Enhancing the Thermal Mineralization of Perfluorooctanesulfonate on Granular Activated Carbon Using Alkali and Alkaline-Earth Metal Additives.

Thermal treatment has emerged as a promising approach for either the end-of-life treatment or regeneration of granular activated carbon (GAC) contaminated with per- and polyfluoroalkyl substances (PFAS). However, its effectiveness has been limited by the requirement for high temperatures, the generation of products of incomplete destruction, and the necessity to scrub HF in the flue gas. This study investigates the use of common alkali and alkaline-earth metal additives to enhance the mineralization of perfluorooctanesulfonate (PFOS) adsorbed onto GAC. When treated at 800 °C without an additive, only 49% of PFOS was mineralized to HF. All additives tested demonstrated improved mineralization, and Ca(OH)2 had the best performance, achieving a mineralization efficiency of 98% in air or N2. Its ability to increase the reaction rate and shift the byproduct selectivity suggests that its role may be catalytic. Moreover, additives reduced HF in the flue gas by instead reacting with the additive to form inorganic fluorine (e.g., CaF2) in the starting waste material. A hypothesized reaction mechanism is proposed that involves the electron transfer from O2- defect sites of CaO to intermediates formed during the thermal decomposition of PFOS. These findings advocate for the use of additives in the thermal treatment of GAC for disposal or reuse, with the potential to reduce operating costs and mitigate the environmental impact associated with incinerating PFAS-laden wastes.

Do Surface Charges on Polymeric Filters and Airborne Particles Control the Removal of Nanoscale Aerosols by Polymeric Facial Masks?

The emergence of facial masks as a critical health intervention to prevent the spread of airborne disease and protect from occupational nanomaterial exposure highlights the need for fundamental insights into the interaction of nanoparticles (<200 nm) with modern polymeric mask filter materials. While most research focuses on the filtration efficiency of airborne particles by facial masks based on pore sizes, pressure drop, or humidity, only a few studies focus on the importance of aerosol surface charge versus filter surface charge and their role in the net particle filtration efficiency of mask filters. In this study, experiments were conducted to assess mask filter filtration efficiency using positively and negatively charged polystyrene particles (150 nm) as challenge aerosols at varying humidity levels. Commercial masks with surface potential (Ψf) in the range of -10 V to -800 V were measured by an electrostatic voltmeter and used for testing. Results show that the mask filtration efficiency is highly dependent on the mask surface potential as well as the charge on the challenge aerosol, ranging from 60% to 98%. Eliminating the surface charge results in a maximum 43% decrease in filtration efficiency, emphasizing the importance of electrostatic charge interactions during the particle capture process. Moreover, increased humidity can decrease the surface charge on filters, thereby decreasing the mask filtration efficiency. The knowledge gained from this study provides insight into the critical role of electrostatic attraction in nanoparticle capture mechanisms and benefits future occupational and environmental health studies.

Seasonal atmospheric water harvesting yield and water quality using electric-powered desiccant and compressor dehumidifiers.

