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A combination of ion mobility mass spectrometry (IMS-MS), collision-induced dissociation (CID), Rice–Ramsperger–Kassel–Marcus modeling, and computational chemistry was used to determine the structure and unimolecular chemistry of dimeric and trimeric sulfonated meso-tetraphenylporphyrins with negative charges from −2 to −5. By comparing experimental collision cross sections obtained from calibrated IMS drift times with calculated cross sections for the lowest energy calculated structures, it was confirmed that dimer species have a bridged structure where the two monomers are connected through iron–sulfonic interactions. Dimer species with the charge states −4 and −5 dissociate into two monomer units where the charge is distributed between the monomers. Dimers with lower charge states also lose neutral SO2 and SO3 groups. For trimeric species with charge states of −3 and −4, IMS identifies three and two isomers, respectively. It was confirmed that the −4 charged trimer isomers consist of one with three stacked monomers and one in which the third monomer unit is connected to a stacked dimer via two iron–sulfonic bonds (bridged/stacked). Both yielded the same CID breakdown diagram confirming that the two isomers likely interconvert prior to dissociation. The significantly larger density of states of the bridged–stacked structure compared with the stacked structure means the former is likely the reactive configuration.

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

Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) are potential contributors to the 11.3 µm band in interstellar observations. To further explore their role in the interstellar medium, we investigated their fate after photoprocessing by VUV radiation; in particular, we studied the dissociative photoionization of the simplest OPAH, benzofuran, with imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. Ionized benzofuran dissociates by loss of CO, followed by a sequential H-atom loss. The parallel HCO-loss channel, leading to the same bicyclic C7H5+ fragment ion, is not competitive at low excess energies above the ionization threshold. However, the collision-induced dissociation tandem mass spectrometry results suggest that CO and HCO may be formed in parallel at higher energies. A Rice–Ramsperger–Kassel–Marcus fragmentation model reproduced the iPEPICO data well, assuming the initial 1,2-H shift transition state to be rate determining to CO loss. The breakdown diagram and the measured dissociation rates agreed well at the CBS-QB3-calculated activation energy of 2.99 eV, which could be relaxed to 3.25 eV, and only a slight adjustment of the ab initio activation entropy. The model barrier to sequential H loss is larger than the computed H-loss threshold and the breakdown diagram rises less steeply than predicted, which indicates suprastatistical kinetic energy release after the tight H-transfer transition state of the first step. HCO cleavage is possible after a ring-opening transition state, which is looser than and isoenergetic with the CO-loss transition state. However, a subsequent ring formation transition state at 3.85 eV is moderately tight, which suppresses HCO loss at low excess energies.

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.

We investigate impacts of Freshwater Salinization Syndrome (FSS) on mobilization of salts, nutrients, and metals in urban streams and stormwater BMPs by analyzing original data on concentrations and fluxes of salts, nutrients, and metals from 7 urban watersheds in the Mid-Atlantic U.S. and synthesizing literature data. We also explore future critical research needs through a survey of practitioners and scientists. Our original data show: (1) sharp pulses in concentrations of salt ions and metals in urban streams directly following both road salt events and stream restoration construction (

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.

Factors driving freshwater salinization syndrome (FSS) influence the severity of impacts and chances for recovery. We hypothesize that spread of FSS across ecosystems is a function of interactions among five state factors: human activities, geology, flowpaths, climate, and time. (1) Human activities drive pulsed or chronic inputs of salt ions and mobilization of chemical contaminants. (2) Geology drives rates of erosion, weathering, ion exchange, and acidification-alkalinization. (3) Flowpaths drive salinization and contaminant mobilization along hydrologic cycles. (4) Climate drives rising water temperatures, salt stress, and evaporative concentration of ions and saltwater intrusion. (5) Time influences consequences, thresholds, and potentials for ecosystem recovery. We hypothesize that state factors advance FSS in distinct stages, which eventually contribute to failures in systems-level functions (supporting drinking water, crops, biodiversity, infrastructure, etc.). We present future research directions for protecting freshwaters at risk based on five state factors and stages from diagnosis to prognosis to cure. This work was supported by: National Science Foundation GCR 2021089, Maryland Sea Grant SA75281870W, the Chesapeake Bay Trust, Pooled Monitoring Initiative, and its funding partners, and the Washington Metropolitan Council of Governments contract 21-001. Published version

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.

