| 1. |
- Vestergren, Johan, 1968-
(författare)
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Analysis and speciation of organic phosphorus in environmental matrices : Development of methods to improve 31P NMR analysis
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Phosphorus (P) is an essential element for life on our planet. It is central in numerous biochemical processes in terrestrial and aqueous ecosystems including food production; and it is the primary growth-limiting nutrient in some of the world’s biomes. The main source of P for use as agricultural fertilizer is mining of non-renewable mineral phosphate. In terrestrial ecosystems the main source is soil P, where the largest fraction is organic P, composed of many species with widely differing properties. This fraction controls the utilization of P by plants and microorganisms and influences ecosystem development and productivity. However, there is only scarce knowledge about the molecular composition of the organic P pool, about the processes controlling its bioavailability, and about its changes as soils develop. Therefore, the aim of this thesis was to develop robust solution- and solid-state 31P nuclear magnetic resonance spectroscopy (NMR) methods to provide molecular information about speciation of the organic P pool, and to study its dynamics in boreal and tropical soils. By studying humus soils of a groundwater recharge/discharge productivity gradient in a Fennoscandian boreal forest by solution- and solid-state NMR, it was found that P speciation changed with productivity. In particular, the level of orthophosphate diesters decreased with increasing productivity while mono-esters such as inositol phosphates increased. Because the use of solution NMR on conventional NaOH/EDTA extracts of soils was limited due to severe line broadening caused by the presence of paramagnetic metal ions, a new extraction method was developed and validated. Based on the removal of these paramagnetic impurities by sulfide precipitation, a dramatic decrease in NMR linewidths was obtained, allowing for the first time to apply modern multi-dimensional solution NMR techniques to soil extracts. Identification of individual soil P-species, and tracking changes in the organic P pools during soil development provided information for connecting P-speciation to bioavailability and ecosystem properties. Using this NMR approach we studied the transformation of organic P in humus soils along a chronosequence (7800 years) in Northern Sweden. While total P varied little, the composition of the soil P pool changed particularly among young sites, where also the largest shift in the composition of the plant community and of soil microorganisms was observed. Very old soils, such as found Africa, are thought to strongly adsorb P, limiting plant productivity. I used NMR to study the effect of scattered agroforestry trees on P speciation in two semi-arid tropical woodlands with different soil mineralogy (Burkina Faso). While the total P concentration was low, under the tree canopies higher amounts of P and higher diversity of P-species were found, presumably reflecting higher microbial activity.
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| 2. |
- Myrstener, Maria, 1989-
(författare)
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The role of nutrients for stream ecosystem function in Arctic landscapes : drivers of productivity under environmental change
- 2020
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Arctic and sub-Arctic freshwaters are currently experiencing substantial ecosystem changes due to the effects of global warming. Global warming effects on these freshwaters include increasing water temperatures, altered hydrological patterns, shifts in riparian vegetation and changes in the export of nutrients and carbon from soils. How these alterations to the physical and chemical hab-itat will affect stream ecosystem functioning largely depends on the responses by autotrophic pro-ducers and heterotrophic primary consumers. In this thesis, I explore how key stream ecosystem processes such as metabolic rates and nutrient cycling vary as a function of climate and landscape drivers, particularly light, temperature, and nutrient and carbon availability. To do this I leveraged natural gradients in vegetation, altitude, disturbance, and precipitation throughout the year in northern Sweden, as well as long- and short-term manipulations of nutrient availability. I also synthesized nutrient limitation data from lakes and streams to more holistically assess the re-sponses of boreal to Arctic freshwaters to changes in nutrients and climate variables. I found that nutrient availability, and especially nitrogen (N), is a main driver of spatial and temporal patterns of biofilm productivity, whole system metabolic rates, and short term N uptake in Arctic and sub-Arctic streams. I also show the importance of light and temperature constraints during early spring and late autumn, which set the limit for the aquatic growing season and annual productivity pat-terns. I present a first comparison of combined drivers of lake and stream responses to nutrient addition, which points to a shared importance of N and phosphorus (P) rather than light or tem-perature in driving the magnitude of nutrient limitation across these systems. Ultimately, I pro-pose that across large ranges in habitat variables, widespread nutrient limitation of Arctic fresh-waters constrain other climate change effects on ecosystem functions. The results presented in this thesis will promote better predictions of climate change effects on Boreal to Arctic stream ecosystem functioning.
