Light element distributions (N, B, Li) in Baltic Basin bentonites record organic sources

Lynda Williams, Jan Środoń, Warren D. Huff, Norbert Clauer, Richard Hervig

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Abstract

Distributions of nitrogen, boron and lithium were studied in illite-smectite from Ordovician-Silurian K-bentonites in the Baltic Basin. These trace elements are linked to thermal maturation of organic matter, creating fluid signatures that are distinct from those in regionally buried sediments. The fluid chemistry is ideally recorded in authigenic illite within the K-bentonite because B substitutes in tetrahedral sites of illite, Li in octahedral sites, and N is fixed in the interlayers as NH4+. Three nanometric size fractions of illite (<0.02. μm; 0.02-0.05. μm; 0.05-0.2. μm) were compared within each sample. Boron and Li-isotope variations (>10‰) among these size fractions relate mainly to changes in fluid composition during illite growth.Bentonite (volcanic ash) layers mark stratigraphic timelines, while illitization of the bentonite (K-bentonite) varies as a function of burial and tectonic temperature gradients. In the central Baltic Basin, bentonites were deposited across a carbonate platform near Estonia, grading to deep basin shales near Denmark and Poland. Compositional variations in illite reflect fluids from different sources. High N illite (>2000. ppm) in the southwest basin transitions to high B (>250. ppm) and high Li (>100. ppm) illite to the northeast. These trends follow a thermal gradient decreasing from southwest (200. °C) to northeast (90. °C). Isotope ratios of B and Li show opposing trends in samples across this thermal gradient: the Bisotopes decrease from southwest to northeast (+18‰ to -4‰), while Li-isotopes increase from +5‰ to +32‰.The Cambrian Alum shale, a regional hydrocarbon source rock, was studied as a potential source of B and Li, as more than 50% of its B and Li was associated with organic matter. With increasing thermal maturity, illite δ11B decreased from 0‰ to -13‰, while δ7Li increased from -20‰ to -5‰. These opposing trends are similar to those observed in the K-bentonites. This suggests that organic sources of N, B and Li dominate fluids in bentonites from the southwestern Baltic Basin, whereas basement derived fluids dominate in the northeastern Baltic Basin. These trace elements record paleofluid changes during illite crystal growth and can identify pathways of chemically distinct oil and gas related fluids.

Original languageEnglish (US)
Pages (from-to)582-599
Number of pages18
JournalGeochimica et Cosmochimica Acta
Volume120
DOIs
StatePublished - Nov 1 2013

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illite
Bentonite
basin
Fluids
bentonite
fluid
Thermal gradients
Trace Elements
Isotopes
Biological materials
Volcanic Eruptions
distribution
trace element
isotope
illitization
organic matter
thermal maturity
Boron
fluid composition
Carbonates

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

Light element distributions (N, B, Li) in Baltic Basin bentonites record organic sources. / Williams, Lynda; Środoń, Jan; Huff, Warren D.; Clauer, Norbert; Hervig, Richard.

In: Geochimica et Cosmochimica Acta, Vol. 120, 01.11.2013, p. 582-599.

Research output: Contribution to journalArticle

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abstract = "Distributions of nitrogen, boron and lithium were studied in illite-smectite from Ordovician-Silurian K-bentonites in the Baltic Basin. These trace elements are linked to thermal maturation of organic matter, creating fluid signatures that are distinct from those in regionally buried sediments. The fluid chemistry is ideally recorded in authigenic illite within the K-bentonite because B substitutes in tetrahedral sites of illite, Li in octahedral sites, and N is fixed in the interlayers as NH4+. Three nanometric size fractions of illite (<0.02. μm; 0.02-0.05. μm; 0.05-0.2. μm) were compared within each sample. Boron and Li-isotope variations (>10‰) among these size fractions relate mainly to changes in fluid composition during illite growth.Bentonite (volcanic ash) layers mark stratigraphic timelines, while illitization of the bentonite (K-bentonite) varies as a function of burial and tectonic temperature gradients. In the central Baltic Basin, bentonites were deposited across a carbonate platform near Estonia, grading to deep basin shales near Denmark and Poland. Compositional variations in illite reflect fluids from different sources. High N illite (>2000. ppm) in the southwest basin transitions to high B (>250. ppm) and high Li (>100. ppm) illite to the northeast. These trends follow a thermal gradient decreasing from southwest (200. °C) to northeast (90. °C). Isotope ratios of B and Li show opposing trends in samples across this thermal gradient: the Bisotopes decrease from southwest to northeast (+18‰ to -4‰), while Li-isotopes increase from +5‰ to +32‰.The Cambrian Alum shale, a regional hydrocarbon source rock, was studied as a potential source of B and Li, as more than 50{\%} of its B and Li was associated with organic matter. With increasing thermal maturity, illite δ11B decreased from 0‰ to -13‰, while δ7Li increased from -20‰ to -5‰. These opposing trends are similar to those observed in the K-bentonites. This suggests that organic sources of N, B and Li dominate fluids in bentonites from the southwestern Baltic Basin, whereas basement derived fluids dominate in the northeastern Baltic Basin. These trace elements record paleofluid changes during illite crystal growth and can identify pathways of chemically distinct oil and gas related fluids.",
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N2 - Distributions of nitrogen, boron and lithium were studied in illite-smectite from Ordovician-Silurian K-bentonites in the Baltic Basin. These trace elements are linked to thermal maturation of organic matter, creating fluid signatures that are distinct from those in regionally buried sediments. The fluid chemistry is ideally recorded in authigenic illite within the K-bentonite because B substitutes in tetrahedral sites of illite, Li in octahedral sites, and N is fixed in the interlayers as NH4+. Three nanometric size fractions of illite (<0.02. μm; 0.02-0.05. μm; 0.05-0.2. μm) were compared within each sample. Boron and Li-isotope variations (>10‰) among these size fractions relate mainly to changes in fluid composition during illite growth.Bentonite (volcanic ash) layers mark stratigraphic timelines, while illitization of the bentonite (K-bentonite) varies as a function of burial and tectonic temperature gradients. In the central Baltic Basin, bentonites were deposited across a carbonate platform near Estonia, grading to deep basin shales near Denmark and Poland. Compositional variations in illite reflect fluids from different sources. High N illite (>2000. ppm) in the southwest basin transitions to high B (>250. ppm) and high Li (>100. ppm) illite to the northeast. These trends follow a thermal gradient decreasing from southwest (200. °C) to northeast (90. °C). Isotope ratios of B and Li show opposing trends in samples across this thermal gradient: the Bisotopes decrease from southwest to northeast (+18‰ to -4‰), while Li-isotopes increase from +5‰ to +32‰.The Cambrian Alum shale, a regional hydrocarbon source rock, was studied as a potential source of B and Li, as more than 50% of its B and Li was associated with organic matter. With increasing thermal maturity, illite δ11B decreased from 0‰ to -13‰, while δ7Li increased from -20‰ to -5‰. These opposing trends are similar to those observed in the K-bentonites. This suggests that organic sources of N, B and Li dominate fluids in bentonites from the southwestern Baltic Basin, whereas basement derived fluids dominate in the northeastern Baltic Basin. These trace elements record paleofluid changes during illite crystal growth and can identify pathways of chemically distinct oil and gas related fluids.

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