The
aim of this study was to assess the soil–water partitioning
behavior of a wider range of per- and polyfluoroalkyl substances (PFASs)
onto soils covering diverse soil properties. The PFASs studied include
perfluoroalkyl carboxylates (PFCAs), perfluoroalkane sulfonates (PFSAs),
fluorotelomer sulfonates (FTSs), nonionic perfluoroalkane sulfonamides
(FASAs), cyclic PFAS (PFEtCHxS), per- and polyfluoroalkyl ether acids
(GenX, ADONA, 9Cl-PF3ONS), and three aqueous film-forming foam (AFFF)-related
zwitterionic PFASs (AmPr-FHxSA, TAmPr-FHxSA, 6:2 FTSA-PrB). Soil–water
partitioning coefficients (log K
d values) of the PFASs ranged from less than zero to approximately
three, were chain-length-dependent, and were significantly linearly
related to molecular weight (MW) for PFASs with MW > 350 g/mol
(R
2 = 0.94, p < 0.0001).
Across
all soils, the K
d values of all short-chain
PFASs (≤5 −CF2– moieties) were similar and varied
less (<0.5 log units) compared to long-chain PFASs (>0.5
to 1.5 log units) and zwitterions AmPr- and TAmPr-FHxSA
(∼1.5 to 2 log units). Multiple soil properties described
sorption of PFASs better than any single property. The effects of
soil properties on sorption were different for anionic, nonionic,
and zwitterionic PFASs. Solution pH could change both PFAS speciation
and soil chemistry affecting surface complexation and electrostatic
processes. The K
d values of all PFASs
increased when solution pH decreased from approximately eight to three.
Short-chain PFASs were less sensitive to solution pH than long-chain
PFASs. The results indicate the complex interactions of PFASs with
soil surfaces and the need to consider both PFAS type and soil properties
to describe mobility in the environment.
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.
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.
Plant protection products containing
nanomaterials that alter the
functionality or risk profile of active ingredients (nano-enabled
pesticides) promise many benefits over conventional pesticide products.
These benefits may include improved formulation characteristics, easier
application, better targeting of pest species, increased efficacy,
lower application rates, and enhanced environmental safety. After
many years of research and development, nano-enabled pesticides are
starting to make their way into the market. The introduction of this
technology raises a number of issues for regulators, including how
does the ecological risk assessment of nano-enabled pesticide products
differ from that of conventional plant protection products? In this
paper, a group drawn from regulatory agencies, academia, research,
and the agrochemicals industry offers a perspective on relevant considerations
pertaining to the problem formulation phase of the ecological risk
assessment of nano-enabled pesticides.
Imminent commercialization of semiconductor quantum dots (QDs) has raised concerns regarding the potential environmental impact of these materials. Understanding the partitioning behavior and obtaining information on the mobility and persistence of QDs in water is key to evaluating potential ecological hazards posed by QDs in the environment The role of natural organic matter (NOM) in the phase transfer of trioctylphosphine oxide-capped CdSe QDs from an organic solvent to water has been investigated. Results show that humic and fulvic acids, which have been used as model NOM, facilitate the stabilization of organic-capped QDs in water in less than 24 h. Spectroscopic studies indicate that some or all of the organic ligands of QDs are conserved during the phase transfer. The displacement of organic ligands by NOM also appears to play a role in phase transfer. This NOM-mediated phase transfer has also been demonstrated using two natural surface water samples. This study presents the first evidence of the stabilization of QDs in water by humic substances in real environmental samples, illustrating that interactions with NOM will play a significant role in the fate and transport of QDs in natural aquatic systems.
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