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1.
  • Arevalo-Martinez, D. L., et al. (författare)
  • Ideas and perspectives: Land-ocean connectivity through groundwater
  • 2023
  • Ingår i: Biogeosciences. - : Copernicus GmbH. - 1726-4170 .- 1726-4189. ; 20:3, s. 647-662
  • Tidskriftsartikel (refereegranskat)abstract
    • For millennia, humans have gravitated towards coastlines for theirresource potential and as geopolitical centres for global trade. A basicrequirement ensuring water security for coastal communities relies on adelicate balance between the supply and demand of potable water. Theinteraction between freshwater and saltwater in coastal settings is,therefore, complicated by both natural and human-driven environmentalchanges at the land-sea interface. In particular, ongoing sea-level rise,warming and deoxygenation might exacerbate such perturbations. In thiscontext, an improved understanding of the nature and variability ofgroundwater fluxes across the land-sea continuum is timely yet remains outof reach. The flow of terrestrial groundwater across the coastal transitionzone and the extent of freshened groundwater below the present-dayseafloor are receiving increased attention in marine and coastal sciencesbecause they likely represent a significant yet highly uncertain componentof (bio)geochemical budgets and because of the emerging interest in thepotential use of offshore freshened groundwater as a resource. At the sametime, "reverse" groundwater flux from offshore to onshore is of prevalentsocio-economic interest, as terrestrial groundwater resources arecontinuously pressured by over-pumping and seawater intrusion in many coastalregions worldwide. An accurate assessment of the land-ocean connectivitythrough groundwater and its potential responses to future anthropogenicactivities and climate change will require a multidisciplinary approachcombining the expertise of geophysicists, hydrogeologists, (bio)geochemistsand modellers. Such joint activities will lay the scientific basis forbetter understanding the role of groundwater in societally relevant issuessuch as climate change, pollution and the environmental status of thecoastal oceans within the framework of the United Nations SustainableDevelopment Goals. Here, we present our perspectives on future researchdirections to better understand land-ocean connectivity through groundwater,including the spatial distributions of the essential hydrogeologicalparameters, highlighting technical and scientific developments and brieflydiscussing the societal relevance of that connectivity in rapidly changing coastal oceans.
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2.
  • Virtasalo, J.J., et al. (författare)
  • Pyritic event beds and sulfidized Fe (oxyhydr)oxide aggregates in metalliferous black mudstones of the Paleoproterozoic Talvivaara formation, Finland
  • 2015
  • Ingår i: Earth and Planetary Science Letters. - : Elsevier BV. - 0012-821X .- 1385-013X. ; 432, s. 449-460
  • Tidskriftsartikel (refereegranskat)abstract
    • The Paleoproterozoic, 2.0–1.9 Ga Talvivaara formation of Finland was deposited during the Shunga Event, a worldwide episode of enhanced accumulation of organic-rich sediments in the aftermath of the Lomagundi–Jatuli carbon isotope excursion. Sulfidic carbonaceous mudstones in the Talvivaara formation contain one of the largest known shale-hosted nickel deposits. In order to gain new insight into this Shungian sedimentary environment, sedimentological, petrographical and in situ S and Fe isotopic microanalyses were carried out on samples representing depositional and early-diagenetic conditions. The event-bedded lithology with tidal signatures in the organic-rich mudstones strongly indicates deposition from predominantly river-delivered mud on a highly-productive coastal area, below storm-wave base. The riverine supply of phosphorus, sulfate and iron supported high primary productivity and resulted in strong lateral and vertical chemical gradients in the nearshore waters with a shallow oxic surface layer underlain by euxinic water. The stratigraphic upper part of the Talvivaara formation contains banded intervals of thin alternating pyrite beds and carbonaceous mudstone beds. The pyrite beds were deposited by seaward excursions of the concentrated, acidic Fe-rich river plume subsequent to droughts or dry seasons, which led to intense pyrite precipitation upon mixing with euxinic waters. δS34 and δFe56 values of the bedded pyrite (median δS34=−10.3‰ and δFe56=−0.79‰) are consistent with the reaction of dissolved Fe(II) with H2S from bacterial sulfate reduction. Organic-rich clayey Fe-monosulfide-bearing granules were transported from the muddy estuary, and enclosed in Fe (oxyhydr)oxide aggregates that were forming by wave and current reworking in nearshore accumulations of river-delivered iron. The isotopic composition of these presently pyrrhotitic inclusions (median δS34=−3.3‰ and δFe56=−1.6‰) indicates microbial iron reduction. The Fe (oxyhydr)oxide aggregates were transported in muddy debris flows to the distal euxinic seafloor. Their Fe (oxyhydr)oxide matrix was replaced by pyrite (median δS34=+5.8‰ and δFe56=+0.81‰) at shallow sediment depths with 34S and 56Fe-enriched porewater. Wavy-crinkly laminae of possible microbial origin developed on the euxinic seafloor during low sedimentation. These results indicate episodic deposition at seasonal to multiannual time scales. δS34 and δFe56 values in the studied Fe-sulfides provide evidence of microbial isotope fractionation processes and syndepositional and early-diagenetic origin, finding no support for the previously proposed local hydrothermal activity in the Talvivaara mudstones.
