The drilling phase of oil and natural gas development is a growing area of environmental justice (EJ) research, particularly in the United States. Its emergence complements the longstanding EJ scholarship on later phases of the oil and gas commodity chain, such as pipeline transport, refining, and consumption. The growing scholarly attention to the EJ implications of drilling has been prompted by the surge in development of unconventional oil and gas resources in recent decades. More specifically, the oil and gas industry’s adoption of horizontal drilling and hydraulic fracturing (a.k.a., “fracking” or “fracing”) as methods for extracting oil and gas from a wider range of geologic formations has simultaneously heightened oil and gas production, brought extractive activities closer to more people, intensified them, and made well pad siting more flexible. Here, we provide a critical review of the novel EJ research questions that are being prompted by these on-the-ground changes in extractive techniques and patterns, propose an interdisciplinary conceptual framework for guiding EJ inquiry in this context, discuss key methodological considerations, and propose a research agenda to motivate future inquiry.

Increasing interest in the acquisition of biotic and abiotic resources from within the deep sea (e.g., fisheries, oil–gas extraction, and mining) urgently imposes the development of novel monitoring technologies, beyond the traditional vessel-assisted, time-consuming, high-cost sampling surveys. The implementation of permanent networks of seabed and water-column-cabled (fixed) and docked mobile platforms is presently enforced, to cooperatively measure biological features and environmental (physicochemical) parameters. Video and acoustic (i.e., optoacoustic) imaging are becoming central approaches for studying benthic fauna (e.g., quantifying species presence, behavior, and trophic interactions) in a remote, continuous, and prolonged fashion. Imaging is also being complemented by in situ environmental-DNA sequencing technologies, allowing the traceability of a wide range of organisms (including prokaryotes) beyond the reach of optoacoustic tools. Here, we describe the different fixed and mobile platforms of those benthic and pelagic monitoring networks, proposing at the same time an innovative roadmap for the automated computing of hierarchical ecological information on deep-sea ecosystems (i.e., from single species’ abundance and life traits to community composition, and overall biodiversity).

Cryoconite is a granular aggregate, comprised of both mineral and biological material, and known to accumulate atmospheric contaminants. In this study, cryoconite was sampled from seven high-elevation glaciers in Western China to investigate the spatial and altitudinal patterns of atmospheric mercury (Hg) accumulation in the cryoconite. The results show that total Hg (Hg_T) concentrations in cryoconite were significant with relatively higher Hg accumulation in the southern glaciers (66.0 ± 29.3 ng g^–1), monsoon-influenced regions, than those in the northern glaciers (42.5 ± 20.7 ng g^–1), westerlies-influenced regions. The altitudinal profile indicates that Hg_T concentrations in the northern glaciers decrease significantly with altitude, while those in the southern glaciers generally increase toward higher elevations. Unexpectedly high accumulation of methyl–Hg (MeHg) with an average of 1.0 ± 0.4 ng g^–1 was also detected in the cryoconite samples, revealing the surface of cryoconite could act as a potential site for Hg methylation in alpine environments. Our preliminary estimate suggests a storage of ∼34.3 ± 17.4 and 0.65 ± 0.28 kg of Hg_T and MeHg from a single year of formation process in the glacier cryoconite. Therefore, glacier cryoconite could play an important role in Hg storage and transformation, which may result in downstream effects on glacier-fed ecosystems under climate warming scenario.

The DNA of aquatic organisms can be identified in water sampled from freshwater ecosystems to detect species presence. Because these DNA-based methods (termed environmental DNA, eDNA) confirm species presence by proxy of DNA in water, the processes influencing eDNA transport and removal from water are critical to the method’s efficacy and interpretation of results. Previous studies of aquatic eDNA transport and fate have employed uncontrolled field experiments, controlled studies in experimental streams, and laboratory column tests. As a step toward understanding the processes controlling eDNA transport and retention, we released and tracked experimental pulses of white sturgeon eDNA (novel to the system) in five fourth-order stream reaches with varied hydrology and geomorphology. We found strong support that stream water transient storage controls eDNA areal uptake rate (or spiraling length). We calculated the median spiraling length to be ∼260 m. Down channel slope correlated with transient storage, suggesting that this slope could be used as a proximate measure of eDNA removal into the benthic zone. Our results suggest that sampling effort should be increased in reaches with longer transient storage (or lower slopes) to compensate for the increase in eDNA retention.

Polybrominated diphenyl ethers (PBDEs) were widely used as fire retardants and have been detected throughout the Great Lakes (GL) ecosystem. The concentration trends (after fish age normalization) of PBDEs in top predator fish (lake trout and walleye) of the GLs were determined from 1979 to 2016, which includes most of the period when PBDEs were manufactured and used in this region. The fish samples were collected by two national (U.S. and Canada) long-term monitoring and surveillance programs. Trends in total concentrations (age-normalized) of the five major PBDE congeners (BDE-47, 99, 100, 153, and 154) found in fish across all five lakes have varied over time. Significant increases were observed from 1990 to 2000 (16.3% per year). Rapidly decreasing concentrations (−19.5% per year) were found from 2000 to 2007. Since 2007, the decreasing trend has become smaller (less than −5.5% per year) and relatively unchanged from 2011 to 2015. BDE-47, the congener with the highest concentrations in lake trout, has decreased continuously (ranging from −6.7% to −16.2% per year) in all lakes except Lake Erie. This decrease can be associated with the voluntary and regulatory phase out of production and/or usage of PBDEs since 2000. However, it has been offset by recent (since 2007) increasing trends of the other four higher brominated BDE congeners, especially BDE-100 and 154. Production and usage of commercial penta- and octa- BDE mixtures containing primarily the five major PBDE congeners was discontinued in 2004 in the U.S.A. and 2008 in Canada. These results indicate increasing fish uptake and bioaccumulation of higher brominated BDE congeners may be related to the transformation of BDE-209 to lower brominated BDE compounds in the GL environment or food web. Considering the abundance of BDE-209 in existing products and sediment in GL region, the duration of the unchanging total PBDE concentration trend in GL fish could be longer than expected.

Biochar was recently identified as an effective soil amendment for CH₄ capture. Corresponding mechanisms are currently recognized to be from physical properties of biochar, providing a favorable growth environment for aerobic methanotrophs which perform aerobic methane (CH₄) oxidation. However, our study shows that the chemical reactivity of biochar can also stimulate anaerobic oxidation of CH₄ (AOM) by anaerobic methanotrophic archaea (ANME) of ANME-2d, which proposes another plausible mechanism for CH₄ mitigation by biochar amendment in anaerobic environments. It was found that, by adding biochar as the sole electron acceptor in an anaerobic environment, CH₄ was biologically oxidized, with CO₂ production of 106.3 ± 5.1 μmol g^–1 biochar. In contrast, limited CO₂ production was observed with chemically reduced biochar amendment. This biological nature of the process was confirmed by mcr gene transcript abundance as well as sustained dominance of ANME-2d in the microbial community during microbial incubations with active biochar amendment. Combined FTIR and XPS analyses demonstrated that the redox activity of biochar is related to its oxygen-based functional groups. On the basis of microbial community evolution as well as intermediate production during incubation, different pathways in terms of direct or indirect interactions between ANME-2d and biochar were proposed for biochar-mediated AOM.

Accurate long-range atmospheric transport (LRAT) modeling of polycyclic aromatic hydrocarbons (PAHs) and PAH oxidation products (PAH-OPs) in secondary organic aerosol (SOA) particles relies on the known chemical composition of the particles. Four PAHs, phenanthrene (PHE), dibenzothiophene (DBT), pyrene (PYR), and benz(a)anthracene (BaA), were studied individually to identify and quantify PAH-OPs produced and incorporated into SOA particles formed by ozonolysis of α-pinene in the presence of PAH vapor. SOA particles were characterized using real-time in situ instrumentation, and collected on quartz fiber filters for offline analysis of PAHs and PAH-OPs. PAH-OPs were measured in all PAH experiments at equal or greater concentrations than the individual PAHs they were produced from. The total mass of PAH and PAH-OPs, relative to the total SOA mass, varied for different experiments on individual parent PAHs: PHE and 6 quantified PHE-OPs (3.0%), DBT and dibenzothiophene sulfone (4.9%), PYR and 3 quantified PYR-OPs (3.1%), and BaA and benz(a)anthracene-7,12-dione (0.26%). Further exposure of PAH-SOA to ozone generally increased the concentration ratio of PAH-OPs to PAH, suggesting longer atmospheric lifetimes for PAH-OPs, relative to PAHs. These data indicate that PAH-OPs are formed during SOA particle formation and growth.

Nitrogen (N) surplus is a useful indicator for improving agricultural N management and controlling N pollution. Few studies have developed benchmark values for cropping systems in China, a country with the largest N fertilizer use in the world. We established N surplus benchmarks for 13 main cropping systems, at optimal N management, using results from >4500 on-farm field experiments and a soil surface balance approach. These cropping systems accounted for about 50% of total N fertilizer consumption in Chinese agriculture in 2009. The results showed that N surplus benchmarks for single cropping systems ranged from 40 to 100 kg N ha^–1 yr^–1 (average 73 kg N ha^–1 yr^–1), and for double cropping systems from 110 to 190 kg N ha^–1 yr^–1 (average 160 kg N ha^–1 yr^–1), roughly twice that of single cropping systems. These N surplus benchmarks may be further refined, following further decreases in N deposition rates and reactive N losses as a result of strict implementation of “4R-nutrient stewardship” and improvements in fertilization techniques and agronomic managements. Our N surplus benchmarks could serve as realistic targets to improve the N management of current conventional practices, and thereby could lay the foundations for a more sustainable N management in China.

