Assessment of toxicity of selenium and cadmium selenium quantum dots: A review.

This paper reviews the current understanding of the toxicity of selenium (Se) to terrestrial mammalian and aquatic organisms. Adverse biological effects occur in the case of Se deficiencies, associated with this element having essential biological functions and a narrow window between essentiality and toxicity. Several inorganic species of Se (-2, 0, +4, and +6) and organic species (monomethylated and dimethylated) have been reported in aquatic systems. The toxicity of Se in any given sample depends not only on its speciation and concentration, but also on the concomitant presence of other compounds that may have synergistic or antagonistic effects, affecting the target organism as well, usually spanning 2 or 3 orders of magnitude for inorganic Se species. In aquatic ecosystems, indirect toxic effects, linked to the trophic transfer of excess Se, are usually of much more concern than direct Se toxicity. Studies on the toxicity of selenium nanoparticles indicate the greater toxicity of chemically generated selenium nanoparticles relative to selenium oxyanions for fish and fish embryos while oxyanions of selenium have been found to be more highly toxic to rats as compared to nano-Se. Studies on polymer coated Cd/Se quantum dots suggest significant differences in toxicity of weathered vs. non-weathered QD's as well as a significant role for cadmium with respect to toxicity.

Effect of humic acid source on humic acid adsorption onto titanium dioxide nanoparticles.

In many studies, different humic acid (HA) sources are used interchangeably to evaluate the effect of organic matter on geochemical processes in the environment. This research looks more specifically at the effect of HA source on HA adsorption onto nano-TiO2 and how HA adsorption affects the fate and transport of nano-TiO2. In this study, six humic acids (HAs) were studied which were derived from soils (SLHA), or from sediments (SDHA) all originating from the state of Florida. Humic acid adsorption onto titanium dioxide nanoparticles (nano-TiO2) and the sedimentation of HA-coated and uncoated nano-TiO2 were monitored by Ultraviolet-visible (UV-vis) spectroscopy. Synchronous scan fluorescence (SSF) spectroscopy was used to complement the study of HA adsorption onto nano-TiO2. Phosphate buffer was found to reduce the amount of HA adsorbed onto nano-TiO2 relative to solutions of NaCl of the same pH and ionic strength. Adsorption constant values (Kads) for HAs varied in the order SLHA>FSDHA (freshwater sedimentary HA)>ESDHA (estuarine sedimentary HA). SSF results suggested that the more highly conjugated fractions of HA, which are more prevalent in SLHAs versus SDHAs, were preferentially adsorbed. In order to better understand the relationship between adsorption and aggregation, sedimentation studies were conducted and it was found that the percentage of nano-TiO2 sedimentation was preferentially enhanced in the order of the presence of SLHA>FSDHA>ESDHA. The extent of nano-TiO2 sedimentation was decreased with increasing HA concentration. TEM imaging of nano-TiO2 confirmed that nano-TiO2 was aggregated in the presence of HAs. The findings in this study suggest that HAs from different sources influence the fate and transport of nano-TiO2 in the environment differently.

Stability studies for titanium dioxide nanoparticles upon adsorption of Suwannee River humic and fulvic acids and natural organic matter.

In many studies humic acid, fulvic acid, or natural organic matter is used interchangeably to model the effect of naturally derived organic matter on geochemical processes in the environment. In this study, the term NOOM (naturally occurring organic matter) is used to include both humic and fulvic acids as well as natural organic matter and compares the effect of NOOM type on NOOM removal onto nano-TiO2. In general, regardless of variations in solution chemistry, the order of the percentage of removal of NOOM onto nano-TiO2 was humic acid>natural organic matter>fulvic acid. The order of adsorption constant values of NOOM onto nano-TiO2 was also found to be humic acid>natural organic matter>fulvic acid under all conditions studied. The extent of NOOM removal by nano-TiO2 was enhanced in the presence of the divalent ions, magnesium and calcium, at pH7.8 when compared to the presence of the monovalent ions, sodium and potassium. Also, lower NOOM removal by nano-TiO2 in the presence of sodium salts of dihydrogen phosphate, bicarbonate and nitrate relative to chloride was observed and was likely due to the competition between polyatomic anions and NOOM adsorption onto the surface of nano-TiO2 indicating an anionic effect. Low concentrations of NOOM (10-20 mg L(-1)) destabilized nano-TiO2 in solution, however, the stability of nano-TiO2 increased as the amount of NOOM adsorbed onto nano-TiO2 increased at higher dissolved NOOM concentrations and significant stabilization was seen at 25 mg L(-1) NOOM. Thus, the three fractions of NOOM, humic and fulvic acids and natural organic matter and their concentrations were found to affect nano-TiO2 stability to different degrees although pH dependent trends in cation and anion effects had similar patterns. While the effects of adsorption of these three commonly used types of NOOM onto nanoparticles are similar, there are important differences that can be related to structural differences.

Transport and deposition of Suwannee River Humic Acid/Natural Organic Matter formed silver nanoparticles on silica matrices: the influence of solution pH and ionic strength.

