The 50 most-cited articles in Environmental Science & Technology, 2018

Soils are essential components of terrestrial ecosystems that experience strong pollution pressure. Microplastic contamination of soils is being increasingly documented, with potential consequences for soil biodiversity and function. Notwithstanding, data on effects of such contaminants on fundamental properties potentially impacting soil biota are lacking. The present study explores the potential of microplastics to disturb vital relationships between soil and water, as well as its consequences for soil structure and microbial function. During a 5-weeks garden experiment we exposed a loamy sand soil to environmentally relevant nominal concentrations (up to 2%) of four common microplastic types (polyacrylic fibers, polyamide beads, polyester fibers, and polyethylene fragments). Then, we measured bulk density, water holding capacity, hydraulic conductivity, soil aggregation, and microbial activity. Microplastics affected the bulk density, water holding capacity, and the functional relationship between the microbial activity and water stable aggregates. The effects are underestimated…

Microplastics (MPs) are small (<5 mm diameter) but have clear implications for the environment. These artificial particles are found in and pose threats to aquatic systems worldwide. MPs have terrestrial sources, but their concentrations and fates in the terrestrial environment are poorly understood. While global plastic production continues to increase, so do the environmental concentrations and impacts of MPs. In this first study of MPs in floodplain soils, we developed a method for identifying, quantifying, and measuring the sizes of most commonly produced MPs in soil by FT-IR microscopy. For small MP (<1 mm) analysis, MP were separated by density separation and oxidation of organic matter. In this study we analyzed 29 floodplains in Swiss nature reserves associated with catchments covering 53% of Switzerland. We found evidence that 90% of Swiss floodplain soils contain MPs. The highest MP concentrations were associated with the concentration of mesoplastics (5 mm - 2.5 cm diameter), indicating plastic waste as source. Furthermore, MP concentration was correlated with the…

Minerals and transitional metal oxides of earth-abundant elements are desirable catalysts for in situ chemical oxidation in environmental remediation. However, catalytic activation of peroxydisulfate (PDS) by manganese oxides was barely investigated. In this study, one-dimension manganese dioxides (α- and β-MnO 2 ) were discovered as effective PDS activators among the diverse manganese oxides for selective degradation of organic contaminants. Compared with other chemical states and crystallographic structures of manganese oxide, β-MnO 2 nanorods exhibited the highest phenol degradation rate (0.044 min –1, 180 min) by activating PDS. A comprehensive study was conducted utilizing electron paramagnetic resonance, chemical probes, radical scavengers, and different solvents to identity the reactive oxygen species (ROS). Singlet oxygen ( 1 O 2 ) was unveiled to be the primary ROS, which was generated by direct oxidation or recombination of superoxide ions and radicals from a metastable manganese intermediate at neutral pH. The study dedicates to the first mechanistic study into PDS…

Environmentally friendly and low-cost catalysts are important for the rapid mineralization of organic contaminants in powerful advanced oxidation processes (AOPs). In this study, we reported N-doped graphitic biochars (N-BCs) as low-cost and efficient catalysts for peroxydisulfate (PDS) activation and the degradation of diverse organic pollutants in water treatment, including Orange G, phenol, sulfamethoxazole, and bisphenol A. The biochars at high annealing temperatures (>700 °C) presented highly graphitic nanosheets, large specific surface areas (SSAs), and rich doped nitrogen. In particular, N-BC derived at 900 °C (N-BC900) exhibited the highest degradation rate, which was 39-fold and 6.5-fold of that on N-BC400 and pristine biochar, respectively, and the N-BC900 surpassed most popular metal or nanocarbon catalysts. Different from the radical-based oxidation in N-BC400/PDS via the persistent free radicals (PFRs), singlet oxygen and nonradical pathways (surface-confined activated persulfate-carbon complexes) were discovered to dominate the oxidation processes in N-BC900/PDS.…

Select persulfate activation processes were demonstrated to initiate oxidation not reliant on sulfate radicals, although the underlying mechanism has yet to be identified. This study explored singlet oxygenation and mediated electron transfer as plausible nonradical mechanisms for organic degradation by carbon nanotube (CNT)-activated peroxymonosulfate (PMS). The degradation of furfuryl alcohol (FFA) as a singlet oxygen ( 1 O 2 ) indicator and the kinetic retardation of FFA oxidation in the presence of l -histidine and azide as 1 O 2 quenchers apparently supported a role of 1 O 2 in the CNT/PMS system. However, the 1 O 2 scavenging effect was ascribed to a rapid PMS depletion by l -histidine and azide. A comparison of CNT/PMS and photoexcited Rose Bengal (RB) excluded the possibility of singlet oxygenation during heterogeneous persulfate activation. In contrast to the case of excited RB, solvent exchange (H 2 O to D 2 O) did not enhance FFA degradation by CNT/PMS and the pH- and substrate-dependent reactivity of CNT/PMS did not reflect the selective nature of 1 O 2 . Alternatively,…

Complex and organic-rich solid substrates such as sludge and soil have been shown to be contaminated by microplastics; however, methods for extracting plastic particles have not yet been systemically tested or standardized. This study investigated four main protocols for the removal of organic material during analysis of microplastics from complex solid matrices: oxidation using H 2 O 2, Fenton’s reagent, and alkaline digestion with NaOH and KOH. Eight common polymer types were used to assess the influence of reagent exposure on particle integrity. Organic matter removal efficiencies were established for test sludge and soil samples. Fenton’s reagent was identified as the optimum protocol. All other methods showed signs of particle degradation or resulted in an insufficient reduction in organic matter content. A further validation procedure revealed high microplastic extraction efficiencies for particles with different morphologies. This confirmed the suitability of Fenton’s reagent for use in conjunction with density separation for extracting microplastics. This approach affords…

