Leif M Abrell

Interests

Research

Environmental contaminants, Organic microconstituents, environmental chemistry, mass spectrometry, sensory systems, prebiotic chemistry, global change science, environmental contamination, pollution, informal learning, nature deficit.

Courses

Scholarly Contributions

Chapters

• Olivares, C. I., Abrell, L. M., Chorover, J. D., Simonich, M., Tanguay, R. L., Sierra-Alvarez, R., & Field, J. A. (2016). Identifying toxic biogransformation products of the insensitive munitions compound, 2,4-dinitroanisole (DNAN), using liquid chromatography coupled to quadrupole time-of-flight mass spectromety (LC-QToF-MS),. In Assessing Transformation Products of Chemicals by Non-Target and Suspect-Screening-Strategies and Workflows(pp 133-145). Chapter 9 Volume 1: Drewes, J. and Letzel (Eds). doi:10.1021/bk-2016-1241.ch009
• Olivares, C. I., Abrell, L. M., Chorover, J. D., Simonich, M., Tanguay, R. L., Sierra-Alvarez, R., & Field, J. A. (2016). Identifying toxic biogransformation products of the insensitive munitions compound,2,4-dinitroanisole (DNAN), using liquid chromatography coupled to quadrupole time-of-flight mass spectromety (LC-QToF-MS),. In Assessing Transformation Products of Chemicals by Non-Target and Suspect-Screening-Strategies and Workflows(pp 133-145). Chapter 9 Volume 1: Drewes, J. and Letzel (Eds). doi:10.1021/bk-2016-1241.ch009

Journals/Publications

• Madeira, C. L., Speet, S. A., Nieto, C. A., Abrell, L. M., Chorover, J. D., Sierra-Alvarez, R., & Field, J. A. (2016). Sequential anaerobic-aerobic biodegradatin of emerging insenstive munitions compound 3-nitro-1,2,4-triazol-5-one (NTO). Chemospher, 167, 478-484.
• Madeira, C. L., Speet, S. A., Nieto, C. A., Abrell, L. M., Chorover, J. D., Sierra-Alvarez, R., Field, J. A., Madeira, C. L., Speet, S. A., Nieto, C. A., Abrell, L. M., Chorover, J. D., Sierra-Alvarez, R., & Field, J. A. (2017). Sequential anaerobic-aerobic biodegradatin of emerging insenstive munitions compound 3-nitro-1,2,4-triazol-5-one (NTO). Chemosphere, 167, 478-484.
• Olivares, C. I., Abrell, L. M., Khatiwada, R., Chorover, J. D., Sierra-Alvarez, R., & Field, J. A. (2016). (Bio)transformation of 2,4-dinitroanisole (DNAN) in soils. J Haz Mater, 304, 214-221.
• Olivares, C. I., Sierra-Alvarez, R., Abrell, L. M., Chorover, J. D., Simonich, M., Tanguay, R. L., & Field, J. A. (2016). Zebrafish embryo toxicity of anaerobic biotransformation products from the insensitive munitions compout 2,4-dintroanisole. Environ. Toxicol. Chem., 35, 2774-2781.
• Suppes, L. M., Ernst, K. C., Abrell, L. M., & Reynolds, K. A. (2015). Validation and Standardization of Swimming Exposure and Pool Operations Questionnaires. International Journal of Hygiene and Environmental Health..
• Abrell, L. M., Mash, E. A., Field, J. A., Chorover, J. D., Sierra Alvarez, M. R., & Bhumasamudram, J. (2014). Synthesis of 13C and 15N labeled 2,4-dinitroanisole. Journal of Labelled Compounds and Radiopharmaceuticals.
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  Abstract Syntheses of [13C6]-2,4-dinitroanisole (ring-13C6) from [13C6]-anisole (ring-13C6) and[15N2]-2,4-dinitroanisole from anisole using in situ generated acetyl nitrate and [15N]-acetylnitrate, respectively, are described. Treatment of [13C6]-anisole (ring-13C6) with acetyl nitrategenerated in 100% HNO3 gave [13C6]-2,4-dinitroanisole (ring-13C6) in 83% yield. Treatment ofanisole with [15N]-acetyl nitrate generated in 10N [15N]-HNO3 gave [15N2]-2,4-dinitroanisole in44% yield after two cycles of nitration. Byproducts in the latter reaction included [15N]-2-nitroanisole and [15N]-4-nitroanisole.
• Jardine, K., Serrano, A. Y., Arneth, A., Abrell, L., Jardine, A., van Haren, J., Artaxo, P., Rizzo, L. V., Ishida, F. Y., Karl, T., Kesselmeier, J., Saleska, S., & Huxman, T. (2014). Within-canopy sesquiterpene ozonolysis in Amazonia. JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 116.
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  Through rapid reactions with ozone, which can initiate the formation of secondary organic aerosols, the emission of sesquiterpenes from vegetation in Amazonia may have significant impacts on tropospheric chemistry and climate. Little is known, however, about sesquiterpene emissions, transport, and chemistry within plant canopies owing to analytical difficulties stemming from very low ambient concentrations, high reactivities, and sampling losses. Here, we present ambient sesquiterpene concentration measurements obtained during the 2010 dry season within and above a primary tropical forest canopy in Amazonia. We show that by peaking at night instead of during the day, and near the ground instead of within the canopy, sesquiterpene concentrations followed a pattern different from that of monoterpenes, suggesting that unlike monoterpene emissions, which are mainly light dependent, sesquiterpene emissions are mainly temperature dependent. In addition, we observed that sesquiterpene concentrations were inversely related with ozone (with respect to time of day and vertical concentration), suggesting that ambient concentrations are highly sensitive to ozone. These conclusions are supported by experiments in a tropical rain forest mesocosm, where little atmospheric oxidation occurs and sesquiterpene and monoterpene concentrations followed similar diurnal patterns. We estimate that the daytime dry season ozone flux of -0.6 to -1.5 nmol m(-2) s(-1) due to in-canopy sesquiterpene reactivity could account for 7%-28% of the net ozone flux. Our study provides experimental evidence that a large fraction of total plant sesquiterpene emissions (46%-61% by mass) undergo within-canopy ozonolysis, which may benefit plants by reducing ozone uptake and its associated oxidative damage.
