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Application of simultaneous multi-laser nanoparticle tracking analysis (NTA) to environmental water samples to investigate nonliving natural organic matter (NNOM) is introduced as an innovative method for observing particles directly in their native media. Multi-laser NTA results of particle visualization, particle number concentration, and particle size distribution elucidated particle dynamics in low and high total dissolved solids (TDS) aqueous environmental samples. A pond water sample and concentrate from a reverse osmosis (RO) treatment process (Stage 1) had 1.3 × 10 8 and 5.62 × 10 19 particles/mL, respectively, (at time = 0) after filtration at 0.45 μm. Beyond the traditional applications for this instrument, this research presents novel evidence-based investigations that probe the existence of supramolecular structures in environmental waters during turbulence or quiescence. The pond water sample exhibited time-dependent aggregation as the volume distribution shifted to greater diameter during quiescence, compared to turbulence. Disaggregation (increased numbers of particles over time) was noted in the >250 nm to <600 nm region, and aggregation of >450 nm particles was also noted in the quiescent RO concentrate sample, indicative of depletion of small particles to form larger ones. Multi-laser NTA and dynamic light scattering (DLS) capabilities were compared and contrasted. DLS and NTA are different (complementary) particle sizing techniques. DLS yielded more information about the physical hydrogel in the NNOM hierarchy whereas multi-laser NTA better characterized meta-chemical and chemical hydrogel characteristics. Operationalization of innovation-moving from fundamental investigations to application-is supported by implementing novel analytical instrumentation as we address issues involving climate change, drought, and the scarcity of potable water. Multi-laser NTA can be used as a tool to study and optimize complex water and wastewater treatment processes. Questions about water treatment efficiencies, membrane fouling, assistance of pollutant transport, and carbon capture cycles affected by NNOM will benefit from insights from multi-laser NTA., Competing Interests: Declaration of competing interest The authors do not have any conflicts of interest or other considerations that would limit publication of the manuscript. Martha J.M. Wells is a chemical consultant to Brown and Caldwell and served in that role while assisting with preparation of this manuscript., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

An observed decrease in total organic carbon (TOC) and dissolved organic carbon (DOC) concentrations following wastewater disinfection with medium pressure (MP, polychromatic) ultraviolet (UV) irradiation during wet weather flows is investigated. When antecedent rainfall in the previous 7-days was >2 in (5 cm), TOC and DOC concentrations decreased dramatically following MP-UV disinfection. Organic carbon surrogate measurements of biological oxygen demand (BOD), TOC, DOC, turbidity, UVA - 254 nm, SUVA (specific UVA), scanning UV-Visible spectra (200-600 nm), fluorescence excitation-emission matrix (EEM) spectra, and light scattering data are presented for wastewater resource recovery facility (WRRF) influent, secondary effluent (pre-UV-disinfection), and MP-UV-disinfected (final effluent) samples. TOC and DOC in wastewater influent and secondary effluent (i.e., pre-UV disinfection) correlated with antecedent rainfall conditions. The percent TOC and DOC removal through secondary treatment (i.e., from influent to effluent pre-UV) and the percent TOC and DOC removal through MP-UV disinfection (i.e., from effluent pre-UV to effluent post-UV) were compared and the latter approached 90 % through MP-UV disinfection during high antecedent rainfall conditions. Spectroscopy (UV, visible, or fluorescence) was performed on samples after filtration through 0.45 μm filters, i.e., the operationally defined DOC fraction of aquatic carbon. Scanning UV-visible spectra indicated transformation of an unidentified wastewater component into light-scattering entities regardless of antecedent rainfall conditions. The types of organic carbon (diagenetic, biogenic, or anthropogenic) and the significance of wet weather are discussed. An organic carbon contribution via infiltration and inflow was attributed as a source-of-interest in this research., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Periods of drought coupled with increasing population growth have prompted increased interest in potable water reuse in Gwinnett County, Georgia, USA. However, such inland water recycling facilities are challenged with treatment approaches where reverse osmosis (RO) membrane concentrate disposal is a barrier to implementation of potable reuse. To evaluate alternative treatment processes, testing of two side-by-side pilot systems using multi-stage ozone and biological filtration without RO was conducted to compare indirect potable reuse (IPR) to direct potable reuse (DPR). Two water sources were investigated-influent from Lake Lanier for the IPR pilot, and a blend of 25 % reclaimed water mixed with lake water (75 %) for the DPR pilot. To assess the nature of organic matter removed