Exposure to mixtures of mercury, cadmium, lead, and arsenic alters the disposition of single metals in tissues of Wistar rats.

Humans throughout the world are exposed regularly to mixtures of environmental toxicants. Four of the most common heavy metal toxicants in the environment are mercury (Hg), cadmium (Cd), lead (Pb), and arsenic (As). Numerous studies have assessed the effects and disposition of individual metals in organ systems; however, humans are usually exposed to mixtures of toxicants or metals rather than to a single toxicant. Therefore, the purpose of the current study was to test the hypothesis that exposure to a mixture of toxic heavy metals alters the disposition of single metals in target organs. Wistar rats (Rattus norvegicus) were exposed to Hg, Cd, Pb, or As as a single metal or as a mixture of metals. Rats were injected intravenously for three days, following which kidneys, liver, brain, and blood were harvested. Samples were analyzed for content of Hg, Cd, Pb, and As via inductively coupled plasma mass spectrometry. In general, exposure to a mixture of metals reduced accumulation of single metals in target organs. Interestingly, exposure to mixtures of metals with Pb and/or As increased the concentration of these metals specifically in the liver. The findings from this study indicate that exposure to mixtures of toxic heavy metals may alter significantly the distribution and accumulation of these metals in target organs and tissues.

Tunable High Entropy Lanthanide Oxide Microspheres via Confined Electroprecipitation in Emulsion Droplet Scaffolds.

Emergent high entropy nanomaterials and their associated complex surface structure hold promise to unlock unique catalytic intermediate pathways and photonic/plasmonic interactions; however, synthetic strategies to tune the size, morphological, and stoichiometric properties remain limited. This work demonstrates a confined electro-precipitation mechanism for the formation of tunable, high-entropy oxide microspheres within emulsion droplet scaffolds. This mechanism complements a traditional confined electrodeposition mechanism and explains the previously observed anomalous formation of thermodynamically unfavorable particles, including lanthanide species. Mass transfer studies reveal that microsphere coverage over a surface may be tuned and modeled by using a time-dependent modified Levich equation. Additionally, morphological tuning was demonstrated as a function of experimental conditions, such as rotation rate and precursor concentration. Finally, extension to multimetallic species permitted the generation of high-entropy lanthanide oxide microspheres, which were confirmed to have equimolar stoichiometries via energy dispersive spectroscopy and inductively coupled plasma mass spectrometry. This novel method promises to generate tunable, complex oxides with applications to thermal catalysis, optics, and applications yet unknown.

Critical metal geochemistry in groundwaters influenced by dredged material.

This study investigated critical metal (CM) geochemistry including rare earth elements (REEs), Co, Ni, and Mn in groundwaters below and surrounding two dredged material placement facilities (DMPFs). Metal concentrations are elevated at both sites, spanning several orders of magnitude. The highest CM concentrations measured exceed many environments considered as aqueous resources (Co and Ni > 1 mg L-1, REEs > 3 mg L-1). Correlations between sulfur and iron, major cations, and CMs indicate that oxidation of sulfides present in the DM releases metals both directly from sulfide minerals and indirectly through acid dissolution of and/or desorption from additional minerals. REE fractionation patterns indicate that their mobility in the groundwaters may be influenced by interactions with silicate, carbonate, and phosphate minerals. Significant positive Gd and Eu anomalies were observed, which may be attributed to increased mobility of Eu2+ and anthropogenic Gd. Nanogeochemical analysis of filtered samples revealed several REE-bearing nanoparticulate (diameter < 100 nm) species, some of which co-occurred with aluminum, suggesting an (oxy)hydroxide or a clay mineral component. Further characterization of soluble and nano scale geochemical speciation is needed to fully assess the viability of CM recovery from DM-associated groundwater. CM recovery from DM-associated waters can provide a beneficial use, both offsetting costs associated with disposal, and supplementing domestic CM resources.

Separation and identification of microplastics in marine organisms by TGA-FTIR-GC/MS: A case study of mussels from coastal China.

Microplastics are ubiquitous in the marine environment but characterizing them in marine organisms is challenging. Herein we describe a method to detect, identify, and quantify microplastics in marine mussels (Mytilus edulis) using thermal gravimetric analysis - Fourier Transform infrared spectroscopy - gas chromatography mass spectrometry (TGA-FTIR-GC/MS) after extracting and isolating the microplastics using chemical digestion, density separation, and filtration. Combining the three instrumental techniques adds discriminatory power as temperature profiles, chromatograms, and vibrational and mass spectra differ among common plastics. First, we tested several digestion schemes after spiking the mussels with plastics commonly found in the marine environment, including polyethylene (PE), polystyrene (PS), polypropylene (PP) and polyvinyl chloride (PVC). KOH (10%, w/v) was the most suitable reagent, providing good recoveries (>97%) without degrading the microplastics. We show that the technique TGA-FTIR-GC/MS can be optimized to readily determine both the type (polymer) and amount (mass) of microplastics in the sample. Applied to 100 mussels from each of six locations along the coast of China, we found an average of 0.58 mg of plastic per kg of tissue (range 0.16-1.71 mg/kg), with PE being the most abundant type of plastic measured. Among the coastal cities, mussels from Dalian had the highest microplastic content. Overall, we demonstrate that the method is a powerful technique to quantify masses of microplastics in marine mussels, a species commonly used as a bioindicator of pollution, and may be applied to other biota as well.

