The Role of Quorum Sensing in the Development of Microcystis aeruginosa Blooms: Gene Expression.

Microcystis aeruginosa (M. aeruginosa) is the dominant cyanobacterial species causing harmful algal blooms in water bodies worldwide. The blooms release potent toxins and pose severe public health hazards to water bodies, animals, and humans who are in contact with or consume this water. The interaction between M. aeruginosa and heterotrophic bacteria is thought to contribute to the development of the blooms. This study strives to provide a specific answer to whether quorum sensing is also a potential mechanism mediating the interaction of different strains/species and the expression by gene luxS or gene mcyB in M. aeruginosa growth. The luxS gene in M. aeruginosa PCC7806 is associated with quorum sensing and was tested by q-PCR throughout a 30-day growth period. The same was performed for the mcyB gene. Heterotrophic bacteria were collected from local water bodies: Cibolo Creek and Leon Creek in San Antonio, Texas. Results revealed that in algal bloom scenarios, there is a similar concentration of gene luxS that is expressed by the cyanobacteria. Gene mcyB, however, is not directly associated with algal blooms, but it is related to cyanotoxin production. Toxicity levels increased in experiments with multiple algal strains, and the HSL treatment was not effective at reducing microcystin levels.

Assessing the performance of sand filter basins in treating urban stormwater runoff.

This study has assessed the efficiency of sand filter basins in treating urban stormwater runoff by analyzing available data in the literature, the International Stormwater BMP Database, and data collected in a sand filter basin located in the main campus of the University of Texas at San Antonio (UTSA). Ten storm events were monitored starting in March 2016 until February 2017. Total suspended solids, volatile suspended solids, nitrate, ortho-phosphate, copper, zinc, lead, pH, and conductivity were measured in the inlet and the outlet of the basin. Statistical analysis, including linear regression modeling, scatter plotting, and non-parametric testing, using data from the literature and the International Stormwater BMP Database was performed. The sand filter basin removed, on average, 94% and 86% of TSS and VSS, respectively. Such high removal rates were not observed for other constituents, with exception of lead (79%) that already showed a low mean concentration in the inlet of the basin (41.47 ± 27.41 µg/L). Nitrate and ortho-phosphate mean concentrations were not significantly different in the outlet than inlet. The basin effluent concentration of zinc was higher than acceptable stormwater benchmarks defined by EPA. The results indicated that the monitored sand filter basin met its primarily design criteria, which is TSS removal by at least 80% of mass. Better stormwater treatment practices, however, are needed to remove other pollutants more efficiently, in particular, because this area is located on top of the recharge zone of the Edwards Aquifer, a major source of water supply for the region.

Identification of a new high-molecular-weight Fe-citrate species at low citrate-to-Fe molar ratios: Impact on arsenic removal with ferric hydroxide.

Ferric hydroxide precipitation and flocculation is the most commonly used method for the removal of arsenic in water treatment. However, citrate often interrupts the precipitation of ferric hydroxides and thus affects arsenic removal. To date, the mechanisms controlling the effects of citrate on arsenic removal with ferric hydroxide flocculation and precipitation at very low citrate-to-Fe molar ratios are not well understood. Herein, we report a new mechanism by which citrate inhibits arsenic removal using ferric hydroxide. At a substoichiometric citrate-to-Fe molar ratio of 0.28, citrate forms a high-molecular-weight Fe-citrate (Fe4Cit) species. The optimized structure of the Fe4Cit species was obtained by the density functional theory calculation. To the best of our knowledge, this study is the first to report the formation and to identify the structure of dominant Fe-citrate species at a very low citrate-to-Fe molar ratio.

Historical data review and source analysis of PCBs/Arochlors in the Lower Leon Creek Watershed.

