Chlorpyrifos fate in the Arctic: Importance of analyte structure in interactions with Arctic dissolved organic matter.

The insecticide and current use pesticide chlorpyrifos (CLP) is transported via global distillation to the Arctic where it may pose a threat to this ecosystem. CLP is readily detected in Arctic environmental compartments, but current research has not studied its partitioning between water and dissolved organic matter (DOM) nor the role of photochemistry in CLP's fate in aquatic systems. Here, the partition coefficients of CLP were quantified with various types of DOM isolated from the Arctic and an International Humic Substances Society (IHSS) reference material Suwannee River natural organic matter (SRNOM). While CLP readily partitions to DOM, CLP exhibits a significantly higher binding constant with Arctic lacustrine DOM relative to fluvial DOM or SRNOM. The experimental partitioning coefficients (KDOC) were compared to a calculated value estimated using poly parameter linear free energy relationship (pp-LFER) and was found to be in good agreement with SRNOM, but none of the Arctic DOMs. We found that Arctic KDOC values decrease with increasing SUVA254, but no correlations were observed for the other DOM compositional parameters. DOM also mediates the photodegradation of CLP, with stark differences in photo-kinetics using Arctic DOM isolated over time and space. This work highlights the chemo-diversity of Arctic DOM relative to IHSS reference materials and highlights the need for in-depth characterization of DOM that transcends the current paradigm based upon terrestrial and microbial precursors.

Behavior of potentially toxic elements from stoker-boiler fly ash in Interior Alaska: paired batch leaching and solid-phase characterization.

Despite significant investigation of fly ash spills and mineralogical controls on the release of potentially toxic elements (PTEs) from fly ash, interactions with the surficial environment remain relatively poorly understood. We conducted 90-day batch leaching studies with paired analysis of supernatant and solid-phase mineralogy to assess the elemental release and transformation of fly ash upon reaction with aquatic media (18 MΩ cm-1 water and simulated rainwater). The fly ash in this study, collected from the University of Alaska Fairbanks stoker-boiler power plant, is high in unburned carbon (~20% LOI) and highly enriched in several PTEs relative to the upper continental crust. Supernatant concentrations of oxyanion-forming elements (e.g., As, Se, Mo, Sb) remained relatively low and constant, suggesting equilibrium with the solid phase, possibly ettringite [Ca6Al2(SO4)3(OH)12•26H2O], which is known to incorporate and sorb oxyanion-forming PTEs and was identified by X-ray diffraction. Synthetic precipitation leaching procedure (SPLP) results failed to capture important temporal trends. Lead and Ba supernatant concentrations consistently exceeded drinking water standards, as well as others upon exposure to simulated physiological solutions. Seven-day experiments with dissolved organic matter-isolate solutions indicated that for certain elements, liberation was influenced by carbon concentration and/or the identity of the isolate. Overall, this paired approach can serve as a model for future studies, bridging existing gaps between batch leaching and single-element mineralogical, sorption, or speciation studies.

Composition and photo-reactivity of organic matter from permafrost soils and surface waters in interior Alaska.

Yedoma permafrost soils are especially susceptible to abrupt thaw due to their exceptional thickness and high ice content. Compared to other mineral soils, yedoma has a high organic carbon content, which has shown to be particularly biolabile. The organic carbon in these deposits needs to be characterised to provide an identification toolkit for detecting and monitoring the thaw, mobilisation and mineralisation of yedoma permafrost. This study characterised organic carbon isolates from thermokarst lakes (either receiving inputs from thaw of original yedoma or refrozen-thermokarst deposits, or lacking recent thaw) during winter and summer seasons within the Goldstream Creek watershed, a discontinuous permafrost watershed in interior Alaska, to identify the extent to which thermokarst-lake environments are impacted by degradation of yedoma permafrost. Waters from lakes of varied age and thermokarst activity, as well as active layer and undisturbed yedoma permafrost soils were isolated and characterised by functional group abundance (multiCP-MAS 13C and SPR-W5-WATERGATE 1H NMR), absorbance and fluorescence, and photobleaching ability. DOM isolated from winter and summer seasons revealed differing composition and photoreactivity, suggesting varied active layer and permafrost influence under differing ground water flow regimes. Water extractable organic matter isolates from permafrost leachates revealed variation in terms of photoreactivity and photolability, with the youngest sampled permafrost isolate being the most photoreactive and photolabile. As temperatures increase, release of permafrost organic matter is inevitable. Obtaining a holistic understanding of DOM composition and photoreactivity will allow for a better prediction of permafrost thaw impacts in the coming decades.

