Uranium accumulation in environmentally relevant microplastics and agricultural soil at acidic and circumneutral pH.

The co-occurrence of microplastics (MPs) with potentially toxic metals in the environment stresses the need to address their physicochemical interactions and the potential ecological and human health implications. Here, we investigated the reaction of aqueous U with agricultural soil and high-density polyethylene (HDPE) through the integration of batch experiments, microscopy, and spectroscopy. The aqueous initial concentration of U (100 µM) decreased between 98.6 and 99.2 % at pH 5 and between 86.2 and 98.9 % at pH 7.5 following the first half hour of reaction with 10 g of soil. In similar experimental conditions but with added HDPE, aqueous U decreased between 98.6 and 99.7 % at pH 5 and between 76.1 and 95.2 % at pH 7.5, suggesting that HDPE modified the accumulation of U in soil as a function of pH. Uranium-bearing precipitates on the cracked surface of HDPE were identified by SEM/EDS after two weeks of agitation in water at both pH 5 and 7.5. Accumulation of U on the near-surface region of reacted HDPE was confirmed by XPS. Our findings suggest that the precipitation of U was facilitated by the weathering of the surface of HDPE. These results provide insights about surface-mediated reactions of aqueous metals with MPs, contributing relevant information about the mobility of metals and MPs at co-contaminated agricultural sites.

Quantitation and identification of microplastics accumulation in human placental specimens using pyrolysis gas chromatography mass spectrometry.

The exponential increase in global plastic usage has led to the emergence of nano- and microplastic (NMP) pollution as a pressing environmental issue due to its implications for human and other mammalian health. We have developed methodologies to extract solid materials from human tissue samples by saponification and ultracentrifugation, allowing for highly specific and quantitative analysis of plastics by pyrolysis-gas chromatography and mass spectrometry (Py-GC-MS). As a benchmark, placenta tissue samples were analyzed using fluorescence microscopy and automated particle count, which demonstrated the presence of >1-micron particles and fibers, but not nano-sized plastic particles. Analyses of the samples (n = 10) using attenuated total reflectance-Fourier transform infrared spectroscopy indicated presence of rayon, polystyrene, polyethylene, and unclassified plastic particles. By contrast, among 62 placenta samples, Py-GC-MS revealed that microplastics were present in all participants' placentae, with concentrations ranging widely from 6.5 to 685 µg NMPs per gram of placental tissue, averaging 126.8 ± 147.5 µg/g (mean±SD). Polyethylene was the most prevalent polymer, accounting for 54% of total NMPs and consistently found in nearly all samples (mean 68.8 ± 93.2 µg/g placenta). Polyvinyl chloride and nylon each represented approximately 10% of the NMPs by weight, with the remaining 26% of the composition represented by 9 other polymers. Together, these data demonstrate advancements in the unbiased quantitative resolution of Py-GC-MS applied to the identification and quantification of NMP species at the maternal-fetal interface. This method, paired with clinical metadata, will be pivotal to evaluating potential impacts of NMPs on adverse pregnancy outcomes.

Interfacial Interactions of Uranium and Arsenic with Microplastics: From Field Detection to Controlled Laboratory Tests.

We studied the co-occurrence of microplastics (MPs) and metals in field sites and further investigated their interfacial interaction in controlled laboratory conditions. First, we detected MPs in freshwater co-occurring with metals in rural and urban areas in New Mexico. Automated particle counting and fluorescence microscopy indicated that particles in field samples ranged from 7 to 149 particles/L. The urban location contained the highest count of confirmed MPs, including polyester, cellophane, and rayon, as indicated by Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy analyses. Metal analyses using inductively coupled plasma (ICP) revealed that bodies of water in a rural site affected by mining legacy contained up to 332.8 µg/L of U, while all bodies of water contained As concentrations below 11.4 µg/L. These field findings motivated experiments in laboratory conditions, reacting MPs with 0.02-0.2 mM of As or U solutions at acidic and neutral pH with poly(methyl-methacrylate), polyethylene, and polystyrene MPs. In these experiments, As did not interact with any of the MPs tested at pH 3 and pH 7, nor U with any MPs at pH 3. Experiments supplied with U and MPs at pH 7 indicated that MPs served as substrate surface for the adsorption and nucleation of U precipitates. Chemical speciation modeling and microscopy analyses (i.e., Transmission Electron Microscopy [TEM]) suggest that U precipitates resemble sodium-compreignacite and schoepite. These findings have relevant implications to further understanding the occurrence and interfacial interaction of MPs and metals in freshwater.

Photoaging of polystyrene microspheres causes oxidative alterations to surface physicochemistry and enhances airway epithelial toxicity.