during potable reuse, excitation-emission matrix (EEM) fluorescence spectroscopy/PARAllel FACtor (PARAFAC) analyses were examined as a fingerprinting tool. The objectives were to determine (a) if a DPR scenario, when preceded by advanced wastewater treatment, could achieve drinking water quality comparable to IPR and (b) if water quality monitoring using EEM/PARAFAC methods could predict results for DPR and IPR water quality, comparable to parameters obtained in a supplementary study that required more expensive, time-consuming, and complicated analytical techniques. Sample scores representing relative concentrations of fluorescing organic matter derived from the EEM-PARAFAC model decreased in the order of reclaimed water > lake water > DPR pilot > IPR pilot, demonstrating that EEM/PARAFAC could distinguish between DPR and IPR water quality. An assessment of a comprehensive list of individual organic compounds (reported separately) validated that blend ratios of 25 % reclaimed water, or higher mixed with lake water (75 %) did not meet primary and secondary drinking water standards. Likewise, in this study, EEM/PARAFAC analysis demonstrated the 25 % blend did not provide drinking water quality indicating this simple, inexpensive method could be used for potable reuse monitoring., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: The authors do not have any conflicts of interest or other considerations that would limit publication of the manuscript. Martha J.M. Wells served as a chemical consultant to CDM Smith and to Brown and Caldwell while assisting with preparation of this manuscript., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Measuring the surrogate parameters total organic carbon and dissolved organic carbon (TOC/DOC) is not adequate, alone, to reveal nuances in organic character for optimizing treatment in potable water reuse. Alternatively, analyzing each organic compound contributing to the surrogate measurement is not possible. As an additional analytical tool applied between these extremes, the use of excitation-emission matrix fluorescence spectroscopy with PARAllel FACtor (EEM-PARAFAC) analysis was investigated in this research to track categories (components) or families of organic compounds during treatment in recycled water schemes. Although not all organic molecules fluoresce, many do, and fluorescence helps track their fate through water treatment processes. The sites investigated in this research were Lake Lanier, in Gwinnett County, Georgia, USA; the F. Wayne Hill Water Resources Center (FWH WRC) advanced wastewater treatment facility; and two pilot facilities operated in parallel representing the current indirect potable reuse (IPR) scheme as well as a pilot that evaluated direct potable reuse (DPR). A four-component nonnegativity PARAFAC model-elucidating protein-like (including tyrosine- and tryptophan-like fluorescence in a single component), soluble microbial product (SMP)-like, fulvic-like, and humic-like components-was fitted to the data. Each of the four components was spectrally and mathematically separated, implying that the fluorescing SMP-like component was not comprised of protein-, fulvic-, or humic-like components. PARAFAC excitation loadings with dual (double) pairs of fluorescing regions centered at the same emission wavelengths but different excitation wavelengths oriented parallel to the excitation axis and perpendicular to the emission axis were attributed to individual PARAFAC components. Significantly, the observation of PARAFAC emission loadings with multiple peaks-where the protein-like component exhibited fluorescence in both protein and fulvic/humic regions-is proposed to signify an intermolecular energy transfer (< 10 nm). Correct identification of EEM-PARAFAC components is fundamental to understanding water treatment., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: The authors do not have any conflicts of interest or other considerations that would limit publication of the manuscript. Martha J.M. Wells served as a chemical consultant to CDM Smith and to Brown and Caldwell while assisting with preparation of this manuscript., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Knowledge of the interactions between gold nanoparticles (GNPs) and dissolved organic matter (DOM) is significant in the development of detection devices for environmental sensing, studies of environmental fate and transport, and advances in antifouling water treatment membranes. The specific objective of this research was to spectroscopically investigate the fundamental interactions between citrate-stabilized gold nanoparticles (CT-GNPs) and DOM. Studies indicated that 30 and 50nm diameter GNPs promoted disaggregation of the DOM. This result-disaggregation of an environmentally important polyelectrolyte-will be quite useful regarding antifouling properties in water treatment and water-based sensing applications. Furthermore, resonance Rayleigh scattering results showed significant enhancement in the UV range which can be useful to characterize DOM and can be exploited as an analytical tool to better sense and improve our comprehension of nanomaterial interactions with environmental systems. CT-GNPs having core size diameters of 5, 10, 30, and 50nm were studied in the absence