Arsenic is ubiquitous in soil and water environments and is consistently at the top of the Agency... more Arsenic is ubiquitous in soil and water environments and is consistently at the top of the Agency for Toxic Substances Disease Registry (ATSDR) substance priority list. It has been shown to induce toxicity even at low levels of exposure. One of the major routes of exposure to arsenic is through drinking water. This review presents current information related to the distribution of arsenic in the environment, the resultant impacts on human health, especially related to diabetes, which is one of the most prevalent chronic diseases, regulation of arsenic in drinking water, and approaches for treatment of arsenic in drinking water for both public utilities and private wells. Taken together, this information points out the existing challenges to understanding both the complex health impacts of arsenic and to implementing the treatment strategies needed to effectively reduce arsenic exposure at different scales.
Critical zone science seeks to develop mechanistic theories that describe critical zone structure... more Critical zone science seeks to develop mechanistic theories that describe critical zone structure, function, and long-term evolution. One postulate is that hydrogeochemical controls on critical zone evolution can be inferred from solute discharges measured down-gradient of reactive flow paths. These flow paths have variable lengths, interfacial compositions, and residence times, and their mixing is reflected in concentration-discharge (C-Q) relations. Motivation for this special section originates from a U.S. Critical Zone Observatories workshop that was held at the University of New Hampshire, 20-22 July 2015. The workshop focused on resolving mechanistic CZ controls over surface water chemical dynamics across the full range of lithogenic (e.g., nonhydrolyzing and hydrolyzing cations and oxyanions) and bioactive solutes (e.g., organic and inorganic forms of C, N, P, and S), including dissolved and colloidal species that may cooccur for a given element. Papers submitted to this special section on ''concentration-discharge relations in the critical zone'' include those from authors who attended the workshop, as well as others who responded to the open solicitation. Submissions were invited that utilized information pertaining to internal, integrated catchment function (relations between hydrology, biogeochemistry, and landscape structure) to help illuminate controls on observed C-Q relations. Plain Language Summary This article introduces the special section of Water Resources Research entitled ''Concentration-Discharge Relations in the Critical Zone''.
Decomposition of soil organic matter (SOM) can be stimulated by fresh organic matter input, a phe... more Decomposition of soil organic matter (SOM) can be stimulated by fresh organic matter input, a phenomenon known as the ‘priming effect’. Despite its global importance, the relationship of the priming effect to mineral weathering and nutrient release remains unclear. Here we show close linkages between mineral weathering in the critical zone and primed decomposition of SOM. Intensified mineral weathering and rock-derived nutrient release are generally coupled with primed SOM decomposition resulting from “triggered” microbial activity. Fluxes of organic matter products decomposed via priming are linearly correlated with weathering congruency. Weathering congruency influences the formation of organo-mineral associations, thereby modulating the accessibility of organic matter to microbial decomposers and, thus, the priming effect. Our study links weathering with primed SOM decomposition, which plays a key role in controlling soil C dynamics in space and time. These connections represent ...
Understanding the temporal effects of organic matter input and water influx on metal lability and... more Understanding the temporal effects of organic matter input and water influx on metal lability and translocation is critical to evaluate the success of the phytostabilization of metalliferous mine tailings. Trends of metal lability, e.g., V, Cr, Mn, Co, Ni, Cu, Zn, and Pb, were investigated for three years following a direct-planting phytostabilization trial at a Superfund mine tailings site in semi-arid central Arizona, USA. Unamended tailings were characterized by high concentrations (mmol kg−1) of Fe (2100), S (3100), As (41), Zn (39), and Pb (11), where As and Pb greatly exceeded non-residential soil remediation levels established by Arizona. Phytostabilization treatments included a no-compost control, 100 g kg−1 compost with seed, and 200 g kg−1 compost with and without seed to the top 20 cm of the tailings profile. All plots received supplemental irrigation, effectively doubling the mean annual precipitation. Tailings cores up to 90 cm were collected at the time of planting and...
Abiotic transformation of anthropogenic compounds by redox-active metal oxides affects contaminan... more Abiotic transformation of anthropogenic compounds by redox-active metal oxides affects contaminant fate in soil. The capacity of birnessite and ferrihydrite to oxidize the insensitive munitions compound, 2,4-dinitroanisol (DNAN), and its amine-containing daughter products, 2-methoxy-5-nitro aniline (MENA) and 2,4-diaminoanisole (DAAN), was studied in stirred reactors at controlled pH (7.0). Aqueous suspensions were reacted at metal oxide solid to solution mass ratios (SSR) of 0.15, 1.5 and 15 g kg and solutions were analyzed after 0-3 h by high performance liquid chromatography coupled with photodiode array or mass spectrometry detection. Results indicate that DNAN was resistant to oxidation by birnessite and ferrihydrite. Ferrihydrite did not oxidize MENA, but MENA was susceptible to rapid oxidation by birnessite, with nitrogen largely mineralized to nitrite. This is the first report on mineralization of nonphenolic aromatics and the release of mineralized N from aromatic amines fo...
Assessment of ecosystem services—the benefits society receives from ecosystems—can be improved by... more Assessment of ecosystem services—the benefits society receives from ecosystems—can be improved by including broader spatial and temporal scales of geosciences perspectives.