Atmospheric water harvesting (AWH) is an emerging technology for decentralized water supply and is proving to be viable for use in emergencies, military deployment, and sustainable industries. The atmosphere is a freshwater reservoir that contains 12,900 km3 of water, 6-fold more than the volume of global rivers. Dehumidification water harvesting technologies can be powered by solar, wind, or electric sources. Compressor/refrigerant-based dehumidifiers operate via dew point condensation and provide a cold surface upon which water vapor can condense. Conversely, desiccant-based technologies saturate water vapor using a sorbent that is then heated, and the supersaturated water vapor condenses on a surface when interacting with cooler ambient process air. This work compares productivity, energy consumption, efficiency, cost and quality of water produced of two water-harvesting mechanisms. Electric-powered compressor and desiccant dehumidifiers were operated outdoors for more than one year in the arid southwestern USA, where temperatures ranged from 3.1 to 43.7 °C and relative humidity (RH) ranged from 6 to 85%. The compressor system harvested >2-fold more water than the desiccant system when average RH during the run cycle was >30%, average temperature was >20 °C, and average dew point temperature was >5 °C. Desiccant systems performed more favorably when average RH during the run cycle was <30%, average temperature was <20 °C, and average dew point temperature was <5 °C. Water collected by compressor-based technologies had conductivity up to 180 µS/cm, turbidity up to 190 NTU, and aluminum, iron and manganese near or above the US EPA secondary drinking water standard. Dissolved organic carbon (DOC) averaged <2 mg C/L but ranged up to 12 mg C/L. Water collected by desiccant-based technologies had significantly lower conductivity, metals, and turbidity, and DOC was always <6 mg/L. Aldehydes such as formaldehyde and acetaldehyde and carboxylic acids such as formic acid and acetic acid were primary contributors to DOC. The differences in harvested water quality were attributed to differences in the condensation method between compressor and desiccant AWH technologies. Multiple strategies could be employed to prevent these volatile organic compounds (VOCs) from contributing to DOC in harvested water, such as pretreating air to remove VOCs or post-treating DOC in harvested liquid water.

Calibration of Low-Cost NO2 Sensors through Environmental Factor Correction.

Low-cost air quality sensors (LCSs) have become more widespread due to their low cost and increased capabilities; however, to supplement more traditional air quality networks, the performance of these LCSs needs to be validated. This study focused on NO2 measurements from eight Clarity Node-S sensors and used various environmental factors to calibrate the LCSs. To validate the calibration performance, we calculated the root-mean-square error (RMSE), mean absolute error (MAE), R2, and slope compared to reference measurements. Raw results from six of these sensors were comparable to those reported for other NO2 LCSs; however, two of the evaluated LCSs had RMSE values ~20 ppb higher than the other six LCSs. By applying a sensor-specific calibration that corrects for relative humidity, temperature, and ozone, this discrepancy was mitigated. In addition, this calibration improved the RMSE, MAE, R2, and slope of all eight LCS compared to the raw data. It should be noted that relatively stable environmental conditions over the course of the LCS deployment period benefited calibration performance over time. These results demonstrate the importance of developing LCS calibration models for individual sensors that consider pertinent environmental factors.

Agricultural practices drive biological loads, seasonal patterns and potential pathogens in the aerobiome of a mixed-land-use dryland.

Air carries a diverse load of particulate microscopic biological matter in suspension, either aerosolized or aggregated with dust particles, the aerobiome, which is dispersed by winds from sources to sinks. The aerobiome is known to contain microbes, including pathogens, as well as debris or small-sized propagules from plants and animals, but its variability and composition has not been studied comprehensibly. To gain a dynamic insight into the aerobiome existing over a mixed-use dryland setting, we conducted a biologically comprehensive, year-long survey of its composition and dynamics for particles less than 10 µm in diameter based on quantitative analyses of DNA content coupled to genomic sequencing. Airborne biological loads were more dependent on seasonal events than on meteorological conditions and only weakly correlated with dust loads. Core aerobiome species could be understood as a mixture of high elevation (e.g. Microbacteriaceae, Micrococcaceae, Deinococci), and local plant and soil sources (e.g. Sphingomonas, Streptomyces, Acinetobacter). Despite the mixed used of the land surrounding the sampling site, taxa that contributed to high load events were largely traceable to proximal agricultural practices like cotton and livestock farming. This included not only the predominance of specific crop plant signals over those of native vegetation, but also that of their pathogens (bacterial, viral and eukaryotic). Faecal bacterial loads were also seasonally important, possibly sourced in intensive animal husbandry or manure fertilization activity, and this microbial load was enriched in tetracycline resistance genes. The presence of the native opportunistic pathogen, Coccidioides spp., by contrast, was detected only with highly sensitive techniques, and only rarely. We conclude that agricultural activity exerts a much stronger influence that the native vegetation as a mass loss factor to the land system and as an input to dryland aerobiomes, including in the dispersal of plant, animal and human pathogens and their genetic resistance characteristics.

