Distributed chemical sensing for CO2 leakage monitoring
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Solid–water interfaces are crucial for clean water, conventional and renewable energy, and effective nuclear waste management. However, reflecting the complexity of reactive interfaces in continuum-scale models is a challenge, leading to oversimplified representations that often fail to predict real-world behavior. This is because these models use fixed parameters derived by averaging across a wide physicochemical range observed at the molecular scale. Recent studies have revealed the stochastic nature of molecular-level surface sites that define a variety of reaction mechanisms, rates, and products even across a single surface. To bridge the molecular knowledge and predictive continuum-scale models, we propose to represent surface properties with probability distributions rather than with discrete constant values derived by averaging across a heterogeneous surface. This conceptual shift in continuum-scale modeling requires exponentially rising computational power. By incorporating our molecular-scale understanding of solid–water interfaces into continuum-scale models we can pave the way for next generation critical technologies and novel environmental solutions.
Here, we describe the solventless catalytic deconstruction of polyethylene-terephthalate (PET) under an aerobic atmosphere, mediated by an earth-abundant, low-cost activated carbon (AC)-supported single-site molybdenum-dioxo catalyst (AC/MoO 2 ). Catalytic amounts of AC/MoO 2 selectively convert waste PET into its monomer, terephthalic acid (TPA), within 4 h at 265 °C with yields as high as 94% under 1 atm air. Pure crystalline TPA product sublimes from the reaction hot zone, crystallizing on the reactor cold zone, thus avoiding the need for separation and purification steps. This process does not employ any hazardous/toxic reducing agents or solvents, and the catalyst can be recycled multiple times without loss of activity, rendering this process highly atom-efficient. According to computational and experimental mechanistic studies, the AC/MoO 2 catalyst mediates a thermoneutral metal-catalyzed β-scission step, followed by an exothermic step that converts the vinyl benzoate intermediate to TPA and acetaldehyde using trace amounts of moisture in the air. The formation of gaseous acetaldehyde makes the isolation of TPA from the reaction mixture facile and industrially favorable, especially since solvents are unnecessary. The present methodology is also extended to the deconstruction of other frequently used polyester plastics, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene furanoate (PEF), and operates equally well with post-consumer waste products. Notably, this process is also compatible with plastic mixtures of polyesters with polyolefins, polyamides, and polycarbonates, leading to the selective conversion of each polyester to the corresponding monomer, leaving the residual polymer unchanged and polyester-free.
This article examines the impact of residential battery energy storage (BES) systems' operational modes on the life (i.e. usable energy capacity) of the battery under several climatic conditions and battery chemistries. The sharp increase in residential BES installations has been a result of decreasing costs of batteries, increase in rate structures motivated applications such as solar self-consumption and time-of-use energy management, and customers purchasing these systems for backup power. While these different modes of operations provide a combination of increased bill savings, reliability of supply, and energy sustainability to the customer, their operational characteristics vary significantly between use-cases. Functional life of BES systems is known to be strongly dependent on their operating conditions. In this article, we analyze the operation of residential BES systems under different rate-based use-cases, for different battery chemistries and cell designs, and under different environmental conditions. This is conducted by simulating the control of BES operations using rate-based cycling algorithms and analyzing the prognosis of multiple battery lifetime models that consider complex nonlinear dependencies of operational stress factors such as state-of-charge, depth-of-discharge, and temperature on degradation. Significant variations in battery life are observed owing to the differences in characteristics of the uses-cases coupled with environmental conditions and battery chemistries. Such differences lead to the conclusion that choice of residential BES technologies and chemistries should account for their intended use-cases.
There are a number of current needs in the development of the Pu and Am separations that underpin larger interest areas including nuclear waste issues, nuclear weapons, nuclear forensics, nuclear fuels and similarly related fields. In the large areas of interest, there are a number of sub-fields that include corrosion chemistry, pyrochemistry, solution-phase chemistry, rapid separations, environmental speciation, and other similar efforts. However, in all of the these fields it is important to realize that the underlying chemistry that underpins these efforts is similar in that Pu and Am are bound to ligands that can be in the solid, aqueous, or gas phase and separations occurs due to the preferential binding of the ligand to Pu or Am based on a number of factors that include pH, concentration, oxidation state, etc. In the past, most of the Pu and Am chemistry has occurred in limited scope within universities where micro-scale and bench-top scale chemistry are the dominate investigative theme. At US national laboratory and their international counterparts, larger scale reactions have been attempted such that industrial scale chemistry has been completed. Some of this technology has been harnessed in radiopharmaceuticals and nuclear fuel reprocessing. However, such bench-top research is expensive to due to the safety and security that is concerned when dealing with Pu, and scale-up of reactions is even more resource intensive. In an effort to offset this expensive, it would be of interest to explore the ability to predict selectivity based on the computational modeling of actinide chemistry. This has historically been limited by the abilities of large supercomputers, but with the emphasis on developing exascale computers within the US and similar efforts by other countries this predictive modeling has potential to produce significant results that would yield improved understanding of actinide chemistry.
