In vitro and in vivo remediation of per- and polyfluoroalkyl substances by processed and amended clays and activated carbon in soil.

Remediation methods for soil contaminated with poly- and perfluoroalkyl substances (PFAS) are needed to prevent their leaching into drinking water sources and to protect living organisms in the surrounding environment. In this study, the efficacy of processed and amended clays and carbons as soil amendments to sequester PFAS and prevent leaching was assessed using PFAS-contaminated soil and validated using sensitive ecotoxicological bioassays. Four different soil matrices including quartz sand, clay loam soil, garden soil, and compost were spiked with 4 PFAS congeners (PFOA, PFOS, GenX, and PFBS) at 0.01-0.2 µg/mL and subjected to a 3-step extraction method to quantify the leachability of PFAS from each matrix. The multistep extraction method showed that PFAS leaching from soil was aligned with the total carbon content in soil, and the recovery was dependent on concentration of the PFAS. To prevent the leaching of PFAS, several sorbents including activated carbon (AC), calcium montmorillonite (CM), acid processed montmorillonite (APM), and organoclays modified with carnitine, choline, and chlorophyll were added to the four soil matrices at 0.5-4 % w/w, and PFAS was extracted using the LEAF method. Total PFAS bioavailability was reduced by 58-97 % by all sorbents in a dose-dependent manner, with AC being the most efficient sorbent with a reduction of 73-97 %. The water leachates and soil were tested for toxicity using an aquatic plant (Lemna minor) and a soil nematode (Caenorhabditis elegans), respectively, to validate the reduction in PFAS bioavailability. Growth parameters in both ecotoxicological models showed a dose-dependent reduction in toxicity with value-added growth promotion from the organoclays due to added nutrients. The kinetic studies at varying time intervals and varying pHs simulating acidic rain, fresh water, and brackish water suggested a stable sorption of PFAS on all sorbents that fit the pseudo-second-order for up to 21 days. Contaminated soil with higher than 0.1 µg/mL PFAS may require reapplication of soil amendments every 21 days. Overall, AC showed the highest sorption percentage of total PFAS from in vitro studies, while organoclays delivered higher protection in ecotoxicological models (in vivo). This study suggests that in situ immobilization with soil amendments can reduce PFAS leachates and their bioavailability to surrounding organisms. A combination of sorbents may facilitate the most effective remediation of complex soil matrices containing mixtures of PFAS and prevent leaching and uptake into plants.

Kinetics of glyphosate and aminomethylphosphonic acid sorption onto montmorillonite clays in soil and their translocation to genetically modified corn.

The co-occurrence of glyphosate (GLP) and aminomethylphosphonic acid (AMPA) in contaminated water, soil, sediment and plants is a cause for concern due to potential threats to the ecosystem and human health. A major route of exposure is through contact with contaminated soil and consumption of crops containing GLP and AMPA residues. However, clay-based sorption strategies for mixtures of GLP and AMPA in soil, plants and garden produce have been very limited. In this study, in vitro soil and in vivo genetically modified corn models were used to establish the proof of concept that the inclusion of clay sorbents in contaminated soils will reduce the bioavailability of GLP and AMPA in soils and their adverse effects on plant growth. Effects of chemical concentration (1-10 mg/kg), sorbent dose (0.5%-3% in soil and 0.5%-1% in plants) and duration (up to 28 days) on sorption kinetics were studied. The time course results showed a continuous GLP degradation to AMPA. The inclusion of calcium montmorillonite (CM) and acid processed montmorillonite (APM) clays at all doses significantly and consistently reduced the bioavailability of both chemicals from soils to plant roots and leaves in a dose- and time-dependent manner without detectable dissociation. Plants treated with 0.5% and 1% APM inclusion showed the highest growth rate (p ≤ 0.05) and lowest chemical bioavailability with up to 76% reduction in roots and 57% reduction in leaves. Results indicated that montmorillonite clays could be added as soil supplements to reduce hazardous mixtures of GLP and AMPA in soils and plants.

Green-engineered clay- and carbon-based composite materials for the adsorption of benzene from air.

