Longitudinal stream synoptic (LSS) monitoring to evaluate water quality in restored streams.

Impervious surface cover increases peak flows and degrades stream health, contributing to a variety of hydrologic, water quality, and ecological symptoms, collectively known as the urban stream syndrome. Strategies to combat the urban stream syndrome often employ engineering approaches to enhance stream-floodplain reconnection, dissipate erosive forces from urban runoff, and enhance contaminant retention, but it is not always clear how effective such practices are or how to monitor for their effectiveness. In this study, we explore applications of longitudinal stream synoptic (LSS) monitoring (an approach where multiple samples are collected along stream flowpaths across both space and time) to narrow this knowledge gap. Specifically, we investigate (1) whether LSS monitoring can be used to detect changes in water chemistry along longitudinal flowpaths in response to stream-floodplain reconnection and (2) what is the scale over which restoration efforts improve stream quality. We present results for four different classes of water quality constituents (carbon, nutrients, salt ions, and metals) across five watersheds with varying degrees of stream-floodplain reconnection. Our work suggests that LSS monitoring can be used to evaluate stream restoration strategies when implemented at meter to kilometer scales. As streams flow through restoration features, concentrations of nutrients, salts, and metals significantly decline (p < 0.05) or remain unchanged. This same pattern is not evident in unrestored streams, where salt ion concentrations (e.g., Na+, Ca2+, K+) significantly increase with increasing impervious cover. When used in concert with statistical approaches like principal component analysis, we find that LSS monitoring reveals changes in entire chemical mixtures (e.g., salts, metals, and nutrients), not just individual water quality constituents. These chemical mixtures are locally responsive to restoration projects, but can be obscured at the watershed scale and overwhelmed during storm events.

On the Gas-Phase Interactions of Alkyl and Phenyl Formates with Water: Ion-Molecule Reactions with Proton-Bound Water Clusters.

Ion-molecule reactions between the neutral ethyl- (EF), isopropyl- (IF), t-butyl- (TF) and phenyl formate (PF) and proton-bound water clusters W2H+ and W3H+ (W = H2O) showed that the major reaction product is water loss from the initial encounter complex, followed ultimately by the formation of the protonated formate. Collision-induced dissociation breakdown curves of the formate-water complexes were obtained as a function of collision energy and modeled to extract relative activation energies for the observed channels. Density functional theory calculations (B3LYP/6-311+G(d,p)) of the water loss reactions were consistent with reactions having no reverse energy barrier in each case. Overall, the results indicate that the interaction of formates with atmospheric water can form stable encounter complexes that will dissociate by sequential water loss to form protonated formates.

The Fate of Protonated Guaiacol and Its Derivatives in the Gas Phase.

Guaiacol (2-methoxyphenol) and its derivatives are a class of semivolatile polar organic molecules possessing low molecular weights. Owing to their volatility, guaiacol and its derivatives can interact with atmospheric water and form protonated methoxyphenols through proton transfer. The aim of the present work is to study the dissociation of these protonated ions and hence, potentially, their atmospheric fate. Tandem mass spectrometry was employed to analyze the unimolecular dissociation of the protonated forms of guaiacol (2-methoxyphenol, 1), creosol (2-methoxy-4-methylphenol, 2), 4-ethylguaiacol (4-ethyl-2-methoxyphenol, 3), 4-vinylguaiacol (2-methoxy-4-vinylphenol, 4), eugenol (2-methoxy-4-prop-2-enylphenol, 5), and vanillin (4-hydroxy-3-methoxybenzaldehyde, 6). Density functional theory at the B3LYP/6-31G(d) (1-5) and B3LYP/6-311+G(d,p) (6) levels of theory were applied to determine the observed minimum energy reaction pathways, and reliable energetics were acquired using CBS-QB3 single-point energy calculations. All the protonated ions, with the exception of 6, exhibit the loss of CH3OH via a series of hydrogen transfers, followed by ring contraction to lose CO. This common dissociation pathway leads to the formation of a cyclopentadienyl ion as the main dissociation product. Conversely, 6 first exhibits the loss of CO, followed by sequential losses of CH3OH and CO to generate a cyclopentadienyl ion. Additionally, minor fragmentation channels are also observed for the different protonated ions: CH2 loss in 1; CH4 and H2O losses in 3; CH3 loss in 4, 5, and 6; C2H4 and CH2CHCH2 losses in 5; H loss in 6. Altogether, the protonated ions primarily lose CH3OH and CO as neutral molecules and generate a cyclopentadienyl ion as a dissociation product.