• Suppes, L. M., Abrell, L. M., A, D. P., Gerba, C. P., Reynolds, K. A., Suppes, L. M., Abrell, L. M., A, D. P., Gerba, C. P., Reynolds, K. A., Suppes, L. M., Abrell, L. M., A, D. P., Gerba, C. P., Reynolds, K. A., Suppes, L. M., Abrell, L. M., A, D. P., Gerba, C. P., , Reynolds, K. A., et al. (2014). Assessment of Swimmer Head Submersion Exposures and Pool Water Ingestion.. Journal of Water and Health, 12(2), 269-279.
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  ABSTRACTEnteric pathogens in pool water can be unintentionally ingested during swimming, increasing the likelihood of acute gastrointestinal illness (AGI). AGI cases in outbreaks are more likely to submerge heads than non-cases, but an association is unknown since outbreak data are self-reported and prone to bias. In the present study, head submersion frequency and duration were observed and analyzed for associations with pool water ingestion measured using ultra high pressure liquid chromatography – tandem mass spectrometry. Frequency of splashes to the face was also quantified. Reliable tools that assess activities associated with pool water ingestion are needed to identify ingestion risk factors and at-risk populations. Objectives were to determine if the observed activities were associated with ingestion, and to test environmental sensor and videography assessment tools. Greater frequency and duration of head submersion were not associated with ingestion, but frequency of splashes to the face, leisurely swimming, and being ≤18 were. Videography was validated for assessing swimmer head submersion frequency. Results demonstrate ingestion risk factors can be identified using videography and urine analysis techniques. Expanding surveys to include questions on leisure swimming participation and frequency of splashes to the face is recommended to improve exposure assessment during outbreak investigations.Keywords: exposure factor; head submersion; ingestion; pool; recreational water; swimming
• Jardine, K. J., Meyers, K., Abrell, L., Alves, E. G., Yanez Serrano, A. M., Kesselmeier, J., Karl, T., Guenther, A., Chambers, J. Q., & Vickers, C. (2013). Emissions of putative isoprene oxidation products from mango branches under abiotic stress. Journal of experimental botany, 64(12).
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  Although several per cent of net carbon assimilation can be re-released as isoprene emissions to the atmosphere by many tropical plants, much uncertainty remains regarding its biological significance. In a previous study, we detected emissions of isoprene and its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) from tropical plants under high temperature/light stress, suggesting that isoprene is oxidized not only in the atmosphere but also within plants. However, a comprehensive analysis of the suite of isoprene oxidation products in plants has not been performed and production relationships with environmental stress have not been described. In this study, putative isoprene oxidation products from mango (Mangifera indica) branches under abiotic stress were first identified. High temperature/light and freeze-thaw treatments verified direct emissions of the isoprene oxidation products MVK and MACR together with the first observations of 3-methyl furan (3-MF) and 2-methyl-3-buten-2-ol (MBO) as putative novel isoprene oxidation products. Mechanical wounding also stimulated emissions of MVK and MACR. Photosynthesis under (13)CO2 resulted in rapid (
• Jardine, K., Wegener, F., Abrell, L., van Haren, J., & Werner, C. (2013). Phytogenic biosynthesis and emission of methyl acetate. Plant, cell & environment.
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  Acetylation of plant metabolites fundamentally changes their volatility, solubility and activity as semiochemicals. Here we present a new technique termed dynamic (13) C-pulse chasing to track the fate of C1-3 carbon atoms of pyruvate into the biosynthesis and emission of methyl acetate (MA) and CO2 . (13) C-labelling of MA and CO2 branch emissions respond within minutes to changes in (13) C-positionally labelled pyruvate solutions fed through the transpiration stream. Strong (13) C-labelling of MA emissions occurred only under pyruvate-2-(13) C and pyruvate-2,3-(13) C feeding, but not pyruvate-1-(13) C feeding. In contrast, strong (13) CO2 emissions were only observed under pyruvate-1-(13) C feeding. These results demonstrate that MA (and other volatile and non-volatile metabolites) derive from the C2,3 atoms of pyruvate while the C1 atom undergoes decarboxylation. The latter is a non-mitochondrial source of CO2 in the light generally not considered in studies of CO2 sources and sinks. Within a tropical rainforest mesocosm, we also observed atmospheric concentrations of MA up to 0.6 ppbv that tracked light and temperature conditions. Moreover, signals partially attributed to MA were observed in ambient air within and above a tropical rainforest in the Amazon. Our study highlights the potential importance of acetyl coenzyme A (CoA) biosynthesis as a source of acetate esters and CO2 to the atmosphere.
• Olivares, C., Liang, J., Abrell, L., Sierra-Alvarez, R., & Field, J. A. (2013). Pathways of reductive 2,4-dinitroanisole (DNAN) biotransformation in sludge. Biotechnology and bioengineering, 110(6).
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  As the use of the insensitive munition compound 2,4-dinitroanisole (DNAN) increases, releases to the environment may pose a threat to local ecosystems. Little is known about the environmental fate of DNAN and the conversions caused by microbial activity. We studied DNAN biotransformation rates in sludge under aerobic, microaerophilic, and anaerobic conditions, detected biotransformation products, and elucidated their chemical structures. The biotransformation of DNAN was most rapid under anaerobic conditions with H2 as a cosubstrate. The results showed that the ortho nitro group in DNAN is regioselectively reduced to yield 2-methoxy-5-nitroaniline (MENA), and then the para nitro group is reduced to give 2,4-diaminoanisole (DAAN). Both MENA and DAAN were identified as important metabolites in all redox conditions. Azo and hydrazine dimer derivatives formed from the coupling of DNAN reduction products in anaerobic conditions. Secondary pathways included acetylation and methylation of amine moieties, as well as the stepwise O-demethylation and dehydroxylation of methoxy groups. Seven unique metabolites were identified which enabled elucidation of biotransformation pathways. The results taken as a whole suggest that reductive biotransformation is an important fate of DNAN leading to the formation of aromatic amines as well as azo and hydrazine dimeric metabolites.
