Direct and indirect photodegradation in aquatic systems mitigates photosensitized toxicity in screening-level substance risk assessments of selected petrochemical structures.

Photochemical processes are typically not incorporated in screening-level substance risk assessments due to the complexity of modeling sunlight co-exposures and resulting interactions on environmental fate and effects. However, for many substances, sunlight exerts a profound influence on environmental degradation rates and ecotoxicities. Recent modeling advances provide an improved technical basis for estimating the effect of sunlight in modulating both substance exposure and toxicity in the aquatic environment. Screening model simulations were performed for 25 petrochemical structures with varied uses and environmental fate properties. Model predictions were evaluated by comparing the ratios of predicted exposure concentrations with and without light to the corresponding ratios of toxicity thresholds under the same conditions. The relative ratios of exposure and hazard in light vs. dark were then used to evaluate how inclusion of light modulates substance risk analysis. Results indicated that inclusion of light reduced PECs by factors ranging from 1.1- to 63-fold as a result of photodegradation, while reducing PNECs by factors ranging from 1- to 49-fold due to photoenhanced toxicity caused by photosensitization. Consequently, the presence of light altered risk quotients by factors that ranged from 0.1- to 17-fold, since the predicted increase in substance hazard was mitigated by the reduction in exposure. For many structures, indirect photodegradation decreases environmental exposures independently of the direct photolysis pathway which is associated with enhanced phototoxicity. For most of the scenarios and chemicals in the present work, photosensitization appears to be mitigated by direct and indirect degradation from sunlight exposure.

Disentangling the History of Deep Ocean Disposal for DDT and Other Industrial Waste Off Southern California.

Ocean disposal of industrial waste from technical DDT [mainly 1,1'-(2,2,2-trichloroethane-1,1-diyl)bis(4-chlorobenzene), or 4,4'-DDT] manufacture occurred historically in the Southern California Bight. However, the paucity of historical records highlights uncertainties as to the mode, location, and timing of disposal or ongoing ecological effects of these wastes. This study combines sampling, chemical analysis, and numerical modeling of deep San Pedro Basin sediments revealing substantial DDT contamination that extends at least 25 km from the mainland. These findings narrate bulk DDT waste disposal to the offshore that peaked in the 1950s, prior to the onset of formal regulations; was agnostic to later-designated disposal sites; and has experienced sluggish transformation. Our findings further indicate an attenuating secondary source for the DDT daughter product, 1-chloro-4-[2,2-dichloro-1-(4-chlorophenyl)ethenyl]benzene (4,4'-DDE), which still deposits into deep San Pedro Basin sediments. While demonstrating the severity of DDT contamination to the region, these findings further define the burial potential of DDT wastes and inform the past, present, and future contamination potential that is needed to understand and predict ecological consequences. This work also points firmly to bulk, not containerized, disposal of DDT waste and to potential alternative contents of collocated waste.

Comprehensive Two-Dimensional Gas Chromatography with Peak Tracking for Screening of Constituent Biodegradation in Petroleum UVCB Substances.

Petroleum substances, as archetypical UVCBs (substances of unknown or variable composition, complex reaction products, or biological substances), pose a challenge for chemical risk assessment as they contain hundreds to thousands of individual constituents. It is particularly challenging to determine the biodegradability of petroleum substances since each constituent behaves differently. Testing the whole substance provides an average biodegradation, but it would be effectively impossible to obtain all constituents and test them individually. To overcome this challenge, comprehensive two-dimensional gas chromatography (GC × GC) in combination with advanced data-handling algorithms was applied to track and calculate degradation half-times (DT50s) of individual constituents in two dispersed middle distillate gas oils in seawater. By tracking >1000 peaks (representing ∼53-54% of the total mass across the entire chromatographic area), known biodegradation patterns of oil constituents were confirmed and extended to include many hundreds not currently investigated by traditional one-dimensional GC methods. Approximately 95% of the total tracked peak mass biodegraded after 64 days. By tracking the microbial community evolution, a correlation between the presence of functional microbial communities and the observed progression of DT50s between chemical classes was demonstrated. This approach could be used to screen the persistence of GC × GC-amenable constituents of petroleum substance UVCBs.

