4000 years of trace metal record in a former iron-smelting district,West Bourgogne (France): multi-proxy paleoenvironmental assessment of human impacts on the landscape
Restricted accessResearch articleFirst published online 2026
4000 years of trace metal record in a former iron-smelting district,West Bourgogne (France): multi-proxy paleoenvironmental assessment of human impacts on the landscape
The geochemical and palynological study of a well-radiocarbon-dated core from the “Les Comailles” peat bog, located in the vicinity of slag heaps in the former iron-metallurgy district of Puisaye (Bourgogne-Franche-Comté region, France), highlights the impact of metallurgical activities on vegetation cover from 2000 cal. BC to cal. AD 1740. The physico-chemical characterization of the peat bog demonstrated its reliability to be used as a chronological archive of past environmental changes. The study recorded evidence of atmospheric emissions of several metals, including arsenic, lead, or zinc, during the Late Bronze Age, even though no archaeometallurgical sites are currently known in the Puisaye district before the Early Iron Age, revealing the possible existence of punctuated bronze metallurgy in Puisaye. Forest clearance of Quercus was evidenced during the Second Iron Age and is related to the intensification of iron-metallurgy and crop cultivation. Comparison of palynological data from the Comailles core with charcoal analyses from slag heaps in the Puisaye district, supported the selection of wood for charcoal production during the Roman Empire and the Middle Ages, as some species present in the landscape are absent in anthracological spectra. We hypothesize that there was a spatial separation between metallurgy and crop activities in Puisaye. Compositional Data Analysis made on 13 trace elements (arsenic, cadmium, cobalt, chromium, copper, lanthanum, nickel, lead, rubidium, antimony, tin, zinc and zirconium) also highlighted two main changes of geochemical composition of peat samples, dated to the beginning of the Late Middle Ages and Modern Times, that could be related to archeologically known changes in iron-metallurgy processes and organization of iron-smelting sites at a regional scale. As forest cover inhibits identification of past settlements, further investigation is advised to identify former rural settlements.
AitchisonJ (1982) The statistical analysis of compositional data. Journal of the Royal Statistical Society. Series B (Methodological)44(2): 139–160.
2.
AitchisonJ (1986) The Statistical Analysis of Compositional Data, Monographs on Statistics and Applied Probability. Chapman and Hall, p.416.
3.
AitchisonJGreenacreM (2002) Biplots of compositional data. Journal of the Royal Statistical Society Series C (Applied Statistics)51: 375–392.
4.
AllanMLe RouxGDe VleeschouwerF, et al. (2013) High-resolution reconstruction of atmospheric deposition of trace metals and metalloids since AD 1400 recorded by ombrotrophic peat cores in Hautes-Fagnes, Belgium. Environmental Pollution178: 381–394. https://doi.org/10.1016/j.envpol.2013.03.018
5.
BardetOFedoroffECausseG (2008) Atlas of the wild flora of Burgundy [Atlas de la flore sauvage de Bourgogne]. Muséum National d’Histoire Naturelle, p.752. Biotope, Mèze.
6.
BeckerFDjurdjevac ConradNEserRA, et al. (2020) The furnace and the goat-A spatio-temporal model of the fuelwood requirement for iron metallurgy on Elba Island, 4th century BCE to 2nd century ce. PLoS One15(11): e0241133. https://doi.org/10.1371/journal.pone.0241133
7.
BerrangerMAubertMBauvaisS, et al. (2019) 2019 PCR activity report: “Iron-metallurgy in Bourgogne-Franche-Comté before the blast furnace. Organization and circulation of products” [Rapport d’activité 2019 PRC “La sidérurgie en Bourgogne-Franche-Comté avant le haut fourneau. Organisation et circulation des productions”]. p.240.
8.
BerrangerMLeroyMLaurentH (2023) Iron production areas in Bourgogne-Franche-Comté: a long-term approach using radiocarbon dating [Les zones de production du fer en Bourgogne-Franche-Comté : une approche sur la longue durée par le radiocarbone]. Archéologie Gaules80(2): 15–48. https://doi.org/10.4000/gallia.6954
9.