• Riffell, J. A., Lei, H., Abrell, L., & Hildebrand, J. G. (2013). Neural basis of a pollinator's buffet: Olfactory specialization and learning in Manduca sexta moth. Science, 339(6116), 200-204.
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  PMID: 23223454;Abstract: Pollinators exhibit a range of innate and learned behaviors that mediate interactions with flowers, but the olfactory bases of these responses in a naturalistic context remain poorly understood. The hawkmoth Manduca sexta is an important pollinator for many night-blooming flowers but can learn - through olfactory conditioning - to visit other nectar resources. Analysis of the flowers that are innately attractive to moths shows that the scents all have converged on a similar chemical profile that, in turn, is uniquely represented in the moth's antennal (olfactory) lobe. Flexibility in visitation to nonattractive flowers, however, is mediated by octopamine-associated modulation of antennal-lobe neurons during learning. Furthermore, this flexibility does not extinguish the innate preferences. Such processing of stimuli through two olfactory channels, one involving an innate bias and the other a learned association, allows the moths to exist within a dynamic floral environment while maintaining specialized associations.
• Ruiz, S. H., Wickramasekara, S., Abrell, L., Gao, X., Chefetz, B., & Chorover, J. (2013). Complexation of trace organic contaminants with fractionated dissolved organic matter: implications for mass spectrometric quantification. Chemosphere, 91(3).
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  Interaction with aqueous phase dissolved organic matter (DOM) can alter the fate of trace organic contaminants of emerging concern once they enter the water cycle. In order to probe possible DOM binding mechanisms and their consequences for contaminant detection and quantification in natural waters, a set of laboratory experiments was conducted with aqueous solutions containing various operationally-defined "hydrophilic" and "hydrophobic" freshwater DOM fractions isolated by resin adsorption techniques from reference Suwannee River natural organic matter (SROM). Per unit mass of SROM carbon, hydrophobic acids (HoA) comprised the largest C fraction (0.63±0.029), followed by hydrophilic-neutrals (HiN, 0.11±0.01) and acids (HiA, 0.09±0.017). Aqueous solutions comprising 8mgL(-1) DOC of each SROM fraction were spiked with a concentration range (10-1000μgL(-1)) of bisphenol A (BPA), carbamazepine (CBZ), or ibuprofen (IBU) as model target compounds in 24mM NH4HCO3 background electrolyte at pH 7.4. Contaminant interaction with the SROM fractions was probed using fluorescence spectroscopy, and effects on quantitative analysis of the target compounds were measured using direct aqueous-injection liquid chromatography tandem mass spectrometry (LC-MS/MS). Total quenching was greater for the hydrophilic fractions of SROM and associations were principally with protein-like and fulvic acid-like constituents. Whereas LC-MS/MS recoveries indicated relatively weak interactions with most SROM factions, an important exception was the HiA fraction, which diminished recovery of CBZ and IBU by ca. 30% and 70%, respectively, indicating relatively strong molecular interactions.
• Beamer, P. I., Luik, C. E., Abrell, L., Campos, S., Martínez, M. E., & Sáez, A. E. (2012). Concentration of trichloroethylene in breast milk and household water from Nogales, Arizona. Environmental science & technology, 46(16).
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  The United States Environmental Protection Agency has identified quantification of trichloroethylene (TCE), an industrial solvent, in breast milk as a high priority need for risk assessment. Water and milk samples were collected from 20 households by a lactation consultant in Nogales, Arizona. Separate water samples (including tap, bottled, and vending machine) were collected for all household uses: drinking, bathing, cooking, and laundry. A risk factor questionnaire was administered. Liquid-liquid extraction with diethyl ether was followed by GC-MS for TCE quantification in water. Breast milk underwent homogenization, lipid hydrolysis, and centrifugation prior to extraction. The limit of detection was 1.5 ng/mL. TCE was detected in 7 of 20 mothers' breast milk samples. The maximum concentration was 6 ng/mL. TCE concentration in breast milk was significantly correlated with the concentration in water used for bathing (ρ = 0.59, p = 0.008). Detection of TCE in breast milk was more likely if the infant had a body mass index
• Hernandez-Ruiz, S., Abrell, L., Wickramasekara, S., Chefetz, B., & Chorover, J. (2012). Quantifying PPCP interaction with dissolved organic matter in aqueous solution: combined use of fluorescence quenching and tandem mass spectrometry. Water research, 46(4).
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  The documented presence of pharmaceuticals and personal care products (PPCPs) in water sources has prompted a global interest in understanding their environmental fate. Dissolved organic matter (DOM) can potentially alter the fate of these contaminants in aqueous systems by forming contaminant-DOM complexes. In-situ measurements were made to assess the interactions between three common PPCP contaminants and two distinct DOM sources: a wastewater treatment plant (WWOM) and the Suwannee River, GA (SROM). Aqueous DOM solutions (8.0 mg L(-1) C, pH 7.4) were spiked with a range of concentrations of bisphenol-A, carbamazepine and ibuprofen to assess the DOM fluorophores quenched by PPCP interaction in excitation-emission matrices (EEM). Interaction effects on target analyte (PPCP) concentrations were also quantified using direct aqueous injection ultra high performance liquid chromatography tandem mass spectrometry (LC-MS/MS). At low bisphenol-A concentration, WWOM fluorescence was quenched in an EEM region attributed to microbial byproduct-like and humic acid-like DOM components, whereas carbamazepine and ibuprofen quenched fulvic acid-like fluorophores. Fluorescence quenching of SROM by bisphenol-A and carbamazepine was centered on humic acid-like components, whereas ibuprofen quenched the fulvic acid-like fluorophores. Nearly complete LC-MS/MS recovery of all three contaminants was obtained, irrespective of analyte structure and DOM source, indicating relatively weak PPCP-DOM bonding interactions. The results suggest that presence of DOM at environmentally-relevant concentration can give rise to PPCP interactions that could potentially affect their environmental transport, but these DOM-contaminant interactions do not suppress the accurate assessment of target analyte concentrations by aqueous injection LC-MS/MSMS.