The thermal dissociation of the atmospheric constituent methyl formate was probed by coupling pyrolysis with imaging photoelectron photoion coincidence spectroscopy (iPEPICO) using synchrotron VUV radiation at the Swiss Light Source (SLS). iPEPICO allows threshold photoelectron spectra to be obtained for pyrolysis products, distinguishing isomers and separating ionic and neutral dissociation pathways. In this work, the pyrolysis products of dilute methyl formate, CH

1. Urban streams are degraded by a suite of factors, including burial beneath urban infrastructure, such as roads or parking lots, which eliminates light and reduces direct organic matter inputs to streams from riparian zones. These changes to stream metabolism and terrestrial carbon contribution will likely have consequences for organic matter metabolism by microbes and dissolved organic matter (DOM) use patterns in streams. Respiration by heterotrophic biofilms drives the nitrogen and phosphorus cycles, but we lack a clear understanding of how stream burial and seasonality affect microbial carbon use. 2. We studied seasonal changes (autumn, spring, and summer) in organic matter metabolism by microbial communities in open and buried reaches of three urban streams in Cincinnati, OH. We characterised DOM quality using fluorescence spectroscopy and extracellular enzyme profiles, and we measured the respiration response to carbon supplements in nutrient diffusing substrata (NDS). We hypothesised: (1) that algal production would lead to higher quality DOM in spring compared to other seasons and in open compared to buried reaches, (2) lower reliance of microbial respiration on recalcitrant carbon sources in spring and in open reaches, and (3) that microbial respiration would increase in response to added carbon in autumn and in buried reaches. 3. Several fluorescence metrics showed higher quality DOM in spring than autumn, but only the metric of recalcitrant humic compounds varied by reach, with more humic DOM in open compared to buried reaches. This likely reflected open reaches as an avenue for direct terrestrial inputs from the riparian zone. 4. Extracellular enzyme assays showed that microbes in buried reaches allocated more effort to degrade recalcitrant carbon sources, consistent with a lack of labile carbon compounds due to limited photosynthesis. Nitrogen acquisition enzymes were highest in autumn coincident with riparian leaf inputs to the streams. Buried and open reaches both responded more strongly to added carbon in autumn when terrestrial leaf inputs dominated compared to the spring when vernal algal blooms were pronounced. 5. Our data show that stream burial affects the quality of the DOM pool with consequences for how microbes use those carbon sources, and that heterotrophic respiration increased on carbon-supplemented NDS in buried and open stream reaches in both seasons. Different carbon quality and use patterns suggest that urban stream infrastructure affects spatiotemporal patterns of bacterial respiration, with likely consequences for nitrogen and/or phosphorus cycling given that carbon use drives other biogeochemical cycles. Management actions that increase light to buried streams could shift the balance between allochthonous and autochthonous DOM in urban streams with consequences for spatiotemporal patterns in bacterial metabolism.

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.

Steric interference of two bay-hydrogen atoms causes the benzo[c]phenanthrene radical cation to be non-planar. The energy required to remove one of these H atoms (2.8 ± 0.1 eV, from iPEPICO spectroscopy) is 1.5 eV lower than that required from the planar tetracene ion due to the formation of a new C C bond. This low dissociation energy precludes benzo[c]phenanthrene ions losing C2H2 (observed from tetracene with an energy of 4.2 eV). The B3-LYP/6-311++G(2d,p) reaction pathways to C2H2 loss are presented and found to be mediated by azulene-containing intermediates. The second IE of tetracene was measured to be 19.0 ± 0.2 eV.

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.

