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At least 91 records · Page 5

Health and Safety Effects of Airborne Soil Dust in the Americas and Beyond

Risks associated with dust hazards are often underappreciated, a gap between the knowledge pool and public awareness that can be costly for impacted communities. This study reviews the emission sources and chemical, physical, and biological characteristics of airborne soil particles (dust) and their effects on human and environmental health and safety in the Pan-American region. American dust originates from both local sources (western United States, northern Mexico, Peru, Bolivia, Chile, and Argentina) and long-range transport from Africa and Asia. Dust properties, as well as the trends and interactions with criteria air pollutants, are summarized. Human exposure to dust is associated with adverse health effects, including asthma, allergies, fungal infections, and premature death. In the Americas, a well-documented and striking effect of soil dust is its association with Coccidioidomycosis, commonly known as Valley fever, an infection caused by inhalation of soil-dwelling fungi unique to this region. Besides human health, dust affects environmental health through nutrients that increase phytoplankton biomass, contaminants that diminish water supply and affect food (crops/fruits/vegetables and ready-to-eat meat), spread crop and marine pathogens, cause Valley fever among domestic and wild animals, transport heavy metals, radionuclides and microplastics, and reduce solar and wind power generation. Dust is also a safety hazard to road transportation and aviation, in the southwestern US where blowing dust is one of the deadliest weather hazards. To mitigate the harmful effects, coordinated regional and international efforts are needed to enhance dust observations and prediction capabilities, soil conservation measures, and Valley fever and other disease surveillance.

health↗

Mercury methylation potential in a sand dune on Lake Michigan's eastern shoreline

Lake Michigan hosts the largest freshwater sand dune system in the world and is economically important for the fishery industry and tourism. Due to industrial pollution and atmospheric mercury (Hg) deposition, toxic levels of methylmercury (MeHg) have been found in the Lake biota, but little information is known regarding MeHg sources and Hg methylation potential in the shoreline sand dunes. In this study, we conducted anaerobic incubation experiments with beach sands collected from Ludington, Michigan, and examined the effects of organic carbon substrate addition, inorganic nitrogen, and mineral magnetite on Hg methylation. Despite nutrient poor and low-organic carbon conditions, appreciable Hg methylation activity coupled with carbon degradation was observed in the sands. Addition of acetate as a carbon source substantially increased MeHg production from 2 to 380 ng/kg sediment while acetate was rapidly degraded in the first 19 days of incubation. Ammonium addition showed little influence on carbon degradation or Hg methylation, whereas iron oxide addition (~1% dry weight) significantly inhibited both carbon degradation and MeHg production (by up to 90%), highlighting strongly coupled interactions between microbes, carbon substrates, and minerals. This research demonstrates the potential of microbial Hg methylation in the sand dunes, which may play a role in MeHg input and bioaccumulation in the Lake Michigan ecosystem.

54 ENVIRONMENTAL SCIENCES↗

Rheinheimera sp . T2C2 Bacterial Biofilm for Bioremediation of Cobalt(II)

Toxic metals, including cobalt, are often the cause of the contamination of rivers and lakes in mining regions. Heavy metal water pollution has been linked to numerous human health problems, prompting the need for environmental remediation. Existing techniques for removing heavy metals from water, such as chemical precipitation and filtration, produce toxic waste, are costly, or require high power consumption for pumping. Biosorption is a potential alternative strategy that is cost-effective and uses readily available and naturally produced biomass and living material to absorb pollutants. Engineering living materials, such as biofilms, which consist of living cells and a secreted polymer matrix, offer the potential to integrate toxin sensing, sequestration, and metabolism capabilities of cells to improve pollution remediation strategies. Alternative biofilm producing candidates need to be explored to implement these material capabilities. Previous biosorption studies have primarily used bacterial biofilms from known pathogens and/or generated toxic waste in the form of the absorbent material combined with the heavy metal. Here, we describe a recently isolated bacterium called Rheinheimera sp. T2C2 that forms biofilms with promising biosorption characteristics. T2C2 is an aquatic bacterium with low nutrient requirements and high biofilm production that is not known to be pathogenic. We demonstrate (1) the efficacy of Rheinheimera sp. T2C2 as a biosorbent for cobalt bioremediation; (2) how biosorption is altered by water conditions to establish the efficacy of this strategy in different environments; and (3) how the metal can be released from the biofilm for metal recycling. Our findings will provide a living materials strategy that overcomes the existing barriers for bioremediation and improves the health of ecosystems and humans through heavy metal removal and recycling.

