SSRN Id4601234

1 Hammerscale and Slag Inclusions: New Insights into Metal Supply During the Early Iron Age in
2 Western Europe
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3 Jean Rodier1*, Marion Berranger2, Vincent Serneels1
4 1 Department of Geosciences, Université de Fribourg, Fribourg, Switzerland

5 2 CNRS, LMC-IRAMAT, UMR7065, Université de Technologie Belfort Montbéliard, CNRS, Montbéliard, France
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6 Characterizing the nature and origin of iron processed in an archaeological smithing workshop is crucial
7 for understanding iron circulation and procurement strategies. However, this task presents challenges.
8 The traditional approach involves studying smithing slags, but their chemical compositions are complex
9 and influenced by various substances accumulated in the smithing hearth. Another method involves
10 analyzing slag inclusions in metallic fragments, which can provide a direct information about the
11 chemical nature of the iron worked. Nevertheless, these fragments are frequently scarce or even
12 absent, rendering it challenging to evaluate the representativeness of the samples. A new approach
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13 focuses on studying hammerscale, which is the waste generated during the hammering of hot iron.
14 Unlike smithing slag, each hammerscale is produced from a single piece of iron. Unlike metal objects,
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15 hammerscale is often found in large quantities. Previous studies on experimental materials have
16 demonstrated that slag inclusions in the worked iron contribute to the formation of hammerscale. The
17 analysis of hammerscale can therefore provide valuable information about the chemical composition
18 and source of the iron that was processed in the smithing workshop. Studying a hammerscale
19 assemblage would allow to assess the diversity of the iron worked in the forge.
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20 The Weyersheim archaeological site in northeastern France, dating back to the early iron age (HAD3-
21 LTA, 5e BC) includes various structures, with a notable forge being of particular importance. Extensive
22 chemical analysis of 300 hammerscale samples and 77 slag inclusions from 6 iron waste has provided
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23 valuable insights. The findings reveal a distinctive geochemical signature characterized by enrichment
24 in elements like Vanadium (V>800 ppm), Chromium (Cr>400 ppm), Rare Earth Elements (REE)
25 (∑REE+Y>1500 ppm), particularly Heavy Rare Earth Elements such as Y (>500 ppm) and Yb (>100 ppm),
26 High Field Strength Elements HFSE (eg. U>30 ppm). The similarity between the hammerscale and slag
27 inclusions measured in iron waste samples points a direct connection between the slag inclusions and
28 hammerscale. The hammerscale samples exhibited a remarkable consistency in their chemical nature,
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29 indicating the utilization of one single chemically homogeneous iron source in the numerous forging
30 operations performed by the blacksmith. This scenario implies either a continuous supply from a single
31 producer or a brief and intensive work utilizing a steady iron stock. This iron source displayed specific
32 characteristics, particularly the enrichment and partitioning pattern of REE, that are uncommon and
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33 suggest a rare and distinct geological deposit or a closely associated group of deposits. Furthermore,
34 comparison with known iron artifacts from the surrounding regions indicated potential connections
35 with the bi-pyramid iron bars, specifically the iron bar recovered from Marsal (France). The elevated
36 levels of V, Cr, Al, REE and HFSE found in the slag inclusions in iron waste and hammerscale samples
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37 from Weyersheim, as well as in the majority of slag inclusions from bi-pyramid iron bars, indicate that
38 the iron ore used underwent substantial enrichment in these elements. Plausibly, the iron ore could
39 correspond to a weathered formation derived from peralkaline rocks. The Vosges and the Black Forest
40 massifs are identified as potential sources for the iron ore, considering their geological history.
41 However, no deposits or iron slag with a comparable composition have been discovered thus far,
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42 requiring further investigation to determine the specific geological formations responsible for the
43 unique geochemical characteristics observed in the worked iron of Weyersheim and most of the bi-
44 pyramid iron bar.
45 *=Corresponding author
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46 Keywords: iron circulation, procurement strategies, hammerscale analysis, slag inclusions analysis,
47 archaeological smithing workshop, early Iron Age
This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4601234
48 Introduction
49 Iron has played a pivotal role in human development throughout history. Its importance stems
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50 from its versatility and efficiency in the production of weapons and tools. As such, ironworking was a
51 crucial activity in past societies, influencing both power dynamics and economic systems. The ability
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52 to create weapons granted military advantage, while the use of iron tools facilitated agricultural and
53 craft production (Serneels, 2011; Mangin et al., 2004). Numerous iron smithies have been discovered
54 on various archaeological sites spanning different time periods. Despite extensive research and studies
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55 conducted to characterize these ironworking sites (Leroy et Cabboi, 2019; Bauvais et al., 2018;
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56 Berranger et al., 2014; Zaour et al., 2014; Serneels, 2014; Veldhuijzen and Rehren, 2007; Serneels et
57 al., 2005; Serneels et al., 2003) determining the origin and procurement of iron used in these
58 workshops remains challenging with current methods. Nevertheless, questions regarding the
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59 provenance and diversity of the worked metal assemblages, which comprise a collection of metallic
60 artifacts or objects processed, shaped, and crafted by skilled iron smiths, are fundamental to gain
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61 insight into the activities of these artisans and, more broadly, comprehending the historical circulation
62 of iron. By unraveling the sources of iron and the patterns of its distribution, one can gain a deeper
63 understanding of the technological advancements, social structures, and economic systems of the
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64 past.
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65 The smithing slag study, as discussed in previous research (Kramar et al., 2015; Le Carlier et al.,
66 2007; Serneels and Perret, 2007; Bauvais and Fluzin, 2006; Serneels and Perret, 2003; Serneels, 1993),
67 provides valuable insights but may not be sufficient to fully address the question of iron smith
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68 procurement. This approach involves examining the plano-convex bottom material that accumulates
69 in the hearth. This material comprises metallic particles, iron oxides, and slag inclusions originating
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70 from the metal being worked. Additionally, it may contain other external substances, such as fluxes
71 employed by the blacksmith, residues from the hearth's bottom and walls, or charcoal ashes, which
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72 can contribute to its composition. It is commonly regarded as the accumulation resulting from a single
73 day's work. Determining the chemical traces of the processed iron is often challenging, primarily
74 because the contribution of slag inclusions is relatively small compared to other factors, except in
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75 instances where the worked iron has undergone minimal refinement (Eschenlor and Serneels, 1991).
76 Additionally, a smithing slag can be the outcome of different pieces of worked iron, resulting in a
77 composite chemical composition.
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78 The analysis of slag inclusions, as described by previous studies (Blakelock et al., 2009;
79 Dillmann and l'Héritier, 2007), offers the advantage of obtaining a direct chemical signature of the
80 smelting slag. However, one of the challenges encountered in many case studies is the scarcity or
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81 absence of well-preserved, non-corroded iron artefacts. This limitation hampers the capacity to carry
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82 out extensive analyses on various iron artifacts, thereby complicating the assessment of how well the
83 analyzed remains represent the broader iron worked assemblage. Without enough well-preserved iron
84 artifacts, it becomes challenging to draw accurate conclusions about the characteristics and origins of
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85 the iron used in ancient smithing. This scarcity of iron artifacts poses a significant obstacle in
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86 understanding the iron circulation and procurement strategies employed. To overcome this limitation,
87 alternative approaches and methodologies may need to be explored.
88 A novel approach involves the analysis of hammerscale, which is the waste produced during
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89 the hammering of hot iron. Hammerscale comprises small particles with diverse morphologies,
90 including flakes, spheres, and irregular shapes. These particles are primarily composed of iron oxides
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91 and contain a more or less important silica component (Fig.1). Spherical hammerscale is known to be
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Figure 1: (A) Secondary electron image of spherical hammerscale, (B) Backscattered electron image of a spherical
hammerscale in a sectional view.
92 more homogeneous than other morphologies, as it crystallizes from melted material (Young., 2011,
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93 Dungworth et Wilkes., 2007). Additionally, spherical hammerscale tends to have a higher silica
94 component compared to flake hammerscale, which is primarily composed of iron oxides (Rodier and
95 Serneels, 2023).
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96 The abundance of hammerscale at archaeological sites makes it a valuable resource for
97 investigation, as it is often more readily available than intact metal objects. Additionally, each
98 hammerscale particle can be linked to a specific section of a single iron piece, distinguishing it from
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99 smithing slag. Previous research conducted in Rodier and Serneels (2023) on experimental
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100 hammerscale has revealed that slag inclusions present in the worked iron could contribute to the
101 chemical composition of hammerscale under specific conditions. The successful detection of slag
102 inclusion fingerprint in hammerscale relies on the presence of an adequate amount of such inclusions
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103 within the worked iron. It is crucial to limit the use of siliceous fluxes during the ironworking process,
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104 as excessive addition of these fluxes can significantly alter the chemical composition of the slag
105 inclusions. This alteration is particularly pronounced for major elements like silicon (Si), as well as
106 certain minor elements such as rubidium (Rb), strontium (Sr), and barium (Ba). However, if these
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107 conditions are met, the chemical composition of the slag inclusions remains intact and can still be
108 detected in hammerscale. In an active iron smith's workshop, where numerous iron pieces are worked,
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109 a substantial amount of hammerscale is generated from each individual iron piece. These particles
110 tend to mix on the workshop’s floor. When analyzing a specific hammerscale collection, such as
111 hundreds of hammerscale samples, it is unlikely to encounter hammerscale produced from the same
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112 iron piece multiple times within that same collection. Consequently, conducting a chemical analysis of
113 a specific quantity of hammerscale offers a valuable opportunity to gain insights into the chemical
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114 diversity of the iron processed by the ironsmith. Addressing the issue of representativeness often
115 encountered when analyzing slag inclusions in iron waste.