• Jardine, K. J., Monson, R. K., Abrell, L., Saleska, S. R., Arneth, A., Jardine, A., Ishida, F. Y., Serrano, A. M., Artaxo, P., Karl, T., Fares, S., Goldstein, A., Loreto, F., & Huxman, T. (2012). Within-plant isoprene oxidation confirmed by direct emissions of oxidation products methyl vinyl ketone and methacrolein. Global Change Biology, 18(3), 973-984.
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  Abstract: Isoprene is emitted from many terrestrial plants at high rates, accounting for an estimated 1/3 of annual global volatile organic compound emissions from all anthropogenic and biogenic sources combined. Through rapid photooxidation reactions in the atmosphere, isoprene is converted to a variety of oxidized hydrocarbons, providing higher order reactants for the production of organic nitrates and tropospheric ozone, reducing the availability of oxidants for the breakdown of radiatively active trace gases such as methane, and potentially producing hygroscopic particles that act as effective cloud condensation nuclei. However, the functional basis for plant production of isoprene remains elusive. It has been hypothesized that in the cell isoprene mitigates oxidative damage during the stress-induced accumulation of reactive oxygen species (ROS), but the products of isoprene-ROS reactions in plants have not been detected. Using pyruvate-2- 13C leaf and branch feeding and individual branch and whole mesocosm flux studies, we present evidence that isoprene (i) is oxidized to methyl vinyl ketone and methacrolein (i ox) in leaves and that i ox/i emission ratios increase with temperature, possibly due to an increase in ROS production under high temperature and light stress. In a primary rainforest in Amazonia, we inferred significant in plant isoprene oxidation (despite the strong masking effect of simultaneous atmospheric oxidation), from its influence on the vertical distribution of i ox uptake fluxes, which were shifted to low isoprene emitting regions of the canopy. These observations suggest that carbon investment in isoprene production is larger than that inferred from emissions alone and that models of tropospheric chemistry and biota-chemistry-climate interactions should incorporate isoprene oxidation within both the biosphere and the atmosphere with potential implications for better understanding both the oxidizing power of the troposphere and forest response to climate change. © 2012 Blackwell Publishing Ltd.
• Jardine, K., Barron-Gafford, G. A., Norman, J. P., Abrell, L., Monson, R. K., Meyers, K. T., Pavao-Zuckerman, M., Dontsova, K., Kleist, E., Werner, C., & Huxman, T. E. (2012). Green leaf volatiles and oxygenated metabolite emission bursts from mesquite branches following light-dark transitions. PHOTOSYNTHESIS RESEARCH, 113(1-3), 321-333.
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  Green leaf volatiles (GLVs) are a diverse group of fatty acid-derived compounds emitted by all plants and are involved in a wide variety of developmental and stress-related biological functions. Recently, GLV emission bursts from leaves were reported following light-dark transitions and hypothesized to be related to the stress response while acetaldehyde bursts were hypothesized to be due to the 'pyruvate overflow' mechanism. In this study, branch emissions of GLVs and a group of oxygenated metabolites (acetaldehyde, ethanol, acetic acid, and acetone) derived from the pyruvate dehydrogenase (PDH) bypass pathway were quantified from mesquite plants following light-dark transitions using a coupled GC-MS, PTR-MS, and photosynthesis system. Within the first minute after darkening following a light period, large emission bursts of both C-5 and C-6 GLVs dominated by (Z)-3-hexen-1-yl acetate together with the PDH bypass metabolites are reported for the first time. We found that branches exposed to CO2-free air lacked significant GLV and PDH bypass bursts while O-2-free atmospheres eliminated the GLV burst but stimulated the PDH bypass burst. A positive relationship was observed between photosynthetic activity prior to darkening and the magnitude of the GLV and PDH bursts. Photosynthesis under (CO2)-C-13 resulted in bursts with extensive labeling of acetaldehyde, ethanol, and the acetate but not the C-6-alcohol moiety of (Z)-3-hexen-1-yl acetate. Our observations are consistent with (1) the "pyruvate overflow" mechanism with a fast turnover time (< 1 h) as part of the PDH bypass pathway, which may contribute to the acetyl-CoA used for the acetate moiety of (Z)-3-hexen-1-yl acetate, and (2) a pool of fatty acids with a slow turnover time (> 3 h) responsible for the C-6 alcohol moiety of (Z)-3-hexen-1-yl acetate via the 13-lipoxygenase pathway. We conclude that our non-invasive method may provide a new valuable in vivo tool for studies of acetyl-CoA and fatty acid metabolism in plants at a variety of spatial scales.
• Jardine, K., Barron-Gafford, G. A., Norman, J. P., Abrell, L., Monson, R. K., Meyers, K. T., Pavao-Zuckerman, M., Dontsova, K., Kleist, E., Werner, C., & Huxman, T. E. (2012). Green leaf volatiles and oxygenated metabolite emission bursts from mesquite branches following light-dark transitions. Photosynthesis research, 113(1-3).
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  Green leaf volatiles (GLVs) are a diverse group of fatty acid-derived compounds emitted by all plants and are involved in a wide variety of developmental and stress-related biological functions. Recently, GLV emission bursts from leaves were reported following light-dark transitions and hypothesized to be related to the stress response while acetaldehyde bursts were hypothesized to be due to the 'pyruvate overflow' mechanism. In this study, branch emissions of GLVs and a group of oxygenated metabolites (acetaldehyde, ethanol, acetic acid, and acetone) derived from the pyruvate dehydrogenase (PDH) bypass pathway were quantified from mesquite plants following light-dark transitions using a coupled GC-MS, PTR-MS, and photosynthesis system. Within the first minute after darkening following a light period, large emission bursts of both C(5) and C(6) GLVs dominated by (Z)-3-hexen-1-yl acetate together with the PDH bypass metabolites are reported for the first time. We found that branches exposed to CO(2)-free air lacked significant GLV and PDH bypass bursts while O(2)-free atmospheres eliminated the GLV burst but stimulated the PDH bypass burst. A positive relationship was observed between photosynthetic activity prior to darkening and the magnitude of the GLV and PDH bursts. Photosynthesis under (13)CO(2) resulted in bursts with extensive labeling of acetaldehyde, ethanol, and the acetate but not the C(6)-alcohol moiety of (Z)-3-hexen-1-yl acetate. Our observations are consistent with (1) the "pyruvate overflow" mechanism with a fast turnover time (3 h) responsible for the C(6) alcohol moiety of (Z)-3-hexen-1-yl acetate via the 13-lipoxygenase pathway. We conclude that our non-invasive method may provide a new valuable in vivo tool for studies of acetyl-CoA and fatty acid metabolism in plants at a variety of spatial scales.