In this work, we investigate the impact of natural organic matter (NOM) and light on silver nanoparticle (AgNP) dissolution kinetics with particular emphasis on determining the (i) mechanism via which NOM affects the oxidative dissolution of AgNPs, (ii) the role of photogenerated organic radicals and reactive oxygen species (ROS) in oxidative dissolution of AgNPs, and (iii) the mechanism of formation of AgNPs in NOM solution under dark and irradiated conditions. We measured the oxidation of citrate stabilized AgNPs by O₂ and hydrogen peroxide (H₂O₂) in the dark and in irradiated Suwannee River fulvic acid (SRFA) solutions at pH 8.0. Results show that the reactivity of AgNPs toward O₂ and H₂O₂ in the dark decreased in the presence of SRFA as a result of blocking of AgNP surface sites through either steric or electrostatic effects. Irradiation promoted dissolution of AgNPs by O₂ and H₂O₂ in the presence of low concentrations (≤20 mg·L^–1) of SRFA as a result of contribution from photogenerated H₂O₂ formed on irradiation of SRFA as well as photofragmentation of AgNPs. Furthermore, our results show that photogenerated superoxide can induce formation of AgNPs by reducing Ag(I) ions. Based on our experimental results, we have developed a kinetic model to explain AgNP transformation by O₂ and H₂O₂ in the dark and in irradiated SRFA solutions with this model of use in predicting the transformation and fate of AgNPs in natural waters.

Pb(II) carbonate solids are corrosion products that form on the inner surfaces of lead service lines (LSLs) and can be oxidized by free chlorine to form Pb(IV) oxide (PbO₂). The formation of PbO₂ can maintain low dissolved lead concentrations in drinking water, but PbO₂ can dissolve if a free chlorine residual is not maintained. Experiments demonstrated that the oxidation of Pb(II) carbonate by free chlorine was faster with manganese (Mn). Without Mn(II), the oxidation of Pb(II) carbonate was an autocatalytic process. With Mn(II), the overall oxidation rate was 2 orders of magnitude faster than without Mn(II). X-ray diffraction and free chlorine consumption profiles indicated that δ-MnO₂ was formed within several minutes of the reaction of Mn(II) with free chlorine, and δ-MnO₂ catalyzed the oxidation of Pb(II) carbonate by free chlorine. Free chlorine consumption profiles for Pb(II) carbonate with and without Mn(II) were interpreted based on the kinetics and stoichiometry of the underlying chemical reactions. These findings highlight the importance of Mn in accelerating the formation of PbO₂ in water with Pb(II) carbonate solids and free chlorine, and it may help explain why PbO₂ is observed on LSLs of some but not all water systems that use free chlorine.

Oxalate and sulfate are ubiquitous components of ambient aerosols with a high complexation affinity to iron. However, their effect on iron-driven secondary brown carbon formation in solution from soluble aromatic and aliphatic reagents was not studied. We report masses and hydrodynamic particle sizes of insoluble particles formed from the dark aqueous phase reaction of catechol, guaiacol, fumaric, and muconic acids with Fe(III) in the presence of oxalate or sulfate. Results show that oxalate decreases particle yield in solution from the reaction of Fe(III), with a stronger effect for guaiacol than catechol. For both compounds, the addition of sulfate results in the formation of more polydisperse (0.1–5 μm) and heavier particles than those from control experiments. Reactions with fumaric and muconic acids show that oxalate (not sulfate) and pH are determining factors in the efficiency of particle formation in solution. Polymerization reactions occur readily in the presence of sulfate in solution producing particles with iron-coordinated and/or pore-trapped sulfate anions. The addition of oxalate to the reactions of Fe(III) with all organics, except guaiacol, produced fewer and larger polymeric particles (>0.5 μm). These results imply that even in the presence of competing ligands, the formation of insoluble and colored particles from soluble organic precursors still dominates over the formation of soluble iron complexes.

The buffering of phosphorus concentrations in soil solution by the soil-solid phase is an important process for providing plant root access to nutrients. Accordingly, the size of labile solid phase-bound phosphorus pool and the rate at which it can resupply phosphorous into the dissolved phase can be important variables in determining when the plant availability of the nutrient may be limited. The phosphorus labile pool (P_labile) and its desorption kinetics were simultaneously evaluated in 10 agricultural UK soils using the diffusive gradients in thin-films (DGT) technique. The DGT-induced fluxes in the soil and sediments model (DIFS) was fitted to the time series of DGT deployments (1–240 h), which allowed the estimation of P_labile, and the system response time (T_c). The P_labile concentration was then compared to that obtained by several soil P extracts including Olsen P, FeO-P, and water extractable P, in order to assess if the data from these analytical procedures can be used to represent the labile P across different soils. The Olsen P concentration, commonly used as a representation of the soil labile P pool, overestimated the desorbable P concentration by 6-fold. The use of this approach for the quantification of soil P desorption kinetic parameters found a wide range of equally valid solutions for T_c. Additionally, the performance of different DIFS model versions working in different dimensions (1D, 2D, and 3D) was compared. Although all models could provide a good fit to the experimental DGT time series data, the fitted parameters showed a poor agreement between different model versions. The limitations of the DIFS model family are associated with the assumptions taken in the modeling approach and the three-dimensional (3D) version is here considered to be the most precise among them.

The chemical composition and evolution of secondary organic aerosol (SOA) in the atmosphere represents one of the largest uncertainties in our current understanding of air quality. Despite vast research, the toxicological mechanisms relating to adverse human health effects upon exposure to particulate matter are still poorly understood. Particle-bound reactive oxygen species (ROS) may substantially contribute to observed health effects by influencing aerosol oxidative potential (OP). The role of radicals in both the formation and aging of aerosol, as well as their contribution to aerosol OP, remains highly uncertain. The profluorescent spin trap BPEAnit (9,10-bis(phenylethynyl)anthracenenitroxide), previously utilized to study combustion-generated aerosol, has been applied to provide the first estimate of particle-bound radical concentrations in SOA. We demonstrate that SOA from different atmospherically important VOC precursors have different particle-bound radical concentrations, estimated for the ozonolysis of α-pinene (0.020 ± 0.0050 nmol/μg), limonene (0.0059 ± 0.0010 nmol/μg), and β-caryophyllene (0.0025 ± 0.00080 nmol/μg), highlighting the potential importance of OH-initiated formation of particle-bound organic radicals. Additionally, the lifetime of particle-bound radical species in α-pinene SOA was estimated, and a pseudo-first-order rate constant of k = 7.3 ± 1.7 × 10^–3 s^–1 was derived, implying a radical lifetime on the order of minutes.

Dichloroacetamide safeners are commonly added to commercial chloroacetamide herbicide formulations and widely used worldwide, but their environmental fate has garnered little scrutiny as a result of their classification as “inert” ingredients. Here, we investigated the photolysis of dichloroacetamide safeners to better understand their persistence and the nature of their transformation products in surface waters. High-resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR) spectroscopy were used to characterize photoproducts. Of the four commonly used dichloroacetamide safeners, only benoxacor undergoes direct photolysis under simulated natural sunlight (t_1/2 ∼ 10 min). Via a photoinitiated ring closure, benoxacor initially yields a monochlorinated intermediate that degrades over longer irradiation time scales to produce two fully dechlorinated diastereomers and a tautomer, which further photodegrade over several days to a structurally related aldehyde confirmed via NMR. Dichlormid, AD-67, and furilazole were more slowly degraded by indirect photolysis in the presence of the photosensitizers nitrate, nitrite, and humic acid. Reactive entities involved in these reactions are likely hydroxyl radical and singlet oxygen based on the use of selective quenchers. These safeners also directly photolyzed under higher energy ultraviolet (UV) light, suggesting their potential transformation in engineered systems using UV for disinfection. The finding that dichloroacetamide safeners can undergo photolysis in environmental systems over relevant time scales demonstrates the importance of evaluating the fate of this class of “inert” agrochemicals.

Oxidative potential (OP), which is the ability of certain components in atmospheric particles to generate reactive oxidative species (ROS) and deplete antioxidants in vivo, is a prevailing toxicological mechanism underlying the adverse health effects associated with exposure to ambient aerosols. While previous studies have identified the high OP of fresh biomass burning organic aerosols (BBOA), it remains unclear how it evolves throughout atmospheric transport. Using the dithiothreitol (DTT) assay as a measure of OP, a combination of field observations and laboratory experiments is used to determine how atmospheric aging transforms the intrinsic OP (OP_mass^DTT) of BBOA. For ambient BBOA collected during the fire seasons in Greece, OP_mass^DTT was observed to increase by a factor of 2.1 ± 0.9 for samples of atmospheric ages up to 68 h. Laboratory experiments indicate that aqueous photochemical aging (aging by UVB and UVA photolysis; as well as OH oxidation), as well as aging by ozone and atmospheric dilution can transform the OP_mass^DTT of the water-soluble fraction of wood smoke within 2 days of atmospheric transport. The results from this work suggest that the air quality impacts of biomass burning emissions can extend beyond regions near fire sites and should be accounted for.

