Journal of Archaeological Science 101 (2019) 52–62

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Journal of Archaeological Science

journal homepage: www.elsevier.com/locate/jas

Questioning Fe isotopes as a provenance tool: Insights from bog iron ores T

and alternative applications in archeometry
Thomas Rosea,∗, Philippe Téloukb, Sabine Kleinc, Horst R. Marschalla
a
Institut für Geowissenschaften, Goethe Universität, Altenhöferallee 1, 60438, Frankfurt am Main, Germany
b
Univ. Lyon, ENS-Lyon, Université Lyon, Lyon, France
c
Forschungsbereich Archäometallurgie, Deutsches Bergbau-Museum Bochum, Am Bergbaumuseum 31, 44791, Bochum, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: Provenancing metal artifacts with scientific methods is an established tool in archeometry to identify the metal
Iron metallurgy deposits, which were exploited for the production of ancient metal objects. It is thus an important method to
Provenancing reconstruct ancient exchange networks and the socio-economic organization of past societies. Previously in-
Bog iron ore troduced isotope-based approaches (Pb, Sr, Os) and chemical analyses of slag inclusions have severe limitations
Iron isotopes
concerning their application or the amount of sample required. Fe isotopes were previously suggested in a quite
MC-ICP-MS
Smelting
early stage of investigation as a potential provenance tracer and it was postulated that they would not fractionate
Organic matter during the smelting procedure. However, previously published analytical data from iron ores indicate a wide
overlap between deposits. Further, the earlier studies on Fe isotopes did not included bog iron ores, despite their
high importance in ancient metallurgy. As geochemical reactions during ore formation are complex and frac-
tionation cannot be generally excluded, the applicability of Fe isotopes as an alternative provenance tracer still
asks for further investigation.
This purely methodological study focuses on specimens from two sites of the formerly mined bog iron ore
deposit Eyller Bruch (Germany), which are analyzed together with products of a smelting experiment based on
these ores. The Fe isotopic composition of the bog iron ore from the investigated region suggests an intra-deposit
zonation caused by environmental parameters and its overall variation is comparable with that of other deposits.
The bog iron ore isotope signature largely overlaps with the isotope range of mineralizations in other regions. As
a consequence of this and although the absence of Fe isotope fractionation during the smelting procedure is
confirmed, the study demonstrates the lack of discriminatory power of Fe isotopes for provenance studies.
Potential applications for archeometry can rather be found in the environmental parameters, especially organic
matter, which seems to have a strong influence on Fe isotope compositions of bog iron ores. Zonations within
deposits might be identified and could help to reconstruct the exploitation history of the deposit or to reconstruct
past bog landscapes.

1. Introduction 1.1. Current approaches to provenancing iron artifacts

The determination of the ore source of metals such as iron is a pi-
votal part in the reconstruction of the socio-economic organization of
ancient societies and exchange networks among them. Iron ores are
more easily accessible than e. g. copper ores due to their wide-spread
occurrence, especially as surficial bog iron ore. In combination with
more desirable mechanical properties, this was presumably one reason
for the wide spread of iron metal for tools, weapons, and other objects.
Provenancing iron artifacts is still a challenging task. The loss of the
original surface by corrosion processes and limited shape variation of
tools due to functionality constraints often renders archeological ap-
proaches (e. g. typology) difficult. Consequently, several scientific
methods for provenancing metal and metallurgical by-products were
developed (Charlton, 2015), but all have some major limitations. In
contrast to other ores like for copper, lead isotopes cannot be used due
to the (often too) low concentrations and its heterogenous distribution
especially in bog iron ores (Schwab et al., 2006). Strontium isotopes
were also investigated as a potential provenance tracer, but

∗
Corresponding author.
E-mail address: thomas.rose@daad-alumni.de (T. Rose).

