Divina A. Navarro

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.

Investigating uptake of water-dispersible CdSe/ZnS quantum dot nanoparticles by Arabidopsis thaliana plants

Interest on the environmental impacts of engineered nanomaterials has rapidly increased over the past years because it is expected that these materials will eventually be released into the environment. The present work investigates the potential root uptake of water-dispersible CdSe/ZnS quantum dots (QDs) by the model plant species, Arabidopsis thaliana. Experiments revealed that Arabidopsis exposed to QDs that are dispersed in Hoaglands solution for 1-7 days did not internalize intact QDs. Analysis of Cd and Se concentrations in roots and leaves by inductively-coupled plasma mass spectrometry indicated that Cd and Se from QD-treated plants were not translocated into the leaves, and remained in the root system of Arabidopsis. Furthermore, fluorescence microscopy showed strong evidence that the QDs were generally on the outside surfaces of the roots, where the amount of QDs adsorbed is dependent on the stability of the QDs in suspension. Despite no evidence of nanoparticle internalization, the ratio of reduced glutathione levels (GSH) relative to the oxidized glutathione (GSSG) in plants decreased when plants were exposed to QD dispersions containing humic acids, suggesting that QDs caused oxidative stress on the plant at this condition.

Assessing antibiotic sorption in soil: a literature review and new case studies on sulfonamides and macrolides

The increased use of veterinary antibiotics in modern agriculture for therapeutic uses and growth promotion has raised concern regarding the environmental impacts of antibiotic residues in soil and water. The mobility and transport of antibiotics in the environment depends on their sorption behavior, which is typically predicted by extrapolating from an experimentally determined soil-water distribution coefficient (Kd). Accurate determination of Kd values is important in order to better predict the environmental fate of antibiotics. In this paper, we examine different analytical approaches in assessing Kd of two major classes of veterinary antibiotics (sulfonamides and macrolides) and compare the existing literature data with experimental data obtained in our laboratory. While environmental parameters such as soil pH and organic matter content are the most significant factors that affect the sorption of antibiotics in soil, it is important to consider the concentrations used, the analytical method employed, and the transformations that can occur when determining Kd values. Application of solid phase extraction and liquid chromatography/mass spectrometry can facilitate accurate determination of Kd at environmentally relevant concentrations. Because the bioavailability of antibiotics in soil depends on their sorption behavior, it is important to examine current practices in assessing their mobility in soil.

Cd Tolerance and Accumulation in the Aquatic Macrophyte, Chara australis: Potential Use for Charophytes in Phytoremediation

We investigated the potential use of the alga Chara australis (R. Br.) forphytore mediation of Cd-contaminated sediments in aquatic systems. Chara tolerated up to 20 mg added Cd (kg soil)⁻¹ in laboratory culture. Chlorophyll a and b levels were not affected even at Cd concentrations that suppressed growth. Levels of glutathione were suppressed at 2-35 mg added Cd (kg soil)⁻¹ to 200-350 nmol GSH (g DW)⁻¹, while control levels were 660 nmol GSH (g DW)⁻¹). Histochemical studies showed Cd occurred throughout cell walls and cytoplasm in plants grown in 5-20 mg Cd (kg soil)⁻¹. Quantification using ICP-MS showed the maximum concentration in shoots was 72 mg Cd (kg DW)⁻¹ at 35 mg added Cd (kg soil)⁻¹, while the maximum in rhizoids was 116 mg Cd (kg DW)⁻¹ at 25 mg added Cd (kg soil)⁻¹. The bioconcentration factor (BCF, concentration in plant/concentration in soil) exceeded 1.0, the critical value for hyperaccumulators, for shoots exposed to 35 mg Cd (kg soil)⁻¹ and rhizoids exposed to ≥25 mg Cd (kg soil)⁻¹. Translocation factors (TF, shoot concentration/rhizoid concentration) did not exceed 1.0 for any treatment. While Chara cannot be considered a hyperaccumulator, it shows promise for use in phytoremediation efforts.