BerrangerMLeroyMPiétakJP, et al. (2026) Bloomery slags from Puisaye (France): Reconstructing technological changes in a major iron production area from the iron age to the late middle ages. Journal of Archaeological Science187: 106475. https://doi.org/10.1016/j.jas.2026.106475
10.
BeugHJ (2004) Guide to pollen identification for Central Europe and adjacent regions [Leitfaden der Pollenbestimmung für Mitteleuropa und angrenzende Gebiete]. Publisher Verlag Friedrich Pfeil, p.542.
11.
BindlerR (2006) Mired in the past — Looking to the future: Geochemistry of peat and the analysis of past environmental changes. Global and Planetary Change53(4): 209–221. https://doi.org/10.1016/j.gloplacha.2006.03.004
12.
BindlerRSegerströmUPettersson-JensenIM, et al. (2011) Early medieval origins of iron mining and settlement in central Sweden: Multiproxy analysis of sediment and peat records from the Norberg mining district. Journal of Archaeological Science38(2): 291–300. https://doi.org/10.1016/j.jas.2010.09.004
13.
BirksHJBLineJM (1992) The use of rarefaction analysis for estimating palynological richness from Quaternary pollen-analytical data. Holocene2(1): 1–10. https://doi.org/10.1177/095968369200200101
14.
BlaauwM (2010) Methods and code for ‘classical’ age-modelling of radiocarbon sequences. Elsevier Quaternary Geochronology5(5): 512–518. https://doi.org/10.1016/j.quageo.2010.01.002
15.
BreitenlechnerEGoldenbergGLutzJ, et al. (2013) The impact of prehistoric mining activities on the environment: A multidisciplinary study at the fen Schwarzenbergmoos (Brixlegg, tyrol, Austria). Vegetation History and Archaeobotany22(4): 351–366. https://doi.org/10.1007/s00334-012-0379-6
16.
BreitenlechnerEHilberMLutzJ, et al. (2010) The impact of mining activities on the environment reflected by pollen, charcoal and geochemical analyses. Journal of Archaeological Science37: 1458–1467. https://doi.org/10.1016/j.jas.2010.01.006
17.
BrunC (2011) Anthropogenic indicators in pollen diagrams in eastern France: A critical review. Vegetation History and Archaeobotany20: 135–142. https://doi.org/10.1007/s00334-010-0277-8
18.
BrunCDessaintFRichardH, et al. (2007) Arable-weed flora and its pollen representation: A case study from the eastern part of France. Review of Palaeobotany and Palynology146: 29–50. https://doi.org/10.1016/j.revpalbo.2007.02.001
19.
CamizuliEMonnaFScheiflerR, et al. (2014) Impact of trace metals from past mining on the aquatic ecosystem: A multi-proxy approach in the Morvan (France). Environmental Research134: 410–419. https://doi.org/10.1016/j.envres.2014.07.008
20.
CarignanJHildPMevelleG, et al. (2001) Routine analyses of trace elements in geological samples using flow injection and low pressure on-line liquid chromatography coupled to ICP-MS: A study of geochemical reference materials BR, DR-N, UB-N, AN-G and GH. Geostandards and Geoanalytical Research25(2–3): 187–198.
21.
CortizasAMMighallTPombalXP, et al. (2005) Linking changes in atmospheric dust deposition, vegetation change and human activities in northwest Spain during the last 5300 years. Holocene15: 698–706. https://doi.org/10.1191/0959683605hl834rp
22.
De VleeschouwerFFagelNCheburkinA, et al. (2009) Anthropogenic impacts in North Poland over the last 1300years — A record of Pb, Zn, Cu, Ni and S in an ombrotrophic peat bog. Science of the Total Environment407(21): 5674–5684. https://doi.org/10.1016/j.scitotenv.2009.07.020
23.
EtienneDRuffaldiPDupoueyJL, et al. (2013) Searching for ancient forests: A 2000 year history of land use in northeastern French forests deduced from the pollen compositions of closed depressions. Holocene23: 678–691. https://doi.org/10.1177/0959683612470173
24.
