Suwannee River Research Articles

Effects of fulvic acids on the electrochemical reactions and mass transfer properties of organic cation toluidine blue: Results of measurements by the method of rotating ring-disc electrode

This study examined effects of aquatic and soil natural organic matter (NOM) exemplified by standard Suwannee River fulvic acid (SRFA) and Pahokee Peat fulvic acid (PPFA), respectively, on the electrochemical (EC) reactivity and mass transfer properties of the cationic organic probe toluidine blue (TB) that forms complexes with NOM. EC measurements that were carried out using the method of rotating ring-disc electrode (RRDE) showed that for disc potentials below −0.4 V vs. the standard Ag/AgCl reference electrode, TB molecules undergo EC reduction accompanied by the formation of EC-active products that undergo oxidation at the ring electrode. EC reactions of TB in the range of potentials −0.2 to −0.4 V were determined to involve free TB+ cations and TB species adsorbed on the electrode surface. The EC reduction of TB species at the disc potentials < −0.4 V was controlled by the mass transfer of the free TB+ cations and TB/NOM complexes to the electrode surface. Formation of TB/NOM complexes caused the mass transfer-controlled TB currents to undergo a consistent decrease. The observed changes were correlated with the extent of TB/NOM complexation and decreases of the diffusion coefficients of TB/NOM complexes that have higher molecular weights (MW) than the free cations. Properties of the intermediates formed upon the reduction of TB+ cations were also affected by NOM. These results demonstrate that RRDE measurements of EC reactions of TB or possibly other EC active probes allow probing the complexation of EC-active organic species with NOM and mass transfer properties of NOM complexes and ultimately NOM itself.

Distinct effects of copper on the degradation of β-lactam antibiotics in fulvic acid solutions during light and dark cycle

This study revealed the dual roles of Cu(II) on the β-lactam antibiotics degradation in Suwannee River fulvic acid (SRFA) solution during day and night cycle. Amoxicillin (AMX) and ampicillin (AMP) were selected as the representative β-lactam antibiotics. Cu(II) played a key role in the dark degradation of AMX and AMP via catalytic hydrolysis and oxidation. However, Cu(II) mainly exhibited an inhibitory effect on SRFA-involved photochemical degradation of AMX and AMP. In the presence of 500 nM of Cu(II), the degradation rate of AMX and AMP in the light condition were around 5 times higher than that in the dark condition, suggesting the photodegradation of β-lactam antibiotics was much more pronounced than catalyzed hydrolysis and oxidation. The triplet excited state of SRFA (3SRFA∗) primarily contributed to AMX and AMP photodegradation. Hydroxyl radicals (•OH) and singlet oxygen (1O2) exhibited limit impacts. The redox cycle of Cu(II)/Cu(I) restricted the electron transfer pathway of 3SRFA∗ with AMX and AMP. During the day and night cycles for 48 h, Cu(II) served as a stronger inhibitor rather than a promotor. These findings highlight the interactions between Cu(II) and SRFA are distinct under day and night conditions, which could further affect the fate of β-lactam antibiotics in natural environments.

Removal of legacy PFAS and other fluorotelomers: Optimized regeneration strategies in DOM-rich waters

We present the first study investigating optimized regeneration strategies for anionic ion exchange (IX) resins during the removal of persistent per- and poly-fluoroalkyl substances (PFAS, including GenX) from surface and treated wastewater effluents. IX regeneration studies are of critical importance from environmental perspectives. Specifically, the knowledge is essential for water utilities who presently operate IX (for PFAS removal) in a single use-and-dispose mode. In this study, legacy PFAS such as PFOA/PFOS were tested along with other harmful short-chained PFAS (PFBA/PFBS) and other toxic perfluorinated substitutes (GenX). Studies were performed on synthetic water (spiked with Suwannee River Natural Organic Matter (SRNOM), Fulvic Acid (SRFA) and Humic Acid (SRHA)), surface water, and wastewater effluents, and the regeneration was performed in batch stirred reactors. The resin service life with and without regeneration was investigated in the presence of background organic matter. In ultra-pure waters, all PFAS (C0 ∼10 μg/L, concentrations similar to that of natural waters) were effectively removed for >100,000 Bed Volume (BV) of operation. This was reduced to ∼23,500 BV in the presence of SRNOM (C0 = 5 mg C/L), 20,500 BV in SRFA and 8500 BV in SRHA, after which the saturated resins required regeneration. More importantly, all resin breakthrough (PFAS> 70 ng/L) corresponded to > 90% resin site saturation (in meqs), an essential information for optimizing IX loading. The competitive dissolved organic matter (DOM) fractions were estimated to be approximately 5–9% of the initial DOC, as estimated by the IAST-EBC model. Finally, it was identified that IX regeneration efficiency improved with increasing brine contact time but effectiveness plateaued for brine concentrations above 10% (W/V). Nonetheless, a regeneration with 10% NaCl solution with a contact time of 2 h was found to be optimal for IX operations in synthetic and natural waters. Therefore, this study provides key knowledge essential for the scientific community and the water industry on optimizing IX operational parameters for DOM and PFAS removal and would be highly valuable for systems which presently operate IX in a use-and-dispose mode.

