Energy supply limits development through fuel constraints and climatic effects. Production of renewable energy is a central pillar of sustainability but will need to play an increasingly important role in energy generation in order to mitigate fossil-fuel based greenhouse-gas emissions. Global freshwaters represent a vast reservoir of biomass and biogenic CH₄. Here we demonstrate the great potential for the optimized use of this nonfossil carbon as a source of energy that is replenishable within a human lifetime. The feasibility of up-scaled adsorption-driven technologies to capture and refine aqueous CH₄ still awaits verification, yet recent estimates of global freshwater CH₄ production imply that the worldwide energy demand could be satisfied by using the “biofuel” building up in lakes and wetlands. Biogenic CH₄ is mostly generated from biomass produced through atmospheric CO₂ uptake. Its exploitation in freshwaters can thus secure large amounts of carbon-neutral energy, helping to sustain the planetary equilibrium.

No one can have missed the growing global environmental problems with plastics ending up as microplastics in food, water, and soil, and the associated effects on nature, wildlife, and humans. A hitherto not specifically investigated source of microplastics is polymer blends. A 1 g polymer blend can contain millions to billions of micrometer-sized species of the dispersed phase and therefore aging-induced fragmentation of the polymer blends can lead to the release of an enormous amount of microplastics. Especially if the stability of the dispersed material is higher than that of the surrounding matrix, the risk of microplastic migration is notable, for instance, if the matrix material is biodegradable and the dispersed material is not. The release can also be much faster if the matrix polymer is biodegradable. The purpose of writing this feature article is to arise public and academic attention to the large microplastic risk from polymer blends during their development, production, use, and waste handling.

Halogenated flame retardants (HFRs) have been extensively used in various consumer products and many are classified as persistent organic pollutants due to their resistance to degradation, bioaccumulation potential and toxicity. HFRs have been widely detected in the municipal wastewater and wastewater treatment solids in wastewater treatment plants (WWTPs), the discharge and agricultural application of which represent a primary source of environmental HFRs contamination. This review seeks to provide a current overview on the occurrence, fate, and impacts of HFRs in WWTPs around the globe. We first summarize studies recording the occurrence of representative HFRs in wastewater and wastewater treatment solids, revealing temporal and geographical trends in HFRs distribution. Then, the efficiency and mechanism of HFRs removal by biosorption, which is known to be the primary process for HFRs removal from wastewater, during biological wastewater treatment processes, are discussed. Transformation of HFRs via abiotic and biotic processes in laboratory tests and full-scale WWTPs is reviewed with particular emphasis on the transformation pathways and functional microorganisms responsible for HFRs biotransformation. Finally, the potential impacts of HFRs on reactor performance (i.e., nitrogen removal and methanogenesis) and microbiome in bioreactors are discussed. This review aims to advance our understanding of the fate and impacts of HFRs in WWTPs and shed light on important questions warranting further investigation.

Atmospheric oxidation of sulfur dioxide (SO₂) forms sulfate-containing aerosol particles that impact air quality, climate, and human and ecosystem health. It is well-known that in-cloud oxidation of SO₂ frequently dominates over gas-phase oxidation on regional and global scales. Multiphase oxidation involving aerosol particles, fog, and cloud droplets has been generally thought to scale with liquid water content (LWC) so multiphase oxidation would be negligible for aerosol particles due to their low aerosol LWC. However, recent field evidence, particularly from East Asia, shows that fast sulfate formation prevails in cloud-free environments that are characterized by high aerosol loadings. By assuming that the kinetics of cloud water chemistry prevails for aerosol particles, most atmospheric models do not capture this phenomenon. Therefore, the field of aerosol SO₂ multiphase chemistry has blossomed in the past decade, with many oxidation processes proposed to bridge the difference between modeled and observed sulfate mass loadings. This review summarizes recent advances in the fundamental understanding of the aerosol multiphase oxidation of SO₂, with a focus on environmental conditions that affect the oxidation rate, experimental challenges, mechanisms and kinetics results for individual reaction pathways, and future research directions. Compared to dilute cloud water conditions, this paper highlights the differences that arise at the molecular level with the extremely high solute strengths present in aerosol particles.

With the increasing severity of global water scarcity, a myriad of scientific activities is directed toward advancing brackish water desalination and wastewater remediation technologies. Flow-electrode capacitive deionization (FCDI), a newly developed electrochemically driven ion removal approach combining ion-exchange membranes and flowable particle electrodes, has been actively explored over the past seven years, driven by the possibility of energy-efficient, sustainable, and fully continuous production of high-quality fresh water, as well as flexible management of the particle electrodes and concentrate stream. Here, we provide a comprehensive overview of current advances of this interesting technology with particular attention given to FCDI principles, designs (including cell architecture and electrode and separator options), operational modes (including approaches to management of the flowable electrodes), characterizations and modeling, and environmental applications (including water desalination, resource recovery, and contaminant abatement). Furthermore, we introduce the definitions and performance metrics that should be used so that fair assessments and comparisons can be made between different systems and separation conditions. We then highlight the most pressing challenges (i.e., operation and capital cost, scale-up, and commercialization) in the full-scale application of this technology. We conclude this state-of-the-art review by considering the overall outlook of the technology and discussing areas requiring particular attention in the future.

Volatile organic compounds (VOCs) are one of the main sources of air pollution, which are of wide concern because of their toxicity and serious threat to the environment and human health. Catalytic oxidation has been proven to be a promising and effective technology for VOCs abatement in the presence of heat or light. As environmentally friendly and low-cost materials, manganese-based oxides are the most competitive and promising candidates for the catalytic degradation of VOCs in thermocatalysis or photo/thermocatalysis. This article summarizes the research and development on various manganese-based oxide catalysts, with emphasis on their thermocatalytic and photo/thermocatalytic purification of VOCs in recent years in detail. Single manganese oxides, manganese-based oxide composites, as well as improving strategies such as morphology regulation, heterojunction engineering, and surface decoration by metal doping or universal acid treatment are reviewed. Besides, manganese-based monoliths for practical VOCs abatementare also discussed. Meanwhile, relevant catalytic mechanisms are also summarized. Finally, the existing problems and prospect of manganese-based oxide catalysts for catalyzing combustion of VOCs are proposed.

Nanomaterial adsorbents (NAs) have shown promise to efficiently remove toxic metals from water, yet their practical use remains challenging. Limited understanding of adsorption mechanisms and scaling up evaluation are the two main obstacles. To fully realize the practical use of NAs for metal removal, we review the advanced tools and chemical principles to identify mechanisms, highlight the importance of adsorption capacity and kinetics on engineering design, and propose a systematic engineering scenario for full-scale NA implementation. Specifically, we provide in-depth insight for using density functional theory (DFT) and/or X-ray absorption fine structure (XAFS) to elucidate adsorption mechanisms in terms of active site verification and molecular interaction configuration. Furthermore, we discuss engineering issues for designing, scaling, and operating NA systems, including adsorption modeling, reactor selection, and NA regeneration, recovery, and disposal. This review also prioritizes research needs for (i) determining NA microstructure properties using DFT, XAFS, and machine learning and (ii) recovering NAs from treated water. Our critical review is expected to guide and advance the development of highly efficient NAs for engineering applications.

Safe and cost-effective geologic carbon storage will require active CO₂ reservoir management, including brine extraction to minimize subsurface pressure accumulation. While past simulation and experimental efforts have estimated brine extraction volumes, carbon management policies must also assess the energy or emissions penalties of managing and disposing of this brine. We estimate energy and CO₂ emission penalties of extracted brine management on a per tonne of CO₂ stored basis by spatially integrating CO₂ emissions from U.S. coal-fired electric generating units, CO₂ storage reservoirs, and brine salinity data sets under several carbon and water management scenarios. We estimate a median energy penalty of 4.4–35 kWh/tonne CO₂ stored, suggesting that brine management will be the largest post capture and compression energy sink in the carbon storage process. These estimates of energy demand for brine management are useful for evaluating end-uses for treated brine, assessing the cost of CO₂ storage at the reservoir level, and optimizing national CO₂ transport and storage infrastructure.

This study aims to reveal the status quo and future trend of thermoelectric water use and water stress in India. We compiled a bottom-up geo-database for all thermal power plants in India and identified the type of cooling technology used. We then estimated thermoelectric water withdrawal and water consumption in India from 2009 to 2018 and projected future trends in thermoelectric water use up to 2027 using the integrated power planning and dispatch model, SWITCH-India. Results show that thermoelectric power generation in India is not a major source of water stress in most basins until 2027. Freshwater withdrawal varied from 14 to 16 billion m3 during the study period, while freshwater consumption increased with growing thermal power generation. The catchment in the middle of the Ganga River basin has the largest freshwater withdrawal and consumption. The volume of water withdrawal accounts for less than 1% of blue water availability in most catchments. It is also likely that a larger proportion of power generation and water withdrawal will occur in catchments that are under lower water stress in the future. Policy interventions should target stressed catchment areas and improve the resilience of thermal power plants to outages due to water stress.

Criticality and supply risk models seek to address concerns of potential disruption to global metal supply. These models need to incorporate disruption events that arise from within the mining industry’s market structure. In this paper, we review what we refer to as events of “mine life cycle disruption”. These include project abandonments, premature closures, care and maintenance, and ownership changes. Life cycle disruptions not only cause production disruptions but also embed social and environmental risks in global metal markets. They arise from the highly variable business environment in which the resources sector operates. Changing commodity prices directly influence mining revenues and drive decisions on whether to halt or push forward a project. While some disruptions are involuntary and induced by external economic conditions, others are purposefully triggered by certain mining companies that use them to their advantage. We examine the frequency of these disruptions based on a contemporary global inventory of 35,000 mining projects and present the findings against recent developments in the research literature. We conclude that life cycle disruption events are an important consideration in balancing the demand for metals and the social and environmental impacts of mining and propose pathways for managing these events and their effects.

Despite decades of declining air pollution, urban U.S. areas are still affected by summertime ozone and wintertime particulate matter exceedance events. Volatile organic compounds (VOCs) are known precursors of secondary organic aerosol (SOA) and photochemically produced ozone. Urban VOC emission sources, including on-road transportation emissions, have decreased significantly over the past few decades through successful regulatory measures. These drastic reductions in VOC emissions have led to a change in the distribution of urban emissions and noncombustion sources of VOCs such as those from volatile chemical products (VCPs), which now account for a higher fraction of the urban VOC burden. Given this shift in emission sources, it is essential to quantify the relative contribution of VCP and mobile source emissions to urban pollution. Herein, ground site and mobile laboratory measurements of VOCs were performed. Two ground site locations with different population densities, Boulder, CO, and New York City (NYC), NY, were chosen in order to evaluate the influence of VCPs in cities with varying mixtures of VCPs and mobile source emissions. Positive matrix factorization was used to attribute hundreds of compounds to mobile- and VCP-dominated sources. VCP-dominated emissions contributed to 42 and 78% of anthropogenic VOC emissions for Boulder and NYC, respectively, while mobile source emissions contributed 58 and 22%. Apportioned VOC emissions were compared to those estimated from the Fuel-based Inventory of Vehicle Emissions and VCPs and agreed to within 25% for the bulk comparison and within 30% for more than half of individual compounds. The evaluated inventory was extended to other U.S. cities and it suggests that 50 to 80% of emissions, reactivity, and the SOA-forming potential of urban anthropogenic VOCs are associated with VCP-dominated sources, demonstrating their important role in urban U.S. air quality.