Rheinheimera↗

Bioaccumulation of contaminants in Scarabaeidae and Silphidae beetles at sites polluted by coal combustion residuals and radiocesium

Anthropogenic contamination from coal-fired power plants and nuclear reactors is a pervasive issue impacting ecosystems across the globe. As a result, it is critical that studies continue to assess the accumulation and effects of trace elements and radionuclides in a diversity of biota. In particular, bioindicator species are a powerful tool for risk assessment of chemically contaminated habitats. Using inductively coupled plasma mass spectrometry (ICP-MS) and auto-gamma counting, we analyzed trace element and radiocesium contaminant concentrations in Scarabaeidae and Silphidae beetles (Order: Coleoptera), important taxa in decomposition and nutrient cycling, at contaminated and reference sites on the Savannah River Site, South Carolina, U.S. Our results revealed variability in trace element concentrations between Scarabaeidae and Silphidae beetles at uncontaminated and contaminated sites. Compared to Scarabaeidae, Silphidae had higher levels of chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), and zinc (Zn). Unexpectedly, concentrations of Cr, Cu, and Ni were higher in both taxa at the uncontaminated sites. Scarabaeidae and Silphidae beetles at the coal combustion waste site consistently had high concentrations of arsenic (As), and Scarabaeidae had high concentrations of selenium (Se). Of the 50 beetles analyzed for radiocesium levels, two had elevated radioactivity concentrations, both of which were from a site contaminated with radionuclides. Furthermore, our results suggest carrion beetles may be particularly sensitive to bioaccumulation of contaminants due to their trophic position and role in decomposition, and thus are useful sentinels of trace element and radionuclide contamination.

59 BASIC BIOLOGICAL SCIENCES↗

Isotopic Evidence for the Source and Fate of Phosphorus in Everglades Wetland Ecosystems

Phosphorus has historically been a limiting nutrient in the Florida Everglades. Increased P loading to the Everglades over the past several decades has led to significant changes in water quality and plant communities. Stormwater runoff that drains agricultural lands and enters the Water Conservation Areas (WCAs) are known to contain elevated levels of P, but the exact source of this P has not been fully determined. Here the results of an O isotope study of dissolved inorganic phosphate (DIP) in both polluted and relatively pristine (or reference) areas of the Everglades are reported. The data reveal spatial and temporal variations in the delta 18O signature of DIP, reflecting the source and the degree of cycling of P. The delta 18O values of DIP collected from the Everglades National Park were close or equal to the predicted delta 18O values of DIP formed in situ in equilibrium with ambient water, indicating that P is quickly cycled in the water column in oligotrophic ecosystems with very low P concentrations. However, most DIP samples collected from areas impacted by agricultural runoff yielded delta 18O values that deviated from the predicted equilibrium DIP delta 18O values based on the delta 18O of water and water temperature, suggesting that biological cycling of P was not rapid enough to remove the fertilizer ?18O signature in the DIP pool from areas receiving high P loading. The delta 18O signature of DIP in impacted areas reflects a mixing of fertilizer P and biologically cycled P, where the relative proportions of biologically cycled vs. fertilizer DIP are controlled by both biological (microbial activities and plant uptake) and hydrologic factors (loading rate and residence time). Using a two-end-member (i.e., fertilizer P and biologically cycled P) mixing model, fertilizers were estimated to contribute about 15 100% of the DIP pool in the highly impacted areas of the northern Everglades, whereas the DIP pool in the reference (i.e., relatively pristine) wetlands in the Everglades National Park was dominated by biologically cycled P. The study shows that O isotopic measurements of dissolved PO(exp 3-, sub 4) can be a useful tool for tracing the fertilizer P inputs to freshwater ecosystems.