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116 This study will delve into the exploration of the Weyersheim archaeological site, situated in the
117 northeastern region of France. This significant site for early iron metallurgy in Europe dates back to the
118 end of the first Iron Age, specifically around the 5th century BC. It is characterized by a concentration
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119 of silos (50), and the remains of at least one forge. 70 kg of smithing slag and 30 kg of hammerscales
120 have been excavated. The total mass of forge residues, considering the non-excavated parts of the
121 silos, is around 130 kg. This substantial quantity of smithing slag indicates the magnitude and intensity
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122 of ironworking that occurred within the forge (Michler et al., 2018) which ranks Weyersheim among
123 the sites delivering the highest concentration of forge waste for this period (Ha D3 - LTA). The primary
124 objective of this study is to deepen our understanding of the procurement strategies employed by the
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125 blacksmiths at the Weyersheim archaeological site. The focus is on investigating whether the
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126 blacksmiths consistently relied on a single type of iron or if they had access to a variety of iron sources.
127 By examining the chemical characteristics of hammerscale and iron waste slag inclusions from the site,
128 the study aims to shed light on the procurement strategies, iron sources, and potential trade networks
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129 that were established by the blacksmiths. The primary focus of the research will be the analysis of 300
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130 hammerscale samples collected from the smithing pit in 4 different stratigraphic units (n=274), and
131 from another pit with metallurgical wastes (n=26), Tab.1. Based on estimations from the smithing slags
132 recovered, it is believed that around 400 kg of iron underwent processing at the Weyersheim ironsmith
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133 (Michler et al., 2018). Considering that the semi-products commonly circulating at that time typically
134 weighed between 5 to 10 kg (Berranger, 2014), a rough approximation suggests that at least anywhere
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135 from 80 to 40 iron semi-products were crafted at Weyersheim. Taking into consideration the number
136 of hammerscale samples analyzed and their recovery from various stratigraphic units, it is highly
137 probable that a substantial portion of the iron pieces or semi-products worked in the forge have been
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138 captured and represented in the hammerscale analysis. In addition, the study will involve examining
139 slag inclusions in six iron waste samples (two fragments of bloom, and four fragment of bars in the
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140 process of being shaped) (Fig.2). 4 were recovered from the smithing pit (WEY1014-15-1, WEY1014-
141 16-3, WEY1014-17-2, WEY1014-15-6) while the remaining two originated from another excavated
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142 structure (WEY32-1, WEY32-2), Tab.1. The chemical comparison between the hammerscale and slag
143 inclusions is a crucial aspect of the study. It will enable to identify any similarities or differences in
144 composition, providing valuable insights into the relationship between the waste materials and the
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145 iron worked. The chemical variability of the iron proceeds in the forge will be discussed as well as the
146 origin of the raw material by comparing the chemical characteristics of the semi products circulating
147 in the same area during the first Iron Age period.
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148
A D
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B E
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C F
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1 cm
Figure 2: Pictures taken in reflected light of the different metallic samples analyzed in this study. A: WEY1014-15-1, B:
WEY1014-15-6, C: WEY1014-16-3, D: WEY1014-17-2, E: WEY32-2, F: WEY32-1
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Iron artefact Slag inclusion Hammerscale

1014 structure WEY1014-15-1 (bar) n=13 n=274
WEY1014-16-3 (bar) n=14
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WEY1014-17-2 (bar) n=14

WEY1014-15-6 (bar) n=15
1003 structure none - n=26
1032 structure WEY32-1, WEY32-2 (fragment of bloom) n=8 ; n=13 none
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Table 1 : Summary of analyzed samples

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149 Methodology
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150 2.1 Slag inclusions
151 To investigate the presence and composition of slag inclusions, six iron waste samples from the
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152 Weyersheim archaeological site were selected for analysis. The objects were first analysed under a
153 metallographic microscope after cutting completely along a longitudinal axis. The samples were
154 polished using silicon carbide paper (ranging from grades 80 to 4000 μm) and diamond suspensions (3
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155 and 1/4 μm). The objective was to determine the proportion and nature of inclusions, and the process
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156 of fabrication (by simple deformation or with welding). The analyses were carried out at the Laboratory
157 Métallurgies and Cultures (IRAMAT-UMR7065, Belfort, France). The major component elements of the
158 inclusions were determined using energy-dispersive X-ray spectrometry (EDX). This involved utilizing a
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159 silicon drift detector coupled with a field-emission gun scanning electron microscope (SEM-FEG, JEOL
160 7001-F at IRAMAT-LAPA-UMR7065, Université Paris-Saclay) to obtain large hyperspectral maps of the
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161 transversal cross-sections studied through metallography. Hundreds to thousands of inclusions were
162 analyzed for each sample during this stage. Subsequently, around 15 smelting inclusions from each
163 sample were selected for further analysis using Laser Ablation-Inductively Coupled Plasma-Mass
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164 Spectrometry (LA-ICP-MS). The analyses were carried out at the Centre Ernest Babelon (IRAMAT-
165 UMR7065, Orléans, France) using a VG Plasma Quad PQXS instrument coupled with a Nd:YAG-type
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166 laser operating at a quadrupled 266-nm wavelength. This technique enabled the determination of
167 trace element composition in the selected inclusions. A total of 39 chemical elements, were measured.
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168 The data were then transformed and normalised into logarithmic ratios following the procedure
169 detailed in Leroy et al. (2012). For each element, an XE value was calculated, which was used
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170 afterwards:
171 XE=log([E])−1/N∑K=1Nlog([EK])
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172 where (EK) is the N least variable and the best measured element.
173 In this study, the elements considered in the statistical analyses and the EK elements were as follows:
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174 Ce, Eu, Gd, Hf, La, Nb, Nd, Pr, Sm, Tb, Th, U, Y and Yb. The application of PCA allowed for the comparison
175 of a large number of analyses, following similar approaches employed in previous studies (Berranger
176 et al., 2020; Hendrickson and Leroy, 2020; Dillmann et al., 2017; Bauvais et al., 2018; Leroy et al., 2018;
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177 Disser et al., 2017; Charlton et al., 2012; Leroy et al., 2012).
178 2.2 Hammerscale
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179 The 300 spherical hammerscale specimens collected from the Weyersheim site were prepared for
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180 analysis using LA-ICP-MS. Out of the total hammerscale samples (n=300), the majority (n=274) were
181 obtained from the 1014 structure (the smithing pit), spanning across four distinct stratigraphic units.
182 The remaining hammerscale samples (n=26) were recovered from the 1003 structure. To prepare the
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183 hammerscale samples, they were fixed in epoxy resin and then polished to reveal the desired sections,
184 starting with a rough polish of 600 µm and 250 µm using silicon carbide discs, followed by a second
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185 polishing with diamond suspensions of 9, 3, 1, and ¼ µm. The LA-ICP-MS analyses were also carried
186 out at the Centre Ernest Babelon (IRAMAT-UMR7065, Orléans, France). The laser repetition rate was
187 set to 6 Hz, with an ablation time of 46 seconds and a laser diameter of 100 µm. Each hammerscale
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188 sample was ablated twice at different locations, and the results reported for each hammerscale
189 represent the average of these two ablations. The variability of the chemical element concentrations
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190 between the two analyses is relatively low, as indicated in the supplementary data. A total of 48
191 elements were measured during the LA-ICP-MS analysis. An uncertainty of 5% was considered for the
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192 measurements. The quantification procedure developed by Gratuze (1999) and Gratuze et al. (2001)
193 was employed.