FægriKIversenJ (1989) Textbook of Pollen Analysis. John Wiley and Sons, p.328.
25.
FilzmoserPHronKReimannC (2009) Principal component analysis for compositional data with outliers. Environmetrics20: 621–632. https://doi.org/10.1002/env.966
26.
FilzmoserPHronKTemplM (2018) Applied Compositional Data Analysis: With Worked Examples in R. Springer Series in Statistics, p.287.
27.
ForelBMonnaFPetitC, et al. (2010) Historical mining and smelting in the Vosges Mountains (France) recorded in two ombrotrophic peat bogs. Journal of Geochemical Exploration107(1): 9–20. https://doi.org/10.1016/j.gexplo.2010.05.004
28.
GabillotMMordantCWirthS (2015) Non-funerary metalwork from the Bronze Age in Burgundy: a review of studies from 1995 to 2007 [La production métallique non funéraire de l’âge du Bronze en Bourgogne : bilan des études 1995 – 2007]. Revue Archéologique de l’Est tome 64: 69–84.
29.
GabrielKR (1971) The biplot graphic display of matrices with application to principal component analysis. Biometrika58(3): 453–467.
30.
GirardclosOJeannotR (2019) Dendro-anthrachology: an exploratory analysis of slag heaps at Montholon (Aillant-sur-Tholon) [Dendro-anthracologie, analyse exploratoire de ferriers à Montholon (Aillant-sur-Tholon)]. In: Berranger, et al. (2019) pp. 103–131.
31.
GoubetP (2021) Report on a study commissioned by the Puisaye-Forterre community of municipalities. Functional assessment of the peatlands in the Puisaye Natura 2000 sites [Compte rendu d’étude commandée par la communauté de communes de Puisaye-Forterre. Diagnostic fonctionnel des tourbières des sites Natura 2000 de Puisaye]. Cabinet Pierre Goubet, Ardes-sur-Couze.
32.
GrimmEC (1987) CONISS: A FORTRAN 77 program for stratigraphically constrained cluster analysis by the method of incremental sum of squares. Computational Geosciences13(1): 13–35. https://doi.org/10.1016/0098-3004(87)90022-7
33.
GrimmEC (1991) TILIA and TILIA*GRAPH.
34.
GuédronSAmourouxDSabatierP, et al. (2016) A hundred year record of industrial and urban development in French alps combining Hg accumulation rates and isotope composition in sediment archives from Lake Luitel. Chemical Geology431: 10–19. https://doi.org/10.1016/j.chemgeo.2016.03.016
HeiriOLotterAFLemckeG (2001) Loss on ignition as a method for estimating organic and carbonate content in sediments: Reproducibility and comparability of results. Journal of Paleolimnology25: 101–110. https://doi.org/10.1023/a:1008119611481
37.
IglesiasVVannièreBJouffroy-BapicotI (2019) Emergence and evolution of anthropogenic landscapes in the western Mediterranean and adjacent Atlantic regions. FIRE: Forum for International Research in Education2(4): 53. https://doi.org/10.3390/fire2040053
38.
IlesL (2016) The role of metallurgy in transforming global forests. Journal of Archaeological Method and Theory23(4): 1219–1241. https://doi.org/10.1007/s10816-015-9266-7
39.
JakobitschTWiesingerSHeissAG, et al. (2022) Wood use and forest management at the Late Bronze Age copper mining site of prigglitz-Gasteil in the Eastern alps – A combined anthracological, archaeological, and palynological approach. Journal of Archaeological Science Reports46: 103673. https://doi.org/10.1016/j.jasrep.2022.103673
40.
Jouffroy-BapicotIPulidoMBaronS, et al. (2007) Environmental impact of early palaeometallurgy: Pollen and geochemical analysis. Vegetation History and Archaeobotany16: 251–258. https://doi.org/10.1007/s00334-006-0039-9
41.