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3.
  • Harazim, Dario, et al. (författare)
  • Exceptional sulfur and iron isotope enrichment in millimetre-sized, early Palaeozoic animal burrows
  • 2020
  • Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322. ; 10:1
  • Tidskriftsartikel (refereegranskat)abstract
    • Pyrite-δ34S and -δ56Fe isotopes represent highly sensitive diagnostic paleoenvironmental proxies that express high variability at the bed (< 10 mm) scale that has so far defied explanation by a single formative process. This study reveals for the first time the paleoenvironmental context of exceptionally enriched pyrite-δ34S and -δ56Fe in bioturbated, storm-reworked mudstones of an early Ordovician storm-dominated delta (Tremadocian Beach Formation, Bell Island Group, Newfoundland). Very few studies provide insight into the low-temperature sulfur and iron cycling from bioturbated muddy settings for time periods prior to the evolution of deep soil horizons on land. Secondary ion mass spectroscopy (SIMS) analyses performed on Beach Formation muddy storm event beds reveal spatially distinct δ34S and δ56Fe values in: (a) tubular biogenic structures and trails (δ34S ~ +40‰; δ56Fe ~ −0.5‰), (b) silt-filled Planolites burrows (δ34S ~ +40‰; δ56Fe ~ +0.5 to + 2.1‰), and (c) non-bioturbated mudstone (δ34S ~ +35‰; δ56Fe ~ +0.5‰). δ34S values of well above + 40.0‰ indicate at least some pyrite precipitation in the presence of a 34S-depleted pore water sulfide reservoir, via closed system (Raleigh-type) fractionation. The preferential enrichment of 56Fe in Planolites burrows is best explained via microbially-driven liberation of Fe(II) from solid iron parent phases and precipitation from a depleted 54Fe dissolved Fe(II) reservoir. Rigorous sedimentological analysis represents a gateway to critically test the paleoenvironmental models describing the formation of a wide range of mudstones and elucidates the origins of variability in the global stable S and Fe isotope record.
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4.
  • Hyttinen, O., et al. (författare)
  • Holocene stratigraphy of the Ångermanälven River estuary, Bothnian Sea
  • 2017
  • Ingår i: Geo-Marine Letters. - : Springer. - 0276-0460 .- 1432-1157. ; 37:3, s. 273-288
  • Tidskriftsartikel (refereegranskat)abstract
    • This study explores the Holocene depositional succession at the IODP Expedition 347 sites M0061 and M0062 in the vicinity of the Ångermanälven River estuary in the Bothnian Sea sector of the Baltic Sea in northern Scandinavia. Site M0061 is located in a coastal offshore setting (87.9 m water depth), whereas site M0062 is fully estuarine (69.3 m water depth). The dataset comprises acoustic profiles and sediment cores collected in 2007 and late 2013 respectively. Three acoustic units (AUs) were recognized. Lowermost AU1 is interpreted as a poorly to discontinuous stratified glaciofluvial deposit, AU2 as a stratified conformable drape of glaciolacustrine origin, and AU3 as a poorly stratified to stratified mud drift. A strong truncating reflector separates AU2 and AU3. Three lithological units (LUs) were defined in the sediment cores. LU1 consists of glaciofluvial sand and silt gradating into LU2, which consists of glaciolacustrine varves. A sharp contact interpreted as a major unconformity separates LU2 from the overlying LU3 (brackish-water mud). In the basal part of LU3, one debrite (site M0061) or two debrites (site M0062) were recognized. Information yielded from sediment physical properties (magnetic susceptibility, natural gamma ray, dry bulk density), geochemistry (total carbon, total organic carbon, total