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194 Results
195 3.1 Slag inclusions in iron waste.
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196 3.1.1 Major elements
197 The Harker diagram plot of major element concentrations in the six studied iron waste samples
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198 WEY1014-15-1, WEY1014-16-3, WEY1014-17-2, WEY1014-15-6, WEY32-2 and WEY32-1 (Fig.3) reveals
199 interesting findings. The concentration of SiO2 in the slag inclusions shows variability not only between
200 different waste samples but also within the same object. For example, the SiO2 content ranges from 2
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201 to 25 wt.% in WEY1014-15-6 and from 35 to 70 wt.% in WEY1014-16-3. The observed variation in SiO2
202 content may be attributed to differences in iron smelting efficiency or a potential iron contamination
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203 during the analysis process. This could be corrected by a normalization without Fe. Fe normalization
204 involves calculating the sum of chemical elements excluding Fe (FeN). However, it is important to note
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205 that Fe normalization will not be applied to the other major elements because their ratios are more
206 discernible when represented in a binary diagram format. In addition to SiO2, other major elements
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207 such as Al2O3, K2O, CaO exhibit relatively high concentrations. The Al2O3 content reaches up to 20 wt.%
208 in WEY1014-15-1, while K2O reaches up to 4,5 wt.% in WEY1014-17-2 and WEY1014-16-3. CaO can also
209 be found in concentrations up to 7 wt.% in WEY1014-16-3 and WEY1014-15-1. The remaining major
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210 elements, MgO, TiO2, show variable concentrations but generally lower than Al2O3, K2O, and CaO. MgO
211 reaches up to 2.5 wt.% in WEY1014-17-2, TiO2 reaches up to 1.5 wt.% in WEY1014-15-1. For the
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212 majority of slag inclusions measured, the content of P2O5, Na2O, and MnO falls below the detection
213 limit of SEM-EDS. There is a positive correlation between Al2O3, MgO, K2O, CaO, TiO2 and SiO2.
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214 Al2O3/SiO2 ratio is relatively consistent among the four iron waste samples WEY1014-16-3, WEY1014-
215 17-2, WEY1014-15-6, and WEY32-2 with a ratio of 0.2. However, in the case of WEY1014-15-1 and
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216 WEY32-1 there is an enrichment in Al2O3 compared to SiO2, resulting in an Al2O3/SiO2 ratio of 0.3.
217 TiO2/SiO2 is also relatively constent for the 6 iron samples, around TiO2/SiO2 = 0,0125. Other ratios such
218 as MgO/SiO2, K2O/SiO2, CaO/SiO2 show some variability between the different iron waste samples. For
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219 example, MgO/SiO2 ranges from 0.25 in WEY32-1 to 0.0125 in WEY1014-15-1, K2O/SiO2 ranges from 1
220 in WEY32-2 to 0.025 in WEY1014-15-6 and CaO ranges from 2 in WEY32-1 to 0,05 in WEY1014-15-6.
25 35
SI in WEY1014-15-1
SI in WEY1014-16-3
SI in WEY1014-17-2 30
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SI in WEY1014-15-6
20 SI in WEY32-2
SI in WEY32-1
25
Al2O3FeN (wt.%)
Al2O3(wt.%)
15
20
15
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10
10
5
5
0 0
0 20 40 60 80 100 0 20 40 60 80 100
SiO2(wt.%) SiO2FeN (wt.%)
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5 3
4,5
2,5
4
3,5
2
MgO (wt.%)
3
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K2O (wt.%)
2,5 1,5
2
1
1,5
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1
0,5
0,5
0 0
0 20 40 60 80 100 0 20 40 60 80 100
SiO2(wt.%) SiO2(wt.%)
3
10
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9
2,5
8
7 2
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6
TiO2(wt.%)
CaO (wt.%)
5 1,5
4
1
3
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2
0,5
1
0 0
0 20 40 60 80 100 0 20 40 60 80 100
221 SiO2 (wt.%) SiO2(wt.%)

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Figure 3: Harker diagram illustrating the concentration of major elements (Al2O3, MgO, CaO, K2O, TiO2) relative to
SiO2 measured in slag inclusions (SI) from the six-iron waste studied. SEM-EDS concentrations have been
normalized to 100 wt.%. In one graphic Al2O3 and SiO2 has been Fe normalized.
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222 3.1.2 Trace elements
223 The slag inclusions in iron waste samples were normalized to the chemical composition of the Upper
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224 Continental Crust (UCC) using Taylor and McLennan, 1985 to identify geochemical anomalies related
225 to both the environment in which the iron ores were formed and the metallurgical processes that took
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226 place. Chondrite normalization seems less appropriate as it represents the geochemical composition
227 of the Bulk Earth. The iron waste samples exhibit significant geochemical anomalies for various
228 elements (Fig.4). Except for WEY32-2, all samples display a substantial beryllium (Be) anomaly, with
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229 concentrations reaching up to 90 times higher than the UCC (CBe = 330 ppm) for WEY1014-15-1, 75
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230 times for WEY1014-16-3, 45 times for WEY1014-15-6, 25 times for WEY1014-17-2, and up to 8 times
231 for WEY32-1. Gallium (Ga) also shows anomalies in all iron waste samples, with concentrations up to
232 26 times higher than the UCC for WEY32-2 and up to 10 times higher for the other iron waste samples,
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233 except for WEY32-2, which is up to 4 times the UCC. The anomalies of vanadium (V), zirconium (Zr),
234 niobium (Nb), hafnium (Hf), tantalum (Ta), thorium (Th), and uranium (U) in the different iron waste
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235 samples are of the same order of magnitude, with concentrations around 10 times higher than the
236 UCC. Concentrations for these elements vary, with CV up to 1100 ppm, CZr up to 1200 ppm, CNb up to
237 80 ppm, CHf up to 35 ppm, CTa up to 5 ppm, CTh up to 50 ppm, and CU up to 30 ppm. All the measured
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238 rare earth elements (REE), including lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium
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239 (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), yttrium (Y), and ytterbium (Yb),
240 exhibit strong anomalies in every iron waste sample (Tab.2).

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Pr
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241
Be V Cr Ga Zr Nb La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu Hf Ta W Th U
Pr
Slag inclusion
Cmax (ppm) 330 1100 n.d 430 1200 85 350 700 100 400 110 33 130 22 n.d 1210 n.d n.d n.d 65 n.d 35 5 n.d 50 30
Cmax/UCC 90 18 n.d 26 7 7 13 11 18 15 24 39 37 37 n.d 55 n.d n.d n.d 35 n.d 6 5 n.d 5 6
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Hammerscale
Cmax (ppm) n.d 650 1200 30 360 20 276 650 65 300 66 16 68 10 66 370 13 35 5 31 5 12 1 78 20 6
Cmax/UCC n.d 12 20 2 2 2 11 10 15 10 15 18 18 20 22 23 19 18 17 17 17 2 1 40 2 2
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Table 2: Maximum concentration (ppm) and maxmium concentration normalized to UCC using Taylor and McLennan
(1985) for measured elements in slag inclusions from the different iron wastes and hammerscale. n.d: no data.
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242 The iron waste samples display variation in the concentration of Fe among the different slag inclusion
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243 analyses. The slag inclusions in WEY32-1 have an average of approximately 80 wt.% Fe2O3 TOT,
244 whereas the slag inclusions in WEY1014-15-1 have an average of around 40 wt.% Fe2O3 TOT. This kind
245 of disparity could be attributed to the factors previously explained. This variability in Fe content can
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246 introduce fluctuations in the measured concentrations of other elements, making direct comparisons
247 challenging. One possible technique that can be employed to address fluctuations in measured
248 concentrations of other elements is normalization without Fe. The dispersion of slag inclusions
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249 chemical content within the same iron waste sample is relatively low for most elements, in 4 specimens
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250 WEY1014-16-3, WEY1014-15-6, WEY32-1, WEY 1014-15-1 with variations less than 4 times the
251 SampleFeN/UCC (Fig.5). V shows higher variability within the same iron waste sample, ranging from 1
252 to 10 times the UCC for WEY1014-16-3 and from 0.1 to 2 times the UCC for WEY1014-15-1. However,
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253 the 2 other specimens WEY1014-17-2 and WEY32-2, exhibit significant variation of up to an order of
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254 magnitude (10 times SampleFe/UCC) for most elements. In terms of chemical patterns, WEY1014-15-
255 1, WEY1014-16-3, WEY1014-15-6, and WEY32-1 show a striking similarity in the distribution of the 21
256 elements analyzed. These samples exhibit specific enrichment in some heavy rare earth elements
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257 (HREE), Y, and Yb compared to light rare earth elements (LREE), with a positive Y anomaly. Positive
258 anomalies in Zr, U, Nb (except for WEY1014-15-1), and a negative anomaly in Ba are also observed.
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259 WEY1014-17-2 shares similar chemical pattern characteristics with the previously mentioned samples,
260 except for a relatively lower chemical partitioning between LREE and HREE. On the other hand, WEY32-
261 2 exhibits a distinct pattern, with a strong positive anomaly in Ga (up to 60 times the UCC) and Ba (up
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262 to 10 times the UCC) compared to the other iron waste samples. Additionally, a significant negative
263 anomaly in Ce is observed in all slag inclusion measurements of WEY32-2, and there is no discernible
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264 chemical partitioning between LREE and HREE, with La being 12 times the UCC and Y being 6 times the
265 UCC for the same slag inclusion.

Pr
13
266 90
SI in WEY1014-15-1
SI in WEY1014-16-3
Be SI in WEY1014-17-2
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SI in WEY1014-15-6
80 SI in WEY32-2
SI in WEY32-1
70
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60
Sample/UCC
50
40
Ga REE
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30
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20
V U
10 ZrNb
Hf
UCC er
0 Pr Sm Gd Dy Ta Th
Be Cr Rb Zr Cs La Ho Tm Lu
V Ga Sr Nb Ba Ce Nd Eu Tb Y Er Yb Hf W U
Figure 4: Concentrations of various elements in slag inclusions measured in six iron waste
samples. The concentrations have been normalized to the Upper Continental Crust (UCC)
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using data from Taylor and McLennan (1985). The elements analyzed include Be, V, Ga, Rb, Sr,
Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Y, Yb, Hf, Ta, Th, and U. Y is plotted as a pseudo-
lanthanide between Dy and Ho. Elements that were not measured are indicated in red. (Cr,
Cs, Dy, Ho, Er, Tm, Lu, W).
1000
SI in WEY1014-15-1
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SI in WEY1014-16-3
SI in WEY1014-17-2
SI in WEY1014-15-6
SI in WEY32-2
SI in WEY32-1
100
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Sample FeN/UCC
10
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1
5 20
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0,1
V Ga Rb Sr Zr Nb Ba La Ce Pr Nd Sm Eu Gd Tb Y Yb Hf Ta Th U
Figure 5: Concentrations normalized without Fe of various elements in slag inclusions measured