The transport and deposition of silver nanoparticles (AgNPs) formed from Ag(+) reduction by Suwannee River Humic Acid (SRHA) and Suwannee River Natural Organic Matter (SRNOM) utilizing a silica matrix is reported. The morphology and stability of the AgNPs was analyzed by transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential measurements. The percentage conversion of the initial [Ag(+)] to [AgNPs] was determined from a combination of atomic absorption (AAS) and UV-Vis spectroscopy, and centrifugation techniques. The results indicate higher AgNP transport and consequently low deposition in the porous media at basic pH conditions and low ionic strength. However, at low acidic pH and high ionic strength, especially with the divalent metallic cations, the mobility of the AgNPs in the porous media was very low, most likely due to NP aggregation. Overall, the results suggest the potential for AgNP contamination of subsurface soils and groundwater aquifers is mostly dependent on their aggregation state, controlled by the soil water and sediment ionic strength and pH.

Organic matter source discrimination by humic acid characterization: synchronous scan fluorescence spectroscopy and Ferrate(VI).

In this study, seven soil and sedimentary humic acid samples were analyzed by synchronous scan fluorescence (SSF) spectroscopy. The spectra of these humic acids were compared to each other and characterized, based on three major SSF peaks centered at approximately 281, 367 and 470 nm. Intensity ratios were calculated based on these peaks that were used to numerically assist in source discrimination. All humic acid samples were then reacted with Ferrate(VI) and were again analyzed with SSF. Upon the addition of Ferrate(VI) SSF spectra were obtained which more readily differentiated humic acid source. This method will assist geochemists and water management districts in tracing sources of organic matter to receiving water bodies and may aid in the elucidation of the chemical nature of humic acids.

Interactions of aqueous Ag+ with fulvic acids: mechanisms of silver nanoparticle formation and investigation of stability.

This study investigated the possible natural formation of silver nanoparticles (AgNPs) in Ag(+)-fulvic acid (FA) solutions under various environmentally relevant conditions (temperature, pH, and UV light). Increase in temperature (24-90 °C) and pH (6.1-9.0) of Ag(+)-Suwannee River fulvic acid (SRFA) solutions accelerated the appearance of the characteristic surface plasmon resonance (SPR) of AgNPs. The rate of AgNP formation via reduction of Ag(+) in the presence of different FAs (SRFA, Pahokee Peat fulvic acid, PPFA, Nordic lake fulvic acid, NLFA) and Suwannee River humic acid (SRHA) followed the order NLFA > SRHA > PPFA > SRFA. This order was found to be related to the free radical content of the acids, which was consistent with the proposed mechanism. The same order of AgNP growth was seen upon UV light illumination of Ag(+)-FA and Ag(+)-HA mixtures in moderately hard reconstituted water (MHRW). Stability studies of AgNPs, formed from the interactions of Ag(+)-SRFA, over a period of several months showed that these AgNPs were highly stable with SPR peak reductions of only ~15%. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements revealed bimodal particle size distributions of aged AgNPs. The stable AgNPs formed through the reduction of Ag(+) by fulvic and humic acid fractions of natural organic matter in the environment may be transported over significant distances and might also influence the overall bioavailability and ecotoxicity of AgNPs.

The effects of monovalent and divalent cations on the stability of silver nanoparticles formed from direct reduction of silver ions by Suwannee River humic acid/natural organic matter.

The formation and characterization of AgNPs (silver nanoparticles) formed from the reduction of Ag⁺ by SRNOM (Suwannee River natural organic matter) is reported. The images of SRNOM-formed AgNPs and the selected area electron diffraction (SAED) were captured by high resolution transmission electron microscopy (HRTEM). The colloidal and chemical stability of SRNOM- and SRHA (Suwannee River humic acid)-formed AgNPs in different ionic strength solutions of NaCl, KCl, CaCl2 and MgCl2 was investigated in an effort to evaluate the key fate and transport processes of these nanoparticles in natural aqueous environments. The aggregation state, stability and sedimentation rate of the AgNPs were monitored by Dynamic Light Scattering (DLS), zeta potential, and UV-vis measurements. The results indicate that both types of AgNPs are very unstable in high ionic strength solutions. Interestingly, the nanoparticles appeared more unstable in divalent cation solutions than in monovalent cation solutions at similar concentrations. Furthermore, the presence of SRNOM and SRHA contributed to the nanoparticle instability at high ionic strength in divalent metallic cation solutions, most likely due to intermolecular bridging with the organic matter. The results clearly suggest that changes in solution chemistry greatly affect nanoparticle long term stability and transport in natural aqueous environments.

Kinetics of the oxidation of sucralose and related carbohydrates by ferrate(VI).