PCBs have been banned since the late 1970s, but concentrations still exist in sediments and riverine fish and continue to exceed regulatory limits which can result in negative health effects. This study looks at historical records of PCB and Arochlor concentrations in surface water, sediments, and fish tissue for the Lower Leon Creek, Bexar County in Texas. Temporal analysis on the concentrations of PCBs and Arochlors was conducted for detection and exceedance of selected screening criteria. In addition, the half-lives of select PCB congeners were calculated for 2007-2012 data to ascertain differences in PCB concentrations with their hydrophobicity. Source analysis was conducted to determine the potential contributing sources of PCB contamination using source data (landfills, outfalls, etc.) and the PCB exceedance data. For sediment and fish tissue sampling results, historic data shows high concentrations of PCB/Arochlors over the course of several decades. The historical data is characterized as being widely variable for detections in Arochlors and concentrations between years, with a dramatic drop in concentrations detected starting in 2009. Overall, the sampling locations adjacent to and downstream from the former Kelly Air Force Base have the highest concentrations of PCB/Arochlors over the longest period of time. The results of this work will aid regulatory agencies in addressing impairment.

Modeling and sensitivity analysis on the transport of aluminum oxide nanoparticles in saturated sand: effects of ionic strength, flow rate, and nanoparticle concentration.

Aluminum oxide nanoparticles have been widely used in various consumer products and there are growing concerns regarding their exposure in the environment. This study deals with the modeling, sensitivity analysis and uncertainty quantification of one-dimensional transport of nano-sized (~82 nm) aluminum oxide particles in saturated sand. The transport of aluminum oxide nanoparticles was modeled using a two-kinetic-site model with a blocking function. The modeling was done at different ionic strengths, flow rates, and nanoparticle concentrations. The two sites representing fast and slow attachments along with a blocking term yielded good agreement with the experimental results from the column studies of aluminum oxide nanoparticles. The same model was used to simulate breakthrough curves under different conditions using experimental data and calculated 95% confidence bounds of the generated breakthroughs. The sensitivity analysis results showed that slow attachment was the most sensitive parameter for high influent concentrations (e.g. 150 mg/L Al2O3) and the maximum solid phase retention capacity (related to blocking function) was the most sensitive parameter for low concentrations (e.g. 50 mg/L Al2O3).

Transport of aluminum oxide nanoparticles in saturated sand: effects of ionic strength, flow rate, and nanoparticle concentration.

The effect of ionic strength (IS), flow rate, and nanoparticle concentration on the transport and deposition of aluminum oxide nanoparticles (Al2O3 NPs) in saturated sand was investigated. Mobility of Al2O3 NPs was influenced by IS, the highest mobility was observed in DI water (97% elution of the influent) and decreased with increasing ionic strength. Decreased mobility of the NPs was due to aggregation as the IS increased. Varying flow conditions did not have a significant effect on mobility. However, increased and faster elution was observed when the influent concentration was increased from 50 mg/L to 400 mg/L. The influent and effluent nanoparticle sizes were also measured using dynamic light scattering. For most conditions, the size was observed to be below 100 nm and there was no significant change to the influent and effluent particle sizes. Significant elution was observed although conditions were electrostatically favorable, which was attributed to the small, stable size (~82 nm) of the particles and blocking. DLVO theory was also applied to the data to better understand the mechanisms of mobility. It is necessary to consider these mechanisms for a reliable prediction of transport through the subsurface and potential removal methods such as filtration.

Regeneration of spent TiO2 nanoparticles for Pb (II), Cu (II), and Zn (II) removal.

Spent sorbents in water treatment processes have potential risks to the environment if released without proper treatment. The aim of this work was to investigate the potential regeneration of commercially prepared nano-TiO2 (anatase) for the removal of Pb (II), Cu (II), and Zn (II) by pH 2 and ethylenediaminetetraacetic acid (EDTA) solutions. The percent of metal adsorption/desorption decreased with the increasing number of regeneration cycles, and the extent of decrease varied for each metal. Competitive effects were observed for the adsorption/desorption of different metals when the nano-TiO2 was regenerated by EDTA solutions. Nano-TiO2 was able to treat simulated metal polluted water with greater than 94 % adsorption and greater than 92 % desorption after four cycles of regeneration using pH 2 solution. These results demonstrated that nano-TiO2 can be regenerated and reused using pH 2 solution compared to an EDTA solution for aquatic metal removal, which makes nanosorbents promising and economically and environmentally more attractive in the application of water purification.