The inorganic fraction of fine particles affects numerous physicochemical processes in the atmosphere. However, there is large uncertainty in its burden and composition due to limited global measurements. Here, we present observations from eleven different aircraft campaigns from around the globe and investigate how aerosol pH and ammonium balance change from polluted to remote regions, such as over the oceans. Both parameters show increasing acidity with remoteness, at all altitudes, with pH decreasing from about 3 to about -1 and ammonium balance decreasing from almost 1 to nearly 0. We compare these observations against nine widely used chemical transport models and find that the simulations show more scatter (generally R 2 < 0.50) and typically predict less acidic aerosol in the most remote regions. These differences in observations and predictions are likely to result in underestimating the model-predicted direct radiative cooling effect for sulfate, nitrate, and ammonium aerosol by 15–39%.
The ability of an organism to cope with environmental stressors varies across the life span because of developmental stage–specific responses and age-related functional declines. In the present study, we examined the effect of age on acute copper toxicity in Japanese medaka (Oryzias latipes). We first determined the median lethal concentration (LC50) at 96 h for embryos, 7-day-old fry, and 6-month-old medaka. Embryos were exposed to 0, 15, 30, 60, 125, 250, and 500 ppb CuSO 4 through hatching. Fry were exposed to 0, 20, 50, 75, 100, 150, 250, and 500 ppb CuSO 4 for 96 h. Adult fish were exposed to 0, 100, 150, 200, 250, and 300 ppb CuSO 4 for 96 h. The 96-h LC50 was 804 ppb for embryos, 262 ppb for embryonically exposed larvae, 60.3 ppb for 7-day-old fry, and 226 ppb for adults. We then challenged cohorts of fish aged 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, and 16 months with a 225-ppb CuSO 4 exposure to determine the acute toxicity across the life span. The fish exhibited a bimodal tolerance to copper, with tolerance peaking in 2- and 3-month-old fish and again at 10 and 11 months of age. Our data demonstrate that copper sensitivity is dynamic throughout the medaka life span and may be influenced by trade-offs with reproduction. Environ Toxicol Chem 2022;41:2999–3006. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Sediments in aquatic systems often act as a major sink for contaminants. Diffusive gradient in thin films (DGTs) and in situ equilibrium dialysis samplers (peepers) are two major in situ pore water sampling devices that overcome the problems associated with conventional pore water sampling methods. In the present study, DGTs and peepers were used to study the spatial and seasonal effects (cool months, October–February; warm months, May–September) on metal bioavailability in the H‐02 constructed wetland and the sink versus source role of the sediments by calculating the metal resupply capacity. Data showed similar seasonal trends in metal concentrations using passive samplers, peepers, and DGTs. Pooled Cu and Zn concentrations measured using DGTs were lower in warm months (1.67 ± 1.50 and 2.62 ± 0.68 μg L –1 , respectively, p < 0.001) versus in cool months (2.12 ± 0.65 and 5.58 ± 1.33 μg L –1 , respectively, p < 0.001; mean ± 95% confidence interval). Sulfate (SO 4 2− ) concentrations were significantly (p = 0.0139) lower in warm months (averaged at 0.22 ± 0.05 mg L –1 ) compared to in cool months (0.16 ± 0.05 mg L –1 ). The increase in SO 4 2− concentration is an indicator of the lower activity of sulfate‐reducing bacteria, which need SO 4 2− during anaerobic respiration, in which SO 4 2− is reduced to sulfide (S 2– ) that forms insoluble salts with Cu and Zn, which could partially explain the higher bioavailability of these metals in the cool season. Metal resupply capacity of the sediments was mostly <0.2 for Cu and Zn. Taken together, the H0‐2 wetland sediments mostly acted as a sink to both Cu and Zn over the course of the present study. Environ Toxicol Chem 2023;42:2726–2736. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Efficient, low-cost solar cells based upon perovskites have the potential to transform the US and global energy portfolio and improve energy security if they can be manufactured in an environmentally sustainable manner. However, previous life cycle analyses (LCA) of perovskite solar cells (PSC) used lab recipes to project the environmental impact of industrial PSC production – using materials and processes that may not be representative of industrial productions due to high material waste and complex synthesis – and such studies were limited to a few single-junction technologies. Thus, the goal of this project was threefold: a) to review the most promising for industrial production