https://doi.org/10.1016/j.jas.2018.11.005
Received 11 July 2018; Received in revised form 31 October 2018; Accepted 19 November 2018
Available online 30 November 2018
0305-4403/ © 2018 Elsevier Ltd. All rights reserved.
T. Rose et al.
compositions are largely controlled by furnace lining and not by the ore
(Degryse et al., 2007, 2009). At the current state osmium isotopes seem
to be a very promising tracer, but their determination requires large
amounts of sampled material and intricate analytical work (Brauns
et al., 2013; Dillmann et al., 2017). For these reasons, the most reliable
and mainly used method is the chemical analysis of slag inclusions
entrapped in the bloom (Blakelock et al., 2009; Coustures et al., 2003;
Desaulty et al., 2009; Dillmann and L'Héritier, 2007). The main and
trace elements of slag inclusions are measured with LA-ICP-MS
(L'Héritier et al., 2016) and multivariate statistics is used to establish a
link between the slag entrapped in the bloom and the ore (e. g. Leroy
et al., 2012). However, this method necessitates experience to differ-
entiate between inclusions from smelting and forging. It also requires a
large amount of sampled material, because a sufficiently large number
of inclusions have to be analyzed (Benvenuti et al., 2016; Dillmann
et al., 2017; Disser et al., 2014). Like for all methods relying on che-
mical or isotopic data, the determination of the ore origin relies on the
exclusion of non-matching origins. For a successful reconstruction of
the ore origin all ore deposits must be characterized and overlapping
compositions as well as mixing renders the reconstruction of the ore
origin difficult or even impossible.
Milot et al. (2016) and Milot (2016), suggested stable iron isotopes
as a potential tool to provenance iron artifacts. It requires only small
amounts of sampled material and they can routinely be analyzed. In
archeology, Fe isotopes were used only once before with the aim to
identify black and red pigments (Eerkens et al., 2014). To evaluate their
potential as a tracer in iron archeometallurgy, Milot et al. (2016) and
Milot (2016) analyzed ores, metallurgical by-products and blooms from
two smelting experiments, as well as semi-products from the Roman
shipwrecks of Les Saintes-Maries-de-la-Mer, France. Previous studies
already established the latter to originate from the Montagne Noire
(Baron et al., 2011; Coustures et al., 2006). They concluded that the Fe
isotope composition of the ore is not altered during smelting. It was
shown that the Fe isotopic composition of the semi-products agrees
with ores from their suspected origin. Hence, the authors suggest a
combination of Fe isotopes with other tracing methods for the prove-
nance reconstruction of iron artifacts.
1.2. Iron isotope fractionation in iron ore deposits
Iron has four stable isotopes, 54Fe, 56Fe, 57Fe, and 58Fe, which have
natural abundances of 5.84%, 91.76%, 2.12%, and 0.28%, respectively
(Hoefs, 2009). Their distribution in terrestrial rocks is comparably
homogeneous (Beard et al., 2003; Poitrasson, 2006). But more surface-
near reduction or oxidation (redox) reactions and biological processes
can alter the rock composition, and are capable of fractionating Fe
isotopes significantly (overall range of Fe isotope compositions: 3.5‰/
atomic mass unit (amu), Hoefs, 2009). Since their first analysis by
Beard and Johnson (1999), the scope of their application steadily in-
creased and today covers the whole range of geochemical research (see
the recent reviews of Albarède, 2015; Dauphas et al., 2017; Dauphas
and Rouxel, 2006).
Concerning ore deposits, notable variations were observed in ar-
cheologically irrelevant banded iron formations (e. g. Frierdich et al.,
2014; Halverson et al., 2011; Steinhoefel et al., 2009) and hydro-
thermal ore deposits (Markl et al., 2006; Wang et al., 2015; Wawryk
and Foden, 2015). Studies focusing on hydrothermal iron ore deposits
are scarce. Before Milot et al. (2016) and Milot (2016), only Markl et al.
(2006), Horn et al. (2006), and Cheng et al. (2015) published data for
non-marine ore deposits. In such deposits isotope fractionation is
mostly driven by supergene processes. These affect surface-near rocks
and minerals along the groundwater level and are influenced by des-
cending atmospheric oxygen and meteoric water. Under these condi-
tions, the deeper and hydrothermally formed metalliferous primary
minerals partly oxidize. While the effect of these processes on e. g.
copper isotopes is well understood now (Mathur and Fantle, 2015;
53
Journal of Archaeological Science 101 (2019) 52–62
Moynier et al., 2017), the small number of studies concerning iron
isotopes allow only a rough assessment. It seems that supergene pro-
cesses slightly enrich the heavier isotopes in the altered products
(Cheng et al., 2015). The interaction of primary hematite with hydro-
thermal fluids seems to preponderantly enrich the lighter isotopes in
the secondary hematite. For siderite, isotopes fractionate in the oppo-
site direction (Markl et al., 2006). Although very limited, these studies
might hint towards the possibility to (generally) distinguish among iron
deposits through their Fe isotope compositions, as pointed out by Milot
et al. (2016).
1.3. Fe isotope fractionation during bog iron ore formation
Especially in Northern and Middle Europe, prehistoric iron me-
tallurgy widely relied exclusively on the supply of bog iron ores because
other high-quality ores were not available (e. g. Halkon, 2014; Joosten
et al., 1998; Larsen and Rundberget, 2014; Schwab et al., 2006;
Thelemann et al., 2017). Consequently, the full potential of Fe isotopes
as a provenance tracer can only be assessed if the full isotopic variation
of bog iron ore deposits is investigated. So far, only the processes in bog
iron ore evolution were investigated but not the isotopic variability of a
