Comprehensive model for predicting toxic equivalents (TEQ) reduction due to dechlorination of polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/F congeners).

Remediation-focused predictive tools for polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) rely on transformation models to evaluate the reduction in total contaminant load and toxic equivalency (TEQ). In this study, a comprehensive model predicting the profiles of PCDD/F congeners and the associated TEQs was developed. The model employs first-order kinetics to describe the transformation of 256 reactions for 75 PCDD congeners and 421 reactions for 135 PCDF congeners.

Control of the Structural Charge Distribution and Hydration State upon Intercalation of CO into Expansive Clay Interlayers.

Numerous experimental investigations indicated that expansive clays such as montmorillonite can intercalate CO preferentially into their interlayers and therefore potentially act as a material for CO separation, capture, and storage. However, an understanding of the energy-structure relationship during the intercalation of CO into clay interlayers remains elusive. Here, we use metadynamics molecular dynamics simulations to elucidate the energy landscape associated with CO intercalation.

Synthesis and evaluation of FeO-impregnated activated carbon for dioxin removal.

Polychlorinated dibenzo-p-dioxins and -furans (PCDD/PCDFs) are highly toxic organic pollutants in soils and sediments which persist over timescales that extend from decades to centuries. There is a growing need to develop effective technologies for remediating PCDD/Fs-contaminated soils and sediments to protect human and ecosystem health. The use of sorbent amendments to sequester PCDD/Fs has emerged as one promising technology.

Natural organic matter does not diminish the mammalian bioavailability of 2,3,7,8-tetrachlorodibenzo-p-dioxin.

2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) is a toxic and persistent organic pollutant found in soils and sediments. It has been linked to several adverse health outcomes in humans and wildlife, including suppression of the immune system. TCDD is strongly sorbed to soils/sediments due to its extremely low water solubility.

Effect of land use on organic matter composition in density fractions of contrasting soils: A comparative study using C NMR and DRIFT spectroscopy.

C CP-MAS nuclear magnetic resonance (NMR) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopies were compared for evaluating their potential to characterise the influence of land use change on organic carbon (OC) chemistry of particulate organic matter (POM) and mineral associated OM (MOM) fractions of different soil types. Surface soil samples of Ferralsol, Luvisol, Vertisol and Solonetz were collected from native and crop lands and isolated into different density fractions. NMR and DRIFT showed distinct OC composition for all the soil fractions of two land uses.

Bioavailability of clay-adsorbed dioxin to Sphingomonas wittichii RW1 and its associated genome-wide shifts in gene expression.

Polychlorinated dibenzo-p-dioxins and dibenzofurans are a group of chemically-related pollutants categorically known as dioxins. Some of their chlorinated congeners are among the most hazardous pollutants that persist in the environment. This persistence is due in part to the limited number of bacteria capable of metabolizing these compounds, but also to their limited bioavailability in soil.

Long-term sorption of lincomycin to biochars: The intertwined roles of pore diffusion and dissolved organic carbon.

Sequestration of anthropogenic antibiotics by biochars from waters may be a promising strategy to minimize environmental and human health risks of antibiotic resistance. This study investigated the long-term sequestration of lincomycin by 17 slow-pyrolysis biochars using batch sorption experiments during 365 days. Sorption kinetics were well fitted to the Weber-Morris intraparticle diffusion model for all tested biochars with the intraparticle diffusion rate constant (k) of 25.

Distinguishing between bulk and edge hydroxyl vibrational properties of 2 : 1 phyllosilicates via deuteration.

Observation of vibrational properties of phyllosilicate edges via a combined molecular modeling and experimental approach was performed. Deuterium exchange was utilized to isolate edge vibrational modes from their internal counterparts. The appearance of a specific peak within the broader D2O band indicates the presence of deuteration on the edge surface, and this peak is confirmed with the simulated spectra.

Activated carbons of varying pore structure eliminate the bioavailability of 2,3,7,8-tetrachlorodibenzo-p-dioxin to a mammalian (mouse) model.