Tidal and Subtidal Variations in Water Level Produced by Ocean‐River Interactions in a Subtropical Estuary

AbstractNear yearlong time series measurements of water level elevation from seven stations along the Suwannee River, Florida, were used to characterize, observationally and analytically, the propagation of tidal and subtidal signals along the estuary resulting from tide‐river interactions. Tidal amplitudes and phases were obtained from least squares fits to observed values and used to compare to an analytical model. Subtidal amplitude and phases were characterized by Hilbert empirical orthogonal functions (HEOFs), obtained through complex principal component analysis, and compared to an analytical solution. The landward attenuation of the tidal signal was replicated analytically. The subtidal signal (periods &gt; tides) was also described analytically with an oceanic wave moving landward and a seaward river pulse. The subtidal analytical solution reproduced the competition between the landward and seaward waves and the zone where each wave dominated over the other. Depending on the phase of these landward and seaward subtidal waves, the resulting subtidal signal amplitude could either (a) attenuate landward to a certain location and then increase or (b) amplify landward up to a certain zone and then decrease.

Poleward expansion of common snook Centropomus undecimalis in the northeastern Gulf of Mexico and future research needs.

Globally, rising temperatures have resulted in numerous examples of poleward shifts in species distribution patterns with accompanying changes in community structure and ecosystem processes. In the Gulf of Mexico, higher mean temperatures and less frequent winter freezes have led to the expansion of tropics-associated marine organisms. Our objectives were to quantify changing environmental conditions and the poleward expansion of the common snook Centropomus undecimalis into the Cedar Keys area of Florida, USA (29 deg N). The snook is an economically and recreationally important sport fish found from southern Brazil to south Florida. Cedar Key and the Lower Suwannee River are north of the snook’s historically documented range, likely due to lethal water temperatures during winter. Using data from a long-term monitoring program, we report an increase in catches of snook in this area since 2007. The spatial and temporal expansion of the species began with adult fish in 2007. By 2018, snook of all sizes were found in the region, and we found strong evidence of local reproduction during 2016–2018. The locations of nursery habitat and winter thermal refuges (e.g., freshwater springs) need to be identified and have implications for land-use policy and minimum-flow regulations for rivers. The arrival of the snook in the northern Gulf of Mexico could affect food web ecology and habitat interactions among estuarine predators, and future studies should evaluate snook’s food habits and competitive interactions with resident fishes in this expanded range. Our study provides an example of how species range expansions due to changing temperatures should result in new research priorities to evaluate impacts of climate change on coastal systems.

Hydroxyl radical scavenging factor measurement using a fluorescence excitation-emission matrix and parallel factor analysis in ultraviolet advanced oxidation processes

The performance of the UV/H2O2 advanced oxidation process (AOP) is dependent on water quality parameters, including the UV absorbance coefficient at 254 nm and hydroxyl radical (•OH) water background demand (scavenging factor, s−1). The •OH scavenging factor represents the •OH scavenging rate of the background substances in the water matrix, and it is known to be one of the key parameters to predict the performance of the UV/H2O2 process. The •OH scavenging factor has been determined experimentally by using a probe compound such as pCBA and rhodamine B. The experimental method has been validated to accurately predict the micropollutants removal in the UV/H2O2 process, but there is a need for an easier and simple method of determining the OH scavenging factor. We evaluated the alternative method to analyze the •OH scavenging factor using fluorescence excitation-emission matrix and parallel factor analysis (F-EEM/PARAFAC). The correlation between •OH scavenging factor and the spectroscopic characteristics and structure of different organic matter types was evaluated. Organic matter was characterized using a fluorescence excitation-emission matrix, parallel factor analysis, and liquid chromatography-organic carbon detection. Second-order reaction rates of humic acid sodium salt, sodium alginate, Suwannee River humic acid and bovine serum albumin were calculated as 1.30 × 108 M−1 s−1, 1.39 × 108 M−1 s−1, 1.03 × 108 M−1 s−1, and 3.17 × 107 M−1 s−1, respectively. Results of PARAFAC analysis, the ratio of humic and fulvic fluorescence component 2 to terrestrial humic-like fluorescence component 1 (C2/C1), and •OH scavenging factor showed high linearity. A predictive model, which combines with the F-EEM/PARAFAC method, predicted the optimal UV and H2O2 dose to achieve target compound removal.

