Nitrogen Chemistry Research Articles

Benchmarking spin-state chemistry in starless core models

Aims. We aim to present simulated chemical abundance profiles for a variety of important species, with special attention given to spin-state chemistry, in order to provide reference results against which present and future models can be compared. Methods. We employ gas-phase and gas-grain models to investigate chemical abundances in physical conditions corresponding to starless cores. To this end, we have developed new chemical reaction sets for both gas-phase and grain-surface chemistry, including the deuterated forms of species with up to six atoms and the spin-state chemistry of light ions and of the species involved in the ammonia and water formation networks. The physical model is kept simple in order to facilitate straightforward benchmarking of other models against the results of this paper. Results. We find that the ortho/para ratios of ammonia and water are similar in both gas-phase and gas-grain models, at late times in particular, implying that the ratios are determined by gas-phase processes. We derive late-time ortho/para ratios of ~0.5 and ~1.6 for ammonia and water, respectively. We find that including or excluding deuterium in the calculations has little effect on the abundances of non-deuterated species and on the ortho/para ratios of ammonia and water, especially in gas-phase models where deuteration is naturally hindered owing to the presence of abundant heavy elements. Although we study a rather narrow temperature range (10-20 K), we find strong temperature dependence in, e.g., deuteration and nitrogen chemistry. For example, the depletion timescale of ammonia is significantly reduced when the temperature is increased from 10 to 20 K; this is because the increase in temperature translates into increased accretion rates, while the very high binding energy of ammonia prevents it from being desorbed at 20 K.

A combined crossed molecular beam and quasiclassical trajectory study of the Titan-relevant N(2D) + D2O reaction

Following a recent investigation on the N(2D) + H2O reaction [Homayoon et al., J. Phys. Chem. Lett. 5, 3508 (2014)], we report on an experimental and theoretical study of the isotopologue N(2D) + D2O reaction. Crossed molecular beam (CMB) experiments were conducted at a collision energy of 10.3 kcal mol–1. Quasiclassical trajectory calculations were performed on a recent potential energy surface to derive the centre-of-mass functions necessary to simulate the CMB laboratory distributions. Excellent agreement was found. The importance of the channel leading to HON/DON was confirmed. The inclusion of this channel, in addition to that leading to the isomer HNO/DNO, can affect the models considering the coupling between nitrogen and oxygen chemistry in the upper atmosphere of Titan.

Nitrogen chemistry and lung physiology.

The versatile chemistry of nitrogen is important to pulmonary physiology. Indeed, almost all redox forms of nitrogen are relevant to pulmonary physiology and to pathophysiology. Here we review the relevance to pulmonary biology of (a) elemental nitrogen; (b) reduced forms of nitrogen such as amines, ammonia, and hydroxylamine; and (c) oxidized forms of nitrogen such as the nitroxyl anion, the nitric oxide free radical, and S-nitrosothiols. Our focus is on oxidized nitrogen in the form of S-nitrosothiol bond-containing species, which are now appreciated to be important to every type of cell-signaling process in the lung. We also review potential clinical applications of nitrogen oxide biochemistry. These principles are being translated into clinical practice as diagnostic techniques and therapies for a range of pulmonary diseases including asthma, cystic fibrosis, adult respiratory distress syndrome, primary ciliary dyskinesia, and pulmonary hypertension.

Organic chemistry in Titan׳s upper atmosphere and its astrobiological consequences: I. Views towards Cassini plasma spectrometer (CAPS) and ion neutral mass spectrometer (INMS) experiments in space