Environmental pollution (Barking, Essex : 1987), Jan 5, 2018
The emerging insensitive munitions compound (IMC) 3-nitro-1,2,4-triazole-5-one (NTO) is currently... more The emerging insensitive munitions compound (IMC) 3-nitro-1,2,4-triazole-5-one (NTO) is currently being used to replace conventional explosives such as 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), but the environmental fate of this increasingly widespread IMC remains poorly understood. Upon release from unexploded solid phase ordinances, NTO exhibits high aqueous solubility and, hence, potential mobilization to groundwater. Adsorption and abiotic transformation at metal oxide surfaces are possible mechanisms for natural attenuation. Here, the reactions at ferrihydrite and birnessite surfaces of NTO and its biotransformation product, 3-amino-1, 2, 4-triazol-5-one (ATO), were studied in stirred batch reactor systems at controlled pH (7.0). The study was carried out at metal oxide solid to solution ratios (SSR) of 0.15, 1.5 and 15 g kg. The samples were collected at various time intervals up to 3 h after reaction initiation, and analyzed using HPLC with photodiode array and mass spect...
Metal(loid)-contamination of the environment due to anthropogenic activities is a global problem.... more Metal(loid)-contamination of the environment due to anthropogenic activities is a global problem. Understanding the fate of contaminants requires elucidation of biotic and abiotic factors that influence metal(loid) speciation from molecular to field scales. Improved methods are needed to assess micro-scale processes, such as those occurring at biogeochemical interfaces between plant tissues, microbial cells, and metal(loid)s. Here we present an advanced method that combines fluorescence in situ hybridization (FISH) with synchrotron-based multiple-energy micro-focused X-ray fluorescence microprobe imaging (ME μXRF) to examine colocalization of bacteria and metal(loid)s on root surfaces of plants used to phytostabilize metalliferous mine tailings. Bacteria were visualized on a small root section using SytoBC nucleic acid stain and FISH probes targeting the domain Bacteria and a specific group (Alphaproteobacteria, Gammaproteobacteria, or Actinobacteria). The same root region was then ...
This study combined concentration-discharge analyses (filtration at 0.45 lm), cascade filtrations... more This study combined concentration-discharge analyses (filtration at 0.45 lm), cascade filtrations (at 1.2, 0.4, and 0.025 lm) and asymmetrical flow field flow fractionation (AF4) to probe the influence of colloidal carriers (dissolved organic matter and inorganic nanoparticles) on observed concentrationdischarge relationships for trace metals in a 155 ha forested catchment of the Santa Catalina Mountains Critical Zone Observatory (SCM CZO), Arizona. Many major elements (Na, Mg, Si, K, Ca) show no colloidal influence, and concentration-discharge relationships for these species are explained by previous work. However, the majority of trace metals (Al, Ti, V, Mn, Fe, Cu, Y, REE, U) show at least some influence of colloids on chemistry when filtered at the standard 0.45 lm cutoff. Concentration-discharge slopes of trace metals with modest colloidal influence are shallow (0.3) similar to that measured for dissolved organic carbon (DOC, 0.24), whereas elements with greater colloidal influence have steeper concentration-discharge slopes approaching that of Al (0.76), the element with the largest colloidal influence in this study (on average 68%). These findings are further supported by AF4 measurements that show distinct and resolvable pools of low hydrodynamic diameter DOC-sized material coexistent with larger diameter inorganic colloids, and the ratio of these carriers changes systematically with discharge because the DOC pool has a concentrationdischarge relationship with shallower slope than the inorganic colloidal pool. Together these data sets illustrate that positive concentration-discharge slopes of trace metals in stream waters may be explained as the relative partitioning of trace metals between DOC and inorganic colloids, with contributions of the latter likely increasing as a result of increased prevalence of macropore flow.
The rare earth elements (REE) are of increasing importance in a variety of science and economic f... more The rare earth elements (REE) are of increasing importance in a variety of science and economic fields, including (bio)geosciences, paleoecology, astrobiology, and mining. Despite their great promise, REE fractionation in early plant-microbe-rock systems has largely remained elusive. We tested the hypothesis that REE mass-partitioning during the incipient weathering of basalt, rhyolite, granite and schist depends on the activity of microbes, plant, and arbuscular mycorrhiza. Pore-water element abundances reflected a rapid transition from abiotic to biotic weathering, the latter associated with lower aqueous loss and higher uptake. Abiotic dissolution contributed 38.6+/-19% to total denudation. Microbes incremented denudation, particularly in rhyolite, this effect associating with decreased bioavailable solid fractions in this rock. Total mobilization (aqueous+uptake) was ten times greater in planted treatments compared to abiotic control, REE masses in plant generally exceeding thos...