Relative sensitivity of hydrodynamic, thermodynamic, and chemical processes for simulating the buoyant multiphase plume and surfacing flows of an oil and gas blowout.

Deepwater hydrocarbon releases experience complex chemical and physical processes. To assess simplifications of these processes on model predictions, we present a sensitivity analysis using simulations for the Deepwater Horizon oil spill. We compare the buoyant multiphase plume metrics (trap height, rise time etc), the hydrocarbon mass flowrates at the near-field plume termination and their mass fractions dissolved in the water column and reaching the water surface. The baseline simulation utilizes a 19-component hydrocarbon model, live-fluid state equations, hydrate dynamics, and heat and mass transfer. Other simulations turn-off each of these processes, with the simplest one using inert oil and methane gas. Plume metrics are the least sensitive to the modeled processes and can be matched by adjusting the release buoyancy flux. The mass flowrate metrics are more sensitive. Both liquid- and gas-phase mass transfer should be modeled for accurate tracking of soluble components (e.g. C1 - C7 hydrocarbons) in the environment.

Modeling the GCxGC Elution Patterns of a Hydrocarbon Structure Library To Innovate Environmental Risk Assessments of Petroleum Substances.

Comprehensive two-dimensional gas chromatography (GCxGC) offers unrivaled separation of petroleum substances, which can contain thousands of constituents or more. However, interpreting substance compositions from GCxGC data is costly and requires expertise. To facilitate environmental risk assessments, industries provide aggregated compositional information known as "hydrocarbon blocks" (HCBs), but these proprietary methods do not transparently associate the HCBs with GCxGC chromatogram data. These obstacles frustrate efforts to study the environmental risks of petroleum substances and associated environmental samples. To address this problem, we developed a GCxGC elution model for user-defined petroleum substance compositions. We calibrated the elution model to experimental GCxGC retention times of 56 known hydrocarbons by fitting three tunable model parameters to two candidate instrument methods. With the calibrated model, we simulated retention times for a library of 15,447-15,455 hydrocarbon structures (plus 40-48 predicted as chromatographically unretained) spanning 11 classes of petroleum substance constituents in the C10-C30 range. The resulting simulation data reveal that GCxGC retention times are quantitatively associated with hydrocarbon class and carbon number information throughout the GCxGC chromatogram. These innovations enable the development of transparent and efficient technical methods to investigate the chemical compositions and environmental properties of petroleum substances, including in environmental and lab-weathered samples.

Development of an offshore response guidance tool for determining the impact of SSDI on released gas and benzene from artificial subsea oil well blowout simulations.

We present an analysis of 2225 simulations of artificial oil well blowouts in nearshore and offshore waters of Newfoundland, Canada. In the simulations, we coupled the VDROP-J and TAMOC models to simulate the fate and transport of oil and gas from the release to the sea surface. Simulations were conducted with and without subsea dispersant injection. We analyzed the simulation database to quantify the mass fraction of oil and gas that surfaces, the mass fraction of released benzene that surfaces, and the horizontal offset to the surfacing zone. These data are also synthesized to yield empirical correlations to predict these output metrics from key input parameters. These correlations are summarized in an excel spreadsheet that allows rapid evaluation of spill dynamics with minimal initial knowledge of spill details. We call this tool an offshore response guidance table, which allows exploration of spill dynamics under diverse spill and response options.

Deepwater Horizon 2010: Subsea dispersants protected responders from VOC exposure.

Controversy remains on the use of Sub-Sea Dispersant Injection (SSDI) during the Deepwater Horizon (DWH) spill to minimize the exposure of responders on surface vessels to volatile organic compounds (VOC). Here, we use extensive evidence (>90,000 VOC measurements) collected near the oil well MC252 site during the DWH spill and demonstrate at a high level of statistical confidence that SSDI enhanced the safety and health conditions of the responders at the water surface through the reduction of airborne VOC concentrations in a dose-dependent manner. VOC levels on ships' decks were clearly diminished (p < 0.001) during subsea dispersant use, and incidents of peak concentrations (>50 ppm VOC) that could have been an immediate concern to worker health were reduced by a factor of ~6 to 19 when dispersants were delivered at the intended rate. SSDI thus played an important role in minimizing potential exposure to VOC, and should be embedded in guidelines and regulations for dispersant use.