Li, Xin↗

Improved Moisture Management Technology for Eco-N-Control Fertilizer

Three fertilizer technologies to manage nitrogen (N) release rates in soil dominate the market today: 1) bulk controlled-release technologies, which use the intrinsic solubility properties of a N-organic co-polymer to control N release; 2) barrier-based controlled-release technologies, which use porous polymer or sulfur coatings as a physical barrier to control N release from encapsulated N nutrients; and 3) slow-release technologies, which use enzyme inhibitors to chemically slow down the transformation of N nutrients into ammonia (NH 3 ) or to temporarily reduce populations of bacteria in the soil that are responsible for converting ammonium (NH 4 + ) to highly soluble nitrates. These technologies are expensive and provide only limited control of N-release rates. Also, from another environmental perspective, synthetic polymer coatings do not decompose easily and will accumulate over time with continuous application of fertilizer. For most of the past two decades we have been developing the Eco-N-Control solid-nitride fertilizer technology, a type of bulk controlled-release technology. With Eco-N-Control, solid-nitride compounds weather like a mineral, slowly releasing N at a rate determined by their composition. Testing by an industrial collaborator, however, showed that earlier versions of Eco-N-Control released at 25% of the desired rate when deployed in unsaturated soils. The overall goal of the current project, therefore, was to strengthen our IP position and the potential for licensing of Eco-N-Control solid-nitride fertilizer technology by developing new ways to manage the level of moisture in contact with the fertilizer when applied to soil thereby ensuring the desired N-release rate. We achieved this goal by developing a biodegradable polymer cross-linking approach that substantially improved performance of our patented solid-nitride fertilizer. We found that cross-linking an environmentally friendly and biodegradable polymer with a mixture of solid nitrides, other N-nutrient compounds and other additives offers several advantages: 1) mechanical robustness of fertilizer beads, 2) chemical stability during storage, 3) maintenance of sufficient water content in the vicinity of the nitride, and 4) control of N-release rates. We also updated our N-release testing protocol to more realistically simulate the conditions found in soil. Finally, we filed an invention disclosure record to protect these new aspects of Eco-N-Control technology, which offers a potential way to lower both agricultural and industrial pollution by providing an efficient N-delivery mechanism to plants.

42 ENGINEERING↗

Manufactured soils for plant growth at a lunar base

Advantages and disadvantages of synthetic soils are discussed. It is pointed out that synthetic soils may provide the proper physical and chemical properties necessary to maximize plant growth, such as a toxic-free composition and cation exchange capacities. The importance of nutrient retention, aeration, moisture retention, and mechanical support as qualities for synthetic soils are stressed. Zeoponics, or the cultivation of plants in zeolite substrates that both contain essential plant-growth cations on their exchange sites and have minor amounts of mineral phases and/or anion-exchange resins that supply essential plant growth ions, is discussed. It is suggested that synthetic zeolites at lunar bases could provide adsorption media for separation of various gases, act as catalysts and as molecular sieves, and serve as cation exchangers in sewage-effluent treatment, radioactive-waste disposal, and pollution control. A flow chart of a potential zeoponics system illustrates this process.

Ming, Douglas W.↗

Electrothermal mineralization of per- and polyfluoroalkyl substances for soil remediation

Abstract Per- and polyfluoroalkyl substances (PFAS) are persistent and bioaccumulative pollutants that can easily accumulate in soil, posing a threat to environment and human health. Current PFAS degradation processes often suffer from low efficiency, high energy and water consumption, or lack of generality. Here, we develop a rapid electrothermal mineralization (REM) process to remediate PFAS-contaminated soil. With environmentally compatible biochar as the conductive additive, the soil temperature increases to >1000 °C within seconds by current pulse input, converting PFAS to calcium fluoride with inherent calcium compounds in soil. This process is applicable for remediating various PFAS contaminants in soil, with high removal efficiencies ( >99%) and mineralization ratios ( >90%). While retaining soil particle size, composition, water infiltration rate, and cation exchange capacity, REM facilitates an increase of exchangeable nutrient supply and arthropod survival in soil, rendering it superior to the time-consuming calcination approach that severely degrades soil properties. REM is scaled up to remediate soil at two kilograms per batch and promising for large-scale, on-site soil remediation. Life-cycle assessment and techno-economic analysis demonstrate REM as an environmentally friendly and economic process, with a significant reduction of energy consumption, greenhouse gas emission, water consumption, and operation cost, when compared to existing soil remediation practices.