Herein, we proposed a new peroxymonosulfate (PMS) activation system employing the Fe(III) doped g-C 3 N 4 (CNF) as catalyst. Quite different from traditional sulfate radical-based advanced oxidation processes (SR-AOPs), the PMS/CNF system was capable of selectively degrading phenolic compounds (e.g., p -chlorophenol, 4-CP) in a wide pH range (3–9) via nonradical pathway. The generated singlet oxygen ( 1 O 2 ) in the PMS/CNF3 (3.46 wt % Fe) system played negligible role in removing 4-CP, and high-valent iron-oxo species fixated in the nitrogen pots of g-C 3 N 4 (≡Fe V ═O) was proposed as the dominant reactive species by using dimethyl sulfoxide as a probe compound. The mechanism was hypothesized that PMS was first bound to the Fe(III)-N moieties to generate ≡Fe V ═O, which effectively reacted with 4-CP via electron transfer. GC-MS analysis indicated that 4-chlorocatechol and 1,4-benzoquinone were the major intermediates, which could be further degraded to carboxylates. The kinetic results suggested that the formation of ≡Fe V ═O was proportional to the dosages of PMS and CNF3 under…

Biochar is the carbon-rich product of the pyrolysis of biomass under oxygen-limited conditions, and it has received increasing attention due to its multiple functions in the fields of climate change mitigation, sustainable agriculture, environmental control, and novel materials. To design a "smart" biochar for environmentally sustainable applications, one must understand recent advances in biochar molecular structures and explore potential applications to generalize upon structure-application relationships. In this review, multiple and multilevel structures of biochars are interpreted based on their elemental compositions, phase components, surface properties, and molecular structures. Applications such as carbon fixators, fertilizers, sorbents, and carbon-based materials are highlighted based on the biochar multilevel structures as well as their structure-application relationships. Further studies are suggested for more detailed biochar structural analysis and separation and for the combination of macroscopic and microscopic information to develop a higher-level biochar structural…

Peroxymonosulfate (HSO 5 – and PMS) is an optional bulk oxidant in advanced oxidation processes (AOPs) for treating wastewaters. Normally, PMS is activated by the input of energy or reducing agent to generate sulfate or hydroxyl radicals or both. This study shows that PMS without explicit activation undergoes direct reaction with a variety of compounds, including antibiotics, pharmaceuticals, phenolics, and commonly used singlet-oxygen ( 1 O 2 ) traps and quenchers, specifically furfuryl alcohol (FFA), azide, and histidine. Reaction time frames varied from minutes to a few hours at pH 9. With the use of a test compound with intermediate reactivity (FFA), electron paramagnetic resonance (EPR) and scavenging experiments ruled out sulfate and hydroxyl radicals. Although 1 O 2 was detected by EPR and is produced stoichiometrically through PMS self-decomposition, 1 O 2 plays only a minor role due to its efficient quenching by water, as confirmed by experiments manipulating the 1 O 2 formation rate (addition of H 2 O 2 ) or lifetime (deuterium solvent isotope effect). Direct reactions…

It is well documented that the traditional Fenton reagent (i.e., the combination of Fe(II) and H 2 O 2 ) produces hydroxyl radical ( • OH) under acidic conditions, while at near-neutral pH the reactive intermediate converts to ferryl ion (Fe(IV)) that can oxidize sulfoxides to produce corresponding sulfones, markedly differing from their • OH-induced products. However, it remains unclear whether Fe(IV) is generated in the Fe(II) activated peroxydisulfate (PDS) process, where sulfate radical (SO 4 •– ) is long recognized as the dominant intermediate in literature. Here we demonstrated that SO 4 •– oxidized methyl phenyl sulfoxide (PMSO, a model sulfoxide) to produce biphenyl compounds rather than methyl phenyl sulfone (PMSO 2 ). Interestingly, the formation of PMSO 2 was observed when PMSO was treated by the Fe(II)/PDS system over a wide pH range, and the yields of PMSO 2 were quantified to be ∼100% at acidic pH 3–5. The identification of Fe(IV) in the Fe(II)/PDS system could also reasonably explain the literature results on alcohol scavenging effect and ESR spectra analysis.…

Chemical oxidants have been applied in water treatment for more than a century, first as disinfectants and later to abate inorganic and organic contaminants. The challenge of oxidative abatement of organic micropollutants is the formation of transformation products with unknown (eco)toxicological consequences. Four aspects need to be considered for oxidative micropollutant abatement: (i) Reaction kinetics, controlling the efficiency of the process, (ii) mechanisms of transformation product formation, (iii) extent of formation of disinfection byproducts from the matrix, (iv) oxidation induced biological effects, resulting from transformation products and/or disinfection byproducts. It is impossible to test all the thousands of organic micropollutants in the urban water cycle experimentally to assess potential adverse outcomes of an oxidation. Rather, we need multidisciplinary and automated knowledge-based systems, which couple predictions of kinetics, transformation and disinfection byproducts and their toxicological consequences to assess the overall benefits of oxidation processes.…

Driven by increasingly stringent restrictions on long-chain per- and polyfluoroalkyl substances (PFASs), novel fluorinated compounds have emerged on the market. Here we report on the occurrences of several perfluoroalkyl ether carboxylic and sulfonic acids (PFECAs and PFESAs), including hexafluoropropylene oxide dimer and trimer acids (HFPO-DA and HFPO-TA), ammonium 4,8-dioxa-3 H-perfluorononanoate (ADONA), chlorinated polyfluorinated ether sulfonic acid (6:2 Cl-PFESA), and its hydrogen-substituted analogue (6:2 H-PFESA) in surface waters from China ( n = 106), the United States ( n = 12), the United Kingdom ( n = 6), Sweden ( n = 10), Germany ( n = 14), The Netherlands ( n = 6), and Korea ( n = 6). Results showed that HFPO-DA, HFPO-TA, and 6:2 Cl-PFESA (median = 0.95, 0.21, and 0.31 ng/L, respectively) were frequently detected in all countries, indicating ubiquitous dispersal and distribution in global surface waters. The presence of 6:2 H-PFESA was widely detected in China (detection rate > 95%) but not in any other country. Only trace levels of ADONA (0.013-1.5 ng/L) were…