Effect of COVID-19 travel restrictions on Phoenix air quality after accounting for boundary layer variations.

Due to the global response to the COVID-19 pandemic, there have been a variety of policy responses that have produced a range of expected and unexpected effects on society and our surrounding environment. One widely reported result of the pandemic response is that travel restrictions have resulted in improvements in regional air quality. This study aims to determine the effect of COVID-19 related Stay at Home precautions on air quality in a metropolitan area. We specifically focus on CO, NO2, and PM10 in Maricopa County (Phoenix), Arizona, as these all contribute to local air quality concerns. The role of meteorological parameters on ambient concentrations for these pollutants was investigated by using the local planetary boundary layer height (PBH) to account for vertical mixing. Across all three sites studied, there was no uniform decrease in either CO or NO2, even when freeway traffic volume was down by ~35%. For PM10, there was a significant decrease of ~45% seen at all the sites for the period most directly impacted by local Stay at Home restrictions compared to the past two years. This indicates that different pollutants have fundamentally different behavior in the local environment and suggests that these pollutants originate from different sources.

The Nature and Oxidative Reactivity of Urban Magnetic Nanoparticle Dust Provide New Insights into Potential Neurotoxicity Studies.

The recent discovery of magnetic nanoparticles (NPs) in human brain tissue has raised concerns regarding their source and neurotoxicity. As previous studies have suggested that magnetite in urban dust may be the source, we collected urban magnetic dust and thoroughly characterized the nature of ambient urban magnetic dust particles prior to investigating their neurotoxic potential. In addition to magnetite, magnetic dust contained an abundance (∼40%) of elemental iron (Fe0). The coexistence of magnetite and elemental iron was found in magnetic dust particles of inhalable (<10 µm) and nanoscale (<200 nm) size ranges with these particles small enough to enter the human brain via the respiratory tract and olfactory bulbs. The magnetic dust also contained nonferrous water-soluble metals (particularly Cu) that can induce formation of reactive oxygen species (ROS). Previous studies used engineered pure-magnetite for in vitro ROS studies. However, while magnetite was present in all magnetic dust particles collected, engineered pure-magnetite was relatively unreactive and contributed minimally to the generation of ROS. We fill a critical knowledge gap between exposure to heterogeneous ambient iron-particles and in vitro experiments with engineered versus ambient, incidental iron-bearing nanoscale minerals. Our work points to the need to further investigate the presence and properties of magnetic NPs in respirable dust with respect to their potential role in neurodegeneration.

Germicidal Ultraviolet Light Does Not Damage or Impede Performance of N95 Masks Upon Multiple Uses.

The COVID-19 pandemic is increasing the need for personal protective equipment (PPE) worldwide, including the demand for facial masks used by healthcare workers. Disinfecting and reusing these masks may offer benefits in the short term to meet urgent demand. Germicidal ultraviolet light provides a nonchemical, easily deployable technology capable of achieving inactivation of H1N1 virus on masks. Working with N95-rated masks and nonrated surgical masks, we demonstrated that neither 254 nor 265 nm UV-C irradiation at 1 and 10 J/cm2 had adverse effects on the masks' ability to remove aerosolized virus-sized particles. Additional testing showed no change in polymer structure, morphology, or surface hydrophobicity for multiple layers in the masks and no change in pressure drop or tensile strength of the mask materials. Results were similar when applying 254 nm low-pressure UV lamps and 265 nm light-emitting diodes. On the basis of the input from healthcare workers and our findings, a treatment system and operational manual were prepared to enable treatment and reuse of N95 facial masks. Knowledge gained during this study can inform techno-economic analyses for treating and reusing masks or lifecycle assessments of options to reduce the enormous waste production of single-use PPE used in the healthcare system, especially during pandemics.

A Laboratory Assessment of 120 Air Pollutant Emissions from Biomass and Fossil Fuel Cookstoves.

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 (PM2.5) 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 PM2.5 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 PM2.5 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.

