Baolin Deng

ROLE OF SULFIDE AND LIGAND STRENGTH IN CONTROLLING NANOSILVER TOXICITY

Nanosilver has been used broadly in nanotechnology enhanced consumer products because of its strong antimicrobial properties. Silver nanoparticles (AgNPs) released from these products will likely enter wastewater collection and treatment systems. This research evaluated the role of sulfide and ligand strength in controlling nanosilver toxicity to nitrifying bacteria that are important in wastewater treatment. The nanosilver toxicity in the absence and presence of ligands (SO(4)(2-), S(2-), Cl(-), PO(4)(3-), and EDTA(-)) commonly present in wastewater was determined from the oxygen uptake rate measurements. Sulfide appeared to be the only ligand to effectively reduce nanosilver toxicity. By adding a small aliquot of sulfide that was stoichiometrically complexed with AgNPs, the nanosilver toxicity to nitrifying organisms was reduced by up to 80%. Scanning electron microscopy coupled with energy dispersive X-ray analysis indicated that AgNPs were highly reactive with sulfide to form new Ag(x)S(y) complexes or precipitates. These complexes were not oxidized after a prolonged period of aeration (18h). This information is useful for wastewater treatment design and operation to reduce nanosilver toxicity via sulfide complexation. While the biotic ligand model was successful in predicting the toxicity of Ag(+) ions, it could not accurately predict the toxicity of AgNPs. Nevertheless, it could be one of the many tools useful in predicting and controlling nanosilver toxicity to wastewater microorganisms.

Uranium(VI) removal by nanoscale zerovalent iron in anoxic batch systems.

This study investigated the influences of pH, bicarbonate, and calcium on U(VI) removal and reduction by synthetic nanoscale zerovalent iron (nanoFe(0)) particles under anoxic conditions. The results showed that the rates of U(VI) removal and reduction by nanoFe(0) varied significantly with pH and concentrations of bicarbonate and/or calcium. For instance, at pH 6.92 the pseudo-first-order rate constants of U(VI) removal decreased by 78.5% and 81.3%, and U(VI) reduction decreased by 90.3% and 89.3%, when bicarbonate and calcium concentrations were increased from 0 to 1 mM, respectively. X-ray photoelectron spectroscopy (XPS) analysis confirmed the formation of UO(2) and iron (hydr)oxides as a result of the redox interactions between U(VI) and nanoFe(0). The study demonstrated the potential of using nanoFe(0) for U(VI)-contaminated site remediation and highlighted the impacts of pH, bicarbonate, and calcium on the U(VI) removal and reduction processes.

Silver nanoparticles in aquatic environments: Physiochemical behavior and antimicrobial mechanisms.

Nanosilver (silver nanoparticles or AgNPs) has unique physiochemical properties and strong antimicrobial activities. This paper provides a comprehensive review of the physicochemical behavior (e.g., dissolution and aggregation) and antimicrobial mechanisms of nanosilver in aquatic environments. The inconsistency in calculating the Gibbs free energy of formation of nanosilver [ΔGf(AgNPs)] in aquatic environments highlights the research needed to carefully determine the thermodynamic stability of nanosilver. The dissolutive release of silver ion (Ag(+)) in the literature is often described using a pseudo-first-order kinetics, but the fit is generally poor. This paper proposes a two-stage model that could better predict silver ion release kinetics. The theoretical analysis suggests that nanosilver dissolution could occur under anoxic conditions and that nanosilver may be sulfidized to form silver sulfide (Ag2S) under strict anaerobic conditions, but more investigation with carefully-designed experiments is required to confirm the analysis. Although silver ion release is likely the main antimicrobial mechanism of nanosilver, the contributions of (ion-free) AgNPs and reactive oxygen species (ROS) generation to the overall toxicity of nanosilver must not be neglected. Several research directions are proposed to better understand the dissolution kinetics of nanosilver and its antimicrobial mechanisms under various aquatic environmental conditions.