in six iron waste. The iron normalized concentrations have been normalized to the Upper
Pr
Continental Crust (UCC) using data from Taylor and McLennan (1985). The elements analyzed
include V, Ga, Rb, Sr, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Y, Yb, Hf, Ta, Th, and U. Y is
plotted as a pseudo-lanthanide between Tb and Yb. The ordinate axis has been logarithmed
14
267 3.2 Hammerscale
ed
269 The Harker diagram presented in Figure 6 showcases the major element concentrations measured in
270 274 hammerscale samples retrieved from structure 1014, as well as 26 hammerscale samples from
iew
271 structure 1003. The hammerscale recovered from the two structures displays a significant range of
272 variability in SiO2 concentration, spanning from a few percent to 70 wt.%. It is important to note that
273 the SiO2 concentrations in the majority of hammerscale samples tend to fall within a relatively narrow
v
274 range, typically ranging from a few to 30 wt.%. This variation in silica content reflects the extent of slag
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275 inclusion involvement in the final mixture. Fe normalization, which was previously utilized for slag
276 inclusions analysis, holds the potential to correct the observed variation in silica content (Fig.6). A
277 significant number of hammerscale samples exhibit a relatively high concentration of Al2O3, with values
er
278 exceeding 6 wt.%. On the other hand, the concentrations of MgO are below 1 wt.%, K2O is below 2
279 wt.%, CaO is below 2 wt.%, TiO2 is below 0.5 wt.%. Evidence suggests a positive correlation among the
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280 elements Al2O3, MgO, K2O, TiO2, and SiO2 within the hammerscale samples. However, this correlation
281 is not observed for CaO. Additionally, certain elements exhibit a relatively constant ratio across the
282 measured hammerscale. Specifically, the Al2O3/SiO2 ratio approximates around 0.3, TiO2/SiO2 around
ot
283 0,015. Other ratios such as MgO/SiO2, K2O/SiO2, show some variability between the different
tn
284 hammerscale. MgO/SiO2 ranges from 0.0125 to 0.025, K2O/SiO2 ranges from 0,1 to 0,035. Based on
285 the major elements, it is not possible to chemically discriminate the hammerscale samples from
286 structures 1003 and 1014.

rin
ep
Pr
15
25 35
Hammerscale from 1003 structure (n=26)
30
ed
20
Al2O3FeN (wt.%)
25
Al2O3(wt.%)
15
20
15
iew
10
10
5
5
0 0
0 20 40 60 80 100 0 20 40 60 80 100
v
re
5 3
4,5
2,5
4
3,5
MgO (wt.%)
er 2
K2O (wt.%)
2,5 1,5
2
1
1,5
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1
0,5
0,5
0 0
0 20 40 60 80 100 0 20 40 60 80 100
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10 3
9
2,5
8
tn
7
2
CaO (wt.%)
TiO2(wt.%)
5 1,5
4
1
rin
2
0,5
1
0 0
0 20 40 60 80 100 0 20 40 60 80 100
ep
287
Figure 6: Harker diagram illustrating the concentration of major elements (Al2O3, MgO, CaO, K2O, TiO2) relative to SiO2
measured in hammerscale from 1014 structure, light orange and 1003 structure, red. In one graphic Al2O3 and SiO2
has been Fe normalized.
Pr
16
288 3.2.2 Trace elements
289 Like slag inclusions in iron waste, chemical concentrations of hammerscale, including minor and trace
ed
290 elements, have been standardized to the Upper Continental Crust (UCC) reference values (Taylor and
291 McLennan, 1985). Analysis of hammerscale have revealed significant variations in the chemical
iew
292 composition compared to the UCC (Fig.7). Geochemical anomalies can be detected for a diverse array
293 of chemical elements including REE and especially HREE (Tab.2). The concentrations of hammerscale
294 have also been normalized without considering the Fe content. The Weyersheim hammerscale exhibits
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295 a relative dispersion in the concentrations of several elements, including V, Ga, Rb, Sr, Ba, La, Ce, Pr,
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296 Nd, Sm, Eu, Gd, Tb, Y, and Yb (Fig.8). These elements show a variation, with differences of more than
297 a factor of 10 between the lowest and highest values of Sample FeN/UCC. On the other hand, elements
298 such as Zr, Nb, Hf, Ta, Th, and U show a lower dispersion, with differences of approximately a factor of
er
299 3 between the lowest and the highest. Upon comparing the 300 Weyersheim hammerscale patterns,
300 it becomes evident that there is a common feature, despite variations observed in a few chemical
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301 elements. Ga, Sr, and Ce exhibit diverse patterns within hammerscale, encompassing both positive and
302 negative anomalies. It is worth noting that these positive anomalies are only present in a small number
303 of hammerscale samples, while the majority of samples do not display such anomalies. Furthermore,
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304 the remaining REE exhibit similar chemical patterns, characterized by a distinct partitioning between
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305 LREE and HREE, along with a positive anomaly observed in Y. For the same hammerscale
306 CLaFeN/UCC=10 and CYFeN/UCC=60. Additionally, the chemical patterns for Zr, Nb, Hf, Ta, Th, and U
307 show notable reproducibility across the hammerscale samples. Based on the trace elements studied,
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308 it is not possible to chemically discriminate the hammerscale samples from structures 1003 and 1014.
309 Therefore, to enhance clarity, the hammerscale from both the 1003 and 1014 structures will be
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310 considered as a single entity for the following discussion.

Pr
17
311 90 Hammerscale from 1014 structure (n=274)
ed
80
70
iew
60
Sample/UCC
50
40
v
30
REE
re
20
Cr
V
W
10
CC Zr Nb Cs er U
0
Be Cr Rb Zr Cs La Pr Sm Gd Dy Ho Tm Lu Ta Th
V Ga Sr Nb Ba Ce Nd Eu Tb Y Er Yb Hf W U
Figure 7: Concentrations of various elements in hammercale. The concentrations have been

normalized to the Upper Continental Crust (UCC) using data from Taylor and McLennan (1985).
pe
The elements analyzed include, V, Cr, Ga, Rb, Sr, Zr, Nb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,
Y, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Th and U. Y is plotted as a pseudo-lanthanide between Dy and Ho.
Elements that were not measured are indicated in red.
1000 Hammerscale from 1014 structure (n=274)

ot
100
tn
Sample FeN/UCC
10
rin
1 5 10 20
ep
0,1
Figure 8: Concentrations normalized without Fe of various elements in hammerscale. The iron

normalized concentrations have been normalized to the Upper Continental Crust (UCC) using data
Pr
from Taylor and McLennan (1985). The elements analyzed include V, Ga, Rb, Sr, Zr, Nb, Ba, La, Ce,
Pr, Nd, Sm, Eu, Gd, Tb, Y, Yb, Hf, Ta, Th, and U. Y is plotted as a pseudo-lanthanide between Tb and
Yb. The Y ordinate scale has been logarithmed. A more detailed version of this figure can be found
in the supplementary data.
18
312 3.3 Comparaison between slag inclusions in iron waste and Hammerscale
ed
314 The slag inclusions measured in the iron waste samples exhibit higher concentrations of major
315 elements compared to the hammerscale (Fig.9). The concentration of Al2O3 in slag inclusions can reach
iew
316 up to 20 wt.%, although the majority of hammerscale samples exhibit a maximum concentration below
317 10 wt%. MgO concentrations can be as high as 2 wt.%, but it reaches a maximum of 1 wt.% in the
318 hammerscale. K2O concentrations can go up to 4,5 wt.%, whereas in the hammerscale, they reach a
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319 maximum of 3,5 wt.%. CaO concentrations can reach up to 7 wt.%, while in the hammerscale, they can
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320 go up to 3 wt.%. TiO2 concentrations can reach up to 1.5 wt.%, but in the hammerscale, they have a
321 maximum of 0.5 wt.%. In most cases, one can observe that the concentration grade of major elements
322 in hammerscale is lower compared to that in slag inclusions. This observed behavior confirms that
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323 hammerscale is typically formed through the process of remelting slag inclusions, accompanied by
324 varying amounts of iron oxides. The chemical ratios of Al2O3/SiO2, MgO/SiO2, CaO/SiO2, K2O/SiO2, and
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325 TiO2/SiO2 in hammerscale exhibit variability that corresponds to the range described by the slag
326 inclusions. The ratio of Al2O3/SiO2 in hammerscale is approximately 0.3, which is consistent with the
327 slag inclusions range of 0.3. Similarly, the ratio of MgO/SiO2 in hammerscale ranges from 0.25 to
ot
328 0.0125, aligning with the slag inclusions range. The ratio of K2O/SiO2 in hammerscale ranges from 1 to
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329 0.025, also falling within the slag inclusions range. The ratio of TiO2/SiO2 in hammerscale is
330 approximately 0.0125, which matches the slag inclusions value. However, the CaO ratio shows
331 significant variability both in slag inclusions and hammerscale, indicating a wide range of values.
rin
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Pr
19
25 35
SI in WEY1014-15-1
SI in WEY1014-16-3
SI in WEY1014-17-2 30
ed
SI in WEY1014-15-6
20 SI in WEY32-2
SI in WEY32-1
25
Al2O3FeN (wt.%)
Hammerscale (all)
Al2O3(wt.%)
15
20
15
10
iew
10
5
5
0 0
0 20 40 60 80 100 0 20 40 60 80 100
v
5 3
re
4,5
2,5
4
3,5
2
MgO (wt.%)
3
K2O (wt.%)
2,5
2
er 1,5
1
1,5
1
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0,5
0,5
0 0
0 20 40 60 80 100 0 20 40 60 80 100
10 3
9
ot
2,5
8
7
2
6
TiO2(wt.%)
CaO (wt.%)
tn
5 1,5
4
1
3
2
0,5
1
rin
0 0
0 20 40 60 80 100 0 20 40 60 80 100
332 SiO2(wt.%) SiO2(wt.%)
Figure 9: Harker diagram illustrating the concentration of major elements (Al2O3, MgO, CaO, K2O, TiO2) relative
to SiO2 measured in hammerscale and in slag inclusions from the 6-iron waste studied. In one graphic Al2O3 and
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SiO2 has been Fe normalized.