Yttrium Residues in MWCNT Enable Assessment of MWCNT Removal during Wastewater Treatment.

Many analytical techniques have limited sensitivity to quantify multi-walled carbon nanotubes (MWCNTs) at environmentally relevant exposure concentrations in wastewaters. We found that trace metals (e.g., Y, Co, Fe) used in MWCNT synthesis correlated with MWCNT concentrations. Because of low background yttrium (Y) concentrations in wastewater, Y was used to track MWCNT removal by wastewater biomass. Transmission electron microscopy (TEM) imaging and dissolution studies indicated that the residual trace metals were strongly embedded within the MWCNTs. For our specific MWCNT, Y concentration in MWCNTs was 76 µg g-1, and single particle mode inductively coupled plasma mass spectrometry (spICP-MS) was shown viable to detect Y-associated MWCNTs. The detection limit of the specific MWCNTs was 0.82 µg L-1 using Y as a surrogate, compared with >100 µg L-1 for other techniques applied for MWCNT quantification in wastewater biomass. MWCNT removal at wastewater treatment plants (WWTPs) was assessed by dosing MWCNTs (100 µg L-1) in water containing a range of biomass concentrations obtained from wastewater return activated sludge (RAS) collected from a local WWTP. Using high volume to surface area reactors (to limit artifacts of MWCNT loss due to adsorption to vessel walls) and adding 5 g L-1 of total suspended solids (TSS) of RAS (3-h mixing) reduced the MWCNT concentrations from 100 µg L-1 to 2 µg L-1. The results provide an environmentally relevant insight into the fate of MWCNTs across their end of life cycle and aid in regulatory permits that require estimates of engineered nanomaterial removal at WWTPs upon accidental release into sewers from manufacturing facilities.

Lower molecular weight fractions of PolyDADMAC coagulants disproportionately contribute to N-nitrosodimethylamine formation during water treatment.

N-nitrosodimethylamine (NDMA) is a chloramine disinfection by-product, and its formation in drinking waters can increase due to the addition of cationic polydiallyldimethylammonium chloride (polyDADMAC). PolyDADMAC is a cationic polymer added as a coagulant or coagulant aid to enhance turbidity removal during sedimentation and filtration. This paper answers two central questions to understanding the nature of the NDMA precursors in polyDADMAC. First, what is the reactivity of different molecular weight (MW) fractions of polyDADMAC with chloramines? NDMA formation potential (NDMAFP) and kinetic experiments with chloramines were conducted for non-fractionated (raw) and size-excluded fractions (<3K, 3-10K, and >10K Da.) of polyDADMAC. The lower MW fraction (<3K Da.) of polyDADMAC solutions was responsible for forming 64 ±â€¯6% of the NDMA, despite containing only 8.7 and 9.8% of the carbon or nitrogen present in the bulk polymer. The chloramine demand kinetics of the lowest MW fraction were also >2× faster than the higher MW fractions. Therefore, in a water treatment application the lower MW polyDADMAC likely contributes to most of the NDMA attributed to the use of polyDADMAC. The second question was: can 1H and 13C nuclear magnetic resonance spectroscopy (NMR) be used to characterize the molecular structures in polyDADMAC that react with chloramines? A peak for 1H NMR dimethylamine (DMA), a known low MW NDMA precursor, was found in a commercial polyDADMAC solution and decreased upon chloramination. The estimated DMA alone could not account for the observed NDMAFP, indicating the presence of other low MW precursors. Diffusion order spectroscopy (DOSY) NMR also showed multiple lower MW organics in polyDADMAC that change upon chloramination, including a 1.5× decrease in MW, suggesting chloramines cleave CC or CN bonds. These reactions may produce intermediates responsible for NDMA formation. Polymer manufacturers could use NMR to synthesize polyDADMAC with less DMA and other low MW compounds that produce NDMA upon chloramination.

Low risk posed by engineered and incidental nanoparticles in drinking water.