Prior studies indicate that patterns of rare earth element (REE) depletion or enrichment in criti... more Prior studies indicate that patterns of rare earth element (REE) depletion or enrichment in critical zone (CZ) weathering systems are sensitive to variation not only in lithology, but also in climatic and/or biological processes. Organic ligands and secondary mineral surfaces vary in complex stability with different lanthanide series metals, which can result in solid-solution fractionation during incongruent mineral dissolution. REE fractionation during precipitation of solid phase weathering products is also expected to vary with host phase affinity and aqueous geochemistry along fluid flow paths. We postulated that patterns of REE fractionation during pedogenic weathering would exhibit mass-dependent trends as a function of depth in the soil profile. We further hypothesized that REE signatures would be influenced by depth-dependent variation in water and dissolved organic carbon (DOC) fluxes resulting from topographic position of the pedon under investigation. Field-based hypothesis testing utilized instrumented pedons derived from rhyolitic bedrock overlain by mixed conifer forest in the Jemez River Basin Critical Zone Observatory (JRB-CZO). REE depletion trends correlated with topographicallyinduced variation in soil pore water and DOC through-fluxes occurring predominantly during winter snowmelt. Bulk regolith analyses indicated that light rare earth elements (LREE) were depleted preferentially relative to medium and heavy REE (MREE and HREE). Lateral fluxes of water and DOC through subsurface horizons in the concave hillslope pedon correlated not only with greater REE depletion, but also with greater fractionation of REE into organo-metal colloid forms (2-23%) relative to a planar site hillslope pedon (3-13%) where vertical water and DOC fluxes were predominant. MREEs were preferentially retained in secondary colloids, indicating a mechanism for their stabilization in the weathering profile. Positive Ce-anomalies in the soils were the result of Ce retention in pedogenic Fe-(oxy)hydroxides. Ce/Ce* -cerium anomaly CZ -Critical Zone DOC -dissolved organic carbon DOM -dissolved organic matter Eu/Eu* -europium anomaly HREE -heavy rare earth elements JRB-CZO -Jemez River Basin Critical Zone Observatory LREE -light rare earth elements LRO -long range order MC -mixed conifer MREE -medium rare earth elements OC -organic carbon PCap -passive capillary sampler REE -rare earth elements REY -rare earth elements and yttrium SE -sequential extraction SOM -soil organic matter SRO -short range order TWI -Topographic wetness index UCC -upper continental crustal WY -water years ZOB -zero order basin
Pedogenesis can be slow or fast depending on the internal chemical response to environmental forc... more Pedogenesis can be slow or fast depending on the internal chemical response to environmental forcing factors. When a shift in the external environment does not produce any pedogenic change even though one is expected, the soil is said to be in a state of pedogenic inertia. In contrast, soil properties sometimes change suddenly and irreversibly in a threshold response to external stimuli or internal change in soil processes. Significant progress has been made in understanding the thermodynamics and kinetics of soil-property change. Even in the open soil system, the direction of change can be determined from measures of disequilibrium. Favorable reactions may proceed in parallel, but the most prevalent and rapid ones have the greatest impact on product formation. Simultaneous acid-base, ion exchange, redox and mineral-transformation reactions interact to determine the direction and rate of change. The nature of the governing reactions is such that soils are well buffered to pH change in the alkaline and strongly acid regions but far less so in the neutral to slightly acid zones. Organic matter inputs may drive oxidation-reduction processes Ž . through a stepwise consumption of electron acceptors thereby producing thresholds but disequilibrium among redox couples and regeneration of redox buffer capacity may attenuate this response. Synthesis of secondary minerals, ranging from carbonates and smectites to kaolinite and oxides, forms a basis for many of the reported cases of pedogenic inertia and thresholds. Mineralogical change tends to occur in a serial, irreversible fashion that, under favorable environmental conditions, can lead to large accumulations of specific minerals whose crystallinity evolves over time. These accumulations and associated AripeningB processes can channel soil processes along existing pathways or they can force thresholds by causing changes in water flux and kinetic pathways.
Changes in surface charge of soil particles that accompany mineral transformations during soil fo... more Changes in surface charge of soil particles that accompany mineral transformations during soil formation were measured for a humid tropical chronosequence in Hawaiian basalt ranging in lava flow age from 0.3 to 4100 kiloyears (ky). Parent mineralogy is dominated by glass, olivine, pyroxene, and feldspar, whereas poorly crystalline (PC) weathering products (allophane, microcrystalline gibbsite, ferrihydrite) accumulate in early to intermediate weathering stages (through 400 ky), and crystalline secondary minerals (kaolinite, gibbsite, goethite) are dominant in the oldest (1400 and 4100 ky) soils. Detailed characterization of the solid phase was accomplished with chemical extractions, X-ray diffraction analysis, and molecular spectroscopy (FTIR and 13 C MAS NMR). Simultaneous proton titration and background ion adsorption measurements were made on LiCl saturated soils over a range in pH (2-9) and ionic strength (0.001 and 0.01 M LiCl). Dependence of variable surface charge on solution composition reflects the changing nature of mineral-organic interactions over the course of pedogenesis. Points of zero net proton charge (PZNPC) ranged from 3.4 to 6.2 and 2.0 to 5.8 at 0.001 and 0.01 M ionic strength (I), respectively. Intermediate-aged soils containing the highest mass concentration of humified soil organic matter (SOM) and its complexes with PC minerals gave rise to the steepest charging curves (largest pH dependence) and highest PZNPC values. Surface charge properties of these soils most closely reflected their weakly acidic Al and Fe hydroxide constituents, which is consistent with metal hydroxide saturation of organic functional groups, rather than organic coating of mineral surfaces. Charging curves were less steep and PZNPC values were lower for the older soils, consistent with SOM coating of more crystalline goethite, kaolinite, and gibbsite surfaces in a soil system less impacted by labile Al and Fe.