Single-Pot Method for the Collection and Preparation of Natural Water for Microplastic Analyses: Microplastics in the Mississippi River System during and after Historic Flooding.

We describe a simple single-pot method for collection and preparation of natural water for microplastic analyses. The method prepares samples in the same vessel (mason jars) that they are collected in right up until the microplastics are transferred onto filters or spectroscopic windows for analyses. The method minimized contamination, degradation, and losses, while increasing recoveries and throughput when compared with conventional sieving. We applied it to surface grab samples collected from the Mississippi River and its major tributaries during and after historic flooding in 2019. Microplastics (>~30 µm) were quantified using Nile red fluorescence detection, and a small subset of samples were identified by micro-Fourier transform infrared imaging spectroscopy. Concentrations were lower during the flooding, likely due to dilution. Concentrations ranged from approximately 14 microplastics/L in the Tennessee River during flooding to approximately 83 microplastics/L in the Ohio River during low-flow (summer) conditions. Loads of microplastics tended to increase downriver and ranged from approximately 87 to approximately 129 trillion microplastics/d near New Orleans. Most of the microplastics (>60%) were in the lower size fraction (~30-90 µm) and consisted primarily of fragments (~85%), followed by fibers (~8%) and beads (~7%), with polyester, polyethylene, polypropylene, and polyacrylate as the primary microplastic types. Overall, we demonstrate that the single-pot method is effective and versatile and, because it uses relatively inexpensive and easily assembled materials, can be adapted for microplastic surveys worldwide, especially those involving sample collection by volunteers from the community and schools. Environ Toxicol Chem 2020;39:986-995. © 2020 SETAC.

Occurrence of Microplastic Pollution at Oyster Reefs and Other Coastal Sites in the Mississippi Sound, USA: Impacts of Freshwater Inflows from Flooding.

Much of the seafood that humans consume comes from estuaries and coastal areas where microplastics (MPs) accumulate, due in part to continual input and degradation of plastic litter from rivers and runoff. As filter feeders, oysters (Crassostrea virginica) are especially vulnerable to MP pollution. In this study, we assessed MP pollution in water at oyster reefs along the Mississippi Gulf Coast when: (1) historic flooding of the Mississippi River caused the Bonnet Carré Spillway to remain open for a record period of time causing major freshwater intrusion to the area and deleterious impacts on the species and (2) the spillway was closed, and normal salinity conditions resumed. Microplastics (~25 µm-5 mm) were isolated using a single-pot method, preparing samples in the same vessel (Mason jars) used for their collection right up until the MPs were transferred onto filters for analyses. The MPs were quantified using Nile Red fluorescence detection and identified using laser direct infrared (LDIR) analysis. Concentrations ranged from ~12 to 381 particles/L and tended to decrease at sites impacted by major freshwater intrusion. With the spillway open, average MP concentrations were positively correlated with salinity (r = 0.87, p = 0.05) for sites with three or more samples examined. However, the dilution effect on MP abundances was temporary, and oyster yields suffered from the extended periods of lower salinity. There were no significant changes in the relative distribution of MPs during freshwater intrusions; most of the MPs (>50%) were in the lower size fraction (~25-90 µm) and consisted mostly of fragments (~84%), followed by fibers (~11%) and beads (~5%). The most prevalent plastic was polyester, followed by acrylates/polyurethanes, polyamide, polypropylene, polyethylene, and polyacetal. Overall, this work provides much-needed empirical data on the abundances, morphologies, and types of MPs that oysters are exposed to in the Mississippi Sound, although how much of these MPs are ingested and their impacts on the organisms deserves further scrutiny. This paper is believed to be the first major application of LDIR to the analysis of MPs in natural waters.

Adaption and use of a quadcopter for targeted sampling of gaseous mercury in the atmosphere.

We modified a popular and inexpensive quadcopter to collect gaseous mercury (Hg) on gold-coated quartz cartridges, and analyzed the traps using cold vapor atomic fluorescence spectrometry. Flight times averaged 16 min, limited by battery life, and yielded > 5 pg of Hg, well above the limit of detection (< 0.2 pg). We measured progressively higher concentrations upon both vertical and lateral approaches to a dish containing elemental Hg, demonstrating that the method can detect Hg emissions from a point source. Using the quadcopter, we measured atmospheric Hg near anthropogenic emission sources in the mid-south USA, including a municipal landfill, coal-fired power plant (CFPP), and a petroleum refinery. Average concentrations (± standard deviation) immediately downwind of the landfill were higher at ground level and 30 m compared to 60 and 120 m (5.3 ± 0.5 ng m-3, 5.4 ± 0.7 ng m-3, 4.2 ± 0.7 ng m-3, and 2.5 ± 0.3 ng m-3, respectively). Concentrations were also higher at an urban/industrial area (Memphis) (3.3 ± 0.9 ng m-3) compared with a rural/background area (1.5 ± 0.2 ng m-3). Due to airspace flight restrictions near the CFPP and refinery, we were unable to access near-field (stack) plumes and did not observe differences between upwind and downwind locations. Overall, this study demonstrates that highly maneuverable multicopters can be used to probe Hg concentrations aloft, which may be particularly useful for evaluating Hg emissions from remote landscapes and transient sources that are inadequately characterized and leading to uncertainties in ecosystem budgets.