Deep soil nitrogen storage slows nitrate leaching through the vadose zone.

Nitrogen (N) fertilizer applications are important for agricultural yield, yet not all the applied N is taken up by crops, leading to surplus N storage in soil or leaching to groundwater and surface water. Leaching loss of fertilizer N represents a cost for farmers and has consequences for human health and the environment, especially in the southern Willamette Valley, Oregon, USA, where groundwater nitrate contamination is prevalent. While improved nutrient management and conservation practices have been implemented to minimize leaching, nitrate levels in groundwater continue to increase in many long-term monitoring wells. To elucidate controls on leaching rates and N dynamics in agricultural soils across soil depths, and in response to seasonal and annual variation in management (e.g., fertilizer input amount and summer irrigation), we intensively monitored the transport of water and nitrate every two weeks for four years through the vadose zone at three depths (0.8, 1.5, and 3.0 m) in a sweet corn (maize) field. Though nitrate leaching was highly variable among lysimeters at the same depth and across years, a strong pattern emerged: annual nitrate leaching significantly decreased with depth across the study, averaging ~104 kg N ha-1 yr-1 near the surface (0.8 m) versus ~56 kg N ha-1 yr-1 in the deep soil (3.0 m), a 54% reduction in leaching between the soil layers. Even though crops were irrigated in summer, most leaching (~72% below 3.0 m) occurred during the wet fall and winter. Based on steady state assumptions, a net equivalent of ~29% of surface N inputs leached below 3.0 m into the deeper soil and groundwater, while ~44% was removed in crop harvest, indicating considerable N retention in the soil (~27% of inputs or approximately 58 kg N ha-1 yr-1). The accumulation and long-term dynamics of deep soil N is a legacy of agricultural management that should be further studied to better manage and reduce nitrate loss to groundwater.

Long-term assessment of floodplain reconnection as a stream restoration approach for managing nitrogen in ground and surface waters.

Stream restoration is a popular approach for managing nitrogen (N) in degraded, flashy urban streams. Here, we investigated the long-term effects of stream restoration involving floodplain reconnection on riparian and in-stream N transport and transformation in an urban stream in the Chesapeake Bay watershed. We examined relationships between hydrology, chemistry, and biology using a Before/After-Control/Impact (BACI) study design to determine how hydrologic flashiness, nitrate (NO3 -) concentrations (mg/L), and N flux, both NO3 - and total N (kg/yr), changed after the restoration and floodplain hydrologic reconnection to its stream channel. We examined two independent surface water and groundwater data sets (EPA and USGS) collected from 2002-2012 at our study sites in the Minebank Run watershed. Restoration was completed during 2004 and 2005. Afterward, the monthly hydrologic flashiness index, based on mean monthly discharge, decreased over time from 2002 and 2008. However, from 2008-2012 hydrologic flashiness returned to pre-restoration levels. Based on the EPA data set, NO3 - concentration in groundwater and surface water was significantly less after restoration while the control site showed no change. DOC and NO3 - were negatively related before and after restoration suggesting C limitation of N transformations. Long-term trends in surface water NO3 - concentrations based on USGS surface water data showed downward trends after restoration at both the restored and control sites, whereas specific conductance showed no trend. Comparisons of NO3 - concentrations with Cl- concentrations and specific conductance in both ground and surface waters suggested that NO3 - reduction after restoration was not due to dilution or load reductions from the watershed. Modeled NO3 - flux decreased post restoration over time but the rate of decrease was reduced likely due to failure of restoration features that facilitated N transformations. Groundwater NO3 - concentrations varied among stream features suggesting that some engineered features may be functionally better at creating optimal conditions for N retention. However, some engineered features eroded and failed post restoration thereby reducing efficacy of the stream restoration to reduce flashiness and NO3 - flux. N management via stream restoration will be most effective where flashiness can be reduced and DOC made available for denitrifiers. Stream restoration may be an important component of holistic watershed management including stormwater management and nutrient source control if stream restoration and floodplain reconnection can be done in a manner to resist the erosive effects of large storm events that can degrade streams to pre-restoration conditions. Long-term evolution of water quality functions in response to degradation of restored stream channels and floodplains from urban stressors and storms over time warrants further study, however.