The discovery of carbocations and carbanions by Ion Neutral Mass Spectrometer (INMS) and the Cassini Plasma Spectrometer (CAPS) instruments onboard the Cassini spacecraft in Titan׳s upper atmosphere is truly amazing for astrochemists and astrobiologists. In this paper we identify the reaction mechanisms for the growth of the complex macromolecules observed by the CAPS Ion Beam Spectrometer (IBS) and Electron Spectrometer (ELS). This identification is based on a recently published paper (Ali et al., 2013. Planet. Space Sci. 87, 96) which emphasizes the role of Olah׳s nonclassical carbonium ion chemistry in the synthesis of the organic molecules observed in Titan׳s thermosphere and ionosphere by INMS. The main conclusion of that work was the demonstration of the presence of the cyclopropenyl cation – the simplest Huckel׳s aromatic molecule – and its cyclic methyl derivatives in Titan׳s atmosphere at high altitudes. In this study, we present the transition from simple aromatic molecules to the complex ortho-bridged bi- and tri-cyclic hydrocarbons, e.g., CH2+ mono-substituted naphthalene and phenanthrene, as well as the ortho- and peri-bridged tri-cyclic aromatic ring, e.g., perinaphthenyl cation. These rings could further grow into tetra-cyclic and the higher order ring polymers in Titan׳s upper atmosphere. Contrary to the pre-Cassini observations, the nitrogen chemistry of Titan׳s upper atmosphere is found to be extremely rich. A variety of N-containing hydrocarbons including the N-heterocycles where a CH group in the polycyclic rings mentioned above is replaced by an N atom, e.g., CH2+ substituted derivative of quinoline (benzopyridine), are found to be dominant in Titan׳s upper atmosphere. The mechanisms for the formation of complex molecular anions are discussed as well. It is proposed that many closed-shell complex carbocations after their formation first, in Titan׳s upper atmosphere, undergo the kinetics of electron recombination to form open-shell neutral radicals. These radical species subsequently might form carbanions via radiative electron attachment at low temperatures with thermal electrons. The classic example is the perinaphthenyl anion in Titan׳s upper atmosphere. Therefore, future astronomical observations of selected carbocations and corresponding carbanions are required to settle the key issue of molecular anion chemistry on Titan. Other than earth, Titan is the only planetary body in our solar system that is known to have reservoirs of permanent liquids on its surface. The synthesis of complex biomolecules either by organic catalysis of precipitated solutes “on hydrocarbon solvent” on Titan or through the solvation process indeed started in its upper atmosphere. The most notable examples in Titan׳s prebiotic atmospheric chemistry are conjugated and aromatic polycyclic molecules, N-heterocycles including the presence of imino >CN–H functional group in the carbonium chemistry. Our major conclusion in this paper is that the synthesis of organic compounds in Titan׳s upper atmosphere is a direct consequence of the chemistry of carbocations involving the ion–molecule reactions. The observations of complexity in the organic chemistry on Titan from the Cassini–Huygens mission clearly indicate that Titan is so far the only planetary object in our solar system that will most likely provide an answer to the question of the synthesis of complex biomolecules on the primitive earth and the origin of life.

Modeling the Nitrogen and Sulfur Chemistry in Pressurized Flue Gas Systems

A rate-based model is developed to elucidate the chemistry behind the simultaneous absorption of NOx and SOx under pressurized conditions (pressures up to 30 bar) that are applicable to the flue gases obtained from CO2 capture systems. The studied flue gas conditions are relevant to oxy-fuel and chemical-looping combustion systems. The kinetics of the reactions implemented in the model is based on a thorough review of the literature. The chemistry of nitrogen, sulfur, and N–S interactions are evaluated in detail, and the most important reaction pathways are discussed. The effects of pH, pressure, and flue-gas composition on the liquid-phase chemistry are also examined and discussed. Simulations that use existing kinetic data reveal that the pH level has a strong influence on the reaction pathway that is followed and the types of products that are formed in the liquid phase. In addition, the pressure level and the presence of NOx significantly affect the removal of SO2 from the flue gas.

Influence of DC plasma modification on the selected properties and the geometrical surface structure of polylactide prior to autocatalytic metallization

The paper presents the results of studies to determine the applicability of plasma modification in the process of polylactide (PLA) surface preparation prior to the autocatalytic metallization. The polylactide plasma modification was carried out in an oxygen or nitrogen chemistry. The samples were tested with the following methods: scanning electron microscopy (SEM), atomic force microscopy (AFM), goniometry and electron spectrophotometry (XPS). Scanning electron microscopy and atomic force microscopy images were demonstrated. The results of surface free energy calculations, performed based on the results of the contact angle measurements have been presented. The results of the qualitative (degree of oxidation or nitridation) and quantitative analysis of the chemical composition of the polylactide surface layer have also been described. The results of the studies show that the DC plasma modification performed in the proposed condition is a suitable as a method of surface preparation for the polylactide metallization.

