The growth of “black crusts” on calcareous building stones in Palermo (Sicily): a first appraisal of anthropogenic and natural sulphur sources

Abstract. To better understand the formation and the oxidation pathways leading to gypsum-forming “black crusts” and investigate their bearing on the whole atmospheric SO2 cycle, we measured the oxygen (δ17O, δ18O, and Δ17O) and sulfur (δ33S, δ34S, δ36S, Δ33S, and Δ36S) isotopic compositions of black crust sulfates sampled on carbonate building stones along a NW–SE cross section in the Parisian basin. The δ18O and δ34S values, ranging between 7.5 ‰ and 16.7±0.5 ‰ (n=27, 2σ) and between −2.66 ‰ and 13.99±0.20 ‰, respectively, show anthropogenic SO2 as the main sulfur source (from ∼2 % to 81 %, average ∼30 %) with host-rock sulfates making the complement. This is supported by Δ17O values (up to 2.6 ‰, on average ∼0.86 ‰), requiring > 60 % of atmospheric sulfates in black crusts. Negative Δ33S and Δ36S values between −0.34 ‰ and 0.00±0.01 ‰ and between −0.76 ‰ and -0.22±0.20 ‰, respectively, were measured in black crust sulfates, which is typical of a magnetic isotope effect that would occur during the SO2 oxidation on the building stone, leading to 33S depletion in black crust sulfates and subsequent 33S enrichment in residual SO2. Except for a few samples, sulfate aerosols mostly have Δ33S values > 0 ‰, and no processes can yet explain this enrichment, resulting in an inconsistent S budget: black crust sulfates could well represent the complementary negative Δ33S reservoir of the sulfate aerosols, thus solving the atmospheric SO2 budget.

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Application of laser ablation ICP-MS and traditional techniques to the study of black crusts on building stones: a new methodological approach

Environmental Science and Pollution Research ◽

10.1007/s11356-010-0329-8 ◽

2010 ◽

Vol 17 (8) ◽

pp. 1433-1447 ◽

Cited By ~ 21

Author(s):

Donatella Barca ◽

Cristina Maria Belfiore ◽

Gino Mirocle Crisci ◽

Mauro Francesco La Russa ◽

Antonino Pezzino ◽

...

Keyword(s):

Laser Ablation ◽

Methodological Approach ◽

Building Stones ◽

Black Crusts ◽

Icp Ms

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A new methodological approach for the chemical characterization of black crusts on building stones: a case study from the Catania city centre (Sicily, Italy)

Journal of Analytical Atomic Spectrometry ◽

10.1039/c0ja00226g ◽

2011 ◽

Vol 26 (5) ◽

pp. 1000 ◽

Cited By ~ 24

Author(s):

Donatella Barca ◽

Cristina Maria Belfiore ◽

Gino Mirocle Crisci ◽

Mauro Francesco La Russa ◽

Antonino Pezzino ◽

...

Keyword(s):

Methodological Approach ◽

Chemical Characterization ◽

City Centre ◽

Building Stones ◽

Black Crusts

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Oxygen and sulfur mass-independent isotopic signatures in black crusts: the complementary negative ∆<sup>33</sup>S-reservoir of sulfate aerosols?

10.5194/acp-2019-971 ◽

2019 ◽

Author(s):

Isabelle Genot ◽

David Au Yang ◽

Erwan Martin ◽

Pierre Cartigny ◽

Erwann Legendre ◽

...

Keyword(s):

Building Stone ◽

Black Crust ◽

Sulfur Source ◽

Building Stones ◽

Sulfate Aerosols ◽

Magnetic Isotope Effect ◽

So2 Oxidation ◽

Isotopic Signatures ◽

Black Crusts ◽

Atmospheric Sulfates

Abstract. To better understand the formation and the oxidation pathways leading to gypsum-forming “black crusts” and investigate their bearing on the whole atmospheric SO2 cycle, we measured the oxygen (δ17O, δ18O and ∆17O) and sulfur (δ33S, δ34S, δ36S, ∆33S and ∆36S) isotopic compositions of black crust sulfates sampled on carbonate building stones along a NW-SE cross-section in the Parisian basin. The δ18O and δ34S, ranging between 7.5 and 16.7 ± 0.5 ‰ (n = 27, 2σ) and between −2.6 and 13.9 ± 0.2 ‰ respectively, show anthropogenic SO2 as the main sulfur source (from 2 to 81 %, in average ~30 %) with host-rock sulfates making the complement. This is supported by ∆17O-values (up to 2.6 ‰, in average ~0.86 ‰), requiring > 60 % of atmospheric sulfates in black crusts. Both negative ∆33S-∆36S-values between −0.34 and 0.00 ± 0.01 ‰ and between −0.7 and −0.2 ± 0.2 ‰ respectively were measured in black crusts sulfates, that is typical of a magnetic isotope effect that would occur during the SO2 oxidation on the building stone, leading to 33S-depletion in black crust sulfates and subsequent 33S-enrichment in residual SO2. Given that sulfate aerosols have mostly ∆33S > 0 ‰ and no processes can yet explain this enrichment, resulting in a non-consistent S-budget, black crust sulfates could well represent the complementary negative ∆33S-reservoir of the sulfate aerosols solving the atmospheric SO2 budget.

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