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| 3. |
- Lundin, Erik, 1982-
(författare)
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The role of inland waters in the carbon cycle at high latitudes
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Understanding the drivers of climate change requires knowledge about the global carbon (C) cycle. Although inland waters play an important role in the C cycle by emitting and burying C, streams and lakes are in general overlooked in bottom-up approached C budgets. In this thesis I estimated emissions of carbon dioxide (CO2) and methane (CH4) from all lakes and streams in a 15 km2 subarctic catchment in northern Sweden, and put it in relation to the total catchment C exchange. I show that high-latitude aquatic systems in general and streams in particular are hotspots for C emission to the atmosphere. Annually, the aquatic systems surveyed in this study emitted about 10.8 ± 4.9 g C m-2 yr-1 (ca. 98 % as CO2) which is more than double the amount of the C laterally exported from the catchment. Although the streams only covered about 4% of the total aquatic area they emitted ca. 95% of the total aquatic C emission. For lake emissions, the ice break-ups were the most important annual events, counting for ca. 45% of the emissions. Overall, streams dominated the aquatic CO2 emission in the catchment while lakes dominated CH4 emission, 96 % and 62 % of the totals, respectively. When summing terrestrial and aquatic C fluxes together it showed that the aquatic emissions alone account for approximately two thirds of the total annual catchment C loss. The consequence of not including inland waters in bottom-up derived C budgets is therefore a risk of overestimating the sink capacity of the subarctic landscape. However, aquatic systems can also act as C sinks, by accumulating C in sediment and thereby storing C over geological time frames. Sediment C burial rates were estimated in six lakes from a chronology based on 210Pb dating of multiple sediment cores. The burial rate ranged between 5 - 25 g C m-2 yr-1, which is of the same magnitude as lake C emissions. I show that the emission:burial ratio is about ten times higher in boreal compared to in subarctic-arctic lakes. These results indicate that the balance between lakes C emission and burial is both directly and indirectly dependent on climate. This process will likely result in a future increase of C emissions from high-latitude lakes, while the C burial capacity of these same lakes sediments weaken.
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| 4. |
- Olsson, Rickard, 1969-
(författare)
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Surface reactions on mineral particles controlling the hydrolysis of glucose phosphates
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Phosphorus (P) is an essential nutrient. A significant amount of soil P may be in the form of organophosphates. Due to the size of these compounds, hydrolysis is often required before P can be assimilated by organisms. Hydrolysis may be mediated by mineral surfaces, or catalyzed by extra cellular enzymes. Since both organophosphates and enzymes have a strong affinity for environmental particles, a study of the hydrolysis of organophosphates must focus on reactions at the water/particle interface. This thesis is a summary of four papers, discussing the adsorption, desorption, and abiotic and enzymatic hydrolysis of glucose-1-phosphate (G1P) and glucose-6-phosphate (G6P) in aqueous goethite suspensions. A new technique for simultaneous infrared and potentiometric titrations (SIPT) allowed in-situ measurements of the interfacial reactions. It was found that glucose phosphates form pH-dependent inner sphere complexes on goethite, which coordinate in a monodentate fashion, and are stabilized by hydrogen bonding. Desorption involves a change in speciation of the surface complexes, illustrating the difficulty in determining desorption rates for individual complexes. The surface mediated hydrolysis is primarily base catalyzed for G1P, and acid catalyzed for G6P. The difference is partly due to electronic factors, and partly to differences in glucose group/goethite interactions. Considerably more extensive is the hydrolysis catalyzed by an acid phosphatase (AcPase). The rate of the enzymatic hydrolysis are strongly dependent on the glucose phosphate surface coverage, showing that surface properties affect the adsorption mode of enzymes, and thus their catalytic activity. In solution, AcPase showed a greater specificity towards G6P, but this specificity was partly lost after adsorption onto goethite.
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| 5. |
- Rocher-Ros, Gerard
(författare)
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Biophysical controls on CO2 evasion from Arctic inland waters
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- CO2 evasion to the atmosphere from inland waters is a major component of the global carbon (C) cycle. Yet spatial patterns of CO2 evasion and the sources of C that fuel evasion remain poorly understood. In this thesis, I use detailed measurements of biological and physical drivers of CO2 evasion to assess how C is transformed and evaded from inland waters in the Arctic (Northern Scandinavia and Alaska). I found that lake size was a master variable controlling lake CO2 evasion in an Arctic catchment and that large lakes play a major role at the landscape scale. In stream networks, I found that catchment topography shapes patterns of CO2 evasion by dictating unique domains with high lateral inputs of C, other domains where biological processes were dominant, and domains where physical forces promoted degassing to the atmosphere. Together, these topographically driven domains created a strong spatial heterogeneity that biases regional and global estimates of CO2 evasion. Further, I found that photosynthetic activity in Arctic streams can produce a large change in CO2 concentrations from night to day, and as a result CO2 evasion is up to 45% higher during night than day. The magnitude of the diel change in CO2 was also affected by the turbulence of the stream and photo-chemical production of CO2. Overall, this thesis offers important insights to better understand landscape patterns of CO2 evasion from inland waters, and suggests that stream metabolic processes largely determine the fate of the C delivered from Arctic soils.