The evolution of infalling sulfur species in Titan’s atmosphere

Aims. We studied the hypothesis that micrometeorites and Enceladus’ plume activity could carry sulfur-bearing species into the upper atmosphere of Titan, in a manner similar to oxygen-bearing species. Methods. We have developed a detailed photochemical model of sulfur compounds in the atmosphere of Titan that couples hydrocarbon, nitrogen, oxygen, and sulfur chemistries. Results. Photochemical processes produce mainly CS and H2CS in the upper atmosphere of Titan and C3S, H2S and CH3SH in the lower atmosphere. Mole fractions of these compounds depend significantly on the source of sulfur species. Conclusions. A possible future detection of CS (or the determination of a low upper limit) could be used to distinguish the two scenarios for the origin of sulfur species, which then could help to di erentiate the various scenarios for the origin of H2O, CO, and CO2 in the stratosphere of Titan.

Temporal Evolution and Variability of Dissolved Inorganic Nitrogen in Beach Pore Water Revealed Using Radon Residence Times

We coupled measurements of beach pore water residence time, determined using the radioisotopic tracer (222)Rn, with dissolved carbon and nitrogen chemistry to identify the temporal evolution and variability of dissolved inorganic nitrogen (DIN) concentrations in beach pore water along the Santa Barbara, California coastline. Pore water dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) ratios (DOC:TDN) were negative exponentially correlated with residence time. Mean pore water residence times were positively correlated with tidal amplitudes, and ranged from 4.4 to 6.4 days. We used this range in mean residence times to model radon residence time distributions (RTDs), and integrated them with modeled DIN vs residence time relationships (DIN-temporal evolution, or DIN-te curves) to derive volume-weighted mean (VWM) DIN concentrations. We observed 1.2-fold and 5.2-fold differences (20% and 420% increases) in VWM DIN concentrations over the range in modeled RTDs and DIN-te curves, respectively, and a maximum 6.4-fold difference (540% increase) in VWM DIN concentrations for an interactive shift in the RTD and the DIN-te curve. Our study suggests that accounting for temporal variability in the RTD and DIN concentration of pore water is necessary to obtain more accurate estimates of DIN delivery to coastal oceans.

Decomposition and reduction of N2O on CaS (100) surface: A theoretical account

The catalytic effect of CaS on N2O decomposition and reduction was investigated using density functional theory calculations. N2O approached the CaS (100) surface and crossed an energy barrier of 1.228eV, decomposing into a free N2 molecule and an adsorbed O atom. The generated adsorbed O atom could be removed through two reaction pathways: binding with a neighboring adsorbed O atom into O2 with the barrier energy of 1.877eV or reacting with another N2O molecule generating an adsorbed O2 with the barrier of 1.863eV. The removal of the surface adsorbed O atom is the rate-determining step of the catalytic decomposition of N2O. In comparison with the homogeneous reaction between N2O and CO, CO accelerated the removal of the adsorbed O atom, hence improving the reduction of N2O on CaS (100). Furthermore, while compared with the CaO-catalytic removal of N2O, CaS is not as active as CaO for the decomposition and reduction of N2O. Our study is the first attempt to theoretically reveal the mechanism of CaS-catalytic decomposition and reduction of N2O, which provides a better understanding of the nitrogen chemistry in the reducing atmosphere zone of circulating fluidized bed boilers.