An Inceptisol A-horizon from Hawaii was subjected to a series of reduction-oxidation cycles-14 d ... more An Inceptisol A-horizon from Hawaii was subjected to a series of reduction-oxidation cycles-14 d cycle length over a 56 d duration-across the ''soil-Fe'' [Fe(OH) 3 .Fe 2+ (aq) , log K o = 15.74] equilibrium in triplicate redox-stat reactors. Each reducing event simulated the flush of organic C and diminished O 2 that accompanies a rainfall-induced leaching of bioavailable reductants from the forest floor into mineral soil. The soil contained considerable amounts of short-range ordered (SRO) minerals (e.g., nano-goethite and allophane) and organic matter (11% org-C). Room temperature and cryogenic 57 Fe Mö ssbauer spectroscopy showed that the iron-bearing minerals were dominated by nano-to micro-scale goethite, and that ferrihydrite was not present. Over the four full cycles, fluctuations in E h (from 200 to 700 mV) and pFe 2+ (from 2.5 to 5.5) were inversely correlated with those of pH (5.5 to 4). Here, we focus on the solubility dynamics of the framework elements (Si, Fe, Ti, and Al) that constitute 35% of the oxygen-free soil dry mass. Intra-cycle oscillations in dissolved (<3 kDa) metals peaked during the reduction half-cycles. Similar intra-cycle oscillations were observed in the HCl and acid ammonium oxalate (AAO) extractable pools. The cumulative response of soil solids during multiple redox oscillations included: (1) a decrease in most HCl and AAO extractable metals and (2) a transformation of SRO Fe (as nano-goethite) to micro-crystalline goethite and micro-crystalline hematite. This may be the first direct demonstration that Fe oxide crystallinity increases during redox oscillationsan a priori unexpected result.
In redox-dynamic soils, iron reduction-oxidation events may initiate wide shifts in the concentra... more In redox-dynamic soils, iron reduction-oxidation events may initiate wide shifts in the concentration of colloidal and dissolved material because of either Fe mineral dissolution or pH shifts associated with Fe oxidation state changes. This can have profound effects on the mobilization of organic and metal constituents. We conducted laboratory studies of colloid dynamics in a Hawaiian soil subjected to four consecutive 14-day reduction-oxidation cycles across the "soil-Fe" (Fe(OH) 3)/(Fe 2+ (aq)) equilibrium. Size fractionated samples were isolated by differential centrifugation and characterized based on analysis of the framework and trace elements (Si, C, Fe, Ti, Al, Zr, Nb, La, and U). Intracycle oscillations in all colloidal (3 kDa to 160 nm) elements peaked during the reduction half-cycles, mobilizing 10% of total soil Ti and from 1-5% of total soil Zr, Nb, La, and U at peak dispersion. Colloid dynamics were dependent on pH shifts accompanying the redox oscillations rather than the fluctuating solubility of Fe oxides. TEM/EDS and massbalance calculations suggest a carbon-based colloid matrix with zones of metal enrichment. The cumulative effects of four redox cycles included an apparent increase in colloid stability. Proton production/consumption associated with Feredox cycling has important implications for mobilization colloid-borne trace elements and sorbed contaminants.
We studied the influence of tree species on soil carbon and nitrogen (N) dynamics in a common gar... more We studied the influence of tree species on soil carbon and nitrogen (N) dynamics in a common garden of replicated monocultures of fourteen angiosperm and gymnosperm, broadleaf and nee
Tree species can influence biogeochemistry through variation in the quantity and chemistry of the... more Tree species can influence biogeochemistry through variation in the quantity and chemistry of their litter, and associated impacts on the soil heterotrophic community. However, the role that different plant traits play in these processes is not well understood, nor is it clear whether species effects on soils largely reflect a gymnosperm vs. angiosperm contrast. Using a replicated, long-term monoculture plot experiment, we examined variation in soils among 14 gymnosperm and angiosperm tree species 30 years after plot establishment, and assessed the role of litter chemistry vis-a `-vis such variation. Differences in litter calcium concentrations among tree species resulted in profound changes in soil acidity and fertility that were similar within and among tree groups. Tree species rich in calcium were associated with increased native earthworm abundance and diversity, as well as increased soil pH, exchangeable calcium, per cent base saturation and forest floor turnover rate.
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...
At Earth's surface, a complex suite of chemical, biological, and physical processes combines... more At Earth's surface, a complex suite of chemical, biological, and physical processes combines to produce soil from bedrock within the zone that extends from the outer limits of vegetation to the lower limits of groundwater (the Critical Zone). This weathering engine transforms primary minerals, provides nutrients to nourish ecosystems and human society, mediates the transport of toxic components within the biosphere, creates water flow paths that shape and weaken bedrock, and contributes to the evolution of landscapes at all ...