Plastic waste pollution is a global environmental problem which could be addressed by biodegradable plastics. The latter are blended together to achieve commercially functional properties, but the environmental fate of these blends is unknown. We have tested neat polymers, polylactic acid (PLA), polyhydroxybutyrate, polyhydroxyoctanoate, poly(butylene succinate), thermoplastic starch, polycaprolactone (PCL), and blends thereof for biodegradation across seven managed and unmanaged environments. PLA is one of the world's best-selling biodegradable plastics, but it is not home compostable. We show here that PLA when blended with PCL becomes home compostable. We also demonstrate that the majority of the tested bioplastics and their blends degrade by thermophilic anaerobic digestion with high biogas output, but degradation times are 3-6 times longer than the retention times in commercial plants. While some polymers and their blends showed good biodegradation in soil and water, the majority of polymers and their blends tested in this study failed to achieve ISO and ASTM biodegradation…

Oxygen-doped graphitic carbon nitride (O–CN) was fabricated via a facile thermal polymerization method using urea and oxalic acid dihydrate as the graphitic carbon nitride precursor and oxygen source, respectively. Experimental and theoretical results revealed that oxygen doping preferentially occurred on the two-coordinated nitrogen positions, which create the formation of low and high electron density areas resulting in the electronic structure modulation of O–CN. As a result, the resultant O–CN exhibits enhanced catalytic activity and excellent long-term stability for peroxymonosulfate (PMS) activation toward the degradation of organic pollutants. The O–CN with modulated electronic structure enables PMS oxidation over the electron-deficient C atoms for the generation of singlet oxygen ( 1 O 2 ) and PMS reduction around the electron-rich O dopants for the formation of hydroxyl radical ( • OH) and sulfate radical (SO 4 •– ), in which 1 O 2 is the major reactive oxygen species, contributing to the selective reactivity of the O–CN/PMS system. Our findings not only propose a novel PMS…

Data on ingestion of microplastics by marine biota are quintessential for monitoring and risk assessment of microplastics in the environment. Current studies, however, portray a wide spread in results on the occurrence of microplastic ingestion, highlighting a lack of comparability of results, which might be attributed to a lack of standardization of methods. We critically review and evaluate recent microplastic ingestion studies in aquatic biota, propose a quality assessment method for such studies, and apply the assessment method to the reviewed studies. The quality assessment method uses ten criteria: sampling method and strategy, sample size, sample processing and storage, laboratory preparation, clean air conditions, negative controls, positive controls, target component, sample (pre)treatment, and polymer identification. The results of this quality assessment show a dire need for stricter quality assurance in microplastic ingestion studies. On average, studies score 8.0 out of 20 points for "completeness of information" and 0 for "reliability". Alongside the assessment method,…

A novel Fenton-like catalyst, metal organic framework MIL-100(Fe) with Fe II /Fe III mixed-valence coordinatively unsaturated iron center (CUS-MIL-100(Fe)), was synthesized, characterized, and used for the degradation of sulfamethazine (SMT). The catalytic performance of CUS-MIL-100(Fe) was investigated on the basis of various parameters, including initial pH, H 2 O 2 concentration, catalyst dosage, and initial SMT concentration. The results showed that CUS-MIL-100(Fe) could effectively degrade SMT, with almost 100% removal efficiency within 180 min (52.4% mineralization efficiency), under the reaction conditions of pH 4.0, 20 mg L –1 SMT, 6 mM H 2 O 2, and 0.5 g L –1 catalyst. Moreover, CUS-MIL-100(Fe) displayed a higher catalytic activity than that of MIL-100(Fe) for SMT degradation. Combined with the physical–chemical characterization, the enhanced catalytic activity can be ascribed to the incorporation of Fe II and Fe III CUSs (coordinatively unsaturated metal sites), the large specific surface area, as well as the formation of mesopores. Furthermore, CUS-MIL-100(Fe) exhibited a…

Recent studies have demonstrated the ability for polystyrene (PS) degradation within the gut of mealworms ( Tenebrio molitor ). To determine whether plastics may be broadly susceptible to biodegradation within mealworms, we evaluated the fate of polyethylene (PE) and mixtures (PE + PS). We find that PE biodegrades at comparable rates to PS. Mass balances indicate conversion of up 49.0 ± 1.4% of the ingested PE into a putative gas fraction (CO 2 ). The molecular weights ( M n ) of egested polymer residues decreased by 40.1 ± 8.5% in PE-fed mealworms and by 12.8 ± 3.1% in PS-fed mealworms. NMR and FTIR analyses revealed chemical modifications consistent with degradation and partial oxidation of the polymer. Mixtures likewise degraded. Our results are consistent with a nonspecific degradation mechanism. Analysis of the gut microbiome by next-generation sequencing revealed two OTUs ( Citrobacter sp. and Kosakonia sp.) strongly associated with both PE and PS as well as OTUs unique to each plastic. Our results suggest that adaptability of the mealworm gut microbiome enables degradation of…

Recycling water from municipal wastewater offers a reliable and sustainable solution to cities and regions facing shortage of water supply. Places including California and Singapore have developed advanced water reuse programs as an integral part of their water management strategy. Membrane technology, particularly reverse osmosis, has been playing a key role in producing high quality recycled water. This feature paper highlights the current status and future perspectives of advanced membrane processes to meet potable water reuse. Recent advances in membrane materials and process configurations are presented and opportunities and challenges are identified in the context of water reuse.