The use of activated carbon (AC) as an in situ sorbent amendment to sequester polychlorinated-dibenzo-p-dioxins and furans (PCDD/Fs) present in contaminated soils and sediments has recently gained attention as a novel remedial approach. This remedy could be implemented at much lower cost while minimizing habitat destruction as compared to traditional remediation technologies that rely on dredging/excavation and landfilling. Several prior studies have demonstrated the ability of AC amendments to reduce pore water concentrations and hence bioaccumulation of PCDD/Fs in invertebrate species.

Impact of Intrinsic Structural Properties on the Hydration of 2:1 Layer Silicates.

Several 2:1 layer silicates comprising di- and trioctahedral smectites of different layer charge between 0.2 and 0.4 per formula unit and a trioctahedral vermiculite were studied by an method that allowed Fourier transform infrared spectroscopy (FTIR) spectra and water vapor sorption isotherms to be obtained simultaneously.

TCDD administered on activated carbon eliminates bioavailability and subsequent shifts to a key murine gut commensal.

Activated carbon (AC) is an increasingly attractive remediation alternative for the sequestration of dioxins at contaminated sites globally. However, the potential for AC to reduce the bioavailability of dioxins in mammals and the residing gut microbiota has received less attention. This question was partially answered in a recent study examining 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-induced hallmark toxic responses in mice administered with TCDD sequestered by AC or freely available in corn oil by oral gavage.

Sequestration of 2,3,7,8-tetrachlorodibenzo-p-dioxin by activated carbon eliminates bioavailability and the suppression of immune function in mice.

The effectiveness of activated carbon in reducing the bioavailability of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was examined from the context of using in situ sorbent amendments to remediate soils/sediments contaminated with polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs). This technology has gained rapid acceptance based on observations that activated carbon amendments predictably lower PCDD/F concentrations in water and bioaccumulation by simple aquatic organisms and earthworms; it has been assumed that bioavailability to mammals is similarly reduced, although this has been disproven for other sorbent materials. In the present study TCDD was absorbed to a microporous activated carbon (TCDD-AC) using the incipient wetness method.

Mechanism Associated with Kaolinite Intercalation with Urea: Combination of Infrared Spectroscopy and Molecular Dynamics Simulation Studies.

Intercalation of urea in kaolinite was investigated using infrared spectroscopy and molecular dynamics simulation. Infrared spectroscopic results indicated the formation of hydrogen bonds between urea and siloxane/alumina surfaces of kaolinite. The carbonyl group (-C=O) of urea acted as H-acceptors for the hydroxyl groups on alumina surfaces.

Initial biochar properties related to the removal of As, Se, Pb, Cd, Cu, Ni, and Zn from an acidic suspension.

This study tests the influence of a diverse set of biochar properties on As(V), Se(IV), Cd(II), Cu(II), Ni(II), Pb(II), or Zn(II) removal from solution at pH 4.5. Six commercial biochars produced using different feedstock and pyrolysis conditions were extensively characterized using physical, chemical, and spectroscopic techniques, and their properties were correlated to anion and cation removal using multiple linear regression.

Sorption of Lincomycin by Manure-Derived Biochars from Water.

The presence of antibiotics in agroecosystems raises concerns about the proliferation of antibiotic-resistant bacteria and adverse effects to human health. Soil amendment with biochars pyrolized from manures may be a win-win strategy for novel manure management and antibiotics abatement. In this study, lincomycin sorption by manure-derived biochars was examined using batch sorption experiments.

Weathering of pyrogenic organic matter induces fungal oxidative enzyme response in single culture inoculation experiments.

The addition of pyrogenic organic matter (PyOM), the aromatic carbon-rich product of the incomplete combustion of plant biomass or fossil fuels, to soil can influence the rate of microbial metabolism of native soil carbon. The interaction of soil heterotrophs with PyOM may be governed by the surficial chemical and physical properties of PyOM that evolve with environmental exposure. We present results of a 36-day laboratory incubation investigating the interaction of a common white-rot fungus, with three forms of C-enriched (2.