Snow serves as a vital scavenging mechanism to gas-phase and particle-phase organic nitrogen substances in the atmosphere, providing a significant link between land-atmosphere flux of nitrogen in the surface-earth system. Here, we used optical instruments (UV–vis and excitation-emission matrix fluorescence) and a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) to elucidate the molecular composition and potential precursors of snow samples collected simultaneously at four megacities in North China. The elemental O/N ratio (≥3), together with the preference in the negative ionization mode, indicates that the one and two nitrogen atom-containing organics (CHON₁ and CHON₂) in snow were largely in the oxidized form (as organic nitrates, −ONO₂). This study assumed that scavenging of particle-phase and gas-phase organic nitrates might be significant sources of CHON in precipitation. A gas-phase oxidation process and a particle-phase hydrolysis process, at a molecular level, were used to trace the potential precursors of CHON. Results show that more than half of the snow CHON molecules may be related to the oxidized and hydrolyzed processes of atmospheric organics. Potential formation processes of atmospheric organics on a molecular level provide a new concept to better understand the sources and scavenging mechanisms of organic nitrogen species in the atmosphere.

A major challenge in assessing the impact of aerosols on climate change is to understand how human activities change aerosol loading and properties relative to the pristine/preindustrial baseline. Here, we combine chemical transport simulations and field measurements to investigate the effect of anthropogenic pollution from an isolated metropolis on the particle number concentration over the preindustrial-like Amazon rainforest through various new-particle formation (NPF) mechanisms and primary particle emissions. To represent organic-mediated NPF, we employ a state-of-the-art model that systematically simulates the formation chemistry and thermodynamics of extremely low volatility organic compounds, as well as their roles in NPF processes, and further update the model to improve organic NPF simulations under human-influenced conditions. Results show that urban pollution from the metropolis increases the particle number concentration by a factor of 5–25 over the downwind region (within 200 km from the city center) compared to background conditions. Our model indicates that NPF contributes over 70% of the total particle number in the downwind region except immediately adjacent to the sources. Among different NPF mechanisms, the ternary NPF involving organics and sulfuric acid overwhelmingly dominates. The improved understanding of particle formation mechanisms will help better quantify anthropogenic aerosol forcing from preindustrial times to the present day.

Black carbon (BC) particles contribute to climate warming by heating the atmosphere and reducing the albedo of snow/ice surfaces. The available Arctic BC deposition records are restricted to the Atlantic and North American sectors, for which previous studies suggest considerable spatial differences in trends. Here, we present first long-term BC deposition and radiocarbon-based source apportionment data from Russia using four lake sediment records from western Arctic Russia, a region influenced by BC emissions from oil and gas production. The records consistently indicate increasing BC fluxes between 1800 and 2014. The radiocarbon analyses suggest mainly (∼70%) biomass sources for BC with fossil fuel contributions peaking around 1960–1990. Backward calculations with the atmospheric transport model FLEXPART show emission source areas and indicate that modeled BC deposition between 1900 and 1999 is largely driven by emission trends. Comparison of observed and modeled data suggests the need to update anthropogenic BC emission inventories for Russia, as these seem to underestimate Russian BC emissions and since 1980s potentially inaccurately portray their trend. Additionally, the observations may indicate underestimation of wildfire emissions in inventories. Reliable information on BC deposition trends and sources is essential for design of efficient and effective policies to limit climate warming.

Vehicular catalytic converters are used to regulate, reduce, and convert toxic and environmentally unfriendly compounds in exhaust gases into relatively inert and less harmful chemical species. The efficiency, however, is largely affected by the operating temperature of the converter which is set by the hot exhaust gas released from the combustion chamber. A major gas released during combustion is CO₂, and its multiply substituted isotopocule, namely, ¹³C¹⁶O¹⁸O, provides a window of opportunity to probe directly the effective temperature of the converter in operation. Here, we report multiple isotopic measurements in exhaust CO₂ (δ¹³C, δ¹⁷O, δ¹⁸O, and Δ₄₇) of diesel (trucks and buses) and gasoline (sedans, trucks, and two-wheel motorcycles)-powered vehicles. For investigating the efficiency of a converter in reducing toxic compounds, we studied NO_x processes through isotopic analysis of the exhaust N₂O. We found that the degree of N₂O reduction to N₂ in gasoline-powered vehicles is high when the temperature is above 200 °C (inferred by Δ₄₇). In contrast, diesel-powered vehicles produce N₂O in abundance, probably a consequence of selective catalytic reduction of NO_x, and the reduction efficiency depends on the converter temperature. In other words, the catalytic converters act as sinks and sources of N₂O to the atmosphere in gasoline- and diesel-operated vehicles, respectively. We also report a new set of field data by measuring the isotopic compositions of CO₂ and N₂O in the Hsuehshan tunnel, a ∼13 km long highway tunnel in Taiwan. Elevated N₂O concentrations inside the tunnel indicate that the emission of N₂O by heavy-duty diesel vehicles is much higher compared to the reduction by gasoline-operated passenger cars, making the vehicular exhausts a net source of N₂O to the atmosphere. The combined study of clumped isotopes and N₂O concentration in exhaust gases suggests that it is useful to probe the operational temperature of catalytic converters and monitor the pollution level in operation, thus providing an opportunity for manufacturers to optimize the catalytic efficiency to reduce the level of toxic pollutants to the environment.

Estimates of ground-level ozone concentrations are necessary to determine the human health burden of ozone. To support the Global Burden of Disease Study, we produce yearly fine resolution global surface ozone estimates from 1990 to 2017 through a data fusion of observations and models. As ozone observations are sparse in many populated regions, we use a novel combination of the M³Fusion and Bayesian Maximum Entropy (BME) methods. With M³Fusion, we create a multimodel composite by bias-correcting and weighting nine global atmospheric chemistry models based on their ability to predict observations (8834 sites globally) in each region and year. BME is then used to integrate observations, such that estimates match observations at each monitoring site with the observational influence decreasing smoothly across space and time until the output matches the multimodel composite. After estimating at 0.5° resolution using BME, we add fine spatial detail from an additional model, yielding estimates at 0.1° resolution. Observed ozone is predicted more accurately (R² = 0.81 at the test point, 0.63 at 0.1°, and 0.62 at 0.5°) than the multimodel mean (R² = 0.28 at 0.5°). Global ozone exposure is estimated to be increasing, driven by highly populated regions of Asia and Africa, despite decreases in the United States and Russia.

The atmospheric chemistry of isoprene has broad implications for regional air quality and the global climate. Allylic radicals, taking 13–17% yield in the isoprene oxidation by ^•Cl, can contribute as much as 3.6–4.9% to all possible formed intermediates in local regions at daytime. Considering the large quantity of isoprene emission, the chemistry of the allylic radicals is therefore highly desirable. Here, we investigated the atmospheric oxidation mechanism of the allylic radicals using quantum chemical calculations and kinetics modeling. The results indicate that the allylic radicals can barrierlessly combine with O₂ to form peroxy radicals (RO₂^•). Under ≤100 ppt NO and ≤50 ppt HO₂^• conditions, the formed RO₂^• mainly undergo two times “successive cyclization and O₂ addition” to finally form the product fragments 2-alkoxy-acetaldehyde (C₂H₃O₂^•) and 3-hydroperoxy-2-oxopropanal (C₃H₄O₄). The presented reaction illustrates a novel successive cyclization-driven autoxidation mechanism. The formed 3-hydroperoxy-2-oxopropanal product is a new isomer of the atmospheric C₃H₄O₄ family and a potential aqueous-phase secondary organic aerosol precursor. Under >100 ppt NO condition, NO can mediate the cyclization-driven autoxidation process to form C₅H₇NO₃, C₅H₇NO₇, and alkoxy radical-related products. The proposed novel autoxidation mechanism advances our current understanding of the atmospheric chemistry of both isoprene and RO₂^•.

Nitrated phenols (NPs) are important atmospheric pollutants that affect air quality, radiation, and health. The recent development of the time-of-flight chemical ionization mass spectrometer (ToF-CIMS) allows quantitative online measurements of NPs for a better understanding of their sources and environmental impacts. Herein, we deployed nitrate ions as reagent ions in the ToF-CIMS and quantified six classes of gaseous NPs in Beijing. The concentrations of NPs are in the range of 1 to 520 ng m^–3. Nitrophenol (NPh) has the greatest mean concentration. Dinitrophenol (DNP) shows the greatest haze-to-clean concentration ratio, which may be associated with aqueous production. The high concentrations and distinct diurnal profiles of NPs indicate a strong secondary formation to overweigh losses, driven by high emissions of precursors, strong oxidative capacity, and high NO_x levels. The budget analysis on the basis of our measurements and box-model calculations suggest a minor role of the photolysis of NPs (<1 ppb h^–1) in producing OH radicals. NPs therefore cannot explain the underestimated OH production in urban environments. Discrepancies between these results and the laboratory measurements of the NP photolysis rates indicate the need for further studies aimed at understanding the production and losses of NPs in polluted urban environments.

Agricultural soil is the main source of nitrous oxide (N₂O) emissions which contribute to global warming and stratospheric ozone depletion. In recent decades, atmospheric nitrogen (N) deposition has increased dramatically as an important agricultural soil N input, while its effect on soil N₂O emissions in the current and future climate change remains unknown. Here, we conducted a thorough analysis of the effect of N deposition and climate change on soil N₂O emissions as well as their trends. Soil N₂O emissions induced by N deposition accounted for 25% of global cropland soil N₂O emissions. Global soil N₂O emissions over croplands increased by 2% yr^–1 during 1996–2013, of which N deposition could explain 15% of the increase. The emission factor of N deposition was ∼7 times that of N fertilizer plus manure (∼1%) through a more direct way, since N deposition including nitrate (NO₃^–) and ammonium (NH₄⁺) could be directly used for nitrification and denitrification. By 2100, N deposition will increase by 80% and cropland soil N₂O emissions will increase by 241% under the RCP8.5 scenario in comparison with the 2010 baseline. These results suggest that, under the background of increasing global N deposition, it is essential to consider its effects on soil N₂O emissions in climatic change studies.

Large amounts of small α-dicarbonyls (glyoxal and methylglyoxal) are produced in the atmosphere from photochemical oxidation of biogenic isoprene and anthropogenic aromatics, but the fundamental mechanisms leading to secondary organic aerosol (SOA) and brown carbon (BrC) formation remain elusive. Methylglyoxal is commonly believed to be less reactive than glyoxal because of unreactive methyl substitution, and available laboratory measurements showed negligible aerosol growth from methylglyoxal. Herein, we present experimental results to demonstrate striking oligomerization of small α-dicarbonyls leading to SOA and BrC formation on sub-micrometer aerosols. Significantly more efficient growth and browning of aerosols occur upon exposure to methylglyoxal than glyoxal under atmospherically relevant concentrations and in the absence/presence of gas-phase ammonia and formaldehyde, and nonvolatile oligomers and light-absorbing nitrogen-heterocycles are identified as the dominant particle-phase products. The distinct aerosol growth and light absorption are attributed to carbenium ion-mediated nucleophilic addition, interfacial electric field-induced attraction, and synergetic oligomerization involving organic/inorganic species, leading to surface- or volume-limited reactions that are dependent on the reactivity and gaseous concentrations. Our findings resolve an outstanding discrepancy concerning the multiphase chemistry of small α-dicarbonyls and unravel a new avenue for SOA and BrC formation from atmospherically abundant, ubiquitous carbonyls and ammonia/ammonium sulfate.