Natural nanoparticles (NNPs) in rivers, lakes, oceans and ground water predate humans, but engineered nanoparticles (ENPs) are emerging as potential pollutants due to increasing regulatory and public perception concerns. This Review contrasts the sources, composition and potential occurrence of NNPs (for example, two-dimensional clays, multifunctional viruses and metal oxides) and ENPs in surface water, after centralized drinking water treatment, and in tap water. While analytical detection challenges exist, ENPs are currently orders of magnitude less common than NNPs in waters that flow into drinking water treatment plants. Because such plants are designed to remove small-sized NNPs, they are also very good at removing ENPs. Consequently, ENP concentrations in tap water are extremely low and pose low risk during ingestion. However, after leaving drinking water treatment plants, corrosion by-products released from distribution pipes or in-home premise plumbing can release incidental nanoparticles into tap water. The occurrence and toxicity of incidental nanoparticles, rather than ENPs, should therefore be the focus of future research.

Size exclusion chromatography with online ICP-MS enables molecular weight fractionation of dissolved phosphorus species in water samples.

Phosphorus (P) is an important and often limiting element in terrestrial and aquatic ecosystem. A lack of understanding of its distribution and structures in the environment limits the design of effective P mitigation and recovery approaches. Here we developed a robust method employing size exclusion chromatography (SEC) coupled to an ICP-MS to determine the molecular weight (MW) distribution of P in environmental samples. The most abundant fraction of P varied widely in different environmental samples: (i) orthophosphate was the dominant fraction (93-100%) in one lake, two aerosols and DOC isolate samples, (ii) species of 400-600 Da range were abundant (74-100%) in two surface waters, and (iii) species of 150-350 Da range were abundant in wastewater effluents. SEC-DOC of the aqueous samples using a similar SEC column showed overlapping peaks for the 400-600 Da species in two surface waters, and for >20 kDa species in the effluents, suggesting that these fractions are likely associated with organic matter. The MW resolution and performance of SEC-ICP-MS agreed well with the time integrated results obtained using conventional ultrafiltration method. Results show that SEC in combination with ICP-MS and DOC has the potential to be a powerful and easy-to-use method in identifying unknown fractions of P in the environment.

Detection and Sizing of Ti-Containing Particles in Recreational Waters Using Single Particle ICP-MS.

Single particle inductively coupled plasma mass spectrometry (spICP-MS) was used to detect Ti-containing particles in heavily-used bathing areas of a river (Salt River) and five swimming pools. Ti-containing particle concentrations in swimming pools ranged from 2.8 × 103 to 4.4 × 103 particles/mL and were an order of magnitude lower than those detected in the Salt River. Measurements from the Salt River showed an 80% increase in Ti-containing particle concentration over baseline concentration during peak recreational activity (at 16:00 h) in the river. Cloud point extraction followed by transmission electron microscopy with energy dispersive X-ray analysis confirmed presence of aggregated TiO2 particles in river samples, showing morphological similarity to particles present in an over-the-counter sunscreen product. The maximum particle mass concentration detected in a sample from the Salt River (659 ng/L) is only slightly lower than the predicted no effect concentration for TiO2 to aquatic organisms (< 1 µg/L).

Prospecting nanomaterials in aqueous environments by cloud-point extraction coupled with transmission electron microscopy.

Increasing application of engineered nanomaterials (ENMs) in industry and consumer products inevitably lead to their release into and impact on aquatic environments. To characterize the NMs efficiently in surface water, a fast and simple method is needed to separate and concentrate nanomaterials from the aqueous matrix without altering their shape and size. Applying cloud-point extraction (CPE) using the surfactant Triton 114 to an array of NMs (titanium dioxide, gold, silver, and silicon dioxide) with different sizes or capping agents in nanopure water resulted in extraction efficiency of 83%-107%. Additional CPE experiments were conducted to extract NMs from surface, potable, and sewage waters, and NMs enriched in the surfactant phase were characterized using transmission electron microscopy coupled with energy dispersive x-ray spectroscopy. The most abundant nanoparticles identified in surface water were silica, titanium dioxide, and iron oxide with 4-99nm diameter. The extraction efficiencies of CPE for silicon, titanium, and iron elements from environmental water samples were 51%, 15%, and 99%, respectively. This study applied CPE with TEM to enrich and analyze popular nanoparticles such as SiO2 and TiO2 from natural waters, which has not been well addressed by previous researches. Overall, CPE coupled with transmission electron microscopy (TEM) can be an effective method to characterize NMs in aqueous water samples, and further optimization will increase the extraction efficiency of NMs in complicated surface water matrix.