Arsenic is ubiquitous in soil and water environments and is consistently at the top of the Agency... more Arsenic is ubiquitous in soil and water environments and is consistently at the top of the Agency for Toxic Substances Disease Registry (ATSDR) substance priority list. It has been shown to induce toxicity even at low levels of exposure. One of the major routes of exposure to arsenic is through drinking water. This review presents current information related to the distribution of arsenic in the environment, the resultant impacts on human health, especially related to diabetes, which is one of the most prevalent chronic diseases, regulation of arsenic in drinking water, and approaches for treatment of arsenic in drinking water for both public utilities and private wells. Taken together, this information points out the existing challenges to understanding both the complex health impacts of arsenic and to implementing the treatment strategies needed to effectively reduce arsenic exposure at different scales.
Critical zone science seeks to develop mechanistic theories that describe critical zone structure... more Critical zone science seeks to develop mechanistic theories that describe critical zone structure, function, and long-term evolution. One postulate is that hydrogeochemical controls on critical zone evolution can be inferred from solute discharges measured down-gradient of reactive flow paths. These flow paths have variable lengths, interfacial compositions, and residence times, and their mixing is reflected in concentration-discharge (C-Q) relations. Motivation for this special section originates from a U.S. Critical Zone Observatories workshop that was held at the University of New Hampshire, 20-22 July 2015. The workshop focused on resolving mechanistic CZ controls over surface water chemical dynamics across the full range of lithogenic (e.g., nonhydrolyzing and hydrolyzing cations and oxyanions) and bioactive solutes (e.g., organic and inorganic forms of C, N, P, and S), including dissolved and colloidal species that may cooccur for a given element. Papers submitted to this special section on ''concentration-discharge relations in the critical zone'' include those from authors who attended the workshop, as well as others who responded to the open solicitation. Submissions were invited that utilized information pertaining to internal, integrated catchment function (relations between hydrology, biogeochemistry, and landscape structure) to help illuminate controls on observed C-Q relations. Plain Language Summary This article introduces the special section of Water Resources Research entitled ''Concentration-Discharge Relations in the Critical Zone''.
Decomposition of soil organic matter (SOM) can be stimulated by fresh organic matter input, a phe... more Decomposition of soil organic matter (SOM) can be stimulated by fresh organic matter input, a phenomenon known as the ‘priming effect’. Despite its global importance, the relationship of the priming effect to mineral weathering and nutrient release remains unclear. Here we show close linkages between mineral weathering in the critical zone and primed decomposition of SOM. Intensified mineral weathering and rock-derived nutrient release are generally coupled with primed SOM decomposition resulting from “triggered” microbial activity. Fluxes of organic matter products decomposed via priming are linearly correlated with weathering congruency. Weathering congruency influences the formation of organo-mineral associations, thereby modulating the accessibility of organic matter to microbial decomposers and, thus, the priming effect. Our study links weathering with primed SOM decomposition, which plays a key role in controlling soil C dynamics in space and time. These connections represent ...
Understanding the temporal effects of organic matter input and water influx on metal lability and... more Understanding the temporal effects of organic matter input and water influx on metal lability and translocation is critical to evaluate the success of the phytostabilization of metalliferous mine tailings. Trends of metal lability, e.g., V, Cr, Mn, Co, Ni, Cu, Zn, and Pb, were investigated for three years following a direct-planting phytostabilization trial at a Superfund mine tailings site in semi-arid central Arizona, USA. Unamended tailings were characterized by high concentrations (mmol kg−1) of Fe (2100), S (3100), As (41), Zn (39), and Pb (11), where As and Pb greatly exceeded non-residential soil remediation levels established by Arizona. Phytostabilization treatments included a no-compost control, 100 g kg−1 compost with seed, and 200 g kg−1 compost with and without seed to the top 20 cm of the tailings profile. All plots received supplemental irrigation, effectively doubling the mean annual precipitation. Tailings cores up to 90 cm were collected at the time of planting and...
Abiotic transformation of anthropogenic compounds by redox-active metal oxides affects contaminan... more Abiotic transformation of anthropogenic compounds by redox-active metal oxides affects contaminant fate in soil. The capacity of birnessite and ferrihydrite to oxidize the insensitive munitions compound, 2,4-dinitroanisol (DNAN), and its amine-containing daughter products, 2-methoxy-5-nitro aniline (MENA) and 2,4-diaminoanisole (DAAN), was studied in stirred reactors at controlled pH (7.0). Aqueous suspensions were reacted at metal oxide solid to solution mass ratios (SSR) of 0.15, 1.5 and 15 g kg and solutions were analyzed after 0-3 h by high performance liquid chromatography coupled with photodiode array or mass spectrometry detection. Results indicate that DNAN was resistant to oxidation by birnessite and ferrihydrite. Ferrihydrite did not oxidize MENA, but MENA was susceptible to rapid oxidation by birnessite, with nitrogen largely mineralized to nitrite. This is the first report on mineralization of nonphenolic aromatics and the release of mineralized N from aromatic amines fo...
Assessment of ecosystem services—the benefits society receives from ecosystems—can be improved by... more Assessment of ecosystem services—the benefits society receives from ecosystems—can be improved by including broader spatial and temporal scales of geosciences perspectives.
