Engineering topics

Giammar, Daniel

Publications and source records attributed to Giammar, Daniel.

10 records

DOE OSTI2024

Adsorption of neodymium, dysprosium, and ytterbium to goethite under varying aqueous chemistry conditions [dataset]

The adsorption of rare earth elements (REEs) to iron oxides can regulate the mobility of REEs in the environment and is heavily influenced by water chemistry. This study utilized batch experiments to examine the adsorption of Nd, Dy, and Yb to goethite under varying pH, electrolyte (type and concentration), and concentrations of dissolved inorganic carbon and citrate. REE adsorption was strongly influenced by pH, with an increase from essentially no adsorption at pH 3.0 to nearly complete adsorption at pH 6.5 and higher. Citrate enhanced the adsorption of REEs at low pH (< 5.0), likely by forming goethite-REE-citrate ternary surface complexes. However, citrate inhibited the adsorption of REEs at higher pH (> 5.0) by forming aqueous REE-citrate complexes. Ionic strength had a small influence on REE adsorption, and the presence of dissolved inorganic carbon had no discernible effect. Equilibrium adsorption was interpreted with a triple layer surface complexation model (SCM). The selection of surface complexation reactions was guided by extended X-ray absorption fine structure spectra. A SCM with a single bidentate inner-sphere surface complexation reaction for Nd and two inner-sphere surface complexation reactions (one monodentate and one bidentate reaction) for Dy and Yb effectively simulated adsorption across a broad range of conditions in the absence of citrate. Accounting for the effects of citrate on REE adsorption required the addition of up to two ternary REE-citrate-goethite surface complexes. The SCM can enable predictions of REE transport in subsurface environments that have goethite as an important adsorbent mineral. This predictive capability could contribute to identifying potential REE sources and facilitating efficient extraction of REEs.

58 GEOSCIENCES↗

DOE OSTI2023

Embracing the Intersections of Environmental Science, Engineering, and Geosciences to Solve Grand Challenges of the 21st Century

The U.S. National Academies report on Environmental Engineering for the 21st Century identified five grand challenges of sustainably supplying food, water, and energy; curbing climate change and adapting to its impacts; designing a future without pollution and waste; creating efficient, healthy, resilient cities; and fostering informed decisions and actions. (1) Addressing many of the grand challenges will require embracing the intersections of environmental science, engineering, and geosciences. These three fields are inherently interdisciplinary, and they naturally intersect with each other (Figure 1). Geosciences, or Earth sciences, study the dynamics of different spheres of Earth. One of its missions is to detect the availability of mineral, water, and fuel resources, for sustainable development, and new research opportunities were identified in “coevolution of life, environment, and climate” and “biogeochemical and water cycles in terrestrial environments and impacts of global change” by the U.S. National Research Council. (2) Environmental science and engineering focus on the spheres that intersect with human activities. Environmental science puts an emphasis on understanding the migration of naturally occurring and anthropogenic contaminants in the environment and their impact on ecosystem and human health, and environmental engineering centers on developing technologies for water supply, mineral exploration, and environmental remediation to mitigate adverse impacts.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Role of copper in nitrous oxide accumulation in wetland soils from Illinois and South Carolina and stream sediments from Tennessee