The fate of persistent organic pollutants in sea ice is a poorly researched area and yet ice serves as an important habitat for organisms at the base of the marine foodweb. This study presents laboratory-controlled experiments to investigate the mechanisms governing the fate of organic contaminants in sea ice grown from artificial seawater. Sea ice formation was shown to result in the entrainment of chemicals from seawater, and concentration profiles in bulk ice generally showed the highest levels in both the upper (ice–atmosphere interface) and lower (ice–ocean interface) ice layers, suggesting their incorporation and distribution is influenced by brine advection. Results from a 1-D sea ice brine dynamics model supported this, but also indicated that other processes may be needed to accurately model low-polarity compounds in sea ice. This was reinforced by results from a melt experiment, which not only showed chemicals were more enriched in saltier brine, but also revealed that chemicals are released from sea ice at variable rates. We use our results to demonstrate the importance of processes related to the occurrence and movement of brine for controlling chemical fate in sea ice which provides a pathway for exposure to ice-associated biota at the base of the pelagic food web.

Short chain chlorinated paraffins (SCCPs) are a group of complex emerging persistent organic pollutants. In this study, the uptake, translocation, and transformation of four constitutionally defined SCCP isomers were studied using whole pumpkin (Cucurbita maxima × C. moschata) and soybean (Glycine max L. Merrill) seedlings via hydroponic exposure. Results showed that the daughter SCCPs were C₁₀Cl_5–8 and C_11–13Cl_5–6. The metabolic transformation of all tested isomers included dechlorination and chlorine rearrangement. In addition, carbon chain decomposition products were found for isomers with trichlorinated carbon atoms (CCl₃-groups) in both pumpkin and soybean seedlings. This study provides the first evidence of carbon chain decomposition of SCCPs in whole plants, and it suggests new metabolism pathways of SCCPs in the environment. The influence of carbon chain length and degree of chlorination of SCCPs on their fate and behavior within different plant species were also investigated. Bioaccumulation of SCCPs in pumpkin and soybean increased with increasing carbon chain length and degree of chlorination. In comparison, soybean translocated and degraded parent SCCPs faster and to a greater extent than pumpkin, but pumpkin accumulated parent SCCPs to a greater extent than soybean. After 10 days exposure, less than 4% of the initial mass of exposed chemicals remained in solution of exposure groups. The parent chemicals accumulated in roots ranging from 23.6% to 59.9% for pumpkin and 1.98% to 54.5% for soybean and in stems ranging from 0.7% to 3.81% for pumpkin and 0.50% to 2.54% for soybean. These results give new perspectives on the transport, transformation, and fate of SCCPs in the environment.

High mountains can trap semivolatile chemicals, such as persistent organic pollutants (POPs), and hinder their dispersion. However, both deep convection and mountain valleys can facilitate POPs’ transport over mountains, which have not been investigated before. In this study, a three-year sampling campaign along a south-north altitudinal transect (100–5200m) across the central Himalayas, coupled with a multicompartment contaminant fate model, was conducted for describing the transport processes of POPs. The results show that POPs emitted in the lowlands of the Himalayas can be transported to high altitudes and further to the inner part of the Tibetan Plateau. Modeling suggests that more than 90% of POPs are trapped along the way due to gaseous deposition to soil/foliage and rainfall scavenging; while 2 × 10^–3 to 1 × 10^–1 Giga-grams/year of POPs are transported across the Himalayas. The transport flux along valleys is 2–3 times higher than that across the mountain ridge. However, due to the limited spatial coverage of mountain valleys, the amount of POPs transported through valleys only accounts for a small part of the total transport. This study shows that POPs can overcome the blocking effect of the Himalayas, and high altitude transport across the mountain ridge is the dominant transport pathway.

Benoxacor is a safener paired with the high-use herbicide S-metolachlor. Commercial formulations containing both compounds are sprayed onto soil pre-emergence to enhance yields of corn. In this study, we evaluated the sunlight photolysis of metolachlor and benoxacor, individually and as mixtures, in three different reaction environments: in water and on two soil-simulating surfaces (quartz and kaolinite). When irradiated individually, benoxacor degraded at least 19 times faster than metolachlor in each reaction environment, consistent with its higher molar absorptivity within the solar spectrum than metolachlor. When metolachlor and benoxacor were irradiated as mixtures, benoxacor promoted metolachlor degradation on quartz and, to a lesser extent, in water, but not on kaolinite. On quartz, at a benoxacor/metolachlor molar ratio of 0.1:1, metolachlor degraded 1.8 times faster than in the absence of benoxacor; as the benoxacor/metolachlor ratio increased, metolachlor degradation rate also increased. The photolysis rate of benoxacor depended on its initial surface concentration and was promoted by metolachlor. Benoxacor photoproducts were capable of absorbing sunlight and serving as photosensitizers for metolachlor degradation. These results illustrate how a safener can influence the photochemistry of its coformulated herbicide and suggest that such mixture effects should be considered when evaluating the environmental fate of agrochemicals.

The current uncertainties in the reactivity and atmospheric persistence of particle-associated chemicals present a challenge for the prediction of long-range transport and deposition of emerging chemicals such as organophosphate flame retardants, which are ubiquitous in the global environment. Here, the OH-initiated heterogeneous oxidation kinetics of organophosphate flame retardants (OPFRs) coated on inert (NH₄)₂SO₄ and redox-active FeSO₄ particles were systematically determined as a function of relative humidity (RH). The derived reaction rate constants for the heterogeneous loss of tricresyl phosphate (TCP; k_TCP) and tris(2-butoxyethyl) phosphate (TBEP; k_TBEP) were in the range of (2.69–3.57) × 10^–12 and (3.06–5.55) × 10^–12 cm³ molecules^–1 s^–1, respectively, depending on the RH and coexisting Fe(II) content. The k_TCP (coated on (NH₄)₂SO₄) was relatively constant over the investigated RH range while k_TBEP was enhanced by up to 19% with increasing RH. For both OPFRs, the presence of Fe(II) enhanced their k by up to 53% over inert (NH₄)₂SO₄. These enhancement effects (RH and Fe(II)) were attributed to fundamental changes in the organic phase state (higher RH lowered particle viscosity) and Fenton-type chemistry which resulted in the formation of reactive oxygen species, respectively. Such findings serve to emphasize the importance of ambient RH, the phase state of particle-bound organics in general, and the presence of coexisting metallic species for an accurate description of the degradation kinetics and aging of particulate OPFRs in models used to evaluate their atmospheric persistence.

Although the distribution of progestagens in aquatic environments has been widely reported, details on their uptake, elimination, and biotransformation in fish have received little attention. This study investigated the uptake, elimination, and biotransformation potential of a progestagen, cyproterone acetate (CPTA), in Nile tilapia (Oreochromis niloticus) exposed to an environmentally relevant concentration under semistatic regimes. CPTA in tilapia tissues followed a similar pattern, reaching a concentration plateau within 4 days of exposure, and dropping to below limits of quantitation within 4 days of elimination. The calculated steady-state bioconcentration factors suggest a low bioconcentration potential of CPTA in juvenile tilapia. Results of enzymatic hydrolysis treatments revealed that no conjugates of CPTA were present in tissues, but conjugated biotransformation products of CPTA were found in bile, liver, and muscle. Most CPTA entered tissues and then was biotransformed into seven different products by phase I and phase II metabolism. The concentrations of endogenous cortisol were significantly influenced by CPTA in plasma and liver during the uptake period. These findings suggest that biotransformation products of CPTA should be considered for the assessment of the bioconcentration potential and ecological effects of progestagens.

A detailed understanding of the mercury footprint at subnational entity levels can facilitate the implementation of the “Minamata Convention on Mercury”, especially for China, the largest mercury emitter worldwide. Some provinces of China have more than 100 million people, with economic activities and energy consumption levels comparable to those of smaller G7 countries. We constructed a stochastic, nested multiregion input–output (MRIO) model, which regionalized the China block in the EXIOBASE global-scale MRIO table, to model the mercury footprint associated with global supply chains spanning China’s regions and other countries. The results show that Tianjin, Shanghai, and Ningxia had the highest per capita mercury footprint in China, which was comparable to the footprint of Australia and Norway and exceeded the footprint of most other countries. Some developed regions in China (e.g., Guangdong, Jiangsu) had higher mercury final product-based inventories (FBI) and consumption-based inventories (CBI) than production-based inventories (PBI), emphasizing the role of these regions as centers of both consumption and economic control. Uncertainties of Chinese provincial mercury footprint varied from 8% to 34%. Our research also revealed that international and inter-regional final product and intermediate product trades reshape the mercury emissions of Chinese provinces and other countries to a certain extent.