Stream restoration is a popular approach for managing nitrogen in degraded, flashy urban streams. Here, we investigated the long-term effects of geomorphic stream restoration 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 flashiness and N concentrations and flux changed after the restoration. We examined two independent surface water and groundwater data sets collected from 2002–2012 at our study sites in the Minebank Run watershed, modeled N flux, and compared our data to similar long-term data from the Baltimore Ecosystem Study LTER (BES) that served as reference sites. Restoration was completed during 2004 and 2005. Afterward, the monthly flashiness index, based on mean monthly discharge, decreased over time from 2002 and 2008. Groundwater nitrate (NO3−) concentrations trended slightly downward over time after the restoration at the restored site while dissolved organic carbon (DOC) concentrations trended upward whereas no trends were observed at the control site. Comparisons of NO3− concentrations with Cl− concentrations and specific conductance in both groundwater and surface water suggested that N reductions over time at the restored sites were not due to dilution. Similar patterns at BES sites suggested that declining NO3− was a function of restoration and watershed management, not larger regional factors such as decreased atmospheric inputs. DOC and NO3− were negatively related before and after restoration suggesting C limitation of N transformation. Long-term trends in surface water NO3− based on USGS data showed downward trends after restoration at both the restored and control sites while specific conductance showed no trend, suggesting that load reductions were not responsible for NO3− patterns. Modeled NO3− flux decreased post restoration in both the short and long-terms. Groundwater NO3− concentrations varied among stream features suggesting that some engineered features may be functionally better at creating optimal conditions for N removal. However, some engineered features eroded and failed post restoration thereby reducing efficacy of the 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.

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.

Nitrate contamination of groundwater is a concern globally, particularly in agricultural regions where decades of fertilizer nitrogen (N) use has led to a legacy of N accumulation in soils and groundwater. Linkages between current management practices and groundwater nitrate dynamics are often confounded by the legacy effect, and other processes unrelated to management. A coupled analysis of dual stable isotopes of water (δH(2)O = δ(2)H and δ(18)O) and nitrate (δNO(3)(−) = δ(15)N and δ(18)O) can be a powerful approach to identify sources and processes responsible for groundwater pollution. To assess how management practices impact groundwater nitrate, we interpreted behavior of δH(2)O and δNO(3)(−), together with nitrate concentrations, in water samples collected from long-term monitoring wells in the Southern Willamette Valley (SWV), Oregon. The source(s) of nitrate and water varied among wells, suggesting that the nitrate concentration patterns were not uniform across the shallow aquifer of the valley. Analyzing the stability versus variability of a well’s corresponding δH(2)O and δNO(3)(−) values over time revealed the mechanisms controlling nitrate concentrations. Wells with stable δH(2)O and δNO(3)(−) values and nitrate concentrations were influenced by one water source with a long residence time and one nitrate source. Variable nitrate concentrations of other wells were attributed to dilution with an alternate water source, mixing of two nitrate sources, or variances in the release of legacy N from overlying soils. Denitrification was not an important process influencing well nitrate dynamics. Understanding the drivers of nitrate dynamics and interaction with legacy N is crucial for managing water quality improvement. This case study illustrates when and where such coupled stable isotope approaches might provide key insights to management on groundwater nitrate contamination issues.

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

Freshwater salinization is an emerging global issue impacting safe drinking water, ecosystem health and biodiversity, and infrastructure. The complex interrelationships between salt ions and chemical, biological, and geologic parameters and consequences on the natural, social, and built environment are called Freshwater Salinization Syndrome (FSS). We analyze and discuss the expanding magnitude and scope of FSS including its discovery of widespread geographic importance in humid regions and connections to human-accelerated weathering and mobilization of ‘chemical cocktails,’ We also present empirical data analyses illustrating changes in FSS and its water quality impacts across time and space. We outline several frontiers in FSS research, and we also identify new management strategies and tradeoffs.

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.