• Wickramasekara, S., Hernández-Ruiz, S., Abrell, L., Arnold, R., & Chorover, J. (2012). Natural dissolved organic matter affects electrospray ionization during analysis of emerging contaminants by mass spectrometry. Analytica chimica acta, 717.
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  Dissolved organic matter (DOM), present in many forms in water, can interfere with analysis of organic contaminants by atmospheric pressure ionization-mass spectrometry. A quantitative analysis of this interference, or matrix effect, on organic contaminant target analyte measurements was carried out using un-fractionated and fractionated dissolved natural organic matter from the Suwannee River, GA (SROM), a standard reference material, that was directly infused into the tandem mass spectrometer during multiple reaction monitoring (MRM) of a suite of endocrine disrupting compounds-pharmaceuticals and personal care products (EDC/PPCPs). Most target analytes suffered signal suppression in the presence of both fractionated and un-fractionated SROM, however greater interferences were measured with fractionated relative to bulk SROM. This finding is consistent with the view of organic matter as a supramolecular association of low molecular mass components having separate charged and structural features revealed only after dissociation.
• Jardine, K., Monson, R. K., Abrell, L. M., Saleska, S. R., Arneth, A., Jardine, A., Karl, T., Fares, S., Goldstein, A., Loreto, F., & Huxman, T. E. (2012). Within-plant isoprene oxidation confirmed by direct emissions of oxidation products methyl vinyl ketone and methacrolein. Global Change Biology, 18, 973-984.
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  Keywords: Amazon; biosphere&amp;#8211;atmosphere interactions; isoprene oxidation; methacrolein; methyl vinyl ketone; reactive oxygen species; temperature stress; thermotoleranceAbstractIsoprene is emitted from many terrestrial plants at high rates, accounting for an estimated 1/3 of annual global volatile organic compound emissions from all anthropogenic and biogenic sources combined. Through rapid photooxidation reactions in the atmosphere, isoprene is converted to a variety of oxidized hydrocarbons, providing higher order reactants for the production of organic nitrates and tropospheric ozone, reducing the availability of oxidants for the breakdown of radiatively active trace gases such as methane, and potentially producing hygroscopic particles that act as effective cloud condensation nuclei. However, the functional basis for plant production of isoprene remains elusive. It has been hypothesized that in the cell isoprene mitigates oxidative damage during the stress-induced accumulation of reactive oxygen species (ROS), but the products of isoprene-ROS reactions in plants have not been detected. Using pyruvate-2-13C leaf and branch feeding and individual branch and whole mesocosm flux studies, we present evidence that isoprene (i) is oxidized to methyl vinyl ketone and methacrolein (iox) in leaves and that iox/i emission ratios increase with temperature, possibly due to an increase in ROS production under high temperature and light stress. In a primary rainforest in Amazonia, we inferred significant in plant isoprene oxidation (despite the strong masking effect of simultaneous atmospheric oxidation), from its influence on the vertical distribution of iox uptake fluxes, which were shifted to low isoprene emitting regions of the canopy. These observations suggest that carbon investment in isoprene production is larger than that inferred from emissions alone and that models of tropospheric chemistry and biota&amp;#8211;chemistry&amp;#8211;climate interactions should incorporate isoprene oxidation within both the biosphere and the atmosphere with potential implications for better understanding both the oxidizing power of the troposphere and forest response to climate change.
• Jardine, K., Serrano, A. Y., Arneth, A., Abrell, L., Jardine, A., Artaxo, P., Alves, E., Kesselmeier, J., Taylor, T., Saleska, S., & Huxman, T. (2011). Ecosystem-scale compensation points of formic and acetic acid in the central Amazon. BIOGEOSCIENCES, 8(12), 3709-3720.
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  Organic acids, central to terrestrial carbon metabolism and atmospheric photochemistry, are ubiquitous in the troposphere in the gas, particle, and aqueous phases. As the dominant organic acids in the atmosphere, formic acid (FA, HCOOH) and acetic acid (AA, CH3COOH) control precipitation acidity in remote regions and may represent a critical link between the terrestrial carbon and water cycles by acting as key intermediates in plant carbon and energy metabolism and aerosol-cloud-precipitation interactions. However, our understanding of the exchange of these acids between terrestrial ecosystems and the atmosphere is limited by a lack of field observations, the existence of biogenic and anthropogenic primary and secondary sources whose relative importance is unclear, and the fact that vegetation can act as both a source and a sink. Here, we first present data obtained from the tropical rainforest mesocosm at Biosphere 2 which isolates primary vegetation sources. Strong light and temperature dependent emissions enriched in FA relative to AA were simultaneously observed from individual branches (FA/AA = 3.0 +/- 0.7) and mesocosm ambient air (FA/AA = 1.4 +/- 0.3). We also present long-term observations of vertical concentration gradients of FA and AA within and above a primary rainforest canopy in the central Amazon during the 2010 dry and 2011 wet seasons. We observed a seasonal switch from net ecosystem-scale deposition during the dry season to net emissions during the wet season. This switch was associated with reduced ambient concentrations in the wet season (FA < 1.3 nmol mol(-1), AA < 2.0 nmol mol(-1)) relative to the dry season (FA up to 3.3 nmol mol(-1), AA up to 6.0 nmol mol(-1)), and a simultaneous increase in the FA/AA ambient concentration ratios from 0.3-0.8 in the dry season to 1.0-2.1 in the wet season. These observations are consistent with a switch between a biomass burning dominated source in the dry season (FA/AA < 1.0) to a vegetation dominated source in the wet season (FA/AA > 1.0). Our observations provide the first ecosystem-scale evidence of bidirectional FA and AA exchange between a forest canopy and the atmosphere controlled by ambient concentrations and ecosystem scale compensation points (estimated to be 1.3 +/- 0.3 nmol mol(-1): FA, and 2.1 +/- 0.4 nmol mol(-1): AA). These results suggest the need for a fundamental change in how future biosphere-atmosphere exchange models should treat FA and AA with a focus on factors that influence net exchange rates (ambient concentrations and ecosystem compensation points) rather than treating emissions and deposition separately.