Environmental pollution (Barking, Essex : 1987), Jan 5, 2018
The emerging insensitive munitions compound (IMC) 3-nitro-1,2,4-triazole-5-one (NTO) is currently... more The emerging insensitive munitions compound (IMC) 3-nitro-1,2,4-triazole-5-one (NTO) is currently being used to replace conventional explosives such as 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), but the environmental fate of this increasingly widespread IMC remains poorly understood. Upon release from unexploded solid phase ordinances, NTO exhibits high aqueous solubility and, hence, potential mobilization to groundwater. Adsorption and abiotic transformation at metal oxide surfaces are possible mechanisms for natural attenuation. Here, the reactions at ferrihydrite and birnessite surfaces of NTO and its biotransformation product, 3-amino-1, 2, 4-triazol-5-one (ATO), were studied in stirred batch reactor systems at controlled pH (7.0). The study was carried out at metal oxide solid to solution ratios (SSR) of 0.15, 1.5 and 15 g kg. The samples were collected at various time intervals up to 3 h after reaction initiation, and analyzed using HPLC with photodiode array and mass spect...
Metal(loid)-contamination of the environment due to anthropogenic activities is a global problem.... more Metal(loid)-contamination of the environment due to anthropogenic activities is a global problem. Understanding the fate of contaminants requires elucidation of biotic and abiotic factors that influence metal(loid) speciation from molecular to field scales. Improved methods are needed to assess micro-scale processes, such as those occurring at biogeochemical interfaces between plant tissues, microbial cells, and metal(loid)s. Here we present an advanced method that combines fluorescence in situ hybridization (FISH) with synchrotron-based multiple-energy micro-focused X-ray fluorescence microprobe imaging (ME μXRF) to examine colocalization of bacteria and metal(loid)s on root surfaces of plants used to phytostabilize metalliferous mine tailings. Bacteria were visualized on a small root section using SytoBC nucleic acid stain and FISH probes targeting the domain Bacteria and a specific group (Alphaproteobacteria, Gammaproteobacteria, or Actinobacteria). The same root region was then ...
This study combined concentration-discharge analyses (filtration at 0.45 lm), cascade filtrations... more This study combined concentration-discharge analyses (filtration at 0.45 lm), cascade filtrations (at 1.2, 0.4, and 0.025 lm) and asymmetrical flow field flow fractionation (AF4) to probe the influence of colloidal carriers (dissolved organic matter and inorganic nanoparticles) on observed concentrationdischarge relationships for trace metals in a 155 ha forested catchment of the Santa Catalina Mountains Critical Zone Observatory (SCM CZO), Arizona. Many major elements (Na, Mg, Si, K, Ca) show no colloidal influence, and concentration-discharge relationships for these species are explained by previous work. However, the majority of trace metals (Al, Ti, V, Mn, Fe, Cu, Y, REE, U) show at least some influence of colloids on chemistry when filtered at the standard 0.45 lm cutoff. Concentration-discharge slopes of trace metals with modest colloidal influence are shallow (0.3) similar to that measured for dissolved organic carbon (DOC, 0.24), whereas elements with greater colloidal influence have steeper concentration-discharge slopes approaching that of Al (0.76), the element with the largest colloidal influence in this study (on average 68%). These findings are further supported by AF4 measurements that show distinct and resolvable pools of low hydrodynamic diameter DOC-sized material coexistent with larger diameter inorganic colloids, and the ratio of these carriers changes systematically with discharge because the DOC pool has a concentrationdischarge relationship with shallower slope than the inorganic colloidal pool. Together these data sets illustrate that positive concentration-discharge slopes of trace metals in stream waters may be explained as the relative partitioning of trace metals between DOC and inorganic colloids, with contributions of the latter likely increasing as a result of increased prevalence of macropore flow.
The rare earth elements (REE) are of increasing importance in a variety of science and economic f... more The rare earth elements (REE) are of increasing importance in a variety of science and economic fields, including (bio)geosciences, paleoecology, astrobiology, and mining. Despite their great promise, REE fractionation in early plant-microbe-rock systems has largely remained elusive. We tested the hypothesis that REE mass-partitioning during the incipient weathering of basalt, rhyolite, granite and schist depends on the activity of microbes, plant, and arbuscular mycorrhiza. Pore-water element abundances reflected a rapid transition from abiotic to biotic weathering, the latter associated with lower aqueous loss and higher uptake. Abiotic dissolution contributed 38.6+/-19% to total denudation. Microbes incremented denudation, particularly in rhyolite, this effect associating with decreased bioavailable solid fractions in this rock. Total mobilization (aqueous+uptake) was ten times greater in planted treatments compared to abiotic control, REE masses in plant generally exceeding thos...