Denitrification is microbially-mediated through enzymes containing metal cofactors. Laboratory studies of pure cultures have highlighted that the availability of copper (Cu), required for the multicopper enzyme nitrous oxide reductase, can limit nitrous oxide (N2O) reduction. However, in natural aquatic systems, such as wetlands and hyporheic zones in stream beds, the role of Cu in controlling denitrification remains incompletely understood. In this study, we collected soils and sediments from three natural environments -- riparian wetlands, marsh wetlands, and a stream -- to investigate their nitrogen species transformation activity at background Cu levels and different supplemented Cu loadings. All of the systems contained solid-phase associated Cu below or around geological levels (40–280 nmol g-1) and exhibited low dissolved Cu (3–50 nM), which made them appropriate sites for evaluating the effect of limited Cu availability on denitrification.The dataset contains the variation in the nutrient (nitrate (NO3-), nitrite (NO2-), and ammonium (NH4+)) and N2O concentrations during the incubation experiments to evaluate the effect of Cu. We have also reported the variation in metal concentrations (Cu, iron(Fe) and manganese (Mn)) and dissolved organic carbon (DOC) concentrations during the incubations. The parameters obtained using a kinetic model to quantitatively report the effect of Cu on nitrogen species conversion in natural aquatic systems are also added in the dataset. The dataset also contains the labile concentration of Cu estimated using a speciation model in MINTEQ. All data are provided in text-based CSV format with header sections indicating the data contained in each file and the corresponding units.Our study suggests that high concentrations of N2O accumulated in all microcosms lacking Cu amendment except for one stream sediment sample. With Cu added to provide dissolved concentrations at trace levels (10–300 nM), the reduction rate of N2O to N2 in the wetland soils and stream sediments was enhanced. A kinetic model could account for the trends in nitrogen species by combining the reactions for microbial reduction of NO3- to NO2-/N2O/N2 and abiotic reduction of NO2 to nitrogen (N2_. The model revealed that the rate of N2O to N2 conversion increased significantly in the presence of Cu. For riparian wetland soils and stream sediments, the kinetic model also suggested that overall denitrification is driven by abiotic reduction of NO2- in the presence of inorganic electron donors. This study demonstrated that natural aquatic systems containing Cu at concentrations less than or equal to crustal abundances may display incomplete reduction of N2O to N2 that would cause N2O accumulation and release to the atmosphere.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Effect of fluctuating redox conditions on trace metal release from wetland soils from South Carolina and stream sediments from Tennessee

Natural aquatic systems undergo fluctuating redox conditions due to microbial activity, varying water saturation levels, and nutrients dynamics. With fluctuating oxic and anoxic conditions, trace metals can be mobilized or sequestered in response to changes in iron and sulfur speciation and the concentrations and lability of organic carbon. We conducted a systematic laboratory-based microcosm study to examine the effect of redox fluctuations on trace metal mobility in samples collected from two different natural aquatic systems: riparian wetlands and a stream. We incubated water-saturated soils under three cycles of anoxic-oxic conditions (τanoxic:τoxic = 3) spanning 24 days and monitored the change in dissolved and bioavailable metal (copper (Cu), nickel (Ni), zinc (Zn), cobalt (Co), iron (Fe), and manganese (Mn)) concentrations. The dataset includes the results of the variation in metal concentrations due to redox fluctuations in wetland soils and stream sediments. Additionally, the variation in the bioavailable concentration of metals obtained using passive samplers based on diffuse gradient in thin-films technique is included in the dataset. We have also reported the change in the pH values and dissolved oxygen concentrations in the microcosms during the entire study of 24 days. The dataset also contains the dissolved organic carbon and sulfate concentrations, and the data on fractions of metals bound to reducible and oxidizable phases. For materials from both the wetlands and the stream, anoxic conditions favored Co and Zn release, which corresponded with the reductive dissolution of iron oxides. In contrast, dissolved Cu concentrations increased under oxic conditions for both sites and correlated positively with the release of sulfate. In wetland soils, dissolution of Fe (hydr)oxides increased Ni solubility; however, in stream sediments, Ni release occurred when sulfides or organic matter were oxidized. For stream sediments, each subsequent redox cycle increased the bioavailability of trace metals. Upon redox fluctuations in wetland soils, the bioavailability of Zn and Cu increased, whereas bioavailable Ni and Co decreased. This study illustrates that different trace metals display distinct bioavailability patterns during oxic-anoxic fluctuations in natural environments. The biogeochemical cycling of carbon and nitrogen in systems with redox fluctuations may be influenced by these patterns in trace metal availability in addition to the availability of electron donors and acceptors.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Uptake and speciation of trace metal inputs to Wetland Soils from Illinois and South Carolina and Stream Sediments from Tennessee