Pr
20
333 3.3.2 Traces elements
334 Hammerscale and slag inclusions show the same geochemical anomaly for the same elements, V, Ga,
ed
335 Zr, Nb, REE, Th, U (Fig.4, Fig.7). The slag inclusions measured in WEY1014-15-1, WEY1014-16-3,
336 WEY1014-17-2, WEY1014-15-6, WEY32-1 and hammerscale exhibit a similar range of Sample FeN/UCC
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337 for most of the chemical elements (Fig.10). However, in WEY1014-16-3, slightly higher values of
338 Sample FeN/UCC are observed for Zr and Nb, reaching up to 8 times the UCC. In WEY1014-15-1, Th
339 shows a slightly higher concentration than the hammerscale. On the other hand, the slag inclusions
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340 measured in WEY32-2 demonstrate higher contents of Ga (CGaFeN/UCC >20) compared to the
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341 hammerscale (CGaFeN/UCC <12). Similarly, Ba also exhibits higher content in slag inclusions measured
342 in WEY32-2, reaching up to 10 times times the UCC content, compared to the hammerscale, which
343 reaches up to 5 times the UCC. The CVFeN/UCC is lower for most of the slag inclusions measured in
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344 WEY1014-15-1 compared to the hammerscale. To facilitate readability, the patterns of slag inclusions
345 from WEY1014-15-1, WEY1014-16-3, WEY1014-17-2, WEY1014-15-6, WEY1014-16-3, and

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346 hammerscale have been averaged in Fig.11. However, it is important to note that this type of
347 representation leads to a significant loss of information on sample variability. In this case study, the
348 slag inclusions measured in iron and hammerscale samples exhibit a significant degree of chemical
ot
349 coherence as a group, with relatively low variation in terms of pattern shape. Nevertheless, it is
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350 important to acknowledge that some variation does exist among the samples. Therefore, it should
351 always be accompanied by the raw patterns (Fig.10) to provide a complete understanding. The
352 averaged pattern of the hammerscale is quite similar to the pattern measured in slag inclusions from
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353 WEY1014-15-1, WEY1014-16-3, WEY1014-17-2, and WEY1014-15-6. They all exhibit an enrichment in
354 HREE compared to LREE, with CLaFeN/UCC=10 versus CYFeN/UCC = 40 and CYbFeN/UCC = 20. However,
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355 the averaged pattern from slag inclusions measured in WEY32-2 differs significantly, with CLaFeN/UCC
356 = 10 versus CYFeN/UCC = 11 and CYbFeN/UCC = 8, a negative Ce anomaly, and a strong positive Ga
Pr
357 anomaly. Utilizing PCA calculations provides an alternative method for representing comparisons. The
358 advantage of using PCA for comparison purposes is that it reveals patterns and relationships between
21
359 samples. This can be particularly useful when exploring complex datasets with multiple variables, as it
ed
360 reduces the dimensionality of the data while retaining important information. However, the use of PCA
361 can overlook important information provided by element concentrations, which is crucial when
362 conducting comparison for provenance studies. Furthermore, the omission of key indicators like V or
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363 Cr in the current element analysis may lead to significant information gaps, potentially affecting the
364 accuracy and comprehensiveness of the comparison between different iron ore sources. Therefore,
365 PCA should be considered as a complementary tool rather than a replacement for concentration-based
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366 analysis. In Fig.12, most of the hammerscale data points closely plot to the iron waste, WEY1014-15-
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367 1, WEY1014-16-3, WEY1014-17-2, WEY1014-15-6, WEY32-1 indicating a strong resemblance.
368 Nevertheless, about twenty of hammerscale stand appart from the group. The slag inclusions
369 measurement from WEY32-2 exhibits a markedly different plot pattern. It appears distinct from the
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370 hammerscale data points and slag inclusions measured in the other iron artefacts. This distinct plot is
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371 due to the lower chemical partionning between LREE and HREE in WEY32-2 than in the other iron
372 pieces. The data points from WEY32-2 are primarily influenced by the variables La, Pr, Sm, Nd. Results
373 from the spider diagrams and PCA correlate well. These two approaches provide valuable information
ot
374 and complement each other in representing and analyzing data, offering distinct perspectives.
tn
rin
ep
Pr
22
1000 SI in WEY1014-15-1
SI in WEY1014-16-3
SI in WEY1014-17-2
ed
SI in WEY1014-15-6
SI in WEY32-2
SI in WEY32-1
Hammerscale (all)
100
Sample FeN/UCC
iew
10
v
5 10 20
1
5 20
re
0,1
375 V Ga Rb Sr Zr Nb Ba La Ce Pr Nd Sm Eu Gd Tb Y Yb Hf Ta Th U
Figure 10: Iron normalized concentrations of various elements in hammerscale and slag inclusions
measured in the 6-iron waste studied. The iron normalized concentrations have been normalized to
er
the Upper Continental Crust (UCC) using data from Taylor and McLennan (1985). The elements analyzed
include V, Ga, Rb, Sr, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Y, Yb, Hf, Ta, Th, and U. Y is plotted as a
pseudo lanthanide between Tb and Yb. The ordinate axis has been logarithmed
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1000 SI in WEY1014-15-1
SI in WEY1014-16-3
SI in WEY1014-17-2
SI in WEY1014-15-6
SI in WEY32-2
SI in WEY32-1
Hammerscale (all)
100
ot
Sample FeN/UCC
tn
10
1
rin
0,1
376 V Ga Rb Sr Zr Nb Ba La Ce Pr Nd Sm Eu Gd Tb Y Yb Hf Ta Th U
ep
Figure 11: Iron normalized and averaged concentrations of various elements in hammerscale and slag
inclusions measured in the 6-iron waste studied. The iron normalized concentrations have been
normalized to the Upper Continental Crust (UCC) using data from Taylor and McLennan (1985). The
elements analyzed include V, Ga, Rb, Sr, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Y, Yb, Hf, Ta, Th, and
U. Y is plotted as a pseudo-lanthanide between Tb and Yb. The ordinate axis has been logarithmed
Pr
23
8 Xe_Nb
Xe_Hf WEY1014-15-1
Xe_Th
Xe_U
WEY1014-16-3
Xe_Y WEY1014-17-2
ed
Xe_Yb WEY1014-15-6
6
Xe_Ce
WEY32-2
WEY32-1
Xe_Pr Hammerscale (n=300)
Xe_La
Xe_Tb Xe_Nd
4 Xe_Gd
Xe_Eu
Xe_Sm
iew
2
F2 (22,02 %)
-2
v
re
-4
-6
-8
-8 -6 -4 -2
er
0 2 4 6 8 10
F1 (38,91 %)
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8
4
ot
2
F3 (17,81 %)
0
tn
-2
-4
rin
Xe_Tb Xe_Gd
Xe_Yb
Xe_Y Xe_Eu Xe_U
Xe_Th
Xe_Sm
Xe_Nb
-6 Xe_Hf Xe_Nd
Xe_Pr
Xe_La
-8
ep
Xe_Ce
-10
-8 -6 -4 -2 0 2 4 6 8 10
377 F1 (38,91 %)
Pr
Figure 12: PCA carried out on the xij of the slag inclusions in Weyersheim iron waste, WEY1014-15-1,
WEY1014-16-3, WEY1014-17-2, WEY1014-15-6 and WEY32-1, WEY32-2 and hammerscale.
24
378 Discussion
379 4.1 Implications for the Weyersheim iron supply
ed
380 The hammerscale and slag inclusions analyzed in the five iron waste samples, WEY1014-15-1,
381 WEY1014-16-3, WEY1014-17-2, WEY1014-15-6 and WEY32-1 exhibit a distinct chemical composition
iew
382 compared to materials from the upper continental crust. These samples display significant enrichment
383 in V, Cr, and REE, particularly HREE such as Y and Yb. Additionally, there is a relative enrichment in
384 other elements like Zr, Nb, Hf, Th, U. Although there are some variations observed in certain elements
v
385 (such as Ga, Sr, and Ce), the utilization of both spider diagrams and PCA for comparative analysis on
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386 hammerscale and iron waste samples highlights a strong overall similarity. This similarity in the
387 chemical composition and ratios of major and trace elements between slag inclusions and
388 hammerscale indicates a clear chemical link. While there may be instances where some hammerscale
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389 samples appear to deviate from the main group, the majority of them exhibit a cohesive grouping. The
390 hammerscale sampling, which is likely indicative of the chemical composition of multiple worked iron
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391 pieces, suggests a remarkable consistency in the chemical nature of the iron throughout the diverse
392 forging operations performed by the blacksmith at Weyersheim. The slag-enrichment in non-reducible
393 elements during the smelting process, could not fully explain the observed strong geochemical
ot
394 anomalies. The extent of enrichment observed in the hammerscale and slag inclusions in iron waste
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395 samples, particularly up to 50 times the values found in the UCC for elements like Y, is beyond what
396 could be explained by smelting alone. This implies that the iron ore used in the smelting process must
397 have been initially very enriched in REE and various other elements. Furthermore, the highly specific
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398 partitioning pattern of REEs strongly suggests that the geological formation used as an iron ore source
399 is unique and distinct. Indeed, only specific conditions lead to REE enrichment, and an even rarer set
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400 of conditions results in the partitioning of HREE and LREE (Hoshino et al., 2016; Kynicky et al., 2012;
401 Chakhmouradian and Zaitsev, 2012). This observation implies that the iron mainly worked in the forge
402 structure is predominantly sourced from a rare and distinct deposit or a closely associated group of
Pr
403 deposits. The relative chemical variability observed in hammerscale could be explained by small
25
404 differences from one batch to another used during the different smelting operations. In contrast, the
ed
405 iron waste sample WEY32-2, a bloom fragment, found in structure 1032 exhibits distinct chemical
406 characteristics compared to the other iron artefacts and hammerscale. It displays a strong positive
407 anomaly in gallium (Ga), a negative anomaly in cerium (Ce), and no partitioning between LREE and
iew
408 HREE. The hammerscale measurements do not match chemically with WEY32-2, indicating that this
409 iron waste was likely imported from another source and was not or minimally worked in structure 1014
410 or 1003. It appears that the majority, of the estimated 400 kg of iron worked in the Weyersheim
v
411 smithing workshop originated from a single source. Macroscopic and metallographic analysis has
re
412 showed that a part of the iron was imported in its raw form (Michler et al. 2018). Two hypotheses can
413 be proposed to explain these findings. Firstly, the ironworking activity within Weyersheim may have
414 been characterized by a brief but intensely productive phase, indicative of the utilization of a singular
er
415 stock of iron with identical chemical composition, all stemming from a common and geologically
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416 distinct source. Secondly, it is also plausible that the iron smith received a continuous and consistent
417 supply over time from a single producer who consistently employed the same specific iron ore. In both
418 cases, this main supply may have been occasionally supplemented by a different source of iron, also
ot
419 imported in its raw form. The absence of a shift in the concentrations of hammerscale towards the
420 siliceous pole in comparison to slag inclusions concentrations suggests that sand fluxes were not
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421 utilized by the blacksmith. Typically, the use of sand fluxes in ironworking processes would result in an
422 increase in silica concentrations in the hammerscale with limited or no influence on the other major
423 and trace elements. However, in the analyzed samples, the concentrations of silica and other major
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424 elements do not show a significant deviation that would indicate the presence of sand fluxes.
425 Nevertheless, variations in calcium levels have been observed and could be attributed to ash
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426 contamination. This observation is important as it provides insights into the specific techniques and
427 materials employed by the blacksmith during the ironworking process.