• Jardine, K., Wegener, F., Abrell, L., van Haren, J., & Werner, C. (2011). Phytogenic biosynthesis and emission of methyl acetate. PLANT CELL AND ENVIRONMENT, 37(2), 414-424.
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  Acetylation of plant metabolites fundamentally changes their volatility, solubility and activity as semiochemicals. Here we present a new technique termed dynamic C-13-pulse chasing to track the fate of C1-3 carbon atoms of pyruvate into the biosynthesis and emission of methyl acetate (MA) and CO2. C-13-labelling of MA and CO2 branch emissions respond within minutes to changes in C-13-positionally labelled pyruvate solutions fed through the transpiration stream. Strong C-13-labelling of MA emissions occurred only under pyruvate-2-C-13 and pyruvate-2,3-C-13 feeding, but not pyruvate-1-C-13 feeding. In contrast, strong (CO2)-C-13 emissions were only observed under pyruvate-1-C-13 feeding. These results demonstrate that MA (and other volatile and non-volatile metabolites) derive from the C-2,C-3 atoms of pyruvate while the C-1 atom undergoes decarboxylation. The latter is a non-mitochondrial source of CO2 in the light generally not considered in studies of CO2 sources and sinks. Within a tropical rainforest mesocosm, we also observed atmospheric concentrations of MA up to 0.6 ppbv that tracked light and temperature conditions. Moreover, signals partially attributed to MA were observed in ambient air within and above a tropical rainforest in the Amazon. Our study highlights the potential importance of acetyl coenzyme A (CoA) biosynthesis as a source of acetate esters and CO2 to the atmosphere.
• Yeomans, L., Muthu, D., Lowery, J. J., Martinez, H. N., Abrell, L., Lin, G., Strom, K., Knapp, B. I., Bidlack, J. M., Bilsky, E. J., & Polt, R. (2011). Phosphorylation of enkephalins: NMR and CD studies in aqueous and membrane-mimicking environments. Chemical biology & drug design, 78(5).
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  Phosphorylation of l-serine-containing enkephalin analogs has been explored as an alternative to glycosylation in an effort to increase blood-brain barrier permeability and CNS bioavailability of peptide pharmacophores. Two enkephalin-based peptides were modified for these studies, a set related to DTLES, a mixed μ/δ-agonist, and one related to DAMGO, a highly selective μ-agonist. Each unglycosylated peptide was compared to its phosphate, its mono-benzylphosphate ester, and its β-d-glucoside. Binding was characterized in membrane preparations from Chinese hamster ovary cells expressing human μ, δ and κ-opiate receptors. Antinociception was measured in mice using the 55 °C tail-flick assay. To estimate bioavailability, the antinociceptive effect of each opioid agonist was evaluated after intracerebroventricular (i.c.v.) or intravenous administration (i.v.) of the peptides. Circular dichroism methods and high-field nuclear magnetic resonance were used in the presence and absence of sodium dodecylsulfate to understand how the presence of a membrane might influence the peptide conformations.
• Abrell, L. M., Jardine, K. J., Sommer, E. D., Saleska, S. R., Huxman, T. E., & Harley, P. C. (2010). Gas phase measurements of pyruvic acid and its volatile metabolites. Environmental science & technology, 44(7).
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  Pyruvic acid, central to leaf carbon metabolism, is a precursor of many volatile organic compounds (VOCs) that impact air quality and climate. Although the pathways involved in the production of isoprenoids are well-known, those of several oxygenated VOCs remain uncertain. We present concentration and flux measurements of pyruvic acid and other VOCs within the tropical rainforest (TRF) biome at Biosphere 2. Pyruvic acid concentrations varied diurnally with midday maxima up to 15 ppbv, perhaps due to enhanced production rates and suppression of mitochondrial respiration in the light. Branch fluxes and ambient concentrations of pyruvic acid correlated with those of acetone, acetaldehyde, ethanol, acetic acid, isoprene, monoterpenes, and sesquiterpenes. While pyruvic acid is a known substrate for isoprenoid synthesis, this correlation suggests that the oxygenated VOCs may also derive from pyruvic acid, an idea supported by leaf feeding experiments with sodium pyruvate which resulted in large enhancements in emissions of both isoprenoids and oxygenated VOCs. While feeding with sodium pyruvate-2-(13)C resulted in large emissions of both (13)C-labeled isoprenoids and oxygenated VOCs, feeding with sodium pyruvate-1-(13)C resulted in only (13)C-labeled isoprenoids. This suggests that acetaldehyde, ethanol, and acetic acid are produced from pyruvic acid via the pyruvate dehydrogenase (PDH) bypass system (in which the 1-C carbon of pyruvic acid is lost as CO(2)) and that acetone is also derived from the decarboxylation of pyruvic acid.
• Jardine, K. J., Henderson, W. M., Huxman, T. E., & Abrell, L. (2010). Dynamic Solution Injection: a new method for preparing pptv-ppbv standard atmospheres of volatile organic compounds. ATMOSPHERIC MEASUREMENT TECHNIQUES, 3(6), 1569-1576.
