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Predicting redox conditions in groundwater at a national scale using random forest classification

Redox conditions in groundwater may markedly affect the fate and transport of nutrients, volatile organic compounds, and trace metals, with significant implications for human health. While many local assessments of redox conditions have been made, the spatial variability of redox reaction rates makes the determination of redox conditions at regional or national scales problematic. In this study, redox conditions in groundwater were predicted for the contiguous United States using random forest classification by relating measured water quality data from over 30,000 wells to natural and anthropogenic factors. The model correctly predicted the oxic/suboxic classification for 78 and 79% of the samples in the out-of-bag and hold-out data sets, respectively. Variables describing geology, hydrology, soil properties, and hydrologic position were among the most important factors affecting the likelihood of oxic conditions in groundwater. Important model variables tended to relate to aquifer recharge, groundwater travel time, or prevalence of electron donors, which are key drivers of redox conditions in groundwater. Partial dependence plots suggested that the likelihood of oxic conditions in groundwater decreased sharply as streams were approached and gradually as the depth below the water table increased. The probability of oxic groundwater increased as base flow index values increased, likely due to the prevalence of well-drained soils and geologic materials in high base flow index areas. The likelihood of oxic conditions increased as topographic wetness index (TWI) values decreased. High topographic wetness index values occur in areas with a propensity for standing water and overland flow, conditions that limit the delivery of dissolved oxygen to groundwater by recharge; higher TWI values also tend to occur in discharge areas, which may contain groundwater with long travel times. A second model was developed to predict the probability of elevated manganese (Mn) concentrations in groundwater (i.e., ≥50 μg/L). The Mn model relied on many of the same variables as the oxic/suboxic model and may be used to identify areas where Mn-reducing conditions occur and where there is an increased risk to domestic water supplies due to high Mn concentrations. Model predictions of redox conditions in groundwater produced in this study may help identify regions of the country with elevated groundwater vulnerability and stream vulnerability to groundwater-derived contaminants.

contiguous United States

Perfluorooctane sulfonamide induced autotoxic effects on the zebrafish immune system

Perfluorooctane sulfonamide (PFOSA) is an immediate perfluorooctanesulfonate (PFOS) precursor (PreFOS). Previous studies have shown PFOSA to induce stronger toxic responses compared to other perfluorinated compounds (PFCs). However, the specific nature of PFOSA-induced toxicity, whether autonomous or mediated by its metabolite PFOS, has not been fully elucidated. This study systematically investigates the immunomodulatory effects of PFOSA and PFOS in zebrafish ( Danio rerio ). Exposure to PFOSA compromised the zebrafish’s ability to defend against pathogenic infections, as evidenced by increased bacterial adhesion to their skin and reduced levels of the biocidal protein lysozyme (LYSO). Moreover, PFOSA exposure was associated with disruptions in inflammatory markers and immune indicators, along with a decrease in immune cell counts. The findings from this study suggest that the immunotoxicity effects of PFOSA are primarily due to its own toxicity rather than its metabolite PFOS. This conclusion was supported by dose-dependent responses, the severity of observed effects, and multivariate analysis. In addition, our experiments using NF-κB-morpholino knock-down techniques further confirmed the role of the Nuclear factor-κappa B pathway in mediating PFOSA-induced immunotoxicity. In conclusion, this study reveals that PFOSA impairs the immune system in zebrafish through an autotoxic mechanism, providing valuable insights for assessing the ecological risks of PFOSA.

Environmental Science and Technology

Geographic drivers of mercury entry into aquatic food webs revealed by mercury stable isotopes in dragonfly larvae

Atmospheric mercury (Hg) emissions and subsequent transport and deposition are major concerns within protected lands, including national parks, where Hg can bioaccumulate to levels detrimental to human and wildlife health. Despite this risk to biological resources, there is limited understanding of the relative importance of different Hg sources and delivery pathways within protected regions. Here, we used Hg stable isotope measurements of a single aquatic bioindicator, dragonfly larvae, to determine if these tracers can resolve spatial patterns in Hg sources, delivery mechanisms, and aquatic cycling at a national scale. Mercury isotope values in dragonfly tissues varied among habitat types (e.g., lentic, lotic, wetland) and geographic location. Photochemical-derived isotope fractionation was habitat-dependent and influenced by factors that impact light penetration directly or indirectly, including dissolved organic matter, canopy cover, and total phosphorus. Strong patterns for Δ 200 Hg emerged in the western US, highlighting the relative importance of wet deposition sources in arid regions in contrast to dry deposition delivery in forested regions. This work highlights the efficacy of dragonfly larvae as biosentinels for Hg isotope studies due to their ubiquity across freshwater ecosystems and ability to track variation in Hg sources and processing attributed to small-scale habitat and large-scale regional patterns.