Pig production contributes considerably to land use and greenhouse gas (GHG) and reactive nitrogen (Nr) emissions. Land use strategies were widely proposed, but the spillover effects on biological flow are rarely explored. Here, we simultaneously assessed the carbon (C), nitrogen (N), and cropland footprints of China’s pig production at the provincial scale in 2017. The environmental impacts of land use strategies were further evaluated. Results show that one kg live-weight pig production generated an average of 1.9 kg CO₂-equiv and 59 g Nr emissions, occupying 3.5 m² cropland, with large regional variations. A large reduction in GHG (58–64%) and Nr (12–14%) losses and occupied cropland (10–11%) could be achieved simultaneously if combined strategies of intensive crop production, improved feed-protein utilization efficiency, and feeding co-products were implemented. However, adopting a single strategy may have environmental side-effects. Reallocating cropland that pigs used for feed to plant food alternatives would enhance human-edible energy (3–20 times) and protein delivery (1–5 times) and reduce C and N footprints, except for rice and vegetables. Reallocating cropland to beef and milk production would decrease energy and protein supply. Therefore, a proper combination of land use strategies is essential to alleviate land use changes and nutrient emissions without sacrificing food supply.

Road vehicles make important contributions to a wide range of pollutant emissions from the street level to global scales. The quantification of emissions from road vehicles is, however, highly challenging given the number of individual sources involved and the myriad factors that influence emissions such as fuel type, emission standard, and driving behavior. In this work, we use highly detailed and comprehensive vehicle emission remote sensing measurements made under real driving conditions to develop new bottom-up inventories that can be compared to official national inventory totals. We find that the total UK passenger car and light-duty van emissions of nitrogen oxides (NO_x) are underestimated by 24–32%, and up to 47% in urban areas, compared with the UK national inventory, despite agreement within 1.5% for total fuel used. Emissions of NO_x at a country level are also shown to vary considerably depending on the mix of vehicle manufacturers in the fleet. Adopting the on-road mix of vehicle manufacturers for six European countries results in up to a 13.4% range in total emissions of NO_x. Accounting for the manufacturer-specific fleets at a country level could have a significant impact on emission estimates of NO_x and other pollutants across the European countries, which are not currently reflected in emission inventories.

Nitrous oxide (N₂O) is a long-lived greenhouse gas that also destroys stratospheric ozone. N₂O emissions are uncertain and characterized by high spatiotemporal variability, making individual observations difficult to upscale, especially in mixed land use source regions like the San Joaquin Valley (SJV) of California. Here, we calculate spatially integrated N₂O emission rates using nocturnal and convective boundary-layer budgeting methods. We utilize vertical profile measurements from the NASA DISCOVER-AQ (Deriving Information on Surface Conditions from COlumn and VERtically Resolved Observations Relevant to Air Quality) campaign, which took place January–February, 2013. For empirical constraints on N₂O source identity, we analyze N₂O enhancement ratios with methane, ammonia, carbon dioxide, and carbon monoxide separately in the nocturnal boundary layer, nocturnal residual layer, and convective boundary layer. We find that an established inventory (EDGAR v4.3.2) underestimates N₂O emissions by at least a factor of 2.5, that wintertime emissions from animal agriculture are important to annual totals, and that there is evidence for higher N₂O emissions during the daytime than at night.

Elucidation of the chemical components of airborne fine particulate matter (PM_2.5) facilitates the characterization of atmospheric contamination sources and associated human exposure risks. In the present study, we employed a high-throughput analytical approach to investigate the abundance and distribution of 163 plastic additives in ambient PM_2.5 collected from 94 different sites across the Pearl River Delta region, China. These chemicals are from six categories, including organophosphate esters (OPEs), phthalate esters (PAEs), PAE replacements, bisphenol analogues, UV stabilizers, and antioxidants. Ninety-three of them exhibited a detection frequency greater than 50% in PM_2.5, while the combined concentrations of target plastic additives ranged from 610 to 49,400 μg/g (median: 3500 μg/g) across sites. By category, concentrations of PAEs (median: 2710 μg/g) were one to three orders of magnitude greater than those of other groups, followed by PAE replacements (540 μg/g) and OPEs (76.2 μg/g). Chemical-dependent exposure risks to PM_2.5-bound plastic additives were characterized via the estimated daily intake and hazard quotient (HQ) approaches, which resulted in two different risk prioritization systems. Although the HQ approach suggested no or very low health concerns when considering individual chemicals, the complexity of co-concurrent chemicals in PM_2.5 raises the concern on potential health risks from exposure to airborne particles and a cocktail of chemical components.

The residential sector is a major source of air pollutant emission inventory uncertainties. A nationwide field emission measurement campaign was conducted in rural China to evaluate the variabilities of realistic emission factors (EFs) from indoor solid fuel combustion. For a total of 1313 burning events, the overall average EFs (±standard deviation) of PM_2.5 were 8.93 ± 6.95 and 7.33 ± 9.01 g/kg for biomass and coals, respectively, and 89.3 ± 51.2 and 114 ± 87 g/kg for CO. Higher EFs were found from burning of uncompressed straws, while lower EFs were found from processed biomass pellets, coal briquettes, and relatively clean anthracite coals. Modified combustion efficiency was found to be the most significant factor associated with variations in CO EFs, whereas for PM_2.5, fuel and stove differences determined its variations. Weak correlations between PM_2.5 and CO indicated high uncertainties in using CO as a surrogate for PM_2.5. EFs accurately fit log-normal distributions, and obvious spatial heterogeneity was observed attributed to different fuel–stove combinations across the country. Emission estimation variabilities, which are determined by the interquartile ranges divided by the median values, were notably reduced when spatially resolved EFs were adopted in the inventory.

Understanding how the sources of an atmospheric organic aerosol (OA) govern its burden is crucial for assessing its impact on the environment and adopting proper control strategies. In this study, the sources of OA over Beijing were assessed year-around based on the combination of two separation approaches for OA, one from chemical fractionation into the high-polarity fraction of water-soluble organic matter (HP-WSOM), humic-like substances (HULIS), and water-insoluble organic matter (WISOM), and the other from statistical grouping using positive matrix factorization (PMF) of high-resolution aerosol mass spectra. Among the three OA fractions, HP-WSOM has the highest O/C ratio (1.36), followed by HULIS (0.56) and WISOM (0.17). The major sources of different OA fractions were distinct: HP-WSOM was dominated by more oxidized oxygenated OA (96%); HULIS by cooking-like OA (40%), less oxidized oxygenated OA (27%), and biomass burning OA (21%); and WISOM by fossil fuel OA (77%). In addition, our results provide evidence that mass spectral-based PMF factors are associated with specific substructures in molecules. These structures are further discussed in the context of the FT-IR results. This study presents an overall relationship of OA groups monitored by chemical and statistical approaches for the first time, providing insights for future source apportionment studies.

US background (US-B) ozone (O₃) is the O₃ that would be present in the absence of US anthropogenic (US-A) emissions. US-B O₃ varies by location and season and can make up a large, sometimes dominant, portion of total O₃. Typically, US-B O₃ is quantified using a chemical transport model (CTM) though results are uncertain due to potential errors in model process descriptions and inputs, and there are significant differences in various model estimates of US-B O₃. We develop and apply a method to fuse observed O₃ with US-B O₃ simulated by a regional CTM (CMAQ). We apportion the model bias as a function of space and time to US-B and US-A O₃. Trends in O₃ bias are explored across different simulation years and varying model scales. We found that the CTM US-B O₃ estimate was typically biased low in spring and high in fall across years (2016–2017) and model scales. US-A O₃ was biased high on average, with bias increasing for coarser resolution simulations. With the application of our data fusion bias adjustment method, we estimate a 28% improvement in the agreement of adjusted US-B O₃. Across the four estimates, we found annual mean CTM-simulated US-B O₃ ranging from 30 to 37 ppb with the spring mean ranging from 32 to 39 ppb. After applying the bias adjustment, we found annual mean US-B O₃ ranging from 32 to 33 ppb with the spring mean ranging from 37 to 39 ppb.

Optimization of MgO adsorbents is predominantly focused on the regulation of appropriate adsorption sites for CO₂ associated with Mg²⁺-O^2– sites of low coordination. Here, for the first time, we conducted transient kinetic experiments to identify and characterize changes of the CO₂ molecular path in MgO-based CO₂ adsorbents upon the addition of molten salt modifiers. Among the optimized samples, addition of 10 mol % NaNO₂ on the surface of MgO exhibited the highest CO₂ uptake (15.7 mmol g^–1) at 350 °C compared to less than 0.1 mmol g^–1 for the unpromoted MgO. Kinetic modeling showed that the interaction of molten salt-promoted MgO with CO₂ at 300 °C involves three different processes, namely, fast surface adsorption associated with surface-active basic sites, chemical reaction associated with MgCO₃ formation, and a slow diffusion step being the rate-limiting step of the carbonation process. Furthermore, transient kinetic studies coupled with mass spectrometry under low CO₂ partial pressure agreed well with the kinetic simulation results based on TGA measurements, demonstrating an in-depth understanding of the CO₂-capturing performance gained and its considerable significance for future practical designs of precombustion CO₂ capture.

A new passive sampling method was developed and characterized to measure atmospheric volatile methyl siloxanes (VMS). The infrastructure of a commercial passive air sampler (PAS) was used along with XAD-2 resin as the adsorbent. Experimental sampling rates (SR) determined using collocated active and passive samplers ranged between 0.0363 (L5) and 0.0561 (D3) m³/day and agreed well with the theoretical ones. VMS uptake was highly linear for eight weeks. The precision of the method was very good (<10%). Compared to the other PASs used for VMS, the new method has several advantages (i.e., the sampler is much smaller, it has commercially available components, and the solvent requirement, equipment needed for extraction, and steps for sample preparation are minimal) while achieving similar or lower method detection limits. The developed method was applied to investigate the spatial distribution and possible sources of atmospheric VMS in the Izmir region. Field sampling covered 42 sites representing different source and land use areas. ΣVMS concentrations ranged between 41.4 and 981 ng/m³. The dominant VMS was D5 followed by D3 and D4. Spatial distributions indicated that the main VMS sources in the area were urban areas, wastewater treatment plants, and landfills where the VMS-containing products are used and disposed.

Nitrogen oxides (NO_X) and methane impact air quality through the promotion of ozone formation, and methane is also a strong greenhouse gas. Despite the importance of these pollutants, emissions in urban areas are poorly quantified. We present measurements of NO_X, CH₄, CO, and CO₂ made at Drexel University in Philadelphia along with NO_X and CO observations at two roadside monitors. Because CO₂ concentrations in the winter result almost entirely from combustion with negligible influence from photosynthesis and respiration, we are able to infer fleet-averaged fuel-based emission factors (EFs) for NO_X and CO, similar in some ways to how EFs are determined from tunnel studies. Comparison of the inferred NO_X and CO fuel-based EF to the National Emissions Inventory (NEI) suggests errors in NEI emissions of either NO_X, CO, or both. From the measurements of CH₄ and CO₂, which are not emitted by the same sources, we infer the ratio of CH₄ emissions (from leaks in the natural gas infrastructure) to CO₂ emissions (from fossil fuel combustion) in Philadelphia. Comparison of the CH₄/CO₂ emission ratios to emission inventories from the Environmental Protection Agency suggests underestimates in CH₄ emissions by almost a factor of 4. These results demonstrate the need for the addition of long-term observations of CH₄ and CO₂ to existing monitoring networks in urban areas to better constrain emissions and complement existing measurements of NO_X and CO.