single-junction and tandem PSC technologies, b) to build life-cycle materials inventories that reflect scalable production of these technologies, and c) to conduct comprehensive life-cycle analysis of these technologies and compare their environmental impact with those of established commercial technologies. In response, this project identified challenges for fabrication transitioning from laboratory to sustainable industrial production, developed life-cycle inventory (LCI) data for scaling to industrial production four promising single-junction and three tandem PSC systems and produced life-cycle-investigations using, as metrics, a complete spectrum of energy, environmental and ecological impact indicators. Special focus was given to the use of lead, silver and indium in PSC. The project used the Life Cycle Assessment (LCA) methodology as standardized by the Society of Environmental Toxicology and Chemistry (SETAC), ISO standards 14040 and 14044, and the International Energy Agency PVPS Task 12 LCA guidelines. LCA allows the calculation of a number of energy and environmental and impact categories, including energy cumulative energy demand (CED), global warming potential (GWP), human toxicity potential (HTP), eco-toxicity potential (ETP), abiotic resource depletion potential (ADP), acidification potential (AP), ozone depletion potential (ODP), photochemical oxidation potential (POP), eutrophication potential (EP). In addition to those, we calculated the Energy Pay-Back Time (EPBT) and the Energy Return On Investment (EROI). We provide LCA impacts for complete perovskite PV systems – including balance of system components – installed at three irradiation levels and considering reference and future potential module efficiencies. Finally, a sensitivity analysis on perovskite lifetime has been performed, considering 10, 20 and 30 years. Contribution analysis of the impacts of each material and layer of PSC shows, that the use of Pb in metalorganic PSC does not result in significant environmental impacts as the major contributions to environmental indicators arise from the use of Ag and encapsulation materials. Solution-based PSC manufacturing was found to be less impactful to the environment than vapor-based fabrication, and roll-to-roll (RtR) printing uses less energy and generates the lowest emissions. PSC produced with RtR manufacturing could reach the same Energy Return on Energy Investment (EROI) as that of crystalline-Si PV within 12 years of life, whereas the most energy demanding spray coating on rigid substrates, would require a 20-yr life to match the EROI of 30-yr lasting silicon PV. This work lays the foundation for sustainability investigations in a comparative context of large-scale production and deployment of PSC. The results of this project have the potential to have a significant impact on the future of PV manufacturing, by providing industry, policy-makers, and academia with insights necessary to choose which, if any, lead-based solar cell life cycles are environmentally sustainable.
This dataset supports a broader study examining the drivers of temporal variability in sediment respiration rates in the Yakima River Basin. The dataset provides periodic (weekly or biweekly) in situ hydrological and water chemistry sensor data, handheld sensor water chemistry data, general environmental context photos, and field metadata collected at six sites within multiple rivers in the Yakima River Basin in Washington, USA. In addition to the sensor data, there are plots of continuous in situ sensor data and R scripts used to generate the plots. Related sample-based water chemistry data are published separately at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1898912.The data package was originally published in September 2022. It was updated in June 2025 (v2; modified files). See the change history section in the readme for more details. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. This dataset is comprised of one main data folder containing two sensor-specific subfolders, and one photographs folder. The main data folder includes file-level metadata (flmd), data dictionary (dd), installation methods, field metadata, handheld sensor data, field data collection protocols, international generic sample number (IGSN) mapping file, and a readme file. Each sensor subfolder (BarotrollAtm and MantaRiverData) contains a subfolder containing sensor timeseries data and plots. The BarotrollAtm Data subfolder contains In Situ Rugged BaroTROLL sensor pressure and air temperature data. The MantaRiverData subfolder contains Eureka Manta+ 35B multisonde temperature, specific conductance, and turbidity. The FieldPhotos folder contains environmental context photographs and videos. All files are .csv, .pdf, .R, .jpg, .jpeg, .heic, .mov, or .mp4.