Introduction to Environmental Chemistry of the Arctic: An Introductory, Lab-Based Course Offered Both Face-to-Face and by Distance.

In this chapter, we present a model for an entry-level lab-based undergraduate environmental chemistry course delivered simultaneously by face-to-face and distance modalities. This course frames conceptual chemistry using the theme of Alaskan Arctic environmental issues in order to increase engagement and perceived relevance of chemical principles. Synchronously delivered lectures and guided discussions along with the incorporation of peer-mentored research projects encourage the development of a learning community among students in the course. Distance students participate in the same virtual and "kitchen" lab experiments as on-campus students, thus providing an educationally equivalent curriculum to all. In mixed teams of on-campus and distance students, all students participate in research projects to allow entry-level students to explore their interests in STEM fields. Students thereby begin to build an identity as a scientist and hopefully this course will serve as a mechanism to improve recruitment and retention of students, especially from traditionally underrepresented groups, in the chemical sciences and other STEM fields of study. Responses from the first course offering communicated positive attitudes toward the course content and methods.

Explicit solvent simulations of the aqueous oxidation potential and reorganization energy for neutral molecules: gas phase, linear solvent response, and non-linear response contributions.

First principles simulations were used to predict aqueous one-electron oxidation potentials (Eox) and associated half-cell reorganization energies (λaq) for aniline, phenol, methoxybenzene, imidazole, and dimethylsulfide. We employed quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations of the oxidized and reduced species in an explicit aqueous solvent, followed by EOM-IP-CCSD computations with effective fragment potentials for diabatic energy gaps of solvated clusters, and finally thermodynamic integration of the non-linear solvent response contribution using classical MD. A priori predicted Eox and λaq values exhibit mean absolute errors of 0.17 V and 0.06 eV, respectively, compared to experiment. We also disaggregate Eox into several well-defined free energy properties, including the gas phase adiabatic free energy of ionization (7.73 to 8.82 eV), the solvent-induced shift in the free energy of ionization due to linear solvent response (-2.01 to -2.73 eV), and the contribution from non-linear solvent response (-0.07 to -0.14 eV). The linear solvent response component is further apportioned into contributions from the solvent-induced shift in vertical ionization energy of the reduced species (ΔVIEaq) and the solvent-induced shift in negative vertical electron affinity of the ionized species (ΔNVEAaq). The simulated ΔVIEaq and ΔNVEAaq are found to contribute the principal sources of uncertainty in computational estimates of Eox and λaq. Trends in the magnitudes of disaggregated solvation properties are found to correlate with trends in structural and electronic features of the solute. Finally, conflicting approaches for evaluating the aqueous reorganization energy are contrasted and discussed, and concluding recommendations are given.

Controlling factors in the rates of oxidation of anilines and phenols by triplet methylene blue in aqueous solution.

Anilines and phenols are structurally similar compound classes that both are susceptible to oxidation by excited state triplet sensitizers but undergo oxidation by different mechanisms. To gain an understanding of the factors that control the rate of oxidation of anilines and phenols by triplet excited states, a kinetic study was performed on the oxidation of substituted anilines and phenols by methylene blue. The rate constants of one-electron transfer from anilines to triplet state methylene blue and their dependence on the reaction free energy are well fit to a Sandros-Boltzmann model. The observed rate constants are also well modeled when aniline oxidation potentials derived computationally are used. For phenols, the proton-coupled electron transfer rate constants were found to correlate primarily with O-H bond dissociation free energy and secondarily with phenol pKa. Rate constants for phenols could be modeled using computed bond dissociation free energies. These results provide a basis for predicting aniline and phenol oxidation rates, which could be valuable, for example, in assessing the likely persistence and fate of aniline- and phenol-based aqueous environmental pollutants.