inorganic carbon and nitrogen), and grain size support the LU division. The depositional succession was formally subdivided into two alloformations: the Utansjö Alloformation and overlying Hemsön Alloformation; the Utansjö Alloformation was further subdivided into two lithostratigraphic formations: the Storfjärden and Åbordsön formations. The Storfjärden (sandy outwash) and Åbordsön (glaciolacustrine rhythmite) formations represent a glacial retreat systems tract, which started at ca. 10.6 kyr BP. Their deposition was mainly controlled by meltwater from the retreating ice margin, glacio-isostatic land uplift and the regressive (glacial) lake level. The Hemsön Alloformation (organic-rich brackish-water mud) represents a period of forced regression, starting possibly at ca. 9.5 kyr BP. At about 7 kyr BP, brackish water reached the study area as a result of the mid-Holocene marine flooding of the Baltic Sea Basin, but the rapid land uplift soon surpassed the associated (Littorina) transgression. Changed near-bottom current patterns, caused by the establishment of a permanent halocline, and the reduced sediment consistency caused by increased organic deposition resulted in a sharp and erosional base of the brackish-water mud. Estuarine processes and salinity stratification at site M0062 started to play a more important role. This study applies a combined allostratigraphic and lithostratigraphic approach over the conventional Baltic Sea stages. This approach makes it more straightforward to study this Baltic Sea deglaciation–postglacial sequence and compare it to other formerly glaciated shallow sea estuaries.
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5.
  • Virtasalo, Joonas J., et al. (författare)
  • Pyritic and baritic burrows and microbial filaments in postglacial lacustrine clays in the northern Baltic Sea
  • 2010
  • Ingår i: Journal of the Geological Society. - : Geological Society of London. - 0016-7649 .- 2041-479X. ; 167:6, s. 1185-1198
  • Tidskriftsartikel (refereegranskat)abstract
    • Holocene postglacial lacustrine clays in the northern Baltic Sea were studied for ichnofossils,petrography, and microscale elemental and 34S/32S composition to understand the impact of benthos-producedorganic matrices on the early diagenesis of sediments. X-radiographs of these clays display intense burrowmottling with discrete Palaeophycus, ‘Mycellia’ and rare Arenicolites. Small burrow-like and irregularlyshaped concretions were separated from these clays. The burrow-like concretions are composed of framboidalpyrite and poorly crystalline FeS2 cement. They formed within worm-produced burrows by the decompositionof mucous coatings on the burrow walls by sulphate reduction. 34SCDT composition of the framboidsindicates saline inflows from the North Sea as the sulphate source. The irregular concretions are microcrystallinepyritic masses that formed in pore spaces with less reactive organic compounds. Their 34SCDT valuesreflect precipitation from the ambient porewater sulphate by sulphate reduction. The burrow-like and irregularconcretions are microcrystalline barite in the lower parts of the clays. ‘Mycellia’ are mineral-replacedfilaments produced by large sulphur-oxidizing bacteria or mycelial fungi. They concentrate in monosulphidebands in the lower substrate levels, but are associated with organic patches upward. This study demonstratesthat substantial amounts of pyrite formed within organic matrices close to the sediment–water interface. Thisdiffers from previous studies that proposed a deeper-burial origin and allochthonous sulphur source.
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6.