bog iron ore deposit.
Bog iron ore forms when reduced, Fe-rich ground water rises near
the surface (Kaczorek and Sommer, 2003; Thelemann et al., 2017).
Mainly through bacterial activity, Fe gets oxidized and precipitates as
Fe hydroxide, which reacts to ferrihydrite (Crerar et al., 1979;
Schwertmann et al., 1999; Teutsch et al., 2005; Yapp, 2001). During
these fast reactions, the heavier isotopes are preferentially adsorbed on
the bacteria (Banning, 2008; Beard et al., 2010) and the ferrihydrite
(Bullen et al., 2001; Frierdich et al., 2015; Mikutta et al., 2009). The
ferrihydrite is stabilized through the adsorption of reduced Fe ions
(Pedersen et al., 2005) and converts to goethite (Poage et al., 2000;
Schwertmann and Murad, 1983). This predominantly grows further
through adsorption of reduced Fe ions (Hansel et al., 2005). Simulta-
neously, preferentially light Fe isotopes from goethite are dissolved
(Jang et al., 2008; Poulson et al., 2005) and with time, a constant ex-
change between small (< 500 nm) goethite crystals and dissolved iron
eventually balances the isotopic composition of both (Handler et al.,
2009; Reddy et al., 2015; Wu et al., 2011). The latter effect is ques-
tionable for larger crystals (Handler et al., 2014), and their initial iso-
topic composition might be preserved instead. Additionally, the content
of organic carbon (Ilina et al., 2013), plants (Fantle and DePaolo, 2004;
Wiederhold et al., 2006), and the silicate content (Wiederhold et al.,
2007; Wu et al., 2011) can alter the isotopic composition of goethite. As
a result, bog iron ores show (a) a homogeneous isotope signature,
which corresponds to some degree to the isotopic composition of the Fe
source or (b) they potentially possess a large variation with isotope
patterns dependent on environmental parameters. The range of isotope
composition might be even larger than those observed in hydrothermal
ore deposits.
1.4. Aim of the study
This entirely methodological study explores the Fe isotopic varia-
bility of a bog iron ore deposit and aims towards a more comprehensive
evaluation of Fe isotopes as a provenance tracer for iron artifacts.
Therefore it does not refer to any specific regional or timely arche-
ological context. Rather it uses own data and published data for an
entirely scientific view on the potential of Fe isotopes as provenance
tool. Although the conclusions drawn from them might seem to be
abstract or unrelated from an archeological point of view, they are part
of the underlying framework for the application of Fe isotopes as pro-
venance tracer.
Data from two different sampling regions will be directly linked to
both, the Fe isotope composition of the source and the isotopic frac-
tionation processes during bog iron ore formation. It will be shown that
T. Rose et al.
variation of Fe isotopes within the bog iron ore deposit is comparable
with other deposit types and gives preliminary evidence for an intra-
deposit zonation.
Additionally, materials from a smelting experiment with bog iron
ore from the same deposit are analyzed to verify whether Fe isotopes do
not fractionate during smelting. Because bog iron ores might show a
very heterogeneous Fe isotope composition, all specimens were sam-
pled multiple times to investigate if the potentially strong hetero-
geneous isotopic composition of the bog iron ore is preserved in the
smelting products. Implications for tracing iron artifacts with Fe iso-
topes are deduced by comparing the bog iron ore data with data from
the literature and with two Lahn-Dill type ores. Moreover, possible
applications beyond provenancing are suggested.
2. Materials
2.1. Bog iron ores
Modern bog iron ores can be regarded as suitable material for the
study for the following reasons: (1) to rule out any influence from al-
teration processes during burial of unsmelted ore; (2) most of the pre-
historically exploited bog iron ore deposits are either completely
exploited or protected and accessible only with special permission; (3)
bog iron ore formation processes are mostly independent from the de-
posit's geographical location and had not changed over time.
Several specimens of bog iron ores were collected from two sites
called “Gelderner Fleuth” and “Tote Rahm”. Both are part of the former
bog iron ore mining area “Nierstal/Eyller Bruch” (Dassel, 2007;
Sommer, 1963) near Krefeld (North Rhine-Westphalia, Germany). The
two areas are less than 10 km apart (Fig. 1a). Ore formation began
about 5 ka ago, when the Niers and its meanders were cut off from the
Rhine main stream. In the cut-off meanders, iron rich ground water
from the sandy and gravel-rich lower Rhine terrace rises up to the
surface, where the dissolved iron is oxidized (Dassel, 2007).
This ore field was chosen because both areas provide very different
kinds of ores, which allows to assess a wide range of any intra-deposit
variation, if present. In the nature reserve “Tote Rahm” (samples la-
beled ore-bog) in the Southern area of the deposit ore formation is still
ongoing and the collected ore pieces consist of soft intense orange-rusty
material without any visible grains (Fig. 2). The sampling location
“Gelderner Fleuth” near Nieukerk was drained and leveled in 1928,
which impeded further ore formation (Sommer, 1963). Two fields were
surveyed here. Although located directly next to each other and only
separated by the small river Schwarze Rahm, ore specimens from one
field are predominantly pieces consisting of sand grains with iron rich
phases as binding material (samples labeled ore-field1, Fig. 2) while the
specimen from the other field (labeled ore-field2) found on the river
bank of the Schwarze Rahm consists of nodules agglomerated by iron-
rich crusts (Fig. 2).
The mineralogical composition of the ores was determined with X-
ray diffraction analysis (XRD) on two nodules from each deposit (ore-