Leachability of endocrine disrupting chemicals (EDCs) in municipal sewage sludge: Effects of EDCs interaction with dissolved organic matter

In this study, experiments were performed to assess the significance of dissolved organic matter (DOM) on the leachability of four common EDCs, i.e., bisphenol A (BPA), 17α-ethinylestradiol (EE2), progesterone (PGT) and testosterone (TST), in municipal sewage sludge (MSS) under landfill conditions. The DOM was derived from two sources: MSS (MDOM), and natural soil represented by organic matter obtained from the Suwannee River (NDOM). Fluorescence excitation-emission matrix quenching combined with parallel factor analysis was adopted to characterize the interaction properties between the EDCs and DOM. The accumulative leachability of the target EDCs ranged from 0.09% (PGT) to 3.8% (TST). In particular, the leaching of BPA, EE2 and TST followed S-shaped curves, while PGT exhibited continuous leaching potential in untreated MSS. With the introduction of DOM, (i) the leachability of BPA and EE2 increased to 13.4% and 61.6%, respectively, whereas those of PGT and TST declined by 61.3% and 45.8%, respectively, and (ii) BPA, EE2 and PGT no longer reached leaching equilibrium but the S-shaped leaching property of TST persisted. The differential effects of MDOM and NDOM at identical concentrations on the EDCs leachability increased with curing time. BPA, EE2 and PGT quenched the MDOM fluorophores attributed to aromatic protein-like components. The fluorescence quenching of NDOM by BPA, EE2 and PGT was centered on soluble microbial by-product-like and humic-like substances. Compared with PGT, EE2 and BPA had greater capability for binding with DOM components largely via hydrophobic interactions, whereas PGT preferentially interacted with the DOM hydrophilic functionalities through specific interactions. TST had no binding capability but displayed potentials competing for sorption sites with DOM moieties. Our findings suggested that the management of MSS increased the risk of environmental contamination by EDCs for a long duration and that DOM was a useful indicator to predict the migration and transport properties of EDCs.

Formation of disinfection by-products from coexisting organic matter during vacuum ultraviolet (VUV) or ultraviolet (UV) treatment following pre-chlorination and their fates after post-chlorination

Vacuum ultraviolet (VUV) treatment is a promising advanced oxidation process for the removal of organic contaminants during water treatment. Here, we investigated the formation of disinfection by-products from coexisting organic matter during VUV or ultraviolet (UV) treatment following pre-chlorination, and their fates after post-chlorination, in a standard Suwannee River humic acid water and a natural lake water. VUV treatment after pre-chlorination decreased the total trihalomethane (THM) concentration but increased total aldehyde and chloral hydrate concentrations; total haloacetic acid (HAA) and haloacetonitrile (HAN) concentrations did not change. UV treatment after pre-chlorination produced similar changes in the by-products as those observed for VUV treatment, with the exception that the total THM concentration was not changed, and the total HAN concentration was increased. The final concentrations of by-products after post-chlorination were increased by VUV or UV treatment, except for the total HAA concentration, which remained unchanged after UV treatment. The increases were greater after VUV treatment than after UV treatment, probably because the larger amount of hydroxyl radicals generated during VUV treatment compared with during UV treatment transformed coexisting organic matter into precursors of by-products that were then converted to by-products during post-chlorination.