Dynamics of Live Oil Droplets and Natural Gas Bubbles in Deep Water.

Explaining the dynamics of gas-saturated live petroleum in deep water remains a challenge. Recently, Pesch et al. [ Environ. Eng. Sci. 2018, 35 (4), 289-299] reported laboratory experiments on methane-saturated oil droplets under emulated deep-water conditions, providing an opportunity to elucidate the underlying dynamical processes. We explain these observations with the Texas A&M Oil spill/Outfall Calculator (TAMOC), which models the pressure-, temperature-, and composition-dependent interactions between oil-gas phase transfer; aqueous dissolution; and densities and volumes of liquid oil droplets, gas bubbles, and two-phase droplet-bubble pairs. TAMOC reveals that aqueous dissolution removed >95% of the methane from ∼3.5 mm live oil droplets within 14.5 min, prior to gas bubble formation, during the experiments of Pesch et al. Additional simulations indicate that aqueous dissolution, fluid density changes, and gas-oil phase transitions (ebullition, condensation) may all contribute to the fates of live oil and gas in deep water, depending on the release conditions. Illustrative model scenarios suggest that 5 mm diameter gas bubbles released at a <470 m water depth can transport methane, ethane, and propane to the water surface. Ethane and propane can reach the water surface from much deeper releases of 5 mm diameter live oil droplets, during which ebullition occurs at water depths of <70 m.

Prediction of aqueous free energies of solvation using coupled QM and MM explicit solvent simulations.

A method based on molecular dynamics simulations which employ two distinct levels of theory is proposed and tested for the prediction of Gibbs free energies of solvation for non-ionic solutes in water. The method consists of two additive contributions: (i) an evaluation of the free energy of solvation predicted by a computationally efficient molecular mechanics (MM) method; and (ii) an evaluation of the free energy difference between the potential energy surface of the MM method and that of a more computationally intensive first-principles quantum-mechanical (QM) method. The latter is computed by a thermodynamic integration method based on a series of shorter molecular dynamics simulations that employ weighted averages of the QM and MM force evaluations. The combined computational approach is tested against the experimental free energies of aqueous solvation for four solutes. For solute-solvent interactions that are found to be described qualitatively well by the MM method, the QM correction makes a modest improvement in the predicted free energy of aqueous solvation. However, for solutes that are found to not be adequately described by the MM method, the QM correction does not improve agreement with experiment. These preliminary results provide valuable insights into the novel concept of implementing thermodynamic integration between two model chemistries, suggesting that it is possible to use QM methods to improve upon the MM predictions of free energies of aqueous solvation.

Gas-Phase Ozone Reactions with a Structurally Diverse Set of Molecules: Barrier Heights and Reaction Energies Evaluated by Coupled Cluster and Density Functional Theory Calculations.

Reactions with ozone transform organic and inorganic molecules in water treatment systems as well as in atmospheric chemistry, either in the aqueous phase, at gas/particle interfaces, or in the gas phase. Computed thermokinetic data can be used to estimate the reactivities of molecules toward ozone in cases where no experimental data are available. Although the gas-phase reactivity of olefins with ozone has been characterized extensively in the literature, this is not the case for the richer chemistry of ozone with polar molecules, which occurs in the aqueous phase or in microhydrated environments. Here, we selected a number of model reactions with small molecules (ethene, ethyne, hydrogen cyanide, hydrogen chloride, ammonia, bromide, and trimethylamine) to study the accuracy of different quantum chemical methods for describing the reactivities of these molecules with ozone. We calculated benchmark electronic energies of gas-phase reactions of these systems with single-reference coupled cluster (CC) theory. These benchmark results for the binding energy in the van der Waals complex, the energy of the transition structure, and the reaction energy were estimated to be accurate within 1-2 kcal mol-1. Singlet oxygen (1O2) is a common product of ozone reactions. Coupled cluster calculations with up to perturbative quadruples (CCSDT( Q)) were needed to obtain reaction energies accurate within 1 kcal mol-1 when this species was involved. In (micro)hydrated environments or at interfaces, coupled cluster methods are prohibitively expensive in most cases. We tested the suitability of some contemporary density functional theory (DFT) methods to reproduce the benchmark electronic energy differences. Range-separated functionals were found to be promising candidates to estimate forward barrier heights, with LC-ωPBE rivaling the accuracy of CCSD( T). For energies of reaction, however, DFT methods exhibited large systematic errors, depending on their fraction of orbital exchange. This was found to worsen when 1O2 is a product, and no safe recommendation can be given for DFT reaction energies in such cases.