bog, ore-field1) and on two different areas from the specimen ore-
field2. To obtain a rough semi-quantitative information on the phase
compositions, Rietveld refinement was carried out with the program
GSAS II (Toby and Dreele, 2013). Specimens from the Tote Rahm
consist entirely of goethite or a mixture of goethite and lepidocrocite
and less than 5% quartz. In the samples from the Gelderner Fleuth, field
1 more than 75% are made up by quartz or feldspar and quartz and the
remaining part is goethite. Samples from the other field at the Gel-
derner Fleuth show a more complex composition. Both of them consist
mostly of carbonates (40–50%), and goethite (20–30%). Additionally
glauconite from the bed rock is present in about 10% and 30%. Ad-
ditionally, the sample with the lower amount of glauconite also consists
of about 10% of joosteite, an iron-manganese phosphate which might
have been introduced by the use of phosphate-rich fertilizers (e. g.
manure) or a prolonged use of this area as grazing land.
54
Journal of Archaeological Science 101 (2019) 52–62
2.2. Smelting experiment
Prior to this study, M. Arians-Kronenberg (Krefeld) conducted a
successful smelting experiment with ore from the Gelderner Fleuth. She
generously provided specimens from the ore (ARC762), roasted ore
(ARC761), slag (ARC760, MAK-Sl), bloom (ARC759), and a forged semi
product (MAK-Fe) for analysis. The smelting process of the ore ran
about 6 h and a total of 30 kg (6 kg/h) were smelted. The ore:charcoal
ratio was 1:1. Subsequently, 1.2 kg of the bloom was further processed
and a piece of 700 g of purified bloom was used to forge, among others,
the semi-product (pers. comm. M. Arians-Kronenberg, 2018).
A polished section of the ore and the roasted ore revealed a het-
erogeneous structure (Fig. 2). In the ore, a lot of plant-like structures
like cross sections of stems or roots seem to be present. In a small cavity
a ferricreted root channel was directly accessible (Fig. 2). XRD analysis
gave a mineralogical composition of siderite and goethite with more
than 50% siderite. The roasted ore shows similar features and consists
of nodule-like light and dark red areas. According to XRD it consists of
almost pure hematite with minor amounts of quartz.
2.3. Additional samples
Additionally to this set of material, two iron ore specimens of the
Lahn-Dill type were collected west of Wetzlar (Hesse, Germany, Fig. 1b)
and analyzed. The area was extensively mined for iron ore from the 18th
century until the 20thcentury. Ore-GF was gathered in the forest near
the iron ore mine Grube Fortuna, today a public mine, and consists
entirely of hematite. Ore-W was picked up from a small ore heap in a
forest about 5 km southwest of Wetzlar. Fe oxides (mostly hematite)
characterize this sample with a weathered surface, which is intensively
crossed by quartz veins.
Although initially sampled for another study, data for the metallic
core of the excavated semi-product SM9-99.242 (generously provided
by L. Long, Marseille) are also reported for comparison with the data of
Milot et al. (2016) and Milot (2016) but will not be discussed in detail
here. It belongs to the cargo of the Roman ship wreck SM9 (14–50 AD),
which is part of the famous ship wreck assemblage found in the Med-
iterranean Sea near Les Saintes-Maries-de-la-Mer (Bouches-du-Rhône),
France (Long et al., 2002; Pagès, 2008; Pagès et al., 2008).
3. Methods
3.1. Sampling procedure
To avoid contamination from steel tools, their use was reduced to a
minimum. Ore specimens were either broken in half and unweathered
material was extracted from the interior with pieces of transparent
plastic and by rubbing the halves together (ore-bog, ore-field1), re-
spectively, or a lancet and tweezers were used to detach small pieces
from the outer and interior areas of the nodules (ore-field2) and also a
small piece of a ferricreted root channel in the specimen ARC762
(sample ARC762-2). Ore-bog5 consists of clay, adhering to one of the
ore specimen. The samples ore-bog4, 6 and 7 are from the clay filling of
a cavity in a specimen, the encrusted cavity walls, and the soft material
outside of the cavity, respectively. Ore-field1-8 is surface material from
specimen ore-field1-7.
All other specimen were sampled with a Dremel 4000 equipped
with a 1.2 mm diamond sputtered steel drill. To avoid contamination
from the steel, the drills were cautiously examined under a stereo mi-
croscope after cleaning for any damages to the drill or remnants of
sample material. Multiple samples were taken from all specimens to
investigate isotopic homogeneity. For samples ARC761 and ARC762
care was taken that each sampling spot was large enough to avoid
mixtures of optically different materials. Additionally to the spatially
resolved samples, several bigger pieces were detached, wrapped in
paper and crushed for bulk analysis (Table 1). All other samples were
T. Rose et al.
Fig. 1. Location of the collected ore specimens from German sites analyzed in this study: (a) Eyller Bruch, and (b) Lahn-Dill ores from the vicinity of Wetzlar.
Additionally, the location area of (c) the Schwarzwald is indicated, where Markl et al. (2006) conducted their study (maps: openstreetmap.org).
spatially-resolved sampled to check for heterogeneity.
3.2. Fe isotope analysis
3.2.1. Sample preparation
Analytical work was carried out in a clean lab under a laminar flow
box at the Institut für Geowissenschaften, Goethe Universität Frankfurt.
Millipore® water with a resistivity of 18.2 MΩ cm, double distilled acids
and PTFE beakers were used throughout the analytical process. All
samples were completely dissolved in a one-step acid digestion. Silicate
containing samples were digested in ∼2 ml of 30 M HF and 6 M HNO3.
Silicate-free samples were digested with 1 ml of each, 6 M HCl and 6 M
HNO3. All samples were heated on a hot plate to 90 °C over-night (si-
