Dr. Root is a geochemist with a research focus on molecular-scale mechanisms of biogeochemical cycling of trace metals and metalloids in the environment and mineral weathering reactions at the rock-water interface. He specializes in the use of synchrotron x- ray spectroscopic and microscopic techniques to determine metal(loid) speciaition from field and laboratory studies of metal(loid) mobilization into the environmental, sequestration/remediation, and bioaccessibility.
Journal of visualized experiments : JoVE, Sep 11, 2016
Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural l... more Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural landscapes can enhance the understanding of coupled Earth-system processes. Such knowledge is imperative in improving predictions of hydro-biogeochemical cycles, especially under climate change scenarios. We present an experimental method, designed to capture sub-surface heterogeneity of an initially homogeneous soil system. This method is based on destructive sampling of a soil lysimeter designed to simulate a small-scale hillslope. A weighing lysimeter of one cubic meter capacity was divided into sections (voxels) and was excavated layer-by-layer, with sub samples being collected from each voxel. The excavation procedure was aimed at detecting the incipient heterogeneity of the system by focusing on the spatial assessment of hydrological, geochemical, and microbiological properties of the soil. Representative results of a few physicochemical variables tested show the development of hete...
This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sedim... more This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sediments using examples from recent field studies that represent a range in oxidation-redox (redox) potential. As a ubiquitous trace element in sediments, As speciation and fate is linked to the abundance and biogeochemical behavior of the generally more abundant redox-active elements Fe, S, and Mn. All four elements are subject to oxidation, reduction, and pH-dependent processes such as sorption, desorption, precipitation, and dissolution, and which may include both biotic and abiotic reaction steps. We have used spectroscopic interrogation and geochemical modeling to characterize As speciation in subsurface sediments in several contrasting environments, including high and low S and Fe settings. Aquifers most at risk for contamination by As include those that are rich in organic matter and nutrients, stimulating high rates of microbial reduction and creating anoxic conditions, but limited i...
Naturally occurring elevated concentrations of arsenic in the runoff of the eastern Sierra Nevada... more Naturally occurring elevated concentrations of arsenic in the runoff of the eastern Sierra Nevada and feed waters of the Los Angeles Aqueduct are remediated by the Los Angeles Department of Power and Water (LADPW) up stream of the Haiwee Reservoir (Olancha, CA). To reduce total arsenic in drinking water supplies, the LADPW adds ferric chloride and a cationic polymer coagulant to the aqueduct. The treatment precipitates as an amorphous iron oxide, spectrally similar to 6-line ferrihydrite, that adsorbs and sequesters arsenic as arsenate. As the channeled flow enters North Haiwee Reservoir, the As(V)-enriched iron floc settles as sediments in the inlet channel. Buried As(V) is reduced to As(III) near the sediment-water interface (0-10cm), and only As(III) is observed at depths below the steep (1-2cm) near-surface redox gradient. Sediment samples from 30-cm push cores were collected from the edge of the reservoir along the inlet channel in tandem with in situ porewater measurements usi...
Mine tailings in semiarid regions are highly susceptible to erosion and are sources of dust pollu... more Mine tailings in semiarid regions are highly susceptible to erosion and are sources of dust pollution and potential avenues of human exposure to toxic metals. One constraint to revegetation of tailings by phytostabilization is the absence of microbial communities critical for biogeochemical cycling of plant nutrients. The objective of this study was to evaluate specific genes as in situ indicators of biological soil response during phytoremediation. The abundance and activity of 16S rRNA, nifH, and amoA were monitored during a nine month phytostabilization study using buffalo grass and quailbush grown in compost-amended, metalliferous tailings. The compost amendment provided a greater than 5-log increase in bacterial abundance, and survival of this compost-inoculum was more stable in planted treatments. Despite increased abundance, the activity of the introduced community was low, and significant increases were not detected until six and nine months in quailbush, and unplanted compo...
Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain un... more Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffracti...
High levels of arsenic are present in a site adjacent to San Francisco Bay (in East Palo Alto, CA... more High levels of arsenic are present in a site adjacent to San Francisco Bay (in East Palo Alto, CA) as a consequence of the activity of a former pesticide manufacturing plant. Most of the readily accessible arsenic at the site has been removed by remedial ...