Tree Trade-Offs in Stream Restoration: Impacts on Riparian Groundwater Quality.

Riparian zones are a vital interface between land and stream and are often the focus of stream restoration efforts to reduce nutrient pollution in waterways. Restoration of degraded stream channels often requires the removal of mature trees during major physical alteration of the riparian zone to reshape streambank topography. We assessed the impact of tree removal on riparian groundwater quality over space and time. Twenty-nine wells were installed across 5 sites in watersheds of the Washington D.C. and Baltimore, Maryland, USA metropolitan areas. Study sites encompassed a chronosequence of restoration ages (5, 10 and 20 years) as well as unrestored comparisons. Groundwater wells were installed as transects of 3 perpendicular to the stream channel to estimate nutrient uptake along groundwater flow paths. Groundwater samples collected over a 2-year period (2018-2019) were analyzed for concentrations of dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), total dissolved nitrogen (TDN), and dissolved components of calcium (Ca), potassium (K), magnesium (Mg), sodium (Na), sulfur (S) and other elements. Results showed some interesting patterns such as: (1) elevated concentrations of some nutrients and carbon in riparian groundwater of recently restored (5 year) sites; (2) decreasing linear trends in concentrations of TDN, K and S in groundwater during a 2 year shift from wet to dry conditions; (3) linear relationships between DOC (organic matter) and plant nutrients in groundwater suggesting the importance of plant uptake and biomass as sources and sinks of nutrients; (4) increasing concentrations in groundwater along hydrologic flow paths from uplands to streams in riparian zones where trees were recently cut, and opposite patterns where trees were not cut. Riparian zones appeared to act as sources or sinks of bioreactive elements based on tree removal. Mean TDN, DOC, and S, concentrations decreased by 78.6%, 12.3%, and 19.3% respectively through uncut riparian zones, but increased by 516.9%, 199.7%, and 34.5% respectively through the 5-year cut transects. Ecosystem recovery and an improvement in groundwater quality appeared to be achieved by 10-20 years after restoration. A better understanding of the effects of riparian tree removal on groundwater quality can inform strategies for minimizing unintended effects of stream restoration on groundwater chemistry.

Fate of Protonated Formates in the Gas Phase.

Formates are a class of organic molecules emitted into the atmosphere from fuel additives and industrial solvents. Formate-derived esters can undergo a vast range of chemical reactions in the atmosphere, most of which are initiated by oxidation by hydroxyl radicals. One potential reaction upon their interaction with atmospheric water is proton transfer to form protonated formates. The goal of the present work is to explore the dissociation of these protonated species and thus their possible atmospheric fate. Tandem mass spectrometry was employed to study the unimolecular dissociation of the protonated forms of methyl- (1), ethyl- (2), isopropyl- (3), tert-butyl- (4), and phenylformate (5). 1 and 2 lose CO as a common fragmentation product, forming a protonated alcohol, and 2 also generates neutral ethanol (forming protonated CO). 3 and 4 readily lose the stable isopropyl and tert-butyl radicals as well as neutral alkenes propene and isobutene. Methanol loss is also observed from both ions. 5 exhibits both phenyl radical loss (similar to 3 and 4) and CO loss (like 1 and 2). Density functional theory was used to explore the observed minimum energy reaction pathways for each ion, and CBS-QB3 single-point energy calculations provided reliable energetics.

Effects of shading and composition on green roof media temperature and moisture.