Petroleum dynamics in the sea and influence of subsea dispersant injection during Deepwater Horizon.

During the Deepwater Horizon disaster, a substantial fraction of the 600,000-900,000 tons of released petroleum liquid and natural gas became entrapped below the sea surface, but the quantity entrapped and the sequestration mechanisms have remained unclear. We modeled the buoyant jet of petroleum liquid droplets, gas bubbles, and entrained seawater, using 279 simulated chemical components, for a representative day (June 8, 2010) of the period after the sunken platform's riser pipe was pared at the wellhead (June 4-July 15). The model predicts that 27% of the released mass of petroleum fluids dissolved into the sea during ascent from the pared wellhead (1,505 m depth) to the sea surface, thereby matching observed volatile organic compound (VOC) emissions to the atmosphere. Based on combined results from model simulation and water column measurements, 24% of released petroleum fluid mass became channeled into a stable deep-water intrusion at 900- to 1,300-m depth, as aqueously dissolved compounds (∼23%) and suspended petroleum liquid microdroplets (∼0.8%). Dispersant injection at the wellhead decreased the median initial diameters of simulated petroleum liquid droplets and gas bubbles by 3.2-fold and 3.4-fold, respectively, which increased dissolution of ascending petroleum fluids by 25%. Faster dissolution increased the simulated flows of water-soluble compounds into biologically sparse deep water by 55%, while decreasing the flows of several harmful compounds into biologically rich surface water. Dispersant injection also decreased the simulated emissions of VOCs to the atmosphere by 28%, including a 2,000-fold decrease in emissions of benzene, which lowered health risks for response workers.

Pixel-by-pixel correction of retention time shifts in chromatograms from comprehensive two-dimensional gas chromatography coupled to high resolution time-of-flight mass spectrometry.

A pixel-by-pixel method for correcting retention time (RT) shifts in whole chromatograms from comprehensive two-dimensional gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC×GC-HRTOFMS) is introduced. A previously developed robust algorithm for correcting RT shifts was extended to high-resolution mass-spectral data. The performance of the new method in terms of decreasing RT shifts and peak volume changes was tested on GC×GC-HRTOFMS data. The RT shift correction algorithm, using linear interpolation for the 1st dimension and Sibson natural neighbor interpolation for the 2nd dimension, performed well for systematically shifted data acquired using two different temperature programs in terms of decreasing RT differences and alterations to the peak volumes and mass spectra. A modified RT shift correction algorithm, using Sibson natural neighbor for both dimensions, performed better for RT shifts caused by column damage, for which the original interpolation method did not appropriately correct RT shifts. Although further investigation would be required for more types of severe shifts, this study shows that the developed method is useful for correcting RT shifts with GC×GC-HRTOFMS.

Predicting Partitioning and Diffusion Properties of Nonpolar Chemicals in Biotic Media and Passive Sampler Phases by GC × GC.

The chemical parameters needed to explain and predict bioavailability, biodynamics, and baseline toxicity are not readily available for most nonpolar chemicals detected in the environment. Here, we demonstrate that comprehensive two-dimensional gas chromatography (GC × GC) retention times can be used to predict 26 relevant properties for nonpolar chemicals, specifically: partition coefficients for diverse biotic media and passive sampler phases; aquatic baseline toxicity; and relevant diffusion coefficients. The considered biotic and passive sampler phases include membrane and storage lipids, serum and muscle proteins, carbohydrates, algae, mussels, polydimethylsiloxane, polyethylene, polyoxymethylene, polyacrylate, polyurethane, and semipermeable membrane devices. GC × GC-based chemical property predictions are validated with a compilation of 1038 experimental property data collected from the literature. As an example application, we overlay a map of baseline toxicity to fathead minnows onto the separated analyte signal of a polychlorinated alkanes (chlorinated paraffins) technical mixture that contains 7820 congeners. In a second application, GC × GC-estimated properties are used to parametrize multiphase partitioning models for mammalian tissues and organs. In a third example, we estimate chemical depuration kinetics for mussels. Finally, we illustrate an approach to screen the GC × GC chromatogram for nonpolar chemicals of potentially high concern, defined based on their GC × GC-estimated biopartitioning properties, diffusion properties, and baseline toxicity.

