterations, can increase running time and thus further reduce rapid modeling and analysis. Using the widely-applied SWAT as an example, this study demonstrates how to parallelize a serial hydrological model in a Windows® environment using a parallel programing technology—Message Passing Interface (MPI). With a case study, we derived the optimal values for the two parameters (the number of processes and the corresponding percentage of work to be distributed to the master process) of the parallel SWAT (P-SWAT) on an ordinary personal computer and a work station. Our study indicates that model execution time can be reduced by 42%–70% (or a speedup of 1.74–3.36) using multiple processes (two to five) with a proper task-distribution scheme (between the master and slave processes). Although the computation time cost becomes lower with an increasing number of processes (from two to five), this enhancement becomes less due to the accompanied increase in demand for message passing procedures between the master and all slave processes. Our case study demonstrates that the P-SWAT with a five-process run may reach the maximum speedup, and the performance can be quite stable (fairly independent of a project size). Overall, the P-SWAT can help reduce the computation time substantially for an individual model run, manual and automatic calibration procedures, and optimization of best management practices. In particular, the parallelization method we used and the scheme for deriving the optimal parameters in this study can be valuable and easily applied to other hydrological or environmental models.

Environmental Modelling and Software↗

USGS2016

Parallelization of the TRIGRS model for rainfall-induced landslides using the message passing interface

We describe a parallel implementation of TRIGRS, the Transient Rainfall Infiltration and Grid-Based Regional Slope-Stability Model for the timing and distribution of rainfall-induced shallow landslides. We have parallelized the four time-demanding execution modes of TRIGRS, namely both the saturated and unsaturated model with finite and infinite soil depth options, within the Message Passing Interface framework. In addition to new features of the code, we outline details of the parallel implementation and show the performance gain with respect to the serial code. Results are obtained both on commercial hardware and on a high-performance multi-node machine, showing the different limits of applicability of the new code. We also discuss the implications for the application of the model on large-scale areas and as a tool for real-time landslide hazard monitoring.

Environmental Modelling and Software↗

USGS2016

High resolution mapping of development in the wildland-urban interface using object based image extraction

The wildland-urban interface (WUI), the area where human development encroaches on undeveloped land, is expanding throughout the western United States resulting in increased wildfire risk to homes and communities. Although census based mapping efforts have provided insights into the pattern of development and expansion of the WUI at regional and national scales, these approaches do not provide sufficient detail for fine-scale fire and emergency management planning, which requires maps of individual building locations. Although fine-scale maps of the WUI have been developed, they are often limited in their spatial extent, have unknown accuracies and biases, and are costly to update over time. In this paper we assess a semi-automated Object Based Image Analysis (OBIA) approach that utilizes 4-band multispectral National Aerial Image Program (NAIP) imagery for the detection of individual buildings within the WUI. We evaluate this approach by comparing the accuracy and overall quality of extracted buildings to a building footprint control dataset. In addition, we assessed the effects of buffer distance, topographic conditions, and building characteristics on the accuracy and quality of building extraction. The overall accuracy and quality of our approach was positively related to buffer distance, with accuracies ranging from 50 to 95% for buffer distances from 0 to 100 m. Our results also indicate that building detection was sensitive to building size, with smaller outbuildings (footprints less than 75 m 2 ) having detection rates below 80% and larger residential buildings having detection rates above 90%. These findings demonstrate that this approach can successfully identify buildings in the WUI in diverse landscapes while achieving high accuracies at buffer distances appropriate for most fire management applications while overcoming cost and time constraints associated with traditional approaches. This study is unique in that it evaluates the ability of an OBIA approach to extract highly detailed data on building locations in a WUI setting.

Colorado↗

USGS2020

Sequential biodegradation of 1,2,4-trichlorobenzene at oxic-anoxic groundwater interfaces in model laboratory columns

Halogenated organic solvents such as chlorobenzenes (CBs) are frequent groundwater contaminants due to legacy spills. When contaminated anaerobic groundwater discharges into surface water through wetlands and other transition zones, aeration can occur from various physical and biological processes at shallow depths, resulting in oxic-anoxic interfaces (OAIs). This study investigated the potential for 1,2,4-trichlorobenzene (1,2,4-TCB) biodegradation at OAIs. A novel upflow column system was developed to create stable anaerobic and aerobic zones, simulating a natural groundwater OAI. Two columns containing (1) sand and (2) a mixture of wetland sediment and sand were operated continuously for 295 days with varied doses of 0.14-1.4 mM sodium lactate (NaLac) as a model electron donor. Both column matrices supported anaerobic reductive dechlorination and aerobic degradation of 1,2,4-TCB spatially separated between anaerobic and aerobic zones. Reductive dechlorination produced a mixture of di- and monochlorobenzene daughter products, with estimated zero-order dechlorination rates up to 31.3 µM/hr. Aerobic CB degradation, limited by available dissolved oxygen, occurred for 1,2,4-TCB and all dechlorinated daughter products. Initial reductive dechlorination did not enhance the overall observed extent or rate of subsequent aerobic CB degradation. Increasing NaLac dose increased the extent of reductive dechlorination, but suppressed aerobic CB degradation at 1.4 mM NaLac due to increased oxygen demand. 16S-rRNA sequencing of biofilm microbial communities revealed strong stratification of functional anaerobic and aerobic organisms between redox zones including the sole putative reductive dechlorinator detected in the columns, Dehalobacter. The sediment mixture column supported enhanced reductive dechlorination compared to the sand column at all tested NaLac doses and growth of Dehalobacter populations up to 4.1×108 copies/g (51% relative abundance), highlighting the potential benefit of sediments in reductive dechlorination processes. Results from these model systems suggest both substantial anaerobic and aerobic CB degradation can co-occur along the OAI at contaminated sites where bioavailable electron donors and oxygen are both present.