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  Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and thermal desorption Gas Chromatography-Mass Spectrometry (GC-MS) allow for absolute quantification of a wide range of atmospheric volatile organic compounds (VOCs) with concentrations in the ppbv to pptv range. Although often neglected, routine calibration is necessary for accurate quantification of VOCs by PTR-MS and GC-MS. Several gas calibration methods currently exist, including compressed gas cylinders, permeation tubes, diffusion tubes, and liquid injection. While each method has its advantages and limitations, no single technique has emerged that is capable of dynamically generating known concentrations of complex mixtures of VOCs over a large concentration range (ppbv to pptv) and is technically simple, field portable, and affordable. We present the development of a new VOC calibration technique based on liquid injection with these features termed Dynamic Solution Injection (DSI). This method consists of injecting VOCs (0.1-0.5 mM) dissolved in cyclohexane (PTR-MS) or methanol (GC-MS) into a 1.0 slpm flow of purified dilution gas in an unheated 25 ml glass vial. Upon changes in the injection flow rate (0.5-4.0 mu l min(-1)), new VOC concentrations are reached within seconds to minutes, depending on the compound, with a liquid injection flow rate accuracy and precision of better than 7% and 4% respectively. We demonstrate the utility of the DSI technique by calibrating a PTR-MS to seven different cyclohexane solutions containing a total of 34 different biogenic compounds including volatile isoprenoids, oxygenated and simplicity, the Dynamic Solution Injection method will be of great use to both laboratory and field VOC studies.
• Jardine, K. J., Sommer, E. D., Saleska, S. R., Huxman, T. E., Harley, P. C., & Abrell, L. (2010). Gas phase measurements of pyruvic acid and its volatile metabolites. Environmental Science and Technology, 44(7), 2454-2460.
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  PMID: 20210357;Abstract: Pyruvic acid, central to leaf carbon metabolism, is a precursor of many volatile organic compounds (VOCs) that impact air quality and climate. Although the pathways involved in the production of isoprenoids are well-known, those of several oxygenated VOCs remain uncertain. We present concentration and flux measurements of pyruvic acid and other VOCs within the tropical rainforest (TRF) biome at Biosphere 2. Pyruvic acid concentrations varied diurnally with midday maxima up to 15 ppbv, perhaps due to enhanced production rates and suppression of mitochondrial respiration in the light. Branch fluxes and ambient concentrations of pyruvic acid correlated with those of acetone, acetaldehyde, ethanol, acetic acid, isoprene, monoterpenes, and sesquiterpenes. While pyruvic acid is a known substrate for isoprenoid synthesis, this correlation suggests that the oxygenated VOCs may also derive from pyruvic acid, an idea supported by leaf feeding experiments with sodium pyruvate which resulted in large enhancements in emissions of both isoprenoids and oxygenated VOCs. While feeding with sodium pyruvate-2-13C resulted in large emissions of both 13C-labeled isoprenoids and oxygenated VOCs, feeding with sodium pyruvate-1-l3C resulted in only relabeled isoprenoids. This suggests that acetaldehyde, ethanol, and acetic acid are produced from pyruvic acid via the pyruvate dehydrogenase (PDH) bypass system (in which the 1-C carbon of pyruvic acid is lost as CO2) and that acetone is also derived from the decarboxylation of pyruvic acid. © 2010 American Chemical Society.
• Jardine, K., Abrell, L. M., Kurc, S. A., Huxman, T. E., Ortega, J., & Guenther, A. (2010). Volatile organic compound emissions from Larrea tridentata (creosotebush). Atmospheric Chemistry and Physics, 10, 12191-12206..
• Riffell, J. A., Lei, H., Abrell, L., Hildebrand, J. G., Abrell, L. M., Lei, H., & Hildebrand, J. G. (2013). Neural basis of a pollinator's buffet: olfactory specialization and learning in Manduca sexta. Science (New York, N.Y.), 339(6116).
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  Pollinators exhibit a range of innate and learned behaviors that mediate interactions with flowers, but the olfactory bases of these responses in a naturalistic context remain poorly understood. The hawkmoth Manduca sexta is an important pollinator for many night-blooming flowers but can learn--through olfactory conditioning--to visit other nectar resources. Analysis of the flowers that are innately attractive to moths shows that the scents all have converged on a similar chemical profile that, in turn, is uniquely represented in the moth's antennal (olfactory) lobe. Flexibility in visitation to nonattractive flowers, however, is mediated by octopamine-associated modulation of antennal-lobe neurons during learning. Furthermore, this flexibility does not extinguish the innate preferences. Such processing of stimuli through two olfactory channels, one involving an innate bias and the other a learned association, allows the moths to exist within a dynamic floral environment while maintaining specialized associations.
• Zakai, U. I., Błoch-Mechkour, A., Jacobsen, N. E., Abrell, L., Lin, G., Nichol, G. S., Bally, T., & Glass, R. S. (2010). Synthesis and structure of m-terphenyl thio-, seleno-, and telluroethers. The Journal of organic chemistry, 75(24).
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  Several routes for the synthesis of m-terphenyl thio-, seleno-, and telluroethers were investigated. m-Terphenyl iodides react with diphenyl diselenides or ditellurides (CsOH·H(2)O, DMSO, 110 °C) to give the desired compounds in 19-84% yield which significantly extends the previously reported such reactions because o-benzyne cannot be an intermediate as previously suggested. However, the most general synthetic route was that involving reaction of 2,6-diaryl Grignard reagents with sulfur, selenium, or tellurium electrophiles. The m-terphenyl thio-, seleno-, and telluroethers were characterized spectroscopically and, in one case, by single-crystal X-ray analysis. Certain of these compounds showed atropisomerism and barriers for interconversion of isomers were determined by variable-temperature NMR spectroscopy. The barriers for interconverting the syn and anti atropisomers increase on going from the analogous S to Se to Te compounds. Calculations on this isomerization revealed that the barriers are due to rotation about the aryl-aryl bond and that the barriers for rotation about the aryl-chalcogen bond are much lower.
• Riffell, J. A., Abrell, L., & Hildebrand, J. G. (2008). Physical processes and real-time chemical measurement of the insect olfactory environment. Journal of chemical ecology, 34(7).
