Omar R. Harvey

An index-based approach to assessing recalcitrance and soil carbon sequestration potential of engineered black carbons (biochars).

The ability of engineered black carbons (or biochars) to resist abiotic and, or biotic degradation (herein referred to as recalcitrance) is crucial to their successful deployment as a soil carbon sequestration strategy. A new recalcitrance index, the R(50), for assessing biochar quality for carbon sequestration is proposed. The R(50) is based on the relative thermal stability of a given biochar to that of graphite and was developed and evaluated with a variety of biochars (n = 59), and soot-like black carbons. Comparison of R(50), with biochar physicochemical properties and biochar-C mineralization revealed the existence of a quantifiable relationship between R(50) and biochar recalcitrance. As presented here, the R(50) is immediately applicable to pre-land application screening of biochars into Class A (R(50) ≥ 0.70), Class B (0.50 ≤ R(50) < 0.70) or Class C (R(50) < 0.50) recalcitrance/carbon sequestration classes. Class A and Class C biochars would have carbon sequestration potential comparable to soot/graphite and uncharred plant biomass, respectively, whereas Class B biochars would have intermediate carbon sequestration potential. We believe that the coupling of the R(50), to an index-based degradation, and an economic model could provide a suitable framework in which to comprehensively assess soil carbon sequestration in biochars.

Metal Interactions at the Biochar-Water Interface: Energetics and Structure-Sorption Relationships Elucidated by Flow Adsorption Microcalorimetry

Plant-derived biochars exhibit large physicochemical heterogeneity due to variations in biomass chemistry and combustion conditions. However, the influence of biochar heterogeneity on biochar-metal interaction mechanisms has not been systematically described. We used flow adsorption microcalorimetry to study structure-sorption relationships between twelve plant-derived biochars and two metals (K(+) and Cd(2+)) of different Lewis acidity. Irrespective of the biochar structure, sorption of K(+) (a hard Lewis acid) occurred predominantly on deprotonated functional groups via ion exchange with molar heats of adsorption (ΔH(ads)) of -4 kJ mol(-1) to -8 kJ mol(-1). By comparison, although ion exchange could not be completely ruled out, our data pointed to Cd(2+) (a soft Lewis acid) sorption occurring predominantly via two distinct cation-π bonding mechanisms, each with ΔH(ads) of +17 kJ mol(-1). The first, evident in low charge-low carbonized biochars, suggested Cd(2+)-π bonding to soft ligands such as -C ═ O; while the second, evident in low charge-highly carbonized biochars, pointed to Cd(2+)-π bonding with electron-rich domains on aromatic structures. Quantitative contributions of these mechanisms to Cd(2+) sorption can exceed 3 times that expected for ion exchange and therefore could have significant implications for the biogeochemical cycling of metals in fire-impacted or biochar-amended systems.

Geochemical implications of gas leakage associated with geologic CO2 storage--a qualitative review.

Gas leakage from deep storage reservoirs is a major risk factor associated with geologic carbon sequestration (GCS). A systematic understanding of how such leakage would impact the geochemistry of potable aquifers and the vadose zone is crucial to the maintenance of environmental quality and the widespread acceptance of GCS. This paper reviews the current literature and discusses current knowledge gaps on how elevated CO(2) levels could influence geochemical processes (e.g., adsorption/desorption and dissolution/precipitation) in potable aquifers and the vadose zone. The review revealed that despite an increase in research and evidence for both beneficial and deleterious consequences of CO(2) migration into potable aquifers and the vadose zone, significant knowledge gaps still exist. Primary among these knowledge gaps is the role/influence of pertinent geochemical factors such as redox condition, CO(2) influx rate, gas stream composition, microbial activity, and mineralogy in CO(2)-induced reactions. Although these factors by no means represent an exhaustive list of knowledge gaps we believe that addressing them is pivotal in advancing current scientific knowledge on how leakage from GCS may impact the environment, improving predictions of CO(2)-induced geochemical changes in the subsurface, and facilitating science-based decision- and policy-making on risk associated with geologic carbon sequestration.