Journal of Contaminant Hydrology↗

USGS2012

An exploratory investigation of the landscape-lake interface: Land cover controls over consumer N and C isotopic composition in Lake Michigan rivermouths

Rivermouth ecosystems are areas where tributary waters mix with lentic near-shore waters and provide habitat for many Laurentian Great Lakes fish and wildlife species. Rivermouths are the interface between terrestrial activities that influence rivers and the ecologically important nearshore. Stable isotopes of nitrogen (N) and carbon (C) in consumers were measured from a range of rivermouths systems to address two questions: 1) What is the effect of rivermouth ecosystems and land cover on the isotopic composition of N available to rivermouth consumers? 2) Are rivermouth consumers composed of lake-like or river-like C? For question 1, data suggest that strong relationships between watershed agriculture and consumer N are weakened or eliminated at the rivermouth, in favor of stronger relationships between consumer N and depositional areas that may favor denitrification. For question 2, despite apparently large riverine inputs, consumers only occasionally appear river-like. More often consumers seem to incorporate large amounts of C from either the nearshore or primary production within the rivermouth itself. Rivermouths appear to be active C and N processing environments, thus necessitating their explicit incorporation into models estimating nearshore loading and possibly contributing to their importance to Great Lakes biota.

Lake Michigan↗

USGS2009

Effects of sediment transport and seepage direction on hydraulic properties at the sediment-water interface of hyporheic settings

Relations between seepage flux and hydraulic properties are difficult to quantify in fluvial settings because of the difficulty in measuring these variables in situ. Tests conducted in a 1.5-m diameter by 1.5-m tall sediment-filled tank indicate that hydraulic gradient increased and hydraulic conductivity (K) decreased following the onset of downward seepage but both parameters were little changed following the onset of upward seepage. Reductions in K during downward seepage were more pronounced when surface-water current was sufficient to mobilize sediment on the bed. Averaged ratios of K determined during upward seepage to K determined during downward seepage (K up /K down ) through a sand-and-gravel bed increased from 1.4 to 1.7 with increasing surface-water velocity, and decreased to slightly greater than 1 when the sediment bed became fully mobile. K up /K down for tests conducted with a silt veneer on the bed surface was greater than 2 for all but the fastest surface-water velocities. Substantial reductions in K also were associated with a silt floc that formed on the bed surface during and following test runs. Although the silt floc was typically less than 0.5 mm in thickness, most of the hydraulic gradient was distributed across this thin layer. K of the thin silt floc was reduced by two to three orders of magnitude relative to the underlying sediment. Directional bias in K and relation between K and surface-water velocity require the presence or absence of a layer of lower-K sediment at or near the bed surface, without which no reduction in K and corresponding increase in hydraulic gradient can occur at the bed surface. The lack of prior observation of the consistent bias in K associated with seepage direction is somewhat surprising given the numerous studies where K has been measured in fluvial settings, but may be explained by the small value of the bias relative to the typical uncertainty associated with field determinations of K. If shown to exist in field settings, this bias and its relation to fluvial processes will be relevant to many studies conducted in hyporheic settings that require determination of fluxes across the sediment-water interface.

Journal of Hydrology↗

USGS2010

Transmission and reassortment of avian influenza viruses at the Asian-North American interface

Twenty avian influenza viruses were isolated from seven wild migratory bird species sampled at St. Lawrence Island, Alaska. We tested predictions based on previous phylogenetic analyses of avian influenza viruses that support spatially dependent trans-hemispheric gene flow and frequent interspecies transmission at a location situated at the Asian–North American interface. Through the application of phylogenetic and genotypic approaches, our data support functional dilution by distance of trans-hemispheric reassortants and interspecific virus transmission. Our study confirms infection of divergent avian taxa with nearly identical avian influenza strains in the wild. Findings also suggest that H16N3 viruses may contain gene segments with unique phylogenetic positions and that further investigation of how host specificity may impact transmission of H13 and H16 viruses is warranted.