and presence of added DOM at 2 and 8 ppm at low ionic strength and near neutral pH (6.0-6.5) approximating surface water conditions. Interactions were monitored by cross-interpretation among ultraviolet (UV)-visible extinction spectroscopy, excitation-emission matrix (EEM) spectroscopy (emission and Rayleigh scattering), and dynamic light scattering (DLS). This comprehensive combination of spectroscopic analyses lends new insights into the antifouling behavior of GNPs. The CT-GNP-5 and -10 controls emitted light and aggregated. In contrast, the CT-GNP-30 and CT-GNP-50 controls scattered light intensely, but did not aggregate and did not emit light. The presence of any CT-GNP did not affect the extinction spectra of DOM, and the presence of DOM did not affect the extinction spectra of the CT-GNPs. The emission spectra (visible range) differed only slightly between calculated and actual mixtures of CT-GNP-5 or -10 with DOM, whereas emissions for mixtures of CT-GNP-30 or -50 with DOM were enhanced at the surface plasmon resonance (SPR) wavelength. The emission spectra (ultraviolet range) for protein-like constituents of DOM were quenched. Resonance Rayleigh scattering (RRS) was more intense for the CT-GNP-30 and -50 than for the CT-GNP-5 and -10 controls. Intensity-based DLS particle size distributions (PSDs) of DOM controls, CT-GNP-5 and -10nm controls, and 5- and 10nm GNP-DOM mixtures exhibited multimodal aggregation. Analyses of CT-GNP-5 and CT-GNP-10nm mixtures with DOM indicated overcoating of DOM molecules occurred in close proximity (<10nm) to GNPs, whereas similar overcoating was not supported for the CT-GNP-30 or -50 mixtures with DOM. These fundamental observations can be exploited to improve our comprehension of nanomaterial interactions with environmental systems., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The interaction of macromolecules with gold nanoparticles (GNPs) is of interest in the emerging field of biomedical and environmental detection devices. However, the physicochemical properties, including spectra, of GNPs in aqueous solution in the absence of metal-macromolecular interactions must first be considered before their activity in biological and environmental systems can be understood. The specific objective of this research was to experimentally illuminate the role of nanoparticle core size on the spectral (simultaneous consideration of extinction, emission, and scattering) versus aggregation behaviors of citrate-coated GNPs (CT-GNPs). It is difficult to find in the literature systematic simultaneous presentation of scattering, emission, and extinction spectra, including the UV range, and thus the present work will aid those who would use such particles for spectroscopic related separations or sensors. The spectroscopic behavior of CT-GNPs with different core sizes (5, 10, 30, and 50nm) was studied in ultra-pure water at pH6.0-6.5 employing UV-visible extinction, excitation-emission matrix (EEM), resonance Rayleigh scattering, and dynamic light scattering (DLS) spectroscopies. The CT-GNP-5 and CT-GNP-10 samples aggregated, absorbed light, and emitted light. In contrast, the CT-GNP-30 and CT-GNP-50 samples did not aggregate and did not emit light, but scattered light intensely. Multimodal peaks were observed in the intensity-based DLS spectra of CT-GNP-5 and CT-GNP-10 samples. Monomodal peaks in the volume-based DLS spectra overestimated particle diameters by 60% and 30% for the CT-GNP-5 and CT-GNP-10 samples, respectively, but underestimated diameters by 10% and 4% for the CT-GNP-30 and CT-GNP-50 samples. The volume-based DLS spectra indicated that dimer and trimer aggregates contributed most to the overall volume of particles in the 5- and 10-nm CT-GNPs, whereas the CT-GNP-30 and CT-GNP-50 samples did not aggregate. Here, we discuss the potential influence that differences in preparation, ionic strength, zeta potential, and conformation of adsorbed citrate anions (due to surface curvature of corona) may exert on the aggregation and spectral observations in these data. In particular, the severe surface curvature of the 5- and 10-nm GNP corona may affect the efficiency of the di-/tribasic citrate compatiblizer molecule to shield the core from interactions with light and from GNP-GNP homoaggregation., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The aggregation of humic substances and their interaction with filtration media (membranes, soils) has implications for our understanding of membrane fouling during water treatment, the facilitated transport of contaminants, and the transport of organic matter through the microbial loop. To investigate the aggregation of fulvic and humic acids in low electrolytic conductivity solutions, laboratory studies of simulated environmental water samples as well as actual environmental water samples were examined. Intensity-, volume-, and number-based particle size distributions (PSDs) were obtained by dynamic light scattering. Aggregates were categorized into three ranges, i.e., 10-100 nm, 100-1000 nm, and >1 μm. Individual biomacromolecules and the aggregates between 10 nm and 1 μm were presumed to be precursors for the formation of a large 5-μm-sized-particle. The self-assembly of the large-in-volume, few-in-number, 5-μm-sized particle was observed in real-time and occurred in unfiltered samples and in samples filtered (0.45 μm) at a nominal size one order of magnitude smaller. The supramicrometer-sized particle formed, dissipated, and spontaneously re-formed over turbulent/quiescent cycles in the presence of sodium azide indicating reversible abiotic self-assembly. Zeta potential analyses demonstrated that colloidal stability increased as concentration increased. DLS studies of the environmental water samples were comparable to those of the simulated laboratory samples. The operational range of the instrumentation used in these experiments was 0.6 nm-6 μm; therefore, aggregates larger than 6 μm may exist in these solutions., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Humic substances (HSs) are precursors for the formation of hazardous disinfection by-products (DBPs) during chlorination of water. Various surrogate parameters have been used to investigate the generation of DBPs by HS precursors and the removal of these precursors by activated carbon treatment. Dissolved organic carbon (DOC)- and ultraviolet absorbance (UVA254)-based isotherms are commonly reported and presumed to be good predictors of the trihalomethane formation potential (THMFP). However, THMFP-based isotherms are rarely published such that the three types of parameters have not been compared directly. Batch equilibrium experiments on activated carbon were used to generate constant-initial-concentration sorption isotherms for well-characterized samples obtained from the International Humic Substances Society (IHSS). HSs representing type (fulvic acid [FA], humic acid [HA]), origin (aquatic, terrestrial), and geographical source (Nordic, Suwannee, Peat, Soil) were examined at pH6 and pH9. THMFP-based isotherms were generated and compared to determine if DOC- and UVA254-based isotherms were good predictors of the THMFP. The sorption process depended on the composition of the HSs and the chemical nature of the activated carbon, both of which were influenced by pH. Activated carbon removal of THM-precursors was pH- and HS-dependent. In some instances, the THMFP existed after UVA254 was depleted., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A pilot study for the qualitative detection of methamphetamine at sites within a sewage collection system adjacent to locations suspected to harbor illegal drug activities was investigated and preliminary findings are reported. Sewage samples were collected over a time interval of four weeks using a Polar Organic Chemical Integrative Sampler (POCIS) deployed directly into the sewer line. The POCIS sorbent was extracted and analyzed via high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). Methamphetamine was found in sewage from one of three sampling sites at a concentration greater than the HPLC-MS/MS method detection limit (MDL) of 3 ng/mL. The goal of this research was to establish proof-of-concept of the feasibility for sampling and analysis using POCIS devices in the sewage collection system. The data encourage further testing and research. The ability to pinpoint the presence of methamphetamine in the sewer may in the future be used as a forensic tool in law enforcement., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Background: Dentists recommend over-the-counter medications for postoperative pain in children, and parents often make dosing errors when administering these medications. The authors compared the dosing accuracy when parents used various measuring devices and aimed to identify risk factors associated with dosing errors., Methods: The authors recruited parent-child pairs visiting the Pediatric Clinic at the College of Dentistry at The University of Tennessee Health Science Center, Memphis, and three private dental offices. The parents completed a survey and a liquid measuring exercise. The authors instructed parents to measure 5 milliliters of liquid by using a medicine cup with clear markings, a medicine cup with printed markings, a cylindrical measuring spoon and an oral syringe. For the medicine cup with printed markings, the authors placed the parents randomly into one of two groups: those receiving text-only instructions or those receiving text-pictogram instructions. The authors weighed each device before and after the measuring exercise and compared the difference in weight with a reference weight of 5 mL., Results: A total of 120 parent-child pairs participated. The results of a McNemar test revealed a significant difference in parents' ability to measure accurate doses with the various devices. The results of a Pearson χ(2) test showed no statistically significant difference between the control and study groups for dosing accuracy. The χ(2) analysis results showed no significant differences in risk factors that could be associated with dosing errors., Conclusions: Medicine cups were the devices parents reported using most frequently. Medicine cups had a higher occurrence of dosing errors when compared with the other devices. No sociodemographic factors were associated with dosing errors. Practical Implications. Dentists can improve pain management in pediatric patients by educating parents about accurate measuring devices, weight-based dosing and correct interpretation of medication dosing charts.