Metals occur in all ecosystems, although their concentrations vary depending on their natural geologic conditions and surrounding human activities. In addition to metals intrinsically present from the geology of a particular system, metals can enter environmental systems from a wide variety of natural and anthropogenic sources, such as sediment re-suspension, mining operations, industrial processes, agricultural activities, and atmospheric deposition. While metals can be toxic at high concentrations, some metals serve as essential micronutrients for biogeochemical processes. Metal transport and availability in engineered and natural water systems depend on processes of adsorption/desorption, oxidation/reduction, dissolution/precipitation, and ligand complexation. Insights into the speciation of metals and their bioavailability will also help advance understanding of the roles of metals in the biogeochemical cycling of nutrients. We conducted batch experiments under anoxic conditions on soils and sediments collected from three different natural aquatic systems to understand their response to influxes of dissolved Cu, Ni and Zn. While soils and sediments from all sites could strongly bind added trace metals, there were substantial differences in trace metal uptake trends between different sites, especially for Cu. There was no distinct correlation between trace metal uptake and the total organic matter, iron, and sulfur content present in the samples. X-ray absorption spectroscopy indicated that the speciation of the freshly added metals taken up by the solids differs substantially from the speciation of the metals originally present in unamended samples. Cu sulfides dominated speciation at low loadings (1 µmol/g), whereas complexation to thiol groups and formation of metallic Cu governed speciation at high loadings (10 µmol/g). For Ni and Zn, adsorption to mineral surfaces and organic matter governed their speciation in materials from most sites. This study suggests that the background speciation of metals in natural aquatic systems is a poor predictor of the speciation and lability of metals introduced to terrestrial aquatic systems from anthropogenic or natural processes. Our findings imply that geochemical processes controlling trace metal speciation may vary considerably with metal loading in different natural systems. Data are provided for marsh wetland soils at Argonne National Laboratory (Marsh 1 and Marsh 2), riparian wetland soils (Riparian 1 and Riparian 2) in the Tims Branch watershed at Savannah River National Laboratory, and stream bed sediments (Stream 1 and Stream 2) from East Fork Poplar Creek near Oak Ridge National Laboratory. Data package includes the results of trace metal uptake experiments conducted on the selected sites for determining their capacity to immobilize metals under different loadings. XANES spectra for Cu, Ni, ad Zn at different loadings are included in the package. The abundance of different trace metal species obtained using linear combination fitting in ATHENA are also included in the data.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Data for EMSL Project 50768 from September 2021

Explore the source record for details and available documents.

Hess, Nancy↗

DOE OSTI2021

National Alliance for Water Innovation (NAWI) Master Technology Roadmap

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2021

National Alliance for Water Innovation (NAWI) Power Sector Technology Roadmap 2021

The National Alliance for Water Innovation (NAWI) is a research consortium formed to accelerate transformative research in desalination and treatment to lower the cost and energy required to produce clean water from nontraditional water sources and realize a circular water economy. NAWI’s goal is to enable the manufacturing of energy-efficient desalination technologies in the United States at a lower cost with the same (or higher) quality and reduced environmental impact for 90 percent of nontraditional water sources within the next 10 years. The nontraditional source waters of interest include brackish water; seawater; produced and extracted water; power, mining, industrial, municipal, and agricultural waste waters. When these desalination and treatment technologies are fully developed and utilized, they will be able to contribute to the water needs for many existing end-use sectors. NAWI has identified five end-use sectors that are critical to the U.S. economy for further exploration: Power, Resource Extraction, Industry, Municipal, and Agriculture (PRIMA). This Power Sector roadmap aims to advance desalination and treatment of nontraditional source waters for beneficial use in public water supplies by identifying research and development (R&D) opportunities that help overcome existing treatment challenges. Under NAWI’s vision, the transition from a linear to a circular water economy with nontraditional source waters will be achieved by advancing desalination and reuse technologies in six key areas: Autonomous operations, Precision separations, Resilient treatment and transport, Intensified brine management, Modular membrane systems, and Electrified treatment systems, collectively known as the A-PRIME areas. Technological advances in these different areas will enable nontraditional source waters to achieve pipe parity with traditional supplies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2021