Bioavailability of silver and silver sulfide nanoparticles to lettuce (Lactuca sativa): Effect of agricultural amendments on plant uptake

Silver nanoparticles (AgNPs) can enter terrestrial systems as sulfidised AgNPs (Ag2S-NPs) through the application of biosolids to soil. However, the bioavailability of Ag2S-NPs in soils is unknown. The two aims of this study were to investigate (1) the bioavailability of Ag to lettuce (Lactuca sativa) using a soil amended with biosolids containing Ag2S-NPs and (2) the effect of commonly used agricultural fertilisers/amendments on the bioavailability of Ag, AgNPs and Ag2S-NPs to lettuce. The study used realistic AgNP exposure pathways and exposure concentrations. The plant uptake of Ag from biosolids-amended soil containing Ag2S-NPs was very low for all Ag treatments (0.02%). Ammonium thiosulfate and potassium chloride fertilisation significantly increased the Ag concentrations of plant roots and shoots. The extent of the effect varied depending on the type of Ag. Ag2S-NPs, the realistic form of AgNPs in soil, had the lowest bioavailability. The potential risk of AgNPs in soils is low; even in the plants that had the highest Ag concentrations (Ag(+)+thiosulfate), only 0.06% of added Ag was found in edible plant parts (shoots). Results from the study suggest that agricultural practises must be considered when carrying out risk assessments of AgNPs in terrestrial systems; such practises can affect AgNP bioavailability.

Characterization and ecological risk assessment of nanoparticulate CeO2 as a diesel fuel catalyst.

Nanoparticulate cerium dioxide (nano-CeO2 ), when combusted as an additive to diesel fuel, was transformed from 6 nm to 14 nm sizes into particles near 43 nm, with no obvious change in the unit cell dimensions or crystalline form. Cerium sulfate, if formed during combustion, was below detection limits. Ceria nanoparticles were agglomerated within the soot matrix, with a mean aerodynamic diameter near 100 nm. The dissolution of cerium from the dried ceria catalyst in synthetic soft water was extremely small (<0.0006% or <0.2 µg Ce/L), with particles being highly agglomerated (<450 nm). Agglomeration was reduced in the presence of humic acid. In the combusted samples, soot was dominant, and the solubility of cerium in soft water showed an almost 100-fold increase in the <1 nm fraction compared to that before combustion. It appeared that the nano-CeO2 remained agglomerated within the soot matrix and would not be present as dispersed nanoparticles in aquatic or soil environments. Despite the increased dissolution, the solubility was not sufficient for the combusted ceria to represent a risk in aquatic ecosystems. The predicted environmental concentrations were still orders of magnitude below the predicted no effects concentration of near 1 mg/L. In the soil environment, any cerium released from soot materials would interact with natural colloids, decreasing cerium concentrations in soil solutions and further minimizing the potential risk to soil organisms.

Differences in Soil Mobility and Degradability between Water-Dispersible CdSe and CdSe/ZnS Quantum Dots

The relative leaching potential and degradation of water-dispersible CdSe and CdSe/ZnS quantum dots (QDs) were evaluated using small-scale soil columns. The potential of QDs to release toxic Cd(2+) and/or Se(2-)/SeO(3)(2-) ions upon degradation is of environmental concern and warrants investigation. Both classes of QDs exhibited limited soil mobility in CaCl(2), with more than 70% of the total Cd and Se species from QDs retained in the top soil after passing 10 column volumes of solution through the soil column. However, mobilization of Cd- and Se-species was observed when EDTA was used as the leaching solution. Approximately 98% of the total Cd(2+) loaded leached out from the Cd(2+)-spiked soil, while only 30% and 60% leached out from the CdSe and CdSe/ZnS QD-spiked soils, respectively. Soil column profiles and analysis of leachates suggest that intact QDs leached through the soil. Longer incubation (15 days) in soil prior to leaching indicated some degradation and/or surface modification of both QDs. These results suggest that chelating agents in the environment can enhance the soil mobility of intact and degraded QDs. It is apparent that QDs in soil, including the polymer-coated CdSe/ZnS QDs that are generally assumed to possess a higher degree of environmental stability, can undergo chemical transformations, which subsequently dictate their overall mobility.