Proceedings of the National Academy of Sciences, 2004
The chemical speciation of arsenic in sediments and porewaters of aquifers is the critical factor... more The chemical speciation of arsenic in sediments and porewaters of aquifers is the critical factor that determines whether dissolved arsenic accumulates to potentially toxic levels. Sequestration of arsenic in solid phases, which may occur by adsorption or precipitation processes, controls dissolved concentrations. We present synchrotron x-ray absorption spectra of arsenic in shallow aquifer sediments that indicate the local structure of realgar (AsS) as the primary arsenic-bearing phase in sulfate-reducing conditions at concentrations of 1–3 mmol·kg –1 , which has not previously been verified in sediments at low temperature. Spectroscopic evidence shows that arsenic does not substitute for iron or sulfur in iron sulfide minerals at the molecular scale. A general geochemical model derived from our field and spectroscopic observations show that the ratio of reactive iron to sulfur in the system controls the distribution of solid phases capable of removing arsenic from solution when co...
Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural l... more Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural landscapes can enhance the understanding of coupled Earth-system processes. Such knowledge is imperative in improving predictions of hydro-biogeochemical cycles, especially under climate change scenarios. We present an experimental method, designed to capture sub-surface heterogeneity of an initially homogeneous soil system. This method is based on destructive sampling of a soil lysimeter designed to simulate a small-scale hillslope. A weighing lysimeter of one cubic meter capacity was divided into sections (voxels) and was excavated layer-by-layer, with sub samples being collected from each voxel. The excavation procedure was aimed at detecting the incipient heterogeneity of the system by focusing on the spatial assessment of hydrological, geochemical, and microbiological properties of the soil. Representative results of a few physicochemical variables tested show the development of hete...
ABSTRACT Nano- to micron-scale particles of mixed-valent iron hydroxide, specifically green rust ... more ABSTRACT Nano- to micron-scale particles of mixed-valent iron hydroxide, specifically green rust (GR [FeII6- x(OH)y FeIIIx(OH)12-y]x+[Anionx- + H2O]x-), have been identified and studied as corrosion products of steel, and recently rediscovered in hydromorphic soils and sediments. Green rusts are intermediate phases produced by biotic and abiotic reductive dissolution of ferric oxyhydroxides, or by oxidation of dissolved ferrous iron. Adsorbed oxyanions can stabilize GR phases and inhibit the formation of thermodynamically favored iron phases such as magnetite or lepidocrocite in subsurface environments. This study used synchrotron XRD to characterize iron (hydr)oxide minerals precipitated from solution and subsequent aging products under different environmental conditions of pH and Eh. Here we show the in situ abiotic development of green rust and its stabilization by the addition of adsorbed oxyanions or alternatively, subsequent rapid transformation to magnetite or lepidocrocite in the absence of added anions. A closed batch reactor with an in-line capillary was used to expose the reaction products to continuous synchrotron radiation. Laue patterns were collected at time intervals of 3-5 minutes and used to detect the formation of crystalline iron (hydr)oxide minerals that precipitate as a function time and chemical perturbations to the system, i.e. changing the pH, redox potential, ratio of Fe2+ to OH- , and addition of an oxyanion, arsenate or phosphate. The reactions were monitored by observing the development of diagnostic green rust XRD d-spacing peak at 10.9 Å (300), the 3.29 Å (210) d- spacing for lepidocrocite, and the 2.53 Å (100) d-spacing for magnetite, with continuous in-line measurement of pH and ORP. We found that green rust was stabilized by the adsorption of arsenate and phosphate. In the presence of arsenate or phosphate at pH =7, green rust transformed to lepidocrocite after several hours when anoxic controls were removed. When pH and Eh were constant, GR did not transform to magnetite or lepidocrocite. However, without arsenate or phosphate, the transformation occurred in less than 1 hour. At pH > 7.5, green rust transformed to magnetite within 1 hour. In the presence of phosphate or arsenate, the transformation was retarded and took up to 8 hours. The rates of transformation and meta- stability of iron (hydr)oxide phases in natural redoximorphic sediments play important roles in the cycling of contaminants and nutrients.
Environmental contextThere is a growing need to understand how insensitive munitions compounds be... more Environmental contextThere is a growing need to understand how insensitive munitions compounds behave in natural environments, particularly in soils, where non-combusted residues accumulate. Here, we tested the ability of sulfate green rust, a naturally occurring mineral, to transform munitions compounds by reacting with the mineral surface. Our results show that both the munitions compounds and the mineral structures are transformed in an oxidation–reduction reaction that alters the compounds’ environmental fates. Abiotic transformation of contaminants by redox-active mineral surfaces plays an important role in the fate and behaviour of pollutants in soils and sediments. However, there is very little information on such transformations for the insensitive munitions compounds (IMCs), 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4-dinitroanisole (DNAN), developed in recent years to replace the traditional munition compounds in explosive mixtures. We tested the ability of sulfate green rus...