Many emerging, and some legacy, pollutants pose risks to humans and ecosystems near the detection limits (DL) of existing analytical systems. As a result, site assessments and management options are often presented with data sets that are sparse, highly skewed, and left-censored. Existing analysis methods are unable to differentiate effects of treatment from covariates, such as space, obscuring influences of site management. As a case study, we computed the mean and variance of censored soil benzene data across four sites over a three year period by gamma distribution with a maximum likelihood. Further, a combined hurdle model to accommodate left-censored concentrations was applied to analyze factors affecting benzene variation. This approach allowed us to assess the success and spatial dependency of a biostimulatory solution in reducing benzene concentrations at very low concentrations. Benzene concentrations decreased due to the addition of biostimulatory solution and spatial effects, but the detection of soil benzene after biostimulation was highly spatially dependent. By combining computed values for censored observations estimated by the hurdle-gamma model and uncensored observations, we can get the pseudocomplete data sets. The combined model is ideally suited to evaluate existing and emerging pollutants, that pose risks to humans and ecosystems but are typically at or near analytical detection limits.

Urban expansion is one of the main factors driving terrestrial carbon storage (TCS) changes. Accurate accounting of TCS and rigorous quantification of its changes caused by historical urban expansion may help us to better predict its changes in the future. This study focuses on the carbon impacts of urbanization in China where the share of the urban population has increased from 18% in 1978 to 59% in 2017 and the growing will continue in the coming decades. Our results show that China’s TCS decreased at an accelerating pace over the past three decades with an average reduction of 0.72TgC/y in 1980–1990 and 8.72TgC/y in 2000–2010, mostly due to conversion from cropland and woodland to urban land. Through simulating urban expansion under four scenarios from 2010 to 2050, we found a potential increasing trend in land conversion from woodland to urban land. This conversion trend would result in carbon storage loss at an average rate of 9.31TgC/y ∼ 12.94TgC/y in 2010–2050. The increasing trend in both land conversion and carbon storage loss is especially visible in the population centers of the Yangtze River Delta and the Pearl River Delta. Considering that the indirect emission effects of urbanization, such as farmland displacement, population migration, and land degradation, may be much larger, the overall emission impact of forthcoming urban expansion in China would increase the uncertainty of the nation’s carbon emissions and potentially undermine China’s targets as committed in the Paris Climate Agreement.

Arsenic (As) release and mobility in groundwater is coupled to the iron (Fe) cycling and the associated transformation of Fe-oxides present in sediments. Recent in situ experiments have provided observations on arsenic mobilization and co-occurring reductive mineral transformation when placing As-loaded ferrihydrite-coated sand for 80 days in wells of an As-contaminated aquifer of Northern China. However, the complex temporal change in solid-associated arsenic and the multiple geochemical processes occurring when the flowing groundwater contacts the As-loaded ferrihydrite-coated sand hamper a detailed evaluation of the experimental data set. In this study, we develop a modeling approach that allows a quantitative interpretation of arsenic release and ferrihydrite transformation observed during the in situ experiments. The model accounts for the interplay of abiotic and biotic geochemical processes (i.e., surface complexation, reductive dissolution, formation of secondary iron minerals, and arsenic sequestration into the newly formed minerals) involved in the transformation of Fe-oxides and controlling arsenic mobility. The results show the capability of the proposed approach to reproduce the temporal trends of solid arsenic and ferrihydrite concentrations, as well as the spatial variability of mineral transformation, observed in different wells using a common set of surface complexation parameters and kinetic rate constants. The simulation outcomes allowed us to disentangle the specific contribution of the different mechanisms controlling the release of arsenic. It was possible to identify an initial rapid but minor release of As (13–23% of the initial surface concentration) due to desorption from ferrihydrite, as well as the reduction of adsorbed As(V) to As(III) upon contact with the flowing anoxic groundwater. Successively, reductive dissolution of ferrihydrite caused the decrease of the amount of the Fe mineral phase and led to a major depletion of solid-associated arsenic. The produced Fe(II) catalyzed the ferrihydrite conversion into more crystalline Fe(III) oxides (i.e., lepidocrocite and goethite) through Ostwald ripening, and resulted in the formation of siderite and mackinawite upon reaction with carbonates and sulfides naturally present in the groundwater. The model results also showed that, whereas the decrease in surface sites during reductive dissolution of ferrihydrite promoted arsenic mobilization, the mineral transformation limited As release through its sequestration into the newly formed secondary mineral phases.

We evaluate fine particulate matter (PM_2.5) exposure–response models to propose a consistent set of global effect factors for product and policy assessments across spatial scales and across urban and rural environments. Relationships among exposure concentrations and PM_2.5-attributable health effects largely depend on location, population density, and mortality rates. Existing effect factors build mostly on an essentially linear exposure–response function with coefficients from the American Cancer Society study. In contrast, the Global Burden of Disease analysis offers a nonlinear integrated exposure–response (IER) model with coefficients derived from numerous epidemiological studies covering a wide range of exposure concentrations. We explore the IER, additionally provide a simplified regression as a function of PM_2.5 level, mortality rates, and severity, and compare results with effect factors derived from the recently published global exposure mortality model (GEMM). Uncertainty in effect factors is dominated by the exposure–response shape, background mortality, and geographic variability. Our central IER-based effect factor estimates for different regions do not differ substantially from previous estimates. However, IER estimates exhibit significant variability between locations as well as between urban and rural environments, driven primarily by variability in PM_2.5 concentrations and mortality rates. Using the IER as the basis for effect factors presents a consistent picture of global PM_2.5-related effects for use in product and policy assessment frameworks.

In marine systems, the loss of nitrogen caused by denitrification in oxygen-deficient zones is balanced by nitrogen fixation mediated by cyanobacteria, which may form extensive blooms in surface waters. In this study, by determining the concentration ratio of nitrogen (N₂) and argon (Ar) in air equilibrated with surface water, we were able to detect changes in the N₂ concentration attributable to N₂ fixation. For this purpose, surface water was pumped continuously into a spray-type equilibrator while the air in the equilibrator’s headspace was analyzed by mass spectrometry. After laboratory tests and model analysis to evaluate the sensitivity of our N₂/Ar approach, feasibility studies were conducted in the central Baltic Sea in the summer of 2015 during the development of a cyanobacterial bloom. Our results showed that N₂ deficits accumulated during periods of low wind and increasing surface water temperatures. A comparison of our results with the N₂ deficits calculated from changes in the partial pressure of carbon dioxide in surface water indicated a similar trend. By demonstrating the ability of the N₂/Ar approach to resolve N₂ deficits in surface water caused by N₂ fixation, our study contributes to assessments of the N₂ fixation efficiency of cyanobacterial blooms.

Fe-bearing clay minerals are abundant in argillaceous rocks as their redox-active structural iron may control the sorption mechanism of redox sensitive elements on the surface of clay minerals. The extent and efficiency of the redox reactions depend on the oxidation state (Fe²⁺/Fe³⁺ ratio) and structural distribution of the substituting cations in the TOT-layer of clay minerals. Even smectites with similar structure originating from different locations might have a distinct arrangement of isomorphic substitutions (e.g., individual iron or Fe–Fe pairs). In this study, the proportion of different iron distribution in Milos–, Wyoming–, and Texas–montmorillonite was determined by combining X-ray absorption spectroscopy (XAS) with ab initio calculations. The relaxed atomic structures of the smectite models with different arrangement of individual Fe atoms and Fe–Fe/Fe–Mg clusters served as the basis for the calculations of the XAS spectra. The combination of simulation results and measured Fe K-edge XAS spectra of Wyoming–, Milos– and Texas–montmorillonites suggested that iron is present as Fe³⁺ in the octahedral sheet. Fe³⁺ in Texas–montmorillonite has a tendency to form clusters, while no definitive statement about clustering or avoidance of Fe–Fe and Fe–Mg pairs can be made for Milos– and Wyoming–montmorillonite.

We present a solid-phase extraction method followed by derivatization with a charged tag to characterize ketone/aldehyde-containing functionalities (proposed photo-oxidation transformation products) in weathered petroleum by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). A photo-oxidation-only microcosm mimics solar irradiation of crude oil in the environment after an oil spill. A biodegradation-only microcosm enables independent determination as to which of the two weathering processes contributes to the formation of oil-soluble ketone/aldehyde species. Results confirm that photo-oxidation produces ketones/aldehydes in crude oil when exposed to solar radiation in laboratory experiments, whereas biodegraded oil samples do not produce ketone/aldehyde compounds. Field samples collected after different time periods and locations after the Deepwater Horizon oil spill are also shown to contain ketones/aldehydes, and comparison of field and photo-oxidation-only microcosm transformation products reveal remarkable similarity. These results indicate that the photo-oxidation microcosm comprehensively represents ketone/aldehyde-formation products in the field, whereas the biodegradation microcosm does not. Solid-phase extraction coupled with derivatization leads to selective identification of ketone/aldehyde species by MS. Although improved dynamic range and slightly reduced mass spectral complexity is achieved by separation/derivatization, comprehensive molecular characterization still requires mass resolving power and mass accuracy provided by FT-ICR MS.

