Dearomatization drives complexity generation in freshwater organic matter.

Dissolved organic matter (DOM) is one of the most complex, dynamic and abundant sources of organic carbon, but its chemical reactivity remains uncertain1-3. Greater insights into DOM structural features could facilitate understanding its synthesis, turnover and processing in the global carbon cycle4,5. Here we use complementary multiplicity-edited 13C nuclear magnetic resonance (NMR) spectra to quantify key substructures assembling the carbon skeletons of DOM from four main Amazon rivers and two mid-size Swedish boreal lakes. We find that one type of reaction mechanism, oxidative dearomatization (ODA), widely used in organic synthetic chemistry to create natural product scaffolds6-10, is probably a key driver for generating structural diversity during processing of DOM that are rich in suitable polyphenolic precursor molecules. Our data suggest a high abundance of tetrahedral quaternary carbons bound to one oxygen and three carbon atoms (OCqC3 units). These units are rare in common biomolecules but could be readily produced by ODA of lignin-derived and tannin-derived polyphenols. Tautomerization of (poly)phenols by ODA creates non-planar cyclohexadienones, which are subject to immediate and parallel cycloadditions. This combination leads to a proliferation of structural diversity of DOM compounds from early stages of DOM processing, with an increase in oxygenated aliphatic structures. Overall, we propose that ODA is a key reaction mechanism for complexity acceleration in the processing of DOM molecules, creation of new oxygenated aliphatic molecules and that it could be prevalent in nature.

Higher Apparent Gas Transfer Velocities for CO2 Compared to CH4 in Small Lakes.

Large greenhouse gas emissions occur via the release of carbon dioxide (CO2) and methane (CH4) from the surface layer of lakes. Such emissions are modeled from the air-water gas concentration gradient and the gas transfer velocity (k). The links between k and the physical properties of the gas and water have led to the development of methods to convert k between gases through Schmidt number normalization. However, recent observations have found that such normalization of apparent k estimates from field measurements can yield different results for CH4 and CO2. We estimated k for CO2 and CH4 from measurements of concentration gradients and fluxes in four contrasting lakes and found consistently higher (on an average 1.7 times) normalized apparent k values for CO2 than CH4. From these results, we infer that several gas-specific factors, including chemical and biological processes within the water surface microlayer, can influence apparent k estimates. We highlight the importance of accurately measuring relevant air-water gas concentration gradients and considering gas-specific processes when estimating k.

Turbulence in a small boreal lake: Consequences for air-water gas exchange.

The hydrodynamics within small boreal lakes have rarely been studied, yet knowing whether turbulence at the air-water interface and in the water column scales with metrics developed elsewhere is essential for computing metabolism and fluxes of climate-forcing trace gases. We instrumented a humic, 4.7 ha, boreal lake with two meteorological stations, three thermistor arrays, an infrared (IR) camera to quantify surface divergence, obtained turbulence as dissipation rate of turbulent kinetic energy (ε) using an acoustic Doppler velocimeter and a temperature-gradient microstructure profiler, and conducted chamber measurements for short periods to obtain fluxes and gas transfer velocities (k). Near-surface ε varied from 10-8 to 10-6 m2 s-3 for the 0-4 m s-1 winds and followed predictions from Monin-Obukhov similarity theory. The coefficient of eddy diffusivity in the mixed layer was up to 10-3 m2 s-1 on the windiest afternoons, an order of magnitude less other afternoons, and near molecular at deeper depths. The upper thermocline upwelled when Lake numbers (L N ) dropped below four facilitating vertical and horizontal exchange. k computed from a surface renewal model using ε agreed with values from chambers and surface divergence and increased linearly with wind speed. Diurnal thermoclines formed on sunny days when winds were < 3 m s-1, a condition that can lead to elevated near-surface ε and k. Results extend scaling approaches developed in the laboratory and for larger water bodies, illustrate turbulence and k are greater than expected in small wind-sheltered lakes, and provide new equations to quantify fluxes.

Unraveling the chemodiversity of halogenated disinfection by-products formed during drinking water treatment using target and non-target screening tools.