Three of the primary functions of green roofs in urban areas are to delay rainwater runoff, moderate building temperatures, and ameliorate the urban heat island (UHI) effect. A major impediment to the survival of plants on an unirrigated extensive green roof (EGR) is the harsh rooftop environment, including high temperatures and limited water during dry periods. Factors that influence EGR thermal and hydrologic performance include the albedo (reflectivity) of the roof and the composition of the green roof substrate (growing media). In this study we used white, reflective shading structures and three different media formulations to evaluate EGR thermal and hydrologic performance in the Pacific Northwest, USA. Shading significantly reduced daytime mean and maximum EGR media temperatures and significantly increased nighttime mean and minimum temperatures, which may provide energy benefits to buildings. Mean media moisture was greater in shaded trays than in exposed (unshaded) trays but differences were not statistically significant. Warmer nighttime media temperatures and lack of dew formation in shaded trays may have partially compensated for greater daytime evaporation from exposed trays. Media composition did not significantly influence media temperature or moisture. Results of this study suggest that adding shade structures to green roofs will combine thermal, hydrologic, and ecological benefits, and help achieve temperature and light regimes that allow for greater plant diversity on EGRs.

Making 'Chemical Cocktails' - Evolution of Urban Geochemical Processes across the Periodic Table of Elements.

Urbanization contributes to the formation of novel elemental combinations and signatures in terrestrial and aquatic watersheds, also known as 'chemical cocktails.' The composition of chemical cocktails evolves across space and time due to: (1) elevated concentrations from anthropogenic sources, (2) accelerated weathering and corrosion of the built environment, (3) increased drainage density and intensification of urban water conveyance systems, and (4) enhanced rates of geochemical transformations due to changes in temperature, ionic strength, pH, and redox potentials. Characterizing chemical cocktails and underlying geochemical processes is necessary for: (1) tracking pollution sources using complex chemical mixtures instead of individual elements or compounds; (2) developing new strategies for co-managing groups of contaminants; (3) identifying proxies for predicting transport of chemical mixtures using continuous sensor data; and (4) determining whether interactive effects of chemical cocktails produce ecosystem-scale impacts greater than the sum of individual chemical stressors. First, we discuss some unique urban geochemical processes which form chemical cocktails, such as urban soil formation, human-accelerated weathering, urban acidification-alkalinization, and freshwater salinization syndrome. Second, we review and synthesize global patterns in concentrations of major ions, carbon and nutrients, and trace elements in urban streams across different world regions and make comparisons with reference conditions. In addition to our global analysis, we highlight examples from some watersheds in the Baltimore-Washington DC region, which show increased transport of major ions, trace metals, and nutrients across streams draining a well-defined land-use gradient. Urbanization increased the concentrations of multiple major and trace elements in streams draining human-dominated watersheds compared to reference conditions. Chemical cocktails of major and trace elements were formed over diurnal cycles coinciding with changes in streamflow, dissolved oxygen, pH, and other variables measured by high-frequency sensors. Some chemical cocktails of major and trace elements were also significantly related to specific conductance (p<0.05), which can be measured by sensors. Concentrations of major and trace elements increased, peaked, or decreased longitudinally along streams as watershed urbanization increased, which is consistent with distinct shifts in chemical mixtures upstream and downstream of other major cities in the world. Our global analysis of urban streams shows that concentrations of multiple elements along the Periodic Table significantly increase when compared with reference conditions. Furthermore, similar biogeochemical patterns and processes can be grouped among distinct mixtures of elements of major ions, dissolved organic matter, nutrients, and trace elements as chemical cocktails. Chemical cocktails form in urban waters over diurnal cycles, decades, and throughout drainage basins. We conclude our global review and synthesis by proposing strategies for monitoring and managing chemical cocktails using source control, ecosystem restoration, and green infrastructure. We discuss future research directions applying the watershed chemical cocktail approach to diagnose and manage environmental problems. Ultimately, a chemical cocktail approach targeting sources, transport, and transformations of different and distinct elemental combinations is necessary to more holistically monitor and manage the emerging impacts of chemical mixtures in the world's fresh waters.

Ion Dissociation Dynamics of 1,2,3,4-Tetrahydronaphthalene: Tetralin as a Test Case For Hydrogenated Polycyclic Aromatic Hydrocarbons.