  • Yu, Changxun, et al. (författare)
  • Iron behavior in a northern estuary: Large pools of non-sulfidized Fe(II) associated with organic matter
  • 2015
  • Ingår i: Chemical Geology. - : Elsevier BV. - 0009-2541 .- 1872-6836. ; 413, s. 73-85
  • Tidskriftsartikel (refereegranskat)abstract
    • The estuaries of the Northern Baltic Sea (Gulf of Bothnia) receive an abundance of diagenetically reactive catchment-derived Fe, which is to a large degree complexed with organicmatter or present as Fe (hydr-) oxides. However, our understanding of sedimentary Fe diagenesis in these estuaries is limited. To address this limitation, the present study examines Fe geochemistry in a 3.5-m-thick estuarine benthic mud layer and three samples of suspended particulate matter of a catchment on the eastern Gulf of Bothnia. The age-depth model of the mud, constructed on the basis of sedimentary features as well as Cs-137 and aquatic plant C-14 determinations, revealed a high average rate of sedimentation (5 cm . yr(-1)) for the upper mud unit (0-182.5 cm, corresponding to 1973-2011), in response to intensive land-use (ditching) in the catchment since the 1960s and 1970s. The intensive land-use has resulted in a strong increase in the Fe accumulation rates, but has not caused a recognizable impact on the diagenetic processes of Fe including features such as degree of sulfidization and solid-phase partitioning. Iron X-ray absorption spectroscopy (XAS) indicated that in the suspended particulate matter, large proportions (47-58%) of Fe occur as Fe(III)-organic complexes and 2-line ferrihydrite. In the mud, the former is completely reduced, and reactive Fe (defined via extraction with 1 MHCl) was high throughout (52-68%, median = 61%) and strongly dominated by Fe(II). This reactive Fe(II) pool was sulfidized to only a limited extent (degree of reactive sulfidization = 11-26%, median = 17%). This phenomenon is attributed to the brackish-water conditions (i.e. low in sulfate) and the abundant input of reactive Fe(III) from the catchment, leading to a surplus of dissolved Fe2+ over dissolved sulfide in the sediment. The low availability of dissolved sulfide, in combination with the high average sedimentation rate, limits the formation of intermediate reduced sulfur compounds at the water-sediment interface, thereby retarding the conversion of FeS into pyrite (ratios of pyrite-S to AVS = 0.17-1.73, median = 0.37; degree of pyritization = 1-17%, median = 3%). Iron XAS, in combination with wavelet transform analysis, of representative sediment segments from the upper and lower mud units suggests that the non-sulfidized Fe(II) pool is dominantly complexed by organic matter, with the remaining Fe(II) occurring as mackinawite. This has implications for the understanding of early Fe diagenesis in settings with a high input of organic matter and relatively low supply of sulfate. (C) 2015 Elsevier B.V. All rights reserved.
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7.
  • Yu, Changxun, et al. (författare)
  • Manganese accumulation and solid-phase speciation in a 3.5 m thick mud sequence from the estuary of an acidic and Mn-rich creek, northern Baltic Sea
  • 2016
  • Ingår i: Chemical Geology. - : Elsevier BV. - 0009-2541 .- 1872-6836. ; 437, s. 56-66
  • Tidskriftsartikel (refereegranskat)abstract
    • In sediments, manganese (Mn) is typically enriched in the form of authigenic Mn hydroxides at the water-sediment interface where intensive redox cycling of Mn occurs. Here we show, based on existing hydrochemical and geochemical (sediment core) data and new detailed chemical and mineralogical characterization of a 3.5 m long sediment core from a Boreal estuary, that the behavior of Mn can be profoundly different and more complex in estuarine settings receiving an abundance of terrestrial Mn. The most notable feature in the 3.5 m long sediment core is two depth intervals (60-155 cm and 181-230 cm) where there are strong fine-scale variations in Mn concentrations with peaks episodically reaching up to 10-25 g kg(-1) and 6.7-12 g kg(-1), respectively. X-ray absorption spectroscopy and sequential chemical extraction show that Mn occurs mainly as authigenic rhodochrosite at these two depth intervals and is mainly surface-sorbed in other sections with relatively low and stable Mn concentrations. The data suggests that the strong fine-scale variations in Mn concentrations are a reflection of the extent of formation and settling of Mn hydroxides, the precursors of the authigenic rhodochrosite (and also of the surface-sorbed Mn), rather than Mn input to the estuary or redox-related Mn translocation within the sediment. There was agreement between the results of linear combination fitting of extended X-ray absorption fine structure data and a 7-step sequential chemical extraction (SCE) in terms of quantification of surface-sorbed Mn species, whereas the SCE experiment failed to fractionate a majority of rhodochrosite into SCE step-2 (1M NH4-acetate at pH 6), which is frequently employed to dissolve carbonate. We ascribe this discrepancy to only partial dissolution of rhodochrosite in the weakly acidic (pH = 6) NH4-acetate leach.
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8.