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  Odor-mediated insect navigation in airborne chemical plumes is vital to many ecological interactions, including mate finding, flower nectaring, and host locating (where disease transmission or herbivory may begin). After emission, volatile chemicals become rapidly mixed and diluted through physical processes that create a dynamic olfactory environment. This review examines those physical processes and some of the analytical technologies available to characterize those behavior-inducing chemical signals at temporal scales equivalent to the olfactory processing in insects. In particular, we focus on two areas of research that together may further our understanding of olfactory signal dynamics and its processing and perception by insects. First, measurement of physical atmospheric processes in the field can provide insight into the spatiotemporal dynamics of the odor signal available to insects. Field measurements in turn permit aspects of the physical environment to be simulated in the laboratory, thereby allowing careful investigation into the links between odor signal dynamics and insect behavior. Second, emerging analytical technologies with high recording frequencies and field-friendly inlet systems may offer new opportunities to characterize natural odors at spatiotemporal scales relevant to insect perception and behavior. Characterization of the chemical signal environment allows the determination of when and where olfactory-mediated behaviors may control ecological interactions. Finally, we argue that coupling of these two research areas will foster increased understanding of the physicochemical environment and enable researchers to determine how olfactory environments shape insect behaviors and sensory systems.
• Riffell, J. A., Alarcón, R., & Abrell, L. (2008). Floral trait associations in hawkmoth-specialized and mixed pollination systems: Datura wrightii and Agave spp. in the Sonoran Desert. Communicative & integrative biology, 1(1).
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  Variation in floral traits including odor, color and morphology, demonstrate the selective pressures imposed by specific pollinator taxa, such as insects and birds. In southern Arizona, Manduca sexta (Sphingidae) hawkmoths are associated with Datura wrightii (Solanaceae) at both the larval (herbivore) and adult (nectar feeding) stages. However during most of the summer Manduca feeds on "bat-adapted" Agave spp. (Agaveacea) flowers, and only use Datura when it is at peak bloom. Manduca's nectar-host use appears to be mediated through innate odor preferences and olfactory learning; they prefer Datura's "hawkmoth-adapted" traits, which facilitate the maintenance of their coevolutionary relationship, yet they are flexible enough to explore and learn to utilize novel resources, such as agave. This behavioral flexibility is likely responsible for the frequent observation of generalized, or mixed, pollination systems. Given that Manduca visit agave species in southern Arizona, we hypothesize that the differences in flower phenotype between two closely related agave species may be associated with the importance of hawkmoths relative to bats. The southernmost agave, Agave palmeri (Agavacea), exhibits floral traits typical of bat pollination, whereas the northernmost species, Agave chrysantha (Agavacea), exhibits mixed floral traits which appear to be adapted to insects, and to a lesser extent, bats. The differences between these agaves are likely correlated with the geographic overlap in migratory bats from Mexico and resident hawkmoth populations. Thus D. wrightii, A. palmeri and A. chrysantha populations represent a unique system in which to examine the evolution of floral traits in both specialized and mixed pollination systems associated with spatially variable pollinator assemblages.
• Jalbout, A. F., Abrell, L. M., Adamowicz, L. -., Polt, R. L., Apponi, A. J., & Ziurys, L. M. (2007). Sugar synthesis from a gas-phase formose reaction. Astrobiology, 7(3).
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  Prebiotic possibilities for the synthesis of interstellar ribose through a protic variant of the formose reaction under gas-phase conditions were studied in the absence of any known catalyst. The ion-molecule reaction products, diose and triose, were sought by mass spectrometry, and relevant masses were observed. Ab initio calculations were used to evaluate protic formose mechanism possibilities. A bilateral theoretical and experimental effort yielded a physical model for glycoaldehyde generation whereby a hydronium cation can mediate formaldehyde dimerization followed by covalent bond formation leading to diose and water. These results advance the possibility that ion-molecule reactions between formaldehyde (CH(2)O) and H(3)O(+) lead to formose reaction products and inform us about potential sugar formation processes in interstellar space.
• Riffell, J. A., Alarcón, R., Abrell, L., Davidowitz, G., Bronstein, J. L., & Hildebrand, J. G. (2008). Behavioral consequences of innate preferences and olfactory learning in hawkmoth-flower interactions. Proceedings of the National Academy of Sciences of the United States of America, 105(9).
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  Spatiotemporal variability in floral resources can have ecological and evolutionary consequences for both plants and the pollinators on which they depend. Seldom, however, can patterns of flower abundance and visitation in the field be linked with the behavioral mechanisms that allow floral visitors to persist when a preferred resource is scarce. To explore these mechanisms better, we examined factors controlling floral preference in the hawkmoth Manduca sexta in the semiarid grassland of Arizona. Here, hawkmoths forage primarily on flowers of the bat-adapted agave, Agave palmeri, but shift to the moth-adapted flowers of their larval host plant, Datura wrightii, when these become abundant. Both plants emit similar concentrations of floral odor, but scent composition, nectar, and flower reflectance are distinct between the two species, and A. palmeri flowers provide six times as much chemical energy as flowers of D. wrightii. Behavioral experiments with both naïve and experienced moths revealed that hawkmoths learn to feed from agave flowers through olfactory conditioning but readily switch to D. wrightii flowers, for which they are the primary pollinator, based on an innate odor preference. Behavioral flexibility and the olfactory contrast between flowers permit the hawkmoths to persist within a dynamic environment, while at the same time to function as the major pollinator of one plant species.

Presentations

• Abrell, L. M., Ramirez, M. D., Kilungo, A. P., Mclain, J. E., & Root, R. (2017, September). Survey of contaminants in harvested rainwater from a southern Arizona pilot study. 14th Biennial Conference of Science & Management on the Colorado Plateau & Southwest Region.
• McLain, J. E., Abrell, L. M., Root, R., Allen, N., & Knerl, A. (2013, May). Assessing biological and chemical quality of harvested rainwater in Arizona: can in-line carbon filters decrease health risks?. Quarterly Meeting: Rainwater/Stormwater Professionals Network. Tucson, Arizona: Rainwater/Stormwater Professionals Network.
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  Presented to audience of 25 researchers, students, and stormwater professionals.

Poster Presentations

• Walston, S., Mclain, J. E., Abrell, L. M., Gerrity, D., & Rock, C. M. (2013, May). Does increasing solids retention time in the wastewater treatment process affect the persistence of antibiotic resistance genes?. 86th Annual AZWater Conference. Glendale, Arizona: AZWater.
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  Poster presentation of Master's Research.