To date, there is no analytical approach available that allows the full identification and characterization of highly complex disinfection by-product (DBP) mixtures. This study aimed at investigating the chemodiversity of drinking water halogenated DBPs using diverse analytical tools: measurement of adsorbable organic halogen (AOX) and mass spectrometry (MS)-based target and non-target analytical workflows. Water was sampled before and after chemical disinfection (chlorine or chloramine) at four drinking water treatment plants in Sweden. The target analysis had the highest sensitivity, although it could only partially explain the AOX formed in the disinfected waters. Non-target Fourier transform ion cyclotron resonance (FT-ICR) MS analysis indicated that only up to 19 Cl and/or Br-CHO formulae were common to all disinfected waters. Unexpectedly, a high diversity of halogenated DBPs (presumed halogenated polyphenolic and highly unsaturated compounds) was found in chloraminated surface water, comparable to that found in chlorinated surface water. Overall, up to 86 DBPs (including isobaric species) were tentatively identified using liquid chromatography (LC)-Orbitrap MS. Although further work is needed to confirm their identity and assess their relevance in terms of toxicity, they can be used to design suspect lists to improve the characterization of disinfected water halogenated mixtures.

Effect of Cobalt, Nickel, and Selenium/Tungsten Deficiency on Mesophilic Anaerobic Digestion of Chemically Defined Soluble Organic Compounds.

Trace elements (TEs) are vital for anaerobic digestion (AD), due to their role as cofactors in many key enzymes. The aim of this study was to evaluate the effects of specific TE deficiencies on mixed microbial communities during AD of soluble polymer-free substrates, thus focusing on AD after hydrolysis. Three mesophilic (37 °C) continuous stirred-tank biogas reactors were depleted either of Co, Ni, or a combination of Se and W, respectively, by discontinuing their supplementation. Ni and Se/W depletion led to changes in methane kinetics, linked to progressive volatile fatty acid (VFA) accumulation, eventually resulting in process failure. No significant changes occurred in the Co-depleted reactor, indicating that the amount of Co present in the substrate in absence of supplementation was sufficient to maintain process stability. Archaeal communities remained fairly stable independent of TE concentrations, while bacterial communities gradually changed with VFA accumulation in Ni- and Se-/W-depleted reactors. Despite this, the communities remained relatively similar between these two reactors, suggesting that the major shifts in composition likely occurred due to the accumulating VFAs. Overall, the results indicate that Ni and Se/W depletion primarily lead to slower metabolic activities of methanogenic archaea and their syntrophic partners, which then has a ripple effect throughout the microbial community due to a gradual accumulation of intermediate fermentation products.

Molecular differences between water column and sediment pore water SPE-DOM in ten Swedish boreal lakes.

Boreal lakes are considered hot spots of dissolved organic matter (DOM) processing within the global carbon cycle. This study has used FT-ICR mass spectrometry and comprehensive data evaluation to assess the molecular differences of SPE-DOM between lake column water SPE-DOM and sedimentary pore water SPE-DOM in 10 Swedish boreal lakes of the Malingsbo area, which were selected for their large diversity of physicochemical and morphological characteristics. While lake column water is well mixed and fairly oxygenated, sedimentary pore water is subject to depletion of oxygen and to confinement of molecules. Robust trends were deduced from molecular compositions present in all compartments and in all 10 lakes ("common compositions") with recognition of relative abundance. Sedimentary pore water SPE-DOM featured higher proportions of heteroatoms N and S, higher average H/C ratios in presence of higher DBE/C ratios, and higher average oxygenation than lake column water SPE-DOM. These trends were observed in all lakes except Ljustjärn, which is a ground water fed kettle lake with an unique lake biogeochemistry. Analogous trends were also observed in case of single or a few lakes and operated also for compounds present solely in either lake column water or sedimentary pore water. Unique compounds detected in either compartments and/or in a few lakes showed higher molecular diversity than the "common compositions". Processing of DOM molecules in sediments included selective preservation for polyphenolic compounds and microbial resynthesis of selected molecules of considerable diversity.

Evaluating gas chromatography with a halogen-specific detector for the determination of disinfection by-products in drinking water.

The occurrence of disinfection by-products (DBPs) in drinking water has become an issue of concern during the past decades. The DBPs pose health risks and are suspected to cause various cancer forms, be genotoxic, and have negative developmental effects. The vast chemical diversity of DBPs makes comprehensive monitoring challenging. Only few of the DBPs are regulated and included in analytical protocols. In this study, a method for simultaneous measurement of 20 DBPs from five different structural classes (both regulated and non-regulated) was investigated and further developed for 11 DBPs using solid-phase extraction and gas chromatography coupled with a halogen-specific detector (XSD). The XSD was highly selective towards halogenated DBPs, providing chromatograms with little noise. The method allowed detection down to 0.05 µg L-1 and showed promising results for the simultaneous determination of a range of neutral DBP classes. Compounds from two classes of emerging DBPs, more cytotoxic than the "traditional" regulated DBPs, were successfully determined using this method. However, haloacetic acids (HAAs) should be analyzed separately as some HAA methyl esters may degrade giving false positives of trihalomethanes (THMs). The method was tested on real water samples from two municipal waterworks where the target DBP concentrations were found below the regulatory limits of Sweden.