Pr
26
428 4.2 Implications for the Provenance of the Weyersheim worked iron.
ed
429 Several studies, including Berranger et al. (2023), Berranger et al. (2021), Bauvais et al. (2021), Bauvais
430 et al. (2018), Berranger and Fluzin (2012), have emphasized the significance of circulating iron semi-
431 products during the early Iron Age in Western Europe. These iron semi-products have been classified
iew
432 into two groups: the bi-pyramid bar and the currency bar. A chronology has been proposed, based on
433 archaeological datas and radiocarbon datings, with the inherent limitation of the method for this
434 period Berranger et al. (2021). The bi-pyramid iron bars have been dated to a narrower time range,
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435 spanning from approximately 800 BCE to 500 BCE. In contrast, the Currency iron bars have a wider
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436 temporal range, extending from around 550 BCE to 200 BCE. Considering the temporal overlap
437 between the iron bars and the archaeological site of Weyersheim, it is plausible that the forge at
438 Weyersheim could have used these iron bars as a supply source. Interestingly, some deposits of these
er
439 artifacts have been found relatively close to the Weyersheim archaeological site (Fig.13). Some
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440 currency bars discovered in the Jura region, the Doubs and Saône river region, and some bipyramid
441 bars discovered close from the Rhine and the Danube River has been previously studied (Berranger et
442 al., 2021; Dillmann et al., 2017). The chemical composition of the slag inclusions has been measured in
ot
443 these artefacts making their findings available for comparison with the results of the current study
444 conducted in Weyersheim (Tab.3).

tn
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ep
Pr
27
ed
v iew
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er
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445
Figure 13: Distribution map of currency (pink) and bi-pyramid bars (green). Mentioned sites are highlighted by red circle
while the Weyersheim site is specifically marked with a cross symbol. 1: Chalon-sur- Saône, 2: Champdivers, 3: Colmar-La
Digue, 4: Durrenentzen, 5: Waiblingen, 6: Farebersviller, 7 : Heiligenberg, 8: Marsal-La Digue, 9: Pouilly-sur-Saône, 10:
Renningen, 11: Romain, 12: Valempoulières, 13: Vix, 14: Hochdorf, 15: Xirocourt.
ot
Locality Specimen N°Fig. 13 Reference

Chalon-sur- Saône SAO 82-07-06 A, SAO 82-07-06 B 1 Berranger et al., 2021
Currency Champdivers CHAMP D.99-17-05 2 Berranger et al., 2021
tn
bar Pouilly-sur-Saône SAO 81-03-01 9 Berranger et al., 2021

Valempoulières VAL01 12 Berranger et al., 2021
Colmar-La Digue Colmar 3 Dillmann et al., 2017
Durrenentzen DUR48, DUR40, DUR6, DUR3 4 Dillmann et al., 2017
rin
Waiblingen Waiblingen 5 Dillmann et al., 2017

Farebersviller Far1 6 Dillmann et al., 2017
Bi- Heiligenberg Heiligenberg41/1, Heiligenberg42 7 Dillmann et al., 2017
pyramid Marsal-La Digue Marsal1, Marsal3 8 Dillmann et al., 2017
Renningen Renningen 10 Dillmann et al., 2017
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Romain Romain1 11 Dillmann et al., 2017

Vix VIX D59-16 13 Dillmann et al., 2017
Hochdorf METC118 14 Dillmann et al., 2017
Xirocourt Xir1 15 Dillmann et al., 2017
Pr
Table 3: Artefacts studied by Berranger et al., 2021 and Dillmann et al., 2017 used for comparison in the current study.
28
446 Among the studied group of currency bar (Berranger et al. 2021), only a few specimens display an
ed
447 enrichment in ∑REE+Y, as well as High Field Strength Elements (HFSE), Zr, Hf, Nb, Ta, Th, U, along with
448 distinctive chemical partitioning between HREE and LREE (n=5/20). These bars include one from the
449 Pouilly-sur-Saône deposit (SAO 81-03-01), two from the Chalon sur Saône deposit (SAO 82-07-06 A,
iew
450 SAO 82-07-06 B), one from Valempoulières (VAL01), and one from Champdivers (CHAMP D.99-17-05).
451 Despite some similarities, particularly regarding the chemical partitioning between LREE and HREE, it
452 is evident from the spider diagram presented in Fig.14 that none of the bars correspond to the iron
v
453 that was worked in Weyersheim. In contrast to the iron pieces and hammerscale from Weyersheim,
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454 all these bars exhibit a significant positive anomaly in Ga, along with a relative depletion in HFSE such
455 as Zr, Nb, Hf, Ta, as well as Th and U, when compared to the REE.
1000 SI avaraged in WEY1014-15-1

er
SI avaraged in WEY32-1
SI avaraged in WEY1014-16-3 Hammerscale avaraged (All)
SI avaraged in WEY1014-17-2 SI avaraged for each REE-enriched currency iron bar (n=5) (Berranger et al., 2021)
SI avaraged in WEY1014-15-6 (VAL01, SAO82-07-06A, SAO82-07-06B, SAO81-03-01, CHAMPD99-17-05)
pe
100
Sample FeN/UCC
VAL01
ot
SAO82-07-06A
10
SAO81-03-01
CHAMPD99-17-05
SAO82-07-06B
tn
1
rin
0,1
Figure 14: Iron normalized concentrations of various elements in hammerscale (300 samples avaraged), slag
ep
inclusions avaraged in WEY1014-15-1, WEY1014-16-3, WEY1014-17-2, WEY1014-15-6, WEY32-1 and SI averaged in