Competitive co-adsorption of bacteriophage MS2 and natural organic matter onto multiwalled carbon nanotubes

A leading challenge in drinking water treatment is to remove small-sized viruses from the water in a simple and efficient manner. Multi-walled carbon nanotubes (MWCNT) are new generation adsorbents with previously demonstrated potential as filter media to improve virus removal. This study therefore aimed to evaluate the field applicability of MWCNT-filters for virus removal in water containing natural organic matter (NOM) as co-solute to viruses, using batch equilibrium experiments. Contrary to previous studies, our results showed with MS2 bacteriophages single-solute systems that the affinity of MWCNT for MS2 was low, since after 3 h of equilibration only 4 log10 reduction value (LRV) of MS2 (20 mL at an initial concentration of 106 PFU MS2/mL) were reached. Single solute experiments with Suwannee river NOM (SRNOM) performed with environmentally-relevant concentrations showed MWCNT surface saturation at initial SRNOM concentrations between 10 and 15 mgC/L, for water pH between 5.2 and 8.7. These results suggested that at NOM:virus ratios found in natural waters, the NOM would competitively suppress virus adsorption onto MWCNT, even at low NOM concentrations. We confirmed this expectation with SRNOM-MS2 co-solute experiments, which showed an exponential decrease of the MS2 LRV by MWCNT with an increase in the initial SRNOM concentration. More interestingly, we showed that pre-equilibrating MWCNT with a SRNOM solution at a concentration as low as 0.4 mgC/L resulted in a LRV decrease of 3 for MS2, due to the formation of a negatively charged SRNOM adlayer on the MWCNT surface. Complementary batch experiments with natural NOM-containing waters and competition experiments with SRNOM in the presence of CaCl2 confirmed that the presence of NOM in waters challenges virus removal by MWCNT-filters, irrespective of the concentration and type of NOM and also in the presence of Ca2+. We therefore conclude that MWCNT-filters produced with commercially available pristine MWCNT cannot be considered as a viable technology for drinking water virus removal.

Absorption Mode Spectral Processing Improves Data Quality of Natural Organic Matter Analysis by Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry.

Natural organic matter (NOM) plays an important role in elemental cycles and ecology. Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) is an ultrahigh resolution technique used to molecularly resolve the complexity of NOM mixtures. However, even the very high mass resolution of FT-ICR-MS may result in multiple formula assignments to peaks in an NOM spectrum, especially at the high mass-to-charge ratio (m/z). The absorption mode is one option to process raw FT-ICR-MS data that can further increase the resolution of the peaks and has not been widely applied in NOM studies. In this study, we show the advantages of using the absorption mode for the analysis of NOM samples using a reference sample (Suwannee River fulvic acid). The absorption mode increased the precision of peak detection as well as the number (+23%) and accuracy of formula assignment (by 28%) when compared to the magnitude mode, besides achieving three times higher resolution. The results presented here highlight the potential to reduce the error threshold used during molecular formula assignment. In conclusion, the absorption mode shows advantages in the processing of NOM samples and other complex mixtures and should be promoted in the NOM community.

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur (DOS) by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM, which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected. The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50% MeOH aqueous solution (731) or 50% ACN aqueous solution (653). Moreover, due to the enhancement of ionization efficiency of DOS during ESI processes, the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100% MeOH as spray solvent, which were hardly obtained using 50% MeOH aqueous solution as spray solvent. The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample. A simple method based on 100% MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied, and the results revealed more molecular information of DOS in sea DOM samples.

A new species rises from beneath Florida: molecular phylogenetic analyses reveal cryptic diversity among the metapopulation of Crangonyx hobbsi Shoemaker, 1941 (Amphipoda: Crangonyctidae)

The phylogenetic structure of 23 populations of Crangonyx hobbsi, a stygobitic amphipod species endemic to the Floridan aquifer, is detailed. Molecular genetic analyses (based on three genes the nuclear 18S rDNA, 28S rDNA, and mitochondrial 16S rDNA) point to the presence of at least two phylogenetic clades within the aquifer. These clades align into two major zoogeographic regions, the Northern Suwannee River Basin and the Coastal and Central Lowlands in the Florida peninsula. Three species delimitation models indicate that the Northern Suwannee River Basin Clade represents a species level differentiation from C. hobbsi sensu stricto. Morphological analyses support the molecular analyses, revealing the presence of several taxonomically significant differences between the two species, including presence/absence of calceoli on the second antennae of males and differences in telson shape in both sexes. Additionally, the molecular diversity of C. hobbsi sensu stricto was shown to be surprisingly variable, suggesting the potential presence of additional diversity within the taxon.