Plastic debris in the environment contains plasticizers, such as phthalates (PAEs), that can be released during plastic aging. Here, two common plastic materials, an insulation layer of electric cables (polyvinyl chloride, PVC-cables) and plastic garbage bag (polyethylene, PE-bags), were incubated in natural seawater under laboratory conditions, and the PAE migration to the seawater phase was studied with varying light and bacterial conditions over a 90-day time course. Free PAEs diluted in seawater were also studied for bacterial degradation. Our results showed that, within the first month of incubation, both plastic materials significantly leached out PAEs into the surrounding water. We found that di-isobutyl phthalate (DiBP) and di- n -butyl phthalate (DnBP) were the main PAEs released from the PE-bags, with the highest values of 83.4 ± 12.5 and 120.1 ± 18.0 ng g –1 of plastic, respectively. Furthermore, dimethyl phthalate (DMP) and diethyl phthalate (DEP) were the main PAEs released from PVC-cables, with mass fractions as high as 9.5 ± 1.4 and 68.9 ± 10.3 ng g –1, respectively.…

Microplastics (MPs, <5 mm) have been reported as emerging environmental contaminants, but reliable data are still lacking. We compared the two most promising techniques for MP analysis, namely, Raman and Fourier transform infrared (FTIR) spectroscopy, by analyzing MPs extracted from North Sea surface waters. Microplastics >500 μm were visually sorted and manually analyzed by μ-Raman and attenuated total reflection (ATR)-FTIR spectroscopy. Microplastics ≤500 μm were concentrated on gold-coated filters and analyzed by automated single-particle exploration coupled to μ-Raman (ASPEx-μ-Raman) and FTIR imaging (reflection mode). The number of identified MPs >500 μm was slightly higher for μ-Raman (+23%) than ATR-FTIR analysis. Concerning MPs ≤500 μm, ASPEx-μ-Raman quantified two-times higher MP numbers but required a four-times higher analysis time compared to FTIR imaging. Because ASPEx-μ-Raman revealed far higher MP concentrations (38–2621 particles m –3 ) compared to the results of previous water studies (0–559 particles m –3 ), the environmental concentration of MPs ≤500 μm may have…

The Earth's atmosphere holds approximately 12 900 billion tons of fresh water distributed all over the world with fast replenishment. Atmospheric water harvesting is emerging as a promising strategy for clean water production in arid regions, land-locked areas, and remote communities. The water vapor sorbent is the key component for atmospheric water harvesting devices based on absorbing-releasing process. In this work, a flexible hybrid photothermal water sorbent composed of deliquescent salt and hydrogel was rationally fabricated. It possesses superior water sorption capacity even in low humidity air thanks to the deliquescent salt and maintains a solid form after it sorbs a large amount of water owing to the hydrogel platform. The harvested water could be easily released under regular sunlight via the photothermal effect, and it can be directly reused without noticeable capacity fading. An "easy-to-assemble-at-household" prototype device with 35 g of the dry hydrogel was tested outdoors under field conditions and delivered 20 g of fresh water within 2.5 h under natural sunlight.…

Nanoscale zerovalent iron (NZVI) is one of the most extensively studied nanomaterials in the fields of wastewater treatment and remediation of soil and groundwater. However, rapid oxidative transformations of NZVI can result in reduced NZVI reactivity. Indeed, the surface passivation of NZVI is considered one of the most challenging aspects in successfully applying NZVI to contaminant degradation. The oxidation of NZVI can lead to the formation of Fe II -bearing phases (e.g., Fe II O, Fe II (OH) 2, Fe II Fe III 2 O 4 ) on the NZVI surface or complete oxidation to ferric (oxyhydr)oxides (e.g., Fe III OOH). This corrosion phenomenon is dependent upon various factors including the composition of NZVI itself, the type and concentration of aqueous species, reaction time and oxic/anoxic environments. As such, the coexistence of different Fe oxidation states on NZVI surfaces may also, in some instances, provide a unique reactive microenvironment to promote the adsorption of contaminants and their subsequent transformation via redox reactions. Thus, an understanding of passivation…

In support of international efforts to reduce mercury (Hg) exposure in humans and wildlife, this paper reviews the literature concerning global Hg emissions, cycling and fate, and presents revised global and oceanic Hg budgets for the 2018 United Nations Global Mercury Assessment. We assessed two competing scenarios about the impacts of 16th - late 19th century New World silver (Ag) mining, which may be the largest human source of atmospheric Hg in history. Consideration of Ag ore geochemistry, historical documents on Hg use, and comparison of the scenarios against atmospheric Hg patterns in environmental archives, strongly support a "low mining emission" scenario. Building upon this scenario and other published work, the revised global budget estimates human activities including recycled legacy emissions have increased current atmospheric Hg concentrations by about 450% above natural levels (prevailing before 1450 AD). Current anthropogenic emissions to air are 2.5 ± 0.5 kt/y. The increase in atmospheric Hg concentrations has driven a ∼ 300% average increase in deposition, and a…

Conventional thin-film composite (TFC) membranes suffer from the trade-off relationship between permeability and selectivity, known as the “upper bound”. In this work, we report a high performance thin-film composite membrane prepared on a tannic acid (TA)-Fe nanoscaffold (TFC n ) to overcome such upper bound. Specifically, a TA-Fe nanoscaffold was first coated onto a polysulfone substrate, followed by performing an interfacial polymerization reaction between trimesoyl chloride (TMC) and piperazine (PIP). The TA-Fe nanoscaffold enhanced the uptake of amine monomers and provided a platform for their controlled release. The smaller surface pore size of the TA-Fe coated substrate further eliminated the intrusion of polyamide into the substrate pores. The resulting membrane TFC n showed a water permeability of 19.6 ± 0.5 L m 2– h –1 bar –1, which was an order of magnitude higher than that of control TFC membrane (2.2 ± 0.3 L m –2 h –1 bar –1 ). The formation of a more order polyamide rejection layer also significantly enhanced salt rejection (e.g., NaCl, MgCl 2, Na 2 SO 4, and MgSO 4 )…

Conductive materials (CM) have been extensively reported to enhance methane production in anaerobic digestion processes. The occurrence of direct interspecies electron transfer (DIET) in microbial communities, as an alternative or complementary to indirect electron transfer (via hydrogen or formate), is the main explanation given to justify the improvement of methane production. Not disregarding that DIET can be promoted in the presence of certain CM, it surely does not explain all the reported observations. In fact, in methanogenic environments DIET was only unequivocally demonstrated in cocultures of Geobacter metallireducens with Methanosaeta harundinacea or Methanosarcina barkeri and frequently Geobacter sp. are not detected in improved methane production driven systems. Furthermore, conductive carbon nanotubes were shown to accelerate the activity of methanogens growing in pure cultures, where DIET is not expected to occur, and hydrogenotrophic activity is ubiquitous in full-scale anaerobic digesters treating for example brewery wastewaters, indicating that interspecies…