5 REE-enriched currency iron bars (Berranger et al., 2021). The corpus of the 5 currency iron bars is composed by
VAL01, SAO82-07-06A, SAO81-03-01, CHAMPD99-17-05, SAO82-07-06B. The iron normalized concentrations have
been normalized to the Upper Continental Crust (UCC) using data from Taylor and McLennan (1985). The elements
analyzed include V, Ga, Rb, Sr, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Y, Yb, Hf, Ta, Th, and U. Y is plotted as a
pseudo lanthanide between Tb and Yb. The ordinate axis has been logarithmed
Pr
29
456 In the group of Bi-pyramid iron bars studied by Dillmann et al. (2017), nearly all specimens (n=14/15)
ed
457 exhibit an enrichment in ∑REE+Y, ranging from 500 ppm to 6000 ppm, as well as HFSE, Zr (up to 1400
458 ppm), Nb (up to 60 ppm), U (up to 200 ppm), along with distinctive chemical partitioning between
459 HREE and LREE. The specific bi-pyramid iron bars that display these characteristics are named
iew
460 Heiligenberg41/1, Heiligenberg42, Renningen, Waiblingen, Colmar, Marsal3, Marsal1, Romain1, Xir1,
461 VIX D59-16, DUR48, DUR40, DUR3, METC118 (Tab.3). The Dur6 bars recovered in Durrenentzen do not
462 fit into the category of REE-enriched bars. On the other hand, the Far-1 bar recovered in Farebersviller
v
463 appears to be the result of a combination of two distinct masses of metal, one being slag inclusions
re
464 REE enriched (Far1-1) and the other being non-slag inclusions REE enriched (Far1-2). Making a proper
465 comparison of the spider diagram (Fig.15) with the extensive dataset and their variability becomes
466 relatively challenging. One notable observation is that despite the distinctive partitioning of LREE and
er
467 HREE, most of the slag inclusions measurements in these bars exhibit a strong negative anomaly for
pe
468 cerium (Ce) and a strong positive anomaly in Gallium (Ga). To enhance readability and emphasize
469 trends, a PCA analysis is presented in Figure 16. The slag inclusions measurements obtained from the
470 bi-pyramid iron bar recovered from the Marsal site (Marsal1 composed by two mass Marsal1-1 and
ot
471 Marsal1-2) align closely with the majority of hammerscale and iron waste samples from Weyersheim.
472 This correspondence is further validated by the spider diagram presented in Figure 17. The chemical
tn
473 patterns observed exhibit an extraordinarily high degree of similarity. Hence, it can be inferred that
474 the iron predominantly worked in Weyersheim is likely connected to the bi-pyramid iron bars,
475 specifically to the iron bar recovered in Marsal. However, a paradox arises when considering the
rin
476 geological conditions required to obtain an iron ore with such unique geochemical characteristics, as
477 they are extremely rare. Yet, this specific signature (LREE and HREE enrichment and partionning) can
ep
478 be identified in most of the bi-pyramid iron bars (n=14/15) and the iron predominantly used in
479 Weyersheim forge. One possible explanation is that a single ore deposit or a group of deposits with a
Pr
480 distinct chemical signature served as the primary source for the majority of iron circulated in the north
481 alpine area during this early period. The REE enrichment in iron ores may be attributed to the chemical
30
482 influence of peralkaline rocks. REE and HFSE are considered incompatible elements, meaning they
ed
483 preferentially concentrate in the liquid phase rather than being incorporated into minerals during
484 fractional crystallization of a magma. In peralkaline magmas, which are often alkaline and silica-
485 undersaturated, the melt composition allows for greater mobility and retention of incompatible
iew
486 elements. This behavior contributes to their enrichment in the resulting peralkaline rocks. Other
487 factors like fluid-magmatic interactions or the nature of the magmatic source can also contribute to
488 REE enrichment in these type of rocks (Dostal, 2017; Schmitt et al., 2002). However, the high
v
489 concentrations of V, Cr, Ga, Al and the chemical partionning between LREE and HREE observed cannot
re
490 be fully accounted by the influence of peralkaline rocks alone. These features are more commonly
491 associated with lateritic rock formations. In lateritic environments rocks undergone geochemical
492 transformation and V, Cr, Ga, and Al tend to accumulate, leading to their higher concentrations in
er
493 lateritic rock and soil profiles (Berger et Frei., 2014; Gu et al., 2013). Therefore, while these elements
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494 may not be characteristic of the original rock type, their presence at elevated levels can be attributed
495 to the influence of weathering processes. The REE enrichment and chemical partitioning between LREE
496 and HREE has been also documented in geological formations that have experienced weathering, such
ot
497 as ionic adsorption clays (Borst et al., 2020; Estrade et al., 2019; Estrade et al., 2014). They refer to a
498 type of clay mineral that could adsorb and retain various ions on its surface. Some of these clay
tn
499 minerals have a higher affinity for HREE and may preferentially adsorb and retain them in their crystal
500 lattice structures (Wu et al., 2023). A suitable iron ore would be then an enriched weathered formation
501 derived from a peralkaline granite protolith. A weathered formation could also provide a plausible
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502 explanation for the observed relative chemical variability in slag inclusions measured in the different
503 iron bar. The composition of the extracted ore may vary depending on the specific horizon from which
ep
504 they were obtained. Considering the distribution area of bi-pyramid iron bars and the localization of
505 the Weyersheim smithing, there are two Variscan alkaline massifs that might have experienced
Pr
506 weathering processes under hot and humid climatic conditions, similar to those during the Eocene
507 period: the Vosges and the Black Forest massifs. Nevertheless, until now no deposits of iron ore or
31
508 iron slag with a similar composition have been successfully recovered or identified (Dillmann et al.,
ed
509 2017). During the Bronze Age, gossans, also known as iron caps, were valuable sources of copper,
510 silver, and antimony (Radivojević et al., 2010; Pernicka et al., 1993). The formation of gossans is a result
511 of the natural weathering and oxidation of sulfide minerals near the Earth's surface. When sulfide
iew
512 minerals encounter oxygen and water, they undergo a chemical reaction called oxidation. This process
513 breaks down the sulfide minerals, releasing metal cations (such as copper, silver, and lead) and sulfuric
514 acid. The metal cations and other dissolved ions migrate through the rocks, they accumulate in the
v
515 upper parts of the formation. Iron-rich secondary minerals like goethite and hematite are commonly
re
516 found in gossans and give them their characteristic reddish-brown or yellowish-brown coloration. The
517 mysterious slag inclusions chemical composition recovered in Weyersheim and in most bi-pyramid iron
518 bars could potentially be attributed to the utilization of gossans formed during peralkaline rocks
er
519 weathering. As discussed in the studies by Erb-Satullo et al. (2020) and Erb-Satullo (2019), the presence
pe
520 of iron caps would have undoubtedly attracted the interest of past societies. These geological
521 formations may have presented intriguing possibilities for early iron extraction. The findings of this
522 study strongly resonate with this theory.

ot
tn
rin
ep
Pr
32
523
ed
1000
Romain1-1
VixD59-16 Colmar
iew
Dur6
100 Heiligenberg 42
Xir 1
Xir 2 Dur40-2
METC118
Dur40-1 Romain1-2
Waiblin-
Sample FeN/UCC
gen Far1-1
Heiligenberg 41/1
Marsal 3
Marsal1-1
Dur48
Marsal1-2
Rennigen
10
v
re
1
0,1
V Ga Rb
SI avaraged in
SI avaraged in
Sr Zr
WEY1014-15-1
WEY1014-16-3
Nb Ba La Ce
er Pr Nd Sm Eu Gd Tb Y Yb Hf Ta Th
SI avaraged for each REE-enriched bi pyramid iron bar (n=15) (Dillmann et al., 2017)
U
(VixD59-16, Colmar, Rennigen, Waiblingen, Dur6, Dur 40 (Dur40-1, Dur 40-2),

SI avaraged in WEY1014-17-2
Dur48 (Dur48-1), Romain1 (Romain1-1,Romain1-2) Heiligenberg 42, Heiligenberg 41/1,
SI avaraged in WEY32-1 METC 118, Far1 (Far1-1), Marsal 1 (Marsal1-1, Marsal 1-2), Marsal 3, Xir 1(Xir1-1, Xir1-2)
pe
524 Hammerscale avaraged (All)
Figure 15: Iron normalized concentrations of various elements in hammerscale (300 samples avaraged),
slag inclusions averaged in WEY1014-15-1, WEY1014-16-3, WEY1014-17-2, WEY1014-15-6, WEY32-1 and
slag inclusions averaged in 14 bi-pyramid iron bars (Dillmann et al., 2017). The corpus of the 14 bi-pyramid
iron bars is composed by VixD59-16, Colmar, Rennigen, Waiblingen, Heiligenberg41/1, Heiligenberg42,
Dur6, Dur 40 (composed by two mass of iron, Dur40-1 and Dur40-2), METC118, Far1(Far1-1), Marsal 1
ot
(composed by two mass of iron, Marsal1-1, Marsal1-2), Marsal 3, Xir1 (composed by two mass, Xir1-1,
Xir1-2). The iron normalized concentrations have been normalized to the Upper Continental Crust (UCC)
using data from Taylor and McLennan (1985). The elements analyzed include V, Ga, Rb, Sr, Zr, Nb, Ba, La,
Ce, Pr, Nd, Sm, Eu, Gd, Tb, Y, Yb, Hf, Ta, Th, and U. Y is plotted as a pseudo lanthanide between Tb and
tn
Yb. The ordinate axis has been logarithmed