A detailed numerical study of NOx kinetics in low calorific value H2/CO syngas flames

The present study provides an extensive and detailed numerical analysis of NOx chemical kinetics in low calorific value H2/CO syngas flames utilizing predictions by five chemical kinetic mechanisms available out of which four deal with H2/CO while the fifth mechanism (GRI 3.0) additionally accounts for hydrocarbon chemistry. Comparison of predicted axial NO profiles in premixed flat flames with measurements at 1 bar, 3.05 bar and 9.15 bar shows considerably large quantitative differences among the various mechanisms. However, at each pressure, the quantitative reaction path diagrams show similar NO formation pathways for most of the mechanisms. Interestingly, in counterflow diffusion flames, the quantitative reaction path diagrams and sensitivity analyses using the various mechanisms reveal major differences in the NO formation pathways and reaction rates of important reactions. The NNH and N2O intermediate pathways are found to be the major contributors for NO formation in all the reaction mechanisms except GRI 3.0 in syngas diffusion flames. The GRI 3.0 mechanism is observed to predict prompt NO pathway as the major contributing pathway to NO formation. This is attributed to prediction of a large concentration of CH radical by the GRI 3.0 as opposed to a relatively negligible value predicted by all other mechanisms. Also, the back-conversion of NNH into N2O at lower pressures (2–4 bar) was uniquely observed for one of the five mechanisms. The net reaction rates and peak flame temperatures are used to correlate and explain the differences observed in the peak [NO] at different pressures. This study identifies key reactions needing assessment and also highlights the need for experimental data in syngas diffusion flames in order to assess and optimize H2/CO and nitrogen chemistry.

ChemInform Abstract: Frustrated Lewis Pair Chemistry of Carbon, Nitrogen and Sulfur Oxides

AbstractReview: 99 refs.

Production and use of 13N labeled N2O5 to determine gas–aerosol interaction kinetics

Abstract Dinitrogen pentoxide has aroused significant interest in atmospheric chemistry because of its importance in the night time chemistry of nitrogen oxides to influence the tropospheric oxidation capacity. We have used an established method of 13N production to synthesize 13N labeled N2O5 for the first time in order to study N2O5 uptake kinetics on aerosol particles. 13N is produced via the 16O(p, α)13N reaction in a gas target attached to the IP2 endstation of the Injector 2 cyclotron at PSI. The 13NO produced in the gas target is transported to a laboratory where it is mixed, under dry conditions, with non-labeled NO and O3 in a gas reactor, giving 13NNO5. The N2O5 thus produced is fed into an aerosol flow tube together with a humidified aerosol gas flow. The gaseous species present in the resulting gas flow are selectively separated via a narrow parallel plate diffusion denuder system, while aerosol particles can be trapped on a particle filter placed at the end of the denuder system. The activity of the 13N labeled species trapped on the denuder plates and in the particle filter can be monitored via scintillation counters. A system for the routine online production of 13N labeled N2O5 has been assembled and used to assess the conformity of the results by kinetic modeling of gas phase N2O5 chemistry, showing good agreement. A few exemplary experiments of uptake of labelled N2O5 to ammonium sulfate and citric acid particles are presented that are in good agreement with results obtained with other methods reported in the literature.

Line strengths of rovibrational and rotational transitions within the X³Σ⁻ ground state of NH.

A new line list for rovibrational and rotational transitions, including fine structure, within the NH X³Σ⁻ ground state has been created. It contains line intensities in the form of Einstein A and f-values, for all possible bands up to v' = 6, and for J up to between 25 and 44. The intensities are based on a new dipole moment function (DMF), which has been calculated using the internally contracted multi-reference configuration interaction method with an aug-cc-pV6Z basis set. The programs RKR1, LEVEL, and PGOPHER were used to calculate line positions and intensities using the most recent spectroscopic line position observations and the new DMF, including the rotational dependence on the matrix elements. The Hund's case (b) matrix elements from the LEVEL output (available as Supplement 1 of the supplementary material) have been transformed to the case (a) form required by PGOPHER. New relative intensities for the (1,0) band have been measured, and the calculated and observed Herman-Wallis effects are compared, showing good agreement. The line list (see Supplement 5 of the supplementary material) will be useful for the study of NH in astronomy, cold and ultracold molecular systems, and in the nitrogen chemistry of combustion.

