Black manganese-rich crusts on a Gothic cathedral

Macholdt, Dorothea S.; Herrmann, Siegfried; Jochum, Klaus Peter; Kilcoyne, A. L. David; Laubscher, Thomas; Pfisterer, Jonas H. K.; Pöhlker, Christopher; Schwager, Beate; Weber, Bettina; Weigand, Markus; Domke, Katrin F.; Andreae, Meinrat O.

doi:10.1016/j.atmosenv.2017.10.022

Title: Black manganese-rich crusts on a Gothic cathedral

Journal Article · Sat Oct 14 00:00:00 EDT 2017 · Atmospheric Environment (1994)

DOI:https://doi.org/10.1016/j.atmosenv.2017.10.022· OSTI ID:1530309

Macholdt, Dorothea S. ^[1]; Herrmann, Siegfried ^[1]; Jochum, Klaus Peter ^[1]; Kilcoyne, A. L. David ^[2]; Laubscher, Thomas ^[3]; Pfisterer, Jonas H. K. ^[1]; Pöhlker, Christopher ^[1]; Schwager, Beate ^[1]; Weber, Bettina ^[1]; Weigand, Markus ^[1]; Domke, Katrin F. ^[1]; Andreae, Meinrat O. ^[4]

Max Planck Society, Mainz (Germany)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Freiburger Münster Münsterbauverein, Freiburg (Germany)
Max Planck Society, Mainz (Germany); King Saud University, Riyadh (Saudi Arabia)

Black manganese-rich crusts are found worldwide on the façades of historical buildings. Here, they were studied exemplarily on the façade of the Freiburger Münster (Freiburg Minster), Germany, and measured in-situ by portable X-ray fluorescence (XRF). The XRF was calibrated to allow the conversion from apparent mass fractions to Mn surface density (Mn mass per area), to compensate for the fact that portable XRF mass fraction measurements from thin layers violate the assumption of a homogeneous measurement volume. Additionally, 200-nm femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs LA-ICP-MS) measurements, scanning transmission X-ray microscopy-near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS), Raman spectroscopy, and imaging by light microscopy were conducted to obtain further insight into the crust material, such as potential biogenic contributions, element distributions, trace element compositions, and organic functional groups. While black crusts of various types are present at many places on the minster's facade, crusts rich in Mn (with a Mn surface density >150 μg cm^-2) are restricted to a maximum height of about 7 m. The only exceptions are those developed on the Renaissance-Vorhalle (Renaissance Portico) at a height of about 8 m. This part of the façade had been cleaned and treated with a silicon resin as recently as 2003. These crusts thus accumulated over a period of only 12 years. Yet, they are exceptionally Mn-rich with a surface density of 1200 μg cm^-2, and therefore require an accumulation rate of about 100 μg cm^-2 Mn per year. Trace element analyses support the theory that vehicle emissions are responsible for most of the Mn supply. Lead, barium, and zinc correlate with manganese, indicating that tire material, brake pads, and resuspended road dust are likely to be the element sources. Microscopic investigations show no organisms on or in the Mn-rich crusts. In contrast, Mn-free black crusts sampled at greater heights (>8 m) exhibited fungal and cyanobacterial encrustation. Carbon-rich spots were found by STXM-NEXAFS underneath one of the Mn-rich crusts. Yet, these carbon occurrences originate from soot and polycyclic aromatic hydrocarbons (PAHs) deposited on top of the crust, rather than from organisms responsible for the crust's formation, as shown by STXM-NEXAFS and Raman spectroscopic measurements. Our results imply that the crusts develop abiogenically, with vehicle emissions as dominant element sources.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Johannes Gutenberg University Mainz (MPGC); King Saud University; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1530309

Alternate ID(s):: OSTI ID: 1549499

Journal Information:: Atmospheric Environment (1994), Vol. 171, Issue C; ISSN 1352-2310

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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manganese crusts
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rock varnish
vehicle emission
manganese deposition mechanisms

Title: Black manganese-rich crusts on a Gothic cathedral

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