Excretion and toxicity of gold-iron nanoparticles.

Though gold nanoparticles have been considered bio-inert, recent studies have questioned their safety. To reduce the potential for toxicity, we developed a nanoclustering of gold and iron oxide as a nanoparticle (nanorose) which biodegrades into subunits to facilitate rapid excretion. In this present study, we demonstrate acid and macrophage lysosomal degradation of nanorose via loss of the near-infrared optical shift, and clearance of the nanorose in vivo following i.v. administration in C57BL/6 mice by showing gold concentration is significantly reduced in 11 murine tissues in as little as 31 days (P < 0.01). Hematology and chemistry show no toxicity of nanorose injected mice up to 14 days after administration. We conclude that the clustering design of nanorose does enhance the excretion of these nanoparticles, and that this could be a viable strategy to limit the potential toxicity of gold nanoparticles for clinical applications. FROM THE CLINICAL EDITOR: The potential toxicity of nanomaterials is a critically important limiting factor in their more widespread clinical application. Gold nanoparticles have been classically considered bio-inert, but recent studies have questioned their safety. The authors of this study have developed a clustering gold and iron oxide nanoparticle (nanorose), which biodegrades into subunits to facilitate rapid excretion, resulting in reduced toxicity.

Removal of Pb(II), Cd(II), Cu(II), and Zn(II) by hematite nanoparticles: effect of sorbent concentration, pH, temperature, and exhaustion.

Nanoparticles offer the potential to improve environmental treatment technologies due to their unique properties. Adsorption of metal ions (Pb(II), Cd(II), Cu(II), Zn(II)) to nanohematite was examined as a function of sorbent concentration, pH, temperature, and exhaustion. Adsorption experiments were conducted with 0.05, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. The adsorption data showed the ability of nanohematite to remove Pb, Cd, Cu, and Zn species from solution with adsorption increasing as the nanoparticle concentration increased. At 0.5 g/L nanohematite, 100 % Pb species adsorbed, 94 % Cd species adsorbed, 89 % Cu species adsorbed and 100 % Zn species adsorbed. Adsorption kinetics for all metals tested was described by a pseudo second-order rate equation with lead having the fastest rate of adsorption. The effect of temperature on adsorption showed that Pb(II), Cu(II), and Cd(II) underwent an endothermic reaction, while Zn(II) underwent an exothermic reaction. The nanoparticles were able to simultaneously remove multiple metals species (Zn, Cd, Pb, and Cu) from both a pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that at pH 8, exhaustion did not occur for the nanoparticles but adsorption does decrease for Cd, Cu, and Zn species but not Pb species. The strong adsorption coupled with the ability to simultaneously remove multiple metal ions offers a potential remediation method for the removal of metals from water.

Evaluation of desorption of Pb (II), Cu (II) and Zn (II) from titanium dioxide nanoparticles.

The adsorption-desorption of toxic compounds onto engineered nanoparticles is an important process that governs their potential as sorbents for treatment applications, their toxicity and their environmental risks. This study was aimed to investigate the desorption of Pb (II), Cu (II) and Zn (II) from commercially prepared nano-TiO(2) (anatase) using batch techniques, with the evaluation of isothermal, kinetic and thermodynamic properties. Results showed that desorption was pH dependent and that more than 98% of all metals desorbed at pH 2. Short term kinetic studies were fit with a pseudo second order model and showed that a significant amount of desorption occurred in the first fifteen minutes. Surface complexation modeling determined a trend of adsorption affinity to be Pb > Zn > Cu and with adjustable surface complexation constant (K(int)) provided good fit to the experimental data. The thermodynamic studies found that desorption was exothermic and non-spontaneous in most cases. The XPS study showed that no change in oxidation state occurred due to desorption and suggested that Pb desorption was due to inner-sphere surface complexation. The results suggest three important points that will improve the capabilities of researchers to understand Pb (II), Cu (II) and Zn (II) adsorption-desorption to nano-TiO(2): (1) the desorption of metals was enhanced at lower pH values suggesting its potential to be regenerated for treatment applications; (2) the possible mechanism for adsorption-desorption varies for different metals; and (3) nano-TiO(2) could interact with metals in the environment if released due to their high sorption capacity and reversible adsorption at lower pH values which could affect the fate and behavior of metals in the environment and enhance nanoparticle toxicity.