Experimental and modeling study of fuel interactions with an alkyl nitrate cetane enhancer, 2-ethyl-hexyl nitrate

This study investigates the autoignition behavior of two gasoline surrogates doped with an alkyl nitrate cetane enhancer, 2-ethyl-hexyl nitrate (2EHN) to better understand dopant interactions with the fuels, including influences of accelerating kinetic pathways and enhanced exothermicity. A primary reference fuel (PRF) blend of n-heptane/iso-octane, and a toluene reference fuel (TRF) blend of n-heptane/iso-octane/toluene are used where the aromatic fraction of the latter is set to 20% (liquid volume), while the content of n-heptane is adjusted so that the overall reactivity of the undoped fuels is similar, e.g., Anti-Knock Index (AKI) of ∼91, Cetane Number (CN) ∼25. Doping levels of 0.1, 1.0 and 3.0% (liquid volume basis) are used where tests are conducted within a rapid compression machine (RCM) at a compressed pressure of 21bar, covering temperatures from 675 to 1025K with stoichiometric fuel–oxygen ratios at O2=11.4%.At the experimental conditions, it is found that the doping effectiveness of 2EHN is fairly similar between the two fuels, though 2EHN is more effective in the aromatic blend at the lowest temperatures, while it is slightly more effective in the non-aromatic blend at intermediate temperatures. Kinetic modeling of the experiments indicates that although some of the reactivity trends can be captured using a detailed model, the extents of predicted Cetane Number enhancement by 2EHN are too large, while differences in fuel interactions for the two fuels result in excessive stimulation of the non-aromatic blend. Sensitivity analysis using the kinetic model indicates that the CH2O and CH3O2 chemistry are very sensitive to the dopant at all conditions. The rate of 2EHN decomposition is only important at low temperatures where its decomposition rate is slow due to the high activation energy of the reaction. At higher temperatures, dopant-derived 3-heptyl radicals are predicted to play an important role stimulating ignition. Finally, nitrogen chemistry is important through the ’NO – NO2 loop’ where this can generate substantial amounts of OH. However, at the highest doping levels the formation of methyl and ethyl nitrite, and nitric acid significantly competes with this so that less OH is generated and this constrains the reactivity enhancement of 2EHN.

Upper limits to interstellar NH+and para-NH2−abundances

The understanding of interstellar nitrogen chemistry has improved significantly with recent results from the Herschel Space Observatory. To set even better constraints, we report here on deep searches for the NH+ ground state rotational transition J = 1.5−0.5 of the 2Π1/2 lower spin ladder, with fine-structure transitions at 1013 and 1019 GHz, and the para-NH2− 11,1−00,0 rotational transition at 934 GHz towards Sgr B2 (M) and G10.6−0.4 (W31C) using the Herschel Heterodyne Instrument for the Far-Infrared (HIFI). No clear detections of NH+ are made and the derived upper limits relative to the total number of hydrogen nuclei are ≲2 × 10-12 and ≲7 × 10-13 in the Sgr B2 (M) molecular envelope and in the G10.6−0.4 molecular cloud, respectively. The searches are, however, complicated by the fact that the 1 013 GHz transition lies only −2.5 km s-1 from a CH2NH line, which is seen in absorption in Sgr B2 (M), and that the hyperfine structure components in the 1019 GHz transition are spread over 134 km s-1. Searches for the so far undetected NH2− anion turned out to be unfruitful towards G10.6−0.4, while the para-NH2− 11,1−00,0 transition was tentatively detected towards Sgr B2 (M) at a velocity of 19 km s-1. Assuming that the absorption occurs at the nominal source velocity of +64 km s-1, the rest frequency would be 933.996 GHz, offset by 141 MHz from our estimated value. Using this feature as an upper limit, we found N(p-NH2−) ≲4 × 1011 cm-2, which implies an abundance of ≲8 × 10-13 in the Sgr B2 (M) molecular envelope. The upper limits for both species in the diffuse line-of-sight gas are less than 0.1 to 2% of the values found for NH, NH2, and NH3 towards both sources, and the abundance limits are ≲2−4 × 10-11. An updated pseudo time-dependent chemical model with constant physical conditions, including both gas-phase and surface chemistry, predicts an NH+ abundance a few times lower than our present upper limits in diffuse gas and under typical Sgr B2 (M) envelope conditions. The NH2− abundance is predicted to be several orders of magnitudes lower than our observed limits, hence not supporting our tentative detection. Thus, while NH2− may be very difficult to detect in interstellar space, it could, on the other hand, be possible to detect NH+ in regions where theionisation rates of H2 and N are greatly enhanced.