Science & Technology - Other Topics↗

Field‐scale analysis of miscanthus production indicates climate change may increase the opportunity for water quality improvement in a key Iowa watershed

Abstract The Raccoon River Basin is the primary source for drinking water in Iowa's largest city and plays a major role in the Mississippi River Basin's high nutrient exports. Future climate change may have major impacts on the biological, physiological, and agronomic processes imposing a threat to ecosystem services. Efforts to reduce nitrogen (N) loads within this basin have included local litigation and the implementation of the Iowa Nutrient Reduction Strategy, which suggest incorporating bioenergy crops (i.e., miscanthus) within the current corn–soybean landscape to reach a 41% reduction in nitrate loads. This study focuses on simulating N export for historical and future land use scenarios by using an agroecosystem model (Agro‐IBIS) and a hydrology model (THMB) at the 500‐m resolution, similar to the scale of agricultural fields. Model simulations are driven by CMIP5 climate data for historical, mid‐century, and late‐century under the RCP 4.5 and 8.5 warming projections. Using recent crop profit analyses for the state of Iowa, profitability maps were generated and nitrogen leaching thresholds were used to determine where miscanthus should replace corn–soybean area to maximize reductions in N pollution. Our results show that miscanthus inclusion on low profit and high N leaching areas can result in a 4% reduction of N loss under current climate conditions and may reduce N loss by 21%–26% under future climate conditions, implying that water quality has the potential continue to improve under future climate conditions when strategically implemented conservation practices are included in future farm management plans.

54 ENVIRONMENTAL SCIENCES↗

Data from Bioenergy Sorghum Maintains Photosynthetic Capacity in Elevated Ozone Concentrations

Elevated tropospheric ozone concentration (O3) significantly reduces photosynthesis and productivity in several C4 crops including maize, switchgrass and sugarcane. However, it is unknown how O3 affects plant growth, development and productivity in sorghum ( Sorghum bicolor L.), an emerging C4 bioenergy crop. Here, we investigated the effects of elevated O3 on photosynthesis, biomass and nutrient composition of a number of sorghum genotypes over two seasons in the field using free-air concentration enrichment (FACE), and in growth chambers. We also tested if elevated O3 altered the relationship between stomatal conductance and environmental conditions using two common stomatal conductance models. Sorghum genotypes showed significant variability in plant functional traits, including photosynthetic capacity, leaf N content and specific leaf area, but responded similarly to O3. At the FACE experiment, elevated O3 did not alter net CO2 assimilation (A), stomatal conductance (gs), stomatal sensitivity to the environment, chlorophyll fluorescence and plant biomass, but led to reductions in the maximum carboxylation capacity of phosphoenolpyruvate and increased stomatal limitation to A in both years. These findings suggest that bioenergy sorghum is tolerant to O3 and could be used to enhance biomass productivity in O3 polluted regions.

Feedstock Production↗

Bioenergy sorghum maintains photosynthetic capacity in elevated ozone concentrations

Abstract Elevated tropospheric ozone concentration (O 3 ) significantly reduces photosynthesis and productivity in several C 4 crops including maize, switchgrass and sugarcane. However, it is unknown how O 3 affects plant growth, development and productivity in sorghum ( Sorghum bicolor L.), an emerging C 4 bioenergy crop. Here, we investigated the effects of elevated O 3 on photosynthesis, biomass and nutrient composition of a number of sorghum genotypes over two seasons in the field using free‐air concentration enrichment (FACE), and in growth chambers. We also tested if elevated O 3 altered the relationship between stomatal conductance and environmental conditions using two common stomatal conductance models. Sorghum genotypes showed significant variability in plant functional traits, including photosynthetic capacity, leaf N content and specific leaf area, but responded similarly to O 3 . At the FACE experiment, elevated O 3 did not alter net CO 2 assimilation ( A ), stomatal conductance ( g s ), stomatal sensitivity to the environment, chlorophyll fluorescence and plant biomass, but led to reductions in the maximum carboxylation capacity of phosphoenolpyruvate and increased stomatal limitation to A in both years. These findings suggest that bioenergy sorghum is tolerant to O 3 and could be used to enhance biomass productivity in O 3 polluted regions.

