Browsing by Subject "MANGANESE"

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  • Silvonen, Soila; Niemistö, Juha; Csibrán, Adrián; Jilbert, Tom; Torma, Péter; Krámer, Tamás; Nurminen, Leena; Horppila, Jukka (2021)
    Hypolimnetic withdrawal (HW) is a lake restoration method that is based on the removal of phosphorus (P) along with near-bottom water. While it has often proven to be effective, the method also sets challenges: it is about balancing between effective P removal and maintenance of the thermal stratification of the lake. The success of different HW projects has been reviewed in some studies retrospectively, but scientific literature still lacks studies that use detailed data on the lake biogeochemistry to scale and optimize the method in advance, and to predict the outcomes of the restoration measure. In the current study, we investigated the seasonal biogeochemistry, P stocks and thermal stratification of a eutrophic lake (Lake Kymijarvi/Myllypohja basin, southern Finland) to determine an optimal withdrawal rate, to assess its effects on stratification, and to evaluate the expected success of HW. We found that by adjusting HW with P diffusive fluxes from the sediment (diffusion-adjusted HW), it is possible to remove a notable part of the cycling P without causing major disturbances to the thermal stratification even in a relatively shallow lake. Our results show that HW can have great potential in lake restoration: diffusion-adjusted HW in our study lake could increase the annual P output by 35-46%, shifting the P budget of the lake to negative. We thus propose a novel approach to optimize HW on the basis of the diffusive flux of P from the sediment, with the goal of extracting P continuously at an equivalent rate to the diffusive flux. We finally discuss how this can be achieved more effectively with HW based on a closed-circuit system. (c) 2020 The Authors. Published by Elsevier B.V.
  • Koho, Karoliina A.; de Nooijer, Lennart J.; Fontanier, Christophe; Toyofuku, Takashi; Oguri, Kazumasa; Kitazato, Hiroshi; Reichart, Gert-Jan (2017)
    The Mn / Ca of calcium carbonate tests of living (rose-Bengal-stained) benthic foraminifera (Elphidium batialis, Uvigerina spp., Bolivina spissa, Nonionellina labradorica and Chilostomellina fimbriata) were determined in relation to pore water manganese (Mn) concentrations for the first time along a bottom water oxygen gradient across the continental slope along the NE Japan margin (western Pacific). The local bottom water oxygen (BWO) gradient differs from previous field study sites focusing on foraminiferal Mn / Ca and redox chemistry, therefore allowing further resolution of previously observed trends. The Mn / Ca ratios were analysed using laser ablation inductively coupled plasma-mass spectrometer (ICP-MS), allowing single-chamber determination of Mn / Ca. The incorporation of Mn into the carbonate tests reflects environmental conditions and is not influenced by ontogeny. The inter-species variability in Mn / Ca reflected foraminiferal in-sediment habitat preferences and associated pore water chemistry but also showed large interspecific differences in Mn partitioning. At each station, Mn / Ca ratios were always lower in the shallow infaunal E. batialis, occupying relatively oxygenated sediments, compared to intermediate infaunal species, Uvigerina spp. and B. spissa, which were typically found at greater depth, under more reducing conditions. The highest Mn / Ca was always recorded by the deep infaunal species N. labradorica and C. fimbriata. Our results suggest that although partitioning differs, Mn / Ca ratios in the intermediate infaunal taxa are promising tools for palaeoceanographic reconstructions as their microhabitat exposes them to higher variability in pore water Mn, thereby making them relatively sensitive recorders of redox conditions and/or bottom water oxygenation.
  • Lizarazo , Clara; Lampi, Anna-Maija; Mäkelä, Pirjo (2021)
    Caraway seeds contain between 0.5-7% essential oil, rich in monoterpenes that have a characteristic aroma and chemical properties. Caraway oil has several bioactive compounds that are of industrial importance, particularly for pharmaceutical and health care products. Carvone and limonene are the main terpenes present in caraway oil, which along with some unique fatty acids (i.e. petroselinic acid) determine caraway (Carum carvi L.) oil quality. Both terpenes are important raw materials for industrial applications and their concentration influences the price of caraway seed and oil, hence there is need for identifying management practices that may increase the concentration of these and other bioactive compounds to improve caraway seed oil quality. A field experiment with five treatments: a control and a series of foliar-applied micronutrients (either Cu, Mg, Mn or Zn was done to identify their potential to enhance caraway oil quality. Solid-phase microextraction and gas chromatography with a flame ionization detector were used to characterize oil quality. Our results indicate that while the micronutrient treatments have a significant effect on essential oil composition, both in carvone and limonene, such an effect was not found on all fatty acids but only in two of them-palmitoleic and vaccenic acid-, which were highest after the Mn treatment. Overall, the carvone content of the seeds decreased the least between years following Mn treatment. Mn treatment also caused an increase in limonene in the second year in contrast to the trend for all other treatments. The Mn foliar spray needs to be studied further to elucidate whether it could have a consistent positive effect on caraway oil seed quality upon adjusting dosage and spraying time.
