TY - JOUR A1 - Eckert, Sebastian A1 - Norell, Jesper A1 - Jay, Raphael Martin A1 - Fondell, Mattis A1 - Mitzner, Rolf A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - T-1 Population as the Driver of Excited-State Proton-Transfer in 2-Thiopyridone JF - Chemistry - a European journal N2 - Excited-state proton transfer (ESPT) is a fundamental process in biomolecular photochemistry, but its underlying mediators often evade direct observation. We identify a distinct pathway for ESPT in aqueous 2-thiopyridone, by employing transient N1s X-ray absorption spectroscopy and multi-configurational spectrum simulations. Photoexcitations to the singlet S-2 and S-4 states both relax promptly through intersystem crossing to the triplet T-1 state. The T-1 state, through its rapid population and near nanosecond lifetime, mediates nitrogen site deprotonation by ESPT in a secondary intersystem crossing to the S-0 potential energy surface. This conclusively establishes a dominant ESPT pathway for the system in aqueous solution, which is also compatible with previous measurements in acetonitrile. Thereby, the hitherto open questions of the pathway for ESPT in the compound, including its possible dependence on excitation wavelength and choice of solvent, are resolved. KW - excited-state proton-transfer KW - intersystem crossing KW - nitrogen KW - photochemistry KW - X-ray absorption Y1 - 2019 U6 - https://doi.org/10.1002/chem.201804166 SN - 0947-6539 SN - 1521-3765 VL - 25 IS - 7 SP - 1733 EP - 1739 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Eckert, Sebastian A1 - Norell, Jesper A1 - Miedema, Piter S. A1 - Beye, Martin A1 - Fondell, Mattis A1 - Quevedo, Wilson A1 - Kennedy, Brian A1 - Hantschmann, Markus A1 - Pietzsch, Annette A1 - Van Kuiken, Benjamin E. A1 - Ross, Matthew A1 - Minitti, Michael P. A1 - Moeller, Stefan P. A1 - Schlotter, William F. A1 - Khalil, Munira A1 - Odelius, Michael A1 - Föhlisch, Alexander T1 - Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale. KW - nitrogen KW - photochemistry KW - protonation KW - RIXS (resonant inelastic X-ray scattering) KW - selective bond cleavage Y1 - 2017 U6 - https://doi.org/10.1002/anie.201700239 SN - 1433-7851 SN - 1521-3773 VL - 56 SP - 6088 EP - 6092 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Klaus, Valentin H. A1 - Hölzel, Norbert A1 - Boch, Steffen A1 - Müller, Jorg A1 - Socher, Stephanie A. A1 - Prati, Daniel A1 - Fischer, Markus A1 - Kleinebecker, Till T1 - Direct and indirect associations between plant species richness and productivity in grasslands regional differences preclude simple generalization of productivity-biodiversity relationships JF - Preslia : the journal of the Czech Botanical Society N2 - Plant species richness of permanent grasslands has often been found to be significantly associated with productivity. Concentrations of nutrients in biomass can give further insight into these productivity-plant species richness relationships, e.g. by reflecting land use or soil characteristics. However, the consistency of such relationships across different regions has rarely been taken into account, which might significantly compromise our potential for generalization. We recorded plant species richness and measured above-ground biomass and concentrations of nutrients in biomass in 295 grasslands in three regions in Germany that differ in soil and climatic conditions. Structural equation modelling revealed that nutrient concentrations were mostly indirectly associated with plant species richness via biomass production. However, negative associations between the concentrations of different nutrients and biomass and plant species richness differed considerably among regions. While in two regions, more than 40% of the variation in plant species richness could be attributed to variation in biomass, K, P. and to some degree also N concentrations, in the third region only 15% of the variation could be explained in this way. Generally, highest plant species richness was recorded in grasslands where N and P were co-limiting plant growth, in contrast to N or K (co-) limitation. But again, this pattern was not recorded in the third region. While for two regions land-use intensity and especially the application of fertilizers are suggested to be the main drivers causing the observed negative associations with productivity, in the third region the little variance accounted for, low species richness and weak relationships implied that former intensive grassland management, ongoing mineralization of peat and fluctuating water levels in fen grasslands have overruled effects of current land-use intensity and productivity. Finally, we conclude that regional replication is of major importance for studies seeking general insights into productivity-diversity relationships. KW - anthropogenic effect KW - Biodiversity Exploratories project KW - fen grasslands KW - generalizability KW - land-use history KW - nitrogen KW - phosphorus KW - potassium KW - plant species richness KW - structural equation modeling Y1 - 2013 SN - 0032-7786 VL - 85 IS - 2 SP - 97 EP - 112 PB - Czech Botanical Soc. CY - Praha ER - TY - JOUR A1 - Kumar, Rohini A1 - Hesse, Fabienne A1 - Rao, P. Srinivasa A1 - Musolff, Andreas A1 - Jawitz, James A1 - Sarrazin, Francois A1 - Samaniego, Luis A1 - Fleckenstein, Jan H. A1 - Rakovec, Oldrich A1 - Thober, S. A1 - Attinger, Sabine T1 - Strong hydroclimatic controls on vulnerability to subsurface nitrate contamination across Europe JF - Nature Communications N2 - Subsurface contamination due to excessive nutrient surpluses is a persistent and widespread problem in agricultural areas across Europe. The vulnerability of a particular location to pollution from reactive solutes, such as nitrate, is determined by the interplay between hydrologic transport and biogeochemical transformations. Current studies on the controls of subsurface vulnerability do not consider the transient behaviour of transport dynamics in the root zone. Here, using state-of-the-art hydrologic simulations driven by observed hydroclimatic forcing, we demonstrate the strong spatiotemporal heterogeneity of hydrologic transport dynamics and reveal that these dynamics are primarily controlled by the hydroclimatic gradient of the aridity index across Europe. Contrasting the space-time dynamics of transport times with reactive timescales of denitrification in soil indicate that similar to 75% of the cultivated areas across Europe are potentially vulnerable to nitrate leaching for at least onethird of the year. We find that neglecting the transient nature of transport and reaction timescale results in a great underestimation of the extent of vulnerable regions by almost 50%. Therefore, future vulnerability and risk assessment studies must account for the transient behaviour of transport and biogeochemical transformation processes. KW - travel time distributions KW - groundwater vulnerability KW - flux tracking KW - transit-time KW - water age KW - nitrogen KW - model KW - dynamics KW - pollution KW - patterns Y1 - 2020 U6 - https://doi.org/10.1038/s41467-020-19955-8 SN - 2041-1723 VL - 11 IS - 1 SP - 1 EP - 10 PB - Nature Publishing Group UK CY - London ER - TY - JOUR A1 - Lachmann, Sabrina C. A1 - Mettler-Altmann, Tabea A1 - Wacker, Alexander A1 - Spijkerman, Elly T1 - Nitrate or ammonium BT - Influences of nitrogen source on the physiology of a green alga JF - Ecology and evolution N2 - In freshwaters, algal species are exposed to different inorganic nitrogen (Ni) sources whose incorporation varies in biochemical energy demand. We hypothesized that due to the lesser energy requirement of ammonium (NH4+)-use, in contrast to nitrate (NO3-)-use, more energy remains for other metabolic processes, especially under CO2-and phosphorus (Pi) limiting conditions. Therefore, we tested differences in cell characteristics of the green alga Chlamydomonas acidophila grown on NH4+ or NO3- under covariation of CO2 and Pi-supply in order to determine limitations, in a full-factorial design. As expected, results revealed higher carbon fixation rates for NH4+ grown cells compared to growth with NO3- under low CO2 conditions. NO3- -grown cells accumulated more of the nine analyzed amino acids, especially under Pi-limited conditions, compared to cells provided with NH4+. This is probably due to a slower protein synthesis in cells provided with NO3-. In contrast to our expectations, compared to NH4+ -grown cells NO3- -grown cells had higher photosynthetic efficiency under Pi-limitation. In conclusion, growth on the Ni-source NH4+ did not result in a clearly enhanced Ci-assimilation, as it was highly dependent on Pi and CO2 conditions (replete or limited). Results are potentially connected to the fact that C. acidophila is able to use only CO2 as its inorganic carbon (Ci) source. KW - amino acids KW - carbon uptake kinetics KW - CO2 conditions KW - nitrogen KW - phosphorus limitation Y1 - 2019 U6 - https://doi.org/10.1002/ece3.4790 SN - 2045-7758 VL - 9 IS - 3 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Leuschner, Christoph A1 - Wulf, Monika A1 - Baeuchler, Patricia A1 - Hertel, Dietrich T1 - Forest continuity as a key determinant of soil carbon and nutrient storage in beech forests on sandy soils in Northern Germany JF - Ecosystems N2 - Forest (or tree) age has been identified as an important determinant of the carbon (C) storage potential of forest soils. A large part of Central Europe's current forested area was affected by land use change with long periods of cultivation in past centuries suggesting that the organic C stocks in the soil (SOC) under recent forest may partly be legacies of the past and that stand age effects have to be distinguished from forest continuity effects (that is, the time since re-afforestation). We examined the influence of mean tree age and forest continuity on the SOC pool and the stores of total N and available P, Ca, Mg, and K in the soil (mineral soil and organic layer) across a sample of 14 beech (Fagus sylvatica) forests on sandy soil with variable tree age (23-189 years) and forest continuity (50-year-old afforestation to ancient ('permanent') forest, that is, > 230 years of proven continuity). Ancient beech forests (> 230 years of continuity) stored on average 47 and 44% more organic C and total N in the soil than recent beech afforestation (50-128 years of continuity). Contrary to expectation, we found