09 BIOMASS FUELS↗

Quantifying co-benefits of water quality policies: An integrated assessment model of land and nitrogen management

Due to the nature of nitrogen cycling, policies designed to address water quality concerns have the potential to provide benefits beyond the targeted water quality improvements. For example, actions to protect water quality by reducing nitrate leaching from agriculture also reduce emissions of nitrous oxide, a potent greenhouse gas. These positive effects, which are incidental to the regulation's intended target, are termed “co-benefits.” To quantify the co-benefits associated with reduced nitrate leaching, we integrate an economic model of farmer decision making with a model of terrestrial nitrogen cycling for the watershed surrounding Lake Mendota, Wisconsin, USA. Our modeling approach provides a framework that links air and water pollutants in an agri-environmental system and offers a direction for future studies. Our model results highlight the finding that the co-benefits from nitrous oxide abatement are substantial, and their inclusion increases the benefit–cost ratio of water quality policies. Consideration of these co-benefits has the potential to reverse the conclusions of benefit–cost analysis in the assessment of current water quality policies.

54 ENVIRONMENTAL SCIENCES↗

Molecular Insights into Novel Struvite–Hydrogel Composites for Simultaneous Ammonia and Phosphate Removal

Struvite (NH 4 MgPO 4 ·6H 2 O) mineralization is an effective technique for removing ammonium and phosphate species from wastewater. However, its wider use faces obstacles because of the copresence of various pollutants in wastewater and the additional requirement for magnesium to achieve proper supersaturation conditions. To address these challenges, this study developed novel mineral–hydrogel composites that can remove ammonium and phosphate simultaneously via heterogeneous struvite and calcium phosphate (CaP) mineralization in hydrogel matrices. The composites include in situ formed struvite and CaP mineral seeds, decreasing the nucleation energy barrier of struvite and CaP formation and promoting their heterogeneous nucleation kinetics even under undersaturation conditions in bulk solution. The dual struvite and CaP seeded composites can simultaneously reduce the ammonium and total phosphate concentrations up to 60% (26.3 mg of N/g) and 91% (9.54 mg of P/g), respectively. Furthermore, the average particle sizes in composites were increased from 6.12 to 14.8 nm after wastewater treatment. Moreover, various ions commonly existing in wastewater did not significantly interfere with the removal of ammonium and phosphate. Thus, these new mineral–hydrogel composites can provide an innovative way to lower nutrient levels before discharge to streams. Moreover, encapsulating ammonium and phosphate in mineral-hydrogel composites enables their upcycling in agricultural or biorefinery applications.

Cations↗

Toward a Universal Model of Hyporheic Exchange and Nutrient Cycling in Streams

In this paper we demonstrate that several ubiquitous hyporheic exchange mechanisms can be represented simply as a one-dimensional diffusion process, where the diffusivity decays exponentially with depth into the streambed. Based on a meta-analysis of 106 previously published laboratory measurements of hyporheic exchange (capturing a range of bed morphologies, hydraulic conditions, streambed properties, and experimental approaches) we find that the reference diffusivity and mixing length-scale are functions of the permeability Reynolds Number and Schmidt Number. These dimensionless numbers, in turn, can be estimated for a particular stream from the median grain size of the streambed and the stream's depth, slope, and temperature. Application of these results to a seminal study of nitrate removal in 72 headwater streams across the United States, reveals: (a) streams draining urban and agricultural landscapes have a diminished capacity for in-stream and in-bed mixing along with smaller subsurface storage zones compared to streams draining reference landscapes; (b) under steady-state conditions nitrate uptake in the streambed is primarily biologically controlled; and (c) median reaction timescales for nitrate removal in the hyporheic zone are 0.5 and 20 hr for uptake by assimilation and denitrification, respectively. While further research is needed, the simplicity and extensibility of the framework described here should facilitate cross-disciplinary discussions and inform reach-scale studies of pollutant fate and transport and their scale-up to watersheds and beyond.