Adsorption and desorption of bivalent metals to hematite nanoparticles.

The use of commercially prepared hematite nanoparticles (37.0 nm) was studied as an adsorbent in the removal of Cd(II), Cu(II), Pb(II), and Zn(II) from aqueous solutions. Single-metal adsorption was studied as a function of metal and adsorbent concentrations, whereas binary metal competition was found to be dependent on the molar ratio between the competing metals. Competitive effects indicated that Pb had strong homogenous affinity to the nanohematite surface, and decreased adsorption of Cd, Cu, and Zn occurred when Pb was present in a binary system. Metal adsorption strength to nanohematite at pH 6.0 increased with metal electronegativity: Pb > Cu > Zn ∼ Cd. Equilibrium modeling revealed that the Langmuir-Freundlich composite isotherm adequately described the adsorption and competitive effects of metals to nanohematite, whereas desorption was best described by the Langmuir isotherm. The desorption of metals from nanohematite was found to be pH dependent, with pH 4.0 > pH 6.0 > pH 8.0, and results showed that greater than 65% desorption was achieved at pH 4.0 within three 24-h cycles for all metals.

Mobilization of trace metals and inorganic compounds during resuspension of anoxic sediments from Trepangier Bayou, Louisiana.

The release of trace metals (Mn, Ni, Co, Cu, Zn, Pb, and Cd) and inorganic compounds (As) from initially anoxic Trepangier Bayou sediments, Louisiana and the sources of the released metals were investigated. After 1 to 2 d aeration, significant amounts of trace metals (Mn, Zn, Cd, Ni, and Co) were released to the aqueous phase with increased acidity, primarily due to the oxidation of acid-volatile sulfide and ferrous iron and iron sulfide minerals. The addition of a bacterial inhibitor, NaN,, to the Trepangier sediment during resuspension inhibited metal release, suggesting that microbial catalysis can regulate metal mobilization during sediment resuspension. In a well buffered system, oxidation of iron sulfides alone did not appear to induce trace metal release. Moreover, when Trepangier sediment was resuspended in anoxic conditions at neutral pH, <1% of the trace metal content was released, whereas a significant release of metal was observed under acidic anoxic conditions. Although oxidation of iron sulfide minerals is an essential prerequisite for the release of Zn, Co, Cd, and Ni, carbonates and oxides also play a role. The trace metals and inorganic compounds investigated could be classified into three groups according to their release characteristics: (i) Mn, Zn, Cd, Ni, and Co; (ii) Fe, Pb, and As; and (iii) Cu. The groupings appeared to depend on the sources of compounds and their relative affinity, after oxidation, to iron oxyhydroxides or organic matter.

Adsorption of Pb, Cd, Cu, Zn, and Ni to titanium dioxide nanoparticles: effect of particle size, solid concentration, and exhaustion.

PURPOSE: Adsorption of metals (Pb, Cd, Cu, Ni, Zn) to TiO(2) nanoparticles and bulk particles was examined for use as a contaminant removal substrate as a function of particle size, sorbent concentration, and exhaustion. METHODS: Adsorption experiments were conducted with 0.01, 0.1, and 0.5 g/L nanoparticles in a pH 8 solution and in spiked San Antonio tap water. RESULTS: When results were normalized by mass, nanoparticles adsorbed more than the bulk particles but when results were surface-area normalized, the opposite was observed. The adsorption data shows the ability of the TiO(2) nanoparticles to remove Pb, Cd, and Ni from solution with similar adsorption at 0.1 and 0.5 g/L. Adsorption kinetics for all metals tested was described by a modified first order rate equation with the nanoparticles having a faster rate of adsorption than the bulk particles. The nanoparticles were able to simultaneously removal multiple metals (Zn, Cd, Pb, Ni, Cu) from both pH 8 solution and spiked San Antonio tap water. Exhaustion experiments showed that both the nanoparticles and bulk particles were exhausted at pH 6 but at pH 8, exhaustion did not occur for the nanoparticles. CONCLUSION: Comparison of K (d), distribution coefficient, with other literature showed that the nanoparticles were better sorbents than other metal oxide nanoparticles and a commercial activated carbon.