Jouffroy-BapicotIVannièreBGauthierÉ, et al. (2013) 7000 years of vegetation history and land-use changes in the Morvan Mountains (France): A regional synthesis. Holocene23: 1888–1902. https://doi.org/10.1177/0959683613508161
42.
KarlssonJRydbergJSegerströmU, et al. (2016) Tracing a bog-iron bloomery furnace in an adjacent lake-sediment record in ängersjö, central Sweden, using pollen and geochemical signals. Vegetation History and Archaeobotany25(6): 569–581. https://doi.org/10.1007/s00334-016-0567-x
43.
KarlssonJSegerströmUBergA, et al. (2015) Tracing modern environmental conditions to their roots in early mining, metallurgy, and settlement in Gladhammar, southeast Sweden: Vegetation and pollution history outside the traditional Bergslagen mining region. Holocene25: 944–955. https://doi.org/10.1177/0959683615574586
44.
KuhryPVittDH (1996) Fossil carbon/nitrogen ratios as a measure of peat decomposition. Ecology77: 271–275. https://doi.org/10.2307/2265676
45.
LeeASHuangJJSBurrG, et al. (2019) High resolution record of heavy metals from estuary sediments of Nankan River (Taiwan) assessed by rigorous multivariate statistical analysis. Quaternary International527: 44–51. https://doi.org/10.1016/j.quaint.2018.11.018
46.
LeguédoisSPartyJPDupoueyJL, et al. (2011) The CNRS vegetation map in the digital Age [La carte de végétation du CNRS à l’ère du numérique]. Cybergeo: European Journal of Geography [Online], Environment, Nature, Landscape, document 559, Online since 27 October 2011. Available at: http://journals.openedition.org/cybergeo/24688
47.
LongmanJVeresDFinsingerW, et al. (2018) Exceptionally high levels of lead pollution in the Balkans from the early Bronze Age to the industrial revolution. Proceedings of the National Academy of Sciences of the United States of America115(25): E5661–E5668. https://doi.org/10.1073/pnas.1721546115
48.
MagnyMMiramontCSivanO (2002) Assessment of the impact of climate and anthropogenic factors on holocene mediterranean vegetation in Europe on the basis of palaeohydrological records. Palaeogeography Palaeoclimatology Palaeoecology186(1–2): 47–59. https://doi.org/10.1016/s0031-0182(02)00442-x
49.
MagnyMPeyronOGauthierE, et al. (2009) Quantitative reconstruction of climatic variations during the bronze and early iron ages based on pollen and lake-level data in the NW alps, France. Quaternary International200(1–2): 102–110. https://doi.org/10.1016/j.quaint.2008.03.011
50.
MarietALBégeotCGimbertF, et al. (2016) Past mining activities in the Vosges Mountains (eastern France): Impact on vegetation and metal contamination over the past millennium. Holocene26: 1225–1236. https://doi.org/10.1177/0959683616638419
51.
MarietALMonnaFGimbertF, et al. (2018a) Tracking past mining activity using trace metals, lead isotopes and compositional data analysis of a sediment core from Longemer Lake, Vosges Mountains, France. Journal of Paleolimnology60: 399–412. https://doi.org/10.1007/s10933-018-0029-9
52.
MarietALPaugetBde VaufleuryA, et al. (2017a) Using bioindicators to assess the environmental risk of past mining activities in the Vosges Mountains (France). Ecological Indicators75: 17–26. https://doi.org/10.1016/j.ecolind.2016.11.042
53.
MarietALSarretGBégeotC, et al. (2017b) Lead highly available in soils centuries after metallurgical activities. Journal of Environmental Quality46(6): 1236–1242. https://doi.org/10.2134/jeq2016.12.0469
54.
MarietAlWalter-SimonnetAVGimbertF, et al. (2018b) High-temporal resolution landscape changes related to anthropogenic activities over the past millennium in the Vosges Mountains (France). Ambio47: 893–907. https://doi.org/10.1007/s13280-018-1044-9
55.
Martínez CortizasALópez-MerinoLBindlerR, et al. (2016) Early atmospheric metal pollution provides evidence for Chalcolithic/Bronze age mining and metallurgy in southwestern Europe. Science of the Total Environment545–546: 398–406. https://doi.org/10.1016/j.scitotenv.2015.12.078
56.
Martínez-CortizasAPontevedra-PombalXMuñozJCN, et al. (1997) Four thousand years of atmospheric Pb, Cd and Zn deposition recorded by the ombrotrophic peat bog of penido vello (northwestern Spain). Water Air & Soil Pollution100: 387–403.
57.
MeyerCDiaz-de-QuijanoMMonnaF, et al. (2015) Characterisation and distribution of deposited trace elements transported over long and intermediate distances in north-eastern France using Sphagnum peatlands as a sentinel ecosystem. Atmospheric Environment101: 286–293. https://doi.org/10.1016/j.atmosenv.2014.11.041
58.
MighallTMTimberlakeSClarkSHE, et al. (2002) A palaeoenvironmental investigation of sediments from the prehistoric mine of Copa Hill, Cwmystwyth, mid-Wales. Journal of Archaeological Science29: 1161–1188. https://doi.org/10.1006/jasc.2001.0772
59.
MighallTTimberlakeSGrattanJ, et al. (2000) Bronze Age lead mining at Copa Hill, Cwmystwyth – fact or fantasy?Historical Metallurgy34(1): 1–12.
60.
MighallTTimberlakeSJenkinsDA, et al. (2006) Chapter 17 using bog archives to reconstruct paleopollution and vegetation change during the late-Holocene. In: MartiniIPMartínez CortizasAChesworthW (eds) Developments in Earth Surface Processes, vol. 9. Elsevier, pp.409–429. https://doi.org/10.1016/S0928-2025(06)09017-1
61.
MighallTTimberlakeSMartínez-CortizasA, et al. (2017) Did prehistoric and Roman mining and metallurgy have a significant impact on vegetation?Journal of Archaeological Science Reports11: 613–625. https://doi.org/10.1016/j.jasrep.2016.12.021
62.
MonnaFGalopDCarozzaL, et al. (2004) Environmental impact of early Basque mining and smelting recorded in a high ash minerogenic peat deposit. Science of the Total Environment327(1–3): 197–214. https://doi.org/10.1016/j.scitotenv.2004.01.010
NieminenTMUkonmaanahoLShotykW (2002) Enrichment of Cu, Ni, Zn, Pb and as in an ombrotrophic peat bog near a Cu-Ni smelter in Southwest Finland. Science of the Total Environment292: 81–89. https://doi.org/10.1016/s0048-9697(02)00028-1
65.
NouvelP (2016) Between city and countryside: forms of settlement and Gallo-Roman elites in Central-Eastern Gaul. Findings from 20 years of archaeological surveys and excavations. Volume 3: Original Dissertation (Habilitation to Supervise Research) [Entre ville et campagne. Formes de l’occupation et élites gallo-romaines dans le centre-est de la Gaule. Apport de 20 années de prospections et de fouilles archéologiques. Volume 3 : mémoire original (Habilitation à Diriger des Recherches)]. Université de Franche-Comté. UFR SLHS.
66.
NriaguJO (1996) A History of global metal pollution. Science272(5259): 223–223.
67.
OksanenJBlanchetGKindtR, et al. (2012) Vegan: community ecology package. R package version 1.17-11.
68.
PasquetCLe MonierPMonnaF, et al. (2016) Impact of nickel mining in New Caledonia assessed by compositional data analysis of lichens. SpringerPlus5(1): 2022. https://doi.org/10.1186/s40064-016-3681-4
69.
PèlachsANadalJSorianoJM, et al. (2009) Changes in Pyrenean woodlands as a result of the intensity of human exploitation: 2,000 years of metallurgy in vallferrera, northeast Iberian Peninsula. Vegetation History and Archaeobotany18: 403–416. https://doi.org/10.1007/s00334-009-0218-6
70.