Sorption characteristics of eight drugs related to recreational and clandestine activity-amphetamine, cocaine, heroin, N-formyl amphetamine, N-formyl methamphetamine, methamphetamine, 3, 4-methylenedioxymethamphetamine (MDMA), and pseudoephedrine-were evaluated on selected kitchen countertop surfaces. Methanol-dampened Whatman 40 filter paper wipes were used to collect samples from eleven surfaces including alkyd resin, ceramic tiles, glass, granite, laminate, limestone, marble, quartz compac, quartz real, soap stone, and stainless steel. The filter paper wipes were analyzed by a rapid three-minute UPLC-QTOF method, following ammonium acetate buffer (pH 5.8-6.2) extraction. The average percentage recoveries after 15 h of exposure to the surface materials tested, was found to be highest for cocaine and MDMA and lowest for amphetamine and methamphetamine. Among the eleven countertop surfaces, overall recoveries for marble were observed to be the least, whereas soapstone, quartz compac and stainless steel were among the highest. Scanning electron microscopic images of the surfaces provided a unique view of surface irregularities that potentially influenced drug recovery. Aging, migration, solvent composition, and volatility were examined. The variation in recovery of drugs was attributed to four key factors: compound volatility, surface composition, surface-compound interaction, and solvent composition., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The identification and quantitation of the non-ecstasy amphetamine-type stimulants (ATSs) amphetamine and methamphetamine in lakes, rivers, wastewater treatment plant influents, effluents, and biosolids are reviewed. Neither monitoring nor reporting is required of these ATSs, which are considered emerging pollutants, but they have been identified in the environment. Amphetamine and methamphetamine enter our water supply by human excretion after legal or illegal consumption and via manufacturing in clandestine laboratories. Analytical methodology for sampling, sample preparation, separation, and detection of ATSs is discussed. Reported occurrences of ATSs in the environment and their use in municipal sewage epidemiology are noted. Future research needs that challenge applications of analytical techniques are discussed. The review focuses on research reported from 2004 to 2009., (Copyright 2010 Elsevier B.V. All rights reserved.)

The significance of this research is that it improves analytical methodology used for organic chemicals in aqueous solutions by establishing the feasibility of heterogeneous chemical derivatization at the liquid-solid interface (i.e., solid-phase reaction or solid-phase derivatization). A solid-phase derivatization method for determining chlorinated herbicide acids was developed. Solid-phase extraction was used to concentrate and retain analytes on sorbents for subsequent solid-phase derivatization. Background interferences were removed from the chromatograms by electronically subtracting the responses of blank, nonfortified analyses from spiked samples. Two extraction sorbents (octadecyl bonded silica and polystyrene-divinylbenzene) and two derivatizing reagents (BF3-MeOH and trimethylsilyldiazomethane) were investigated. Recovery of 13 chlorinated herbicide acids--including pentachlorophenol, dinoseb, and bentazon (having a derivatizable functional group, -OH or -NH, bonded directly to a phenyl group); dicamba, picloram, acifluorfen, 3,5-dichlorobenzoic acid, and dacthal (having a derivatizable functional group, -COOH, bonded directly to a phenyl group); and 2,4-D, 2,4,5-T, dichlorprop, 2,4,5-TP, and 2,4-DB (having a derivatizable functional group, -COOH, bonded directly to a sp3 carbon atom)--was tested. The analytical method developed was proven successful for determining acidic herbicides, except for the dacthal diacid metabolite, in aqueous samples.

The significance of this research is the application of thin-layer chromatography (TLC) to fractionate well-characterized aquatic humic materials coupled with the novel evaluation of the trihalomethane formation potential (THMFP) of the fractionated materials. Disinfection by-products such as trihalomethanes (THMs) form when natural water is treated by chlorination. Nordic Aquatic and Suwannee River fulvic and humic acids, obtained from the International Humic Substances Society, were prepared at pH 6 and 9 and fractionated on silica gel plates using a mobile phase consisting of methanol and ethyl acetate (2:1, v:v). Based on retention factor (R(f)) values, three common fractions were identified in all substances examined. Additionally, other fractions were noted that were characteristic of specific humic substances. Each of the three primary fractions derived from Nordic Aquatic fulvic acid at pH 6 demonstrated the potential to contribute to formation of THMs. This research provides data to support the hypothesis that differences in the chemical structure and composition of natural organic matter (NOM) significantly affect the potential to react with chlorine to form THMs.

Analyses of fatty acid (FA) composition in freshwater fishes promote understanding of the potential relationship between fish health or human nutrition and specific FAs. Therefore, the chemical identity of FAs in endemic fishes must be established. Paddlefish, sauger, and white bass were collected from the Ohio River. The structural identification of esterified FAs from fish-fillet lipids was conducted using gas chromatography-mass spectrometry (GC-MS). The same 13 FAs, composing more than 90% of the mass of FAs extracted by techniques used in this research, were found in all three species examined. Carbon chain length and degree and position of unsaturation were determined from the characteristic ionization and fragmentation of FA methyl esters (FAMEs) resulting from GC-MS electron impact (EI) and chemical ionization (CI) modes. Assignment of structure to the extracted FAs required complementary interpretation of both EI and CI MS. The EI spectra observed substantiate findings reported in the literature. The novelty of this research is in the thorough interpretation of CI spectra for which less data are available. The observations reported for analyses of fishes will be useful to all researchers studying FAs regardless of sample media.