Toward an Internally Consistent Model for Hg(II) Chemical Speciation Calculations in Bacterium-Natural Organic Matter-Low Molecular Mass Thiol Systems.

To advance the scientific understanding of bacteria-driven mercury (Hg) transformation processes in natural environments, thermodynamics and kinetics of divalent mercury Hg(II) chemical speciation need to be understood. Based on Hg LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopic information, combined with competitive ligand exchange (CLE) experiments, we determined Hg(II) structures and thermodynamic constants for Hg(II) complexes formed with thiol functional groups in bacterial cell membranes of two extensively studied Hg(II) methylating bacteria: Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132. The Hg EXAFS data suggest that 5% of the total number of membranethiol functionalities (Mem-RStot = 380 ± 50 μmol g–1 C) are situated closely enough to be involved in a 2-coordinated Hg(Mem-RS)2 structure in Geobacter. The remaining 95% of Mem-RSH is involved in mixed-ligation Hg(II)-complexes, combining either with low molecular mass (LMM) thiols like Cys, Hg(Cys)(Mem-RS), or with neighboring O/N membrane functionalities, Hg(Mem-RSRO). We report log K values for the formation of the structures Hg(Mem-RS)2, Hg(Cys)(Mem-RS), and Hg(Mem-RSRO) to be 39.1 ± 0.2, 38.1 ± 0.1, and 25.6 ± 0.1, respectively, for Geobacter and 39.2 ± 0.2, 38.2 ± 0.1, and 25.7 ± 0.1, respectively, for ND132. Combined with results obtained from previous studies using the same methodology to determine chemical speciation of Hg(II) in the presence of natural organic matter (NOM; Suwannee River DOM) and 15 LMM thiols, an internally consistent thermodynamic data set is created, which we recommend to be used in studies of Hg transformation processes in bacterium–NOM–LMM thiol systems.

A significant correlation between kinetics of nitrobenzene reduction by sulfide and electron transfer capacity of mediating dissolved humic substances

Dissolved humic substances (DHS) are ubiquitous in surface and subsurface aquatic environments and greatly affect the redox transformation of organic contaminants as reactants and/or electron transfer mediators. However, little is known about the quantitative relationship between the mediation efficiency of DHS and the physicochemical properties of DHS. Using sulfide-induced nitrobenzene reduction as a model system, we measured the reduction rate of nitrobenzene in the presence of 12 different DHS (20 mgC·L−1), including 4 commercial humic substances (Suwannee River humic and fulvic acids and Pahokee Peat humic and fulvic acids) and 8 soil humic substances collected as leachates from a wide variety of soils. In addition to the UV–vis absorption and fluorescence spectra, the electron donating/accepting capacities (EDC/EAC) of the tested DHS were measured using an electrochemical approach. A significant linear correlation (r = 0.99, P < .0001) was observed between the observed pseudo-first-order rate constant (kobs) of nitrobenzene reduction and the sum of EDC and EAC which is defined as electron transfer capacity (ETC) of DHS. A relatively good positive correlation (r = 0.69, P < .2) was shown between the kobs and the specific UV-absorbance at 254 nm (SUVA254), whereas no good correlation was shown between the kobs and the fluorescence of the C1-C4 components identified by the excitation emission matrices and parallel factor (EEM-PARAFAC) analysis. This study provides a new framework for accurate prediction of the capability of DHS in mediating the redox transformation of organic contaminants. CapsuleA significant linear correlation exists between the kinetics of nitrobenzene reduction by sulfide and electron transfer capacity of mediating dissolved humic substances.

Trends in Oyster Populations in the Northeastern Gulf of Mexico: An Assessment of River Discharge and Fishing Effects over Time and Space

AbstractWithin the Big Bend region of the northeastern Gulf of Mexico, one of the least developed coastlines in the continental USA, intertidal and subtidal populations of eastern oyster Crassostrea virginica (hereafter referred to as “oyster”) are a critical ecosystem and important economic constituent. We assessed trends in intertidal oyster populations, river discharge, and commercial fishing activity in the Suwannee River estuary within the Big Bend region using fisheries‐independent data from irregular monitoring efforts and publicly available environmental data. We used generalized linear models to evaluate counts of oysters from line‐transect surveys over time and space. We assessed model performance using simulation to understand potential bias and then evaluated whether these counts were related to freshwater inputs from the Suwannee River and commercial oyster fishing effort and landings at different time lags. We found that intertidal oyster counts have declined over time and that most of these declines are found in inshore intertidal oyster bars, which are becoming degraded. We also found a significant relationship between oyster counts and a 1‐year lag on mean daily Suwannee River discharge, but including commercial fishery trips or landings did not improve model fit. It is unclear whether declines in intertidal oyster bars are offset by formation of new oyster reefs elsewhere. These results quantify rapid declines in intertidal oyster reefs in a region of coastline with high conservation value that can be used to inform ongoing and proposed restoration projects in the region.