Anthropogenic nutrient overenrichment, coupled with rising temperatures, and an increasing frequency of extreme hydrologic events (storms and droughts) are accelerating eutrophication and promoting the expansion of harmful algal blooms (HABs) across the freshwater-to-marine continuum. All HABs-with a focus here on cyanobacterial blooms-pose serious consequences for water supplies, fisheries, recreational uses, tourism, and property values. As nutrient loads grow in watersheds, they begin to compound the effects of legacy stores. This has led to a paradigm shift in our understanding of how nutrients control eutrophication and blooms. Phosphorus (P) reductions have been traditionally prescribed exclusively for freshwater systems, while nitrogen (N) reductions were mainly stressed for brackish and coastal waters. However, because most systems are hydrologically interconnected, single nutrient (e.g., P only) reductions upstream may not necessarily reduce HAB impacts downstream. Reducing both N and P inputs is the only viable nutrient management solution for long-term control of HABs…

Stocks of virgin-mined materials utilized in linear economic flows continue to present enormous challenges. E-waste is one of the fastest growing waste streams, and threatens to grow into a global problem of unmanageable proportions. An effective form of management of resource recycling and environmental improvement is available, in the form of extraction and purification of precious metals taken from waste streams, in a process known as urban mining. In this work, we demonstrate utilizing real cost data from e-waste processors in China that ingots of pure copper and gold could be recovered from e-waste streams at costs that are comparable to those encountered in virgin mining of ores. Our results are confined to the cases of copper and gold extracted and processed from e-waste streams made up of recycled TV sets, but these results indicate a trend and potential if applied across a broader range of e-waste sources and metals extracted. If these results can be extended to other metals and countries, they promise to have positive impact on waste disposal and mining activities…

Microplastics contaminate global oceans and are accumulating in sediments at levels thought sufficient to leave a permanent layer in the fossil record. Despite this, the processes that vertically transport buoyant polymers from surface waters to the benthos are poorly understood. Here we demonstrate that laboratory generated marine snows can transport microplastics of different shapes, sizes, and polymers away from the water surface and enhance their bioavailability to benthic organisms. Sinking rates of all tested microplastics increased when incorporated into snows, with large changes observed for the buoyant polymer polyethylene with an increase in sinking rate of 818 m day –1 and for denser polyamide fragments of 916 m day –1 . Incorporation into snows increased microplastic bioavailability for mussels, where uptake increased from zero to 340 microplastics individual –1 for free microplastics to up to 1.6 × 10 5 microplastics individual –1 when incorporated into snows. We therefore propose that marine snow formation and fate has the potential to play a key role in the…

While plastic pollution in marine and freshwater systems is an active area of research, there is not yet an in-depth understanding of the distributions, chemical compositions, and fates of plastics in aquatic environments. In this study, the magnitude, distribution, and common polymers of microplastic pollution in surface waters in western Lake Superior are determined. Analytical methodology, including estimates of ambient contamination during sample collection and processing, are described and employed. Microscopy, pyrolysis-gas chromatography/mass spectrometry (Pyr-GC/MS), and Fourier transform infrared spectroscopy (FTIR) were used to quantify and identify microplastic particles. In surface waters, fibers were the most frequently observed morphology, and, based upon PyGC/MS analysis, polyvinyl chloride was the most frequently observed polymer, followed by polypropylene and polyethylene. The most common polymer identified by FTIR was polyethylene. Despite the low human population in Lake Superior's watershed, microplastic particles (particularly fibers, fragments, and films) were…

The mechanisms involved in the activation of persulfate by nanosized zero-valent iron (NZVI) were elucidated and the NZVI transformation products identified. Two distinct reaction stages, in terms of the kinetics and radical formation mechanism, were found when phenol was oxidized by the persulfate/NZVI system. In the initial stage, lasting 10 min, Fe 0 (s) was consumed rapidly and sulfate radicals were produced through activation by aqueous Fe 2+ . The second stage was governed by Fe catalyzed activation in the presence of aqueous Fe 3+ and iron (oxyhydr)oxides in the NZVI shells. The second stage was 3 orders of magnitude slower than the initial stage. An electron balance showed that the sulfate radical yield per mole of persulfate was more than two times higher in the persulfate/NZVI system than in the persulfate/Fe 2+ system. Radicals were believed to be produced more efficiently in the persulfate/NZVI system because aqueous Fe 2+ was supplied slowly, preventing sulfate radicals being scavenged by excess aqueous Fe 2+ . In the second stage, the multilayered shell conducted…

A sustainable supply of clean water is essential for the development of modern society, which has become increasingly dependent on desalination technology since 96.5% of the water on Earth is salt water. Thousands of desalination plants are producing massive waste brine as byproduct, and the direct discharge of brine raises serious concerns about its ecological impact. The concept of zero liquid discharge (ZLD) desalination is regarded as the solution, but the current ZLD technologies are hampered by their intensive use of energy and high cost. In this work, a 3D cup shaped solar evaporator was fabricated to achieve ZLD desalination with high energy efficiency via solar distillation. It produces solid salt as the only byproduct and uses sunlight as the only energy source. By rationally separating the light absorbing surface from the salt precipitation surface, the light absorption of the 3D solar evaporator is no longer affected by the salt crust layer as in conventional 2D solar evaporators. Therefore, it can be operated at an extremely high salt concentration of 25 wt % without…