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| 6. |
- Esberg, Camilla, 1977-
(författare)
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Phosphorus availability and microbial respiration across biomes : from plantation forest to tundra
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Phosphorus is the main limiting nutrient for plant growth in large areas of the world and the availability of phosphorus to plants and microbes can be strongly affected by soil properties. Even though the phosphorus cycle has been studied extensively, much remains unknown about the key processes governing phosphorus availability in different environments.In this thesis the complex dynamics of soil phosphorus and its availability were studied by relating various phosphorus fractions and soil characteristics to microbial respiration kinetics. The soils used represent a range of aluminium, iron, carbon and total phosphorus content, and were located in four different biomes: subtropical forest, warm temperate forest, boreal forest and tundra.The results showed that NaOH extractable phosphorus, a fraction previously considered to be available to plants only over long time scales, can be accessed by microbes in days or weeks. Microbial phosphorus availability was not related to aluminium or iron content in any of the studied systems, not even in highly weathered soils with high aluminium and iron content. This is in contrast with other studies of soils with high sorption capacity and shows the variability of factors that govern phosphorus availability in different environments.In the boreal forest chronosequence, no difference could be seen with age in total phosphorus content or concentrations of occluded phosphorus forms. However, there were lower concentrations of labile phosphorus forms in older systems, which were correlated with a decrease in microbial respiration. This was most likely related to organic matter quality in the system, and not to geochemical factors.Phosphorus availability was linked to differences in topography (water regime) and vegetation in the tundra ecosystems. The results suggest that the availability of phosphorus, both for microbes and plants, was lower on the meadow vegetation sites compared to the two types of heath vegetation.Many factors are important for phosphorus availability in soils, but these results suggest that microbes can access less available phosphorus if not restricted by carbon, and this may be important in regard to forest management practices as well as effects of environmental change.
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| 7. |
- Haddad, Lenny, et al.
(författare)
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Small molecules dominate organic phosphorus in NaOH-EDTA extracts of soils as determined by 31P NMR
- 2024
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Ingår i: Science of the Total Environment. - : Elsevier. - 0048-9697 .- 1879-1026. ; 931
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the composition of organic phosphorus (P) in soils is relevant to various disciplines, from agricultural sciences to ecology. Despite past efforts, the precise nature of soil organic P remains an enigma, especially that of the orthophosphate monoesters, which dominate 31P NMR spectra of NaOH-EDTA extracts of soils worldwide. The monoester region often exhibits an unidentified, broad background believed to represent high molecular weight (MW) P. We investigated this monoester background using 1D 31P NMR and 2D 1H[sbnd]31P NMR, as well as 31P transverse relaxation (T2) measurements to calculate its intrinsic linewidth and relate it to MW. Analyzing seven soils from different ecosystems, we observed linewidths of 0.5 to 3 Hz for resolved monoester signals and the background, indicating that it consists of many, possibly >100, sharp signals associated with small (<1.5 kDa) organic P molecules. This result was further supported by 2D 1H[sbnd]31P NMR spectra revealing signals not resolved in the 1D spectra. Our findings align with 31P NMR studies detecting background signals in soil-free samples and modern evidence that alkali-soluble soil organic matter consists of self-assemblies of small organic compounds mimicking large molecules.
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| 8. |
- Vincent, Andrea, et al.
(författare)
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Soil phosphorus forms show only minor changes across a 5000-year-old boreal wildfire chronosequence
- 2022
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Ingår i: Biogeochemistry. - : Springer. - 0168-2563 .- 1573-515X. ; 159, s. 15-32
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Tidskriftsartikel (refereegranskat)abstract
- Wildfire is the main disturbance in most boreal forests. In the prolonged absence of wildfire, ecosystem retrogression occurs, which is characterized by reduced productivity, plant biomass and belowground process rates. Previous evidence suggests that phosphorus (P) decreases during retrogression, but the mechanisms involved remain poorly understood. Here we use 1-D 31P and 2-D, 1H-31P NMR to characterize changes in humus P composition across a 5000 year post-fire chronosequence in northern Sweden, to understand why P availability declines during long term fire absence. Against expectations, humus P composition varied only modestly with increasing time since fire. Using a method to back-calculate the in situ soil organic P speciation, we found that it was dominated by biologically active compounds such as RNA (41%), phospholipids (28%) and DNA (22%). The concentration of DNA and pyrophosphate was 19% and 29% lower, respectively, on infrequently burnt than recently burnt islands, and the concentration of DNA, phospholipids and nucleotides was positively correlated with net primary productivity (NPP). Given the lack of evidence for the accumulation of “recalcitrant” P or a geochemical P sink, reductions in P availability during retrogression may be associated with impaired P cycling through slower decomposition rates, and increasing humus depth separating surface humus from P-rich mineral soil. Our findings align with observed negative relationships between NPP and organic P concentration across other chronosequences. They also suggest that changing fire regimes in the boreal zone could indirectly affect the P cycle through changes in NPP and soil microflora rather than through changes in humus P composition.
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