Prior studies indicate that patterns of rare earth element (REE) depletion or enrichment in criti... more Prior studies indicate that patterns of rare earth element (REE) depletion or enrichment in critical zone (CZ) weathering systems are sensitive to variation not only in lithology, but also in climatic and/or biological processes. Organic ligands and secondary mineral surfaces vary in complex stability with different lanthanide series metals, which can result in solid-solution fractionation during incongruent mineral dissolution. REE fractionation during precipitation of solid phase weathering products is also expected to vary with host phase affinity and aqueous geochemistry along fluid flow paths. We postulated that patterns of REE fractionation during pedogenic weathering would exhibit mass-dependent trends as a function of depth in the soil profile. We further hypothesized that REE signatures would be influenced by depth-dependent variation in water and dissolved organic carbon (DOC) fluxes resulting from topographic position of the pedon under investigation. Field-based hypothesis testing utilized instrumented pedons derived from rhyolitic bedrock overlain by mixed conifer forest in the Jemez River Basin Critical Zone Observatory (JRB-CZO). REE depletion trends correlated with topographicallyinduced variation in soil pore water and DOC through-fluxes occurring predominantly during winter snowmelt. Bulk regolith analyses indicated that light rare earth elements (LREE) were depleted preferentially relative to medium and heavy REE (MREE and HREE). Lateral fluxes of water and DOC through subsurface horizons in the concave hillslope pedon correlated not only with greater REE depletion, but also with greater fractionation of REE into organo-metal colloid forms (2-23%) relative to a planar site hillslope pedon (3-13%) where vertical water and DOC fluxes were predominant. MREEs were preferentially retained in secondary colloids, indicating a mechanism for their stabilization in the weathering profile. Positive Ce-anomalies in the soils were the result of Ce retention in pedogenic Fe-(oxy)hydroxides. Ce/Ce* -cerium anomaly CZ -Critical Zone DOC -dissolved organic carbon DOM -dissolved organic matter Eu/Eu* -europium anomaly HREE -heavy rare earth elements JRB-CZO -Jemez River Basin Critical Zone Observatory LREE -light rare earth elements LRO -long range order MC -mixed conifer MREE -medium rare earth elements OC -organic carbon PCap -passive capillary sampler REE -rare earth elements REY -rare earth elements and yttrium SE -sequential extraction SOM -soil organic matter SRO -short range order TWI -Topographic wetness index UCC -upper continental crustal WY -water years ZOB -zero order basin
Pedogenesis can be slow or fast depending on the internal chemical response to environmental forc... more Pedogenesis can be slow or fast depending on the internal chemical response to environmental forcing factors. When a shift in the external environment does not produce any pedogenic change even though one is expected, the soil is said to be in a state of pedogenic inertia. In contrast, soil properties sometimes change suddenly and irreversibly in a threshold response to external stimuli or internal change in soil processes. Significant progress has been made in understanding the thermodynamics and kinetics of soil-property change. Even in the open soil system, the direction of change can be determined from measures of disequilibrium. Favorable reactions may proceed in parallel, but the most prevalent and rapid ones have the greatest impact on product formation. Simultaneous acid-base, ion exchange, redox and mineral-transformation reactions interact to determine the direction and rate of change. The nature of the governing reactions is such that soils are well buffered to pH change in the alkaline and strongly acid regions but far less so in the neutral to slightly acid zones. Organic matter inputs may drive oxidation-reduction processes Ž . through a stepwise consumption of electron acceptors thereby producing thresholds but disequilibrium among redox couples and regeneration of redox buffer capacity may attenuate this response. Synthesis of secondary minerals, ranging from carbonates and smectites to kaolinite and oxides, forms a basis for many of the reported cases of pedogenic inertia and thresholds. Mineralogical change tends to occur in a serial, irreversible fashion that, under favorable environmental conditions, can lead to large accumulations of specific minerals whose crystallinity evolves over time. These accumulations and associated AripeningB processes can channel soil processes along existing pathways or they can force thresholds by causing changes in water flux and kinetic pathways.
Changes in surface charge of soil particles that accompany mineral transformations during soil fo... more Changes in surface charge of soil particles that accompany mineral transformations during soil formation were measured for a humid tropical chronosequence in Hawaiian basalt ranging in lava flow age from 0.3 to 4100 kiloyears (ky). Parent mineralogy is dominated by glass, olivine, pyroxene, and feldspar, whereas poorly crystalline (PC) weathering products (allophane, microcrystalline gibbsite, ferrihydrite) accumulate in early to intermediate weathering stages (through 400 ky), and crystalline secondary minerals (kaolinite, gibbsite, goethite) are dominant in the oldest (1400 and 4100 ky) soils. Detailed characterization of the solid phase was accomplished with chemical extractions, X-ray diffraction analysis, and molecular spectroscopy (FTIR and 13 C MAS NMR). Simultaneous proton titration and background ion adsorption measurements were made on LiCl saturated soils over a range in pH (2-9) and ionic strength (0.001 and 0.01 M LiCl). Dependence of variable surface charge on solution composition reflects the changing nature of mineral-organic interactions over the course of pedogenesis. Points of zero net proton charge (PZNPC) ranged from 3.4 to 6.2 and 2.0 to 5.8 at 0.001 and 0.01 M ionic strength (I), respectively. Intermediate-aged soils containing the highest mass concentration of humified soil organic matter (SOM) and its complexes with PC minerals gave rise to the steepest charging curves (largest pH dependence) and highest PZNPC values. Surface charge properties of these soils most closely reflected their weakly acidic Al and Fe hydroxide constituents, which is consistent with metal hydroxide saturation of organic functional groups, rather than organic coating of mineral surfaces. Charging curves were less steep and PZNPC values were lower for the older soils, consistent with SOM coating of more crystalline goethite, kaolinite, and gibbsite surfaces in a soil system less impacted by labile Al and Fe.