The greatest problem in the Fe(II)/H 2 O 2 Fenton reaction is the low production of ·OH owing to the inefficient Fe(III)/Fe(II) cycle and the low decomposition efficiency of H 2 O 2 (<30%). Herein, we report a new discovery regarding the significant co-catalytic effect of WS 2 on the decomposition of H 2 O 2 in a photoassisted Fe(II)/H 2 O 2 Fenton system. With the help of WS 2 co-catalytic effect, the H 2 O 2 decomposition efficiency can be increased from 22.9% to 60.1%, such that minimal concentrations of H 2 O 2 (0.4 mmol/L) and Fe 2+ (0.14 mmol/L) are necessary for the standard Fenton reaction. Interestingly, the co-catalytic Fenton strategy can be applied to the simultaneous oxidation of phenol (10 mg/L) and reduction of Cr(VI) (40 mg/L), and the corresponding degradation and reduction rates can reach up to 80.9% and 90.9%, respectively, which are much higher than the conventional Fenton reaction (52.0% and 31.0%). We found that the expose reductive W 4+ active sites on the surface of WS 2 can greatly accelerate the rate-limiting step of Fe 3+ /Fe 2+ conversion, which plays the…

Previous studies have identified microplastics (MPs) in commercial table salts but could not exactly address the origin of the MPs because of several limitations. The present study is based on the hypothesis that commercial sea salts can act as an indicator of MP pollution in the surrounding environment unless the MPs are filtered out during the manufacturing process. A total of 39 different salt brands produced at geospatially different sites, including 28 sea salt brands from 16 countries/regions on six continents, were investigated. A wide range of MP content (in number of MPs per kg of salt; n/kg) was found: 0–1674 n/kg (excluding one outlier of 13 629 n/kg) in sea salts, 0–148 n/kg in rock salt, and 28–462 n/kg in lake salt. Relatively high MP content was identified in sea salts produced in Asian countries/regions. The abundance of MPs in unrefined sea salts ( n = 25) exhibited significant linear correlations with plastic emissions from worldwide rivers ( r 2 = 0.33; p = 0.003) and with the MP pollution levels in surrounding seawater ( r 2 = 0.46; p = 0.021) in the published…

Abstract Previous studies of uptake and effects of nanoplastics by marine organisms have been conducted at what may be unrealistically high concentrations. This is a consequence of the analytical challenges in tracking plastic particles in organisms at environmentally relevant concentrations and highlights the need for new approaches. Here, we present pulse exposures of 14C-radiolabeled nanopolystyrene to a commercially important mollusk, Pecten maximus, at what have been predicted to be environmentally relevant concentrations (<15 μg L–1). Uptake was rapid and was greater for 24 nm than for 250 nm particles. After 6 h, autoradiography showed accumulation of 250 nm nanoplastics in the intestine, while 24 nm particles were dispersed throughout the whole-body, possibly indicating some translocation across epithelial membranes. However, depuration was also relatively rapid for both sizes; 24 nm particles were no longer detectable after 14 days, although some 250 nm particles were still detectable after 48 days. Particle size thus apparently influenced the biokinetics and suggests a…

Although using anammox communities for efficient wastewater treatment has attracted much attention, the pure anammox bacteria are difficult to obtain, and the potential roles of symbiotic bacteria in anammox performance are still elusive. Here, we combined long-term reactor operation, genome-centered metagenomics, community functional structure, and metabolic pathway reconstruction to reveal multiple potential cross-feedings during anammox reactor start-up according to the 37 recovered metagenome-assembled genomes (MAGs). We found Armatimonadetes and Proteobacteria could contribute the secondary metabolites molybdopterin cofactor and folate for anammox bacteria to benefit their activity and growth. Chloroflexi-affiliated bacteria encoded the function of biosynthesizing exopolysaccharides for anammox consortium aggregation, based on the partial nucleotide sugars produced by anammox bacteria. Chlorobi-affiliated bacteria had the ability to degrade extracellular proteins produced by anammox bacteria to amino acids to affect consortium aggregation. Additionally, the…

Chemical products are ubiquitous in modern society. The chemical sector is the largest industrial energy consumer and the third largest industrial emitter of carbon dioxide. The current portfolio of mitigation options for the chemical sector emphasizes upstream "supply side" solutions, whereas downstream mitigation options, such as material efficiency, are given comparatively short shrift. Key reasons for this are the scarcity of data on the sector's material flows, and the highly intertwined nature of its complex supply chains. We provide the most up to date, comprehensive and transparent data set available publicly, on virgin production routes in the chemical sector: from fossil fuel feedstocks to chemical products. We map global mass flows for the year 2013 through a complex network of transformation processes, and by taking account of secondary reactants and by-products, we maintain a full mass balance throughout. The resulting data set partially addresses the dearth of publicly available information on the chemical sector's supply chain, and can be used to prioritise downstream…

Although the Fe(VI)–sulfite process has shown great potential for the rapid removal of organic contaminants, the major active oxidants (Fe(IV)/Fe(V) versus SO 4 •– / • OH) involved in this process are still under debate. By employing sparingly soluble CaSO 3 as a slow-releasing source of SO 3 2–, this study evaluated the oxidation performance of the Fe(VI)–CaSO 3 process and identified the active oxidants involved in this process. The process exhibited efficient oxidation of a variety of compounds, including antibiotics, pharmaceuticals, and pesticides, at rates that were 6.1–173.7-fold faster than those measured for Fe(VI) alone, depending on pH, CaSO 3 dosage, and the properties of organic contaminants. Many lines of evidence verified that neither SO 4 •– nor • OH was the active species in the Fe(VI)–CaSO 3 process. The accelerating effect of CaSO 3 was ascribed to the direct generation of Fe(IV)/Fe(V) species from the reaction of Fe(VI) with soluble SO 3 2– via one-electron steps as well as the indirect generation of Fe(IV)/Fe(V) species from the self-decay of Fe(VI) and Fe(VI)…