Enhanced mercury ion adsorption by amine-modified activated carbon

Mercury (Hg) is one of the most toxic metals found in water and sediments. In an effort to develop an effective adsorbent for aqueous Hg removal, activated carbon (AC) was modified with an amino-terminated organosilicon (3-aminopropyltriethoxysilane, APTES). Surface properties of the APTES-modified AC (MAC) were characterized by the scanning electron microscopy in conjunction with the energy-dispersive spectroscopy (SEM-EDS), the Fourier transform infrared spectroscopy (FT-IR), and potentiometry. The impacts of solvent, APTES concentration, reactive time and temperature on the surface modification were evaluated. The aqueous Hg adsorptive kinetics and capacity were also determined. Results demonstrated that the strong Hg-binding amine ligands were effectively introduced onto the AC surfaces through the silanol reaction between carbon surface functional groups (-COOH, -COH) and APTES molecules. The modification lowered the pH at the point of zero charge (pH(pzc)) to 4.54 from 9.6, favoring cation adsorption. MAC presented a faster rate of the Hg (II) adsorption and more than double adsorptive capacity as compared with AC.

Effects of Biomass Types and Carbonization Conditions on the Chemical Characteristics of Hydrochars

Effects of biomass types (bark mulch versus sugar beet pulp) and carbonization processing conditions (temperature, residence time, and phase of reaction medium) on the chemical characteristics of hydrochars were examined by elemental analysis, solid-state ¹³C NMR, and chemical and biochemical oxygen demand measurements. Bark hydrochars were more aromatic than sugar beet hydrochars produced under the same processing conditions. The presence of lignin in bark led to a much lower biochemical oxygen demand (BOD) of bark than sugar beet and increasing trends of BOD after carbonization. Compared with those prepared at 200 °C, 250 °C hydrochars were more aromatic and depleted of carbohydrates. Longer residence time (20 versus 3 h) at 250 °C resulted in the enrichment of nonprotonated aromatic carbons. Both bark and sugar beet pulp underwent deeper carbonization during water hydrothermal carbonization than during steam hydrothermal carbonization (200 °C, 3 h) in terms of more abundant aromatic C but less carbohydrate C in water hydrochars.

Water-source characterization and classification with fluorescence EEM spectroscopy: PARAFAC analysis

Water-quality protection and environmental forensics require rapid water monitoring and source identification. In this paper, parallel factor analysis (PARAFAC) of fluorescence excitation-emission matrix spectra (EEMS) was used to characterize and classify water samples from landfills, wastewater treatment plants, lakes, and rivers. The study showed that the optimal number of components was four to represent the data set. The fluorescence fingerprints for water samples from different sources were sufficiently different, so qualitative water classification could be achieved. Specifically, Component 1 was the major fluorescing centre in river waters, with characteristics consistent with humic-like fluorophores; Component 2 was the dominant fluorophore in the treated wastewaters; Component 3 was the characteristic fluorophore in landfill leachates; and Components 1, 3, and 4 existed in lake waters at comparable weight, among which Component 4 may be considered as a protein- or amino acid-like fluorophore.

Parallel factor analysis of fluorescence EEM spectra to identify THM precursors in lake waters

Dissolved organic matter (DOM) can react with chlorine and yield undesirable disinfection byproducts (DBPs), e.g., trihalomethanes (THMs). Numerous studies have demonstrated that various DOM constituents have DBP formation potentials. We explored in this study the use of fluorescence excitation–emission (EEM) spectroscopy to identify THM precursors in 55 lakes in Missouri, USA. EEMs of the lake waters were decomposed into five factors of different origins through parallel factor analysis. The correlations between the component scores of the factors and THM formation potentials reveal that factors 1 and 2 are likely THM precursors and provided better surrogates than SUVA (dissolved organic carbon-normalized UV254) for predicting DBP formation potential. Thus, monitoring the component scores of the DOM-origin factors would provide a practical tool to identify THM precursors and facilitate utilities to choose appropriate techniques for DBP mitigation and optimize the degree of water treatment.