Alaska↗

USGS2002

Transport of suspended solids from a karstic to an alluvial aquifer: The role of the karst/alluvium interface

This study focuses on the coupled transport of dissolved constituents and particulates, from their infiltration on a karst plateau to their discharge from a karst spring and their arrival at a well in an alluvial plain. Particulate markers were identified and the transport of solids was characterised in situ in porous and karstic media, based on particle size analyses, SEM, and traces. Transport from the sinkhole to the spring appeared to be dominated by flow through karst: particulate transport was apparently conservative between the two sites, and there was little difference in the overall character of the particle size distribution of the particulates infiltrating the sinkhole and of those discharging from the spring. Qualitatively, the mineralogy of the infiltrating and discharging material was similar, although at the spring an autochthonous contribution from the aquifer was noted (chalk particles eroded from the parent rock by weathering). In contrast, transport between the spring and the well appears to be affected by the overlying alluvium: particles in the water from the well, showed evidence of considerable size-sorting. Additionally, SEM images of the well samples showed the presence of particles originating from the overlying alluvial system; these particles were not found in samples from the sinkhole or the spring. The differences between the particulates discharging from the spring and the well indicate that the water pumped from the alluvial plain is coming from the karst aquifer via the very transmissive, complex geologic interface between the underlying chalk formation and the gravel at the base of the overlying alluvial system. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Hydrology↗

USGS2026

Widespread occurrence of Magnéli phases in wildland-urban interface fire ashes

The increasing activity of wildland–urban interface (WUI) fires has raised concerns regarding the potential environmental and human health impacts of residual ash remaining after burning. In this study, we investigated the concentration and speciation of titanium in WUI fire ash. Total titanium concentrations in WUI fire ash ranged from 0.53 to 80 g kg –1 . Synchrotron-based macro- and microscale X-ray absorption near-edge structure (XANES and μXANES, respectively) spectroscopy were used to quantify the relative abundance of major Ti phases in the fire ash, and the results were corroborated by high resolution-transmission electron microscopy (HR-TEM) measurements. Rutile (α-TiO 2 ), anatase (β-TiO 2 ), ilmenite (FeTiO 3 ), and titanium(III) oxide (Ti 2 O 3 ) were detected in all 20 ashes investigated by XANES and accounted for 0.26–0.83, 0.19–0.83, 0.33, and 0.17–0.72 of the spectral weight, respectively. Deeper analysis by μXANES of one sample demonstrated that Ti-bearing particles occurred as a mixture of rutile (α-TiO 2 ), anatase (β-TiO 2 ), ilmenite (FeTiO 3 ), and titanium(III) oxide Ti 2 O 3, with the absence of a pure Ti 2 O 3 phase. The presence of Ti 2 O 3 in the WUI fire ash is ascribed to the reduction of rutile and anatase to Magnéli titania (Ti n O 2 n– 1 , n = 4–9), which is estimated to be the dominant phase of titanium in the 20 WUI fire ashes investigated by XANES. The occurrence of Magnéli titania was corroborated by HR-TEM. Our findings demonstrate the impact of WUI fires on titanium speciation; fires convert titanium dioxides (e.g., rutile and anatase) to reduced titanium phases (e.g., Magnéli titania). Based on HR-TEM analyses, most of the titanium-bearing particles were less than 500 nm in size. Magnéli particles have been shown to be more toxic than rutile and anatase and have been linked to reduced lung function. Therefore, this study provides critical insights into the pollution characteristics and potential health risks of WUI fire ashes and associated particles, which are currently poorly understood.

California↗

USGS2003

Effects of dissolved carbonate on arsenate adsorption and surface speciation at the hematite-water interface

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite−water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [ P CO 2 = 10 - 3.5 atm and ∼0; CO 2 -free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L - 1 , [As(V)] 0 = 1.5 mM and I = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L - 1 , [As(V)] 0 = 0.5 mM and I = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems ( P CO 2 = 10 - 3.5 atm) than in the CO 2 -free argon system at pH 4−7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (≈2.8 Å) and bidentate binuclear (≈3.3 Å) bonding at pH 4.5−8 and loading levels of 0.46−3.10 μM m - 2 . Using the results of the pseudo-equilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the P CO 2 = 10 - 3.5 atm and the CO 2 -free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO 2 (g).

Environmental Science & Technology↗

USGS2005

Arsenate adsorption mechanisms at the allophane: Water interface

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As(V)] o from 50 to 1000 μM (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0−10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline Al−As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane−water interface are attributable to ligand exchange reactions between As(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H 2 PO 4 2 - and H 2 AsO 4 2 - ) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The inner-sphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments.

Environmental Science & Technology↗

USGS2004

Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

Environmental Science & Technology↗