rin
ep
Pr
33
12
Xe_Pr Xe_Nd Xe_La
ed
10 Xe_U
Xe_Sm Xe_Gd
Xe_Th
8
Xe_Hf Xe_Tb
Xe_Y
Xe_Nb Xe_Yb
6 Xe_Eu
Xe_Ce
iew
F2 (22,99 %)
Marsal1-1
v
-2 Marsal1-2 Hammerscale (n=300)
WEY32-1
WEY32-2
re
-4 WEY1014-15-6
WEY1014-15-1
WEY1014-16-3
-6
WEY1014-17-2
Dur3
Dur6
-8 Dur48-1
-10 -8 -6 -4 -2 0
er 2 4 6 8
Dur 40-1
Romain 1-1
F1 (29,16 %) Romain 1-2
8 Xir 1-1
Xir 1-2
Far1-1
Xe_Sm Far1-2
pe
Xe_Eu Xe_Nd Marsal 3
6
Xe_Pr Marsal 1-1
Xe_Ce Xe_Gd
Marsal 1-2
Xe_Tb Heiligenberg 41/1
Heiligenberg 42
4 Xe_Yb Xe_La
METC118
Xe_Y
Xe_Nb
Xe_Hf
Xe_Th
Xe_U Waiblingen
Renningen
ot
2 Colmar
F3 (16 ,95 %)
0 Marsal1-2
tn
Marsal1-1
-2
rin
-4
-6
-10 -5 0 5 10 15
ep
525 F2 (22 ,99 %)
Figure 16: PCA carried out on the xij of the slag inclusions in Weyersheim iron waste, WEY1014-15-1, WEY1014-
16-3, WEY1014-17-2, WEY1014-15-6, WEY32-1, WEY32-2, hammerscale and slag inclusions in bi-pyramid iron bar
corpus (Dillmann et al., 2017) composed by VixD59-16, Colmar, Rennigen, Waiblingen, Heiligenberg41/1,
Pr
Heiligenberg42, Dur6, Dur 40 (composed by two mass of iron, Dur40-1 and Dur40-2), METC118, Far1(Far1-1),
Marsal 1 (composed by two mass of iron, Marsal1-1, Marsal1-2), Marsal 3, Xir1 (composed by two mass, Xir1-1,
Xir1-2).
34
1000
ed
100
Sample FeN/UCC
iew
10
v
1
re
0,1
V Ga Rb Sr Zr Nb Ba La er Ce Pr Nd Sm Eu Gd Tb Y Yb Hf Ta Th U
SI measured in Marsal1 bi-pyramid iron bar (Marsal1-1 and Marsal1-2) (Dillmann et al.,2017)
pe
SI avaraged in WEY32-1
526 Hammerscale avaraged (All)
Figure 17: Iron normalized concentrations of various elements in hammerscale (300 samples avaraged), slag
inclusions avaraged in WEY1014-15-1, WEY1014-16-3, WEY1014-17-2, WEY1014-15-6, WEY32-1 and slag
inclusions measured in Marsal1 bi-pyramid iron bar composed by two iron mass, Marsal 1-1 and Marsal 1-2
(Dillmann et al., 2017). The iron normalized concentrations have been normalized to the Upper Continental Crust
ot
(UCC) using data from Taylor and McLennan (1985). The elements analyzed include V, Ga, Rb, Sr, Zr, Nb, Ba, La,
Ce, Pr, Nd, Sm, Eu, Gd, Tb, Y, Yb, Hf, Ta, Th, and U. Y is plotted as a pseudo lanthanide between Tb and Yb. The
ordinate axis has been logarithmed
tn
rin
ep
Pr
35
527 Conclusion
ed
528 The chemical analysis of hammerscale and slag inclusions in iron waste specimens from Weyersheim
529 offers valuable insights into iron provenance and iron supply strategy employed by the iron smith. The
530 hammerscale and iron waste samples revealed highly distinctive compositional characteristics when
iew
531 compared to materials from the upper continental crust. Notably, significant enrichment in V, Cr and
532 REE, particularly HREE such as Y and Yb, was observed in these samples. Additionally, other elements
533 like Zr, Nb, Hf, Th, and U showed relative enrichment. Despite some variations in certain elements, the
v
534 utilization of spider diagrams and PCA for comparative analysis highlighted a strong overall similarity
re
535 between the hammerscale and slag inclusions, suggesting a clear chemical link between the two types
536 of materials. Moreover, the hammerscale samples exhibited a remarkable consistency in their
537
er
chemical nature, indicating the utilization of a chemically identical iron source in the numerous forging
538 operations performed by the blacksmith in Weyersheim. Suggesting either a short and intensive
pe
539 activity with one stock of metal, or a continuous supply from the same producer. This iron source
540 displayed specific characteristics, particularly the enrichment and partitioning pattern of REE, that are
541 uncommon and suggest a rare and distinct geological deposit or a closely associated group of deposits.
ot
542 Furthermore, comparison with known iron artifacts from the surrounding regions indicated potential
543 connections with the bi-pyramid iron bars, specifically one of the iron bars coming from the Marsal
tn
544 deposit, a place situated 100 km from Weyersheim. Despite exploring possible leads, the geological
545 conditions required to produce iron ore with such unique geochemical characteristics remain elusive
rin
546 and warrant further investigation. This study has broader implications for understanding the early Iron
547 Age ironworking practices in Western Europe. The presence of iron caps and the potential utilization
548 of weathered formations as potential iron ore sources add depth to the narrative of early iron
ep
549 exploitation in this region. The findings of this study also raise intriguing questions about the iron
550 circulation and supply system employed by the ancient iron smiths during this early period. Conducting
Pr
551 further research with hammerscale analysis to decipher the iron supply among different iron smiths
552 holds the potential to yield interesting and informative outcomes.
36
553 Acknowledgments
554 The authors would like to express their sincere gratitude to several individuals and institutions who
ed
555 have contributed significantly to this work. Firstly, we extend our thanks to the Centre de Conservation
556 et d’étude Alsace, and especially Héloïse Koehler, for generously providing access to the samples. We
iew
557 also would like to thanks Matthieu Michler for his insightful discussions about the Weyersheim
558 archaeological site and for his assistance in facilitating access to the samples. Special thanks go to
559 Bernard Gratuze for his expert guidance and support during the LA-ICP-MS analysis. Additionally, we
v
560 are grateful to Guillaume Estrade for engaging discussions on rare earth elements and ionic adsorption
re
561 clay. We would like to express our gratitude to Alexandre Salzmann and Patrick Dietsche for their
562 support during the sample preparation process. Last but not least, we extend our appreciation to
563 Audrey Niederer for her diligent work in editing and improving the English language of this manuscript.
er
564
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565 Credit
566 Jean Rodier: Conceptualization, Writing-Original Draft, Writing-Review & editing, Data acquisition.
567 Marion Berranger: Conceptualization, Writing-Review & editing, Data acquisition. Vincent Serneels:
568 Writing-Review & editing, Project administration, Funding acquisition
ot
tn
rin
ep
Pr
37
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1 Hammerscale and Slag Inclusions: New Insights into Metal Supply During the Early Iron Age in

4 1 Department of Geosciences, Université de Fribourg, Fribourg, Switzerland

77 composite chemical composition.

87 alternative approaches and methodologies may need to be explored.

115 encountered when analyzing slag inclusions in iron waste.

Iron artefact Slag inclusion Hammerscale

WEY1014-17-2 (bar) n=14

Table 1 : Summary of analyzed samples

178 2.2 Hammerscale

193 was employed.

195 3.1 Slag inclusions in iron waste.

SiO2(wt.%) SiO2FeN (wt.%)

221 SiO2 (wt.%) SiO2(wt.%)

240 exhibit strong anomalies in every iron waste sample (Tab.2).

265 UCC for the same slag inclusion.

Figure 5: Concentrations normalized without Fe of various elements in slag inclusions measured

268 3.2.1 Major elements

286 structures 1003 and 1014.

310 considered as a single entity for the following discussion.

Figure 7: Concentrations of various elements in hammercale. The concentrations have been

1000 Hammerscale from 1014 structure (n=274)

Figure 8: Concentrations normalized without Fe of various elements in hammerscale. The iron

313 3.3.1 Major elements

332 SiO2(wt.%) SiO2(wt.%)

SiO2 has been Fe normalized.

345 from WEY1014-15-1, WEY1014-16-3, WEY1014-17-2, WEY1014-15-6, WEY1014-16-3, and

379 4.1 Implications for the Weyersheim iron supply

427 materials employed by the blacksmith during the ironworking process.

444 conducted in Weyersheim (Tab.3).

Locality Specimen N°Fig. 13 Reference

bar Pouilly-sur-Saône SAO 81-03-01 9 Berranger et al., 2021

Waiblingen Waiblingen 5 Dillmann et al., 2017

Romain Romain1 11 Dillmann et al., 2017

1000 SI avaraged in WEY1014-15-1

inclusions avaraged in WEY1014-15-1, WEY1014-16-3, WEY1014-17-2, WEY1014-15-6, WEY32-1 and SI averaged in

522 study strongly resonate with this theory.

(VixD59-16, Colmar, Rennigen, Waiblingen, Dur6, Dur 40 (Dur40-1, Dur 40-2),

Yb. The ordinate axis has been logarithmed

Xe_Pr Xe_Nd Xe_La

525 F2 (22 ,99 %)

552 holds the potential to yield interesting and informative outcomes.

612 2293. https://doi.org/10.1016/j.jas.2012.02.037

648 China. Journal of Geochemical Exploration 130, 44–59. https://doi.org/10.1016/j.gexplo.2013.03.003

698 occidentale. Cahiers d’archéologie romande 61, Lausanne.

702 other material remains. Archaeometallurgy in Europe II, 469–478.

716 « Pleines » à Orval (Manche). ArcheoSciences 38, 165–181.

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