  • Åström, Mats E., 1963-, et al. (författare)
  • Extensive accumulation of rare earth elements in estuarine sediments affected by leaching of acid sulfate soils
  • 2020
  • Ingår i: Boreal Environment Research. - : Finnish Environmental Inst. - 1239-6095 .- 1797-2469. ; 25, s. 105-120
  • Tidskriftsartikel (refereegranskat)abstract
    • The concentrations, loads and speciation of rare earth elements (REEs) were studied in a 3.5 m thick mud depositional succession from an estuary in the Gulf of Bothnia. The uppermost 182.5 cm of the mud, estimated to have deposited from the early 1970s to 2011 (sampling year), had very high REE concentrations (596-1456 ppm) and accumulation rates (5.2-28 g m(-2) year(-1)). This was explained by large REE export from acid sulfate soils after they became efficiently drained with modern drainage techniques. Geochemical and synchrotron-based spectroscopic (XANES) analyses showed that the REEs in the mud are relatively firmly bound in non-clastic phases, likely adsorbed by clay minerals and also to some extent by iron oxyhydroxides. Below 182.5 cm, the REE concentrations successively decreased down to background values at the base at 3.5 m, reflecting less efficient drainage and leaching of the acid sulfate soils in previous decades and centuries.
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9.
  • Kotilainen, Aarno T., et al. (författare)
  • Echoes from the Past : A Healthy Baltic Sea Requires More Effort
  • 2014
  • Ingår i: Ambio. - : Springer Science and Business Media LLC. - 0044-7447 .- 1654-7209. ; 43:1, s. 60-68
  • Tidskriftsartikel (refereegranskat)abstract
    • Integrated sediment multiproxy studies and modeling were used to reconstruct past changes in the Baltic Sea ecosystem. Results of natural changes over the past 6000 years in the Baltic Sea ecosystem suggest that forecasted climate warming might enhance environmental problems of the Baltic Sea. Integrated modeling and sediment proxy studies reveal increased sea surface temperatures and expanded seafloor anoxia (in deep basins) during earlier natural warm climate phases, such as the Medieval Climate Anomaly. Under future IPCC scenarios of global warming, there is likely no improvement of bottom water conditions in the Baltic Sea. Thus, the measures already designed to produce a healthier Baltic Sea are insufficient in the long term. The interactions between climate change and anthropogenic impacts on the Baltic Sea should be considered in management, implementation of policy strategies in the Baltic Sea environmental issues, and adaptation to future climate change.
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10.
  • Lougheed, Bryan C., et al. (författare)
  • Using an independent geochronology based on palaeomagnetic secular variation (PSV) and atmospheric Pb deposition to date Baltic Sea sediments and infer 14C reservoir age
  • 2012
  • Ingår i: Quaternary Science Reviews. - : Elsevier BV. - 0277-3791. ; 42, s. 43-58
  • Tidskriftsartikel (refereegranskat)abstract
    • Dating of sediment cores from the Baltic Sea has proven to be difficult due to uncertainties surrounding the C-14 reservoir age and a scarcity of macrofossils suitable for dating. Here we present the results of multiple dating methods carried out on cores in the Gotland Deep area of the Baltic Sea. Particular emphasis is placed on the Littorina stage (8 ka ago to the present) of the Baltic Sea and possible changes in the C-14 reservoir age of our dated samples. Three geochronological methods are used. Firstly, palaeomagnetic secular variations (PSV) are reconstructed, whereby ages are transferred to PSV features through comparison with varved lake sediment based PSV records. Secondly, lead (Pb) content and stable isotope analysis are used to identify past peaks in anthropogenic atmospheric Pb pollution. Lastly, C-14 determinations were carried out on benthic foraminifera (Elphidium spec.) samples from the brackish Littorina stage of the Baltic Sea. Determinations carried out on smaller samples (as low as 4 mu g C) employed an experimental, state-of-the-art method involving the direct measurement of CO2 from samples by a gas ion source without the need for a graphitisation step - the first time this method has been performed on foraminifera in an applied study. The PSV chronology, based on the uppermost Littorina stage sediments, produced ten age constraints between 6.29 and 1.29 cal ka BP, and the Pb depositional analysis produced two age constraints associated with the Medieval pollution peak. Analysis of PSV data shows that adequate directional data can be derived from both the present Littorina saline phase muds and Baltic Ice Lake stage varved glacial sediments. Ferrimagnetic iron sulphides, most likely authigenic greigite (Fe3S4), present in the intermediate Ancylus Lake freshwater stage sediments acquire a gyroremanent magnetisation during static alternating field (AF) demagnetisation, preventing the identification of a primary natural remanent magnetisation for these sediments. An inferred marine reservoir age offset (Delta R) is calculated by comparing the foraminifera C-14 determinations to a PSV & Pb age model. This Delta R is found to trend towards younger values upwards in the core, possibly due to a gradual change in hydrographic conditions brought about by a reduction in marine water exchange from the open sea due to continued isostatic rebound. (C) 2012 Elsevier Ltd. All rights reserved.