A sorption kinetics model for arsenic adsorption to magnetite nanoparticles.

INTRODUCTION: Arsenic is a well known water contaminant that causes toxicological and carcinogenic effects. In this work magnetite nanoparticles were examined as possible arsenic sorbents. The objective of this work was to develop a sorption kinetics model, which could be used to predict the amount of arsenic adsorbed by magnetite nanoparticles in the presence of naturally occurring species using a first-order rate equation, modified to include adsorption, described by a Langmuir isotherm. DISCUSSION: Arsenate and arsenite adsorption to magnetite nanoparticles was studied, including the effect of naturally occurring species (sulfate, silica, calcium magnesium, dissolved organic matter, bicarbonate, iron, and phosphate) on adsorption. CONCLUSION: The model accurately predicts adsorption to magnetite nanoparticles used in a batch process to remove arsenic from spiked Houston, TX tap water, and contaminated Brownsville, TX groundwater.

Adsorption of arsenic to magnetite nanoparticles: effect of particle concentration, pH, ionic strength, and temperature.

Little work has been conducted on the adsorption of arsenic to the mixed iron [Fe(II)/(III)] oxide magnetite and the effect that environmental parameters, such as pH, ionic strength, and temperature, have on adsorption. Magnetite nanoparticles are unique because of their affinity for both arsenate and arsenite and increased adsorption capacity from their bulk counterparts. This article shows the effect of various magnetite nanoparticle concentrations on arsenic adsorption kinetics. The adsorption data show the ability of the magnetite nanoparticles to remove arsenate and arsenite from solution in both synthetic and natural waters, and the data fit a first-order rate equation. Because of the increased surface area of these particles, less than 1 g/L of magnetite nanoparticles was needed. The results suggest that arsenic adsorption to the nanoparticles was not significantly affected by the pH, ionic strength and temperature in the ranges tested, which are typical of most potable water sources.

Resistant desorption of hydrophobic organic contaminants in typical chinese soils: implications for long-term fate and soil quality standards.

Soil contamination is an enormous problem in China and severely threatens environmental quality and food safety. Establishing realistic soil quality standards is important to the management and remediation of contaminated sites and must be based on thorough understanding of contaminant desorption from soil. In the present study, we evaluated sorption and desorption behaviors of naphthalene, phenanthrene, atrazine, and lindane (four common soil contaminants in China) in two of the most common Chinese soils. The desorption of these compounds exhibited clear biphasic pattern-a fraction of contaminants in soil was much less available to desorption and persisted much longer than what was predicted with the conventional desorption models. The unique thermodynamic characteristics associated with the resistant-desorption fraction likely have important implications for the mechanism(s) controlling resistant desorption. Experimental observations in the present study are consistent with our previous work with chlorinated compounds and different adsorbents and could be well modeled with a biphasic desorption isotherm. We therefore suggest that more accurate biphasic desorption models should be used to replace the conventional linear sorption/desorption model that is still widely adopted worldwide in contaminant fate prediction and soil quality standard calculations.

Low-field magnetic separation of monodisperse Fe3O4 nanocrystals.

Magnetic separations at very low magnetic field gradients (<100 tesla per meter) can now be applied to diverse problems, such as point-of-use water purification and the simultaneous separation of complex mixtures. High-surface area and monodisperse magnetite (Fe3O4) nanocrystals (NCs) were shown to respond to low fields in a size-dependent fashion. The particles apparently do not act independently in the separation but rather reversibly aggregate through the resulting high-field gradients present at their surfaces. Using the high specific surface area of Fe3O4 NCs that were 12 nanometers in diameter, we reduced the mass of waste associated with arsenic removal from water by orders of magnitude. Additionally, the size dependence of magnetic separation permitted mixtures of 4- and 12-nanometer-sized Fe3O4 NCs to be separated by the application of different magnetic fields.