Microplastics represent an emerging environmental contaminant, with large gaps in our understanding of human health impacts. Furthermore, environmental factors may modify the plastic chemistry, further altering the toxic potency. Ultraviolet (UV) light is one such unavoidable factor for airborne microplastic particulates and a known modifier of polystyrene surface chemistry. As an experimental model, we aged commercially available polystyrene microspheres for 5 weeks with UV radiation, then compared the cellular responses in A549 lung cells with both pristine and irradiated particulates. Photoaging altered the surface morphology of irradiated microspheres and increased the intensities of polar groups on the near-surface region of the particles as indicated by scanning electron microscopy and by fitting of high-resolution X-ray photoelectron spectroscopy C 1s spectra, respectively. Even at low concentrations (1-30 µg/ml), photoaged microspheres at 1 and 5 µm in diameter exerted more pronounced biological responses in the A549 cells than was caused by pristine microspheres. High-content imaging analysis revealed S and G2 cell cycle accumulation and morphological changes, which were also more pronounced in A549 cells treated with photoaged microspheres, and further influenced by the size, dose, and time of exposures. Polystyrene microspheres reduced monolayer barrier integrity and slowed regrowth in a wound healing assay in a manner dependent on dose, photoaging, and size of the microsphere. UV-photoaging generally enhanced the toxicity of polystyrene microspheres in A549 cells. Understanding the influence of weathering and environmental aging, along with size, shape, and chemistry, on microplastics biocompatibility may be an essential consideration for incorporation of different plastics in products.

Characterization of root-associated fungi and reduced plant growth in soils from a New Mexico uranium mine.

Characterizing the diverse, root-associated fungi in mine wastes can accelerate the development of bioremediation strategies to stabilize heavy metals. Ascomycota fungi are well known for their mutualistic associations with plant roots and, separately, for roles in the accumulation of toxic compounds from the environment, such as heavy metals. We sampled soils and cultured root-associated fungi from blue grama grass (Bouteloua gracilis) collected from lands with a history of uranium (U) mining and contrasted against communities in nearby, off-mine sites. Plant root-associated fungal communities from mine sites were lower in taxonomic richness and diversity than root fungi from paired, off-mine sites. We assessed potential functional consequences of unique mine-associated soil microbial communities using plant bioassays, which revealed that plants grown in mine soils in the greenhouse had significantly lower germination, survival, and less total biomass than plants grown in off-mine soils but did not alter allocation patterns to roots versus shoots. We identified candidate culturable root-associated Ascomycota taxa for bioremediation and increased understanding of the biological impacts of heavy metals on microbial communities and plant growth.

Uptake and Toxicity of Respirable Carbon-Rich Uranium-Bearing Particles: Insights into the Role of Particulates in Uranium Toxicity.

Particulate matter (PM) presents an environmental health risk for communities residing close to uranium (U) mine sites. However, the role of the particulate form of U on its cellular toxicity is still poorly understood. Here, we investigated the cellular uptake and toxicity of C-rich U-bearing particles as a model organic particulate containing uranyl citrate over a range of environmentally relevant concentrations of U (0-445 µM). The cytotoxicity of C-rich U-bearing particles in human epithelial cells (A549) was U-dose-dependent. No cytotoxic effects were detected with soluble U doses. Carbon-rich U-bearing particles with a wide size distribution (<10 µm) presented 2.7 times higher U uptake into cells than the particles with a narrow size distribution (<1 µm) at 100 µM U concentration. TEM-EDS analysis identified the intracellular translocation of clusters of C-rich U-bearing particles. The accumulation of C-rich U-bearing particles induced DNA damage and cytotoxicity as indicated by the increased phosphorylation of the histone H2AX and cell death, respectively. These findings reveal the toxicity of the particulate form of U under environmentally relevant heterogeneous size distributions. Our study opens new avenues for future investigations on the health impacts resulting from environmental exposures to the particulate form of U near mine sites.

Emerging investigator series: entrapment of uranium-phosphorus nanocrystals inside root cells of Tamarix plants from a mine waste site.

We investigated the mechanisms of uranium (U) uptake by Tamarix (salt cedars) growing along the Rio Paguate, which flows throughout the Jackpile mine near Pueblo de Laguna, New Mexico. Tamarix were selected for this study due to the detection of U in the roots and shoots of field collected plants (0.6-58.9 mg kg-1), presenting an average bioconcentration factor greater than 1. Synchrotron-based micro X-ray fluorescence analyses of plant roots collected from the field indicate that the accumulation of U occurs in the cortex of the root. The mechanisms for U accumulation in the roots of Tamarix were further investigated in controlled-laboratory experiments where living roots of field plants were macerated for 24 h or 2 weeks in a solution containing 100 µM U. The U concentration in the solution decreased 36-59% after 24 h, and 49-65% in two weeks. Microscopic and spectroscopic analyses detected U precipitation in the root cell walls near the xylems of the roots, confirming the initial results from the field samples. High-resolution TEM was used to study the U fate inside the root cells, and needle-like U-P nanocrystals, with diameter <7 nm, were found entrapped inside vacuoles in cells. EXAFS shell-by-shell fitting suggest that U is associated with carbon functional groups. The preferable binding of U to the root cell walls may explain the U retention in the roots of Tamarix, followed by U-P crystal precipitation, and pinocytotic active transport and cellular entrapment. This process resulted in a limited translocation of U to the shoots in Tamarix plants. This study contributes to better understanding of the physicochemical mechanisms affecting the U uptake and accumulation by plants growing near contaminated sites.

Effect of Calcium on the Bioavailability of Dissolved Uranium(VI) in Plant Roots under Circumneutral pH.