Abstract Historical use of lead arsenate as a pesticide in former orchards of eastern Washington State (USA) has resulted in legacy lead (Pb) and arsenic (As) soil contamination. However, the impacts on plant growth in soils with residual Pb and As contamination have not yet been quantified. To this end, a comparative study of plant growth impacts was performed for native bluegrass ( Poa secunda ), invasive cheatgrass ( Bromus tectorum ), and buttercrunch lettuce ( Lactuca sativa ). Using standard plant growth protocols, germination frequency and biomass growth were measured over a wide range of Pb and arsenate concentrations, with maximum concentrations of 3400 and 790 mg kg −1 for Pb and As, respectively. Results indicated that only the biomass growth for all species decreased in soils with the highest concentrations of Pb and As in the soil, with no impacts on soils with lower residual Pb and arsenate concentrations. No impact on percentage of germination was observed at any soil concentration. These results can be used to determine site‐specific soil screening levels for use in ecological risk assessments for Pb and arsenate in soils. Environ Toxicol Chem 2022;41:1459–1465. © 2022 Battelle Memorial Institute. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
The Evans Canyon Fire occurred in Washington in August 2020 and burned 76,000 acres of the semi-arid shrub-steppe landscape at low to moderate severities. This fire burned across the Wenas Creek watershed, allowing for a sampling design that included a portion of the stream within the burned area and a reference site upstream of the burn. Monthly data was collected at an unburned (W10) and burned (W20) site from November 2020 to August 2022 for in situ hydrological and water chemistry sensor data, handheld sensor water chemistry data, general environmental context photos, and field metadata. This dataset is comprised of one folder with field photos and one main data folder containing (1) sensor and sample field protocols; (2) file-level metadata (flmd); (3) data dictionary (dd); (4) international geo-sample number (IGSN) mapping file; (5) field metadata; (6) readme; (7) methods codes; (8) dissolved organic carbon (DOC; measured as non-purgeable organic carbon; NPOC); (9) total nitrogen (TN); (10) total suspended solids (TSS); (11) sensor data (specific conductance, pH, total dissolved solids, temperature, pressure, dissolved oxygen, and turbidity) averages; and (12) sensor installation methods. All files are .csv, .jpg, .jpeg, or .pdf.
Abstract Since the early 1980s, the Antarctic environment has served as a natural field laboratory for researchers to investigate the effects of stratospheric ozone depletion, which has resulted in increased surface ultraviolet radiation levels. However, its effective threats still present gaps. We report new pieces of evidence of increased ultraviolet radiation impacting West Antarctica sea salt aerosols. Salt aerosols, particularly in the Southern Ocean Sea, play an important role in the radiative earth balance. To disclose the molecular details of sea salt aerosols, we used a synchrotron-based multi-element microscopic speciation of individual microparticles (Scanning Transmission X-ray Microscopy with Near-Edge X-ray Absorption Fine Structure Spectroscopy combined with Computer-Controlled Scanning Electron Microscopy). Here we identified substantial abundances of chlorine-enriched aerosols in sea salt generated by photolytic products, whereas ice core records revealed increased chlorine depletion from the onset of ozone depletion. Our findings reveal that modern sea salt modification has no Holocene precedent.
This information bulletin is intended to generate a heightened awareness of illicit pesticide importation, distribution, and use in the United States. This bulletin focuses on solid, fumigant materials which are primarily used in the production of marijuana growth and cultivation. Exposure to illicit pesticides, fumigant fumes, or residual materials may pose a public health and officer safety concern. Many illegal fumigant pesticide products have been seized and determined to consist of a mixture of several pesticides and is often in contrast with the pesticide labelling. This information bulletin is not a complete account of all illegal pesticides found in country; it serves to highlight frequently encountered materials and present patterns in product presentation, packaging, and shipment containment which are intended to aid in identification and intervention. Other varieties of illegal pesticide fumigants are known to exist, and additional variations are expected to be encountered in policing intervention. This bulletin includes information on the presentation of illegal pesticides, label review recommendations, a field reference guide, which includes example photographs of seized pesticide/fumigants and their labels, and related United States federal regulation information, including relevant tariff code information for reference.
