Degradation of terrigenous organic matter on the East Siberian Arctic Shelf assessed by lipid and lignin oxidation products

<p>Warming-induced permafrost thawing is expected to intensify the remobilization of terrigenous organic matter (terrOM) to the East Siberian Arctic Shelf (ESAS) via increasing river discharge and coastal erosion. Earlier studies have focused on source apportionment and transport of terrOM, with less emphasis on its degradation state during cross-shelf transport. Since degradation of terrOM is the link between permafrost thawing and release of GHGs such as CO<sub>2</sub>, this study focuses on the degradation characteristics. Hence, the main objective of this study is to assess the patterns of terrOM degradation across the East Siberian Arctic Shelf using molecular proxies that are specific to terrOM.</p><p>Lignin phenols and high molecular weight (HMW) n-alkanes and n-alkanoic acids are only produced by terrestrial plants which make them suitable biomarkers to assess degradation of terrestrial material throughout the ESAS. The lignin-based proxies acid to aldehyde ratios of vanillyl (Vd/Vl) and syringyl (Sd/Sl) structural units, as well as the ratio of 3,5-dihydroxybenzoic acid over vanillin (3,5-Bd/V) are expected to increase during degradation under oxic conditions. Fresh terrestrial plant material is predominated by long odd-numbered (>C<sub>25</sub>) and even-numbered (>C<sub>24</sub>) carbon chain length of n-alkanes and n-alkanoic acids, respectively. This dominance is described in the Carbon Preference Index (CPI). When degradation takes place, CPI values decrease accordingly, describing how much of the original material was preserved. Ratios of HMW n-alkanoic acids to HMW n-alkanes are also expected to decrease during microbial degradation owing to preferential loss of functional groups.</p><p>The data show increasing Vd/Vl, Sd/Sl and 3,5-Bd/V ratios, and decreasing HMW n-alkanes CPI values toward the outer shelf, consistent with continuous degradation of terrOM across the ESAS. While Vd/Vl and HMW n-alkane CPI did not show strong differences between east and west, Sd/Sl ratios were highest in the outer western ESAS, and 3,5-Bd/V ratios were highest in the outer east. These differences may reflect different terrOM pools along the ESAS due to differences in vegetation zones releasing the input material through river discharge and coastal erosion. In contrast, HMW n-alkanoic acid to HMW n-alkane ratio and HMW n-alkanoic acid CPI showed inconsistent patterns across the ESAS; reasons for it are currently being investigated. These results will also be complemented by additional biomarkers to better understand the degradation of terrOM during cross-shelf transport.</p>

Exploiting the Natural Diversity of RhlA Acyltransferases for the Synthesis of the Rhamnolipid Precursor 3-(3-Hydroxyalkanoyloxy)Alkanoic Acid

ABSTRACT While rhamnolipids of the Pseudomonas aeruginosa type are commercially available, the natural diversity of rhamnolipids and their origin have barely been investigated. Here, we collected known and identified new rhlA genes encoding the acyltransferase responsible for the synthesis of the lipophilic rhamnolipid precursor 3-(3-hydroxyalkanoyloxy)alkanoic acid (HAA). Generally, all homologs were found in Betaproteobacteria and Gammaproteobacteria. A likely horizontal gene transfer event into Actinobacteria is the only identified exception. The phylogeny of the RhlA homologs from Pseudomonas and Burkholderia species is consistent with the organism phylogeny, and genes involved in rhamnolipid synthesis are located in operons. In contrast, RhlA homologs from the Enterobacterales do not follow the organisms’ phylogeny but form their own branch. Furthermore, in many Enterobacterales and Halomonas from the Oceanospirillales, an isolated rhlA homolog can be found in the genome. The RhlAs from Pseudomonas aeruginosa PA01, Pseudomonas fluorescens LMG 05825, Pantoea ananatis LMG 20103, Burkholderia plantarii PG1, Burkholderia ambifaria LMG 19182, Halomonas sp. strain R57-5, Dickeya dadantii Ech586, and Serratia plymuthica PRI-2C were expressed in Escherichia coli and tested for HAA production. Indeed, except for the Serratia RhlA, HAAs were produced with the engineered strains. A detailed analysis of the produced HAA congeners by high-performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) highlights the congener specificity of the RhlA proteins. The congener length varies from 4 to 18 carbon atoms, with the main congeners consisting of different combinations of saturated or monounsaturated C10, C12, and C14 fatty acids. The results are discussed in the context of the phylogeny of this unusual enzymatic activity. IMPORTANCE The RhlA specificity explains the observed differences in 3-(3-hydroxyalkanoyloxy)alkanoic acid (HAA) congeners. Whole-cell catalysts can now be designed for the synthesis of different congener mixtures of HAAs and rhamnolipids, thereby contributing to the envisaged synthesis of designer HAAs.

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

We measured organic and inorganic gas-phase acids in the Front Range of Colorado to better understand their tropospheric sources and sinks using a high-resolution time-of-flight chemical ionization mass spectrometer. Measurements were conducted from 4 to 13 August 2014 at the Boulder Atmospheric Observatory during the Front Range Air Pollution and Photochemistry Éxperiment. Diurnal increases in mixing ratios are consistent with photochemical sources of HNO3, HNCO, formic, propionic, butyric, valeric, and pyruvic acid. Vertical profiles taken on the 300 m tower demonstrate net surface-level emissions of alkanoic acids, but net surface deposition of HNO3 and pyruvic acid. The surface-level alkanoic acid source persists through both day and night, and is thus not solely photochemical. Reactions between O3 and organic surfaces may contribute to the surface-level alkanoic acid source. Nearby traffic emissions and agricultural activity are a primary source of propionic, butyric, and valeric acids, and likely contribute photochemical precursors to HNO3 and HNCO. The combined diel and vertical profiles of the alkanoic acids and HNCO are inconsistent with dry deposition and photochemical losses being the only sinks, suggesting additional loss mechanisms.

Tropospheric sources and sinks of gas-phase acids in the Colorado Front Range

We measured organic and inorganic gas-phase acids in the Front Range of Colorado to better understand their tropospheric sources and sinks using a high-resolution time-of-flight chemical ionization mass spectrometer. Measurements were conducted from 4 to 13 August 2014 at the Boulder Atmospheric Observatory during the Front Range Air Pollution and Photochemistry Éxperiment. Diurnal increases in mixing ratios are consistent with photochemical sources of HNO3, HNCO, formic, propionic, butyric, valeric, and pyruvic acid. Vertical profiles taken on the 300 m tower demonstrate net surface-level emissions of alkanoic acids, but net surface deposition of HNO3 and pyruvic acid. The surface-level alkanoic acid source persists through both day and night, and is thus not solely photochemical. Reactions between O3 and organic surfaces may contribute to the surface-level alkanoic acid source. Nearby traffic emissions and agricultural activity are a primary source of propionic, butyric, and valeric acid, and likely contribute photochemical precursors to HNO3 and HNCO. The combined diel and vertical profiles of the alkanoic acids and HNCO are inconsistent with dry deposition and photochemical losses being the only sinks, suggesting additional loss mechanisms.