Presence Of Suwannee River Fulvic Acid Research Articles

Simulated sunlight-induced inactivation of tetracycline resistant bacteria and effects of dissolved organic matter

The transmission of antibiotic resistance in surface water has attracted much attention due to its increasing threat to human health. The role of sunlight irradiation and the effect of dissolved organic matter (DOM) on the transmission of antibiotic resistance are still unclear. In this study, photo-inactivation of antibiotic resistant bacteria (ARB) was investigated using antibiotic resistant E. coli (AR E. coli) that contained the tetracycline resistance gene (Tc-ARG) as a representative. The results showed that AR E. coli underwent significant photo-inactivation due to the membrane damage induced by direct irradiation and by the generated reactive oxygen species. Simulated sunlight irradiation specifically suppressed the expression of tetracycline resistance, which is attributed to the destruction of tetracycline-specific efflux pump. Tetracycline inhibited the photo-inactivation of AR E. coli due to its selective pressure on tetracycline resistant E. coli and competitive light absorption effect. Suwannee River fulvic acid (SRFA), a representative DOM, promoted the inactivation of AR E. coli and further inhibited the expression of tetracycline resistance gene due to the generation of its excited triplet state, singlet oxygen, and hydroxyl radical. The extracellular Tc-ARG also underwent fast photodegradation under light irradiation and in the presence of SRFA, which leads to the decrease of its transformation efficiency. This study provided insight into the sunlight-induced inactivation of ARB, which is of significance for understanding the transmission of tetracycline resistance in surface water.

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.

Impact of light and Suwanee River Fulvic Acid on O2 and H2O2 Mediated Oxidation of Silver Nanoparticles in Simulated Natural Waters.

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

Potential impact of natural organic ligands on the colloidal stability of silver nanoparticles

Interaction of natural organic matter (NOM) with engineered nanoparticles (NPs) determine NP fate, transport, and environmental persistence. However, the effect of NOM chemical composition, structure, and concentration on aggregation kinetics and dissolution behavior of silver nanoparticles (AgNPs) are still poorly understood because of heterogeneity and variability in NOM and AgNP properties. Here, aggregation behavior of citrate-coated silver nanoparticles (cit-AgNPs with a z-average diameter of 18nm) was investigated in the presence of l-cysteine (l-cys) and N-acetyl l-cysteine (NAL-cys) using UV–vis spectroscopy. We also investigated the effect of Suwannee River fulvic acid (SRFA) and a NOM isolated from the Yukon River (YRNOM) on the stability of cit-AgNPs. The dissolution of cit-AgNPs decreased with increased L-cys and NAL-cys concentration from 0 to 10μM. The critical coagulation concentration (CCC) of cit-AgNPs decreased in the presence of l-cys and increased in the presence of NAL-cys. Similarly, l-cys destabilizes cit-AgNPs in the presence of SRFA. The differences in the stability of cit-AgNPs in the presence of l-cys and NAL-cys can be attributed to the differences in the functional groups in these two cysteine molecules. l-cys has both negatively charged carboxylic group and a positively charged amine group, resulting in bridging between different particles. NAL-cys is a derivative of cysteine wherein an acetyl group is attached to the nitrogen atom thus shielding the positive charge on the amine group and therefore eliminating the bridging interaction mechanism. SRFA and YRNOM enhanced the stability of cit-AgNPs and increased the CCC value to higher counter ion concentrations. The concentration of SRFA (1–5mgL−1) did not affect the CCC, whereas the increased concentration of YRNOM increased the CCC of cit-AgNPs to high Na+ concentrations likely due to increased sorption of higher molecular weight compounds on the surface of cit-AgNPs. The outcome of this study suggests the importance of understanding the molecular properties of NOM (e.g. functional groups and molecular weight) in determining cit-AgNP environmental behaviors.

Effect of phosphate buffer on aggregation kinetics of citrate-coated silver nanoparticles induced by monovalent and divalent electrolytes.