Elevated Concentrations of 4-Bromobiphenyl and 1,3,5-Tribromobenzene Found in Deep Water of Lake Geneva Based on GC×GC-ENCI-TOFMS and GC×GC-µECD.

We quantified the concentrations of two little-studied brominated pollutants, 1,3,5-tribromobenzene (TBB) and 4-bromobiphenyl (4BBP), in the deep water column and sediments of Lake Geneva. We found aqueous concentrations of 625 ± 68 pg L-1 for TBB and 668 ± 86 pg L-1 for 4BBP over a depth range of 70-191.5 m (near-bottom depth), based on duplicate measurements taken at five depths during three separate 1 month sampling periods at our sampling site near Vidy Bay. These levels of TBB and 4BBP were 1 or 2 orders of magnitude higher than the quantified aqueous concentrations of the components of the pentabrominated biphenyl ether technical mixture, which is a flame retardant product that had a high production volume in Europe before 2001. We observed statistically significant vertical concentration trends for both TBB and 2,2',4,4',6-pentabromobiphenyl ether in the deep water column, which indicates that transport and/or degradation processes affect these compounds. These measurements were enabled by application of a comprehensive two-dimensional gas chromatograph coupled to an electron capture negative chemical ionization time-of-flight mass spectrometer (GC×GC-ENCI-TOFMS) and to a micro-electron capture detector (GC×GC-µECD). GC×GC-ENCI-TOFMS and GC×GC-µECD were found to be >10× more sensitive toward brominated pollutants than conventional GC×GC-EI-TOFMS (with an electron impact (EI) ionization source), the latter of which had insufficient sensitivity to detect these emerging brominated pollutants in the analyzed samples. GC×GC also enabled the estimation of several environmentally relevant partitioning properties of TBB and 4BBP, further confirming previous evidence that these pollutants are bioaccumulative and have long-range transport potential.

Equilibria and Speciation of Chloramines, Bromamines, and Bromochloramines in Water.

The stabilities and speciation of the halamines in water are difficult to characterize experimentally. We provide theoretical estimates of aqueous standard free energies of formation for inorganic chloramines, bromamines, and bromochloramines, based on high-accuracy theoretical standard free energies of formation in gas phase combined with quantum chemical estimates of Henry's law constant. Based on comparisons between several theoretical and experimental datasets, we assign an error of 1.1-1.2 log unit for equilibrium constants of several reactions leading to halamines in water. The reactions of ammonia with HOCl or HOBr that lead to dichloramine, trichloramine, and tribromamine are found to be thermodynamically more favorable than was previously believed. The newly reported equilibrium data also allow us to propose rate constant values for some hydrolysis and disproportionation reactions of dichloramine, monobromamine, and bromochloramine. Finally, theoretical results indicate aqueous acid dissociation constant (pKa) values of 1.5 ± 1 for NH3Cl+, 0.8 ± 1 for NH3Br+, 11.8 ± 1 for NHCl2, and 12.5 ± 1 for NHBrCl. The present report provides a comprehensive data set describing the free energies of the neutral inorganic halamines, the anionic conjugate base species, and the cationic conjugate acid species, with approximately uniform uncertainty bounds assigned throughout.

Formation and reactivity of inorganic and organic chloramines and bromamines during oxidative water treatment.