Benzene is a carcinogenic volatile organic compound (VOC) that is ubiquitously detected in enclosed spaces due to emissions from cooking activities, building materials, and cleaning products. To remove benzene and other VOCs from indoor air and protect public health, traditional fabric filters have been modified to contain activated carbons to enhance the filtration efficacy. In this study, composites derived from natural clay minerals and activated carbon were individually green-engineered with chlorophylls and were attached to the surface of filter materials. These systems were assessed for their adsorption of benzene from air using in vitro and in silico methods. Isothermal, thermodynamic, and kinetic experiments indicated that all green-engineered composites had improved binding profiles for benzene, as demonstrated by increased binding affinities (Kf ≥ 900 vs 472) and lower values of Gibbs free energy (ΔG = -16.8 vs -15.2) compared to activated carbon. Adsorption of benzene to all composites was achieved quickly (< 30 min), and the green-engineered composites also showed low levels of desorption (≤ 25%). While free chlorophyll is known to be photosensitive, chlorophylls in the green-engineered composites showed photostability and maintained high binding rates (≥ 70%). Additionally, the in silico simulations demonstrated the significant contribution of chlorophyll for the overall binding of benzene in clay systems and that chlorophyll could contribute to benzene binding in the carbon-based systems. Together, these studies indicated that novel, green-engineered composite materials can be effective filter sorbents to enhance the removal of benzene from air.

Toxicity of representative organophosphate, organochlorine, phenylurea, dinitroaniline, carbamate, and viologen pesticides to the growth and survival of H. vulgaris, L. minor, and C. elegans.

Pesticides are commonly found in the environment and pose a risk to target and non-target species; therefore, employing a set of bioassays to rapidly assess the toxicity of these chemicals to diverse species is crucial. The toxicity of nine individual pesticides from organophosphate, organochlorine, phenylurea, dinitroaniline, carbamate, and viologen chemical classes and a mixture of all the compounds were tested in three bioassays (Hydra vulgaris, Lemna minor, and Caenorhabditis elegans) that represent plant, aquatic, and soil-dwelling species, respectively. Multiple endpoints related to growth and survival were measured for each model, and EC10 and EC50 values were derived for each endpoint to identify sensitivity patterns according to chemical classes and target organisms. L. minor had the lowest EC10 and EC50 values for seven and five of the individual pesticides, respectively. L. minor was also one to two orders of magnitude more sensitive to the mixture compared to H. vulgaris and C. elegans, where EC50 values were calculated to be 0.00042, 0.0014, and 0.038 mM, respectively. H. vulgaris was the most sensitive species to the remaining individual pesticides, and C. elegans consistently ranked the least sensitive to all tested compounds. When comparing the EC50 values across all pesticides, the endpoints of L. minor were correlated with each other while the endpoints measured in H. vulgaris and C. elegans were clustered together. While there was no apparent relationship between the chemical class of pesticide and toxicity, the compounds were more closely clustered based on target organisms (herbicide vs insecticide). The results of this study demonstrate that the combination of these plant, soil, and aquatic specie can serve as representative indicators of pesticide pollution in environmental samples.

Using L. minor and C. elegans to assess the ecotoxicity of real-life contaminated soil samples and their remediation by clay- and carbon-based sorbents.