We integrated field measurements, hydroponic experiments, microscopy, and spectroscopy to investigate the effect of Ca(II) on dissolved U(VI) uptake by plants in 1 mM HCO3- solutions at circumneutral pH. The accumulation of U in plants (3.1-21.3 mg kg-1) from the stream bank of the Rio Paguate, Jackpile Mine, New Mexico served as a motivation for this study. Brassica juncea was the model plant used for the laboratory experiments conducted over a range of U (30-700 µg L-1) and Ca (0-240 mg L-1) concentrations. The initial U uptake followed pseudo-second-order kinetics. The initial U uptake rate ( V0) ranged from 4.4 to 62 µg g-1 h-1 in experiments with no added Ca and from 0.73 to 2.07 µg g-1 h-1 in experiments with 12 mg L-1 Ca. No measurable U uptake over time was detected for experiments with 240 mg L-1 Ca. Ternary Ca-U-CO3 complexes may affect the decrease in U bioavailability observed in this study. Elemental X-ray mapping using scanning transmission electron microscopy-energy-dispersive spectrometry detected U-P-bearing precipitates within root cell walls in water free of Ca. These results suggest that root interactions with Ca and carbonate in solution affect the bioavailability of U in plants. This study contributes relevant information to applications related to U transport and remediation of contaminated sites.

Metal Reactivity in Laboratory Burned Wood from a Watershed Affected by Wildfires.

We investigated interfacial processes affecting metal mobility by wood ash under laboratory-controlled conditions using aqueous chemistry, microscopy, and spectroscopy. The Valles Caldera National Preserve in New Mexico experiences catastrophic wildfires of devastating effects. Wood samples of Ponderosa Pine, Colorado Blue Spruce, and Quaking Aspen collected from this site were exposed to temperatures of 60, 350, and 550 °C. The 350 °C Pine ash had the highest content of Cu (4997 ± 262 mg kg-1), Cr (543 ± 124 mg kg-1), and labile dissolved organic carbon (DOC, 11.3 ± 0.28 mg L-1). Sorption experiments were conducted by reacting 350 °C Pine, Spruce, and Aspen ashes separately with 10 µM Cu(II) and Cr(VI) solutions. Up to a 94% decrease in Cu(II) concentration was observed in solution while Cr(VI) concentration showed a limited decrease (up to 13%) after 180 min of reaction. X-ray photoelectron spectroscopy (XPS) analyses detected increased association of Cu(II) on the near surface region of the reacted 350 °C Pine ash from the sorption experiments compared to the unreacted ash. The results suggest that dissolution and sorption processes should be considered to better understand the potential effects of metals transported by wood ash on water quality that have important implications for postfire recovery and response strategies.

Lead bioaccumulation in Opuntia ficus-indica following foliar or root exposure to lead-bearing apatite.

The contamination of edible leafy vegetables by atmospheric heavy metal-bearing particles is a major issue in environmental toxicology. In this study, the uptake of lead by cladodes of Opuntia ficus-indica (Ofi), traditionally used in Mexican cuisine and in livestock fodder, is investigated after a 4-months exposure of either cladodes or roots to synthetic Pb-fluorapatite particles. Atomic Absorption Spectroscopy (AAS) for the quantitative analysis of Pb levels, Scanning Electron Microscopy coupled with Energy Dispersive X-Ray Spectroscopy (SEM-EDX) for the examination of the cladode surface and fate of particles, and Micro-X-ray fluorescence (µXRF) measurements for elemental mapping of Pb in cladodes, were used. The results evidence that foliar contamination may be a major pathway for the transfer of Pb within Ofi cladodes. The stomata, areoles, and cuticle of cladode surface, play an obvious role in the retention and the incorporation of lead-bearing apatite, thus revealing the hazard of eating contaminated cladodes. The possibility of using series of successive cladodes for biomonitoring the atmospheric pollution in arid and semi-arid regions is also rapidly discussed.

Potential of Opuntia ficus-indica for air pollution biomonitoring: a lead isotopic study.

Opuntia ficus-indica (Ofi) is a long-domesticated cactus that is widespread throughout arid and semiarid regions. Ofi is grown for both its fruits and edible cladodes, which are flattened photosynthetic stems. Young cladodes develop from mother cladodes, thus forming series of cladodes of different ages. Therefore, successive cladodes may hold some potential for biomonitoring over several years the local atmospheric pollution. In this study, cladodes, roots, dust deposited onto the cladodes, and soil samples were collected in the vicinity of three heavily polluted sites, i.e., a fertilizer industry, the road side of a highway, and mine tailings. The lead content was analyzed using atomic absorption spectroscopy (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS). Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) was used to characterize the cladode surfaces and the nature of dust deposit, and the lead isotopes were analyzed to identify the origin of Pb. The results show that (i) Ofi readily bioaccumulates Pb, (ii) the lead isotopic composition of cladodes evidences a foliar pathway of lead into Ofi and identifies the relative contributions of local Pb sources, and (iii) an evolution of air quality is recorded with successive cladodes, which makes Ofi a potential biomonitor to be used in environmental and health studies.