The kinetics of the oxidation of sucralose, an emerging contaminant, and related monosaccharides and disaccharides by ferrate(VI) (Fe(VI)) were studied as a function of pH (6.5-10.1) at 25°C. Reducing sugars (glucose, fructose, and maltose) reacted faster with Fe(VI) than did the non-reducing sugar sucrose or its chlorinated derivative, sucralose. Second-order rate constants of the reactions of Fe(VI) with sucralose and disaccharides decreased with an increase in pH. The pH dependence was modeled by considering the reactivity of species of Fe(VI), (HFeO(4)(-) and FeO(4)(2-)) with the studied substrates. Second-order rate constants for the reaction of Fe(VI) with monosaccharides displayed an unusual variation with pH and were explained by considering the involvement of hydroxide in catalyzing the ring opening of the cyclic form of the carbohydrate at increased pH. The rate constants for the reactions of carbohydrates with Fe(VI) were compared with those for other oxidant species used in water treatment and were briefly discussed.

Differences in perceptions of child sexual abuse based on perpetrator age and respondent gender.

Child sexual abuse changes the lives of countless children. Child sexual abuse victims experience short and long term negative outcomes that affect their daily functioning. In this study, undergraduate students' perceptions of CSA were obtained using vignettes with an adult or child perpetrator and a general questionnaire. Results indicated participants receiving the child-on-child vignette were less likely to rate the vignette as abuse, saw the abuse as less severe, and assigned less blame to the perpetrator than participants reading the adult-on-child vignette. On a general questionnaire, male participants saw child-on-child abuse as less severe and more encouraged by society than did female participants. The information can be utilized by professionals in treatment planning and preventing revictimization at disclosure.

Humic acid-induced silver nanoparticle formation under environmentally relevant conditions.

The formation of silver nanoparticles (AgNPs) via reduction of silver ions (Ag(+)) in the presence of humic acids (HAs) under various environmentally relevant conditions is described. HAs tested originated from the Suwannee River (SUW), and included samples of three sedimentary HAs (SHAs), and five soils obtained across the state of Florida. The time required to form AgNPs varied depending upon the type and concentration of HA, as well as temperature. SUW and all three SHAs reduced Ag(+) at 22 °C. However, none of the soil HAs formed absorbance-detectable AgNPs at room temperature when allowed to react for a period of 25 days, at which time experiments were halted. The appearance of the characteristic surface plasmon resonance (SPR) of AgNPs was observed by ultraviolet-visible spectroscopy in as few as 2-4 days at 22 °C for SHAs and SUW. An elevated temperature of 90 °C resulted in the accelerated appearance of the SPR within 90 min for SUW and all SHAs. The formation of AgNPs at 90 °C was usually complete within 3 h. Transmission electron microscopy and atomic force microscopy images showed that the AgNPs formed were typically spherical and had a broad size distribution. Dynamic light scattering also revealed polydisperse particle size distributions. HAs appeared to colloidally stabilize AgNPs based on lack of any significant change in the spectral characteristics over a period of two months. The results suggest the potential for direct formation of AgNPs under environmental conditions from Ag(+) sources, implying that not all AgNPs observed in natural waters today may be of anthropogenic origin.

Quantitative determination of corticosteroids in bovine milk using mixed-mode polymeric strong cation exchange solid-phase extraction and liquid chromatography-tandem mass spectrometry.

A new method was developed to identify and quantify corticosteroids (prednisolone, methylprednisone, flumetasone, dexamethasone, and methylprednisolone) in raw bovine milk by liquid chromatography-tandem mass spectrometry (LC-MS/MS) utilizing mixed-mode polymeric strong cation exchange and reversed-phase (MCX) solid-phase extraction (SPE) to reduce ion effects in a multimode ion (MMI) source. The main advantage of this method over other commonly used methods includes the use of a single SPE cartridge with a low volume for sample preparation and fast separation on the HPLC system with reduced ion suppression. This study is the first to report the determination of methylprednisone, a metabolite of methylprednisolone, in bovine milk. This method was validated in accordance with the European Union (EU) Commission Decision 2002/657/EC. The recoveries vary between 90% and 105%. The within-laboratory reproducibility (precision) is less than 30%. The decision limits and detection capabilities were calculated along with LODs, which ranged from 0.02 to 0.07 microg/kg. The method was further enhanced by its successful adaptation to other LC-MS/MS systems equipped with the newly developed ion source, Agilent Jet Stream (AJS). After optimization of the AJS ion source and MS parameters, even lower LOD values were achieved (0.001-0.006 microg/kg) for the corticosteroids. Analytical results obtained with the AJS were characterized by an enhanced area response and similar noise level comparable to those obtained with conventional orthogonal atmospheric ionization (API).

Aquatic arsenic: toxicity, speciation, transformations, and remediation.

This paper reviews the current knowledge on the toxicity, speciation and biogeochemistry of arsenic in aquatic environmental systems. The toxicity of arsenic is highly dependent on the chemical speciation. The effects of pH, E(h), adsorbing surfaces, biological mediation, organic matter, and key inorganic substances such as sulfide and phosphate combine in a complex and interwoven dynamic fashion to produce unique assemblages of arsenic species. The number of different arsenic species found in environmental samples and an understanding of the transformations between arsenic species has increased over the past few decades as a result of new and refined analytical methods. Changes in arsenic speciation and in total arsenic content of foods upon processing have suggested possible risks associated with processed and unprocessed food. Arsenic removal from water using adsorbents, chemical oxidation, photolysis and photocatalytic oxidation techniques is also reviewed.