The attachment efficiency (α) is an important parameter that can be used to characterize nanoparticle (NPs) aggregation behavior and has been a topic of discussion of several papers in the past few years. The importance of α is because it is one of the key parameters that can be used to model NP environmental fate and behavior. This study uses UV-vis and laser Doppler electrophoresis to monitor the aggregation behavior of citrate-coated silver nanoparticles (cit-AgNPs) induced by Na+ and Ca2+ as counter ions in the presence and absence of Suwannee River fulvic acid (SRFA) as a surrogate of natural organic matter and different concentrations of phosphate buffer (0-1mM). Results demonstrate that phosphate buffer, which serves to maintain pH nearly constant over the course of a reaction, is an important determinant of NP aggregation behavior. Increasing phosphate buffer concentration results in a decrease in the critical coagulation concentrations (CCC) of cit-AgNPs to lower counter ion concentration and an increase of α at the same counter ion concentration, both in the absence and presence of SRFA. SRFA stabilizes AgNPs and increases the CCC to higher counter ion concentrations. The outcome of this study can be used to rationalize the variation in α and CCC values reported in the literature for NPs with similar physicochemical properties, where different α and CCC values are reported when different types of buffers and buffer concentrations are used in different studies.

The concentration-dependent aggregation of Ag NPs induced by cystine

Cystine is widely used in cell culture media. Cysteine, the reduced form of cystine, is widely used to scavenge dissolved Ag in eco-toxicological studies to differentiate dissolved vs. nanoparticle uptake and toxicity. However, little is known about the impact of cysteine and cystine on the aggregation behavior of Ag NPs, in particular as a function of Ag NP concentration. Herein, we investigate how cystine (0–300μM) affects the stability of citrate-, polyvinylpyrrolidone-, and polyethylene glycol-coated silver nanoparticles (cit-Ag NPs, PVP-Ag NPs and PEG-Ag NPs, respectively) with and without Suwannee River fulvic acid (SRFA) as a function of Ag NPs concentration using UV–vis spectroscopy at environmentally and ecotoxicologically relevant Ag NP concentrations (ca. 125–1000μgL−1). The results demonstrate, for the first time, the concentration-dependent aggregation of cit-Ag NPs in the presence of cystine with a shift in the critical coagulation concentration (CCC) to lower cystine concentrations at lower cit-Ag NP concentrations. At the highest cit-Ag NP concentration (1000μgL−1), reaction limited aggregation was only observed and no CCC was measured. SRFA slowed the aggregation of cit-Ag NPs by cystine and aggregation occurred in reaction limited aggregation (RLA) regime only. No CCC value was measured in the presence of SRFA. Cystine replaces citrate, PVP and PEG coatings, resulting in aggregation of both electrostatically and sterically stabilized Ag NPs. These findings are important in understanding the factors determining the behavior of Ag NPs in cell culture media. Also due to the similarity between cystine and cysteine, these results are important in understanding the uptake and toxicity of Ag NPs vs. Ag ions, and suggest that the reduction of the toxicity of Ag NPs in the presence of cysteine could be due to a combined effect of scavenging Ag+ ions and Ag NP aggregation in the presence of cysteine.

Aggregation behaviour of TiO2 nanoparticles in natural river water

The purpose of this study was to determine and understand the aggregation behaviour of industrial nanoparticulate TiO2 (NPs) in the river water near a TiO2 production plant. The aggregation was tested in near-reality conditions with industrial NPs and the filtered river water in which they are potentially released. The initial size of TiO2 NPs is around 5 nm. The evolution of the hydrodynamic diameters of the TiO2 aggregates in the presence of added Suwannee River fulvic acid (SRFA) and illite in the filtered river water was measured at pH 8 for at least 30 min with dynamic light scattering and laser diffraction. The experiments performed in the filtered river water allowed the determination of the attachment efficiency coefficients, and the experiments performed under conditions facilitating aggregation (with higher Ca2+ content) were used to understand the potential aggregation processes. When no Ca2+ was added into the river water, the initially aggregated TiO2 did not develop a secondary aggregation in the presence of SRFA and illite. Upon the addition of 2.75 mM Ca2+, TiO2 was shown to heteroaggregate with illite at all tested concentrations. Consequently, in the studied river, the fate of the TiO2 NPs does not seem to be related to that of the clay suspended particles upstream of the plant. However, the behaviours of the TiO2 NPs and the clays are closely linked in the water with higher salt content, which is the case downstream of one of the industrial effluent release points.