Chromium(III) Oxidation Coupled with Microbially Mediated Mn(II) Oxidation

Abstract Reductive immobilization of Cr(VI) has been widely explored as a cost-effective approach for Cr-contaminated site remediation. In soils containing manganese oxides, however, the immobilized form of chromium, i.e., Cr(III), could potentially be reoxidized. In this study, batch experiments were conducted to assess whether there were any microbial processes that could accelerate Cr(III) oxidation in aerobic, manganese-containing systems. The results showed that in the presence of at least one species of manganese oxidizers, Pseudomonas putida, Cr(III) oxidation took place at low concentrations of Cr(III). About 30–50% of added Cr(III) (10–200 μ M) was oxidized to Cr(VI) within five days in the systems with P. putida and biogenic Mn oxides. The rate of Cr(III) oxidation was approximately proportional to the initial concentration of Cr(III) up to 100 μ M, but the growth of P. putida was partially inhibited by Cr(III) at 200 μ M and totally stopped when it reached 500 μ M. Cr(III) oxidation was dependent upon the biogenic formation of Mn oxides, though the oxidation rate was not directly proportional to the amount of Mn oxides formed. Chromium(III) oxidation took place through a catalytic pathway, in which the microbes mediated Mn(II) oxidation to form Mn-oxides, and Cr(III) was subsequently oxidized by the biogenic Mn-oxides.

Influence of soil minerals on chromium(VI) reduction by sulfide under anoxic conditions

The effects of soil minerals on chromate (CrVIO42-, noted as Cr(VI)) reduction by sulfide were investigated in the pH range of 7.67 to 9.07 under the anoxic condition. The examined minerals included montmorillonite (Swy-2), illite (IMt-2), kaolinite (KGa-2), aluminum oxide (γ-Al2O3), titanium oxide (TiO2, P-25, primarily anatase), and silica (SiO2). Based on their effects on Cr(VI) reduction, these minerals were categorized into three groups: (i) minerals catalyzing Cr(VI) reduction – illite; (ii) minerals with no effect – Al2O3; and (iii) minerals inhibiting Cr(VI) reduction- kaolinite, montmorillonite, SiO2 and TiO2 . The catalysis of illite was attributed primarily to the low concentration of iron solubilized from the mineral, which could accelerate Cr(VI) reduction by shuttling electrons from sulfide to Cr(VI). Additionally, elemental sulfur produced as the primary product of sulfide oxidation could further catalyze Cr(VI) reduction in the heterogeneous system. Previous studies have shown that adsorption of sulfide onto elemental sulfur nanoparticles could greatly increase sulfide reactivity towards Cr(VI) reduction. Consequently, the observed rate constant, kobs, increased with increasing amounts of both iron solubilized from illite and elemental sulfur produced during the reaction. The catalysis of iron, however, was found to be blocked by phenanthroline, a strong complexing agent for ferrous iron. In this case, the overall reaction rate at the initial stage of reaction was pseudo first order with respect to Cr(VI), i.e., the reaction kinetics was similar to that in the homogeneous system, because elemental sulfur exerted no effect at the initial stage prior to accumulation of elemental sulfur nanoparticles. In the suspension of kaolinite, which belonged to group (iii), an inhibitive effect to Cr(VI) reduction was observed and subsequently examined in more details. The inhibition was due to the sorption of elemental sulfur onto kaolinite, which reduced or completely eliminated the catalytic effect of elemental sulfur, depending on kaolinite concentration. This was consistent with the observation that the catalysis of externally added elemental sulfur (50 μM) on Cr(VI) reduction would disappear with a kaolinite concentration of more than 5.0 g/L. In kaolinite suspension, the overall reaction rate law was:-d[Cr(VI)]/dt = kobs[H+]2[Cr(VI)][HS-]0.70

Impacts of Goethite Particles on UV Disinfection of Drinking Water

ABSTRACT A unique association between bacterial cells and small goethite particles (∼0.2 by 2 μm) protected Escherichia coli and Pseudomonas putida from UV inactivation. The protection increased with the particle concentration in the turbidity range of 1 to 50 nephelometric turbidity units and with the bacterium-particle attachment time prior to UV irradiation. The lower degree of bacterial inactivation at longer attachment time was mostly attributed to the particle aggregation surrounding bacteria that provided shielding from UV radiation.