Restoration and reconnection of floodplain systems provide multiple societal and ecosystem benefits, while providing municipalities the opportunity to attempt alternative approaches to maintain infrastructure protection and function. In some restored floodplains, treated wastewater effluent discharge is redirected over land instead of directly into rivers to allow natural flow and infiltration, to facilitate restoration designs such as levee setback, and to provide additional freshwater to floodplain ecosystems. However, indirect discharge of treated effluent over land may pose risks to surface and groundwater when pollutants like excess nutrients enter the floodplain and undergo transformation. We investigated the consequences for groundwater and surface water quality when effluent was redirected as open water channels over a floodplain surface. In this study, seasonal floodplain nutrient concentrations in groundwater and surface water were observed for more than 5 years as a floodplain and wastewater treatment plant underwent a major restoration project that included river-floodplain reconnection with levee setback and redirection of effluent discharge from a river channel to open flow across the restored floodplain. Nutrient loading to the surrounding floodplain groundwater and surface water was observed, but based on measures of hydrological connectivity, groundwater flow paths, and biogeochemistry, nutrients from the effluent moved within the floodplain with minimal effect to the surrounding floodplain water quality. We did not find evidence of substantial additional processing that could replace advanced nutrient treatment in this system, however we did observe evidence of diverse nutrient processes that may support enhanced retention if treatment channels were designed to enhance these processes. We suggest that indirect discharge of high quality treated effluent in a restored floodplain is a viable alternative to direct discharge into a river when groundwater flow directs that discharge to habitats where minimal nutrient sensitivity is expected.

The unimolecular dissociations of four nitro-substituted polycyclic aromatic hydrocarbon (PAH) ions were explored using tandem mass spectrometry, imaging photoelectron photoion coincidence (iPEPICO) spectroscopy and computational chemistry. Ionized 1-nitronaphthalene and 9-nitroanthracene both exhibit the loss of C2O2 (likely sequential loss of two CO molecules), NO and CO2 as primary fragmentation channels, while for the larger 3-nitrofluoranthene and 1-nitropyrene ions CO2 loss is replaced by NO2 loss. The reaction pathways for 1-nitropyrene ions were calculated at the CCSD/6-31G(d)//B3-LYP/6-31G(d) level of theory. NO loss is preceded by a nitro-to-nitrite isomerization requiring 2.09 eV, while NO2 loss was found to form the triplet state [pyrene – H]+ ion (requiring 2.36 eV), consistent with the behavior of this class of PAH ions. iPEPICO-derived energies for these two reactions are in excellent agreement with theory, 2.05 ± 0.09 eV and 2.38 ± 0.12 eV, respectively. The iPEPICO-derived reaction energy for C2O2 loss is 2.76 ± 0.08 eV, but we were unable to calculate this reaction pathway. The most energetically-favorable products of sequential CO loss lie 3.2 eV and 2.05 eV, respectively, lower in energy than the precursor ion, indicating that what was measured was an effective barrier height for this reaction.

Este artículo contiene 25 páginas, 9 figuras., In the Anthropocene, watershed chemical transport is increasingly dominated by novel combinations of elements, which are hydrologically linked together as ‘chemical cocktails.’ Chemical cocktails are novel because human activities greatly enhance elemental concentrations and their probability for biogeochemical interactions and shared transport along hydrologic flowpaths. A new chemical cocktail approach advances our ability to: trace contaminant mixtures in watersheds, develop chemical proxies with high-resolution sensor data, and manage multiple water quality problems. We explore the following questions: (1) Can we classify elemental transport in watersheds as chemical cocktails using a new approach? (2) What is the role of climate and land use in enhancing the formation and transport of chemical cocktails in watersheds? To address these questions, we first analyze trends in concentrations of carbon, nutrients, metals, and salts in fresh waters over 100 years. Next, we explore how climate and land use enhance the probability of formation of chemical cocktails of carbon, nutrients, metals, and salts. Ultimately, we classify transport of chemical cocktails based on solubility, mobility, reactivity, and dominant phases: (1) sieved chemical cocktails (e.g., particulate forms of nutrients, metals and organic matter); (2) filtered chemical cocktails (e.g., dissolved organic matter and associated metal complexes); (3) chromatographic chemical cocktails (e.g., ions eluted from soil exchange sites); and (4) reactive chemical cocktails (e.g., limiting nutrients and redox sensitive elements). Typically, contaminants are regulated and managed one element at a time, even though combinations of elements interact to influence many water quality problems such as toxicity to life, eutrophication, infrastructure corrosion, and water treatment. A chemical cocktail approach significantly expands evaluations of water quality signatures and impacts beyond single elements to mixtures. High-frequency sensor data (pH, specific conductance, turbidity, etc.) can serve as proxies for chemical cocktails and improve real-time analyses of water quality violations, identify regulatory needs, and track water quality recovery following storms and extreme climate events. Ultimately, a watershed chemical cocktail approach is necessary for effectively co-managing groups of contaminants and provides a more holistic approach for studying, monitoring, and managing water quality in the Anthropocene., This work was funded by USDA (award # 2016-67019-25280) and NSF-EPSCoR (#1641157) for supporting collaborations at the AGU Chapman Conference on Extreme Climate Events. Significant funding for data collection/analyses in this paper was provided by NSF EAR1521224, NSF CBET1058502, NSF Coastal SEES1426844, NSF DEB-0423476 and DEB-1027188, NSF RI EPSCoR NEWRnet Grant No. IIA-1330406, EPA ORD, Chesapeake Bay Trust, and Multi-state Regional Hatch Project S-1063.

