Glacier meltwater and monsoon precipitation drive Upper Ganges Basin dissolved organic matter composition

Author Posting. © The Author(s), 2019. This is the author's version of the work. It is posted here by permission of Elsevier Ltd. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 244 (2019): 216-228, doi:10.1016/j.gca.2018.10.012.Mountain glaciers store dissolved organic carbon (DOC) that can be exported to river networks and subsequently respired to CO2. Despite this potential importance within the global carbon cycle, the seasonal variability and downstream transport of glacier-derived DOC in mountainous river basins remains largely unknown. To provide novel insight, here we present DOC concentrations and molecular-level dissolved organic matter (DOM) compositions from 22 nested, glaciated catchments (1.4 – 81.8 % glacier cover by area) in the Upper Ganges Basin, Western Himalaya over the course of the Indian summer monsoon (ISM) in 2014. Aliphatic and peptide-like compounds were abundant in glaciated headwaters but were overprinted by soil-derived phenolic, polyphenolic and condensed aromatic material as DOC concentrations increase moving downstream. Across the basin, DOC concentrations and soil-derived compound class contributions decreased sharply from pre- to post-ISM, implying increased relative contribution of glaciated headwater signals as the monsoon progresses. Incubation experiments further revealed a strong compositional control on the fraction of bioavailable DOC (BDOC), with glacier-derived DOC exhibiting the highest bioavailability. We hypothesize that short-term (i.e. in the coming decades) increases in glacier melt flux driven by climate change will further bias exported DOM toward an aliphatic-rich, bioavailable signal, especially during the ISM and post-ISM seasons. In contrast, eventual decreases in glacier melt flux due to mass loss will likely lead to more a soil-like DOM composition and lower bioavailability of exported DOC in the long term.We thank Britta Voss (WHOI) for assisting with sample collection; Travis Drake (FSU), and Ekaterina Bulygina (Woods Hole Research Center) for laboratory assistance; and the NHMFL ICR user program (NSF-DMR-1157490) for aiding in data acquisition and analysis. This study was partly supported by NSF-DEB-1145932 to R.G.M.S. J.D.H. was partially supported by the NSF Graduate Research Fellowship Program under grant number 2012126152, with additional support in the form of travel grants awarded by the MIT Houghten Fund and NHMFL. All data used in this study are available in the Supporting Information Tables S1 and S2

An international laboratory comparison of dissolved organic matter composition by high resolution mass spectrometry: Are we getting the same answer?

High-resolution mass spectrometry (HRMS) has become a vital tool for dissolved organic matter (DOM) characterization. The upward trend in HRMS analysis of DOM presents challenges in data comparison and interpretation among laboratories operating instruments with differing performance and user operating conditions. It is therefore essential that the community establishes metric ranges and compositional trends for data comparison with reference samples so that data can be robustly compared among research groups. To this end, four identically prepared DOM samples were each measured by 16 laboratories, using 17 commercially purchased instruments, using positive-ion and negative-ion mode electrospray ionization (ESI) HRMS analyses. The instruments identified ~1000 common ions in both negative- and positive-ion modes over a wide range of m/z values and chemical space, as determined by van Krevelen diagrams. Calculated metrics of abundance-weighted average indices (H/C, O/C, aromaticity, and m/z) of the commonly detected ions showed that hydrogen saturation and aromaticity were consistent for each reference sample across the instruments, while average mass and oxygenation were more affected by differences in instrument type and settings. In this paper we present 32 metric values for future benchmarking. The metric values were obtained for the four different parameters from four samples in two ionization modes and can be used in future work to evaluate the performance of HRMS instruments

The Pediatric Obsessive-Compulsive Disorder Treatment Study II: rationale, design and methods

This paper presents the rationale, design, and methods of the Pediatric Obsessive-Compulsive Disorder Treatment Study II (POTS II), which investigates two different cognitive-behavior therapy (CBT) augmentation approaches in children and adolescents who have experienced a partial response to pharmacotherapy with a serotonin reuptake inhibitor for OCD. The two CBT approaches test a "single doctor" versus "dual doctor" model of service delivery. A specific goal was to develop and test an easily disseminated protocol whereby child psychiatrists would provide instructions in core CBT procedures recommended for pediatric OCD (e.g., hierarchy development, in vivo exposure homework) during routine medical management of OCD (I-CBT). The conventional "dual doctor" CBT protocol consists of 14 visits over 12 weeks involving: (1) psychoeducation, (2), cognitive training, (3) mapping OCD, and (4) exposure with response prevention (EX/RP). I-CBT is a 7-session version of CBT that does not include imaginal exposure or therapist-assisted EX/RP. In this study, we compared 12 weeks of medication management (MM) provided by a study psychiatrist (MM only) with two types of CBT augmentation: (1) the dual doctor model (MM+CBT); and (2) the single doctor model (MM+I-CBT). The design balanced elements of an efficacy study (e.g., random assignment, independent ratings) with effectiveness research aims (e.g., differences in specific SRI medications, dosages, treatment providers). The study is wrapping up recruitment of 140 youth ages 7–17 with a primary diagnosis of OCD. Independent evaluators (IEs) rated participants at weeks 0,4,8, and 12 during acute treatment and at 3,6, and 12 month follow-up visits