The unimolecular dissociation of ionized tetralin was probed by tandem mass spectrometry, imaging photoelectron photoion coincidence (iPEPICO) spectroscopy, and theory. The major reactions observed were the loss of the hydrocarbons CH3•, C2H4, and C3H5• together with H•-atom loss. RRKM modeling of the iPEPICO data suggested a two-well potential energy surface. Ionized tetralin can lose all four neutrals via H-shift and ring-opening reactions or CH3• and C2H4 after interconversion to the 1-methylindane ion, a process similar to that found for ionized 1,2-dihydronaphthalene (isomerizing to form the 1-methylindene ion structure). This was confirmed at the B3LYP/6-31+G(d,p) level of theory, and potential mechanisms for all reactions are described. The ionization energy of tetralin was established from the threshold photoelectron spectrum to be 8.46 ± 0.01 eV.

Why Do Large Ionized Polycyclic Aromatic Hydrocarbons Not Lose C2H2?

The reaction mechanisms for the loss of C2H2 from the ions of anthracene, phenanthrene, tetracene, and pyrene were calculated at the B3-LYP/6-311++G(2d,p) level of theory and compared to that previously published for ionized naphthalene. A common pathway emerged involving the isomerization of the molecular ions to azulene-containing analogues, followed by the contraction of the seven-member ring into a five- and four-member fused ring system, leading to the cleavage of C2H2. The key transition state was found to be for this last process, and its relative energy was consistent going from naphthalene to tetracene. That for pyrene, though, was significantly higher due to the inability of the azulene moiety to achieve a stable conformation because of the presence of the three fused rings. Thus, C2H2 loss is discriminated against in pericondensed PAHs. For catacondensed PAHs, C2H2 loss also drops in relative abundance as the PAH gets larger due to the increase in the number of available hydrogen atoms, increasing the rate constant for H atom loss over that for C2H2 loss as PAH size increases. The unimolecular reactions of four cyano-substituted polycyclic aromatic hydrocarbon (PAH) ions were also probed as a function of collision energy by collision-induced dissociation tandem mass spectrometry. As the size of the ring system increases, HCN loss decreases in importance relative to other processes (H and C2H2 loss). 9-Cyanophenanthrene ions were chosen for further exploration by theory and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. The calculated reaction pathway and energetics for C2H2 loss were consistent with those found above. The calculations suggest that larger PAHs of interest in the interstellar environment will behave independently of a CN substituent.

Hydroxy-Substituted Polycyclic Aromatic Hydrocarbon Ions as Sources of CO and HCO in the Interstellar Medium.

Tandem mass spectrometry was used to explore the trends in the unimolecular fragmentation of the ionized hydroxy-substituted polycyclic aromatic hydrocarbons 1-naphthol, 9-hydroxyphenanthrene, and 1-hydroxypyrene. The main dissociation reactions across all ring systems were CO- and HCO-losses, with ionized 1-naphthol also losing H atoms. Both ionized 1-naphthol and 9-hydroxyphenanthrene displayed the sequential loss of C2H2 and C4H2 from the [M-HCO]+ ions, reminiscent of unsubstituted PAH ions. CO-loss is slightly favored for 1-naphthol and 9-hydroxyphenanthrene, at low collision energy, but less so for 1-hydroxypyrene. Reaction mechanisms for HCO- and CO-losses from 1-hydroxypyrene were derived from CCSD/6-31G(d)//B3-LYP/6-31G(d) calculations. The CO-loss mechanism is dominated by two transition states: TS-A governing a 1,3-H shift in the molecular ion and TS-C which governs a ring-closing step to form a five-member ring in the product ion. HCO-loss occurs over a much flatter potential energy surface with the intermediate being the product ion bound to the carbon atom of HCO. Imaging photoelectron photoion coincidence spectroscopy of 1-hydroxypyrene yielded threshold photon-energy resolved breakdown curves and time-of-flight distributions that were modeled with RRKM theory to give 0 K reaction energies for HCO- and CO-losses of 3.92 ± 0.05 and 2.91 ± 0.05 eV, respectively. The entropies of activation for the two channels were very different, 14 and 95 JK-1 mol-1, respectively, a result consistent with the calculated mechanisms. The threshold photoelectron spectrum yielded an IE value of 7.14 ± 0.01 eV for 1-hydroxypyrene.