Dissolved organic carbon reduces uranium toxicity to the unicellular eukaryote Euglena gracilis

The influence of dissolved organic carbon (DOC), in the form of Suwannee River fulvic acid (SRFA), on uranium (U) toxicity to the unicellular eukaryote, Euglena gracilis (Z strain), was investigated at pH 6. In a background medium without SRFA, exposure of E. gracilis to 57 μg L(-1) U resulted in a 50% reduction in growth (IC(50)). The addition of 20 mg L(-1) DOC (as SRFA), reduced U toxicity 4 to 5-fold (IC(50) increased to 254 μg L(-1) U). This reduction in toxicity was also evident at more sensitive effect levels with a 10% reduction in growth (IC(10)) occurring at 5 μg L(-1) U in the background medium and at 17 μg L(-1) U in the SRFA medium, respectively. This amelioration of toxicity with the addition of SRFA was linked to a decrease in the bioavailability of U, with geochemical speciation modelling predicting 84% of U would be complexed by SRFA. The decrease in bioavailability of U in the presence of SRFA was also evident from the 11-14 fold reduction in the cellular concentration of U compared to that of E. gracilis in the background medium. Stepwise multiple linear regression analyses indicated that UO(2)(2+) alone explained 51% of the variation in measured U toxicity to E. gracilis. Preliminary U exposures to E. gracilis in the presence of a reactive oxygen species probe, suggest exposure to ≥60 μg L(-1) U may induce oxidative stress, but this endpoint was not considered to be a sensitive biological indicator.

Impact of CuO NPs to Alga Microcystis Aeruginosa: Effect of Dissolved Organic Matter

With the rapid development and versatile applications of nanotechnology, a large quantity of nanoparticles (NPs) has been released into the environment. It has been one of the most popular studies that concerning the toxic effect of NPs to the algae in aquatic ecosystem. The membrane integrity of algal cells was assessed using different methods when algae were treated by CuO NPs in the absence and presence of Suwannee river fulvic acid (SRFA), one of DOM. We found SRFA could increase the toxicity of CuO NPs to cell membrane due to the more stable NPs suspension in the presence of SRFA. Results additionally indicate that maybe oxidative damage caused by CuO NPs was the primary reason that led to membrane structure and function failed.

Impact of CuO NPs to Alga Microcystis Aeruginosa: Effect of Dissolved Organic Matter

With the rapid development and versatile applications of nanotechnology, a large quantity of nanoparticles (NPs) has been released into the environment. It has been one of the most popular studies that concerning the toxic effect of NPs to the algae in aquatic ecosystem. The membrane integrity of algal cells was assessed using different methods when algae were treated by CuO NPs in the absence and presence of Suwannee river fulvic acid (SRFA), one of DOM. We found SRFA could increase the toxicity of CuO NPs to cell membrane due to the more stable NPs suspension in the presence of SRFA. Results additionally indicate that maybe oxidative damage caused by CuO NPs was the primary reason that led to membrane structure and function failed.

Interactions of Silver Nanoparticles with Pseudomonas putida Biofilms

Silver nanoparticles (Ag NPs) may present a risk to the environment due to their expected toxicity and wide exposure. The interactions between Ag NPs and laboratory-grown Pseudomonas putida biofilms were investigated under a range of environmentally relevant conditions (pH 6 and 7.5; presence and absence of Suwannee River fulvic acid (SRFA)) over 4 days. In the absence of SRFA, there was extensive sloughing of the biofilm bacteria into suspension implying NP-bacterial interactions and potential effects on NP transport in the environment. In the presence of SRFA, sloughing of cells into suspension was reduced under some conditions and Ag NPs and their aggregates were observed and quantified on and in the bacterial cells in the biofilm. Viability of the cells in all cases appear unchanged by the presence of Ag NPs. Cell viability was independent of the concentration of NPs in solution, but sloughing rates varied substantially, sometimes in a dose-dependent manner. The results suggest that biofilms are impacted by Ag NPs when SRFA was not present, and that SRFA increases uptake and bioaccumulation of Ag NPs to biofilms, perhaps resulting in longer term effects, which need further investigation.