Environmental Science and Technology

Structurally selective ozonolysis of p-phenylenediamines and toxicity in coho salmon and rainbow trout

The tire-rubber-derived ozonation product of N -(1,3-dimethylbutyl)- N ′-phenyl- p -phenylenediamine (6PPD), N -(1,3-dimethylbutyl)- N ′-phenyl- p -phenylenediamine-quinone (6PPD-Q), was recently discovered to cause acute mortality in coho salmon ( Oncorhynchus kisutch ). para -Phenylenediamines (PPDs) with variable side chains distinct from 6PPD have been identified as potential replacement antioxidants, but their toxicities remain unclear under environmentally relevant ozone conditions. We herein tested the multiphase gas-surface ozone reactivity of four select PPDs [6PPD, N -isopropyl- N ′-phenyl- p -phenylenediamine (IPPD), N , N ′-diphenyl- p -phenylenediamine (DPPD), and N -phenyl- N ′-cyclohexyl- p -phenylenediamine (CPPD)] and evaluated the toxicity of their reaction mixtures in coho salmon, rainbow trout ( Oncorhynchus mykiss ), and fathead minnow ( Pimephales promelas ). 6PPD and IPPD were found to rapidly react with ozone, while no significant multiphase ozone reactivity was observed for DPPD or CPPD. The viability of coho salmon CSE-119 cells was strongly affected by the ozonolysis products of 6PPD but not by those of the other three PPDs. Acute mortality was only observed in juvenile rainbow trout that were exposed to oxidized 6PPD, suggesting a common mechanism of toxic action in the two salmonid fish species. This study reports the structurally selective ozone reactivity of PPDs and the unique toxicity of 6PPD ozonolysis mixtures, which demonstrates that other PPDs are potential alternative antioxidants.

Environmental Science and Technology

Predictive understanding of stream salinization in a developed watershed using machine learning

Stream salinization is a global issue, yet few models can provide reliable salinity estimates for unmonitored locations at the time scales required for ecological exposure assessments. Machine learning approaches are presented that use spatially limited high-frequency monitoring and spatially distributed discrete samples to estimate the daily stream-specific conductance across a watershed. We compare the predictive performance of space- and time-unaware Random Forest models and space- and time-aware Recurrent Graph Convolution Neural Network models (KGE: 0.67 and 0.64, respectively) and use explainable artificial intelligence methods to interpret model predictions and understand salinization drivers. These models are applied to the Delaware River Basin, a developed watershed with diverse land uses that experiences anthropogenic salinization from winter deicer applications. These models capture seasonality for the winter first flush of deicers, and the streams with elevated predictions correspond well with indicators of deicer application. This result suggests that these models can be used to identify potential salinity-impaired streams for winter best management practices. Daily salinity predictions are driven primarily by land cover (urbanization) trends that may represent anthropogenic salinization processes and weather at time scales up to three months. Such modeling approaches are likely transferable to other watersheds and can be applied to further understand salinization risks and drivers.

Environmental Science and Technology

Immediate effect of floating solar energy deployment on greenhouse gas dynamics in ponds

Floating photovoltaic (FPV) solar energy offers promise for renewable electricity production that spares land for other societal benefits. FPV deployment may alter greenhouse gas (GHG) production and emissions from waterbodies by changing physical, chemical, and biological processes, which can have implications for the carbon cost of energy production with FPV. Here, we use an ecosystem-scale experiment to assess how GHG dynamics in ponds respond to installation of operationally representative FPV. Following FPV deployments of 70% array coverage, daily whole-pond GHG emissions increased by 26.8% on a carbon dioxide-equivalent (CO 2 -eq) basis, and dissolved oxygen availability rapidly decreased. Despite increased emissions following FPV deployment, FPV-derived GHG emissions from waterbodies are likely lower than landscape GHG emissions associated with terrestrial solar and hydropower production on a CO 2 -eq kWh –1 basis. Adaptive management strategies like bubbler installation may reduce the magnitude of FPV impacts on GHG and dissolved oxygen dynamics.