Integrating structural and thermodynamic mechanisms for sorption of PCBs by montmorillonite.

Strong sorption of planar nonionic organic chemicals by clay minerals has been observed for important classes of organic contaminants including polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and dioxins, and such affinity was hypothesized to relate to the interlayer hydrophobicity of smectite clays. In batch sorption experiments of two trichlorobiphenyls on homoionic Na-, K-, Cs-montmorillonites, considerably greater sorption coefficient (Kw) was observed for coplanar 3,3',5-trichlorobiphenyl (PCB 36); log Kw for Na-, K-, and Cs-montmorillonite were 3.69, 3.

Soilless plant growth media influence the efficacy of phytohormones and phytohormone inhibitors.

Plant growth regulators, such as hormones and their respective biosynthesis inhibitors, are effective tools to elucidate the physiological function of phytohormones in plants. A problem of chemical treatments, however, is the potential for interaction of the active compound with the growth media substrate. We studied the interaction and efficacy of propiconazole, a potent and specific inhibitor of brassinosteroid biosynthesis, with common soilless greenhouse growth media for rice, sorghum, and maize.

Influence of mineral characteristics on the retention of low molecular weight organic compounds: a batch sorption-desorption and ATR-FTIR study.

Batch experiments were conducted to evaluate the sorption-desorption behaviour of (14)C-labelled carboxylic acids (citric and oxalic) and amino acids (glutamic, alanine, phenylalanine and lysine) on pure minerals (kaolinite, illite, montmorillonite, ferrihydrite and goethite). The sorption experiments were complemented by ATR-FTIR spectroscopy to gain possible mechanistic insight into the organic acids-mineral interactions. In terms of charge, the organic solutes ranged from strongly negative (i.

Nature of the interlayer environment in an organoclay optimized for the sequestration of dibenzo-p-dioxin.

A Na-smectite clay (Na-SWy-2) was exchanged with various amounts of dimethyldioctadecylammonium bromide (DODA-Br) up to twice the cation exchange capacity (CEC). The organoclay (DODA-SWy-2) with DODA-Br added at 2 × CEC exhibited a maximum 4.2 nm d-spacing and a 31.

Interaction of biological molecules with clay minerals: a combined spectroscopic and sorption study of lysozyme on saponite.

The interaction of hen egg white lysozyme (HEWL) with Na- and Cs-exchanged saponite was investigated using sorption, structural, and spectroscopic methods as a model system to study clay-protein interactions. HEWL sorption to Na- and Cs-saponite was determined using the bicinchoninic acid (BCA) assay, thermogravimetric analysis, and C and N analysis. For Na-saponite, the TGA and elemental analysis-derived sorption maximum was 600 mg/g corresponding to a surface coverage of 0.

Suppression of humoral immune responses by 2,3,7,8-tetrachlorodibenzo-p-dioxin intercalated in smectite clay.

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) is a highly toxic environmental contaminant found in soils and sediments. Because of its exceptionally low water solubility, this compound exists predominantly in the sorbed state in natural environments. Clay minerals, especially expandable smectite clays, are one of the major component geosorbents in soils and sediments that can function as an effective adsorbent for environmental dioxins, including TCDD.

Clay mediated route to natural formation of Polychlorodibenzo-p-dioxins.

Recent studies have documented the ubiquitous occurrence of polychlorodibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of unknown origin in soils and clay deposits. Interestingly, the PCDD/F congener profiles do not match any known natural or anthropogenic source, and global PCDD/F budgets fail to account for the observed levels in soils. To reconcile these observations, clay minerals had been hypothesized to play a central role in the natural in situ synthesis of PCDD/Fs.

Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: density functional theory and fourier transform infrared studies.

Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay. (1) Here, we used in situ Fourier transform infrared (FTIR) methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated.