Holy Smoke in Medieval Funerary Rites: Chemical Fingerprints of Frankincense in Southern Belgian Incense Burners

In the paper

“However, comparison of their mass spectra with those of isolated incensol [47] and serratol [48] reveals that compound 127 was correctly identified as incensol but that compound 128 corresponds to serratol, a diterpenoid common to Boswellia species, particularly B. sacra, B. carterii and B. serrata [46], [48], [49].”

What the sources say

• ?Not checked — no full text of the sourcecites [47] A Moussaieff, 2007, Incensole acetate, a novel anti-inflammatory compound isolated from Boswellia resin, inhibits nuclear factor-kappa B activation, Molecular Pharmacology source
• ?Not checked — no full text of the sourcecites [48] TJ Schmidt, 2011, Complete Structural Assignment of Serratol, a Cembrane-Type Diterpene from Boswellia serrata, and Evaluation of Its Antiprotozoal Activity, Planta Medica source
• ?Not checked — no full text of the sourcecites [46] Paul M (2012) Chemotaxonomic investigations on resins of the frankincense species Boswellia papyrifera, Boswellia serrata and Boswellia sacra, respectively Boswellia carterii [dissertation]. Saarland University, Saarbrücken. source

In the paper

“Incensol and serratol are not fully derivatized (Figure 2) and the free alcohols show almost full coelution (retention indices 2150 and 2152, respectively).”

In the paper

“The latter include tetracyclic hydrocarbons, e.g. des-A-ursa-5(10),12-diene, des-A-26,27-dinorursa-5,7,9,11,13-pentaene and 1,9-dimethylchrysene, as well as pentacyclic hydrocarbons, e.g. 24,25-dinorursa-1,3,5(10),12-tetraene, 24,25,26,27-tetranorursa-1,3,5(10),6,8,10,13-heptaene, 1,2,9-trimethyl-1,2,3,4-tetrahydropicene, 2,9-dimethylpicene.”

In the paper

“The absorbed residues from samples R2 and R9 contain only trace amounts of triterpenoids such as 24-norursa-3,12-diene, 24-norursa-3,12-dien-11-one, α-amyrenone and corresponding oleanane compounds. No other molecule classes are present.”

In the paper

“We were able to successfully resolve these co-eluting compounds by mass spectral deconvolution, with the summed peak areas of the extracted compound chromatograms (ECCs) amounting to 95% of the peak area of the total ion count chromatogram (Figure 3).”

In the paper

“It amounts to 1 for B. serrata and 4–7 in B. sacra, B. carterii and B. papyrifera.”

In the paper

“Chemotaxonomic screening of the lipid extracts has provided unambiguous proof for frankincense, viz. the oleo-gum resin of Boswellia sp., but also revealed that the chemical signatures were greatly altered and differed almost completely from those of fresh frankincense (cf. Figure 2).”

In the paper

“Furthermore, traces of juniper and possibly pine tar demonstrate that small amounts of locally available fragrances were mixed with frankincense, most likely to reduce its cost.”

In the paper

“Original cembrane alcohols, tirucallic acids, boswellic and lupeolic acids were only recovered in trace amounts. Instead, 24-nortriterpenoids, amyrin derivatives and Δ2-triterpenoids were identified as major compounds.”

In the paper

“Most abundant are palmitic acid (C16∶0) and stearic acid (C18∶0) exhibiting absolute concentrations of 3.5 µg g−1 and 3.0 µg g−1, respectively.”

In the paper

“In addition, the chromatogram displays trace amounts of 16-nordehydroabietic acid, 16,17-bisnordehydroabietic acid, 7-oxo-18-norabieta-8,11,13-triene, 15,16,17-trisnordehydroabietic acid, simonellite, 5α- and 5β-9,10-secodehydroabietic acid as well as polycyclic aromatic hydrocarbons (PAHs) such as phenanthrene, methylphenanthrenes, pimanthrene, 7-ethyl-1-methylphenanthrene, methylcyclopentenophen”

In the paper

“A total of 1854 charcoal fragments has been identified from the content of the different funerary pots, resulting in a minimum number of 11 identified taxa (Table 3).”

In the paper

“The lipid profile of the absorbed residues is almost identical to that of the surface residue, except for small peaks of coprostanol, epicoprostanol, cholesterol and sitosterol which are only detected in the surface residue.”

In the paper

“Diterpenoid profiles of the commercial Boswellia resins are dominated by incensol and serratol in B. carterii (61% and 24% of total identified diterpenoids, respectively), by serratol in B. sacra (63%) and B. serrata (76%), and by verticilla-4(20),7,11-triene, incensol and incensol acetate in B. papyrifera (24%, 25% and 43%, respectively).”

In the paper

“Contrary to the triterpenoid predominance in most samples, the lipid composition of samples Q10 and N13 was dominated by diterpenoids and aliphatic lipids, respectively.”

In the paper

“Other minor constituents of frankincense are also present, mostly in trace abundances (0.1–0.3 µg g−1). These include lupeolic acid (sample R9), its Δ2 derivative (sample Q11), tirucallic acids (samples R9 and Q11) and serratol and incensol (samples Q11, L14 and L15).”

In the paper

“Their deconvoluted mass spectra (Figure 4a and 4b) are nearly identical and show clear features of a boswellic acid derivative, viz. ions with m/z 73, 175, 203, 218 and 292 [20], [26].”

What the sources say

• ?Not checked — no full text of the sourcecites [20] C Mathe, 2004, Characterization of archaeological frankincense by gas chromatography-mass spectrometry, J Chromatogr A source
• ?Not checked — no full text of the sourcecites [26] Basar S (2005) Phytochemical investigations on Boswellia species [dissertation]. University of Hamburg.

In the paper

“Furthermore, ring A contracted neotriterpenoids (samples R9, Q11, L14 and L15) and polyunsaturated or aromatic hydrocarbons (samples R2, R9, Q11, Q12, L14 and L15) are observed in minor amounts.”

In the paper

“No exotic taxa have been found and none of the identified taxa has specific odoriferous or aromatic characteristics.”

In the paper

“Tirucallol and tirucallic acids such as β-elemonic acid, β-elemolic acid and β-elemolic acid acetate are also present and their relative abundance is higher in B. serrata and B. papyrifera than in B. sacra and B. carterii.”

In the paper

“These charred remains include seeds or fragments of seeds from Pisum sativum, unidentified Fabaceae and cereals as well as bone fragments from unidentified mammalian bones and herring vertebrae (Q. Goffette and S. Preiss, personal communication).”

In the paper

“that they were not only reserved for the elite, for the clergy nor for any other social class (cf. supra)”

In the paper

“The fact that most perforated vessels are ordinary domestic ceramics and have been pierced after firing suggests that the vessels had an earlier use-phase prior to their use as censers.”

In the paper

“Inter-species variation in chemical composition was verified by analyzing commercial resins of B. carterii, B. papyrifera, B. sacra and B. serrata. Our results are summarized in Table 2 and correspond well to published data [20], [26], [46].”

What the sources say

• ?Not checked — no full text of the sourcecites [20] C Mathe, 2004, Characterization of archaeological frankincense by gas chromatography-mass spectrometry, J Chromatogr A source
• ?Not checked — no full text of the sourcecites [26] Basar S (2005) Phytochemical investigations on Boswellia species [dissertation]. University of Hamburg.
• ?Not checked — no full text of the sourcecites [46] Paul M (2012) Chemotaxonomic investigations on resins of the frankincense species Boswellia papyrifera, Boswellia serrata and Boswellia sacra, respectively Boswellia carterii [dissertation]. Saarland University, Saarbrücken. source

In the paper

“Especially coprostanol and epicoprostanol are biomarkers for faeces from an omnivore [65].”

What the sources say

• Check pendingcites [65] J Baeten, 2012, Faecal biomarker and archaeobotanical analyses of sediments from a public latrine shed new light on ruralisation in Sagalassos, Turkey, J Archaeol Sci source

In the paper

“Dehydration reactions may have taken place during mild pyrolysis or during prolonged contact with desiccants such as charcoal.”

In the paper

“These are highly diagnostic for the Cupressaceae (e.g. Tetraclinis, Juniperus, Cupressus) and Podocarpaceae family (e.g. Podocarpus) and also occur in Cedrus atlantica [60].”

What the sources say

• ?Not checked — no full text of the sourcecites [60] A Otto, 2001, Sesqui-, Di-, and triterpenoids as chemosystematic markers in extant conifers - A review, Botanical Review source

In the paper

“The resulting profile is characterized by a relatively high amount of stearyl moieties and small amounts of C15 and C17 fatty acyl moieties, which are characteristic features of ruminant fats.”

In the paper

“Amyrins, their acetates and oxidized forms are widespread phytochemicals and are produced by many higher plants [67], including Boswellia sp. [20], [26].”

What the sources say

• ?Not checked — no full text of the sourcecites [67] BRT Simoneit, 2002, Biomass burning - A review of organic tracers for smoke from incomplete combustion, Applied Geochemistry source
• ?Not checked — no full text of the sourcecites [20] C Mathe, 2004, Characterization of archaeological frankincense by gas chromatography-mass spectrometry, J Chromatogr A source
• ?Not checked — no full text of the sourcecites [26] Basar S (2005) Phytochemical investigations on Boswellia species [dissertation]. University of Hamburg.

In the paper

“The scant grave goods in late medieval burials comprise laterally perforated pottery vessels which are usually filled with charcoal.”

In the paper

“Fortunately, the diagnostic carboxylic acid group on C-24 is preserved which makes these compounds suitable as univocal biomarkers for degraded frankincense.”

In the paper

“Frankincense, or olibanum, is an oleogum resin that exudes in pale yellow to red tears from incisions in the bark of certain Boswellia trees (Burseraceae family) thriving in arid regions in the horn of Africa and southern Arabia [1].”

What the sources say

• Not checked yetcites [1] Langenheim JH (2003) Plant resins. Chemistry, evolution, ecology and ethnobotany. Cambridge: Timber Press. 586 p.

In the paper

“These minor components are not necessarily related to the use-phases of the pots but may have intruded the residues during prolonged contact with soil particles and during transportation in plastic bags, respectively [50], [51].”

What the sources say

• Not checked yetcites [50] Kimpe K (2003) Chemical analysis of the lipid fraction from ancient ceramics of Sagalassos. [dissertation]. KU Leuven.
• ?Not checked — no full text of the sourcecites [51] JJ Brocks, 2008, Assessing biomarker syngeneity using branched alkanes with quaternary carbon (BAQCs) and other plastic contaminants, Geochim Cosmochim Ac source

In the paper

“Neotriterpenoids are formed from amyrins through a Nametkin rearrangement [54] and the Δ9(11),12 double bond constitutes the dehydrated form of Δ12 triterpenoids with an alcohol functionality on C-11 such as 11-hydroxyboswellic acids which are naturally present in frankincense [55].”

What the sources say

• ?Not checked — no full text of the sourcecites [54] HL ten Haven, 1992, Delta-2-Triterpenes - Early Intermediates in the Diagenesis of Terrigenous Triterpenoids, Geochim Cosmochim Ac source
• ?Not checked — no full text of the sourcecites [55] HL ten Haven, 1992, Early Diagenetic Transformation of Higher-Plant Triterpenoids in Deep-Sea Sediments from Baffin-Bay, Geochim Cosmochim Ac source

In the paper

“Δ2-boswellic and Δ2-lupeolic acids constitute another group of diagnostic compounds, which are identified here for the first time. They were not detected when analyzing the modern reference resins and may be considered as first stage degradation products of boswellic and lupeolic acids, i.e. they are most likely formed by dehydration of the 3α alcohol functionality (Figure 8) as is the case for am”

What the sources say

• ?Not checked — no full text of the sourcecites [54] HL ten Haven, 1992, Delta-2-Triterpenes - Early Intermediates in the Diagenesis of Terrigenous Triterpenoids, Geochim Cosmochim Ac source

In the paper

“They occur in most regions of western Europe and are interpreted as incense burners but have never been investigated with advanced analytical techniques.”

In the paper

“These types of reactions also act upon abietane and pimarane diterpenoids during pine tar or pitch production (cf. diterpenoid profile of sample Q10; [58], [70]) and during pine wood combustion [71].”

What the sources say

• ?Not checked — no full text of the sourcecites [58] IM Egenberg, 2002, Characterisation of traditionally kiln produced pine tar by gas chromatography-mass spectrometry, J Anal Appl Pyr source
• ?Not checked — no full text of the sourcecites [70] N Robinson, 1987, Proof of A Pine Wood Origin for Pitch from Tudor (Mary Rose) and Etruscan Shipwrecks - Application of Analytical Organic-Chemistry in Archaeology, Analyst source
• ?Not checked — no full text of the sourcecites [71] BRT Simoneit, 2000, Molecular characterization of smoke from campfire burning of pine wood (Pinus elliottii), Chemosphere - Global Change Science source

In the paper

“The ratio of 3-O-acetyl-11-keto-β-boswellic acid to 11-keto-β-boswellic acid has been proposed as a further species-specific criterium [45], [46].”

What the sources say

• ?Not checked — no full text of the sourcecites [45] B Buchele, 2003, Analysis of pentacyclic triterpenic acids from frankincense gum resins and related phytopharmaceuticals by high-performance liquid chromatography. Identification of lupeolic acid, a novel pentacyclic triterpene, Journal of Chromatography B-Analytical Technologies in the Biomedical and Life Sciences source
• ?Not checked — no full text of the sourcecites [46] Paul M (2012) Chemotaxonomic investigations on resins of the frankincense species Boswellia papyrifera, Boswellia serrata and Boswellia sacra, respectively Boswellia carterii [dissertation]. Saarland University, Saarbrücken. source

In the paper

“By contrast, 24-nortriterpenoids such as Δ3,12-ursadienes and Δ3,9(11),12-ursatrienes are much more specific. They were already identified in Boswellia resin pyrolysates and are produced from boswellic acids and their corresponding acetates (Figure 8). They are formed through a combined decarboxylation and dehydration (resp. deacetoxylation) in which the carboxylic acid at C-24 plays a crucial”

What the sources say

• ?Not checked — no full text of the sourcecites [22] PF van Bergen, 1997, Chemical evidence for archaeological frankincense: Boswellic acids and their derivatives in solvent soluble and insoluble fractions of resin-like materials, Tetrahedron Lett source

In the paper

“Tetracyclic hydrocarbons such as des-A-ursa-5(10),12-diene are formed by a Norrish type cleavage of the A ring [69] and, like pentacyclic oleanane and ursane compounds, may undergo a series of dehydrogenation, demethylation and progressive aromatization reactions to form PAHs such as dimethylchrysene and dimethylpicene (Figure 8) [53].”

What the sources say

• ?Not checked — no full text of the sourcecites [69] B Corbet, 1980, Photo-Chemical Or Photo-Mimetic Fossil Triterpenoids in Sediments and Petroleum, Journal of the American Chemical Society source
• ?Not checked — no full text of the sourcecites [53] SA Stout, 1992, Aliphatic and Aromatic Triterpenoid Hydrocarbons in A Tertiary Angiospermous Lignite, Org Geochem source

In the paper

“In contrast, in the 7 pots recovered from a single pit in the central nave of the parish church of Saint-Géry (Rebecq), only charcoal from beech has been found. This might be an indication for intentionally produced charcoal as this is likely to result in a monospecific assemblage [79]–[81].”

What the sources say

• ?Not checked — no full text of the sourcecites [79] E Asouti, 2005, Reconstructing Woodland Vegetation and its Exploitation by Past Societies, based on the Analysis and Interpretation of Archaeological Wood Charcoal Macro-Remains, Environmental Archaeology source
• ?Not checked — no full text of the sourcecites [80] K Deforce, 2013, Selective woodland exploitation for charcoal production. A detailed analysis of charcoal kiln remains (ca. 1300–1900 AD) from Zoersel (northern Belgium), J Archaeol Sci source
• ?Not checked — no full text of the sourcecites [81] K Deforce, 2012, Ashes to ashes. Fuelwood selection in Roman cremation rituals in northern Gaul, J Archaeol Sci source

In the paper

“In 1571, Pope Pius V allowed that Peru balsam (Myroxylon pereirae) could be used for incense and later in 1606, the Caeremoniale Episcoporum decreed that frankincense should be used in pure grade or, when admixed with other materials, should be the major incense constituent [15].”

What the sources say

• Not checked yetcites [15] Pfeifer M (1997) Der Weihrauch. Geschichte, Bedeutung, Verwendung. Regensburg: Verlag Friedrich Pustet. 224 p.

In the paper

“Moreover, juniper berries have been commonly used in medieval Europe as a fragrant material [76] and contain totarol as the major diterpenoid constituent [77].”

What the sources say

• Not checked yetcites [76] De Cleene M, Lejeune MC (2002) Compendium of Symbolic and Ritual Plants in Europe: herbs (Vol. 1). Ghent: Man & Culture Publishers. 885 p.
• ?Not checked — no full text of the sourcecites [77] S Vichi, 2008, Assessment of some diterpenoids in commercial distilled gin, Anal Chim Acta source

In the paper

“Almost all perforated pots in this study were recovered from burials within ecclesiastical buildings (Table 1) and thus belonged most likely to clergy members or nobleman [82].”

What the sources say

• Not checked yetcites [82] Prigent D (1996) Les céramiques funéraires (XIe-XVIIe siècle). In: Galinié H, Zadora-Rio E, editors. Archéologie du cimetière chrétien. Actes du 2e colloque A.R.C.H.E.A. Tours. pp. 215–224.

In the paper

“that the vessels are indeed of inferior value as more elaborate wares of higher quality (other techniques, typology, etc.) have been made in this period”

In the paper

“At mild pyrolytic conditions, viz. temperatures between 100–200°C, abietic acid dehydrogenates to its more stable and monoaromatic derivative dehydroabietic acid [58].”

What the sources say

• ?Not checked — no full text of the sourcecites [58] IM Egenberg, 2002, Characterisation of traditionally kiln produced pine tar by gas chromatography-mass spectrometry, J Anal Appl Pyr source

In the paper

“Furthermore, diterpenoids have been found to be resistant to chemical changes in pyrolysis experiments [26] and were recovered in traces amounts in samples Q11, L14 and L15.”

What the sources say

• ?Not checked — no full text of the sourcecites [26] Basar S (2005) Phytochemical investigations on Boswellia species [dissertation]. University of Hamburg.

In the paper

“Further thermal treatment of the tars at temperatures above 300°C initiates decarboxylation, dealkylation and aromatization reactions, which generate partially and fully aromatic hydrocarbons such as retene and pimanthrene [71]–[73].”

What the sources say

• ?Not checked — no full text of the sourcecites [71] BRT Simoneit, 2000, Molecular characterization of smoke from campfire burning of pine wood (Pinus elliottii), Chemosphere - Global Change Science source
• ?Not checked — no full text of the sourcecites [72] M Keiluweit, 2012, Solvent-Extractable Polycyclic Aromatic Hydrocarbons in Biochar: Influence of Pyrolysis Temperature and Feedstock, Environmental Science & Technology source
• ?Not checked — no full text of the sourcecites [73] J Connan, 2003, Conifer tar on the keel and hull planking of the Ma’agan Mikhael Ship (Israel, 5th century BC): identification and comparison withnatural products and artefacts employed in boat construction, J Archaeol Sci source

In the paper

“With the Christianization of Europe, the tradition of grave gifts, particularly in its northwestern regions, was gradually abandoned with a total disappearance by the 8th century.”

In the paper

“Medieval funerary ceramics in northwestern Europe are generally interpreted as incense burners, and in some rare cases as containers for holy water, based on their appearance in historical manuscripts, e.g. Durandus’ Rationale Divinorum Officiorum, and iconographic sources, e.g. miniatures from the Book of Hours (Figure S2) [30], [32].”

What the sources say

• ?Not checked — no full text of the sourcecites [30] Gilchrist R, Sloane B (2005) Requiem: the medieval monastic cemetery in Britain. Museum of London Archaeology Service. 273 p.
• ?Not checked — no full text of the sourcecites [32] PK Madsen, 1983, A French connection: Danish funerary pots - a group of Medieval pottery, Journal of Danish Archaeology source

In the paper

“Podocarpaceae and Cedrus Atlantica are unlikely sources as these conifers are native to the southern hemisphere and the Atlas mountains in Morocco and Algeria, respectively.”

In the paper

“Pine tar and pitch have been widely used to coat ceramics to make them impermeable for liquids such as wine, oils or garum [91], with the earliest evidence dating back to the 7th century BC [70].”

What the sources say

• ?Not checked — no full text of the sourcecites [91] K Romanus, 2009, Wine and olive oil permeation in pitched and non-pitched ceramics: relation with results from archaeological amphorae from Sagalassos, Turkey, J Archaeol Sci source
• ?Not checked — no full text of the sourcecites [70] N Robinson, 1987, Proof of A Pine Wood Origin for Pitch from Tudor (Mary Rose) and Etruscan Shipwrecks - Application of Analytical Organic-Chemistry in Archaeology, Analyst source

In the paper

“According to the deconvoluted diterpenoid profiles in the commercial resins, the dominance of serratol in the archaeological samples corresponds to B. sacra or B. serrata and thus excludes B. papyrifera and B. carterii.”

In the paper

“The vessel from Namur (N13), however, lacks clear evidence for incense burning, which possibly indicates that the vessel was pierced to adapt it for use in funerary rituals but has never been actually used for that purpose.”

In the paper

“Nevertheless, pine pitch continued to be used as a waterproofing material which is evidenced by analyses of contemporary naval timbers like that of the Mary Rose, the flagship of king Henry VIII [70], [94], and the Bremer Kogge [95].”

What the sources say

• ?Not checked — no full text of the sourcecites [70] N Robinson, 1987, Proof of A Pine Wood Origin for Pitch from Tudor (Mary Rose) and Etruscan Shipwrecks - Application of Analytical Organic-Chemistry in Archaeology, Analyst source
• ?Not checked — no full text of the sourcecites [94] RP Evershed, 1985, Pine Wood Origin for Pitch from the Mary-Rose, Nature source
• ?Not checked — no full text of the sourcecites [95] W Lange, 1983, Die Untersuchung eines mittelalterlichen Holzteers aus dem Fund der Bremer Kogge, Berliner Beiträge zur Archäometrie

In the paper

“Absorbed residues from vessels R2 and R9 did not contain lipids which could be related to a vessel use other than incense burning, although markers for pine tar in the corresponding surface residues might relate to an earlier use associated with liquid handling or storage.”

In the paper

“The organic remains from the studied pots from Rebecq, Quaregnon and Liège show not only univocal evidence for burned frankincense (except for sample Q10); some of the vessels also contain potential evidences that frankincense was not used in a pure grade but has been admixed with other scents such as juniper and possibly pine tar.”

In the paper

“Today, incense in the catholic church is composed of various ingredients including frankincense, myrrh, styrax, storax, sandalwood, cloves and lavender (cf.www.threekingsproducts.com) [2].”

What the sources say

• ?Not checked — no full text of the sourcecites [2] AO Tucker, 1986, Frankincense and Myrrh, Economic Botany source

In the paper

“From the Cupressaceae family, juniper (Juniperus communis L.) is the only species that occurred in Belgium during the middle ages although it was probably rare in the study area as it prefers poor, sandy soils like the coastal dunes and the Campine region.”

In the paper

“The scant literary evidences of incense mixtures date from later periods but let believe that diluting frankincense has indeed been common practice for some time, whether it was officially allowed or not.”

In the paper

“Moreover, there are evidences of late medieval pitch production sites like that of Ruppersdorf in Germany [96].”

What the sources say

• Not checked yetcites [96] RD Bleck, 1967, Des Pech von Ruppersdorf, Alt-Thüringen

In the paper

“Funerary ceramics were common in Roman tombs and were used as a container of cremated remains or food offerings.”

In the paper

“In any event, the appearance of funerary incense pots from the 11–12th century onwards indicates a growing concern about a person’s fate, a life after death, and how the latter may be improved.”

In the paper

“Nevertheless, perforated pots can also be found in outdoor burials, sometimes in graves without a coffin, suggesting that the pots were not only reserved for the elite.”

In the paper

“The presence of heated ruminant fats in this sample is clearly not consistent with an incense-related function but rather suggests that the vessel has been used for preparing foods (see below).”