licates) or for several hours until complete dissolution was achieved
(non-silicates). They were evaporated to dryness at the same tempera-
ture, dissolved in 6 M HCl and dried down again. Finally, they were
taken up in 0.5 ml 6 M HCl over-night for ion exchange chromato-
graphy (IEC).
IEC was carried out according to an adapted protocol based on Sossi
et al. (2015). Columns of 70 mm length with an inner diameter of 4 mm
and the resin AG1-X8 (100–200 mesh) were used. IEC induced Fe iso-
tope fractionation was examined by splitting some samples before IEC
and proven to be absent. After IEC, samples were dried down at ∼70 °C.
They were re-dissolved in 1 ml 6 M HNO3 and evaporated to dryness
again to remove remnants of resin.
55
Journal of Archaeological Science 101 (2019) 52–62
3.2.2. Mass spectrometry
Fe isotope analysis was carried out at the Laboratoire de Géologie de
Lyon, École Normale Supérieure de Lyon with the multi-collector
plasma mass spectrometer (MC-ICP-MS) ThermoFisher Scientific
NeptunePlus in high resolution mode (Weyer and Schwieters, 2003).
Samples were dissolved on site in 2% HNO3 and further diluted with
0.05 N HNO3. The MC-ICP-MS was equipped with Ni cones, a cyclonic
spray chamber and a Glass Expansion MicroMist nebulizer with an
uptake rate of 100 μl/min. Uptake time for standard and samples was
50 s and blanks were measured before each standard and sample with
130 s uptake time and 180 s wash time. 1 ppm of IRMM-014 yielded an
intensity of ∼10 V on 56Fe. Mass bias and drift was corrected by
standard-sample-bracketing with the international reference material
IRMM-014 (Craddock and Dauphas, 2011; Taylor et al., 1992) and
doping with 1 ppm Ni (Maréchal et al., 1999; Poitrasson and Freydier,
2005) prepared from the Alfa-Aesar Specpure® Ni plasma standard so-
lution.
Mass bias correction was carried out online during acquisition and δ
values were calculated in a spreadsheet according to the following
equation:
⎡ ( )F56 e
F54 e smp
⎤
δ56Fe [‰] = ⎢ − 1⎥*1000
⎢ ⎥
⎢
⎣
( )
F56 e
F54 e IRMM − 014 ⎥
⎦
Here, the index smp denotes the ratio 56Fe/54Fe of the sample and
the index IRMM-014 denotes the ratio of the international reference
T. Rose et al.
Fig. 2. Several nodules collected from the site Gelderner Fleuth, field1 (ore-field1) and Tote Rahm (ore-bog) as well as the specimen collected at Gelderner Fleuth,
field 2 (ore-field2) and polished sections of the ore from the Gelderner Fleuth used in the smelting experiments (ARC762) and the roasted ore (ARC761). The scales
for ore-field1, ore-field2, and ore-bog are the same. Also ARC761 and ARC762 have the same scale. Numbers in the big nodule of ore-bog as well as in ARC762
indicate sampling location of the respectively numbered sample.
material. The δ57Fe values are calculated accordingly.
Each sample was run twice as duplicates and some samples were
repeatedly measured in different sessions to check for inter-run stabi-
lity. All data were further processed with R (R Core Team, 2017) in
RStudio® after acquisition. Outliers were identified and not regarded
further, if their δ values derived from both isotope ratios differed more
than the instrumental reproducibility of 0.045‰/amu between dupli-
cates and/or within the same analysis. The δ 56Fe values of all other
analyses were averaged per sample. Intensities of procedural blanks
were more than 10000 times lower than sample intensities. The pre-
cision (external reproducibility) of the data is < 0.05‰ (2σ ), which is
comparable to previous studies (Albarède et al., 2011; Balter et al.,
2013).
3.3. Loss on ignition
According to literature, the content of organic carbon (Ilina et al.,
2013) and plants (Fantle and DePaolo, 2004; Wiederhold et al., 2006)
might have an influence on the iron isotopic composition of the bog
iron ores. To take such a possible influence into account, loss on igni-
tion (LOI) was determined on samples from all bog iron ores to measure
the amount of organic matter. Carbonates were removed with 5% HCl
previously to the temperature treatment. The samples were washed
several times in de-ionized water and dried at 105 °C for 18 h. Subse-
quently the samples were ignited at 1050 °C to constant weight.
56
Journal of Archaeological Science 101 (2019) 52–62
4. Results
4.1. Iron isotope analyses
All data are given in Table 1. Data for the bog iron ore deposit
ranges between δ 56Fe = −1.29‰ and 1.16‰, which is nearly three
times larger than the range of the ores from the Montagne Noire given
in Milot (2016) and similar to the known overall range for hydro-
thermal ore deposits (2.40‰, cf. Fig. 6).
Specimens collected at the Tote Rahm (ore-bog) gave isotopic
compositions in the range from δ 56Fe = −0.39‰ to 0.03‰ and scatter
around the clay sample ore-bog5, which yielded −0.23 ± 0.09‰.
Compared to this sample, the clay found in a cavity (ore-bog4) is sig-
nificantly enriched in the heavier isotopes with a δ 56Fe value of 0.03 ±
0.09‰. A clear trend towards isotopically lighter values can be ob-
served towards the crust and the soft ore of the same specimen (Fig. 3).
At the Gelderner Fleuth, the sandy ore (ore-field1) shows a similar
variation and isotopic composition as the ones from Tote Rahm.
However, the samples ore-field1-1 and ore-field1-2 are enriched in 54Fe
and are more comparable with the specimen ore-field2. Interestingly,
specimen from both fields show contrasting trends between material
from the interior and the surface. While in ore-field1 the interior (ore-
field1-8) is slightly enriched in 54Fe and still within the range of the
other specimens and the exterior of the same specimen (ore-field1-7),
the surface sampled as ore-field2-2 shows a marked depletion compared
to the other samples from this field. The latter observation is consistent
T. Rose et al. Journal of Archaeological Science 101 (2019) 52–62

Table 1
Fe isotope compositions of the analyzed samples. Analytical precision for all
samples is 0.09‰ for δ56Fe and 0.14‰ for δ57Fe. The last column (n) gives the
number of analyses per sample.
Sample Material δ56Fe [‰] δ57Fe [‰] n

Bog iron ores from the Eyller Bruch

Tote Rahm
ore-bog1 Ore nodule −0.11 −0.14 2
ore-bog2 Ore nodule −0.39 −0.57 5
ore-bog3 Ore nodule −0.22 −0.28 2
ore-bog4 Clay filling in cavity of nodule ore- 0.03 0.04 2
bog7
ore-bog5 Clay adhering to nodules −0.23 −0.37 3
ore-bog6 Crust around cavity in nodule ore- −0.11 −0.14 2
bog7
ore-bog7 Ore nodule −0.28 −0.38 3
Gelderner Fleuth, field 1 (sandy ore)
ore-field1-1 Ore nodule −0.70 −0.97 1
ore-field1-2 Ore nodule −0.75 −1.10 2
ore-field1-3 Ore nodule −0.36 −0.50 2
ore-field1-4 Ore nodule −0.09 −0.14 1
ore-field1-5 Ore nodule −0.30 −0.39 1
ore-field1-6 Ore nodule −0.31 −0.51 2
ore-field1-7 Ore nodule, same as ore-field1-8, −0.22 −0.32 2
from exterior areas
ore-field1-8 Ore nodule, same as ore-field1-7, −0.45 −0.71 3 Fig. 3. Fe isotope compositions of the bog iron ores from Eyller Bruch: Samples
from the interior from Tote Rahm (ore-bog) and Gelderner Fleuth, field 1 (ore-field1) represent
Gelderner Fleuth, field 2 different ore nodules except the ones additionally labeled on the right side of
ore-field2-2 Crust around surficial nodule −1.29 −1.94 2 the data points. These labeled samples belong to the same nodule per site and
ore-field2-3 Interior of surficial nodule −0.84 −1.23 3 the labels specify the sampling region of the respective nodule. For Gelderner
ore-field2-4 material from thicker crust −0.77 −1.16 6
Fleuth, field 2 (ore-field2) and the ore from the Gelderner Fleuth used for the
Gelderner Fleuth, ore used for smelting experiment
smelting experiment (ARC762) samples were taken from one specimen per
ARC762-1 Sampling location: see Fig. 2 0.03 0.02 2
ARC762-2 Encrusted root channel, see Fig. 2 1.16 1.70 2 deposit (cf. Table 1).
ARC762-3 Nodule-like piece 0.47 0.68 2
ARC762-4 Crust around big cavity 0.07 0.07 2
with isotope fractionation during weathering processes (e. g. Kiczka
ARC762-5 Bulk analysis 0.05 0.07 2
Materials from smelting experiment et al., 2011), but is an isolated case and thus will not be discussed
Roasted ore further.
ARC761-1 Loose material −0.08 −0.11 3 The ore used for the smelting experiment (ARC762) is slightly en-
ARC761-2 Piece of roasted ore −0.27 −0.42 4 riched in the heavier isotopes when the bulk sample ARC762-5 is
ARC761-3 Dark red material 0.27 0.37 2
ARC761-4 Light red material −0.14 −0.23 2
compared to the other ore specimens from the Gelderner Fleuth (Fig. 3).
ARC761-5 Piece of roasted ore 0.18 0.28 2 The sample ARC762-1 and the crust ARC762-4 also gave slightly po-
Bloom sitive δ 56Fe values of 0.03 ± 0.09‰ and 0.07 ± 0.09‰, respectively.
ARC759-1 −0.27 −0.42 2 In contrast to them the encrusted root channel ARC762-2 shows a
ARC759-2 −0.11 −0.23 2
pronounced shift of about one per mil towards higher δ 56Fe values and
ARC759-3 −0.12 −0.18 4
ARC759-4 −0.03 −0.05 2 sample ARC762-3 lies in-between with δ 56Fe = 0.47 ± 0.09‰
Slag (Fig. 3).
ARC760-1 −0.12 −0.23 2 In the roasted ore (ARC761) differences in the color of the sampled
ARC760-2 −0.14 −0.22 2 material also seem to indicate different isotopic compositions. The dark
ARC760-3 −0.16 −0.23 4
MAK-Sl1 −0.21 −0.35 1
red material ARC761-3 gave an δ 56Fe value of 0.27 ± 0.09‰ while
MAK-Sl2 −0.14 −0.20 2 the light red material ARC761-4 yielded δ 56Fe = −0.14 ± 0.09‰.
MAK-Sl3 −0.16 −0.22 2 The bulk samples ARC761-1 lies in the middle of them with an isotopic
Half product composition of δ 56Fe = −0.08 ± 0.09‰. Samples ARC761-5 and
MAK-Fe1 −0.05 −0.11 2
ARC761-2 are close to ARC761-3 and ARC761-4, respectively.
MAK-Fe2 −0.03 −0.04 2
MAK-Fe3 −0.05 −0.09 4 All other materials from the smelting experiment yielded widely
Lahn-Dill ores overlapping isotopic compositions (Fig. 4) and all of them overlap
Ore specimen from the Grube Fortuna within the analytical precision with the bulk samples of the ore and the
ore-GF1 0.61 0.89 2 roasted ore.
ore-GF2 0.51 0.74 2
ore-GF3 0.62 0.93 2
The Lahn-Dill-ores display a significantly heavier isotopic compo-
ore-GF4 0.55 0.86 2 sition than the bog iron ores (Table 1). All samples from ore-GF yielded
ore-GF5 0.53 0.78 2 isotopic compositions around δ 56Fe = 0.56‰. In contrast, samples
ore-GF6 0.52 0.79 2 from ore-W scatter between δ 56Fe = 0.49 ± 0.09‰ and 1.00 ± 0.09‰.
Ore specimen from ore heap near Wetzlar
The unaltered metallic core of the Roman semi-product SM9-
ore-W1 0.76 1.12 2
ore-W2 1.00 1.48 1 99.242. yielded an isotopic composition of δ 56Fe = −0.31 ± 0.09‰,
ore-W3 0.69 1.03 1 similar to δ 56Fe = −0.385‰, the value reported by Milot et al. (2016)
ore-W4 0.49 0.71 2 for the semi-product SM9-99.248 of the same wreck. It is slightly hea-
Les-Saintes-Maries-de-la-Mer, Roman semi product vier than the isotopic compositions of the other semi-products he re-
SM9-99.242.4 metallic core −0.31 −0.48 2
ports, but still within analytical precision.

57
T. Rose et al. Journal of Archaeological Science 101 (2019) 52–62

Fig. 4. Fe isotope compositions of the materials gained from the smelting ex-
periment with ore ARC762. In a polished section of the ore, a lot of plant-like
structures resembling cross-sections of stems and roots are visible. According to
literature, the considerably positive δ 56Fe values of the ore and the roasting ore
might be caused by a high content of organic matter, which is indicated by the
high loss on ignition of the ore (see chap. 5.2. for a detailed discussion).
Fig. 6. Fe isotope compositions for iron ores. Data from: Milot (2016) (Bassar,
Departement Tarn), Milot et al., (2016) (Montagne Noire), this study (Lahn-Dill
ore, Eyller Bruch), Cheng et al., (2015) (Gaosong), Markl et al., (2006)
(Schwarzwald). A compilation of the data can be found in the supplementary
data.

Table 2
Loss on ignition of the different ore samples.
Sample Material LOI (%)

ARC762-LOIc crusts 27.6 ± 2.3

ARC762-LOIs soft material 21.0 ± 0.8
ore-bog-LOI2 ore nodule 20.4 ± 1.0
ore-bog-LOI3 ore nodule 26.8 ± 0.5
ore-bog-LOI4 ore nodule 26.6 ± 1.0
ore-field1-LOI1 ore nodule 9.5 ± 0.8
ore-field1-LOI2 ore nodule 22.7 ± 1.8
ore-field1-LOI4 ore nodule 10.0 ± 0.7
ore-field1-LOI5 ore nodule 12.6 ± 0.4
ore-field1-LOI6 ore nodule 11.0 ± 1.0
ore-field1-LOI7 ore nodule 10.7 ± 3.9
ore-field2-LOIc crust around nodule 25.8 ± 0.9
ore-field2-LOIn complete nodule 28.9 ± 1.2