Abstract While it is widely recognized that the operating temperature significantly affects the energy density and cycle life of lithium‐ion batteries, the consequence of electrode‐electrolyte interphase chemistry to sudden environmental temperature changes remains inadequately understood. Here, we systematically investigate the effects of a temperature pulse (T pulse) on the electrochemical performance of LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) pouch full cells. By utilizing advanced characterization tools, such as time‐of‐flight secondary‐ion mass spectrometry, we reveal that the T pulse can lead to an irreversible degradation of cathode‐electrolyte interphase chemistry and architecture. Despite negligible immediate impacts on the solid‐electrolyte interphase (SEI) on graphite anode, aggregated cathode‐to‐anode chemical crossover gradually degrades the SEI by catalyzing electrolyte reduction decomposition and inducing metallic dead Li formation because of insufficient cathode passivation after the T pulse. Consequently, pouch cells subjected to the T pulse show an inferior cycle stability to those free of the T pulse. This work unveils the effects of sudden temperature changes on the interphase chemistry and cell performance, emphasizing the importance of a proper temperature management in assessing performance.
This dataset supports a broader study examining the drivers of temporal variability in sediment respiration rates in the Yakima River Basin. The dataset provides periodic (bi-weekly or monthly) in situ hydrological and water chemistry sensor data, handheld sensor water chemistry data, general environmental context photos, and field metadata collected at six sites across the Yakima River Basin in Washington, USA. Sample and sensor data from previous years (2021-2022) can be found at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1898912 and https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1892054, respectively. Related sample data from 2022-2024 are available at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/2562910. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes all column/row headers and variable definitions This dataset contains a folder of environmental context photographs and videos and (1) file-level metadata; (2) data dictionary; (3) readme; (4) field metadata; (5) field protocols; (6) international generic sample number (IGSN) mapping file; (7) handheld sensor data; and (8) two sensor subfolders. Each sensor subfolder (BarotrollAtm and MantaRiverData) contains a subfolder containing sensor time series data and plots. The BarotrollAtm Data subfolder contains In Situ Rugged BaroTROLL sensor pressure and air temperature data. The MantaRiverData subfolder contains Eureka Manta+ 35B multisonde temperature, specific conductance, and chlorophyll A. All files are .csv, .pdf, .jpg, .jpeg, .mp4, .png, or .mov.
Process intensification and integration for sustainable design play an essential role in addressing and alleviating severe sustainable development challenges. It is prudent to evaluate a process design in its early stage development to ensure the process can achieve sustainability goals. The primary goal of a sustainability evaluation is to assess the impact of systems on areas sought to be protected and maintained over time, such as human well-being and ecosystems (Schaubroeck, T. and Rugani, B. (2017). A revision of what life cycle sustainability assessment should entail: towards modeling the net impact on human well-being. Journal of Industrial Ecology 21 (6): 1464-1477). Parenthetically, sustainable process design to convert biomass to fuels and chemicals plays an integral part in the bioeconomy sustainability. It is recognized that the integration of sustainability in process design is core to the mission in developing renewable fuels and should be considered a necessary practice in biorefinery design. This study demonstrates the use of Gauging Reaction Effectiveness for ENvironmental Sustainability of Chemistries with a multi-Objective Process Evaluator (GREENSCOPE) as a tool to help track progress on process sustainability performance attributed to conversion improvement. With the incorporation of a wide range of indicators, GREENSCOPE captures the multi-dimensional aspect of the process design and operation. As opposed to conventional techno-economic analysis and life cycle assessment (in which the focuses are limited to economic and environmental aspects), GREENSCOPE enables the consideration of process intensification and integration for sustainable design. A high-octane gasoline production from woody biomass feedstock is used as a case study to demonstrate the approach.
Despite the propensity of waterfowl species to readily accumulate anthropogenic contaminants within polluted environments, few studies have examined bioaccumulation rates over time when entering such a contaminated site. We examined mercury (Hg) and radiocesium ( 137 Cs) bioaccumulation over time in two waterfowl species released into a wetland system containing legacy contamination on the US Department of Energy's Savannah River Site in South Carolina. Released birds were collected at select time intervals over an exposure period of 94 days. We quantified total Hg concentrations in blood, muscle, and liver tissues, and 137 Cs activity in whole-body and muscle tissues. The relationship between the contaminant burdens of different body tissue types was examined over time. Likely a result of microhabitat selection, mallards in our study readily accumulated both Hg and 137 Cs at consistent rates over time within our study system, while ring-neck ducks did not. The findings demonstrated that whole blood can be used as a robust, nondestructive sampling alternative to estimate Hg burdens within muscle and liver, and whole-body 137 Cs activity is a good predictor of muscle burdens. Understanding such bioaccumulation information in waterfowl is useful for the assessment of the potential health risk in wildlife, as well as being important for human risk assessment toward the consumption of popular game species. Environ Toxicol Chem 2022;41:2479–2487. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.