Sulphate reduction - methane oxidation: a potential role of this process in the origin of C isotope environmental record in freshwater carbonates

Jędrysek, M. O.

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Sulphate reduction - methane oxidation: a potential role of this process in the origin of C isotope environmental record in freshwater carbonates

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Jędrysek M. O.

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It is demonstrated that microbial oxidation of organic compounds (including methane), in freshwater sediments, may result in precipitation of carbonates, which may become an important geochemical archive of palaeoenvironmental variations. Most probably low ¹³C value in calcite in eutrophic systems results from an advanced oxidation of organic compounds in turbulent or/and sulphate-rich conditions. Likewise, high ¹³C value in calcite from organic-rich sediments may evidence low red-ox potential of the freshwater system. More advanced studies might help to calibrate a new tool for palaeoenvironmental reconstructions. Oxidation of methane and organic matter results in significant isotope effects in sulphates dissolved in water. Therefore, to better understand the origin of carbon isotope signal in carbonates, concentration and stable isotope measurements in dissolved sulphate (water column), bubble methane and calcite (freshwater sediments) have been carried out in 24 lakes, 2 ponds and 4 rivers in Poland. Dissolved sulphate is a major compound of freshwater systems and sulphur, being an important bioelement, controls many processes in lakes therefore quality of water (e.g. microbial sequestration of organic compounds, inhibitor of methane ebullitive flux). The highest concentration of sulphate has been detected in rivers (85.47 SO₄^2-mg/l) and an artificial lake (70.3 SO₄^{2 -}mg/l) located in the extremely -polluted region called the "Black Triangle". The lowest concentration of sulphate are found in dystrophic and mountain lakes (from 0.5 to about 3 SO₄^2-mg/l ). The lowest δ³⁴S(SO₄^2-) and δ¹⁸O(SO₄^2-) values occur in unpolluted lakes in Eastern Poland (-0.94 and 1.38‰, respectively). The highest δ³⁴S(SO₄^2-) and δ¹⁸O(SO₄^2-) values are found in polluted lakes in western Poland and dystrophic lakes (12.95 and 16.15‰, respectively). It is proposed that δ³⁴S(SO₄^2-) and δ¹⁸O(SO₄^2-13C(CH₄) water column, in a strongly contaminated lake, is observed. This is probably due to a loss of biological buffering potential of the lake accompanied by an active oxidation of methane precursors.

W pracy wykazano, że węglany jeziorne powstałe w wyniku mikrobiologicznego utleniania związków organicznych (w tym metanu), przy redukcji jonów siarczanowych, mogą stanowić ważny geochemiczny zapis zmian środowiskowych. Najprawdopodobniej niskie wartości ¹³C w kalcycie, w rzekach i jeziorach eutroficznych wynikają z silnego utleniania związków organicznych w warunkach turbulencji i/lub podwyższonych stężeń siarczanu. Podobnie, wysokie wartości ¹³C w kalcycie, zawartym w osadach słodkowodnych bogatych w materię organiczną, mogą wskazywać na niski potencjał redox. Na podstawie tego typu badania wydaje się możliwe wykalibrowanie nowego narzędzia do rekonstrukcji palaeośrodowiskowych. Z drugiej strony, utlenianie metanu (związków organicznych) może powodować wzbogacenie rezydualnego jonu siarczanowego w ciężkie izotopy tlenu i siarki. Dlatego, aby lepiej zrozumieć sygnał izotopowy w węglanach jeziornych, wykonano badania stężenia i badania izotopowe siarczanu kolumny wodnej oraz badania metanu i kalcytu w osadach 24 jezior, 2 stawów i 4 rzek w Polsce. Rozpuszczony jon siarczanowy jest jednym z głównych składników rozpuszczonych w wodach jeziornych, a siarka, jako istotny biopierwiastek, wpływa na procesy zachodzące w jeziorach, w tym na jakość wód (mikrobiologiczny rozkład związków organicznych, inhibitor metanogenezy). Najwyższe stężenie jonu siarczanowego stwierdzono w rzekach (85,47 ncentration of sulphate has been detected in rivers (85.47 SO₄^2- mg/l) i sztucznym jeziorze (70,3 SO₄^{2 -}42- mg/l) w regionie silnego zanieczyszczenia (tzw. "Czarny Trójkąt") w Polsce południowo-zachodniej. Najniższe stężenie siarczanu stwierdzono w jeziorach dystroficznych i oligotroficznych - górskich (od 0,5 do 3 mg/l SOSO₄^{2 -}). Najniższe wartości δ³⁴S(SO₄^2-) i δ¹⁸O(SO₄^2-) występują w niezanieczyszczonych jeziorach wschodniej Polski (-0,94 i 1,38‰). Najwyższe wartości δ³⁴S(SO₄^2-) i δ¹⁸O(SO₄^2-) stwierdzono w Polsce zachodniej i jeziorach dystroficznych (12,95 i 16,15‰). Wykazano, że. δ³⁴S(SO₄^2- i δ¹⁸O(SO₄^2-) jezior mogą być dobrym narzędziem do ilościowej charakterystyki antropopresji (kwaśne opady) oraz do monitorowania zmian trofii i procesów redoks związanych z biodegradacją związków organicznych w osadach i kolumnie wodnej. W przeciwieństwie do czystych jezior, jeziora silnie zanieczyszczone jonem siarczanowym wykazują wzrost wartościδ¹³C(CH₄) wraz ze wzrostem głębokości kolumny wodnej. Może to być wskaźnikiem utraty przez jezioro mikrobiologicznej zdolności buforującej.

Słowa kluczowe

fresh water carbon oxygen sulphur methane carbonates sulphates isotopes anthropogenic impact

woda słodka węgiel tlen siarka metan węglany siarczany izotopy antropopresja

Wydawca

Państwowy Instytut Geologiczny - Państwowy Instytut Badawczy

Czasopismo

Polish Geological Institute Special Papers

Rocznik

2005

Tom

Vol. 16

Strony

18--34

Opis fizyczny

Bibliogr. 108 poz., rys., tab., wykr.

Twórcy

autor

Jędrysek M. O.

Institute of Geological Sciences, University of Wrocław, Cybulskiego 30, 50-205 Wrocław, Poland, morion@ing.uni.wroc.pl

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