Vertical measurements are essential for the characterization of aerosol and boundary layer interactions; yet, our knowledge of vertical profiles of primary and secondary aerosol species in megacities is limited. Here, we conducted comprehensive vertical measurements of aerosol particle composition on a 325 m meteorological tower with two aerosol chemical speciation monitors in winter in urban Beijing. The simultaneous measurements at ground level, 140, and 240 m illustrated similar aerosol bulk composition at these three heights. However, the vertical ratios varied significantly among different aerosol species. Particularly, the vertical ratios of the aqueous phase and photochemical-related secondary organic aerosol (SOA) (aqOOA/OOA) decreased significantly, accompanied by the increases in ratios of secondary to primary OA, highlighting different chemical properties of OA between ground level and aloft, and the large impacts of vertical changes in meteorology and gaseous precursors on SOA formation. The vertical changes in NO₃/SO₄ ratios, however, were mostly insignificant, likely due to the low relative humidity and aerosol water content that inhibited nocturnal heterogeneous reactions in the residual layer. Considerable increases in the ratios of 240 m to ground level in the early morning were also observed for most aerosol species, demonstrating impact of residual layer on the air pollution of 2nd day.

Methoxyphenols are an important class of compounds emerging from biomass combustion, and their reactions with ozone can generate secondary organic aerosols in the atmosphere. Here, we use a vertical wetted wall flow tube reactor to evaluate the effect of ionic strength on the heterogeneous reaction of gas-phase ozone (O₃) with a liquid film of o-vanillin (o-VL) (2-hydroxy-3-methoxybenzaldehyde), as a proxy for methoxyphenols. Typical for moderately acidic aerosols, at fixed pH = 5.6, the uptake coefficients (γ) of O₃ on o-VL ([o-VL] = 1 × 10^–5 mol L^–1) increase from γ = (1.9 ± 0.1) × 10^–7 in the absence of Na₂SO₄ to γ = (6.8 ± 0.3) × 10^–7 at I = 0.2 mol L^–1, and then, it decreases again. The addition of NO₃^– ions only slightly decreases the uptakes of O₃. Ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals that the formation of multicore aromatic compounds is favored upon heterogeneous O₃ reaction with o-VL, in the presence of SO₄^2– and NO₃^– ions. The addition of NO₃^– ions favors the formation of nitrooxy (−ONO₂) or oxygenated nitrooxy group of organonitrates, which are components of brown carbon that can affect both climate and air quality.

Secondary organic aerosol (SOA) plays a critical role in sustained haze pollution in megacities. Traditional observation of atmospheric aerosols usually analyzes the ambient organic aerosol (OA) but neglects the SOA formation potential (SOAFP) of precursors remaining in ambient air. Knowledge on SOAFP is still limited, especially in megacities suffering from frequent haze. In this study, the SOAFP of ambient air in urban Beijing was characterized at different pollution levels based on a two-year field observation using an oxidation flow reactor (OFR) system. Both OA and SOAFP increased as a function of ambient pollution level, in which increasing concentrations of precursor volatile organic compounds (VOCs) and decreasing atmospheric oxidation capacity were found to be the two main influencing factors. To address the role of the atmospheric oxidation capacity in SOAFP, a relative OA enhancement ratio (ER_OA = 1 + SOAFP/OA) and the elemental composition of the OA were investigated in this study. The results indicated that the atmospheric oxidation capacity was weakened and resulted in higher SOAFP on more polluted days. The relationship found between SOAFP and the atmospheric oxidation capacity could be helpful in understanding changes in SOA pollution with improving air quality in the megacities of developing countries.

The discovery of complete ammonia oxidation (comammox) has altered our understanding of nitrification, which is the rate-limiting process in the global nitrogen cycle. However, understanding the ecological role of comammox or its contribution to nitrification in both natural and artificial ecosystems is still in its infancy. Here, we investigated the community distribution and function of comammox bacteria in riparian ecosystems and analyzed interactions between comammox and other nitrogen cycling microorganisms. The comammox bacterial abundance and rate were higher in summer than in winter and higher in nonrhizosphere soils than in the rhizosphere. Fringe soils in the riparian zone comprise a comammox hotspot, where the abundance (2.58 × 10⁸ copies g^–1) and rate (0.86 mg N kg^–1 d^–1) of comammox were not only higher than at other sampling sites but also higher than those of other ammonia oxidation processes. The comammox rate correlated significantly positively with relative abundance of the comammox species Candidatus Nitrospira nitrificans but not with that of the species Candidatus Nitrospira nitrosa. Analysis of comammox interaction with other ammonia-oxidizing processes revealed ammonia-oxidizing archaea to dominate interface soils, comammox to dominate in fringe soils, and anaerobic ammonium oxidation (anammox) to dominate in interface sediments of the riparian zone. These results indicate that comammox may constitute an important and currently underestimated process of microbial nitrification in riparian zone ecosystems.

Urban rivers worldwide are affected directly by macrophyte growth, causing reduced flow velocity and risks of flooding. Therefore, cutting macrophytes is a common management practice to ensure free drainage. The impacts of macrophyte removal on transient storage dynamics and microbial metabolic activity of wastewater-fed urban streams are unknown, preventing any assessment of the hydrodynamic and biogeochemical consequences of this management practice. Slug tracer injections were performed with the conservative tracer uranine and the reactive tracer resazurin to quantify the implications of macrophyte cutting on stream flow dynamics and metabolism. Macrophyte cutting reduced mean tracer arrival times in managed stream reaches but did not significantly decrease whole-stream microbial metabolic activity. In fact, transient storage indices were found to have increased after cutting, suggesting that macrophyte removal and the resulting increase in flow velocity may have enhanced hyporheic exchange flow through streambed sediments. Our results evidence that macrophyte cutting in nutrient-rich urban streams does not necessarily lead to lower in-stream storage and metabolism but that the gain in hyporheic exchange and streambed microbial metabolic activity can compensate for reduced in-stream storage. Increased stream flow resulting from macrophyte removal may therefore even enhance nutrient and pollutant attenuation capacity of streambed sediments.

Geological disposal is the globally preferred long-term solution for higher activity radioactive wastes (HAW) including intermediate level waste (ILW). In a cementitious disposal system, cellulosic waste items present in ILW may undergo alkaline hydrolysis, producing significant quantities of isosaccharinic acid (ISA), a chelating agent for radionuclides. Although microbial degradation of ISA has been demonstrated, its impact upon the fate of radionuclides in a geological disposal facility (GDF) is a topic of ongoing research. This study investigates the fate of U(VI) in pH-neutral, anoxic, microbial enrichment cultures, approaching conditions similar to the far field of a GDF, containing ISA as the sole carbon source, and elevated phosphate concentrations, incubated both (i) under fermentation and (ii) Fe(III)-reducing conditions. In the ISA-fermentation experiment, U(VI) was precipitated as insoluble U(VI)-phosphates, whereas under Fe(III)-reducing conditions, the majority of the uranium was precipitated as reduced U(IV)-phosphates, presumably formed via enzymatic reduction mediated by metal-reducing bacteria, including Geobacter species. Overall, this suggests the establishment of a microbially mediated “bio-barrier” extending into the far field geosphere surrounding a GDF is possible and this biobarrier has the potential to evolve in response to GDF evolution and can have a controlling impact on the fate of radionuclides.

Soil contamination with tetrabromobisphenol A (TBBPA) has been an environmental concern for many years, but in situ studies of the fate and potential risk of TBBPA are lacking. In this study, we investigated the dissipation, metabolism, strong alkali-hydrolytic (SAH-TBBPA), and vertical movement of TBBPA in the field with and without rice-wheat rotation and reed growth for 1225 days. After 342 days of incubation, 21.3% of the TBBPA remained in the surface soil accompanied by obvious leaching to deeper soil layers in the first 92 days. By day 1225, TBBPA was nearly absent from the surface soil layer. A very low amount of SAH-TBBPA (2.31–3.43 mg/kg) was detected during the first 342 days of incubation. In the surface soil, five metabolites were identified that represented four interconnected pathways: oxidative skeletal cleavage, O-methylation, type II ipso-substitution, and reductive debromination. Both rice–wheat rotation and monocultural reed growth accelerated TBBPA removal in the field by stimulating the anaerobic debromination and aerobic O-methylation, especially the oxidative skeletal cleavage of TBBPA in the rhizosphere soil. Though far from comprehensive, our study investigated the natural attenuation and metabolism of TBBPA in situ and the influence by crops to estimate the environmental risk of TBBPA in a field scale.

The simulation of nitrogen dynamics in urban channel confluences is essential for the evaluation and improvement of water quality. The omics-based modeling approaches that have been rapidly developed have been increasingly applied to characterize metabolisms of the microbial community and transformation of the associated materials. However, the transport of microorganisms and chemicals within and among different phases, which could be the rate-limiting step for the nitrogen dynamics, are always neglected or oversimplified in omics-based models. Therefore, this study proposes a novel simulation system coupling genomic and hydraulic information to simulate transport and transformation processes and provide predictions of nitrogen dynamics in a confluence. The proposed model was able to capture multiphase mass transport, microbial population dynamics, and nitrogen transformation and accurately predict gene abundances and nitrogen concentrations in both water and sediment; the mean relative errors were all lower than 40%. The model emphasized the importance of transport processes, which contributed more than 90% to gene abundances and chemical concentrations. Moreover, the simulation of reaction rates exhibited the specific nitrogen transformation processes in the confluence. The sulfide oxidation and the nitrate reduction and anaerobic ammonium oxidation, with the participation of the genes nap and hzo, respectively, were promoted as the main processes of nitrate and nitrite reduction.

This article investigates a novel data fusion method to predict clay content and cation exchange capacity using visible near-infrared (visNIR) spectroscopy, portable X-ray fluorescence (pXRF), and X-ray diffraction (XRD) techniques. A total of 367 soil samples from two study areas in regional Australia were analyzed and intra- and interarea calibration options were explored. Cubist models were constructed using information from each device independently and in combination. pXRF produced the most accurate predictions of any individual device. Models based on fused data significantly improved the accuracy of predictions compared with those based on individual devices. The combination of pXRF and visNIR had the greatest performance. Overall, the relative increase in Lin’s concordance correlation coefficient ranged from 1% to 12% and the corresponding decrease in root-mean-square error (RMSE) ranged from 10% to 46%. Provision of XRD data resulted in a decrease in observed RMSE values, although differences were not significant. Validation metrics were less promising when models were calibrated in one study area and then transferred to the other. Observed RMSE values were ∼2 to 3 times larger under this model transfer scenario and independent use of XRD was found to have the best overall performance.