An assessment of the performance of the Monitor for AeRosols and GAses in ambient air (MARGA): a semi-continuous method for soluble compounds

Abstract. Ambient air monitoring as part of the US Environmental Protection Agency's (US EPA's) Clean Air Status and Trends Network (CASTNet) currently uses filter packs to measure weekly integrated concentrations. The US EPA is interested in supplementing CASTNet with semi-continuous monitoring systems at select sites to characterize atmospheric chemistry and deposition of nitrogen and sulfur compounds at higher time resolution than the filter pack. The Monitor for AeRosols and GAses in ambient air (MARGA) measures water-soluble gases and aerosols at an hourly temporal resolution. The performance of the MARGA was assessed under the US EPA Environmental Technology Verification (ETV) program. The assessment was conducted in Research Triangle Park, North Carolina, from 8 September to 8 October 2010 and focused on gaseous SO2, HNO3, and NH3 and aerosol SO42-, NO3-, and NH4+. Precision of the MARGA was evaluated by calculating the median absolute relative percent difference (MARPD) between paired hourly results from duplicate MARGA units (MUs), with a performance goal of ≤ 25%. The accuracy of the MARGA was evaluated by calculating the MARPD for each MU relative to the average of the duplicate denuder/filter pack concentrations, with a performance goal of ≤ 40%. Accuracy was also evaluated by using linear regression, where MU concentrations were plotted against the average of the duplicate denuder/filter pack concentrations. From this, a linear least squares line of best fit was applied. The goal was for the slope of the line of best fit to be between 0.8 and 1.2. The MARGA performed well in comparison to the denuder/filter pack for SO2, SO42−, and NH4+, with all three compounds passing the accuracy and precision goals by a significant margin. The performance of the MARGA in measuring NO3- could not be evaluated due to the different sampling efficiency of coarse NO3- by the MUs and the filter pack. Estimates of "fine" NO3- were calculated for the MUs and the filter pack. Using this and results from a previous study, it is concluded that if the MUs and the filter pack were sampling the same particle size, the MUs would have good agreement in terms of precision and accuracy. The MARGA performed moderately well in measuring HNO3 and NH3, though neither met the linear regression slope goals. However, recommendations for improving the measurement of HNO3 and NH3 are discussed. It is concluded that SO42-, SO2, NO3-, HNO3, NH4+, and NH3 concentrations can be measured with acceptable accuracy and precision when the MARGA is operated in conjunction with the recommendations outlined in the manuscript.

WATER CLOUDS IN Y DWARFS AND EXOPLANETS

The formation of clouds affects brown dwarf and planetary atmospheres of nearly all effective temperatures. Iron and silicate condense in L dwarf atmospheres and dissipate at the L/T transition. Minor species such as sulfides and salts condense in mid-late T dwarfs. For brown dwarfs below Teff=450 K, water condenses in the upper atmosphere to form ice clouds. Currently over a dozen objects in this temperature range have been discovered, and few previous theoretical studies have addressed the effect of water clouds on brown dwarf or exoplanetary spectra. Here we present a new grid of models that include the effect of water cloud opacity. We find that they become optically thick in objects below Teff=350-375 K. Unlike refractory cloud materials, water ice particles are significantly non-gray absorbers; they predominantly scatter at optical wavelengths through J band and absorb in the infrared with prominent features, the strongest of which is at 2.8 microns. H2O, NH3, CH4, and H2 CIA are dominant opacity sources; less abundant species such as may also be detectable, including the alkalis, H2S, and PH3. PH3, which has been detected in Jupiter, is expected to have a strong signature in the mid-infrared at 4.3 microns in Y dwarfs around Teff=450 K; if disequilibrium chemistry increases the abundance of PH3, it may be detectable over a wider effective temperature range than models predict. We show results incorporating disequilibrium nitrogen and carbon chemistry and predict signatures of low gravity in planetary- mass objects. Lastly, we make predictions for the observability of Y dwarfs and planets with existing and future instruments including the James Webb Space Telescope and Gemini Planet Imager.