Role of fulvic acid on lead bioaccumulation by Chlorella kesslerii.

To better understand the relationship between lead speciation and bioavailability in natural freshwaters, the interaction of lead with the freshwater alga Chlorella kesslerii was studied in the presence of the Suwannee River fulvic acid (SRFA). Special attention was paid to direct interactions of the fulvic acid on the algae, as well as potential physiological (membrane permeability and algal metabolism) influences. Lead-free ion concentration measurements were carried out using a novel ion-selective electrode. Pb uptake decreased in the presence of SRFA with respect to noncomplexed Pb, but uptake fluxes, cellular Pb, Pb bound to the transport sites, and total adsorbed Pb were all higher than predicted from Pb2+ activities, in accordance with the free ion activity model (FIAM). The discrepancies between the observed values and those predicted by the FIAM in the presence and absence of synthetic ligands increased with increasing concentration of SRFA. Several hypotheses were examined to explain the observed differences. No contributions of labile and/or hydrophobic Pb-SRFA complexes were found. Furthermore, direct biological effects, including variations in membrane permeability or algal metabolism, could not account for the observations. On the other hand, changes in the algal surface charge due to SRFA adsorption seemed to account, at least partially, for the observed increase in lead uptake in the presence of SRFA as compared to that corresponding to the same Pb2+ concentration in the presence of synthetic ligands.

Chemiluminescence of luminol in the presence of iron(II) and oxygen: oxidation mechanism and implications for its analytical use.

The validity of chemiluminescence-based methods relies upon the uniqueness of the relationship between the concentration of the analyte and the intensity of chemiluminescence produced. We have examined the chemiluminescence of luminol (5-amino-2,3-dihydro-1,4-phthalazinedione) in the presence of O2, without added H202, to measure nanomolar concentrations of total Fe(II) (both inorganically and organically complexed) in aqueous samples. To test the validity of the method, we have developed a kinetic model that describes the two-step oxidation of luminol by superoxide and hydroxyl (or hydroxyl-like) radicals produced from the oxidation of Fe-(II) by O2 by synthesis of existing published data. This model was coupled with a model for Fe(II) oxidation by O2 in the presence and absence of the naturally occurring Suwannee River fulvic acid (SRFA). The production of chemiluminescence depended upon the concentrations of free radicals in both the sample and luminol reagent and the pH at which the reactions were performed. The relationship between Fe(II) concentration and chemiluminescence intensity was found to be unique at Fe(II) concentrations from 1 nM to 1 microM without organic complexation and from 1 to 32 nM in the presence of SRFA despite strong signal quenching in the latter case. This type of behavior will likely ensure a similarly unique relationship in the presence of a wide range of organic compounds; however, when other systems are being investigated, the technique should be carefully evaluated.

ADSORPTION OF FULVIC ACID ON ALGAL SURFACES AND ITS EFFECT ON CARBON UPTAKE

Adsorption of Suwannee River fulvic acid (SRFA) to algal surfaces of three green algae was studied at environmentally relevant pH values (4 –7) and SRFA concentrations (5–100 mg·L−1). The influence of adsorbed SRFA on carbon uptake of Scenedesmus subspicatus Chodat was also examined. Although no adsorption was observed at neutral pH values (pH 6 and 7), at pH 4 up to 31 mg SRFA·m−2 and at pH 5 up to 4 mg SRFA·m−2 was adsorbed to the algal surfaces. Electrophoretic mobility measurements of S. subspicatus demonstrated an increase in the negative surface charge of the alga in the presence of SRFA at pH 4. The adsorbed SRFA also influenced 14C uptake in S. subspicatus; in this case, enhanced carbon uptake could be related to the amount of adsorbed SRFA. The binding of humic substances by algal surfaces was interpreted as the result of hydrogen bonding and hydrophobic interactions.