Tris(2,2′-bipyridine)ruthenium(II) and similar complexes containing the 1,10-phenanthroline ligand were formed by spraying a ligand solution and a ruthenium trichloride solution through two independent electrospray (ESI) emitters. This was confirmed by comparing ion mobility drift time, mass spectra, and energy-resolved collision-induced dissociation (CID) breakdown curves with the corresponding reference standards. The complexes of 2,2′-bipyridine and 1,10-phenantroline with iron(II), and their mixed-ligand complexes formed by dual-spray exhibited two additional hydrogen atoms. By CID, these unique gas phase complexes showed similar initial ligand loss to the reference standards, however the sequential ligand loss showed unique dissociation channels and energetics. Density functional theory calculations of the [Fe(phen) 3 + 2H] 2+ complex and its fragment ions suggest that, after the initial loss of one ligand, the additional hydrogen atoms transfer to the central iron atom. The relative energy of the dissociation channels showed good agreement with experimental breakdown curves.

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

In early 2015, clinicians throughout Zambia noted a range of unpredictable adverse events after the administration of propofol, including urticaria, bronchospasm, profound hypotension, and most predictably an inadequate depth of anesthesia. Suspecting that the propofol itself may have been substandard, samples were procured and sent for testing.Three vials from 2 different batches were analyzed using gas chromatography-mass spectrometry methods at the John L. Holmes Mass Spectrometry Facility.Laboratory gas chromatography-mass spectrometry analysis determined that, although all vials contained propofol, its concentration differed between samples and in all cases was well below the stated quantity. Two vials from 1 batch contained only 44% ± 11% and 54% ± 12% of the stated quantity, whereas the third vial from a second batch contained only 57% ± 9%. The analysis found that there were no hexane-soluble impurities in the samples.None of the analyzed vials contained the stated amount of propofol; however, our analysis did not detect additional contaminants that would explain the adverse events reported by clinicians. Our results confirm the presence of substandard propofol in Zambia; however, anecdotal accounts of substandard anesthetic medicines in other countries abound and warrant further investigation to provide estimates of the prevalence and scope of this global problem.

Emission spectra from collisions of 8 keV He + and H 2 + with neutral naphthalene, benzene, acetylene and methane were acquired over 190–1020 nm on a modified double-focusing mass spectrometer. The bands, emission intensities and the minimum excitation energy to produce the observed transitions (Emin) were compared for the two projectile ions. Emin values were the same for both projectiles but the emission intensity is greater in the case of He + . This is consistent with calculations at the CISD/6-311+G(2df) level on the excited states of the respective collision complexes which exhibited two distinct state-crossing points for He + collisions but none for H 2 + collisions.

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 X+ 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.

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.

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.

Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) have been considered as potential carriers of the 11.3 μm band in interstellar observations. To begin to probe their potential contribution to chemistry in the interstellar medium, we report here threshold photoelectron spectra (TPES) for seven oxygen-containing polycyclic aromatic hydrocarbons 2,3-benzofuran (BF), 2,3-dihydrobenzofuran (DHF), phthalan (PH), dibenzofuran (DBF), dibenzo(B,F)oxepine (DBO), benzo[b]naphtho[2,3-d]furan (BNF) and benzo[b]naphtho[1,2-d]furan (cBNF). Vertical ionization energies to the ground and excited ion states were calculated with the outer-valence Green’s function method, and Franck–Condon simulations, based on harmonic (time-dependent) density functional theory results, were used to explore vibrational excitation upon ionization. CBS-QB3 calculations are also reported. Adiabatic ionization energies (IE) could be measured accurately for five of the molecules: BF (8.35 ± 0.01 eV), PH (8.76 ± 0.01 eV), DBF (8.12 ± 0.02 eV), BNF (7.64 ± 0.02 eV), and cBNF (7.62 ± 0.02 eV). For BF and cBNF, excited state optimizations also allowed Franck–Condon simulations of excited-state bands. The TPES of DHF and DBO feature broad ionization onsets due to large geometry changes upon ionization, as both become planar when an electron is removed. The band maxima yield the vertical IE for these two molecules: 8.2 ± 0.2 eV and 8.0 ± 0.2 eV, respectively, while the best estimate of the adiabatic IE for DHF is 7.98 ± 0.05 eV.

Increasing trends in base cations, pH, and salinity of freshwaters have been documented in US streams over 50 years. These patterns, collectively known as freshwater salinization syndrome (FSS), are driven by multiple processes, including applications of road salt and human-accelerated weathering of impervious surfaces, reductions in acid rain, and other anthropogenic legacies of change. FSS mobilizes chemical cocktails of distinct elemental mixtures via ion exchange, and other biogeochemical processes. We analyzed impacts of FSS on streamwater chemistry across five urban watersheds in the Baltimore-Washington, USA metropolitan region. Through combined grab-sampling and high-frequency monitoring by USGS sensors, regression relationships were developed among specific conductance and major ion and trace metal concentrations. These linear relationships were statistically significant in most of the urban streams (e.g. R 2 = 0.62 and 0.43 for Mn and Cu, respectively), and showed that specific conductance could be used as a proxy to predict concentrations of major ions and trace metals. Major ions and trace metals analyzed via linear regression and principal component analysis showed co-mobilization (i.e. correlations among combinations of specific conductance (SC), Mn, Cu, Sr2+, and all base cations during certain times of year and hydrologic conditions). Co-mobilization of metals and base cations was strongest during peak snow events but could continue over 24 h after SC peaked, suggesting ongoing cation exchange in soils and stream sediments. Mn and Cu concentrations predicted from SC as a proxy indicated acceptable goodness of fit for predicted vs. observed values (Nash–Sutcliffe efficiency > 0.28). Metals concentrations remained elevated for days after SC decreased following snowstorms, suggesting lag times and continued mobilization after road salt use. High-frequency sensor monitoring and proxies associated with FSS may help better predict contaminant pulses and contaminant exceedances in response to salinization and impacts on aquatic life, infrastructure, and drinking water.

Green roofs are among the most popular type of green infrastructure implemented in highly urbanized watersheds due to their low cost and efficient utilization of unused or under-used space. In this study, we examined the effectiveness of green roofs to attenuate stormwater runoff across a large metropolitan area in the Pacific Northwest, United States. We utilized a spatially explicit ecohydrological watershed model called Visualizing Ecosystem Land Management Assessments (VELMA) to simulate the resulting stormwater hydrology of implementing green roofs over 25%, 50%, 75%, and 100% of existing buildings within four urban watersheds in Seattle, Washington, United States. We simulated the effects of two types of green roofs: extensive green roofs, which are characterized by shallow soil profiles and short vegetative cover, and intensive green roofs, which are characterized by deeper soil profiles and can support larger vegetation. While buildings only comprise approximately 10% of the total area within each of the four watersheds, our simulations showed that 100% implementation of green roofs on these buildings can achieve approximately 10–15% and 20–25% mean annual runoff reductions for extensive and intensive green roofs, respectively, over a 28-year simulation. These results provide an upper limit for volume reductions achievable by green roofs in these urban watersheds. We also showed that stormwater runoff reductions are proportionately smaller during higher flow regimes caused by increased precipitation, likely due to the limited storage capacity of saturated green roofs. In general, green roofs can be effective at reducing stormwater runoff, and their effectiveness is limited by both their areal extent and storage capacity. Our results showed that green roof implementation can be an effective stormwater management tool in highly urban areas, and we demonstrated that our modeling approach can be used to assess the watershed-scale hydrologic impacts of the widespread adoption of green roofs across large metropolitan areas.

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.