Phloem phytochemistry and aphid responses to elevated CO2, nitrogen fertilization and endophyte infection

Abstract Rising atmospheric CO2 has been shown to alter plant nitrogen metabolism, growth and secondary chemistry. We hypothesized that altered aphid performance under elevated CO2 is linked to phloem nitrogen chemistry. Rhopalosiphum padi performance on endophyte‐infected or uninfected tall fescue was examined under three levels of CO2 (ambient, 800 and 1000 p.p.m.) and high and low nitrogen fertilization. Ethylenediaminetetracetic acid‐facilitated exudation was used to sample phloem sap, followed by quantification of relative amino acid concentrations using reverse‐phase high‐performance liquid chromatography. Aphid abundance was reduced at 800 p.p.m. relative to ambient CO2 but returned to baseline at 1000 p.p.m. The density of aphids was reduced in both the elevated CO2 treatments. Aphids were unsuccessful at colonizing endophyte‐infected plants, possibly as a result of the presence of loline alkaloids. Multivariate analysis showed that certain groups of phloem amino acids were altered by nitrogen fertilization and CO2. We found that four amino acids (valine, arginine, glutamine and aspartate) were correlated with aphid performance. These findings partially explained the effect of plant nitrogen fertilization and elevated CO2 on aphids. The present study represents a first step toward providing a mechanistic explanation of the aphid performance changes that may result from rising atmospheric CO2.

Addendum to: “A global assessment of precipitation chemistry and deposition of sulfur, nitrogen, sea salt, base cations, organic acids, acidity and pH, and phosphorus”

Addendum to: “A global assessment of precipitation chemistry and deposition of sulfur, nitrogen, sea salt, base cations, organic acids, acidity and pH, and phosphorus”

Groundwater flow path dynamics and nitrogen transport potential in the riparian zone of an agricultural headwater catchment

summary Shallow groundwater dynamics play a critical role in determining the chemistry and movement of nitrogen (N) in the riparian zone. In this study, we characterized N concentration variability and hydrologic transport pathways in shallow groundwater draining areas of a riparian area with and without emergent groundwater seeps. The study was conducted in FD36, an agricultural headwater catchment in the Ridge and Valley physiographic region of central Pennsylvania, USA. Three seep and adjacent non-seep areas were each instrumented with a field of 40 piezometers installed in a grid pattern (1.5-m spacing) at both 20- and 60-cm depths. Piezometers were monitored seasonally for approximately two years (October 2010–May 2012). Results showed that hydraulic head within seep areas was variable and some regions exhibited upward vertical hydraulic gradients of 0.18–0.27. Non-seep areas were characterized by uniform hydraulic head levels and were relatively hydrostatic. Nitrate-N (NO3-N) concentrations in seep areas were significantly greater than those in the non-seep areas at two of the three study sites. A two-component mixing model using chloride as a conservative tracer indicated that shallow groundwater in seep areas was primarily (53–75%) comprised of water from a shallow fractured aquifer, which had elevated NO3-N concentrations (5.7 mg L � 1 ). Shallow groundwater in non-seep areas, however, was comprised (58–82%) of perched water on top of the fragipan that was likely recharged locally in the riparian zone and had low NO3-N concentrations (0.6 mg L � 1 ). Higher NO3-N concentrations, variable hydraulic head, and groundwater emergence onto the land surface in seep areas provided evidence for preferential flow paths as an important conduit for water and N movement in these areas of the riparian zone. We conclude that the potential for N delivery to the stream in FD36 was much greater from seep areas compared to non-seep areas. Targeted management of seeps should be a priority in efforts to reduce NO3-N levels in riparian zones within headwater agricultural catchments. Published by Elsevier B.V.