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11.
  • Paul, K. Mareike, et al. (författare)
  • Sedimentary molybdenum and uranium : Improving proxies for deoxygenation in coastal depositional environments
  • 2023
  • Ingår i: Chemical Geology. - : Elsevier BV. - 0009-2541. ; 615
  • Tidskriftsartikel (refereegranskat)abstract
    • Sedimentary molybdenum (Mo) and uranium (U) enrichments are widely used to reconstruct changes in bottom water oxygen conditions in aquatic environments. Until now, most studies using Mo and U have focused on restricted suboxic-euxinic basins and continental margin oxygen minimum zones (OMZs), leaving mildly reducing and oxic (but eutrophic) coastal depositional environments vastly understudied. Currently, it is unknown: (1) to what extent Mo and U enrichment factors (Mo- and U-EFs) can accurately reconstruct oxygen conditions in coastal sites experiencing mild deoxygenation, and (2) to what degree secondary (depositional environmental) factors impact Mo- and U-EFs. Here we investigate 18 coastal sites with varying bottom water redox conditions, which we define by means of five “redox bins”, ranging from persistently oxic to persistently euxinic, from a variety of depositional environments. Our results demonstrate that Mo- and U-EF-based redox proxies and sedimentary Mo and U contents can be used to differentiate bottom water oxygen concentration among a range of modern coastal depositional environments. This is underpinned by the contrasting EFs of Mo and U along the redox gradient, which shows a substantial difference of Mo-EFs between redox bins 3–5 (ir/regularly suboxic – ir/regularly dysoxic – persistently oxic) and of U-EFs between redox bins 1–2 (persistently euxinic – ir/regularly euxinic). Surprisingly, we observe comparatively low redox proxy potential for U in environments of mild deoxygenation (redox bins 3–5). Further, we found that secondary factors can bias Mo-and U-EFs to such an extent that EFs do not reliably reflect bottom water redox conditions. We investigate the impact of limited Mo sedimentary sequestration in sulfidic depositional environments (i.e., the “basin reservoir effect”, equilibrium with FeMoS4), Fe/Mn-(oxy)(hydr)oxide “shuttling”, oxidative dissolution, the sulfate methane transition zone in the sediment, sedimentation rate, and the local Al background on Mo- and U-EFs.
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12.
  • Virtasalo, Joonas J., et al. (författare)
  • Enrichment of trace metals from acid sulfate soils in sediments of the Kvarken Archipelago, eastern Gulf of Bothnia, Baltic Sea
  • 2020
  • Ingår i: Biogeosciences. - : Copernicus Gesellshaft MBH. - 1726-4170 .- 1726-4189. ; 17:23, s. 6097-6113
  • Tidskriftsartikel (refereegranskat)abstract
    • Rivers draining the acid sulfate soils of western Finland are known to deliver large amounts of trace metals with detrimental environmental consequences to the recipient estuaries in the eastern Gulf of Bothnia, northern Baltic Sea. However, the distribution of these metals in the coastal sea area and the relevant metal transport mechanisms have been less studied. This study investigates the spatial and temporal distribution of metals in sediments at nine sites in the Kvarken Archipelago, which is the recipient system of Laihianjoki and Sulvanjoki rivers that are impacted by acid sulfate soils. The contents of Cd, Co, Cu, La, Mn, Ni, and Zn increased in the cores during the 1960s and 1970s as a consequence of intensive artificial drainage of the acid sulfate soil landscape. Metal deposition has remained at high levels since the 1980s. The metal enrichment in sea floor sediments is currently visible at least 25 km seaward from the river mouths. Comparison with sediment quality guidelines shows that the metal contents are very likely to cause detrimental effects on marine biota more than 12 km out from the river mouths. The dynamic sedimentary environment of the shallow archipelago makes these sediments potential future sources of metals to the ecosystem. Finally, the strong association of metals and nutrients in the same sediment grain size class of 2-6 pm suggests that the transformation of dissolved organic matter and metals to metal-organic aggregates at the river mouths is the key mechanism of seaward trace metal transport, in addition to co-precipitation with Mn oxyhydroxides identified in previous studies. The large share of terrestrial organic carbon in the total organic C in these sediments (interquartile range - 39 %-48 %) highlights the importance of riverine organic matter supply. These findings are important for the estimation of environmental risks and the management of biologically sensitive coastal sea ecosystems.