What Will Photo-Processing of Large, Ionized Amino-Substituted Polycyclic Aromatic Hydrocarbons Produce in the Interstellar Medium?

Collision-energy resolved tandem mass spectrometry was used to probe the trends in unimolecular fragmentation in a series of ionized amino-substituted polycyclic aromatic hydrocarbons ranging from naphthalene to pyrene. As the ring system expands, the dominant dissociation process changes from HNC loss (aniline) to H loss for 1-aminopyrene. Imaging photoelectron photoion coincidence spectroscopy of 1-aminopyrene yielded threshold photon-energy resolved breakdown curves, the Rice-Ramsperger-Kassel-Marcus modeling of which gave a 0 K activation energy, E0, for H loss of 3.8 ± 0.4 eV. Calculations at the CCSD/6-31G(d)//B3LYP/6-31G(d) level of theory were used to explore the possible reaction mechanisms for H, HNC, and C,N,H2 losses, and details of the reaction pathways are presented. The H atom loss was found to be due both to direct N-H bond cleavage and isomerization to form an azepine derivative.

Trifluoroacetic Acid and Trifluoroacetic Anhydride Radical Cations Dissociate near the Ionization Limit.

The threshold photoelectron spectra (TPES) and ion dissociation breakdown curves for trifluoroacetic acid (TFA) and trifluoroacetic anhydride (TFAN) were measured by imaging photoelectron photoion coincidence spectroscopy employing both effusive room-temperature samples and samples introduced in a seeded molecular beam. The fine structure in the breakdown diagram of TFA mirroring the vibrational progression in the TPES suggests that direct ionization to the X̃+ state leads to parent ions with a lower "effective temperature" than nonresonant ionization in between the vibrational progression. Composite W1U, CBS-QB3, CBS-APNO, G3, and G4 calculations yielded an average ionization energy (IE) of 11.69 ± 0.06 eV, consistent with the experimental value of 11.64 ± 0.01 eV, based on Franck-Condon modeling of the TPES. The measured 0 K appearance energies (AE0K) for the reaction forming CO2H+ + CF3 from TFA were 11.92 for effusive data and 11.94 ± 0.01 eV for molecular beam data, consistent with the calculated composite method 0 K reaction energy of 11.95 ± 0.08 eV. Together with the 0 K heats of formation (ΔfH0K) of CO2H+ and CF3, this yields a ΔfH0K of neutral TFA of -1016.6 ± 1.5 kJ mol-1 (-1028.3 ± 1.5 kJ mol-1 at 298 K). TFAN did not exhibit a molecular ion at room-temperature conditions, but a small signal was observed when rovibrationally cold species were probed in a molecular beam. The two observed dissociation channels were CF3C(O)OC(O)+ + CF3 and the dominant, sequential reaction CF3CO+ + CF3 + CO2. Calculations revealed a low-energy isomer of ionized TFAN, incorporating the three moieties CF3CO+, CF3, and CO2 joined in a noncovalent complex, mediating its unimolecular dissociation.

A framework for optimizing hydrologic performance of green roof media.