Partitioning of hydrophobic CdSe quantum dots into aqueous dispersions of humic substances: Influence of capping-group functionality on the phase-transfer mechanism

Studies of the fate and transport of engineered nanomaterials are invaluable in predicting environmental impact, bioavailability, and toxicity. We report on the influence of humic and fulvic acids (models of natural organic matter) on the phase transfer of organic-capped CdSe quantum dots (QDs) from hexane to water. QDs capped with tri-n-octylphosphine oxide, tetradecylphosphonic acid, and oleic acid, which were otherwise insoluble in water, were transferred into aqueous solutions of humic substances (HS) (Suwannee River humic acid and fulvic acid standards) within 1-10 days after mixing. Phase transfer was characterized by infrared and UV/Vis absorption spectroscopy, emission spectroscopy, dynamic light scattering, electron microscopy, and inductively coupled plasma mass spectrometry. Phase-transferred QDs were intact and temporarily stabilized by HS. On longer timescales, Cd(2+) leached into aqueous solution. Our data suggest that two mechanisms promote the phase transfer of QD-HS agglomerates: (1) an overcoating mechanism involving dispersion interactions between non-polar moieties of HS and hydrocarbon chains of organic capping groups and (2) a coordinative mechanism involving displacement of capping groups by Lewis basic functionalities of HS. The structure of the capping group of QDs influenced the relative contributions of the two mechanisms and the extent to which Cd(2+) leached into water.

Behaviour of fullerenes (C60) in the terrestrial environment: Potential release from biosolids-amended soils

Owing of their wide-range of commercial applications, fullerene (C60) nanoparticles, are likely to reach environments through the application of treated sludge (biosolids) from wastewater treatment plants to soils. We examined the release behaviour of C60 from contaminated biosolids added to soils with varying physicochemical characteristics. Incubation studies were carried out in the dark for up to 24 weeks, by adding biosolids spiked (1.5mg/kg) with three forms of C60 (suspended in water, in humic acid, and precipitated/particulate) to six contrasting soils. Leaching of different biosolids+soil systems showed that only small fractions of C60 (<5% of applied amount) were released, depending on incubation time and soil properties (particularly dissolved organic carbon content). Release of C60 from unamended soils was greater (at least twice as much) than from biosolids-amended soils. The form of C60 used to spike the biosolids had no significant effect on the release of C60 from the different systems. Contact time of C60 in these systems only slightly increased the apparent release up to 8 weeks, followed by a decrease to 24 weeks. Mass balance analysis at the completion of the experiment revealed that 20-60% of the initial C60 applied could not be accounted for in these systems; the reasons for this are discussed.

Combined effects of cadmium and zinc on growth, tolerance, and metal accumulation in Chara australis and enhanced phytoextraction using EDTA

Chara australis (R. Br.) is a macrophytic alga that can grow in and accumulate Cd from artificially contaminated sediments. We investigated the effects of Zn independently and in combination with Cd on C. australis growth, metal tolerance, and uptake. Plant growth was reduced at concentrations ≥ 75 mg Zn (kg soil)⁻¹. Zn also increased the concentration of glutathione in the plant, suggesting alleviation of stress. Phytotoxic effects were observed at ≥ 250 mg added Zn (kg soil)⁻¹. At 1.5mg Zn (kg soil)⁻¹, the rhizoid bioconcentration factor (BCF) was >1.0 for both Cd and Zn. This is a criterion for hyperaccumulator status, a commonly used benchmark for utility in remediation of contaminated soils by phytoextraction. There was no significant interaction between Cd and Zn on accumulation, indicating that Chara should be effective at phytoextraction of mixed heavy metal contamination in sediments. The effects of the chelator, ethylenediaminetetraacetic acid (EDTA), were also tested. Moderate levels of EDTA increased Cd and Zn accumulation in rhizoids and Cd BCF of shoots, enhancing Charas potential in phytoremediation. This study demonstrates for the first time the potential of macroalgae to remove metals from sediments in aquatic systems that are contaminated with a mixture of metals.