large and significant C and N pool differences between the forest categories in the mineral soil but not in the organic layer indicating that decade- or century-long cultivation has reduced the subsoil C and nutrient stores while the organic layer element pools have approached a new equilibrium after only 50-128 years. PCA and correlation analyses suggest that forest continuity cannot be ignored when trying to understand the variation in soil C stocks between different stands. Forest clearing, subsequent cultivation, and eventual re-afforestation with beech resulted in similar relative stock reductions of C and N and, thus, no change in soil C/N ratio. We conclude that the continuity of forest cover, which may or may not be related to tree age, is a key determinant of the soil C and nutrient stores of beech forests in the old cultural landscape of Central Europe. KW - afforestation KW - ancient forests KW - available phosphorus KW - calcium KW - Fagus sylvatica KW - forest clear-cut KW - magnesium KW - nitrogen KW - potassium KW - sandy soil Y1 - 2014 U6 - https://doi.org/10.1007/s10021-013-9738-0 SN - 1432-9840 SN - 1435-0629 VL - 17 IS - 3 SP - 497 EP - 511 PB - Springer CY - New York ER - TY - JOUR A1 - Neill, Christopher A1 - Coe, Michael T. A1 - Riskin, Shelby H. A1 - Krusche, Alex V. A1 - Elsenbeer, Helmut A1 - Macedo, Marcia N. A1 - McHorney, Richard A1 - Lefebvre, Paul A1 - Davidson, Eric A. A1 - Scheffler, Raphael A1 - Figueira, Adelaine Michela e Silva A1 - Porder, Stephen A1 - Deegan, Linda A. T1 - Watershed responses to Amazon soya bean cropland expansion and intensification JF - Philosophical transactions of the Royal Society of London : B, Biological sciences N2 - The expansion and intensification of soya bean agriculture in southeastern Amazonia can alter watershed hydrology and biogeochemistry by changing the land cover, water balance and nutrient inputs. Several new insights on the responses of watershed hydrology and biogeochemistry to deforestation in Mato Grosso have emerged from recent intensive field campaigns in this region. Because of reduced evapotranspiration, total water export increases threefold to fourfold in soya bean watersheds compared with forest. However, the deep and highly permeable soils on the broad plateaus on which much of the soya bean cultivation has expanded buffer small soya bean watersheds against increased stormflows. Concentrations of nitrate and phosphate do not differ between forest or soya bean watersheds because fixation of phosphorus fertilizer by iron and aluminium oxides and anion exchange of nitrate in deep soils restrict nutrient movement. Despite resistance to biogeochemical change, streams in soya bean watersheds have higher temperatures caused by impoundments and reduction of bordering riparian forest. In larger rivers, increased water flow, current velocities and sediment flux following deforestation can reshape stream morphology, suggesting that cumulative impacts of deforestation in small watersheds will occur at larger scales. KW - soya beans KW - watersheds KW - nitrogen KW - phosphorus KW - soil Y1 - 2013 U6 - https://doi.org/10.1098/rstb.2012.0425 SN - 0962-8436 SN - 1471-2970 VL - 368 IS - 1619 PB - Royal Society CY - London ER - TY - JOUR A1 - Radosavljevic, Boris A1 - Lantuit, Hugues A1 - Knoblauch, Christian A1 - Couture, Nicole A1 - Herzschuh, Ulrike A1 - Fritz, Michael T1 - Arctic nearshore sediment dynamics - an example from Herschel Island - Qikiqtaruk, Canada JF - Journal of marine science and engineering N2 - Increasing arctic coastal erosion rates imply a greater release of sediments and organic matter into the coastal zone. With 213 sediment samples taken around Herschel Island-Qikiqtaruk, Canadian Beaufort Sea, we aimed to gain new insights on sediment dynamics and geochemical properties of a shallow arctic nearshore zone. Spatial characteristics of nearshore sediment texture (moderately to poorly sorted silt) are dictated by hydrodynamic processes, but ice-related processes also play a role. We determined organic matter (OM) distribution and inferred the origin and quality of organic carbon by C/N ratios and stable carbon isotopes delta C-13. The carbon content was higher offshore and in sheltered areas (mean: 1.0 wt.%., S.D.: 0.9) and the C/N ratios also showed a similar spatial pattern (mean: 11.1, S.D.: 3.1), while the delta C-13 (mean: -26.4 parts per thousand VPDB, S.D.: 0.4) distribution was more complex. We compared the geochemical parameters of our study with terrestrial and marine samples from other studies using a bootstrap approach. Sediments of the current study contained 6.5 times and 1.8 times less total organic carbon than undisturbed and disturbed terrestrial sediments, respectively. Therefore, degradation of OM and separation of carbon pools take place on land and continue in the nearshore zone, where OM is leached, mineralized, or transported beyond the study area. KW - permafrost KW - Arctic Ocean KW - stable carbon isotopes KW - nitrogen KW - sediment KW - chemistry KW - sediment dynamics KW - Beaufort Sea KW - grain size Y1 - 2022 U6 - https://doi.org/10.3390/jmse10111589 SN - 2077-1312 VL - 10 IS - 11 PB - MDPI CY - Basel ER -