One of the primary functions of green roofs in urban areas is to moderate rainwater runoff, and one of the major impediments to the survival of plants on an extensive green roof (EGR) is a lack of available water during dry periods. Runoff moderation and water storage are both influenced by the composition of the growing media. Here we present a framework for evaluating the hydrologic performance of EGR growing media and also provide hydrologic attribute data for several commonly used EGR media constituents. In this three-phase study, we: 1) measured hydrologic attributes of individual EGR media constituents, 2) predicted attributes of media mixtures using individual constituent data, and 3) tested the seven top-ranking mixtures to evaluate hydrologic performance. Hydrologic attributes included wet weight and water held at maximum retentive capacity, long-term water retention, and hydraulic conductivity. Because perlite was light in weight yet held the greatest amount of water both at its maximum retentive capacity and in the long term, media mixtures dominated by perlite were predicted to have the best overall hydrologic performance. Mixtures dominated by pumice were also predicted to perform relatively well but were heavier. Despite the slightly greater weight and slightly lower performance, pumice may be a preferred alternative to perlite because perlite is a processed constituent with greater estimated embodied energy. Results indicate that performance of mixtures can be adequately predicted using performance of individual constituents for wet weight, water held, and long-term water retention. Hydraulic conductivity was less predictable because the pore volume in mixtures can be unrelated to the pore volume of the individual constituents. The framework presented here can be used to evaluate the performance of other EGR media, and the media attribute data can be used in formulating EGR media mixtures for specific applications. In addition, the attribute data can serve as a benchmark for evaluating other EGR media. Our results underscore the need for standardization of methods for more effective comparisons of EGR substrates, and also reinforce the need to evaluate EGR components using real-world scenarios.

Unimolecular reaction energies for polycyclic aromatic hydrocarbon ions.

Imaging photoelectron photoion coincidence spectroscopy was employed to explore the unimolecular dissociation of the ionized polycyclic aromatic hydrocarbons (PAHs) acenaphthylene, fluorene, cyclopenta[d,e,f]phenanthrene, pyrene, perylene, fluoranthene, dibenzo[a,e]pyrene, dibenzo[a,l]pyrene, coronene and corannulene. The primary reaction is always hydrogen atom loss, with the smaller species also exhibiting loss of C2H2 to varying extents. Combined with previous work on smaller PAH ions, trends in the reaction energies (E0) for loss of H from sp2-C and sp3-C centres, along with hydrocarbon molecule loss were found as a function of the number of carbon atoms in the ionized PAHs ranging in size from naphthalene to coronene. In the case of molecules which possessed at least one sp3-C centre, the activation energy for the loss of an H atom from this site was 2.34 eV, with the exception of cyclopenta[d,e,f]phenanthrene (CPP) ions, for which the E0 was 3.44 ± 0.86 eV due to steric constraints. The hydrogen loss from PAH cations and from their H-loss fragments exhibits two trends, depending on the number of unpaired electrons. For the loss of the first hydrogen atom, the energy is consistently ca. 4.40 eV, while the threshold to lose the second hydrogen atom is much lower at ca. 3.16 eV. The only exception was for the dibenzo[a,l]pyrene cation, which has a unique structure due to steric constraints, resulting in a low H loss reaction energy of 2.85 eV. If C2H2 is lost directly from the precursor cation, the energy required for this dissociation is 4.16 eV. No other fragmentation channels were observed over a large enough sample set for trends to be extrapolated, though data on CH3 and C4H2 loss obtained in previous studies is included for completeness. The dissociation reactions were also studied by collision induced dissociation after ionization by atmospheric pressure chemical ionization. When modeled with a simple temperature-based theory for the post-collision internal energy distribution, there was reasonable agreement between the two sets of data.

Unimolecular Dissociation of 1-Methylpyrene Cations: Why Are 1-Methylenepyrene Cations Formed and Not a Tropylium-Containing Ion?

1-Methylpyrene radical cations undergo the loss of a hydrogen atom at internal energies above the first dissociation threshold. Imaging photoelectron photoion coincidence spectroscopy was employed in combination with RRKM modeling to determine a 0 K activation energy of 2.78 ± 0.25 eV and an entropy of activation of 6 ± 19 J K-1 mol-1 for this H-loss reaction. The ionization energy of 1-methylpyrene was measured by mass-selected threshold photoelectron spectroscopy to be 7.27 ± 0.01 eV. These values were found to be consistent with calculations at the CCSD/6-31G(d)//B3-LYP/6-31G(d) level of theory showing that the formation of the 1-methylenepyrene cation (resulting from H loss from the methyl group) is kinetically more favorable than the formation of a tropylium-containing product ion that is structurally analogous to the formation of the tropylium cation in H loss from ionized toluene. The shift away from a tropylium-containing structure was found to be due to the increased ring strain imposed on the C7 moiety when it is bound to three fused benzene rings. The RRKM results allow for the derivation of the Δf H0o (1-methylenepyrene cation) of 945 ± 31 kJ mol-1.