Iron hydroxides are important scavengers for dissolved chromium (Cr) via coprecipitation processes; however, the influences of organic matter (OM) on Cr sequestration in Fe/Cr-OM ternary systems and the stability of the coprecipitates are not well understood. Here, Fe/Cr-OM coprecipitation was conducted at pH 3, and Cr hydroxide was undersaturated. Acetic acid (HAc), poly(acrylic acid) (PAA), and Suwannee River natural organic matter (SRNOM) were selected as model OMs, which showed different complexation capabilities with Fe/Cr ions and Fe/Cr hydroxide particles. HAc had no significant effect on the coprecipitation, as the monodentate carboxyl ligand in HAc did not favor complexation with dissolved Fe/Cr ions or Fe/Cr hydroxide nanoparticles. Contrarily, PAA and SRNOM with polydentate carboxyl ligand had strong complexation with Fe/Cr ions and Fe/Cr hydroxide nanoparticles, leading to significant amounts of PAA/SRNOM sequestered in the coprecipitates, which caused the structural disorder and fast aggregation of the coprecipitates. In comparison with that of PAA, preferential complexation of Cr ions with SRNOM resulted in higher Cr/Fe ratios in the coprecipitates. This study advances the fundamental understanding of Fe/Cr-OM coprecipitation and mechanisms controlling the composition and stability of the coprecipitates, which is essential for successful Cr remediation and removal in both natural and engineered settings.

Biodegradable mulch films have been developed as a suitable alternative to conventional nondegradable polyethylene films. However, the key factors controlling the degradation speed of biodegradable mulch films in soils remain unclear. Here, we linked changes in the soil microbiome with the degradation rate of a promising biodegradable material poly(butylene adipate-co-terephthalate) (PBAT) in four soil types, a lou soil (LS), a fluvo-aquic soil (CS), a black soil (BS), and a red soil (RS), equivalent to Inceptisols (the first two soils), Mollisols, and Ultisols, using soil microcosms. The PBAT degradation rate differed with the soil type, with PBAT mineralization levels of 16, 9, 0.3, and 0.9% in LS, CS, BS, and RS, respectively, after 120 days. Metagenomic analysis showed that the microbial community in LS was more responsive to PBAT than the other three soils. PBAT hydrolase genes were significantly enriched in LS but were not significantly stimulated by PBAT in CS, BS, or RS. Several members of Proteobacteria were identified as novel potential degraders, and their enrichment extent was significantly positively correlated with PBAT degradation capacity. Overall, our results suggest that soil environments harbored a range of PBAT-degrading bacteria and the enrichment of potential degraders drives the fate of PBAT in the soils.

Microplastics (MPs) pollution has caused a threat to soil ecosystem diversity and functioning globally. Recently, an increasing number of studies have reported effects of MPs on soil ecosystems. However, these studies mainly focused on soil bacterial communities and a few limited functional genes, which is why MPs effects on soil ecosystems are still not fully understood. Fertilization treatment often coinsides with MPs exposure in practice. Here, we studied effects of an environmentally relevant concentration of polyethylene on soil properties, microbial communities, and functions under different soil types and fertilization history. Our results showed that 0.2% PE MPs exposure could affect soil pH, but this effect varied according to soil type and fertilization history. Long-term fertilization history could alter effects of MPs on soil bacterial and fungal communities in diverse farmland ecosystems (P < 0.05). Soil fungal communities are more sensitive to MPs than bacterial communities under 0.2% PE MPs exposure. MPs exposure has a greater impact on the soil ecosystem with a lower microbial diversity and functional genes abundance and increases the abundance of pathogenic microorganisms. These findings provided an integrated picture to aid our understanding of the impact of MPs on diverse farmland ecosystems with different fertilization histories.

For the most complex artificial chlorinated environmental contaminants, much less is known for medium-chain CPs than short-chain CPs. In this research, the spatial distributions of MCCPs and SCCPs in farmland soil and maize leaves near a CP production facility were found marginally influenced by seasonal winds. The levels of ∑MCCPs and ∑SCCPs were in the ranges of <1.51–188 and 5.41–381 ng/g dw for soils; and 77.6–52930 and 119–61999 ng/g dw for maize leaf, respectively. Bioaccumulation and tissue distributions of the CPs within maize plants were specifically analyzed. Most of the CPs were contained in the tissues directly exposed to airborne CPs. Though the estimated risk of CPs to humans through ingestion of kernels appears to be minimal, the edible safety of MCCPs in maize plants for cattle was nearly in the designated range of adverse effects. To our knowledge, this is the first report on bioaccumulation of CPs in mature maize plants, especially in the parts eaten by humans and domestic animals. It provides a baseline reference to the edible risks of CPs in agricultural food plants and alerts us to the problematic environmental behavior of MCCPs, a probable future replacement for SCCPs commercially.

Neonicotinoids from insecticidal seed coatings can contaminate soil in treated fields and adjacent areas, posing a potential risk to nontarget organisms and ecological function. To determine if cover crops can mitigate neonicotinoid contamination in treated and adjacent areas, we measured neonicotinoid concentrations for three years in no-till corn-soybean rotations, planted with or without neonicotinoid seed coatings, and with or without small grain cover crops. Although neonicotinoids were detected in cover crops, high early season dissipation provided little opportunity for winter-planted cover crops to absorb significant neonicotinoid residues; small grain cover crops failed to mitigated neonicotinoid contamination in either treated or untreated plots. As the majority of neonicotinoids from seed coatings dissipated shortly after planting, residues did not accumulate in soil, but persisted at concentrations below 5 ppb. Persistent residues could be attributed to historic neonicotinoid use and recent, nearby neonicotinoid use. Tracking neonicotinoid concentrations over time revealed a large amount of local interplot movement of neonicotinoids; in untreated plots, contamination was higher when plots were less isolated from treated plots.

Environmental proteins (eProteins), such as Cry proteins associated with genetically engineered (GE) organisms, are present in ecosystems worldwide, but only rarely reach concentrations with detectable ecosystem-level impacts. Despite their ubiquity, the degradation and fate of Cry and other eProteins are mostly unknown. Here, we report the results of an experiment where we added Cry proteins leached from GE Bt maize to a suite of 19 recirculating experimental streams. We found that Cry exhibited a biphasic degradation with an initial phase of rapid and variable degradation within 1 h, followed by a slow and steady phase of degradation with traces of protein persisting after 48 h. The initial degradation was correlated with heterotrophic respiration and water column dissolved oxygen, confirming a previously documented association with stream metabolism. However, protein degradation persisted even with no biofilm and was faster at a more acidic pH, suggesting that water chemistry is also a critical factor in both degradation and subsequent detection. We suggest that Cry, as well as other eProteins, will have a rapid degradation caused by denaturation of proteins and pH changes, which confirms that the detection of Cry proteins in natural streams must be the result of steady and consistent leaching into the environment.

Zwitterionic per- and polyfluoroalkyl substances (PFASs) used in aqueous film-forming foams (AFFFs) could face diverse environmental fates once released at military bases, airports, fire-training areas, and accidental release sites. Here, we studied for the first time the transformation potential of four electrochemical fluorination (ECF)-based PFAS zwitterions (two carboxyl betaines and two tertiary amines) in aerobic soils. The two perfluoroalkyl sulfonamide derivatives were precursors to perfluorooctanesulfonate (PFOS), while the amide derivatives were precursors to perfluorooctane carboxylate (PFOA). These zwitterions and four other previously reported zwitterions or cations were compared for their transformation pathways and kinetics. Structural differences, especially the nitrogen head groups, largely influenced the persistence of these compounds in aerobic soils. The perfluoroalkyl sulfonamide-based compounds showed higher microbial stability than the corresponding perfluoroalkyl amide-based ones. Their stability in aerobic soils is ranked based on the magnitude of DT₅₀ (time for 50% of substance to disappear): quaternary ammonium ≈ carboxyl betaine ≫ tertiary amine > amine oxide. The PFASs containing quaternary ammonium or betaine groups showed high stability in soils, with the longest DT₅₀ likely to be years or decades, while those with tertiary amine or amine oxide groups showed DT₅₀ of weeks or months. These eight ECF-based precursors provide insights into the degradation pathways and persistence in surface soils of other perfluoroalkyl cations and zwitterions present in AFFFs.

The multidecadal expansion of northern Gulf of Mexico continental shelf hypoxia is a striking example of the adverse effects of anthropogenic nutrient enrichment on coastal oceans. Increased nutrient inputs and widespread shelf hypoxia have resulted in numerous dissolved oxygen (DO) water quality problems in nearshore coastal waters of Louisiana. A large hydrographic dataset compiled from research programs spanning 30 years and the three-dimensional hydrodynamic-biogeochemical model CGEM (Coastal Generalized Ecosystem Model) were integrated to explore the interconnections of low DO waters across the continental shelf to nearshore coastal waters of Louisiana. Cross-shelf vertical profiles showed contiguous low DO bottom waters extending from the shelf to coastal waters nearly every year in the 30+ year time series, which were concurrent with strong cross-shelf pycnoclines. A threshold Brunt–Väisälä frequency of 40 cycles h^–1 was critical to maintaining the cross-shelf subpycnocline layers and facilitating the formation of a contiguous low DO water mass. Field observations and model simulations identified periods of wind-driven bottom water upwelling lasting between several days to several weeks, resulting in both physical advection of oxygen-depleted offshore waters to the nearshore and enhanced nearshore stratification. Both the upwelling of low DO bottom waters and in situ respiration were of sufficient temporal and spatial extent to drive DO below Louisiana’s DO water quality criteria. Basin-wide nutrient management strategies aimed at reducing nutrient inputs and shelf hypoxia remain essential to improving the nearshore coastal water quality across the northern Gulf of Mexico.

Current approaches are often limited to evaluating the contribution of pesticide dissipation processes in water–sediment systems as both degradation and phase transfer, that is, sorption–desorption, contribute to the apparent decrease of pesticide concentration. Here, the dissipation of widely used herbicides acetochlor and S-metolachlor was examined in laboratory by water–sediment microcosm experiments under oxic and anoxic conditions. Compound-specific isotope analysis (CSIA) emphasized insignificant carbon isotope fractionation in the sediment, indicating prevailing pesticide degradation in the water phase. Conceptual modeling accounting for phase transfer and biodegradation indicated that biodegradation may be underestimated when phase transfer is not included. Phase transfer does not affect carbon isotope fractionation for a wide spectrum of molecules and environmental conditions, underscoring the potential of pesticide CSIA as a robust approach to evaluate degradation in water–sediment systems. CSIA coupled with the identification of transformation products by high-resolution tandem mass spectrometry suggests the degradation of acetochlor and S-metolachlor to occur via nucleophilic substitution and the predominance of oxalinic acids as transformation products under both anoxic and oxic conditions. Altogether, combining the pesticide CSIA, the identification of transformation products, and the use of conceptual phase-transfer models improves the interpretation of pesticide dissipation in water–sediment systems.

Humans spend 90% of their time indoors, but the majority of indoor pollutants remain unknown. In this study, a nontarget screening algorithm with reduced false discovery rates was developed to screen indoor pollutants using the Toxic Substances Control Act (TSCA) database. First, a putative lock mass algorithm was developed for post-acquisition calibration of Orbitrap mass spectra to sub-ppm mass accuracy. Then, a one-stop screening algorithm was developed by combining MS¹ spectra, isotopic peaks, retention time prediction, and in silico MS² spectra. A sufficient true positive rate (73%) and false discovery rate (5%) were achieved for the screening of halogenated compounds at a score cutoff of 0.28. Above this cutoff, 427 chemicals were detected from 24 house dust samples, including 39 chlorinated compounds. While some identified halogenated compounds (e.g., triclosan) are well known, 18 previously unrecognized chlorinated azo dyes were detected with high abundance as the largest class of chlorinated compounds. Two chlorinated azo dyes were confirmed with authentic standards, but the two most abundant chlorinated azo dyes were missed by the algorithm due to the limited breadth of the TSCA database. These compounds were annotated as chlorinated analogues of Disperse Blue 373 and Disperse Violet 93 using the DIPIC-Frag method. This study revealed the presence of highly abundant chlorinated azo dyes in house dusts, highlighting their potential health risks in the indoor environment.