Dissolved organic matter adsorption from surface waters by granular composites versus granular activated carbon columns: An applicable approach

Many new sorbents have been introduced as an alternative for granular activated carbon (GAC), the most common sorbent for dissolved organic matter (DOM) removal. In the current study, we developed an applicable granular composite based on a flocculant commonly employed for drinking water treatment adsorbed to montmorillonite. DOM adsorption from surface waters, Lake Kinneret and Suwannee River, with low and high specific ultraviolet absorption (SUVA), respectively, by composite and GAC columns, was studied. Adsorption of DOM from Suwannee River was significantly higher by the composite column, in comparison to the GAC column, while an opposite trend was obtained for the adsorption of DOM from Lake Kinneret. In-situ regeneration of the columns with a brine solution was extremely efficient and inefficient for the composite and GAC columns, respectively. Adsorption, of both waters, post-regeneration by the composite column was not compromised, while GAC effectiveness decreased. The opposite trend in DOM adsorption from Suwannee River and Lake Kinneret was explained by the different affinities of the sorbents towards various DOM molecules. Distinguishing between different DOM components adsorbed by GAC and the composite was supported by 13C NMR and direct pyrolysis-GC-MS measurements. Furthermore, we demonstrated that the kinetics and adsorption at the equilibrium of five organic molecules to the composite and GAC can be correlated to their chemical-physical properties. Indeed, combining the properties of both sorbents, by integrating them into a single column, yielded higher DOM removal than by the individual columns. Furthermore, since DOM removal by GAC and by the composite, increases, and decreases with temperature, respectively, the integrated column, mitigates the changes in removal, stabilizing the adsorption performance. Such an integrated filter may minimize additional seasonal and water quality fluctuations.

Countereffect of glutathione on divalent mercury removal by nanoscale zero-valent iron in the presence of natural organic matter

Although there have been multiple studies on the effects of natural organic matter (NOM) on zero-valent iron (ZVI) removal of several regulated heavy metal ions from contaminated water, the role of NOM on Hg(II) removal by nanoscale ZVI (nZVI) has not yet been studied. The experimental results showed that in the presence of 100 mg L−1 of Suwannee River NOM (SRNOM), the Hg(II) removal ratio by nZVI decreased from 89% to 36% after 80 min of reaction. Similar trends were observed in the long-term test maintained for 15 days, attributable to the surface passivation of nZVI by SRNOM. In contrast, addition of 100 μM glutathione (GSH) to the nZVI suspensions increased the Hg(II) removal ratio from 85% to 96% after 15 days of reaction. Furthermore, adding 100 μM of GSH to the nZVI and SRNOM suspensions largely improved the removal efficiency of Hg(II) to be > 99% after 9 days of reaction, related to the enhanced dissolution of Fe(II) and consequent formation of lepidocrocite and maghemite on the nZVI surface. The addition of thiolic compounds is suggested as a promising step in overcoming the inhibitory effect of SRNOM for the remediation of Hg(II) using nZVI technology.

Phototransformation of roxithromycin in the presence of dissolved organic matter: Characteriazation of the degradation products and toxicity evaluation