Embedding co-production and addressing uncertainty in watershed modeling decision-support tools: successes and challenges.

Decision-support tools (DSTs) are often produced from collaborations between technical experts and stakeholders to address environmental problems and inform decision making. Studies in the past two decades have provided key insights on the use of DSTs and the importance of bidirectional information flows among technical experts and stakeholders - a process that is variously referred to as co-production, participatory modeling, structured decision making, or simply stakeholder participation. Many of these studies have elicited foundational insights for the broad field of water resources management; however, questions remain on approaches for balancing co-production with uncertainty specifically for watershed modeling decision support tools. In this paper, we outline a simple conceptual model that focuses on the DST development process. Then, using watershed modeling case studies found in the literature, we discuss successful outcomes and challenges associated with embedding various forms of co-production into each stage of the conceptual model. We also emphasize the "3 Cs" (i.e., characterization, calculation, communication) of uncertainty and provide evidence-based suggestions for their incorporation in the watershed modeling DST development process. We conclude by presenting a list of best practices derived from current literature for achieving effective and robust watershed modeling decision-support tools.

Human-accelerated weathering increases salinization, major ions, and alkalinization in fresh water across land use.

Human-dominated land uses can increase transport of major ions in streams due to the combination of human-accelerated weathering and anthropogenic salts. Calcium, magnesium, sodium, alkalinity, and hardness significantly increased in the drinking water supply for Baltimore, Maryland over almost 50 years (p<0.05) coinciding with regional urbanization. Across a nearby land use gradient at the Baltimore Long-Term Ecological Research (LTER) site, there were significant increases in concentrations of dissolved inorganic carbon (DIC), Ca2+, Mg2+, Na+, and Si and pH with increasing impervious surfaces in 9 streams monitored bi-weekly over a 3-4 year period (p<0.05). Base cations in urban streams were up to 60 times greater than forest and agricultural streams, and elemental ratios suggested road salt and carbonate weathering from impervious surfaces as potential sources. Laboratory weathering experiments with concrete also indicated that impervious surfaces increased pH and DIC with potential to alkalinize urban waters. Ratios of Na+ and Cl- suggested that there was enhanced ion exchange in the watersheds from road salts, which could mobilize other base cations from soils to streams. There were significant relationships between Ca2+, Mg2+, Na+, and K+ concentrations and Cl-, SO42-, NO3- and DIC across land use (p<0.05), which suggested tight coupling of geochemical cycles. Finally, concentrations of Na+, Ca2+, Mg2+, and pH significantly increased with distance downstream (p<0.05) along a stream network draining 170 km2 of the Baltimore LTER site contributing to river alkalinization. Our results suggest that urbanization may dramatically increase major ions, ionic strength, and pH over decades from headwaters to coastal zones, which can impact integrity of aquatic life, infrastructure, drinking water, and coastal ocean alkalinization.

Structure and Stability of Carbohydrate-Lipid Interactions. Methylmannose Polysaccharide-Fatty Acid Complexes.

We report a detailed study of the structure and stability of carbohydrate-lipid interactions. Complexes of a methylmannose polysaccharide (MMP) derivative and fatty acids (FAs) served as model systems. The dependence of solution affinities and gas-phase dissociation activation energies (Ea ) on FA length indicates a dominant role of carbohydrate-lipid interactions in stabilizing (MMP+FA) complexes. Solution (1) H NMR results reveal weak interactions between MMP methyl groups and FA acyl chain; MD simulations suggest the complexes are disordered. The contribution of FA methylene groups to the Ea is similar to that of heats of transfer of n-alkanes from the gas phase to polar solvents, thus suggesting that MMP binds lipids through dipole-induced dipole interactions. The MD results point to hydrophobic interactions and H-bonds with the FA carboxyl group. Comparison of collision cross sections of deprotonated (MMP+FA) ions with MD structures suggests that the gaseous complexes are disordered.