The quantification of anammox bacteria is crucial to manipulation and management of anammox biosystems. In this study, we proposed a protocol specifically optimized for quantification of anammox bacteria abundance in anammox sludge samples using catalyzed reporter deposition-fluorescence in situ hybridization (CARD-FISH) and flow cytometry (FCM) in combination (Flow-CARD-FISH). We optimized the pretreatment procedures for FCM-compatibility, as well as the permeabilization, hybridization and staining protocols of the CARD-FISH. The developed method was compared with other methods for specific bacteria quantification (standard FISH, 16S rRNA sequencing and quantitative polymerase chain reaction). Anammox sludge samples could be disaggregated effectively by sonication (specific energy of 90 kJ·L^–1 with MLVSS of 3–5 g·L^–1) with the mixed ionic and nonionic dispersants Triton X-100 (5%) and sodium pyrophosphate (10 mM). Lysozyme treatment for permeabilizing bacterial cell walls and H₂O₂ incubation for completely quenching endogenous peroxidase of anammox sludges were essential to fluorescence enhancement and false positive signals control, respectively. Horseradish peroxidase molecules labeling at 20 °C for 12 h and the fluorescent tyramide labeling at 25 °C for 30 min with a fluorescent substrate concentration of 1:50 maintained the balance between increasing the signal and preventing nonspecific binding. Flow-CARD-FISH results showed that anammox bacteria absolute abundance in two different sludge samples were (2.31 ± 0.01) × 10⁷ and (1.20 ± 0.06) × 10⁷ cells·mL^–1, respectively, with the relative abundances of 36.7 ± 4.1% and 26.5 ± 3.7%, respectively, comparable with those of qPCR and 16S rRNA sequencing analysis. The enhanced fluorescence signals induced by CARD-FISH combined with the high quantitative fluorescence sensitivity of FCM provide a rapid and sensitive method that yields accurate quantification results that will be valuable in future studies of microbial community determination.

Human exposure to airborne ultrafine (≪1 μm) particulate pollution may pose substantial hazards to human health, particularly in urban roadside environments where very large numbers of people are frequently exposed to vehicle-derived ultrafine particles (UFPs). For mitigation purposes, it is timely and important to quantify the deposition of traffic-derived UFPs onto leaves of selected plant species, with particularly efficient particle capture (high deposition velocity), which can be installed curbside, proximal to the emitting vehicular sources. Here, we quantify the size-resolved capture efficiency of UFPs from diesel vehicle exhaust by nine temperate-zone plant species, in wind tunnel experiments. The results show that silver birch (79% UFP removal), yew (71%), and elder (70.5%) have very high capabilities for capture of airborne UFPs. Metal concentrations and metal enrichment ratios in leaf leachates were also highest for the postexposure silver birch leaves; scanning electron microscopy showed that UFPs were concentrated along the hairs of these leaves. For all but two species, magnetic measurements demonstrated substantial increases in the concentration of magnetic particles deposited on the leaves after exposure to the exhaust particulates. Together, these new data show that leaf-deposition of UFPs is chiefly responsible for the substantial reductions in particle numbers measured downwind of the vegetation. It is critical to recognize that the deposition velocity of airborne particulate matter (PM) to leaves is species-specific and often substantially higher (∼10 to 50 times higher) than the “standard” V_d values (e.g., 0.1–0.64 cm s^–1 for PM_2.5) used in most modeling studies. The use of such low V_d values in models results in a major under-estimation of PM removal by roadside vegetation and thus misrepresents the efficacy of selected vegetation species in the substantial (≫20%) removal of PM. Given the potential hazard to health posed by UFPs and the removal efficiencies shown here (and by previous roadside measurements), roadside planting (maintained at or below head height) of selected species at PM “hotspots” can contribute substantially and quickly to improve in urban air quality and reductions in human exposure. These findings can contribute to the development and implementation of mitigation policies of traffic-derived PM on an international scale.

During catalytic ozonation, Al₂O₃-supported catalysts usually have stable structures but relatively low surface activity, while carbon-supported catalysts are opposite. To encourage their synergisms, we designed a Ni-induced C-Al₂O₃-framework (_NiCAF) and reinforced it with a Cu–Co bimetal to create an efficient catalyst (CuCo/_NiCAF) with a core–multishell structure. The partial graphitization of carbon adjacent to Ni crystals formed a strong out-shell on the catalyst surface. The rate constant for total organic carbon removal of CuCo/_NiCAF (0.172 ± 0.018 min^–1) was 67% and 310% higher than that of Al₂O₃-supported catalysts and Al₂O₃ alone, respectively. The metals on CuCo/_NiCAF contributed to surface-mediated reactions during catalytic ozonation, while the embedded carbon enhanced reactions within the solid–liquid boundary layer and in the bulk solution. Moreover, carbon embedment provided a 76% increase in ·OH-production efficiency and an 86% increase in organic-adsorption capacity compared to Al₂O₃-supported catalysts. During the long-term treatment of coal-gasification wastewater (∼5 m³ day^–1), the pilot-scale demonstration of CuCo/_NiCAF-catalyzed ozonation revealed a 120% increase in ozone-utilization efficiency (ΔCOD/ΔO₃ = 2.12) compared to that of pure ozonation (0.96). These findings highlight catalysts supported on _NiCAF as a facile and efficient approach to achieve both high catalytic activity and excellent structural stability, demonstrating that they are highly viable for practical applications.

Promotion of iron solubility using ligands is the preliminary step in the homogeneous electro-Fenton (EF) process at a mild pH, but the chelate efficiencies of most organic ligands are unsatisfactory, resulting in insufficient Fe(II) availability. In this study, atomic H* was, for the first time, introduced to the EF process to accelerate the regeneration of the Fe(II)-complex at a mild pH using a Ni-deposited carbon felt (Ni-CF) cathode. The introduction of atomic H* significantly elevated total organic carbon (TOC) abatement of ciprofloxacin (CIP) from 42% (CF) to 81% (Ni-CF) at a natural pH. In the presence of humic acids (HAs), atomic H* introduced via Ni-CF enhanced the CIP degradation rate to 10 times that of the CF at a mild pH. The electron spin resonance (ESR), density functional theory (DFT) calculations, electrochemical characterization, and in situ electrochemical Raman study clearly demonstrated that the atomic H* generated from the Ni-CF cathode was highly efficient at reducing Fe(III)-complexes at a natural pH. Additionally, the Ni-CF could generate atomic H* without significant nickel leaching. Thus, the atomic H* could continuously facilitate iron cycling and, consequently, enhance pollutant mineralization via the homogeneous EF process at a mild pH in an environmentally friendly manner.

Increasing numbers of cement furnaces have applied selective catalytic reduction (SCR) units for advanced treatment of NO in the flue gas. However, the SCR catalysts may face various poisons, such as acidic, alkaline, and heavy metal species, in the fly ash. In this work, we studied the deactivation mechanisms of multipoisons (Ca, Pb, and S) on the CeO₂–WO₃/TiO₂ catalyst, using the in situ diffuse reflectance infrared Fourier transform spectroscopy method. Calcium promoted the conversion of Ce(III) to Ce(IV) and, thus, (i) suppressed the redox cycle, (ii) decreased the NO adsorption (monodentate NO₃^– and bridged NO₂^–), and (iii) enriched the Lewis acid sites. Pb(IV) blocked Ce₂(WO₄)₃, aggravating the electronegativity of W⁶⁺, which inhibited (i) the binding stability of tungsten and ammonia species, (ii) bridged NO₃^– (bonded to tungsten), and (iii) the Brønsted acid sites. The multipoisoning processes enriched O^2– by repairing partial surface oxygen defects, which suppressed O₂^2– and O^–. Sulfur occupied the surface base sites and formed PbSO₄ after Ce₂(WO₄)₃ was saturated.

The conversion of excess ammonia N into harmless N₂ is a primary challenge for wastewater treatment. We present here a method to generate ClO^• directionally for quick and efficient decomposition of NH₄⁺ N to N₂. ClO^• was produced and enhanced by a bifacial anode, a front WO₃ photoanode and a rear Sb–SnO₂ anode, in which HO^• generated on WO₃ reacts with HClO generated on Sb–SnO₂ to form ClO^•. Results show that the ammonia decomposition rate of Sb–SnO₂/WO₃ is 4.4 times than that of WO₃ and 3.3 times than that of Sb–SnO₂, with achievement of the removal of NH₄⁺ N on Sb–SnO₂/WO₃ and WO₃ being 99.2 and 58.3% in 90 min, respectively. This enhancement is attributed to the high rate constant of ClO^• with NH₄⁺ N, which is 2.8 and 34.8 times than those of Cl^• and HO^•, respectively. The steady-state concentration of ClO^• (2.5 × 10^–13 M) is 10² times those of HO^• and Cl^•, and this is further confirmed by kinetic simulations. In combination with the Pd–Cu/NF cathode to form a denitrification exhaustion system, Sb–SnO₂/WO₃ shows excellent total nitrogen removal (98.4%), which is more effective than WO₃ (47.1%) in 90 min. This study provides new insight on the directed ClO^• generation and its application on ammonia wastewater treatment.