54 ENVIRONMENTAL SCIENCES↗

Testing unified theories for ozone response in C 4 species

Abstract There is tremendous interspecific variability in O 3 sensitivity among C 3 species, but variation among C 4 species has been less clearly documented. It is also unclear whether stomatal conductance and leaf structure such as leaf mass per area (LMA) determine the variation in sensitivity to O 3 across species. In this study, we investigated leaf morphological, chemical, and photosynthetic responses of 22 genotypes of four C 4 bioenergy species (switchgrass, sorghum, maize, and miscanthus) to elevated O 3 in side‐by‐side field experiments using free‐air O 3 concentration enrichment (FACE). The C 4 species varied largely in leaf morphology, physiology, and nutrient composition. Elevated O 3 did not alter leaf morphology, nutrient content, stomatal conductance, chlorophyll fluorescence, and respiration in most genotypes but reduced net CO 2 assimilation in maize and photosynthetic capacity in sorghum and maize. Species with lower LMA and higher stomatal conductance tended to show greater losses in photosynthetic rate and capacity in elevated O 3 compared with species with higher LMA and lower stomatal conductance. Stomatal conductance was the strongest determinant of leaf photosynthetic rate and capacity. The response of both area‐ and mass‐based leaf photosynthetic rate and capacity to elevated O 3 were not affected by LMA directly but negatively influenced by LMA indirectly through stomatal conductance. These results demonstrate that there is significant variation in O 3 sensitivity among C 4 species with maize and sorghum showing greater sensitivity of photosynthesis to O 3 than switchgrass and miscanthus. Interspecific variation in O 3 sensitivity was determined by direct effects of stomatal conductance and indirect effects of LMA. This is the first study to provide a test of unifying theories explaining variation in O 3 sensitivity in C 4 bioenergy grasses. These findings advance understanding of O 3 tolerance in C 4 grasses and could aid in optimal placement of diverse C 4 bioenergy feedstock across a polluted landscape.

54 ENVIRONMENTAL SCIENCES↗

Circular Perspective for Utilization of Industrial Wastewaters via Phytoremediation

Wastewater generated in municipal rendering facilities requires multi-step treatment, but it may also serve as a source of nutrients and water and thus may be valorized before or instead of the necessary wastewater treatment operations. In this work, wastewaters from a composting plant were utilized to support the growth of Miscanthus x giganteus, known as both a remediation plant and an energy biomass source. A pot experiment was established to compare the effects of different wastewater doses (0, 50, 100, and 200 mL per pot per week) on the miscanthus biomass yield, phytoextraction of heavy metals, biomass heat of combustion, and plant condition. The increase in the wastewater dose resulted in increases in both biomass yield (from about 44 to 139%) and biomass heat of combustion (from 7 to 17%) when compared to the control sample, with no adverse effects on plant physiological parameters. The highest concentrations of metals were found in miscanthus grown with the highest dose of wastewaters. It was found that higher wastewater dose correlates to both higher phytoextraction and phytorecovery of metals from plant substrate and wastewaters. The highest metal uptake was identified for Fe (431 mg·pot −1 ), followed by Al, Zn, Mn, Cu, Ni, Cr. The lowest metal uptake was noted for Pb, Co and Cd (0.88, 0.11, and 0.95 mg·pot −1 , respectively). The results indicate that miscanthus can be recommended for industrial wastewater treatment. In addition, due to high absorption efficiency of the substrate components, miscanthus can be used as a remediation tool, e.g., for the ecological stabilization of remediation of metal-polluted soils, especially in municipal facilities like rendering plants. This presents a circular perspective for the valorization of post-fermentation wastewaters with subsequent growth of energy crops, with other potential benefits for the environment, such as soil treatment, absorption of CO 2 , and air purification.

Miscanthus x giganteus↗

Transformative Impacts of Laser-Induced Breakdown Spectroscopy on Environmental and Biological Research at Oak Ridge National Laboratory