National Alliance for Water Innovation (NAWI) Municipal Sector Technology Roadmap 2021

The National Alliance for Water Innovation (NAWI) is a research consortium formed to accelerate transformative research in desalination and treatment to lower the cost and energy required to produce clean water from nontraditional water sources and realize a circular water economy. NAWI's goal is to enable the manufacturing of energy-efficient desalination technologies in the United States at a lower cost with the same (or higher) quality and reduced environmental impact for 90 percent of nontraditional water sources within the next 10 years. The nontraditional source waters of interest include brackish water; seawater; produced and extracted water; power, mining, industrial, municipal, and agricultural waste waters. When these desalination and treatment technologies are fully developed and utilized, they will be able to contribute to the water needs for many existing end-use sectors. NAWI has identified five end-use sectors that are critical to the U.S. economy for further exploration: Power, Resource Extraction, Industry, Municipal, and Agriculture (PRIMA). This Municipal Sector roadmap aims to advance desalination and treatment of nontraditional source waters for beneficial use in public water supplies by identifying research and development (R&D) opportunities that help overcome existing treatment challenges. Under NAWI's vision, the transition from a linear to a circular water economy with nontraditional source waters will be achieved by advancing desalination and reuse technologies in six key areas: Autonomous operations, Precision separations, Resilient treatment and transport, Intensified brine management, Modular membrane systems, and Electrified treatment systems, collectively known as the A-PRIME areas. Technological advances in these different areas will enable nontraditional source waters to achieve pipe parity with traditional supplies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2021

Soil and Water Chemistry and Trace Metal Extractability and Speciation in Wetland Soils from Illinois and South Carolina and Stream Sediments from Tennessee

Dataset revised on October 15, 2021. This revision adds sulfur and iron X-ray absorption near-edge structure spectra for the wetland soils and stream sediments from the field areas. It also renames the sample locations in a way that is more intuitive to readers of the companion paper that is under review. Finally, the data filenames and organization have been updated in their labeling to parallel the data sources in the associated paper. The abstract text and methods were also revised to reflect the data that was added to the dataset.Trace metals are essential for microbially-mediated biogeochemical processes occurring in anoxic wetland soils and stream bed sediments, such as denitrification, methanogenesis, and mercury methylation. Low availability of these elements may potentially inhibit key components of anaerobic carbon and nitrogen cycling and contaminant transformation. The solid-phase speciation of trace metals likely plays an important role in controlling their bioavailability. Metal speciation is well studied in contaminated soils and sediments as well as those naturally elevated in trace metals. However, less is known regarding the chemical forms of trace metals in systems having concentrations similar to geological background levels, the very settings where metal limitations may be most prevalent. We have investigated trace metal concentrations, extractability, and solid-phase speciation in three freshwater subsurface aquatic systems: marsh wetland soils, riparian wetland soils, and the sediments of a streambed.Data are provided for marsh wetland soils at Argonne National Laboratory, riparian wetland soils in the Tims Branch watershed at Savannah River National Laboratory, and stream bed sediments from East Fork Poplar Creek near Oak Ridge National Laboratory. Soil and sediment elemental abundances, mineralogy, and extractable nutrients as well as dissolved major elements, anions, trace metals, and nutrients in the overlying surface waters are provided. In addition, the results of sequential chemical extraction for the trace metals cobalt, nickel, copper, and zinc from the soils and sediment are reported as well as X-ray absorption near-edge structure (XANES) spectra in these materials are reported. To aid interpretation of these data, XANES spectra of sulfur in the soils and sediments as well as both XANES and extended X-ray absorption fine structure (EXAFS) spectra of iron in these materials are reported. The data package also includes the XANES spectra of reference standards and a potential interferent in the measurements. All data are provided in text-based CSV format with header sections indicating the data contained in each file and the corresponding units. Note that "u" is used in place of Greek lower case mu to indicate the micro prefix on units.

54 ENVIRONMENTAL SCIENCES↗