LC/QTOF-MS fragmentation of N-nitrosodimethylamine precursors in drinking water supplies is predictable and aids their identification.

N-Nitrosodimethylamine (NDMA) is carcinogenic in rodents and occurs in chloraminated drinking water and wastewater effluents. NDMA forms via reactions between chloramines and mostly unidentified, N-containing organic matter. We developed a mass spectrometry technique to identify NDMA precursors by analyzing 25 model compounds with LC/QTOF-MS. We searched isolates of 11 drinking water sources and 1 wastewater using a custom MATLAB® program and extracted ion chromatograms for two fragmentation patterns that were specific to the model compounds. Once a diagnostic fragment was discovered, we conducted MS/MS during a subsequent injection to confirm the precursor ion. Using non-target searches and two diagnostic fragmentation patterns, we discovered 158 potential NDMA precursors. Of these, 16 were identified using accurate mass combined with fragment and retention time matches of analytical standards when available. Five of these sixteen NDMA precursors were previously unidentified in the literature, three of which were metabolites of pharmaceuticals. Except methadone, the newly identified precursors all had NDMA molar yields of less than 5%, indicating that NDMA formation could be additive from multiple compounds, each with low yield. We demonstrate that the method is applicable to other disinfection by-product precursors by predicting and verifying the fragmentation patterns for one nitrosodiethylamine precursor.

Source Identification of Coarse Particles in the Desert Southwest, USA using Positive Matrix Factorization.

The Desert Southwest Coarse Particulate Matter Study was undertaken to further our understanding of the spatial and temporal variability and sources of fine and coarse particulate matter (PM) in rural, arid, desert environments. Sampling was conducted between February 2009 and February 2010 in Pinal County, AZ near the town of Casa Grande where PM concentrations routinely exceed the U.S. National Ambient Air Quality Standards (NAAQS) for both PM10 and PM2.5. In this desert region, exceedances of the PM10 NAAQS are dominated by high coarse particle concentrations, a common occurrence in this region of the United States. This work expands on previously published measurements of PM mass and chemistry by examining the sources of fine and coarse particles and the relative contribution of each to ambient PM mass concentrations using the positive matrix factorization receptor model (Clements et al., 2014). Coarse particles within the region were apportioned to nine sources including primary biological aerosol particles (PBAPs - 25%), crustal material (20%), re-entrained road dust (11%), feedlot (11% at the site closest to a cattle feedlot), secondary particles (10%), boron-rich crustal material (9%), and transported soil (6%), with minor contributions from ammonium nitrate, and salt (considered to be NaCl). Fine particles within the region were apportioned to six sources including motor vehicles (37%), road dust (29%), lead-rich (10%), with minor contributions from brake wear, crustal material, and salt. These results can help guide local air pollution improvement strategies designed to reduce levels of PM to below the NAAQS.

Sorption and desorption of organic matter on solid-phase extraction media to isolate and identify N-nitrosodimethylamine precursors.