Exploring the aqueous vertical ionization of organic molecules by molecular simulation and liquid microjet photoelectron spectroscopy.

To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIEaq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIEaq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIEaq, was found to range from ≈-0.5 to -0.91 eV. The ΔVIEaq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIEaq appeared largely controlled by differences in solute-solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV.

Critical Evaluation of Implicit Solvent Models for Predicting Aqueous Oxidation Potentials of Neutral Organic Compounds.

Quantum chemical implicit solvent models are used widely to estimate aqueous redox potentials. We compared the accuracy of several popular implicit solvent models (SM8, SMD, C-PCM, IEF-PCM, and COSMO-RS) for the prediction of aqueous single electron oxidation potentials of a diverse test set of neutral organic compounds for which accurate experimental oxidation potential and gas-phase ionization energy data are available. Using a thermodynamic cycle, we decomposed the free energy of oxidation into contributions arising from the gas-phase adiabatic ionization energy, the solvation free energy of the closed-shell neutral species, and the solvation free energy of the radical cation species. For aqueous oxidation potentials, implicit solvent models exhibited mean unsigned errors (MUEs) ranging from 0.27 to 0.50 V, depending on the model. The principal source of error was attributed to the computed solvation free energy of the oxidized radical cation. Based on these results, a recommended implicit solvation approach is the SMD model for the solvation free energy combined with CBS-QB3 for the gas-phase ionization energy. With this approach, the MUE in computed oxidation potentials was 0.27 V, and the MUE in solvation free energy of the charged open-shell species was 0.32 eV. This baseline assessment provides a compiled benchmark test set of vetted experimental data that may be used to judge newly developed solvation models for their ability to produce improved predictions for aqueous oxidation potentials and related properties.

Photodegradation of ormetoprim in aquaculture and stream-derived dissolved organic matter.

Ormetoprim (OMP) is an antibiotic approved for use in the United States to prevent the spread of disease in freshwater aquaculture. It has been shown in the previous literature to be photochemically stable to direct photolysis, but the role of photosensitization processes in the presence of dissolved organic matter (DOM) on the rate of degradation is not well understood. The present results show that water and DOM (specifically the fulvic acid fraction) isolated from a eutrophic aquaculture catfish pond and a nearby stream (Deer Creek) at the Mississippi State University Delta Research and Extension Center facility in Stoneville, MS, significantly increased the phototransformation of OMP relative to direct photolysis. Similar results were reported for reference fulvic acids obtained from the International Humic Substances Society. Results from a combination of scavenging experiments and experiments conducted under anoxic conditions indicate the indirect photodegradation pathway occurs by hydroxyl radical, singlet oxygen attack, and reaction with triplet excited-state DOM.

Photochemical fate of sulfadimethoxine in aquaculture waters.

Sulfadimethoxine (SDM) is an antibiotic often used in combination with ormetoprim to prevent the spread of disease in freshwater aquaculture. It is known to undergo photochemical degradation in natural sunlit surface waters, but the role of dissolved organic matter (DOM) in this process is poorly understood. Our results show that water from a eutrophic catfish pond at the Mississippi State University Delta Research and Extension Center facility in Stoneville, MS facilitates the rapid phototransformation of SDM. In contrast, water from a nearby stream (Deer Creek) whose DOM is derived from allochthonous precursors does not enhance SDM photodegradation. We attribute these disparate results to DOM composition, whereby dissolved organic matter originating from highly eutrophic water bodies is a better SDM photosensitizer. Experiments conducted concurrently using respective autochthonous (Pony Lake, Antarctica) and allochthonous (Suwannee River) derived fulvic acids corroborate these findings. Scavenging experiments and experiments conducted anoxically show that the main indirect photodegradation pathway occurs by triplet excited-state DOM oxidation. Finally, transformation products assayed by mass spectrometry reveal the same major SDM photoproducts in the presence and absence of dissolved organic matter.