Environmental Science and Technology

Adaptable plasmonic membrane sensors for fast and reliable detection of trace low micrometer microplastics in lake water

In freshwater environments, low-micrometer microplastics (LMMPs) have captured significant attention due to their prevalence and toxicity. Yet, rapid detection of LMMPs (1–10 μm) at the single-particle level within complex freshwater matrices remains a hurdle. We developed an adaptable plasmonic membrane sensor for fast detection of individual LMMPs in eutrophic lake waters. The plasmonic membrane sensor functions both as a membrane filter and as a sensor for LMMP collection and analysis. Among the four types of membrane sensors, polycarbonate track-etch (PCTE) membrane sensors exhibit superior imaging quality for LMMPs due to their flat and homogeneous surfaces. Besides the significantly improved imaging contrast and reduced background interferences, the Raman intensity of LMMPs is enhanced by 48% ± 25% on PCTE membrane sensors compared to unmodified membranes. The increased Raman intensities of a chemical probe with an increasing gold layer thickness and a decreasing membrane pore size suggest a surface-enhanced Raman scattering effect from the membrane sensors. The membrane sensors achieve a detection limit of 1 μg/L and an ultrafast scanning time of 0.01 s for individual LMMPs across natural eutrophic lake water. The developed membrane sensors offer an adaptable tool for the swift and reliable detection of individual LMMPs in complex environmental matrices.

Environmental Science and Technology

Ecosystem drivers of freshwater mercury bioaccumulation are context-dependent: Insights from continental-scale modeling

Significant variation in mercury (Hg) bioaccumulation is observed across the diversity of freshwater ecosystems in North America. While there is support for the major drivers of Hg bioaccumulation, the relative influence of different external factors can vary widely among waterbodies, which makes predicting Hg risk across large spatial scales particularly challenging. We modeled Hg bioaccumulation by coupling Hg concentrations in more than 21,000 dragonflies collected across the United States from 2008 to 2021 with a suite of chemical (e.g., dissolved organic carbon (DOC), pH, sulfate) and landscape (e.g., soil characteristics, land cover) variables representing external drivers of Hg methylation, transport, and uptake. Model predictions explained 85% of the variation in dragonfly Hg concentrations across the United States. Certain predictor variables were more important than others (e.g., DOC, pH, and percent wetland), and they varied among waterbodies. Variation in Hg bioaccumulation was explained by including habitat and ecosystem type in a hierarchical modeling framework, which confirms the context-dependency of external factors in explaining Hg bioaccumulation across disparate freshwater ecosystems. This continent-scale model provides valuable insights into the processes underlying landscape-scale patterns in Hg exposure risk and demonstrates that drivers of Hg methylation and bioaccumulation are habitat- and ecosystem-dependent.

Environmental Science and Technology

Intersection of wildfire and legacy mining poses risk to water quality

Mining and wildfires are both landscape disturbances that pose elevated and substantial hazards to water supplies and ecosystems due to increased erosion and transport of sediment, metals, and debris to downstream waters. The risk to water supplies may be amplified when these disturbances occur in the same watershed. This work describes mechanisms by which the intersection of mining and wildfire may lead to elevated metal concentrations in downstream waters: (1) conveyance of metal-rich ash and soil to surface waters, (2) increased dissolution and transport of dissolved metals due to direct contact of precipitation with mine waste, (3) increased erosion and transport of metal-rich sediment from mining waste, (4) remobilization of previously deposited metal-contaminated floodplain sediment by higher postfire flood flows, and (5) increased metal transport from underground mine workings. Predicted increases in wildfire size, frequency, and burn severity, together with the ongoing need for metal resources, indicate that improved mapping, monitoring, modeling, and mitigation techniques are needed to manage the geochemical hazard of the intersection of wildfire and mining and implications for water availability.

Environmental Science and Technology

Municipal and industrial wastewater treatment plant effluent contributions to per- and polyfluoroalkyl substances in the Potomac River: A basin-scale measuring and modeling approach

Managing per- and polyfluoroalkyl substances (PFAS) in water resources requires a basin-scale approach. Predicted environmental concentrations (PEC) and stream-vulnerability scores for PFAS were determined for the Potomac River watershed in the eastern United States. Approximately 15% of stream reaches contained municipal and/or industrial wastewater treatment plant (WWTP) discharges that are presumptive PFAS sources, comprising from <1 to >90% of streamflow. Mean annual PEC, based on the summed concentrations of eight PFAS detected in WWTP effluents (ΣPFAS PEC ), for all stream reaches in the watershed was 3.8 ng L –1 , and stream reaches impacted by WWTP had perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) PEC of 0.39 and 0.14 ng L –1 . For locations where measured-environmental concentrations (MEC) were determined, municipal and industrial WWTP contributed 7.8% (0 to 65%) of the total annual streamflow and MEC were greater than PEC in 99% of the samples, indicating additional potential PFAS sources. The mean ΣPFAS PEC was 9.1 ng L –1 compared to a mean sum of PFAS MEC of 34 ng L –1 . Under mean-August low-flow, 17% and 9.4% of the water-supply intakes had maximum PFOA and PFOS PEC exceeding drinking water maximum contaminant levels.

Maryland, Pennsylvania, Virginia, West Virginia

Sulfate reduction drives elevated methylmercury formation in water column of eutrophic freshwater lake

Mercury (Hg) contamination of aquatic food webs is controlled in part by the formation and accumulation of toxic and bioaccumulative methylmercury (MeHg). MeHg production is mediated by metabolically diverse microorganisms carrying the hgcAB gene pair, while the demethylation reaction is mediated by several biotic and abiotic processes. However, the relative importance of these two processes on MeHg accumulation and the environmental factors that influence them are poorly characterized, especially in eutrophic environments. In this study, both Hg methylation and MeHg demethylation in a eutrophic freshwater lake were linked to ambient MeHg concentrations and hgcA abundance and expression. High methylation rate potentials indicated in situ MeHg formation was a key source of MeHg to the water column, driven by high hgcA abundance and transcription. Molybdate treatment decreased methylation rate potentials, highlighting the importance of sulfate reduction in driving MeHg formation. Sulfate-reducing bacteria accounted for over 50% of the hgcA gene transcription, despite representing less than 10% of the hgcA -carrying microbial community. An arsR -like transcriptional regulator preceded many hgcA sequences; these were transcriptionally active and linked to lower hgcA expression. Overall, this study elucidates the microbial and biogeochemical processes that influence the in situ formation of MeHg in understudied eutrophic freshwater environments.

Wisconsin

Selenium differentially influences methylmercury retention across mayfly life stages

Though high mercury and selenium concentrations are individually toxic to organisms, there is a hypothesized antagonistic relationship. This potential mercury–selenium interaction is under-studied in aquatic macroinvertebrates, particularly in relation to complex life histories. We examined the proposed effect of selenium on methylmercury accumulation between four life stages for a parthenogenetic mayfly ( Neocloeon triangulifer ). We exposed diatoms to elevated methylmercury concentrations and fed them to mayflies exposed to elevated aqueous selenomethionine. We found some support for the mercury–selenium antagonism hypothesis, but it was context-specific. Selenium reduced methylmercury accumulation in high but not low methylmercury environments. Though terrestrial adult life stages had higher mercury concentrations compared to aquatic larval life stages, cumulative life history transfer factor (LHTF; ratio of methylmercury in adult imago to late instar larvae) differed by treatment. LHTF was constant for all aqueous selenium exposure levels at high dietary methylmercury (selenium impacts on methylmercury uptake and loss) but increased with aqueous selenium exposures at low dietary methylmercury (selenium impacts on methylmercury uptake only), suggesting a synergistic enhancement of MeHg transfer between life stages with increased aqueous Se exposure levels. These results suggest that animals eating adult aquatic insects are exposed to higher concentrations of methylmercury than those feeding on larval insects across selenium and methylmercury levels, but interference of selenium on methylmercury accumulation is only present at high methylmercury environments.

Environmental Science and Technology

Ecological factors decouple Great Lakes fish mercury concentrations trends decadal declines in mercury emissions

Atmospheric mercury (Hg) deposition has been declining in North America but remains the dominant delivery mechanism to the Great Lakes. The Lakes are highly efficient at bioaccumulating methylmercury, making the fish excellent sentinels for tracking shifts in atmospheric Hg deposition. Invasive mussels have altered biogeochemical processes, prey populations and fish dietary strategies asynchronously and to varied extents across the lower four lakes, impacting fish Hg exposure. To test if fish are adapting to new biogeochemical conditions, we analyzed a 40 year fish archive for carbon and nitrogen isotope ratios and amino acid-specific nitrogen isotope ratios. To assess Hg sources, we measured Hg isotope ratios. We reconstructed and compared energetic pathways that impact fish Hg concentrations to Hg-source trends. We found fish-Hg concentrations are declining but not monotonically due to ecological disturbances. Fish-Hg isotope values, unimpacted by ecological disturbance, confirm that sources of bioaccumulated Hg shift contemporaneously with changes in atmospheric Hg concentrations. Across Lakes, the degree of responsiveness to changes in atmospheric Hg concentrations mirrors the proportion of atmospheric-delivered Hg we previously modeled. Changes in both fish concentrations and fish isotope values outpace paleolimnetic reconstructions suggesting declines in atmospheric Hg concentrations impact fish Hg more than sediment.

Great Lakes

The effects of forest harvesting on total and methylmercury concentrations in surface waters depend on harvest practices and physical site characteristics

Forest harvesting can lead to mercury (Hg) mobilization from soils to aquatic habitats and promote the transformation of inorganic Hg to highly neurotoxic and bioaccumulative methyl-Hg (MeHg). Multiple past studies reveal broad variation of stream water MeHg and total Hg (THg) concentrations responses to forest harvesting, which has confounded messaging to forest and resource managers. To advance beyond divergent and sometimes contradictory findings, we synthesize information for 23 previously studied catchments in North America and Fennoscandia, and compiled a uniform set of soil, landscape, and harvesting properties to identify forest management, riparian, and hillslope factors that influence responses of stream water MeHg and THg concentrations. From this synthesis, we found catchments with high soil moisture and organic soil layers > 100 cm to be at highest risk for disturbance-induced increases in MeHg formation after harvest, but not necessarily affecting concentrations of MeHg in stream waters. Instead, the combination of MeHg formation in soils along with factors that affect mobilization with runoff to streams most influenced how forest harvest affects MeHg concentrations in stream waters.

Environmental Science and Technology

Hydraulic connectivity and hydrochemistry influence microbial community structure in agriculturally-affected alluvial aquifers in the Midwestern United States

Alluvial aquifers can provide ecosystem services and drinking water, but much remains unknown about human effects on aquifer microbiomes. Therefore, we used amplicon sequencing and hydrochemical characterization to pair microbial communities with environmental conditions across 37 alluvial aquifer wells. The study region spanned eastern Iowa and southern Minnesota (USA) and contained a combination of drinking water and monitoring wells. In terms of microbial ecology, dominant phyla across the wells included Proteobacteria, Bacteroidota, Patescibacteria, Planctomycetota, and Nitrospirota. Tritium, an indicator of infiltration and surface water influence, was the highest correlated variable with the Shannon index (α-diversity) by the Spearman rank sum (ρ = 0.60) and one of only four significant environmental variables in the constrained correspondence analysis. We built random forest regression models to predict tritium concentrations from microbial family relative abundance (held-out testing coefficient of determination ( R 2 ) = 0.77 and mean absolute percentage error = 7%) and interpreted the models with Shapley additive explanation values. The most important families for predicting tritium concentrations were Nitrosopumilaceae and Methylomirabilaceae . Upwelling methane could contribute to the unusual coupling of ammonia oxidation by Nitrosopumilaceae with simultaneous nitrite-dependent methane oxidation by Methylomirabilaceae . Taken together, we illuminate the relationship among hydrochemistry, hydraulic connectivity, and alluvial aquifer microbiomes.