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13.
  • Wasiljeff, Joonas, et al. (författare)
  • Morphology-Dependent Magnetic Properties in Shallow-Water Ferromanganese Concretions
  • 2024
  • Ingår i: Geochemistry Geophysics Geosystems. - 1525-2027. ; 25:5
  • Tidskriftsartikel (refereegranskat)abstract
    • Ferromanganese concretions commonly occur in shallow-water coastal regions worldwide. In the Baltic Sea, they can record information about past and present underwater environments and could be a potential source for critical raw materials. We report on their microstructural characteristics and magnetic properties and link them to their formation mechanisms and environmental significance. Microstructural investigations from nano- and micro-computed tomography, electron microscopy, and micro-X-ray fluorescence elemental mapping reveal diverse growth patterns within concretions of different morphologies. Alternating Fe- and Mn-rich growth bands indicate fluctuating redox conditions during formation. Bullet-shaped magnetofossils, produced by magnetotactic bacteria, are present, which suggests the influence of bacterial activity on concretion formation. Spheroidal concretions, which occur in deeper and more tranquil environments, have enhanced microbial biomineralization and magnetofossil preservation. Conversely, crusts and discoidal concretions from shallower and more energetic environments contain fewer magnetofossils and have a greater detrital content. Our results provide insights into concretion formation mechanisms and highlight the importance of diagenetic processes, oxygen availability, and bacterial activity in the Baltic Sea.
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14.
  • Yu, Changxun, et al. (författare)
  • Arsenic removal from contaminated brackish sea water by sorption onto Al hydroxides and Fe phases mobilized by land-use
  • 2016
  • Ingår i: Science of the Total Environment. - : Elsevier BV. - 0048-9697 .- 1879-1026. ; 542, s. 923-934
  • Tidskriftsartikel (refereegranskat)abstract
    • This study examines the spatial and temporal distribution patterns of arsenic (As) in solid and aqueous materials along the mixing zone of an estuary, located in the south-eastern part of the Bothnian Bay and fed by a creek running through an acid sulfate (AS) soil landscape. The concentrations of As in solution form (<1 kDa) increase steadily from the creek mouth to the outer estuary, suggesting that inflowing seawater, rather than AS soil, is the major As source in the estuary. In sediments at the outer estuary, As was accumulated and diagenetically cycled in the surficial layers, as throughout much of the Bothnian Bay. In contrast, in sediments in the inner estuary, As concentrations and accumulation rates showed systematical peaks at greater depths. These peaks were overall consistent with the temporal trend of past As discharges from the Ronnskar smelter and the accompanied As concentrations in past sea-water of the Bothnian Bay, pointing to a connection between the historical smelter activities and the sediment-bound As in the inner estuary. However, the concentrations and accumulation rates of As peaked at depths where the smelter activities had already declined, but a large increase in the deposition of Al hydroxides and Fe phases occurred in response to intensified land-use in the mid 1960's and early 1970's. This correspondence suggests that, apart from the inflowing As-contaminated seawater, capture by Al hydroxides, Fe hydroxides and Fe-organic complexes is another important factor for As deposition in the inner estuary. After accumulating in the sediment, the solid-phase As was partly remobilized, as reflected by increased pore-water As concentrations, a process favored by As(V) reduction and high concentrations of dissolved organic matter. (C) 2015 Elsevier B.V. All rights reserved.
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15.