Transition metal (cerium and cobalt) doped γ-MnO 2 (M-γ-MnO 2, where M represents Ce, Co) catalysts were successfully synthesized and characterized. Cerium-doped γ-MnO 2 materials showed ozone (O 3 ) conversion of 96% for 40 ppm of O 3 under relative humidity (RH) of 65% and space velocity of 840 L g –1 h –1 after 6 h at room temperature, which is far superior to the performance of the Co-γ-MnO 2 (55%) and γ-MnO 2 (38%) catalysts. Under space velocity of 840 L g –1 h –1, the conversion of ozone over the Ce-γ-MnO 2 catalyst under RH = 65% and dry conditions within 96 h was 60% and 100%, respectively, indicating that it is a promising material for ozone decomposition. XRD and HRTEM data suggested that Ce-γ-MnO 2 formed mixed crystals consisting of α-MnO 2 and γ-MnO 2 with specific surface area increased from 74 m 2 /g to 120 m 2 /g compared to undoped γ-MnO 2, thus more surface defects were introduced. H 2 -TPR, O 2 -TPD, XPS, Raman, and EXAFS confirmed that Ce-γ-MnO 2 exhibited more surface oxygen vacancies and surface defects, which play a key role during the decomposition of ozone.…

The long satellite aerosol data record enables assessments of historical PM 2.5 level in regions where routine PM 2.5 monitoring began only recently. However, most previous models reported decreased prediction accuracy when predicting PM 2.5 levels outside the model-training period. In this study, we proposed an ensemble machine learning approach that provided reliable PM 2.5 hindcast capabilities. The missing satellite data were first filled by multiple imputation. Then the modeling domain, China, was divided into seven regions using a spatial clustering method to control for unobserved spatial heterogeneity. A set of machine learning models including random forest, generalized additive model, and extreme gradient boosting were trained in each region separately. Finally, a generalized additive ensemble model was developed to combine predictions from different algorithms. The ensemble prediction characterized the spatiotemporal distribution of daily PM 2.5 well with the cross-validation (CV) R 2 (RMSE) of 0.79 (21 μg/m 3 ). The cluster-based subregion models outperformed national…

Abstract Despite its emerging significant public health concern, the presence of antibiotic resistance genes (ARGs) in urban air has not received significant attention. Here, we profiled relative abundances (as a fraction, normalized by 16S rRNA gene) of 30 ARG subtypes resistant to seven common classes of antibiotics, which are quinolones, β-lactams, macrolides, tetracyclines, sulfonamides, aminoglycosides, and vancomycins, in ambient total particulate matter (PM) using a novel protocol across 19 world cities. In addition, their longitudinal changes in PM2.5 samples in Xi’an, China as an example were also studied. Geographically, the ARGs were detected to vary by nearly 100-fold in their abundances, for example, from 0.07 (Bandung, Indonesia) to 5.6 (San Francisco, USA). The β-lactam resistance gene blaTEM was found to be most abundant, seconded by quinolone resistance gene qepA; and their corresponding relative abundances have increased by 178% and 26%, respectively, from 2004 to 2014 in Xi’an. Independent of cities, gene network analysis indicates that airborne ARGs were…

Although reduction of highly mobile U(VI) to less soluble U(IV) has been long considered an effective approach to in situ environmental remediation of uranium, candidate reducing agents are largely limited to Fe-based materials and microbials. The importance of titanium-containing compounds in natural uranium ore deposits suggests a role for titanium in uranium migration. Herein, for the first time, a two-dimensional transition metal carbide, Ti 2 CT x, is shown to efficiently remove uranium via a sorption-reduction strategy. Batch experiments demonstrate that TiC 2 T x exhibits excellent U(VI) removal over a wide pH range, with an uptake capacity of 470 mg g –1 at pH 3.0. The mechanism for U(VI) to U(IV) reduction by Ti 2 CT x was deciphered by X-ray absorption spectroscopy and diffraction and photoelectron spectroscopy. The reduced U(IV) species at low pH is identified as mononuclear with bidendate binding to the MXene substrate. At near-neutral pH, nanoparticles of the UO 2+ x phase adsorb to the substrate with some Ti 2 CT x transformed to amorphous TiO 2 . A subsequent in-depth…

Nanoscale zerovalent iron (nZVI) likely finds its application in source zone remediation. Two approaches to modify nZVI have been reported: bimetal (Fe–Me) and sulfidated nZVI (S-nZVI). However, previous research has primarily focused on enhancing particle reactivity with these two modifications under more plume-like conditions. In this study, we systematically compared the trichloroethene (TCE) dechlorination pathway, rate, and electron selectivity of Fe-Me (Me: Pd, Ni, Cu, and Ag), S-nZVI, and nZVI with excess TCE simulating source zone conditions. TCE dechlorination on Fe-Me was primarily via hydrogenolysis while that on S-nZVI and nZVI was mainly via β-elimination. The surface-area normalized TCE reduction rate ( k ′ SA ) of Fe–Pd, S-nZVI, Fe–Ni, Fe–Cu, and Fe–Ag were ∼6800-, 190-, 130-, 20-, and 8-fold greater than nZVI. All bimetallic modification enhanced the competing hydrogen evolution reaction (HER) while sulfidation inhibited HER. Fe–Cu and Fe–Ag negligibly enhanced electron utilization efficiency (ε e ) while Fe–Pd, Fe–Ni, and S-nZVI dramatically increased ε e from 2% to…

Abstract We demonstrate the fabrication of a loose, negatively charged nanofiltration (NF) membrane with tailored selectivity for the removal of perfluoroalkyl substances with reduced scaling potential. A selective polyamide layer was fabricated on top of a poly(ether sulfone) support via interfacial polymerization of trimesoyl chloride and a mixture of piperazine and bipiperidine. Incorporating high molecular weight bipiperidine during the interfacial polymerization enables the formation of a loose, nanoporous selective layer structure. The fabricated NF membrane possessed a negative surface charge and had a pore diameter of ∼1.2 nm, much larger than a widely used commercial NF membrane (i.e., NF270 with pore diameter of ∼0.8 nm). We evaluated the performance of the fabricated NF membrane for the rejection of different salts (i.e., NaCl, CaCl2, and Na2SO4) and perfluorooctanoic acid (PFOA). The fabricated NF membrane exhibited a high retention of PFOA (∼90%) while allowing high passage of scale-forming cations (i.e., calcium). We further performed gypsum scaling experiments to…