Iowa, Minnesota

Comparison of Microcystin-LR degradation by UV222 and UV254

Microcystin-LR (MC-LR), a toxin produced during some cyanobacterial harmful algal blooms (cyanoHABs), can harm ecosystems and require consideration in water treatment. Ultraviolet (UV)-C treatment has the potential to degrade cyanotoxins with less harmful byproducts than other treatments. This study compares MC-LR degradation in three different water types using UV-C light emitted from a krypton-chlorine excimer lamp (UV light at 222 nm, UV 222 ) or a low-pressure (LP) Hg lamp (UV light at 254 nm, UV 254 ). Quantitative analyses by enzyme-linked immunosorbent assay (ELISA), ultra-performance liquid chromatography with photodiode array detection (UPLC-PDA), and high-performance liquid chromatography-high-resolution mass spectrometry (LC-HRMS) demonstrated that UV 222 had a degradation rate constant 2.4–4.2 times greater than UV 254 . This aligns with the MC-LR molar absorption (ε) and quantum yield (Φ) in deionized (DI) water. LC-HRMS revealed the photoisomer concentration increasing with UV dose. Trends of abundant photoisomers indicate further degradation. Together, these trends indicate UV 222 is a more complete pathway toward protein phosphatase inhibition 2A (PP2A) inactive compounds than UV 254 . Electrical energy per order ( E EO ) for UV 222 and UV 254 was similar across all water matrices and analytical methods, demonstrating that UV 222 has the potential to surpass the degradation and electrical efficiency of UV 254 used in water disinfection.

Environmental Science and Technology

Evaluation of 6PPD-quinone lethal toxicity and sublethal effects on disease resistance and swimming fitness in coastal cutthroat trout (Oncorhynchus clarkii clarkii)

6PPD-quinone (6PPDQ), derived from the tire-protectant 6PPD reacting with ozone, is an emerging contaminant of concern owing to its role in coho salmon ( Oncorhynchus kisutch ) deaths via urban runoff mortality syndrome (URMS). Given the impact of 6PPDQ on aquatic life in urban streams, we addressed the acute toxicity of 6PPDQ exposure on coastal cutthroat trout (CCT) ( Oncorhynchus clarkii clarkii ), a species sympatric with coho salmon in natal watersheds. Using static exposures coupled with analytical chemistry, we determined the 24-h LC 50 values for alevin (297.2 ng/L), swim-up fry (39.6 ng/L), 5-month parr (103.3 ng/L), and 13-month juveniles (185.9 ng/L)─values similar to toxicity observed in coho salmon. Additionally, the 96-h LC 50 (77.6 ng/L) was 2.4 times more lethal for juvenile CCT. We assessed potential effects of sublethal 6PPDQ exposure on disease resistance to infectious hematopoietic necrosis (IHN), an endemic viral disease of Pacific salmon, and to swimming performance. Sublethal 6PPDQ (53.6 ng/L) did not affect survival of parr exposed to IHN virus compared to virus alone. Conversely, 6PPDQ exposure as low as 72.2 ng/L significantly reduced 15- and 24-month juvenile swimming performance, and 120.5 ng/L 6PPDQ increased blood hematocrit. Overall, CCT are the second most sensitive species tested to date for 6PPDQ sensitivity which further emphasizes the need for identifying alternatives to 6PPD.

Environmental Science and Technology

Dietary bioavailability of uranium to a model freshwater invertebrate

Uranium (U) mining increases environmental exposures. Understanding how U is taken up by organisms can aid in evaluating the potential for bioaccumulation and toxicity. Although the importance of aqueous geochemical speciation is well recognized for U bioavailability after dissolved exposures, far less is known about the processes controlling U bioavailability after dietary exposures. This study characterizes the biogeochemical drivers of dietary U uptake in the freshwater snail Lymnaea stagnalis in laboratory experiments. Solids tested included benthic diatoms pre-exposed to dissolved U(VI), soils from contaminated U mine sites, and colloidal hydrous ferric oxide (HFO) synthesized in the presence of dissolved U(VI) or with U complexed by natural organic matter (NOM). Results showed that U was bioavailable from all solids. Uranium assimilation efficiency (AE), a proxy for dietary U bioavailability, varied among solids. AE was lowest for the U-contaminated soils (25 ± 17%) and highest for the U-laden diatoms (71 ± 13%). AE varied slightly among HFO preparations, suggesting modest influences of NOM and iron on U bioavailability. Increases in dietary U exposures reduced feeding rates, and the extent of feeding inhibition appeared inversely related to U bioavailability. The high U assimilation and range of bioavailability have implications for toxicity risks inferred without considering dietary uptake.

Environmental Science and Technology