Journal of visualized experiments : JoVE, Sep 11, 2016
Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural l... more Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural landscapes can enhance the understanding of coupled Earth-system processes. Such knowledge is imperative in improving predictions of hydro-biogeochemical cycles, especially under climate change scenarios. We present an experimental method, designed to capture sub-surface heterogeneity of an initially homogeneous soil system. This method is based on destructive sampling of a soil lysimeter designed to simulate a small-scale hillslope. A weighing lysimeter of one cubic meter capacity was divided into sections (voxels) and was excavated layer-by-layer, with sub samples being collected from each voxel. The excavation procedure was aimed at detecting the incipient heterogeneity of the system by focusing on the spatial assessment of hydrological, geochemical, and microbiological properties of the soil. Representative results of a few physicochemical variables tested show the development of hete...
This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sedim... more This talk will review molecular mechanisms of As mobilization and attenuation in subsurface sediments using examples from recent field studies that represent a range in oxidation-redox (redox) potential. As a ubiquitous trace element in sediments, As speciation and fate is linked to the abundance and biogeochemical behavior of the generally more abundant redox-active elements Fe, S, and Mn. All four elements are subject to oxidation, reduction, and pH-dependent processes such as sorption, desorption, precipitation, and dissolution, and which may include both biotic and abiotic reaction steps. We have used spectroscopic interrogation and geochemical modeling to characterize As speciation in subsurface sediments in several contrasting environments, including high and low S and Fe settings. Aquifers most at risk for contamination by As include those that are rich in organic matter and nutrients, stimulating high rates of microbial reduction and creating anoxic conditions, but limited i...
Naturally occurring elevated concentrations of arsenic in the runoff of the eastern Sierra Nevada... more Naturally occurring elevated concentrations of arsenic in the runoff of the eastern Sierra Nevada and feed waters of the Los Angeles Aqueduct are remediated by the Los Angeles Department of Power and Water (LADPW) up stream of the Haiwee Reservoir (Olancha, CA). To reduce total arsenic in drinking water supplies, the LADPW adds ferric chloride and a cationic polymer coagulant to the aqueduct. The treatment precipitates as an amorphous iron oxide, spectrally similar to 6-line ferrihydrite, that adsorbs and sequesters arsenic as arsenate. As the channeled flow enters North Haiwee Reservoir, the As(V)-enriched iron floc settles as sediments in the inlet channel. Buried As(V) is reduced to As(III) near the sediment-water interface (0-10cm), and only As(III) is observed at depths below the steep (1-2cm) near-surface redox gradient. Sediment samples from 30-cm push cores were collected from the edge of the reservoir along the inlet channel in tandem with in situ porewater measurements usi...
Mine tailings in semiarid regions are highly susceptible to erosion and are sources of dust pollu... more Mine tailings in semiarid regions are highly susceptible to erosion and are sources of dust pollution and potential avenues of human exposure to toxic metals. One constraint to revegetation of tailings by phytostabilization is the absence of microbial communities critical for biogeochemical cycling of plant nutrients. The objective of this study was to evaluate specific genes as in situ indicators of biological soil response during phytoremediation. The abundance and activity of 16S rRNA, nifH, and amoA were monitored during a nine month phytostabilization study using buffalo grass and quailbush grown in compost-amended, metalliferous tailings. The compost amendment provided a greater than 5-log increase in bacterial abundance, and survival of this compost-inoculum was more stable in planted treatments. Despite increased abundance, the activity of the introduced community was low, and significant increases were not detected until six and nine months in quailbush, and unplanted compo...
Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain un... more Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffracti...
High levels of arsenic are present in a site adjacent to San Francisco Bay (in East Palo Alto, CA... more High levels of arsenic are present in a site adjacent to San Francisco Bay (in East Palo Alto, CA) as a consequence of the activity of a former pesticide manufacturing plant. Most of the readily accessible arsenic at the site has been removed by remedial ...
Proceedings of the National Academy of Sciences, 2004
The chemical speciation of arsenic in sediments and porewaters of aquifers is the critical factor... more The chemical speciation of arsenic in sediments and porewaters of aquifers is the critical factor that determines whether dissolved arsenic accumulates to potentially toxic levels. Sequestration of arsenic in solid phases, which may occur by adsorption or precipitation processes, controls dissolved concentrations. We present synchrotron x-ray absorption spectra of arsenic in shallow aquifer sediments that indicate the local structure of realgar (AsS) as the primary arsenic-bearing phase in sulfate-reducing conditions at concentrations of 1–3 mmol·kg –1 , which has not previously been verified in sediments at low temperature. Spectroscopic evidence shows that arsenic does not substitute for iron or sulfur in iron sulfide minerals at the molecular scale. A general geochemical model derived from our field and spectroscopic observations show that the ratio of reactive iron to sulfur in the system controls the distribution of solid phases capable of removing arsenic from solution when co...
Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural l... more Studying co-evolution of hydrological and biogeochemical processes in the subsurface of natural landscapes can enhance the understanding of coupled Earth-system processes. Such knowledge is imperative in improving predictions of hydro-biogeochemical cycles, especially under climate change scenarios. We present an experimental method, designed to capture sub-surface heterogeneity of an initially homogeneous soil system. This method is based on destructive sampling of a soil lysimeter designed to simulate a small-scale hillslope. A weighing lysimeter of one cubic meter capacity was divided into sections (voxels) and was excavated layer-by-layer, with sub samples being collected from each voxel. The excavation procedure was aimed at detecting the incipient heterogeneity of the system by focusing on the spatial assessment of hydrological, geochemical, and microbiological properties of the soil. Representative results of a few physicochemical variables tested show the development of hete...
ABSTRACT Nano- to micron-scale particles of mixed-valent iron hydroxide, specifically green rust ... more ABSTRACT Nano- to micron-scale particles of mixed-valent iron hydroxide, specifically green rust (GR [FeII6- x(OH)y FeIIIx(OH)12-y]x+[Anionx- + H2O]x-), have been identified and studied as corrosion products of steel, and recently rediscovered in hydromorphic soils and sediments. Green rusts are intermediate phases produced by biotic and abiotic reductive dissolution of ferric oxyhydroxides, or by oxidation of dissolved ferrous iron. Adsorbed oxyanions can stabilize GR phases and inhibit the formation of thermodynamically favored iron phases such as magnetite or lepidocrocite in subsurface environments. This study used synchrotron XRD to characterize iron (hydr)oxide minerals precipitated from solution and subsequent aging products under different environmental conditions of pH and Eh. Here we show the in situ abiotic development of green rust and its stabilization by the addition of adsorbed oxyanions or alternatively, subsequent rapid transformation to magnetite or lepidocrocite in the absence of added anions. A closed batch reactor with an in-line capillary was used to expose the reaction products to continuous synchrotron radiation. Laue patterns were collected at time intervals of 3-5 minutes and used to detect the formation of crystalline iron (hydr)oxide minerals that precipitate as a function time and chemical perturbations to the system, i.e. changing the pH, redox potential, ratio of Fe2+ to OH- , and addition of an oxyanion, arsenate or phosphate. The reactions were monitored by observing the development of diagnostic green rust XRD d-spacing peak at 10.9 Å (300), the 3.29 Å (210) d- spacing for lepidocrocite, and the 2.53 Å (100) d-spacing for magnetite, with continuous in-line measurement of pH and ORP. We found that green rust was stabilized by the adsorption of arsenate and phosphate. In the presence of arsenate or phosphate at pH =7, green rust transformed to lepidocrocite after several hours when anoxic controls were removed. When pH and Eh were constant, GR did not transform to magnetite or lepidocrocite. However, without arsenate or phosphate, the transformation occurred in less than 1 hour. At pH > 7.5, green rust transformed to magnetite within 1 hour. In the presence of phosphate or arsenate, the transformation was retarded and took up to 8 hours. The rates of transformation and meta- stability of iron (hydr)oxide phases in natural redoximorphic sediments play important roles in the cycling of contaminants and nutrients.
Environmental contextThere is a growing need to understand how insensitive munitions compounds be... more Environmental contextThere is a growing need to understand how insensitive munitions compounds behave in natural environments, particularly in soils, where non-combusted residues accumulate. Here, we tested the ability of sulfate green rust, a naturally occurring mineral, to transform munitions compounds by reacting with the mineral surface. Our results show that both the munitions compounds and the mineral structures are transformed in an oxidation–reduction reaction that alters the compounds’ environmental fates. Abiotic transformation of contaminants by redox-active mineral surfaces plays an important role in the fate and behaviour of pollutants in soils and sediments. However, there is very little information on such transformations for the insensitive munitions compounds (IMCs), 3-nitro-1,2,4-triazol-5-one (NTO) and 2,4-dinitroanisole (DNAN), developed in recent years to replace the traditional munition compounds in explosive mixtures. We tested the ability of sulfate green rus...
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