Pontevedra-PombalXMighallTMNóvoa-MuñozJC, et al. (2013) Five thousand years of atmospheric Ni, Zn, As, and Cd deposition recorded in bogs from NW Iberia: prehistoric and historic anthropogenic contributions. Journal of Archaeological Science40: 764–777. https://doi.org/10.1016/j.jas.2012.07.010
71.
PuntW (1976) Northwest European Pollen Flora. Elsevier.
72.
PuntWBlackmoreSClarkeGCS (1988) Northwest European Pollen Flora. Elsevier.
73.
PuntWClarkeGCS (1980) Northwest European Pollen Flora. Elsevier.
74.
PuntWClarkeGCS (1981) Northwest European Pollen Flora. Elsevier.
75.
PuntWClarkeGCS (1984) Northwest European Pollen Flora. \.
76.
PyVVéronAEdouardJL, et al. (2014) Interdisciplinary characterisation and environmental imprints of mining and forestry in the upper Durance valley (France) during the holocene. Quaternary International353: 74–97. https://doi.org/10.1016/j.quaint.2014.05.002
77.
R Core Team (2020) R: A Language and Environment for Statistical Computing. R Foundation for Statistical Computing, http://www.Rproject.org
78.
ReilleM (1992) Pollen et spores d’Europe et d’Afrique du Nord. Laboratoire de botanique historique et palynologie, URA CNRS 1152.
79.
ReilleM (1995) Pollen et spores d’Europe et d’Afrique du Nord : supplément 1. Marseille : Laboratoire de Botanique Historique et Palynologie.
80.
ReimannCde CaritatP (2005) Distinguishing between natural and anthropogenic sources for elements in the environment: Regional geochemical surveys versus enrichment factors. Science of the Total Environment337: 91–107. https://doi.org/10.1016/j.scitotenv.2004.06.011
81.
RobertsNFyfeRMWoodbridgeJ, et al. (2018) Europe’s lost forests: A pollen-based synthesis for the last 11,000 years. Scientific Reports8: 716. https://doi.org/10.1038/s41598-017-18646-7
ShotykW (1996) Natural and anthropogenic enrichments of As, Cu, Pb, Sb, and Zn in ombrotrophic versus minerotrophic peat bog profiles, Jura Mountains, Switzerland. Water Air & Soil Pollution90: 375–405. https://doi.org/10.1007/bf00282657
84.
StockmarrJ (1971) Tablets with spores used in absolute pollen analysis. Pollen et Spores13: 615–621.
85.
SzymczykANitaM (2021) Holocene environmental changes in a prehistoric mining and metallurgical region in the light of paleobotanical studies of the bogs of the Brynica river drainage basin (southern Poland). Science of the Total Environment788: 147755. https://doi.org/10.1016/j.scitotenv.2021.147755
86.
TolksdorfJFElburgRSchröderF, et al. (2015) Forest exploitation for charcoal production and timber since the 12th century in an intact medieval mining site in the Niederpöbel Valley (Erzgebirge, Eastern Germany). Journal of Archaeological Science Reports4: 487–500. https://doi.org/10.1016/j.jasrep.2015.10.018
87.
van Den BoogartKGTolosana-DelgadoR (2013) Analyzing Compositional Data with R. In Use R!. Springer Berlin Heidelberg, Freiberg, Germany.
88.
ViehweiderBLutzJOegglK (2015) Late-Holocene land use changes caused by exploitation in the mining region of Kitzbühel (tyrol, Austria). Vegetation History and Archaeobotany24: 711–729. https://doi.org/10.1007/s00334-015-0527-x
89.
WardJH (1963) Hierarchical grouping to optimize an objective function. Journal of the American Statistical Association58: 236–244. https://doi.org/10.2307/2282967
90.
WeissDShotykWApplebyPG, et al. (1999) Atmospheric Pb deposition since the Industrial Revolution recorded by five Swiss peat profiles: enrichment factors, fluxes, isotopic composition, and Sources. Environmental Science & Technology33: 1340–1352. https://doi.org/10.1021/es980882q
Supplementary Material
Please find the following supplemental material available below.
For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.
For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.