The transmission mode of shoot-associated endophytes in hyperaccumulators and their roles in root microbiome assembly and heavy metal accumulation remain unclear. Using 16S rRNA gene profiling, we investigated the vertical transmission of shoot-associated endophytes in relation to growth and Cd/Zn accumulation of Sedum alfredii (Crassulaceae). Endophytes were transmitted from shoot cuttings to the rhizocompartment of new plants in both sterilized (γ-irradiated) and native soils. Vertical transmission was far more efficient in the sterile soil, and the transmitted endophytes have become a dominant component of the newly established root-associated microbiome. Based on 16S rRNA genes, the vertically transmitted taxa were identified as the families of Streptomycetaceae, Nocardioidaceae, Pseudonocardiaceae, and Rhizobiaceae. Abundances of Streptomycetaceae, Nocardioidaceae, and Pseudonocardiaceae were strongly correlated with increased shoot biomass and total Cd/Zn accumulation. Inoculation of S. alfredii with the synthetic bacterial community sharing the same phylogenetic relatedness with the vertically transmitted endophytes resulted in significant improvements in plant biomass, root morphology, and Cd/Zn accumulation. Our results demonstrate that successful vertical transmission of endophytes from shoots of S. alfredii to its rhizocompartments is possible, particularly in soils with attenuated microbiomes. Furthermore, the endophyte-derived microbiome plays an important role in metal hyperaccumulation.

Intelligent defect engineering to harness surface molecular processes is at the core of selective oxidation catalysis. Here, we demonstrate that the two-electron-trapped oxygen vacancy (V_O) of BiOCl, a prototypical F center (V_Ő′′), is a superb site to confine O₂ toward efficient and selective NO oxidation to nitrate. Stimulated by solar light, V_Ő′′ accomplishes NO oxidation through a two-electron charging (V_Ő′′ + O₂ → V_Ő′′-O₂^2–) and subsequent one-electron decharging process (V_Ő′′-O₂^2– + NO → V_O-NO₃^– + e^–). The back-donated electron is retrapped by V_O to produce a new single-electron-trapped V_O (V_O′), simultaneously triggering a second round of NO oxidation (V_O′-O₂ + NO → V_O-NO₃^–). This unprecedented interfacial charging–decharging scheme alters the peroxide-associated NO oxidation selectivity from NO₂ to NO₃^– with a high efficiency and thus hold great promise for the treatment of risky NO_x species in indoor air.

Cobalt-mediated activation of peroxymonosulfate (PMS) has been widely investigated for the oxidation of organic pollutants. Herein, we employ cobalt-doped Black TiO₂ nanotubes (Co-Black TNT) for the efficient, stable, and reusable activator of PMS for the degradation of organic pollutants. Co-Black TNTs induce the activation of PMS by itself and stabilized oxygen vacancies that enhance the bonding with PMS and provide catalytic active sites for PMS activation. A relatively high electronic conductivity associated with the coexistence of Ti⁴⁺ and Ti³⁺ in Co-Black TNT enables an efficient electron transfer between PMS and the catalyst. As a result, Co-Black TNT is an effective catalyst for PMS activation, leading to the degradation of selected organic pollutants when compared to other TNTs (TNT, Co-TNT, and Black TNT) and other Co-based materials (Co₃O₄, Co-TiO₂, CoFe₂O₄, and Co₃O₄/rGO). The observed organic compound degradation kinetics are retarded in the presence of methanol and natural organic matter as sulfate radical scavengers. These results demonstrate that sulfate radical is the primary oxidant generated via PMS activation on Co-Black TNT. The strong interaction between Co and TiO₂ through Co–O–Ti bonds and rapid redox cycle of Co²⁺/Co³⁺ in Co-Black TNT prevents cobalt leaching and enhances catalyst stability over a wide pH range and repetitive uses of the catalyst. Electrode-supported Co-Black TNT facilitates the recovery of the catalyst from the treated water.

Graphitic carbon nitride has emerged as a promising material for high-performance membranes with both filtration and catalytic abilities. However, the scalable construction of carbon-nitride-based membranes is seriously restricted by the poor ability to tailor the structure and poor solvent solubility of bulk nanostructures. Herein, carbon nitride sol was prepared in high yield and used as a precursor to assemble photo-Fenton-like membranes. Intermolecular hydrogen-bond interactions between carbon nitride nanofibers were found to be vitally important for the repolymerization of hydrolyzed molecules into dense and solid membranes. Intercalated Fe-containing polyoxometalates (Fe-POMs) not only acted as molecular linkers to construct carbon nitride membranes but also provided new opportunities for the catalytic functionality. Benefiting from the hydrophobic nanocapillaries in 2D carbon nitride for ultralow water–carbon friction, self-assembled membranes effectively rejected pollutant molecules with high water permeation flux. The integration of carbon nitride photocatalysts with Fenton-like Fe-POMs contributed to the in situ degradation of retained pollutants. Thus, our work manifested a facile bottom-up strategy to construct photo-Fenton-like membranes with antifouling abilities for wastewater treatment.

Low temperature NH₃ selective catalytic reduction (NH₃-SCR) technology is an efficient and economical strategy for cutting NO_x emissions from power-generating equipment. In this study, a novel and highly efficient NH₃-SCR catalyst, tourmaline-modified FeMnTiO_x is presented, which was synthesized by a simple one-step sol–gel method. We found that the amount of tourmaline has an important impact on the catalytic performance of the modified FeMnTiO_x-based catalysts, and the NO_x conversion exceeded 80% from 160 to 380 °C with the addition of 5 wt % tourmaline. Compared with the pure FeMnTiO_x, the catalytic efficiency at a temperature below 100 °C was increased by nearly 18.9%, and the operation temperature window was broadened significantly. The enhanced catalytic performance of the FeMnTiO_x catalyst was mainly attributed to the small spherical nanoparticles structure around the tourmaline powders, resulting in the increased content of Mn³⁺, Mn⁴⁺, and chemical oxygen on the catalytic surface. These as-developed tourmaline-modified FeMnTiO_x materials have been demonstrated to be promising as a new type highly efficient low temperature NH₃-SCR catalyst.

Factors influencing organic contaminant accumulation in sharks, especially across ontogeny, are not well-known. Contaminant concentrations were measured in three species of sharks (Blue, Shortfin Mako, and Common Thresher) across a range of size classes (neonatal to adult) that vary in their ecological and physiological characteristics. Empirical data was compared to a theoretical framework that predicted the shape of lifetime accumulation curves. We found that a one-size-fits-all accumulation model was not appropriate as species-specific characteristics had a significant effect on contaminant accumulation trajectories. Maternal offloading likely has an important effect on determining neonatal shark contaminant starting points, and trophic ecology and physiology may interact to affect the shape of species’ contaminant accumulation curves. Makos were found to have the highest accumulation potential and Blues the lowest, with Threshers being intermediate in accumulation potential. Changes in species’ ecology and/or physiology were also reflected in contaminant signature changes over ontogeny. If contaminant concentrations are to be used as a proxy for risk, species-specific characteristics need to be taken into account when estimating contaminant exposure and its potential negative effects on shark health and human consumption safety.

N-Nitrosamines are drinking water disinfection byproducts that pose a high carcinogenic risk. We hypothesized that raw water treatment processes influence the types and concentrations of nitrosamines in drinking water, thereby posing differential health risks. We compared the finished water of two water treatment plants (WTP-A, WTP-B) serving Shanghai, China. Both plants use the Qingcaosha reservoir as a water source to generate drinking water with conventional but distinct treatment processes, namely preoxidation with sodium hypochlorite (WTP-A) vs ozone (WTP-B). Average nitrosamine concentrations, especially that of the probable human carcinogen (2A) N-nitrosodimethylamine, were higher in finished (drinking) water from WTP-A (35.83 ng/L) than from WTP-B (5.07 ng/L). Other differences in mean nitrosamines in drinking water included N-nitrosodipropylamine (42.62 ng/L) and N-nitrosomethylethylamine (26.73 ng/L) in WTP-A in contrast to N-nitrosodiethylamine (7.26 ng/L) and N-nitrosopyrrolidine (59.12 ng/L) in WTP-B. The estimated adult cancer risk from exposure to mixed nitrosamines was 1.83 times higher from WTP-A than from WTP-B drinking water. Children exposed to nitrosamines had a significantly higher cancer risk than adults (p < 0.05). Disease burden exceeded 10⁶ person-years. Taken together, these data suggest that use of ozone in the preoxidation step can reduce nitrosamine formation in drinking water and thereby lower the population cancer health risk.