  • Yu, Changxun, 1983-, et al. (författare)
  • Manganese cycling and transport in boreal estuaries impacted by acidic Mn-rich drainage
  • 2024
  • Ingår i: GEOCHIMICA ET COSMOCHIMICA ACTA. - : Elsevier. - 0016-7037 .- 1872-9533 .- 0046-564X. ; 365, s. 136-157
  • Tidskriftsartikel (refereegranskat)abstract
    • As critical transition zones between the land and the sea, estuaries are not only hotspots of hydrogeochemical and microbial processes/reactions, but also play a vital role in processing and transferring terrestrial fluxes of metals and nutrients to the sea. This study focused on three estuaries in the Gulf of Bothnia. All of them expe-rience frequent inputs of acidic and Mn/metal-rich creek waters due to flushing of acid sulfate soils that are widespread in the creeks catchments. Analyzing existing long-term water chemistry data revealed a strong sea-sonal variation of Mn loads, with the highest values in spring (after snow melt) and autumn (after heavy rains). We sampled surface waters, suspended particulate matter (SPM), and sediments from the estuarine mixing zones and determined the loads and solid-phase speciation of Mn as well as the composition and metabolic potentials of microbial communities. The results showed that the removal, cycling, and lateral transport of Mn were governed by similar phases and processes in the three estuaries. Manganese X-ray absorption spectroscopy data of the SPM suggested that the removal of Mn was regulated by silicates (e.g., biotite), organically complexed Mn(II), and MnOx (dominated by groutite and phyllomanganates). While the fractional amounts of silicate-bound Mn(II) were overall low and constant throughout the estuaries, MnOx was strongly correlated with the Mn loadings of the SPM and thus the main vector for the removal of Mn in the central and outer parts of the estuaries, along with organically complexed Mn(II). Down estuary, both the fractional amounts and average Mn oxidation state of the MnOx phases increased with (i) the total Mn loads on the SPM samples and (ii) the relative abundances of several potential Mn-oxidizing bacteria (Flavobacterium, Caulobacter, Mycobacterium, and Pedobacter) in the surface waters. These features collectively suggested that the oxidation of Mn, probably mediated by the potential Mn-oxidizing microorganisms, became more extensive and complete towards the central and outer parts of the es-tuaries. At two sites in the central parts of one estuary, abundant phyllomanganates occurred in the surface sediments, but were converted to surface-sorbed Mn(II) phases at deeper layers (>3-4 cm). The occurrence of phyllomanganates may have suppressed the reduction of sulfate in the surface sediments, pushing down the methane sulfate transition zone that is typically shallow in estuarine sediments. At the outermost site in the estuary, deposited MnOx were reduced immediately at the water-sediment interface and converted most likely to Mn carbonate. The mobile Mn species produced by the Mn reduction processes (e.g., aqueous Mn(II) and ligand complexed Mn(III)) could partly diffuse into the overlying waters and, together with the estuarine Mn loads carried by the surface waters, transfer large amounts of reactive Mn into open coastal areas and subsequently contribute to Mn shuttling and inter-linked biogeochemical processes over the seafloor. Given the widespread occurrence of acid sulfate soils and other sulfidic geological materials on many coastal plains worldwide, the identified Mn attenuation and transport mechanisms are relevant for many estuaries globally.
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16.
  • Åström, Mats E., 1963-, et al. (författare)
  • Sources, transport and sinks of beryllium in a coastal landscape affected by acidic soils
  • 2018
  • Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier. - 0016-7037 .- 1872-9533. ; 232, s. 288-302
  • Tidskriftsartikel (refereegranskat)abstract
    • Beryllium (Be) sources, transport and sinks were studied in a coastal landscape where acidic soils (acid sulfate soils) have developed after drainage of fine-grained sulfide-bearing sediments. The study included the determination of total abundance and speciation of Be in a variety of solid and aqueous materials in both the terrestrial and estuarine parts of the landscape. A major feature was that despite normal (background) Be concentration in the sulfide-bearing sediments, the Be leaching from these sediments after O2-exposure and acid sulfate soil development were extensive, with concentrations up to 76 μg L−1 in soil water, 39 μg L−1 in runoff and 12 μg L−1 in low-order streams. These high Be concentrations were mainly in the solution form (i.e., passing a 1 kilodalton filter) and modelled to be dominated by free Be2+. The extensive Be release within, and leaching from the acid sulfate soils was controlled by pH, with a critical value of 4.0 below which the Be concentrations increased strongly. Although plagioclase and mica were most likely the main carriers of Be within these soils, it is suggested that other minerals such as Be hydroxides, Al hydroxides carrying Be, and Be sulfides are the main contributors of the abundance of dissolved Be in the acidic waters. When the acidic and Be-rich creek water was neutralized in the estuary of relatively low salinity, the dominating solution form of Be was removed by transformation to particles, reflected in the suspended particulate matter that had hydroxylamine hydrochloride extractable Be up to 17 mg kg−1 and ammonium acetate EDTA extractable Be up to 4 mg kg−1. In corresponding pristine materials (parent material of the acid sulfate soils) in the catchment, the median Be extractability with these reagents were only 0.3 and 0.05 mg kg−1, respectively. As the Be-rich suspended particulate matter ultimately became benthic sediment, the Be was preserved in terms of total concentrations but underwent to some extent changes in speciation, including release from hydroxides and concomitant scavenging by organic matter and particle surfaces.
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17.
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