Kinetics and energetics of phosphate sorption in a multi-component Al(III)–Fe(III) hydr(oxide) sorbent system

Multi-component Al-Fe hydr(oxides) are ubiquituous in soil and aquatic environments, where they exhibit biogeochemical controls on nutrients and contaminants. Although, sorption on single-component Al and Fe hydr(oxides) have been extensively studied, limited studies have been done on their multi-component counterparts. In this study, effects of Al/Fe content on the kinetics and energetics of phosphate sorption in a poorly-crystalline co-precipitated mixed Al-Fe hydr(oxide) system were investigated using a combination of traditional batch techniques and flow adsorption calorimetry. Differences in Al/Fe content was found to influence the structural development and anion exchange capacity of the hydr(oxides) and subsequently their phosphate sorption characteristics. Higher structural development decreased phosphate sorption, while higher AEC was associated with increased phosphate sorption, initial sorption rate, and smaller losses in sorption with increasing pH. Results from flow adsorption calorimetry indicated that at pH 4.8 phosphate sorption: (i) occurred irreversibly on anion exchange sites, with a loss of 1.9 moles of AEC per mole of phosphate sorbed, and (ii) was exothermic, with molar heats of adsorption between -25 and -39 kJmol(-1). Molar heats of adsorption were ten times that for anion exchange and independent of hydr(oxide) composition with the amount of energy evolved being directly proportional to the quantity of phosphate sorbed.

Generalized Two-Dimensional Perturbation Correlation Infrared Spectroscopy reveals Mechanisms for the Development of Surface Charge and Recalcitrance in Plant-derived Biochars

Fundamental knowledge of how biochars develop surface-charge and resistance to environmental degradation is crucial to their production for customized applications or understanding their functions in the environment. Two-dimensional perturbation-based correlation infrared spectroscopy (2D-PCIS) was used to study the biochar formation process in three taxonomically different plant biomass, under oxygen-limited conditions along a heat-treatment-temperature gradient (HTT; 200-650 °C). Results from 2D-PCIS pointed to the systematic, HTT-induced defragmenting of lignocellulose H-bonding network and demethylenation/demethylation, oxidation, or dehydroxylation/dehydrogenation of lignocellulose fragments as the primary reactions controlling biochar properties along the HTT gradient. The cleavage of OH(...)O-type H-bonds, oxidation of free primary hydroxyls to carboxyls (carboxylation; HTT ≤ 500 °C), and their subsequent dehydrogenation/dehydroxylation (HTT > 500 °C) controlled surface charge on the biochars; while the dehydrogenation of methylene groups, which yielded increasingly condensed structures (R-CH(2)-R →R═CH-R →R═C═R), controlled biochar recalcitrance. Variations in biochar properties across plant biomass type were attributable to taxa-specific transformations. For example, apparent inefficiencies in the cleavage of wood-specific H-bonds, and their subsequent oxidation to carboxyls, lead to lower surface charge in wood biochars (compared to grass biochars). Both nontaxa and taxa-specific transformations highlighted by 2D-PCIS could have significant implications for biochar functioning in fire-impacted or biochar-amended systems.

Reduction of Chromium(VI) mediated by zero-valent magnesium under neutral pH conditions

In an effort to assess the potential use of ZVMg in contaminant treatments, we examined Cr(VI) reduction mediated by ZVMg particles under neutral pH conditions. The reduction of Cr(VI) was tested with batch experiments by varying [Cr(VI)](0) (4.9, 9.6, 49.9 or 96.9 μM) in the presence of 50 mg/L ZVMg particles ([Mg(0)](0) = 2.06 mM) at pH 7 buffered with 50 mM Na-MOPS. When [Cr(VI)](0) = 4.9 or 9.6 μM, Cr(VI) was completely reduced within 60 min. At higher [Cr(VI)](0) (49.9 or 96.9 μM), by contrast, the reduction became retarded at >120 min likely due to rapid ZVMg dissolution in water and surface precipitation of Cr(III) on ZVMg particles. Surface precipitation was observed only when [Cr(VI)](0) = 49.9 or 96.9 μM and increased with increasing [Cr(VI)](0). The effect of dissolved oxygen was negligible on the rate and extent of Cr(VI) reduction. Experimental results indicated that Cr(VI) was reduced not directly by ZVMg but by reactive intermediates produced from ZVMg-water reaction under the experimental conditions employed in this study. In addition, the observed rates of Cr(VI) reduction appeared to follow an order below unity (0.19) with respect to [Cr(VI)](0). These results imply that ZVMg-mediated Cr(VI) reduction likely occurred via an alternative mechanism to the direct surface-mediated reduction typically observed for other zero-valent metals. Rapid and complete Cr(VI) reduction was achieved when a mass ratio of [ZVMg](0):[Cr(VI)](0) ≥ 100 at neutral pH under both oxic and anoxic conditions. Our results highlights the potential for ZVMg to be used in Cr(VI) treatments especially under neutral pH conditions in the presence of dissolved oxygen.