  • Jilbert, Tom; Jokinen, Sami; Saarinen, Timo; Mattus-Kumpunen, Ulpu; Simojoki, Asko; Saarni, Saija; Salminen, Sarianna; Niemist, Juha; Horppila, Jukka (2020)
    Using biogeochemical analyses of sediments and porewaters, we investigate the legacy of a brief, intense period of eutrophication on sedimentary phosphorus (P) cycling in a boreal lake (Enonselka basin, Lake Vesijarvi, Finland). Point-source sewage inputs in the twentieth century caused deoxygenation of the lake and accelerated the focusing of iron (Fe) and manganese (Mn) oxides into deeper areas. Early diagenesis under Fe-Mn-rich conditions now favors rapid burial of P in these areas, likely as a combination of both oxide-bound P phases and authigenic manganous vivianite. A new P budget for Enonselka basin shows that P burial causes an annual drawdown of 1.2% (+/- 0.2%) of the surface sediment P inventory, supporting a long-term trend towards recovery since the construction of a wastewater treatment plant in the mid-1970s. However, remineralization of organic matter and associated dissolution of Fe-Mn oxides continues to regenerate P from a deep reactive layer (20-60 cm depth) deposited at the height of past eutrophication, leading to an upwards diffusive flux of dissolved phosphate towards the surface sediments. The magnitude of this flux is similar to that of external P loading to the lake. The combined incoming fluxes of P are likely to retard the complete recovery from eutrophication by decades, despite ongoing restoration actions.
  • Myllykangas, Jukka-Pekka; Rissanen, Antti J.; Hietanen, Susanna; Jilbert, Tom (2020)
    Methane is produced microbially in vast quantities in sediments throughout the world's oceans. However, anaerobic oxidation of methane (AOM) provides a near-quantitative sink for the produced methane and is primarily responsible for preventing methane emissions from the oceans to the atmosphere. AOM is a complex microbial process that involves several different microbial groups and metabolic pathways. The role of different electron acceptors in AOM has been studied for decades, yet large uncertainties remain, especially in terms of understanding the processes in natural settings. This study reports whole-core incubation methane oxidation rates along an estuarine gradient ranging from near fresh water to brackish conditions, and investigates the potential role of different electron acceptors in AOM. Microbial community structure involved in different methane processes is also studied in the same estuarine system using high throughput sequencing tools. Methane oxidation in the sediments was active in three distinct depth layers throughout the studied transect, with total oxidation rates increasing seawards. We find extensive evidence of non-sulphate AOM throughout the transect. The highest absolute AOM rates were observed below the sulphate-methane transition zone (SMTZ), strongly implicating the role of alternative electron acceptors (most likely iron and manganese oxides). However, oxidation rates were ultimately limited by methane availability. ANME-2a/b were the most abundant microbial phyla associated with AOM throughout the study sites, followed by ANME-2d in much lower abundances. Similarly to oxidation rates, highest abundances of microbial groups commonly associated with AOM were found well below the SMTZ, further reinforcing the importance of non-sulphate AOM in this system.
  • Taboada-Puig, Roberto; Lu-Chau, Thelmo A.; Moreira, Maria T.; Feijoo, Gumersindo; Lema, Juan M.; Fagerstedt, Kurt; Ohra-Aho, Taina; Liitia, Tiina; Heikkinen, Harri; Ropponen, Jarmo; Tamminen, Tarja (2018)
    The objective of this study was to evaluate the ability of one versatile peroxidase and the biocatalytically generated complex Mn(III)-malonate to polymerize coniferyl alcohol (CA) to obtain dehydrogenation polymers (DHPs) and to characterize how closely the structures of the formed DHPs resemble native lignin. Hydrogen peroxide was used as oxidant and Mn2+ as mediator. Based on the yields of the polymerized product, it was concluded that the enzymatic reaction should be performed in aqueous solution without organic solvents at 4.5pH6.0 and with 0.75H(2)O(2):CA ratio1. The results obtained from the Mn3+-malonate-mediated polymerization showed that the yield was almost 100%. Reaction conditions had, however, effect on the structures of the formed DHPs, as detected by size exclusion chromatography and pyrolysis-GC/MS. It can be concluded that from the structural point of view, the optimal pH for DHP formation using the presently studied system was 3 or 4.5. Low H2O2/CA ratio was beneficial to avoid oxidative side reactions. However, the high frequency of - linkages in all cases points to dimer formation between monomeric CA rather than endwise polymerization. (c) 2017 American Institute of Chemical Engineers Biotechnol. Prog., 34:81-90, 2018
  • Joost, Maximilian; Nieger, Martin; Lutz, Martin; Ehlers, Andreas W.; Slootweg, Jacob Christiaan (Chris); Lammertsma, Koop (2020)
    O- and S-heterocyclic carbenes (OHCs, SHCs) are shown experimentally and computationally to be stronger pi acceptors than NHCs and lack, of course, substituents at the heteroatoms. These different electronic and steric characteristics make OHCs and SHCs interesting ligands for coordination chemistry. Convenient synthetic routes are presented to access their iridium(I), iridium(III), and coinage-metal(I) (Cu, Ag, Au) complexes in good yields by means of dissociation of olefins, deprotonation of precursor salts, and transmetalation from a silver carbene complex Molecular structures and detailed bonding analyses of these complexes are presented.