Improved analytical methods can quantify hundreds of pesticide transformation products (TPs), but understanding of TP occurrence and potential toxicity in aquatic ecosystems remains limited. We quantified 108 parent pesticides and 116 TPs in more than 3 700 samples from 442 small streams in mostly urban basins across five major regions of the United States. TPs were detected nearly as frequently as parents (90 and 95% of streams, respectively); 102 TPs were detected at least once and 28 were detected in >20% samples in at least one region—TPs of 9 herbicides, 2 fungicides (chlorothalonil and thiophanate-methyl), and 1 insecticide (fipronil) were the most frequently detected. TPs occurred commonly during baseflow conditions, indicating chronic environmental TP exposures to aquatic organisms and the likely importance of groundwater as a TP source. Hazard quotients based on acute aquatic-life benchmarks for invertebrates and nonvascular plants and vertebrate-centric molecular endpoints (sublethal effects) quantify the range of the potential contribution of TPs to environmental risk and highlight several TP exposure–response data gaps. A precautionary approach using equimolar substitution of parent benchmarks or endpoints for missing TP benchmarks indicates that potential aquatic effects of pesticide TPs could be underestimated by an order of magnitude or more.

Metal-reducing microorganisms such as Shewanella oneidensis MR-1 reduce highly soluble species of hexavalent uranyl (U(VI)) to less mobile tetravalent uranium (U(IV)) compounds. The biologically mediated immobilization of U(VI) is being considered for the remediation of U contamination. However, the mechanistic underpinnings of biological U(VI) reduction remain unresolved. It has become clear that a first electron transfer occurs to form pentavalent (U(V)) intermediates, but it has not been definitively established whether a second one-electron transfer can occur or if disproportionation of U(V) is required. Here, we utilize the unusual properties of dpaea^2– ((dpaeaH₂═bis(pyridyl-6-methyl-2-carboxylate)-ethylamine)), a ligand forming a stable soluble aqueous complex with U(V), and investigate the reduction of U(VI)–dpaea and U(V)–dpaea by S. oneidensis MR-1. We establish U speciation through time by separating U(VI) from U(IV) by ion exchange chromatography and characterize the reaction end-products using U M₄-edge high resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy. We document the reduction of solid phase U(VI)–dpaea to aqueous U(V)–dpaea but, most importantly, demonstrate that of U(V)–dpaea to U(IV). This work establishes the potential for biological reduction of U(V) bound to a stabilizing ligand. Thus, further work is warranted to investigate the possible persistence of U(V)–organic complexes followed by their bioreduction in environmental systems.

Natural toxins are multifunctional, often ionizable organic compounds increasingly detected in the environment. Surprisingly little is known about their interactions with soil organic carbon, although sorption largely controls transport, bioavailability, and dissipation. For a set of 117 natural toxins from 36 compound classes the pH-dependent organic carbon–water distribution coefficient (D_oc) was quantified using a soil column chromatography approach under changing conditions with regards to pH, ionic strength, and the major inorganic cation in solution. Natural toxins could be assigned to groups with either hydrophobic partitioning or specific interactions (complexation reactions, cation exchange) as dominating sorption mechanisms. The complex interplay of interactions in the sorption of natural toxins was equally influenced by sorbate, sorbent, and solution specific characteristics. High variability in sorption was particularly observed in the presence of Ca²⁺ resulting in D_oc being enhanced by a factor of 10 when the pH was increased from 4.5 to 6. Sorbates following this trend contain either functional groups able to form ternary complexes via Ca²⁺ or aromatic moieties adjacent to protonated N presumably stabilizing cation exchange reactions. Although sorption was often stronger than predicted, investigated natural toxins were highly mobile under all considered conditions.

Determining whether aqueous diffusion and dispersion lead to significant isotope fractionation is important for interpreting the isotope ratios of organic contaminants in groundwater. We performed diffusion experiments with modified Stokes diaphragm cells and transverse-dispersion experiments in quasi-two-dimensional flow-through sediment tank systems to explore isotope fractionation for benzene, toluene, ethylbenzene, 2,6-dichlorobenzamide, and metolachlor at natural isotopic abundance. We observed very small to negligible diffusion- and transverse-dispersion-induced isotope enrichment factors (ε < −0.4 ‰), with changes in carbon and nitrogen isotope values within ±0.5‰ and ±1‰, respectively. Isotope effects of diffusion did not show a clear correlation with isotopologue mass with calculated power-law exponents β close to zero (0.007 < β < 0.1). In comparison to ions, noble gases, and labeled compounds, three aspects stand out. (i) If a mass dependence is derived from collision theory, then isotopologue masses of polyatomic molecules would be affected by isotopes of multiple elements resulting in very small expected effects. (ii) However, collisions do not necessarily lead to translational movement but can excite molecular vibrations or rotations minimizing the mass dependence. (iii) Solute–solvent interactions like H-bonds can further minimize the effect of collisions. Modeling scenarios showed that an inadequate model choice, or erroneous choice of β, can greatly overestimate the isotope fractionation by diffusion and, consequently, transverse dispersion. In contrast, available data for chlorinated solvent and gasoline contaminants at natural isotopic abundance suggest that in field scenarios, a potential additional uncertainty from aqueous diffusion or dispersion would add to current instrumental uncertainties on carbon or nitrogen isotope values (±1‰) with an additional ±1‰ at most.

The globally raising concern for nanoplastics (NPs) pollution calls for analytical methods for investigating their occurrence, fates, and effects. Counting NPs with sizes down to 50 nm in real environmental waters remains a great challenge. Herein, we developed a full method from sample pretreatment to quantitative detection for NPs in environmental waters. Various NPs of common plastic types and sizes (50–1200 nm) were successfully labeled by in situ growth of gold nanoparticles and counted by single particle inductively coupled plasma mass spectrometry. Sucrose density gradient centrifugation enables the isolation of gold-labeled NPs from homogeneously nucleated Au nanoparticles, enhancing the particle number detection limit to 4.6 × 10⁸ NPs/L for 269 nm spherical polystyrene NPs. For real environmental water samples, the pretreatment of acid digestion with a mixture of 5 mM HNO₃ and 40 mM HF eliminates the coexisting inorganic nanoparticles, while the following dual cloud-point extraction efficiently isolates NPs from various matrices and thus improves the Au-labeling efficiency. The high spiked recoveries (72.9%–92.8%) of NPs in different waters demonstrated the applicability of this method in different scenarios.

The microbial diversity of several environments has been explored by researchers for the biodegradation of pyrethroids. In this study, a new approach was employed aiming at the use of Bacillus thuringiensis Berliner, a strain commercially available as bioinsecticide, for Cypermethrin (Cyp) biodegradation. This bacterial strain grew in the presence of Cyp and biodegraded this xenobiotic in a liquid medium. A central composite design for surface response methodology was employed for biodegradation. Under optimized conditions (50 mg·L^–1 of Cyp, pH 8.5, 37 °C), 83.5% biodegradation was determined with the production of 12.0 ± 0.6 mg·L^–1 3-phenoxybenzoic acid after 5 days. Moreover, a biodegradation pathway with the 18 compounds identified by GC-MS and LC-MS/MS was proposed. Experiments in soil for 28 days at 30 °C were performed, and 16.7% Cyp degradation was determined under abiotic conditions, whereas 36.6 ± 1.9% biodegradation was observed for B. thuringiensis Berliner with the native microbiome, indicating that bioaugmentation with this strain promoted a significant increase in the Cyp decontamination. Therefore, B. thuringiensis Berliner can act as biodegrader agent and insecticide at the same time, promoting decontamination of chemicals as Cyp while maintaining the protection of crops against insects. Moreover, B. thuringiensis species can produce bacteriocins with antifungal activity, which may increase agricultural productivity.

Microplastics were recently found to aggregate in the blue carbon ecosystems (BCEs), which are known for their ability to store carbon by slowing down the water flow. However, evidence is largely lacking on how the accumulation of microplastics is related to carbon sequestration in BCEs and if this trap effect is driven by its biological characteristics. In this study, the trap effect of microplastics by BCEs was evaluated for various seagrasses (Zostera japonica, Halophila ovalis, and Halophila beccarii) and mangroves (Aegiceras corniculatum and Avicennia marina). Significant accumulation was found in the seagrass meadow dominated by H. beccarii and the mangrove forest dominated by A. marina, with microplastics enriched by 1.3 to 17.6 times compared to their corresponding unvegetated sites. The abundance of microplastics varied greatly from 17.68 ± 8.10 to 611.75 ± 81.52 particles per kg of dry sediment, with the highest abundance in A. marina mangrove sediments. A strong positive correlation was found between the abundance of microplastics and the particulate organic carbon content at all study sites (Pearson, R = 0.86, p < 0.01). Higher diversity of microplastic colors and size was found in the H. beccarii meadow, and higher diversity of shapes was found in the A. marina forest. Our results added new insights to the understanding of the mechanism of microplastic trapping by BCEs and coupled the behavior of microplastics with the organic carbon in the sediment.

Vanadium, a potentially toxic metal, is enriched in the environment from anthropogenic releases, particularly during fossil fuel production and use and steel manufacturing. Metal stable isotopes are sophisticated tools to trace pollution; however, only recent analytical advances have allowed for the accurate and precise measurement of vanadium isotope ratios (δ⁵¹V). To examine its potential as a tracer in terrestrial and aquatic ecosystems, δ⁵¹V was measured in soil, plant, lichen, marten, and lake sediment from sites near vanadium emissions at oil sands mines (Alberta, Canada) and in the sediment and biota (algae, zooplankton, fish) from a remote subarctic lake (Northwest Territories, Canada). Samples from Alberta had distinct δ⁵¹V values with marten liver the lowest (−1.7 ± 0.3‰), followed by lichen (−0.9 ± 0.1‰), soil (−0.7 ± 0.1‰), sediment (−0.5 ± 0.2‰), and plant root (−0.3 ± 0.2‰). Average values were lower than Alberta bitumen and petroleum coke (−0.1 ± 0.1‰). Plant roots had systematically higher δ⁵¹V than the soil from which they grew (Δ⁵¹V_plant-soil = 0.4 ± 0.1‰), while δ⁵¹V of lichen and aquatic biota were lower (0.1–0.3‰) than likely crustal sources. These δ⁵¹V measurements in terrestrial and aquatic biota demonstrate promise for tracer applications, although further study of its biological fractionation is needed.