The main objective of this study is to examine how the charge densities of four monovalent anions—fluoride (F – ), chloride (Cl – ), bromide (Br – ), and nitrate (NO 3 – )—influence their Donnan (charge) exclusion by a charged nanofiltration (NF) membrane. We systematically studied the rejection behavior of ternary ion solutions containing sodium cation (Na + ) and two of the monovalent anions as a function of the pH with a polyamide NF membrane. In the solutions containing F – and Cl – or F – and Br –, F – rejection was higher than Cl – or Br – rejection only when the solution pH was higher than 5.5, suggesting that F – (which has a higher charge density) was repelled more strongly by the negatively charged membrane. The order of change in the activation energy for the transport of the four anions through the polyamide membrane as a response to the increase of the membrane negative charge was the following: F – > Cl – > NO 3 – > Br – . This order corroborates our main hypothesis that an anion with a smaller ionic radius, and hence a higher charge density, is more affected by the…

Many different aerobic and anaerobic biological processes and treatment schemes are available for transforming organics and/or removing nitrogen from domestic wastewaters. Significant reductions in oxygen requirements and absence of a need for organics for nitrogen reduction are often indicated as advantageous for using the newer anammox organism approach for nitrogen removal rather than the traditional nitrification/denitrification method, the most common one in use today. However, treatment schemes differ, and there are some in which such suggested advantages may not hold. When nitrification/denitrification is used, an anoxic tank is now commonly used first and the nitrate formed by nitrification later is recycled back to that tank for oxidation of wastewater organics. This greatly reduces oxygen requirements and the need for adding organics. So when are such claims correct and when not? What factors in wastewater composition, regulatory requirements, and treatment flow sheet alter which treatment process is best to use? As an aid in making such judgments under different…

Abstract Now that microplastics have been detected in lakes, rivers, and estuaries all over the globe, evaluating their effects on biota has become an urgent research priority. This is the first study that aims at determining the effect thresholds for a battery of six freshwater benthic macroinvertebrates with different species traits, using a wide range of microplastic concentrations. Standardized 28 days single species bioassays were performed under environmentally relevant exposure conditions using polystyrene microplastics (20–500 μm) mixed with sediment at concentrations ranging from 0 to 40% sediment dry weight (dw). Microplastics caused no effects on the survival of Gammarus pulex, Hyalella azteca, Asellus aquaticus, Sphaerium corneum, and Tubifex spp. and no effects were found on the reproduction of Lumbriculus variegatus. No significant differences in growth were found for H. azteca, A. aquaticus, S. corneum, L. variegatus, and Tubifex spp. However, G. pulex showed a significant reduction in growth (EC10 = 1.07% sediment dw) and microplastic uptake was proportional with…

The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δ 13 C-dissolved organic carbon (DOC) and Δ 14 C-DOC), optical properties (absorbance and fluorescence), and molecular composition (ultrahigh resolution mass spectrometry). Isolates encompassed end-members of allochthonous and autochthonous DOM from sites across the United States, the Pacific Ocean, and Antarctic lakes. Modern Δ 14 C-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA 254 ), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δ 13 C-DOC and optical properties reflecting autochthonous end-members were positively correlated to more aliphatic compounds. Furthermore, the two sets of autochthonous end-members (Pacific…

Using a bipolymer system consisting of polyvinylpyrrolidone (PVP) and poly(vinylidene fluoride) (PVDF), P25-TiO 2 was immobilized into thin film mats of porous electrospun fibers. Pores were introduced by dissolving sacrificial PVP to increase surface area and enhance access to TiO 2 . The highest photocatalytic activity was achieved using a PVDF:PVP weight ratio of 2:1. Methylene blue (MB) was used to visualize contaminant removal, assess the sorption capacity (5.93 ± 0.23 mg/g) and demonstrate stable removal kinetics ( k MB > 0.045 min –1 ) under UVA irradiation (3.64 × 10 –9 einstein/cm 2 /s) over 10 cycles. Treatment was also accomplished via sequential MB sorption in the dark and subsequent photocatalytic degradation under UVA irradiation, to illustrate that these processes could be uncoupled to overcome limited light penetration. The photocatalytic mat degraded bisphenol A and 17α-ethynylestradiol in secondary wastewater effluent (17 mg TOC/L), and (relative to TiO 2 slurry) immobilization of TiO 2 in the mat mitigated performance inhibition by co-occurring organics that…

This is the first survey to investigate the vertical distribution and composition of microplastics >20 μm at the surface (0–0.2 m; bulk sample) and in the water column (3–58 m depth; pump) of six semi-enclosed bays and two nearshore areas of South Korea. The average microplastic abundance of 41 stations at all sampling depths was 871 particles/m 3, and the microplastic abundance near urban areas (1051 particles/m 3 ) was significantly higher than that near rural areas (560 particles/m 3 ). Although the average microplastic abundances in the midcolumn (423 particles/m 3 ) and bottom water (394 particles/m 3 ) were approximately 4 times lower than that of surface water (1736 particles/m 3 ), microplastics prevailed throughout the water column in concentrations of 10–2000 particles/m 3 . The average sizes of fragment and fiber type microplastics were 197 and 752 μm, respectively. Although the polymer composition differed by depth depending on the particle size and density, polypropylene and polyethylene predominated throughout the water column regardless of their low density and…

Through controlling the phase transformation and chromium species under hydrothermal condition, the Cr(VI) was extracted fully from hazardous Cr(VI)-containing gypsum sludge, with a very high efficiency of more than 99.5%. Scanning transmission electron microscopy, X-ray absorption fine structure, and density functional theory calculation results revealed that the dissolution-recrystallization of CaSO 4 ·2H 2 O into CaSO 4 was the key factor to fully release the encapsulated Cr(VI). Moreover, the mineralizer (persulfate salt) provided H + and SO 4 2– ions, the former made an acidic condition to transform the released CrO 4 2– into the specie (Cr 2 O 7 2– ) with less similarity to SO 4 2–, which further prevented the recombination of the released Cr(VI) with gypsum; and the latter was essential to accelerate crystal growth of calcium sulfate so as to enhance Cr(VI) extraction. This work would provide an instructive guidance to fully extract heavy metals from hazardous solid wastes via the control of crystal transformation and the pollutant species.