Geochemical Implications of CO2 Leakage Associated with Geologic Storage: A Review

Leakage from deep storage reservoirs is a major risk factor associated with geologic sequestration of carbon dioxide (CO2). Different scientific theories exist concerning the potential implications of such leakage for near-surface environments. The authors of this report reviewed the current literature on how CO2 leakage (from storage reservoirs) would likely impact the geochemistry of near surface environments such as potable water aquifers and the vadose zone. Experimental and modeling studies highlighted the potential for both beneficial (e.g., CO2 re sequestration or contaminant immobilization) and deleterious (e.g., contaminant mobilization) consequences of CO2 intrusion in these systems. Current knowledge gaps, including the role of CO2-induced changes in redox conditions, the influence of CO2 influx rate, gas composition, organic matter content and microorganisms are discussed in terms of their potential influence on pertinent geochemical processes and the potential for beneficial or deleterious outcomes. Geochemical modeling was used to systematically highlight why closing these knowledge gaps are pivotal. A framework for studying and assessing consequences associated with each factor is also presented in Section 5.6.

Phosphate alteration of chloride behavior at the boehmite-water interface: New insights from ion-probe flow adsorption microcalorimetry.

Surface complexation of phosphate to aluminum oxyhydroxides can alter surface reactivity depending on the time-scale and mode of attachment. The effects of phosphate adsorption on reactivity of boehmite (γ-AlOOH) particles were investigated using ion-probe flow adsorption microcalorimetry (ipFAMC). Consistent with previous studies on adsorption energetics, probing the surface of pristine γ-AlOOH with chloride ions yielded endothermically unimodal temperature signals with a measured molar heat of exchange (ΔH(exc)) of -3.1 kJ/mol. However, when the surface of γ-AlOOH was probed with chloride following phosphate complexation, significant changes in surface reactivity resulted. Irrespective of phosphate loading, the typical endothermic response of the chloride-surface hydroxyl interaction was replaced with a multi-modal energy signature consisting of exothermic and endothermic features. These features indicate that in the presence of phosphate, the overall nature of the interaction of chloride with specific surface hydroxyls located on different exposed planes and their subsequent reactivity was transformed to a more complex environment accompanied by two or more short-lived secondary reactions. It was also shown that phosphate-promoted surface alteration of γ-AlOOH was highly selective to probing with chloride since no changes in reactivity were observed when nitrate was employed as the primary ion probe under identical experimental conditions.

Physical Processes Dictate Early Biogeochemical Dynamics of Soil Pyrogenic Organic Matter in a Subtropical Forest Ecosystem

Quantifying links between pyOM dynamics, environmental factors and processes is central to predicting ecosystem function and response to future perturbations. In this study, changes in carbon (TC), nitrogen (TN) , pH and relative recalcitrance (R50) for pine- and cordgrass-derived pyOM were measured at 3-6 weeks intervals throughout the first year of burial in the soil. Objectives were to 1) identify key environmental factors and processes driving early-stage pyOM dynamics, and 2) develop quantitative relationships between environmental factors and changes in pyOM properties. The study was conducted in sandy soils of a forested ecosystem in the Longleaf pine range, US with a focus on links between changes in pyOM properties, fire history (FH), cumulative precipitation (Pcum), average temperature (Tavg) and soil residence time (SRT). Pcum, SRT and Tavg were the main factors controlling TC and TN accounting for 77-91% and 64-96% of their respective variability. Fire history, along with Pcum, SRT and Tavg, exhibited significant controlling effects on pyOM, pH and R50 - accounting for 48-91% and 88-93% of respective variability. Volatilization of volatiles and leaching of water-soluble components (in summer) and the sorption of exogenous organic matter (fall through spring) were most plausibly controlling pyOM dynamics in this study. Overall, our results point to climatic and land management factors and physicochemical process as the main drivers of pyOM dynamics in the pine ecosystems of the Southeastern US.

Killing the Ettringite Reaction in Sulfate-Bearing Soils

The formation of ettringite in sulfate-bearing clay soils often results in rapid and significant expansion when calcium-based stabilizers are added to the soil. The researchers tested the hypothesis that ettringite crystal growth could be inhibited by adding a specific chemical that would prevent nucleation of ettringite crystallites, much like retarding the setting of portland cement by using organic additives. The researchers created ettringite in the laboratory by using clay mineral standards mixed with hydrated lime, gypsum, and water, with an ultrasonic homogenizer to catalyze the reaction. A natural soil from Texas (State Highway 289) that had caused sulfate-induced heave problems was also used. Diatomaceous earth, volcanic glass (amorphous silica), and calcium phosphate monobasic monohydrate were added in different proportions to see whether the formation of ettringite could be stopped. The diatomaceous earth and volcanic glass did not inhibit the growth of ettringite in any of the clay mineral standards or natural soil tested. However, the calcium phosphate monobasic monohydrate generated tricalcium aluminate monosulfate hydrate instead of ettringite in the kaolinite and in the natural soil, prevented the formation of both ettringite and tricalcium aluminate monosulfate hydrate. Therefore, phosphates may be a viable additive for prevention of heave in sulfate-bearing soils.