Unused or expired pharmaceutical and personal care products (PPCPs) are usually discharged into municipal solid wastes, then travel to landfills, and eventually percolate into leachates. However, knowledge of their occurrence and temporal dynamics in leachates is limited, making landfill leachate an underappreciated emission source of PPCPs. Furthermore, the differences in PPCP variations in landfill leachates emphasize the necessity for identifying the influencing factors and elucidating the mechanisms for PPCP fluctuations. In this study, successive monthly monitoring of PPCPs in leachates throughout an entire year was performed to determine their seasonal variations and identify their influencing factors. Furthermore, five pairs of additional sampling campaigns were conducted before and after rainfall events during wet seasons to elucidate the influencing mechanisms. The results showed that there was a distinct seasonal variation in PPCPs in landfill leachates—elevated levels during the wet period (from April to September, with a mean concentration of 17.0 μg/L for total monitored PPCPs)—when compared to other months (mean concentration of 3.8 μg/L). Rainfall played a considerable role in mediating PPCP concentrations in leachates. The PPCP responses to five rainfall episodes further verified the influence of rainfall and demonstrated that the tendency to PPCP concentration increase was related to rainfall precipitation. Torrential rain events (i.e., 24 h cumulative precipitation of 50–99.9 mm) led to the most significant increases in PPCP concentrations in landfill leachates. In addition, the hydrophilicity of PPCPs contributed to the different fluctuations during the 1 year investigation and different responses to rainfall. To the best of our knowledge, this study provides the first direct evidence supporting the influence of rainfall on PPCPs in landfill leachates, which can help better understand the occurrence and behavior of emerging contaminants in this underappreciated emission source.

Bioremediation of chlorinated ethenes in anoxic aquifers hinges on organohalide-respiring Dehalococcoidia expressing vinyl chloride (VC) reductive dehalogenase (RDase). The tceA gene encoding the trichloroethene-dechlorinating RDase TceA is frequently detected in contaminated groundwater but not recognized as a biomarker for VC detoxification. We demonstrate that tceA-carrying Dehalococcoides mccartyi (Dhc) strains FL2 and 195 grow with VC as an electron acceptor when sufficient vitamin B₁₂ (B₁₂) is provided. Strain FL2 cultures that received 50 μg L^–1 B₁₂ completely dechlorinated VC to ethene at rates of 14.80 ± 1.30 μM day^–1 and attained 1.64 ± 0.11 × 10⁸ cells per μmol of VC consumed. Strain 195 attained similar growth yields of 1.80 ± 1.00 × 10⁸ cells per μmol of VC consumed, and both strains could be consecutively transferred with VC as the electron acceptor. Proteomic analysis demonstrated TceA expression in VC-grown strain FL2 cultures. Resequencing of the strain FL2 and strain 195 tceA genes identified non-synonymous substitutions, although their consequences for TceA function are currently unknown. The finding that Dhc strains expressing TceA respire VC can explain ethene formation at chlorinated solvent sites, where quantitative polymerase chain reaction analysis indicates that tceA dominates the RDase gene pool.

Pesticide dissipation from plant surfaces depends on a variety of factors including meteorological conditions, the pesticide’s physicochemical properties, and plant characteristics. Models already exist for describing pesticide behavior in agriculture fields; however, they do not account for pesticide-specific, condition-specific foliar photodegradation and the importance of this component in such models has not yet been investigated. We describe here the Pesticide Dissipation from Agricultural Land (PeDAL) model, which combines (a) multiphase partitioning to predict volatilization, (b) a new kinetics module for predicting photodegradation on leaf surfaces under varying light conditions based on location and timing, and (c) a generic foliar penetration component. The PeDAL model was evaluated by comparing measured pesticide dissipation rates from field experiments, described as the time for the pesticide concentration on leaves to decrease by half (DT₅₀), to ones generated by the model when using the reported field conditions. A sensitivity analysis of the newly developed foliar photodegradation component was conducted. We also showed how the PeDAL could be used by applicators and regulatory agencies. First, we used the model to examine how pesticide application timing affects dissipation rates. Second, we demonstrated how the model can be used to produce emission flux values for use in atmospheric dispersion and transport models.

Sulfur amendment of zerovalent iron (ZVI) materials has been shown to improve the reactivity and selectivity of ZVI toward a select group of organohalide contaminants in groundwater, most notably trichloroethene (TCE). In previous studies, chemical or mechanochemical sulfidation methods were used; however, the potential of using sulfate-reducing bacteria (SRB) to enable sulfur amendment has not been closely examined. In this study, lab-synthesized nanoscale ZVI (nZVI) and Peerless iron particles (ZVI^PLS) were treated in a sulfate-reducing monoculture (D. desulfuricans) and an enrichment culture derived from freshwater sediments (AMR-1) prior to reactivity assessments with TCE as the model contaminant. ZVI conditioned in both cultures exhibited higher dechlorination efficiencies compared to unamended ZVIs. Remarkably, nZVI and ZVI^PLS exposed to AMR-1 attained similar TCE dechlorination rates as their counterparts receiving chemical sulfidation (i.e., S-nZVI) using previously reported method. Product distribution data show that, in the SRB-ZVI system, abiotic dechlorination is the dominant TCE reduction pathway. In addition to dissolved sulfide, biogenic or synthesized FeS particles can enhance nZVI reactivity even as nZVI and FeS were not in direct contact, implying that SRB may influence the reactivity of ZVI via multiple mechanisms in different remediation situations. A shift in Archaea abundance in AMR-1 with nZVI amendment was observed but not with ZVI^PLS. Overall, the synergy exhibited in the SRB-ZVI system may offer a valuable remediation strategy to overcome limitations of standalone biological or abiotic dechlorination approaches for chlorinated solvent abatement.

We examined the uptake of Tl(I) by two hexagonal birnessites and related phase transformations in laboratory experiments over 12 sequential additions of 0.01 M Tl(I)/Mn at pH 4.0, 6.0, and 8.0. The Tl-reacted Mn oxides were characterized for their structure, Tl binding, and morphology using X-ray diffraction, X-ray photoelectron and X-ray absorption spectroscopies, and transmission electron microscopy. Very limited Tl oxidation was observed in contrast to previous works, where equal Tl(I)/Mn was added in a single step. Instead, both birnessites transformed into a 2 × 2 tunneled phase with dehydrated Tl(I) in its tunnels at pH 4, but only partially at pH 6, and at pH 8.0 they remained layered. The first four to nine sequential Tl(I)/Mn additions resulted in lower residual dissolved Tl⁺ concentrations than when the same amounts of Tl(I)/Mn were added in single steps. This study thus shows that the repeated reaction of hexagonal birnessites with smaller Tl(I)/Mn at ambient temperature triggers a complete phase conversion with Tl(I) as the sole reacting cation. The novel pathway found may be more relevant for contaminated environments and may help explain the formation of minerals like thalliomelane [Tl⁺(Mn_7.5⁴⁺Cu_0.5²⁺)O₁₆]; it also points to the possibility that other reducing species trigger similar Mn oxide transformation reactions.

The interaction of Eu(III) with thin sections of migmatized gneiss from the Bukov Underground Research Facility (URF), Czech Republic, was characterized by microfocus time-resolved laser-induced luminescence spectroscopy (μTRLFS) with a spatial resolution of ∼20 μm, well below typical grain sizes of the material. By this approach, sorption processes can be characterized on the molecular level while maintaining the relationship of the speciation with mineralogy and topography. The sample mineralogy was characterized by powder X-ray diffraction and Raman microscopy, and the sorption was independently quantified by autoradiography using ¹⁵²Eu. Representative μTRLFS studies over large areas of multiple mm² reveal that sorption on the heterogeneous material is not dominated by any of the typical major constituent minerals (quartz, feldspar, and mica). Instead, minor phases such as chlorite and prehnite control the Eu(III) distribution, despite their low contribution to the overall composition of the material, as well as common but less studied phases like Mg–hornblende. In particular, prehnite shows high a sorption uptake as well as strong binding of Eu to the mineral surface. Sorption on prehnite and hornblende happens at the expense of feldspar, which showed the highest sorption uptake in a previous spatially resolved study on granitic rock. Similarly, sorption on quartz is reduced, even though only low quantities of strongly bound Eu(III) were found here previously. Our results illustrate how competition of mineral surfaces for adsorbing cations drives the metal distribution in heterogeneous systems.

Wastewater-based epidemiology is an emerging tool to monitor COVID-19 infection levels by measuring the concentration of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) RNA in wastewater. There remains a need to improve wastewater RNA extraction methods’ sensitivity, speed, and reduce reliance on often expensive commercial reagents to make wastewater-based epidemiology more accessible. We present a kit-free wastewater RNA extraction method, titled “Sewage, Salt, Silica and SARS-CoV-2” (4S), that employs the abundant and affordable reagents sodium chloride (NaCl), ethanol, and silica RNA capture matrices to recover sixfold more SARS-CoV-2 RNA from wastewater than an existing ultrafiltration-based method. The 4S method concurrently recovered pepper mild mottle virus (PMMoV) and human 18S ribosomal subunit rRNA, which have been proposed as fecal concentration controls. The SARS-CoV-2 RNA concentrations measured in three sewersheds corresponded to the relative prevalence of COVID-19 infection determined via clinical testing. Lastly, controlled experiments indicate that the 4S method prevented RNA degradation during storage of wastewater samples, was compatible with heat pasteurization, and in our experience, 20 samples can be processed by one lab technician in approximately 2 h. Overall, the 4S method is promising for effective, economical, and accessible wastewater-based epidemiology for SARS-CoV-2, providing another tool to fight the global pandemic.

Crops can initiate various defense responses to environmental stresses. The process is often accompanied by extensive transcriptional and metabolic changes to reallocate metabolites. However, it remains unclear how organic pollutants activate the defense systems to reallocate metabolites in crops. The current study demonstrates that three defense systems, including the cytochrome P450s (CYP450s), glutathione S-transferases (GSTs), and phenylpropanoid biosynthesis, were sequentially activated after Oryza sativa was exposed to 2,3,4,5-tetrachlorobipheny l (PCB 61) and its derivatives 4′-hydroxy-2,3,4,5-tetrachlorobiphenyl (OH-PCB 61) and 4′-methoxy-2,3,4,5-tetrachlorobiphenyl (MeO-PCB 61), respectively. Genes encoding CYP76Ms and CYP72As were significantly upregulated after 0.5 h of exposure, followed by the GST-coding gene GSTU48, suggesting that the biotransformation and detoxification of PCB 61, OH-PCB 61, and MeO-PCB 61 occurred. Subsequently, CCR1 and CCR10 involved in phenylpropanoid biosynthesis were activated after 12 h, potentially reducing the oxidative stress induced by PCB 61 and its derivatives. Furthermore, β-d-glucan exohydrolase involved in both phenylpropanoid biosynthesis and starch and sucrose metabolism was significantly downregulated by 7.04-fold in the OH-PCB 61-treated group, potentially contributing to the inhibition of sugar hydrolysis. These findings provide insights into increasing rice adaptability to organic pollutants by reinforcing the enzyme-mediated defense systems, characterizing a novel and critical strategy that enables augmented crop outputs and quality in environments stressed by organic contaminants.