Toxic substances, such as polycyclic aromatic hydrocarbons (PAHs) and heavy metals, can accumulate in soil, posing a risk to human health and the environment. To reduce the risk of exposure, rapid identification and remediation of potentially hazardous soils is necessary. Adsorption of contaminants by activated carbons and clay materials is commonly utilized to decrease the bioavailability of chemicals in soil and environmental toxicity in vitro, and this study aims to determine their efficacy in real-life soil samples. Two ecotoxicological models (Lemna minor and Caenorhabditis elegans) were used to test residential soil samples, known to contain an average of 5.3, 262, and 9.6 ppm of PAHs, lead, and mercury, for potential toxicity. Toxicity testing of these soils indicated that 86% and 58% of soils caused ≤50% inhibition of growth and survival of L. minor and C. elegans, respectively. Importantly, 3 soil samples caused ≥90% inhibition of growth in both models, and the toxicity was positively correlated with levels of heavy metals. These toxic soil samples were prioritized for remediation using activated carbon and SM-Tyrosine sorbents, which have been shown to immobilize PAHs and heavy metals, respectively. The inclusion of low levels of SM-Tyrosine protected the growth and survival of L. minor and C. elegans by 83% and 78%, respectively from the polluted soil samples while activated carbon offered no significant protection. These results also indicated that heavy metals were the driver of toxicity in the samples. Results from this study demonstrate that adsorption technologies are effective strategies for remediating complex, real-life soil samples contaminated with hazardous pollutants and protecting natural soil and groundwater resources and habitats. The results highlight the applicability of these ecotoxicological models as rapid screening tools for monitoring soil quality and verifying the efficacy of remediation practices.

Adsorption and detoxification of glyphosate and aminomethylphosphonic acid by montmorillonite clays.

The co-occurrence of mixtures of glyphosate (GLP) and aminomethylphosphonic acid (AMPA) in contaminated water, soil, sediment, and plants is a cause for concern due to potential threats to the ecosystem and human health. Major routes of exposure include contact with contaminated water and soil and through consumption of crops containing GLP and AMPA residues. Calcium montmorillonite (CM) and acid-processed montmorillonite (APM) clays were investigated for their ability to tightly sorb and detoxify GLP and AMPA mixtures. In vitro adsorption and desorption isotherms and thermodynamic analysis indicated saturable Langmuir binding of both chemicals with high capacities, affinities, enthalpies, and free energies of sorption and low desorption rates. In silico computational modeling indicated that both GLP and AMPA can be readily absorbed onto clay surfaces through electrostatic interactions and hydrogen bonding. The safety and efficacy of the clays were confirmed using well-established living organisms, including an aquatic cnidarian (Hydra vulgaris), a soil nematode (Caenorhabditis elegans), and a floating plant (Lemna minor). Low levels of clay inclusion (0.05% and 0.2%) in the culture medium resulted in increased growth and protection against chemical mixtures based on multiple endpoints. Results indicated that montmorillonite clays may be used to bind mixtures of GLP and AMPA in water, soil, and plants.

Development and characterization of chlorophyll-amended montmorillonite clays for the adsorption and detoxification of benzene.

After disasters, such as forest fires and oil spills, high levels of benzene (> 1 ppm) can be detected in the water, soil, and air surrounding the disaster site, which poses a significant health risk to human, animal, and plant populations in the area. While remediation methods with activated carbons have been employed, these strategies are limited in their effectiveness due to benzene's inherent stability and limited retention to most surfaces. To address this problem, calcium and sodium montmorillonite clays were amended with a mixture of chlorophyll (a) and (b); their binding profile and ability to detoxify benzene were characterized using in vitro, in silico, and well-established ecotoxicological (ecotox) bioassay methods. The results of in vitro isothermal analyses indicated that chlorophyll-amended clays showed an improved binding profile in terms of an increased binding affinity (Kf = 668 vs 67), increased binding percentage (52% vs 11%), and decreased rates of desorption (28% vs 100%), compared to the parent clay. In silico simulation studies elucidated the adsorption mechanism and validated that the addition of the chlorophyll to the clays increased the adsorption of benzene through Van der Waals forces (i.e., aromatic π-π stacking and alkyl-π interactions). The sorbents were also assessed for their safety and ability to protect sensitive ecotox organisms (Lemna minor and Caenorhabditis elegans) from the toxicity of benzene. The inclusion of chlorophyll-amended clays in the culture medium significantly reduced benzene toxicity to both organisms, protecting C. elegans by 98-100% from benzene-induced mortality and enhancing the growth rates of L. minor. Isothermal analyses, in silico modeling, and independent bioassays all validated our proof of concept that benzene can be sequestered, tightly bound, and stabilized by chlorophyll-amended montmorillonite clays. These novel sorbents can be utilized during disasters and emergencies to decrease unintentional exposures from contaminated water, soil, and air.