This manuscript will present an advancement of transformative research that has been conducted at Oak Ridge National Laboratory (ORNL) over a 25-year period (2000–2025) on a variety of environmental and biological matrices. These investigations derived a fundamental understanding of how elemental detection and analysis of these matrices led to the knowledge and discovery of natural processes in plants and the environment. Each project led to the initiation of a new research area which unearthed awesome and novel breakthroughs. Highlights are listed below: 1. The preliminary research at ORNL centered on the detection of aerosols utilizing Laser-induced Breakdown Spectroscopy (LIBS) technology. The Clean Air Act Amendment (CAAA) of 1990 highlighted the importance of identifying hazardous air pollutants (HAPs) due to their impact on environmental and human health, thereby underscoring the need to detect various toxic elements. Research in aerosol chemistry aimed to identify these harmful elements released by factories during periods of increased emissions in their manufacturing processes. LIBS emerged as the most effective method for real-time, in situ measurements of metal species in both gaseous and aerosol phases. 2. An understanding of the presence of total carbon in soils gives perspective on how to develop carbon sequestration strategies. The recognition that carbon sinks can evolve back to carbon sources to emit back to the atmosphere was an important consideration. Also, the concentration of carbon in soil indicates the health of land areas for growing crops successfully. 3. The direct detection of most of the elements in a wood sample in a single emission spectrum, without sample preparation, encouraged the research to use the LIBS technique for preservative treated wood coupled with use of multivariate statistical methodology. Additionally, it encouraged the researchers to try to differentiate natural woods from different parts of the country, and it was successfully demonstrated that LIBS coupled with MVA analysis could differentiate wood of different species from each other and of similar species grown in different environments based on their elemental spectra. This was a breakthrough since it revealed a systematic approach to connect elemental scarcity and abundance to either drought or typical rainfall conditions for the hardwood trees grown in specific areas. 4. Furthermore, the research progressed to reveal physiological and developmental processes contributing to biomass production such that the variation in leaf elemental composition increases our understanding of terrestrial nutrient cycles, as well as tracking the transfer of toxic elements from soils to living organisms. 5. Recently another breakthrough viz., ionomics initiated the correlation of elements to specific genes, uncovering the function that the element performed in the plant. More recently, this has been extended from plants to fungi as well as fungi growing in symbiotic relations with plants.

09 BIOMASS FUELS↗

Thermodynamics of Minerals Stable near Earth's Surface

Project “Thermodynamics of Minerals Stable Near the Earth’s Surface” uses specialized calorimetric techniques to obtain new thermochemical data for solid phases of interest in the Earth’s “critical zone”, the near surface regions of the planet most directly affecting and affected by human activity. Major activity was in three areas: manganese oxide materials, aluminum clusters which are precursors to aluminum oxyhydroxide precipitates, and zeolites. All these classes of minerals are potential carriers of heavy metals and radionuclides in the environment, both within their crystal structures and as adsorbed layers or colloids. Their thermodynamic stability, as well as the sequence of stability of competing phases, governs the aqueous solubility of contaminants (and nutrients) in soil, groundwater, and sediments. The thermodynamics of these phases is strongly affected by particle size and crystallinity, since they often occur as very fine particles which do not coarsen in the near-surface environment. Many of these materials exhibit extensive polymorphism, multicomponent solid solution, and variable hydration states. Thus, one must define and systematize important thermodynamic variables, since one cannot make measurements on each and every possible phase, particle size, and composition. A major finding of the work on manganese oxides was labile water-induced oxidation-reduction reactions. These will be studied further by a combination of thermodynamic and synchrotron-based spectroscopic methods, the latter in collaboration with Peggy O’Day at UC Merced. The adsorption of other species, including simple organics, on such redox-active surfaces will also be investigated by a combination of thermochemical and spectroscopic studies. Studies of the energetics of water adsorption on mineral surfaces will be expanded to emphasize the adsorption of CO2 and small organic molecules, relevant to soil, groundwater, and the subsurface environment. Gas adsorption calorimetry, immersion calorimetry, and solution calorimetry will be combined with appropriate analytical and spectroscopic techniques to obtain a comprehensive picture of the interactions and their energetics. The evolution of aqueous aluminum clusters to form aluminum oxyhydroxide precipitates will be studied in detail by a combination of calorimetric and structural methods applied to aqueous samples aged at room temperature. The energetics of new classes of clusters will be explored. The project addresses several common themes relevant to the broad mission of the Department of Energy. Thermochemical data for minerals stable near the Earth’s surface, though still incomplete, are essential for understanding both natural and anthropogenic processes that affect our very existence on this planet. Such data contribute to the fundamental underpinning for mitigation and management strategies for the extraction and use of energy. Fundamental thermodynamic and mechanistic understanding is required to model processes ranging from heavy metal pollution to nuclear waste disposal to climate change.

58 GEOSCIENCES↗