Changes in dissolved organic matter during the treatment processes of a drinking water plant in Sweden and formation of previously unknown disinfection byproducts.

The changes in dissolved organic matter (DOM) throughout the treatment processes in a drinking water treatment plant in Sweden and the formation of disinfection byproducts (DBPs) were evaluated by using ultra-high-resolution mass spectrometry (resolution of ∼500,000 at m/z 400) and nuclear magnetic resonance (NMR). Mass spectrometric results revealed that flocculation induced substantial changes in the DOM and caused quantitative removal of DOM constituents that usually are associated with DBP formation. While half of the chromophoric DOM (CDOM) was removed by flocculation, ∼4-5 mg L(-1) total organic carbon remained in the finished water. A conservative approach revealed the formation of ∼800 mass spectrometry ions with unambiguous molecular formula assignments that contained at least one halogen atom. These molecules likely represented new DBPs, which could not be prevented by the flocculation process. The most abundant m/z peaks, associated with formed DBPs, could be assigned to C5HO3Cl3, C5HO3Cl2Br, and C5HO3ClBr2 using isotope simulation patterns. Other halogen-containing formulas suggested the presence of halogenated polyphenolic and aromatic acid-type structures, which was supported by possible structures that matched the lower molecular mass range (maximum of 10 carbon atoms) of these DBPs. 1H NMR before and after disinfection revealed an ∼2% change in the overall 1H NMR signals supporting a significant change in the DOM caused by disinfection. This study underlines the fact that a large and increasing number of people are exposed to a very diverse pool of organohalogens through water, by both drinking and uptake through the skin upon contact. Nontarget analytical approaches are indispensable for revealing the magnitude of this exposure and to test alternative ways to reduce it.

Methane and carbon dioxide emissions from inland waters in India - implications for large scale greenhouse gas balances.

Inland waters were recently recognized to be important sources of methane (CH4 ) and carbon dioxide (CO2 ) to the atmosphere, and including inland water emissions in large scale greenhouse gas (GHG) budgets may potentially offset the estimated carbon sink in many areas. However, the lack of GHG flux measurements and well-defined inland water areas for extrapolation, make the magnitude of the potential offset unclear. This study presents coordinated flux measurements of CH4 and CO2 in multiple lakes, ponds, rivers, open wells, reservoirs, springs, and canals in India. All these inland water types, representative of common aquatic ecosystems in India, emitted substantial amounts of CH4 and a major fraction also emitted CO2 . The total CH4 flux (including ebullition and diffusion) from all the 45 systems ranged from 0.01 to 52.1 mmol m(-2)  d(-1) , with a mean of 7.8 ± 12.7 (mean ± 1 SD) mmol m(-2)  d(-1) . The mean surface water CH4 concentration was 3.8 ± 14.5 µm (range 0.03-92.1 µm). The CO2 fluxes ranged from -28.2 to 262.4 mmol m(-2)  d(-1) and the mean flux was 51.9 ± 71.1 mmol m(-2)  d(-1) . The mean partial pressure of CO2 was 2927 ± 3269 µatm (range: 400-11 467 µatm). Conservative extrapolation to whole India, considering the specific area of the different water types studied, yielded average emissions of 2.1 Tg CH4  yr(-1) and 22.0 Tg CO2  yr(-1) from India's inland waters. When expressed as CO2 equivalents, this amounts to 75 Tg CO2 equivalents yr(-1) (53-98 Tg CO2 equivalents yr(-1) ; ± 1 SD), with CH4 contributing 71%. Hence, average inland water GHG emissions, which were not previously considered, correspond to 42% (30-55%) of the estimated land carbon sink of India. Thereby this study illustrates the importance of considering inland water GHG exchange in large scale assessments.

Automated flux chamber for investigating gas flux at water-air interfaces.

Aquatic ecosystems are major sources of greenhouse gases (GHG). Representative measurements of GHG fluxes from aquatic ecosystems to the atmosphere are vital for quantitative understanding of relationships between biogeochemistry and climate. Fluxes occur at high temporal variability at diel or longer scales, which are not captured by traditional short-term deployments (often in the order of 30 min) of floating flux chambers. High temporal frequency measurements are necessary but also extremely labor intensive if manual flux chamber based methods are used. Therefore, we designed an inexpensive and easily mobile automated flux chamber (AFC) for extended deployments. The AFC was designed to measure in situ accumulation of gas in the chamber and also to collect gas samples in an array of sample bottles for subsequent analysis in the laboratory, providing two independent ways of CH(4) concentration measurements. We here present the AFC design and function together with data from initial laboratory tests and from a field deployment.