P17858_Barium Ion Adduct Mass Spectrometry to Identify Carboxylic Acid Photoproducts from Crude Oil–water Systems Under Solar Irradiation

Petroleum derived dissolved organic matter (DOMHC) samples were successfully cationized with barium, revealing many [M–H + Ba]+ peaks in both dark and simulated sunlight treatments. The DOMHC samples generated after light exposure exhibited a greater number of [M–H + Ba]+ peaks compared to the dark control. Multiple [M–H + Ba]+ peaks were investigated in the irradiated DOMHC using low resolution MS/MS in order to confirm the presence of diagnostic fragment ions, m/z 139, 155 and 196 in each treatment. Due to the high complexity of the bariated DOMHC mixture, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS/MS) was employed to obtain molecular level information for both irradiated and dark treatments. The irradiated DOMHC treatments had more bariated oxygenated species over a wide range of H/C and O/C when compared to the dark controls. Doubly bariated species were also observed in DOMHC, which provides evidence that photochemistry transforms DOMHC to even more complex mixtures with multiple oxygenations per molecule. This study provides evidence that barium adduct mass spectrometry can be successfully applied to DOMHC screening for the presence of COOHs, both in dark samples and solar irradiated samples. Furthermore, direct evidence and molecular composition of aqueous phase crude oil photoproducts is provided by this technique

P19325_Tomco_Photo-enhanced toxicity of dispersed and burned crude oil to arctic mussels

A portion of this work was performed at the National High Magnetic Field Laboratory ICR UserFacility, which is supported by the National Science Foundation Division of Chemistry andDivision of Materials Research through DMR-1644779 and the State of Florida

Weathering of Oil Spilled in the Marine Environment

Crude oil is a complex mixture of many thousands of mostly hydrocarbon and nitrogen-, sulfur-, and oxygen-containing compounds with molecular weights ranging from below 70 Da to well over 2,000 Da. When this complex mixture enters the environment from spills, ruptures, blowouts, or seeps, it undergoes a continuous series of compositional changes that result from a process known as weathering. Spills of petroleum involving human activity generally result in more rapid input of crude oil or refined products (diesel, gasoline, heavy fuel oil, and diluted bitumens) to the marine system than do natural processes and urban runoffs. The primary physicochemical processes involved in weathering include evaporation, dissolution, emulsification, dispersion, sedimentation/flocculation, microbial degradation, and photooxidation

Weathering of Oil Spilled in the Marine Environment

Crude oil is a complex mixture of many thousands of mostly hydrocarbon and nitrogen-, sulfur-, and oxygen-containing compounds with molecular weights ranging from below 70 Da to well over 2,000 Da. When this complex mixture enters the environment from spills, ruptures, blowouts, or seeps, it undergoes a continuous series of compositional changes that result from a process known as weathering. Spills of petroleum involving human activity generally result in more rapid input of crude oil or refined products (diesel, gasoline, heavy fuel oil, and diluted bitumens) to the marine system than do natural processes and urban runoffs. The primary physicochemical processes involved in weathering include evaporation, dissolution, emulsification, dispersion, sedimentation/flocculation, microbial degradation, and photooxidation

DOC export is exceeded by C fixation in May Creek: A late-successional watershed of the Copper River Basin, Alaska.

Understanding the entirety of basin-scale C cycling (DOC fluxes and CO2 exchanges) are central to a holistic perspective of boreal forest biogeochemistry today. Shifts in the timing and magnitude of dissolved organic carbon (DOC) delivery in streams and eventually into oceans can be expected, while simultaneously CO2 emission may exceed CO2 fixation, leading to forests becoming stronger CO2 sources than sinks amplifying rising trace gases in the atmosphere. At May Creek, a representative late-successional boreal forest watershed at the headwaters of the Copper River Basin, Alaska, we quantified the seasonality of DOC flux and landscape-scale CO2 exchange (eddy covariance) over two seasonal cycles. We deployed in situ fDOM and conductivity sensors, performed campaign sampling for water quality (DOC and water isotopes), and used fluorescence spectroscopy to ascertain DOC character. Simultaneously, we quantified net CO2 exchange using a 100 ft eddy covariance tower. Results indicate DOC exports were pulse-driven and mediated by precipitation events. Both frequency and magnitude of pulse-driven DOC events diminished as the seasonal thaw depth deepened, with inputs from terrestrial sources becoming major contributors to the DOC pool with decreasing snowmelt contribution to the hydrograph. A three-component parallel factorial analysis (PARAFAC) model indicated DOC liberated in late-season may be bioavailable (tyrosine-like). Combining Net Ecosystem Exchange (NEE) measurements indicate that the May Creek watershed fixes 142-220 g C m-2 yr-1 and only 0.40-0.57 g C m-2 yr-1 is leached out as DOC. Thus, the May Creek watershed and similar mature spruce forest dominated watersheds in the Copper River Basin are currently large ecosystem C sinks and exceeding C conservative. An understanding of DOC fluxes from Gulf of Alaska watersheds is important for characterizing future climate change-induced seasonal shifts