The formation and further reactions of halamines during oxidative water treatment can be relevant for water quality. In this study, we investigated the formation and reactivity of several inorganic and organic halamines (monochloramine, N-chloromethylamine, N-chlorodimethylamine, monobromamine, dibromamine, N-bromomethylamine, N,N-dibromomethylamine, and N-bromodimethylamine) by kinetic experiments, transformation product analysis, and quantum chemical computations. Kinetic model simulations were conducted to evaluate the relevance of halamines for various water treatment scenarios. Halamines were quickly formed from the reaction of chlorine and bromine with ammonia or organic amines. Species-specific second-order rate constants for the reaction of chlorine and bromine with ammonia, methyl- and dimethylamine were in the order of 106-108 M-1s-1. The formed halamines were found to be reactive towards phenolic compounds, forming halogenated phenols via electrophilic aromatic substitution (phenol and resorcinol) or quinones via electron transfer (catechol and hydroquinone). At near neutral pH, apparent second-order rate constants for these reactions were in the order of 10-4-10-1 M-1s-1 for chloramines and 101-102 M-1s-1 for bromamines. Quantum chemical computations were used to determine previously unknown aqueous pKa values, gas phase bond dissociation energies (BDE) and partial atomic charges of the halamines, allowing a better understanding of their reactivities. Kinetic model simulations, based on the results of this study, showed that during chlorination inorganic and organic chloramines are the main halamines formed. However, their further reactions with organic matter are outcompeted kinetically by chlorine. During ozonation, mainly inorganic bromamines are formed, since ozone quickly oxidizes organic amines. The further reactions of bromamine are typically outcompeted by ozone and thus generally of minor importance. The use of peracetic acid for saline ballast water treatment can result in the formation of substantial amounts of bromamines, which can react with dissolved organic matter and contribute to the formation of brominated products.

Correction: Benchmark thermochemistry of chloramines, bromamines, and bromochloramines: halogen oxidants stabilized by electron correlation.

Correction for 'Benchmark thermochemistry of chloramines, bromamines, and bromochloramines: halogen oxidants stabilized by electron correlation' by Daniela Trogolo et al., Phys. Chem. Chem. Phys., 2015, 17, 3584-3598.

Impacts of Polar Changes on the UV-induced Mineralization of Terrigenous Dissolved Organic Matter.

Local climates in the Northern and Southern Hemisphere are influenced by Arctic Amplification and by interactions of the Antarctic ozone hole with climate change, respectively. Polar changes may affect hydroclimatic conditions in temperate regions, for example, by increasing the length and intensity of precipitation events at Northern Hemisphere midlatitudes. Additionally, global warming has led to the thawing of ancient permafrost soils, particularly in Arctic regions, due to Arctic Amplification. Both heavy precipitation events and thawing of permafrost are increasing the net transfer of terrestrially derived dissolved organic matter (DOM) from land to surface waters. In aquatic ecosystems, UV-induced oxidation of terrigenous DOM (tDOM) produces atmospheric CO2 and this process is one of several mechanisms by which natural organic matter in aquatic and soil environments may play an important role in climate feedbacks. The Arctic is particularly affected by these processes: for example, melting of Arctic sea ice allows solar UV radiation to penetrate into the ice-free Arctic Ocean and to cause photochemical reactions that result in bleaching and mineralization of tDOM. Open questions, in addition to those shown in the Graphical Abstract, remain regarding the resulting contributions of tDOM photomineralization to CO2 production and global warming.

Simulating Gas-Liquid-Water Partitioning and Fluid Properties of Petroleum under Pressure: Implications for Deep-Sea Blowouts.

With the expansion of offshore petroleum extraction, validated models are needed to simulate the behaviors of petroleum compounds released in deep (>100 m) waters. We present a thermodynamic model of the densities, viscosities, and gas-liquid-water partitioning of petroleum mixtures with varying pressure, temperature, and composition based on the Peng-Robinson equation-of-state and the modified Henry's law (Krychevsky-Kasarnovsky equation). The model is applied to Macondo reservoir fluid released during the Deepwater Horizon disaster, represented with 279-280 pseudocomponents, including 131-132 individual compounds. We define >n-C8 pseudocomponents based on comprehensive two-dimensional gas chromatography (GC × GC) measurements, which enable the modeling of aqueous partitioning for n-C8 to n-C26 fractions not quantified individually. Thermodynamic model predictions are tested against available laboratory data on petroleum liquid densities, gas/liquid volume fractions, and liquid viscosities. We find that the emitted petroleum mixture was ∼29-44% gas and ∼56-71% liquid, after cooling to local conditions near the broken Macondo riser stub (∼153 atm and 4.3 °C). High pressure conditions dramatically favor the aqueous dissolution of C1-C4 hydrocarbons and also influence the buoyancies of bubbles and droplets. Additionally, the simulated densities of emitted petroleum fluids affect previous estimates of the volumetric flow rate of dead oil from the emission source.