Besides the ecotoxicological consequences of microplastics and associated chemicals, the association of microbes on plastics has greater environmental implications as microplastics may select for unique microbiome participating in environmentally significant functions. Despite this, the functional potential of the microbiome associated with different types of plastics is understudied. Here, we investigate the interaction between plastic and marine biofilm-forming microorganisms through a whole-genome sequencing approach on four types of microplastics incubated in the marine environment. Taxonomic analysis suggested that the microplastic surfaces exhibit unique microbial profiles and niche partitioning among the substrates. In particular, the abundance of Vibrio alginolyticus and Vibrio campbellii suggested that microplastic pollution may pose a potential risk to the marine food chain and negatively impact aquaculture industries. Microbial genera involved in xenobiotic compound degradation, carbon cycling, and genes associated with the type IV secretion system, conjugal transfer protein TraG, plant–pathogen interaction, CusA/CzcA family heavy metal efflux transfer proteins, and TolC family proteins were significantly enriched on all the substrates, indicating the variety of processes operated by the plastic–microbiome. The present study gives a detailed characterization of the rapidly altering microbial composition and gene pools on plastics and adds new knowledge surrounding the environmental ramifications of marine plastic pollution.

Upon exposure, most bisphenol analogues (BPs) are rapidly metabolized to BP conjugates in organisms. Monitoring studies on BPs in aquatic organisms have been mainly focused on free-form BPs. However, the relative amount of conjugated BPs in organisms is still not well known, especially in marine organisms. In this study, we collected marine organisms (13 species; n = 74), as well as seawater (n = 15), from East China Sea, and analyzed them for bisphenol A (BPA) and its eight analogues. In seawater, BPA was the predominant BP (mean ± standard deviation (SD), 18 ± 9.7 ng/L), followed by bisphenol S (BPS; 3.7 ± 2.8 ng/L), bisphenol F (BPF; 0.31 ± 0.17 ng/L), and bisphenol AF (BPAF; 0.24 ± 0.15 ng/L). The whole body of each marine organism was used for BP analysis in this study. BPA (mean 3.8 ng/g, range 1.2–7.7 ng/g) and BPS (1.5 ng/g, 0.19–6.1 ng/g) were still the predominant BPs in marine organisms without hydrolysis. After enzymatic hydrolysis treatment, mean concentrations of BPs increased 1.8 (BPS)–3.7 (BPA) times in marine organisms. Correspondingly, on average, 74, 52, 49, 48, and 45% of BPA, bisphenol Z, BPF, BPS, and BPAF were present in conjugated forms, respectively, in marine organisms. Moreover, bioaccumulation and biomagnification of BPs were evaluated using pooled marine organism samples. We first found that the mean log BAF values of BPs increased 0.091 (BPAF) to 0.31 (BPA) times in marine organisms after hydrolysis. Overall, this study first determines the amount of BPs present in conjugated forms in marine organisms, which are helpful for better understanding the occurrence of BPs in organisms.

Interindividual variation in prey specialization is an essential yet overlooked aspect of wildlife feeding ecology, especially as it relates to intrapopulation variation in exposure to toxic contaminants. Here, we assessed blubber concentrations of an extensive suite of persistent organic pollutants in Icelandic killer whales (Orcinus orca). Polychlorinated biphenyl (PCB) concentrations in blubber were >300-fold higher in the most contaminated individual relative to the least contaminated, ranging from 1.3 to 428.6 mg·kg^–1 lw. Mean PCB concentrations were 6-to-9-fold greater in individuals with a mixed diet including marine mammals than in fish specialist individuals, whereas males showed PCB concentrations 4-fold higher than females. Given PCBs have been identified as potentially impacting killer whale population growth, and levels in mixed feeders specifically exceeded known thresholds, the ecology of individuals must be recognized to accurately forecast how contaminants may threaten the long-term persistence of the world’s ultimate marine predator.

Anthropogenic macrolitter (>0.5 cm) in rivers is of increasing concern. It has been found to have an adverse effect on riverine ecosystem health, and the livelihoods of the communities depending on and living next to these ecosystems. Yet, little is known on how macrolitter reaches and propagates through these ecosystems. A better understanding of macrolitter transport dynamics is key in developing effective reduction, preventive, and cleanup measures. In this study, we analyzed a novel dataset of citizen science riverbank macrolitter observations in the Dutch Rhine–Meuse delta, spanning two years of observations on over 200 unique locations, with the litter categorized into 111 item categories according to the river-OSPAR protocol. With the use of regression models, we analyzed how much of the variation in the observations can be explained by hydrometeorology, observer bias, and location, and how much can instead be explained by temporal trends and seasonality. The results show that observation bias is very low, with only a few exceptions, in contrast with the total variance in the observations. Additionally, the models show that precipitation, wind speed, and river flow are all important explanatory variables in litter abundance variability. However, the total number of items that can significantly be explained by the regression models is 19% and only six item categories display an R² above 0.4. This suggests that a very substantial part of the variability in macrolitter abundance is a product of chance, caused by unaccounted (and often fundamentally unknowable) stochastic processes, rather than being driven by the deterministic processes studied in our analyses. The implications of these findings are that for modeling macrolitter movement through rivers effectively, a probabilistic approach and a strong uncertainty analysis are fundamental. In turn, point observations of macrolitter need to be planned to capture short-term variability.

In this study, the mechanisms of environmentally relevant doses of Cu and Zn mixtures influencing lipid deposition and metabolism were investigated in freshwater teleost yellow catfish Pelteobagrus fulvidraco (2 months old, 4.95 (t0.01 g, mean ± SEM). Our study indicated that waterborne Cu exposure increased lipid content, while Zn activated lipophagic flux and alleviated Cu-induced lipid accumulation. Yellow catfish hepatocytes treated with Zn or Zn + Cu activated autophagy-specific lipophagy, decreased lipid storage, and increased nonesterified fatty acid (NEFA) release, suggesting a causal relationship between lipophagy and lipid droplet (LD) breakdown under Zn and Zn + Cu conditions. Our further investigation found that Beclin1 deacetylation by sirtuin 1 (SIRT1) was required for Zn- and Zn + Cu-induced lipophagy and lipolysis, and lysine residues 427 and 434 were key sites for Beclin1 deacetylation. Taken together, these findings show that the Zn-induced deacetylation of Beclin1 promotes lipophagy as an important pathway to alleviate Cu-induced lipid accumulation in fish, which reveals a previously unidentified mechanism for understanding the antagonistic effects of Cu and Zn on metabolism at their environmentally relevant concentrations. Our results highlight the importance of combined exposure when the biological effects of heavy metals are evaluated during environmental risk assessments.

The environmental mobility of antimony (Sb) is controlled by interactions with iron (Fe) oxides, such as ferrihydrite. Under near-neutral pH conditions, Fe(II) catalyzes the transformation of ferrihydrite to more stable phases, thereby potentially altering the partitioning and speciation of associated Sb. Although largely unexplored, Sb itself may also influence ferrihydrite transformation pathways. Here, we investigated the impact of Sb on the Fe(II)-induced transformation of ferrihydrite at pH 7 across a range of Sb(V) loadings (Sb:Fe(III) molar ratios of 0, 0.003, 0.016, and 0.08). At low and medium Sb loadings, Fe(II) induced rapid transformation of ferrihydrite to goethite, with some lepidocrocite forming as an intermediate phase. In contrast, the highest Sb:Fe(III) ratio inhibited lepidocrocite formation, decreased the extent of goethite formation, and instead resulted in substantial formation of feroxyhyte, a rarely reported FeOOH polymorph. At all Sb loadings, the transformation of ferrihydrite was paralleled by a decrease in aqueous and phosphate-extractable Sb concentrations. Extended X-ray absorption fine structure spectroscopy showed that this Sb immobilization was attributable to incorporation of Sb into Fe(III) octahedral sites of the neo-formed minerals. Our results suggest that Fe oxide transformation pathways in Sb-contaminated systems may strongly differ from the well-known pathways under Sb-free conditions.

The effects of flagella and their properties on bacterial transport and deposition behaviors were examined by using four types of Escherichia coli (E. coli) with or without flagella, as well as with normal or sticky flagella. Packed column, quartz crystal microbalance with dissipation, visible parallel-plate flow chamber system, and visible flow chamber packed with porous media system were employed to investigate the deposition mechanisms of bacteria with different properties of flagella. We found that the presence of flagella favored E. coli deposition onto quartz sand/silica surfaces. Moreover, by changing the porous media porosity and directly observing the bacterial deposition process, local sites with high roughness, narrow flow channels, and grain-to-grain contacts were found to be the major sites for bacterial deposition. Particularly, flagella could help bacteria swim near and then deposit at these sites. In addition, we found that due to the stronger adhesive forces, sticky flagella could further enhance bacterial deposition onto quartz sand/silica surfaces. Elution experiments indicated that flagella could help bacteria attach onto sand surfaces more irreversibly. Clearly, flagella and their properties would have obvious impacts on the transport/deposition behaviors of bacteria in porous media.

The direct and indirect photochemical degradation of rotenone (ROT) and deguelin (DEG), the primary reduced nicotinamide adenine dinucleotide-inhibiting rotenoid components of the piscicide CFT Legumine, were investigated under simulated sunlight conditions relevant to their dissipation from high-latitude surface waters. Photochemical degradation dominated the elimination of ROT and DEG from surface waters with half-lives ranging from 1.17 to 2.32 and 4.18 to 20.12 h for DEG and ROT, respectively, when the rotenoids were applied in the formulation CFT Legumine. We assessed enhanced degradation processes using argon-purged and cesium chloride-amended water, which demonstrated the rotenoids to rapidly decompose from excited triplet states. We further assessed the influence of reactive oxygen species by hydroxyl radical quenching and thermal generation of singlet oxygen. The studied reactive oxygen species did not significantly contribute; however, alcohols such as isopropanol may inhibit degradation by quenching ROT excited states or preventing intersystem crossing. Finally, we compared photochemical degradation in water collected from Hope Lake, Alaska, to a solution of Suwanee River fulvic acids, which demonstrated that dissolved organic matter (DOM) quality is a major factor that modulates ROT attenuation through a combination of shielding (light attenuation) and excited-state quenching mechanisms and is temperature-dependent. Molecular-level characterizations of DOM may help account for the site-specific degradation of these rotenoids in the environment.

A contamination with the ubiquitous radioactive fission product ¹³⁷Cs cannot be assigned per se to its source. We used environmental samples with varying contamination levels from various parts of the world to establish their characteristic ¹³⁵Cs/¹³⁷Cs isotope ratios and thereby allow their distinction. The samples included biological materials from Chernobyl and Fukushima, historic ashed human lung tissue from the 1960s from Austria, and trinitite from the Trinity Test Site, USA. After chemical separation and gas reaction shifts inside a triple quadrupole ICP mass spectrometer, characteristic ¹³⁵Cs/¹³⁷Cs isotope signatures (all as per March 11, 2011) were obtained for Fukushima- (∼0.35) and Chernobyl-derived (∼0.50) contaminations, in agreement with the literature for these contamination sources. Both signatures clearly distinguish from the characteristic high ratio (1.9 ± 0.2) for nuclear-weapon-produced radiocesium found in human lung tissue. Trinitite samples exhibited an unexpected, anomalous pattern by displaying a low (<0.4) and nonuniform ¹³⁵Cs/¹³⁷Cs ratio. This exemplifies a ¹³⁷Cs-rich fractionation of the plume in a nuclear explosion, where ¹³⁷Cs is a predominant species in the fireball. The onset of ¹³⁵Cs was delayed because of the longer half-life of its parent nuclide ¹³⁵Xe, causing a spatial separation of gaseous ¹³⁵Xe from condensed ¹³⁷Cs, which is the reason for the atypical ¹³⁵Cs/¹³⁷Cs fractionation in the fallout at the test site.