#x02010;Nitrosodimethylamine is mutagenic in rodents, a drinking water contaminant, and a byproduct of drinking water disinfection by chloramination. Nitrosodimethylamine precursor identification leads to their control and improved understanding of nitrosodimethylamine formation during chloramination. Mass balances on nitrosodimethylamine precursors were evaluated across solid-phase extraction cartridges and in eluates to select the best combination of solid-phase media and eluent that maximized recovery of nitrosodimethylamine precursors into a solvent amenable to time-of-flight mass spectrometry analysis. After reviewing literature and comparing various solid-phase cartridges and eluent combinations, a method was obtained to efficiently recover nitrosodimethylamine precursors. The approach with the greatest recoveries of nitrosodimethylamine precursors involved cation exchange resin loaded with water samples at pH 3 and eluted with 5% NH4 OH in methanol. This indicated that nitrosodimethylamine precursors are amines that protonate at low pH and deprotonate at high pH. Quaternary amines were irreversibly sorbed to the cation exchange cartridge and did not account for a large fraction of precursors. Overall, a median recovery of 82% for nitrosodimethylamine precursors was achieved from 11 surface waters and one wastewater. Applying this method allowed discovery of methadone as a new nitrosodimethylamine precursor in wastewater effluent and drinking water treatment plant intakes.

Potential Environmental Impacts and Antimicrobial Efficacy of Silver- and Nanosilver-Containing Textiles.

For textiles containing nanosilver, we assessed benefit (antimicrobial efficacy) in parallel with potential to release nanosilver (impact) during multiple life cycle stages. The silver loading and method of silver attachment to the textile highly influenced the silver release during washing. Multiple sequential simulated household washing experiments for fabric swatches in deionized water with or without detergent showed a range of silver release. The toxicity of washing experiment supernatants to zebrafish (Danio rerio) embryos was negligible, with the exception of the very highest Ag releases (∼1 mg/L Ag). In fact, toxicity tests indicated that residual detergent exhibited greater adverse response than the released silver. Although washing the fabrics did release silver, it did not affect their antimicrobial efficacy, as demonstrated by >99.9% inhibition of E. coli growth on the textiles, even for textiles that retained as little as 2 µg/g Ag after washing. This suggests that very little nanosilver is required to control bacterial growth in textiles. Visible light irradiation of the fabrics reduced the extent of Ag release for textiles during subsequent washings. End-of-life experiments using simulated landfill conditions showed that silver remaining on the textile is likely to continue leaching from textiles after disposal in a landfill.

Survey of food-grade silica dioxide nanomaterial occurrence, characterization, human gut impacts and fate across its lifecycle.

There is increasing recognition of the importance of transformations in nanomaterials across their lifecycle, yet few quantitative examples exist. We examined food-grade silicon dioxide (SiO2) nanomaterials from its source (bulk material providers), occurrence in food products, impacts on human gastrointestinal tract during consumption, and fate at wastewater treatment plants. Based upon XRD, XPS and TEM analysis, pure SiO2 present in multiple food-grade stock SiO2 exhibited consistent morphologies as agglomerates, ranging in size from below 100nm to >500nm, with all primary particle size in the range of 9-26nm and were most likely amorphous SiO2 based upon high resolution TEM. Ten of 14 targeted foods purchased in the USA contained SiO2 of the same morphology and size as the pristine bulk food-grade SiO2, at levels of 2 to 200mg Si per serving size. A dissolution study of pristine SiO2 showed up to 7% of the dissolution of the silica, but the un-dissolved SiO2 maintained the same morphology as the pristine SiO2. Across a realistic exposure range, pristine SiO2 exhibited adverse dose-response relationships on a cell model (microvilli) of the human gastro-intestinal tract, association onto microvilli and evidence that SiO2 lead to production of reactive oxygen species (ROS). We also observed accumulation of amorphous nano-SiO2 on bioflocs in tests using lab-cultured activated sludge and sewage sludges from a full-scale wastewater treatment plant (WWTP). Nano-scale SiO2 of the same size and morphology as pristine food-grade SiO2 was observed in raw sewage at a WWTP, but we identified non-agglomerated individual SiO2 particles with an average diameter of 21.5±4.7nm in treated effluent from the WWTP. This study demonstrates an approach to track nanomaterials from source-to-sink and establishes a baseline occurrence of nano-scale SiO2 in foods and WWTPs.