An Inceptisol A-horizon from Hawaii was subjected to a series of reduction-oxidation cycles-14 d ... more An Inceptisol A-horizon from Hawaii was subjected to a series of reduction-oxidation cycles-14 d cycle length over a 56 d duration-across the ''soil-Fe'' [Fe(OH) 3 .Fe 2+ (aq) , log K o = 15.74] equilibrium in triplicate redox-stat reactors. Each reducing event simulated the flush of organic C and diminished O 2 that accompanies a rainfall-induced leaching of bioavailable reductants from the forest floor into mineral soil. The soil contained considerable amounts of short-range ordered (SRO) minerals (e.g., nano-goethite and allophane) and organic matter (11% org-C). Room temperature and cryogenic 57 Fe Mö ssbauer spectroscopy showed that the iron-bearing minerals were dominated by nano-to micro-scale goethite, and that ferrihydrite was not present. Over the four full cycles, fluctuations in E h (from 200 to 700 mV) and pFe 2+ (from 2.5 to 5.5) were inversely correlated with those of pH (5.5 to 4). Here, we focus on the solubility dynamics of the framework elements (Si, Fe, Ti, and Al) that constitute 35% of the oxygen-free soil dry mass. Intra-cycle oscillations in dissolved (<3 kDa) metals peaked during the reduction half-cycles. Similar intra-cycle oscillations were observed in the HCl and acid ammonium oxalate (AAO) extractable pools. The cumulative response of soil solids during multiple redox oscillations included: (1) a decrease in most HCl and AAO extractable metals and (2) a transformation of SRO Fe (as nano-goethite) to micro-crystalline goethite and micro-crystalline hematite. This may be the first direct demonstration that Fe oxide crystallinity increases during redox oscillationsan a priori unexpected result.
In redox-dynamic soils, iron reduction-oxidation events may initiate wide shifts in the concentra... more In redox-dynamic soils, iron reduction-oxidation events may initiate wide shifts in the concentration of colloidal and dissolved material because of either Fe mineral dissolution or pH shifts associated with Fe oxidation state changes. This can have profound effects on the mobilization of organic and metal constituents. We conducted laboratory studies of colloid dynamics in a Hawaiian soil subjected to four consecutive 14-day reduction-oxidation cycles across the "soil-Fe" (Fe(OH) 3)/(Fe 2+ (aq)) equilibrium. Size fractionated samples were isolated by differential centrifugation and characterized based on analysis of the framework and trace elements (Si, C, Fe, Ti, Al, Zr, Nb, La, and U). Intracycle oscillations in all colloidal (3 kDa to 160 nm) elements peaked during the reduction half-cycles, mobilizing 10% of total soil Ti and from 1-5% of total soil Zr, Nb, La, and U at peak dispersion. Colloid dynamics were dependent on pH shifts accompanying the redox oscillations rather than the fluctuating solubility of Fe oxides. TEM/EDS and massbalance calculations suggest a carbon-based colloid matrix with zones of metal enrichment. The cumulative effects of four redox cycles included an apparent increase in colloid stability. Proton production/consumption associated with Feredox cycling has important implications for mobilization colloid-borne trace elements and sorbed contaminants.
We studied the influence of tree species on soil carbon and nitrogen (N) dynamics in a common gar... more We studied the influence of tree species on soil carbon and nitrogen (N) dynamics in a common garden of replicated monocultures of fourteen angiosperm and gymnosperm, broadleaf and nee
Tree species can influence biogeochemistry through variation in the quantity and chemistry of the... more Tree species can influence biogeochemistry through variation in the quantity and chemistry of their litter, and associated impacts on the soil heterotrophic community. However, the role that different plant traits play in these processes is not well understood, nor is it clear whether species effects on soils largely reflect a gymnosperm vs. angiosperm contrast. Using a replicated, long-term monoculture plot experiment, we examined variation in soils among 14 gymnosperm and angiosperm tree species 30 years after plot establishment, and assessed the role of litter chemistry vis-a `-vis such variation. Differences in litter calcium concentrations among tree species resulted in profound changes in soil acidity and fertility that were similar within and among tree groups. Tree species rich in calcium were associated with increased native earthworm abundance and diversity, as well as increased soil pH, exchangeable calcium, per cent base saturation and forest floor turnover rate.
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...
At Earth's surface, a complex suite of chemical, biological, and physical processes combines... more At Earth's surface, a complex suite of chemical, biological, and physical processes combines to produce soil from bedrock within the zone that extends from the outer limits of vegetation to the lower limits of groundwater (the Critical Zone). This weathering engine transforms primary minerals, provides nutrients to nourish ecosystems and human society, mediates the transport of toxic components within the biosphere, creates water flow paths that shape and weaken bedrock, and contributes to the evolution of landscapes at all ...
Uploads
Papers by Jon Chorover