Phenolic disinfection byproducts (phenolic-DBPs) have been identified in recent years. However, the toxicity data for phenolic-DBPs are scarce, hampering their risk assessment and the development of regulations on the acceptable concentration of phenolic-DBPs in water. In this study, the binding potency and underlying interaction mechanism between human transthyretin (hTTR) and five groups of representative phenolic-DBPs (2,4,6-trihalo-phenols, 2,6-dihalo-4-nitrophenols, 3,5-dihalo-4-hydroxybenzaldehydes, 3,5-dihalo-4-hydroxybenzoic acids, halo-salicylic acids) were determined and probed by competitive fluorescence displacement assay integrated with in silico methods. Experimental results implied that 2,4,6-trihalo-phenols, 2,6-dihalo-4-nitrophenols, and 3,5-dihalo-4-hydroxybenzaldehydes have a high binding affinity with hTTR. The hTTR binding potency of the chemicals with electron-withdrawing groups on their molecular structures were higher than that with electron-donor groups. Molecular modeling methods were used to decipher the binding mechanism between model compounds and hTTR. The results documented that ionic pair, hydrogen bonding and hydrophobic interactions were dominant interactions. Finally, a mechanism-based model for predicting the hTTR binding affinity was developed. The determination coefficient (R²), leave-one-out cross validation Q² (Q_LOO²), bootstrapping coefficient (Q_BOOT²), external validation coefficient (Q_EXT²) and concordance correlation coefficient (CCC) of the developed model met the acceptable criteria (Q² > 0.600, R² > 0.700, CCC > 0.850), implying that the model had good goodness-of-fit, robustness, and external prediction performances. All the results indicated that the phenolic-DBPs have the hTTR disrupting effects, and further studies are needed to investigate their other mechanism of endocrine disruption.

Melamine and cyanuric acid have been reported to occur in animal products. Nevertheless, information that pertains to the occurrence of melamine and cyanuric acid in cattle feed and urine is lacking. In this study, the occurrence of melamine and its three derivatives (i.e., cyanuric acid, ammeline, and ammelide) was determined in 183 bovine urine and 29 matched feed samples collected from China, India, and the United States. ∑Melamine (sum of four target compounds) was found in all urine samples at concentrations that ranged from 4.2 to 5280 ng/mL (median: 370 ng/mL); cyanuric acid was the major derivative, accounting for 97% of the total concentrations, followed by melamine (2.2%). The ubiquitous occurrence of ∑Melamine in feed (21–6230 ng/g) suggests that it is the major source of melamine and its derivatives in bovines. Urinary concentrations of melamine and cyanuric acid varied significantly among the three countries, with samples from China as having the highest concentrations, followed by the United States and India. The calculated cumulative daily intakes of melamine and cyanuric acid were at least 10-fold below the current tolerable daily intake recommended for humans. Our study provides evidence-based data on exposure patterns and sources of melamine and cyanuric acid in cattle.

The dopaminergic effect of PAH and PFAS mixtures, prepared according to environmentally relevant concentrations, has been studied in juvenile female Atlantic cod (Gadus morhua). Benzo[a]pyrene, dibenzothiophene, fluorene, naphthalene, phenanthrene, and pyrene were used to prepare a PAH mixture, while PFNA, PFOA, PFOS, and PFTrA were used to prepare a PFAS mixture. Cod were injected intraperitoneally twice, with either a low (1×) or high (20×) dose of each compound mixture or their combinations. After 2 weeks of exposure, levels of plasma 17β-estradiol (E2) were significantly elevated in high PAH/high PFAS treated group. Brain dopamine/metabolite ratios (DOPAC/dopamine and HVA+DOPAC/dopamine) changed with E2 plasma levels, except for high PAH/low PFAS and low PAH/high PFAS treated groups. On the transcript levels, th mRNA inversely correlated with dopamine/metabolite ratios and gnrh2 mRNA levels. Respective decreases and increases of drd1 and drd2a after exposure to the high PAH dose were observed. Specifically, high PFAS exposure decreased both drds, leading to high plasma E2 concentrations. Other studied end points suggest that these compounds, at different doses and combinations, have different toxicity threshold and modes of action. These effects indicate potential alterations in the feedback signaling processes within the dopaminergic pathway by these contaminant mixtures.

Humans spend most of their time indoors and thus have long-term exposure to chemicals. Dust is a sink for most indoor chemicals, and its ingestion is an important pathway for chemical uptake. Therefore, the chemical atlas from dust is an ideal environmental sample to investigate the indoor exposome and associated risk. In this study, we aimed to establish an indoor exposome database through comprehensive data mining on the occurrence of identified compounds in dust, and we prioritize chemicals of health concern. Through an extensive literature review (2849 articles), 355 chemicals and their concentrations were documented and analyzed for human exposure. Together with 81 compounds without concentration and 75 volatile organic compounds, we have established an indoor exposome database with 511 chemicals. Sixteen toxicological end points were selected for toxicity prioritization. Toxic equivalency factor (TEF)-based toxicity, calculated from EPA’s ToxCast database, revealed a comprehensive atlas of the chemicals that had a primary contribution. Many of the prioritized compounds are currently neglected or are not actively studied. Overall, this investigation provides one of the most comprehensive analyses on chemical occurrence in indoor dust and prioritizes their chemical toxicity. Our findings can be used as a database for future exposome studies of the indoor environment and provide guidance for indoor risk assessments.

Container-based sanitation (CBS) within a comprehensive service system value chain offers a low-cost sanitation option with potential for revenue generation but may increase microbial health risks to sanitation service workers. This study assessed occupational exposure to rotavirus and Shigella spp. during CBS urine collection and subsequent struvite fertilizer production in eThekwini, South Africa. Primary data included high resolution sequences of hand-object contacts from annotated video and measurement of fecal contamination from urine and surfaces likely to be contacted. A stochastic model incorporated chronological surface contacts, pathogen concentrations in urine, and literature data on transfer efficiencies of pathogens to model pathogen concentrations on hands and risk of infection from hand-to-mouth contacts. The probability of infection was highest from exposure to rotavirus during urine collection (∼10^–1) and struvite production (∼10^–2), though risks from Shigella spp. during urine collection (∼10^–3) and struvite production (∼10^–4) were non-negligible. Notably, risk of infection was higher during urine collection than during struvite production due to contact with contaminated urine transport containers. In the scale-up of CBS, disinfection of urine transport containers is expected to reduce pathogen transmission. Exposure data from this study can be used to evaluate the effectiveness of measures to protect sanitation service workers.

Microplastics are ubiquitous across ecosystems, yet the exposure risk to humans is unresolved. Focusing on the American diet, we evaluated the number of microplastic particles in commonly consumed foods in relation to their recommended daily intake. The potential for microplastic inhalation and how the source of drinking water may affect microplastic consumption were also explored. Our analysis used 402 data points from 26 studies, which represents over 3600 processed samples. Evaluating approximately 15% of Americans’ caloric intake, we estimate that annual microplastics consumption ranges from 39000 to 52000 particles depending on age and sex. These estimates increase to 74000 and 121000 when inhalation is considered. Additionally, individuals who meet their recommended water intake through only bottled sources may be ingesting an additional 90000 microplastics annually, compared to 4000 microplastics for those who consume only tap water. These estimates are subject to large amounts of variation; however, given methodological and data limitations, these values are likely underestimates.

Microplastic debris is a pervasive environmental contaminant that has the potential to impact the health of biota, although its modes of action remain somewhat unclear. The current study tested the hypothesis that exposure to fibrous and particulate microplastics would alter feeding, impacting on lipid accumulation, and normal development (e.g., growth, moulting) in an ecologically important coldwater copepod Calanus finmarchicus. Preadult copepods were incubated in seawater containing a mixed assemblage of cultured microalgae (control), with the addition of ∼50 microplastics mL^–1 of nylon microplastic granules (10–30 μm) or fibers (10 × 30 μm), which are similar in shape and size to the microalgal prey. The additive chemical profiles showed the presence of stabilizers, lubricants, monomer residues, and byproducts. Prey selectivity was significantly altered in copepods exposed to nylon fibers (ANOVA, P < 0.01) resulting in a nonsignificant 40% decrease in algal ingestion rates (ANOVA, P = 0.07), and copepods exposed to nylon granules showed nonsignificant lipid accumulation (ANOVA, P = 0.62). Both microplastics triggered premature moulting in juvenile copepods (Bernoulli GLM, P < 0.01). Our results emphasize that the shape and chemical profile of a microplastic can influence its bioavailability and toxicity, drawing attention to the importance of using environmentally relevant microplastics and chemically profiling plastics used in toxicity testing.

Dissolved organic compounds are major contaminants in oil sands process-affected water (OSPW), of which naphthenic acids (NAs) are one of the main persistent toxicants. In the present study, we explore the toxic effects of the organic fraction extracted from OSPW (OSPW-OF) in mice during pregnancy and lactation. Here, we report that acute oral exposure of female Balb/c mice during gestation, and subchronic exposure throughout gestation and lactation to OSPW-OF (containing naturally occurring levels of NAs found in tailings ponds), had negligible effects on their reproductive performance. Specifically, mating behavior, pregnancy success, embryonic implantation, gestation period, litter size, and offspring viability were not affected by OSPW-OF containing up to 55 mg/L NAs. OSPW-OF exposure also did not affect plasma concentrations of pregnancy-associated hormones or pro- and anti-inflammatory cytokines, and it had minimal effects on liver stress gene expression. This study presents the first comprehensive in vivo analysis of mammalian toxicity associated with OSPW-OF exposure. Overall, our results suggest that the risk of acute and subchronic toxicity to mice exposed to OSPW-OF at environmentally relevant concentrations of NAs in contaminated drinking water is likely negligible.