Roxithromycin (ROX) is a widely used macrolide antibiotic and its environmental fate and ecotoxicity have attracted considerable attention. In this study, the phototransformation kinetics and products of ROX under the irradiation of simulated sunlight were investigated. The ecotoxicity of ROX before and after phototransformation were also examined using the bioluminescence bioassay and algae growth inhibition test. The results showed that ROX underwent direct photolysis and indirect photolysis in the presence of Suwannee River humic acid (SRHA) and Suwannee River natural organic matter (SRNOM). The kinetic rate constant of the photodegradation of ROX in the presence of 20 mg·L−1 SRHA and SRNOM were 4.0 and 3.6 times higher than direct photolysis in the absence of dissolved organic matter (DOM). A total of 20 phototransformation products (PTPs) formed as a result of the photodegradation of ROX by simulated solar irradiation were identified, and 10 of them were reported for the first time. The PTPs were generally formed through the N-demethylation, O-demethylation or direct cleavage of the side chain, desosamine or cladinose moiety from ROX. Solutions containing ROX and its PTPs showed an increased toxicity to Vibrio fischeri, demonstrating some PTPs were more toxic to V. fischeri. On the other hand, the toxicity of ROX after irradiation to Chlorella pyrenoidosa decreased, suggesting the phototransformation of ROX in the environment may be a positive outcome in the context of the growth of green algae.

Influence of pH on the Kinetics and Mechanism of Photoreductive Dissolution of Amorphous Iron Oxyhydroxide in the Presence of Natural Organic Matter: Implications to Iron Bioavailability in Surface Waters.

In this study, we investigate the influence of pH on the kinetics and mechanism of photoreductive dissolution of amorphous iron oxyhydroxide (AFO) in view of the recognition that the light-mediated dissolution of iron oxides controls Fe availability in many natural waters. Our results show that both ligand-to-metal charge transfer (LMCT) and photogenerated superoxide (O2•-) play an important role in AFO photoreductive dissolution in the presence of the chosen surrogate of natural organic matter, Suwannee river fulvic acid (SRFA). The pH dependence of LMCT-mediated AFO photoreductive dissolution is mainly controlled by the influence of pH on AFO solubility. A decrease in pH increases the concentration of the dissolved and more photolabile Fe(III)-SRFA complex present in equilibrium with AFO, a complex in which Fe(III) is readily reduced by LMCT. The pH dependence of superoxide-mediated Fe(III) reduction (SMIR) is also controlled by the influence of pH on AFO solubility with an increase in the dissolved inorganic Fe(III) concentration with the decrease in pH resulting in an increased rate of SMIR. No influence of pH was observed on the steady-state O2•- concentration generated on SRFA irradiation as well as the O2•- decay rate in the presence of SRFA, suggesting that the concentration and lifetime of O2•- are not important factors in controlling the pH dependence of O2•--mediated AFO dissolution. Overall, the results of this study show that the impact of acidification of natural waters on Fe availability will be much more pronounced when Fe is present as iron oxyhydroxide compared to that observed when organically bound Fe dominates with this effect because of the strong dependency of iron oxyhydroxide solubility on pH. The increased rate and extent of dissolution of iron oxyhydroxides on the acidification of natural waters will also have implications to the fate of other contaminants (such as heavy metals and organic compounds) that may be present on the iron oxyhydroxide surface.

Evaluation of aliphatic/aromatic compounds and fluorophores in dissolved organic matter of contrasting natural waters by SEC-HPLC with multi-wavelength absorbance and fluorescence detections.

The analytical high performance size exclusion liquid chromatography (SEC-HPLC) with multi-wavelength absorbance and fluorescence detections and fluorescence 3D-excitation/emission matrix (EEM) were used for the analysis of average molecular size (MS), molecular size distribution of aliphatic/aromatic compounds and fluorophores in dissolved organic matter (DOM) from Suwannee River (SRDOM) and two Karelian lakes (Vodoprovodnoe Lake - L1DOM and Onego Lake - L2DOM). The average MS of DOM samples varied in the order SRDOM>L1DOM>L2DOM. The absorbance ratios A250/A365 and A210/A254 have been used for the DOM samples characterization. The absorbance ratio A250/A365 provided significant information about average MS of the bulk aquatic DOMs but was not exactly correlated with the results of SEC-HPLC data. The absorbance ratio A210/A254 in combination with SEC was well correlated with the content of DOM aliphatic/aromatic compounds and could be used as an important water quality index to estimate the level of protein-like material in the aquatic DOM. Regardless of the origin (river or lakes), different geographical locations and different average MS of DOM, several similar types of humic-like SEC-separated fluorophores were found within the samples. In all DOM samples the decrease of the fluorophores emission maxima paralleled the decrease of their relative MS. The combination of SEC-HPLC with multi-wavelength fluorescence and absorbance detection and EEM analyses appears very useful for DOM characterization and for tracking of microbial activity resulting from anthropogenic and/or eutrophic impact in aquatic environments.