Bisphenol A (BPA) is an important endocrine disrupting chemical. Although high levels of BPA in some new clothes have been reported, the occurrence of bisphenol chemicals including BPA in daily clothes is still unknown, and the human exposure to BPA in clothes has not been well assessed. In this study, used/washed clothes were collected from residents’ wardrobes and the concentrations of BPA and its analogues were detected. BPA was present in all the used clothes at concentrations ranging from <3.30 to 471 ng/g (median: 34.2 ng/g; mean ± SD: 57.5 ± 93.6 ng/g), while bisphenol S was also detected in 29% of the samples. Although higher average concentration (88.4 ± 289 ng/g) and maximum concentration (1823 ng/g) of BPA were found in the new clothes, the median concentration of BPA in the used clothes (34.2 ng/g) was even higher than that in the new clothes (17.7 ng/g). Cross contamination of BPA during laundering was identified by a simulated laundry experiment, which explained the homogenizing tendency of bisphenol contaminants in the used clothes. An estimated dermal exposure dose of 52.1 ng/kg BW/d was obtained for BPA exposure in children from the highly polluted sweaty clothes (with BPA concentration of 199 ng/g). This indicates a relatively high exposure risk in humans. Compared to other exposure routes, the contribution of dermal exposure dose of BPA from the daily clothes should not be neglected.

The global and U.S. domestic effort to develop a clean energy economy and curb environmental pollution incentivizes the use of hydrogen as a transportation fuel, owing to its zero tailpipe pollutant emissions and high fuel efficiency in fuel cell electric vehicles (FCEVs). However, the hydrogen production process is not emissions free. Conventional hydrogen production via steam methane reforming (SMR) is energy intensive, coproduces carbon dioxide, and emits air pollutants. Thus, it is necessary to quantify the environmental impacts of SMR hydrogen production alongside the use-phase of FCEVs. This study fills the information gap, analyzing the greenhouse gas (GHG) and criteria air pollutant (CAP) emissions associated with hydrogen production in U.S. SMR facilities by compiling and matching the facility-reported GHG and CAP emissions data with facilities’ hydrogen production data. The actual amounts of hydrogen produced at U.S. SMR facilities are often confidential. Thus, we have developed four approaches to estimate the hydrogen production amounts. The resultant GHG and CAP emissions per MJ of hydrogen produced in individual facilities were aggregated to develop emission values for both a national median and a California state median. This study also investigates the breakdown of facility emissions into combustion emissions and noncombustion emissions.

Cookstoves emit many pollutants that are harmful to human health and the environment. However, most of the existing scientific literature focuses on fine particulate matter (PM_2.5) and carbon monoxide (CO). We present an extensive data set of speciated air pollution emissions from wood, charcoal, kerosene, and liquefied petroleum gas (LPG) cookstoves. One-hundred and twenty gas- and particle-phase constituents—including organic carbon, elemental carbon (EC), ultrafine particles (10–100 nm), inorganic ions, carbohydrates, and volatile/semivolatile organic compounds (e.g., alkanes, alkenes, alkynes, aromatics, carbonyls, and polycyclic aromatic hydrocarbons (PAHs))—were measured in the exhaust from 26 stove/fuel combinations. We find that improved biomass stoves tend to reduce PM_2.5 emissions; however, certain design features (e.g., insulation or a fan) tend to increase relative levels of other coemitted pollutants (e.g., EC ultrafine particles, carbonyls, or PAHs, depending on stove type). In contrast, the pressurized kerosene and LPG stoves reduced all pollutants relative to a traditional three-stone fire (≥93% and ≥79%, respectively). Finally, we find that PM_2.5 and CO are not strong predictors of coemitted pollutants, which is problematic because these pollutants may not be indicators of other cookstove smoke constituents (such as formaldehyde and acetaldehyde) that may be emitted at concentrations that are harmful to human health.

Unconventional oil and gas development (UOGD) in the United States is increasingly being conducted on multiwell pads (MWPs) and in residential areas. We measured air pollution, noise, and truck traffic during four distinct phases of UOGD: drilling, hydraulic fracturing, flowback, and production. We monitored particulate matter (PM_2.5), black carbon (BC), A-weighted (dBA), and C-weighted (dBC) noise using real-time instruments on 1 and 5 min time scales, and truck traffic for 4–7 days per phase at a large 22-well pad sited in a residential area of Weld County, Colorado. Hydraulic fracturing, which requires frequent truck trips to move supplies and diesel engines to power the process, had the highest median air pollution levels of PM_2.5 and BC and experienced the greatest number of heavy trucks per hour compared to other phases. Median air pollution was lowest during drilling at this MWP, possibly because an electric drill rig was used. The equivalent continuous noise level (L_eq) exceeded guidelines of 50 dBA and 65 dBC for A-weighted and C-weighted noise, respectively, during all development phases. Our data show that these multiple stressors are present around the clock at these sites, and this work provides baseline measurements on likely human exposure levels near similarly sized MWPs.

Efforts to develop safe and effective next-generation energy and carbon-storage technologies in the subsurface require novel means to control undesired fluid migration. Here we demonstrate that the carbonation of calcium silicates can produce reaction products that dramatically reduce the permeability of porous media and that are stable. Most calcium silicates react with CO₂ to form solid carbonates but some polymorphs (here, pseudowollastonite, CaSiO₃) can react to form a range of crystalline calcium silicate hydrates (CCSHs) at intermediate pH. High-pressure (1.1–15.5 MPa) column and batch experiments were conducted at a range of temperatures (75–150 °C) and reaction products were characterized using SEM-EDS and synchrotron μXRD and μXRF. Two characteristics of CCSH precipitation were observed, revealing unique properties for permeability control relative to carbonate precipitates. First, precipitation of CCSHs tends to occur on the surface of sand grains and into pore throats, indicating that small amounts of precipitation relative to the total pore volume can effectively block flow, compared to carbonates which precipitate uniformly throughout the pore space. Second, the precipitated CCSHs are more stable at low pH conditions, which may form more secure barriers to flow, compared to carbonates, which dissolve under acidic conditions.

Photoelectrocatalysis (PEC) produces high-efficiency electron–hole separation by applying a bias voltage between semiconductor-based electrodes to achieve high photocatalytic reaction rates. However, using PEC to treat polluted gas in a gas-phase reaction is difficult because of the lack of a conductive medium. Herein, we report an efficient PEC system to oxidize NO gas by using parallel photoactive composites (TiO₂ nanoribbons–carbon nanotubes) coated on stainless-steel mesh as photoanodes in a gas-phase chamber and Pt foil as the working electrode in a liquid-phase auxiliary cell. Carbon nanotubes (CNTs) were utilized as conductive scaffolds to enhance the interaction between TiO₂ and stainless-steel skeletons for accelerated photogenerated electron transfer. Such a PEC system exhibited super-high performance for the treatment of indoor NO gas (550 ppb) with high selectivity for nitrate under UV-light irradiation owing to the conductive, intertwined network structure of the photoanode, fast photocarrier separation, and longer photogenerated hole lifetime. The photogenerated holes were proven to be the most important active sites for directly driving PEC oxidation of indoor NO gas, even in the absence of water vapor. This work created an efficient PEC air-purification filter for treating indoor polluted air under ambient conditions.

Shale gas pipeline development can have negative environmental impacts, including adverse effects on species and ecosystems through habitat degradation and loss. From a societal perspective, pipeline development planning processes should account for such externalities. We develop a multiobjective binary integer-programming model, called the Multi Objective Pipeline Siting (MOPS) model, to incorporate habitat externalities into pipeline development and to estimate the trade-offs between pipeline development costs and habitat impacts. We demonstrate the utility of the model using an application from Bradford and Susquehanna counties in northeastern Pennsylvania. We find that significant habitat impacts can be avoided for relatively low cost, but the avoidance of the additional habitat impacts becomes gradually and increasingly costly. For example, 10% of the habitat impacts can be avoided at less than a two percent pipeline cost increase relative to a configuration that ignores habitat impacts. MOPS or a similar model could be integrated into the pipeline siting and permitting process so oil and gas companies, communities, and states can identify cost-effective options for habitat conservation near shale gas development.

As the world’s fifth-largest economy, California has committed to reduce its greenhouse gas (GHG) emissions by 80% below 1990 levels by 2050. While previous studies have shown that GHG reductions could synergistically decrease air pollutant emissions and protect public health, limited research has been conducted to compare the health cobenefits of different technology pathways toward deep decarbonization. Using an integrated approach that combines energy and emission technology modeling, high-resolution chemical transport simulation, and health impact assessment, we find that achievement of the 80% GHG reduction target would bring substantial air quality and health cobenefits. The cobenefits, however, highly depend on the selected technology pathway largely because of California’s relatively clean energy structure. Compared with the business-as-usual levels, a decarbonization pathway that focuses on electrification and clean renewable energy is estimated to reduce concentrations of fine particulate matter (PM_2.5) by 18–37% in major metropolitan areas of California and subsequently avoid about 12 100 (9600–14 600) premature deaths. In contrast, only a quarter of such health cobenefits, i.e., 2800 (2300–3400) avoided deaths, can be achieved through a pathway focusing more on combustible renewable fuels. After subtracting the cost, the net monetized benefit of the electrification-focused pathway still exceeds that of the renewable fuel-focused pathway, indicating that a cleaner but more expensive decarbonization pathway may be more preferable in California.