Fig. 5. The loss on ignition in per cent on carbonate-free samples from each
sampled bog iron ore site of the deposit Eyller Bruch.
4.2. Loss on ignition
Results for the LOI on carbonate-free samples from bog iron ores of
each site are shown in Fig. 5 and are given in Table 2. The ores ARC762,
ore-bog and ore-field2 show loss on ignitions between 20 and 30%. In
contrast to them the quartz and feldspar rich samples from Gelderner
Fleuth, field 1 (ore-field 1) only lost about 6 and 15% of their weight
except for one nodule (ore-field1-LOI2), which shows a similar weight
loss like the ores from the other sites.
5. Discussion
5.1. Fe isotope variation in bog iron ores
Isotopic variability of bog iron ores is very small within individual
unaltered ore specimens. This is particularly true for the specimens
ARC762 and ore-field2, for which all unaltered samples of the two
yielded nearly the same δ 56Fe value, and for the specimens of ore-bog.
In ore-field1 most of the ore specimens show identical isotopic com-
positions, only the samples ore-field1-1 and ore-field1-2 are sig-
nificantly more enriched in 54Fe. Regarding the variation within the
whole deposit, three groups are visible (Fig. 3). The isotopically light
group consists of the samples from ore-field2 as well as orefield1-1 and
ore-field1-2. Most other samples fall within the group with slightly
negative values. The third group is established by the samples ARC762-
2 and ARC762-3, which are strongly enriched in the heavier isotopes.
This observation coincides with current geochemical models of Fe
isotope fractionation during the precipitation of goethite in iron de-
posits. The heavier isotopes of dissolved reduced Fe in ionized form
preferentially oxidize and are adsorbed in the solid minerals, when iron
(hydr)oxide minerals and goethite forms (Bullen et al., 2001; Frierdich
et al., 2015; Mikutta et al., 2009). However, a very complex chemical
mechanism provides permanent exchange of the isotopes between
goethite and the dissolved iron (Beard et al., 2010; Handler et al., 2009;
Zarzycki and Rosso, 2017): Dissolved iron and goethite grains of small
size (< 100 nm) had identical isotopic compositions after 30 days of
equilibration (experiments of Handler et al., 2009), and extending this,
Handler et al. (2014) questioned a complete exchange for larger par-
ticles. Besides the grain sizes, the pH level of the solution might also
affect the exchange mechanism, although sufficiently long time scales
are proposed to balance the deferring effect of a lower pH (Handler
et al., 2014; Reddy et al., 2015).
In the case of the Eyller Bruch, flow velocity of the ground water is
low in both areas and the groundwater table is close enough to the
surface to ensure water saturation throughout most of the year. This
provides sufficient time for complete exchange between dissolved Fe
and iron (hydr)oxides at each site. Additionally, in the Schwarze Rahm
a thin film of iron (hydr)oxide particles was observed on the water
surface, indicating floating particles and, hence, undisturbed exchange
between the particles and the water.
However, this mechanism does not account for the difference in the
Fe isotopic composition between the three groups. A possible ex-
planation for the more positive δ 56Fe values of ore-bog and ARC762 is

58
T. Rose et al.
the high amount of organic matter, indicated by their large LOI. There
are multiple complementary explanations available: Fantle and
DePaolo (2004) observed a preferential uptake of isotopically light iron
by plants, leading to an enrichment of isotopically heavier dissolved
iron in the ground water. Ilina et al. (2013) concluded that a higher
content of organic carbon preferentially enriches the heavier isotopes in
goethite due to a higher bond strength in bonds with carbon compared
to carbon-free bonds. Additionally, the lighter Fe isotopes are favored
during goethite dissolution with oxalate (Wiederhold et al., 2006). All
the processes enriches the heavier isotopes in the mineral component.
We are unable to differentiate from our data between these mechan-
isms, but it seems highly likely that one of these processes or a com-
bination of them caused the slight but significant shift of ARC762 and
ore-bog towards heavier isotopic compositions compared with ore-
field2 and some samples from ore-field1. ARC762 in fact shows textural
traces of plant material in the polished section and ferricreted root
channels. Concerning ore-bog, the survey area is densely covered with
plants and the soil is intensely rooted.
The extent of such effects can be particularly well seen in ARC762-2
and ARC762-3. The first one is an encrusted root channel and yielded
the most positive isotopic composition of all samples analyzed. The
latter does not show such a strongly positive δ 56Fe value, but is still well
separated from all other ore samples, which might indicate an area with
an higher content of organic carbon than in the other samples. The
organic carbon content might also explain the intra-specimen differ-
ences between clay (ore-bog4) and surrounding iron (hydr)oxides (ore-
bog7).
But two aspects seem to contradict this interpretation. Firstly,
samples from the specimen ore-field2 yielded a LOI as high as in the
ores ARC762 and ore-bog but show the isotopically lightest isotopic
compositions of all ores. The combination of a high content of organic
matter and light Fe isotope compositions indicate, that no noticeable
influence of carbon containing bonds is present. The appearance of the
ore, nodules agglomerated by crusts, implies no or only a few plants
during the formation of this bog ore. Additionally, this is the only
sample containing a phosphate mineral. This mineral could point to-
wards a prolonged use of the field as grazing land or the prolonged
application of a phosphate rich fertilizer like manure. In both cases, big
amounts of organic matter would have been introduced into the soil.
Therefore we suggest that organic matter in this ore specimen was
mostly incorporated through remains of degraded or digested (plant)
remains. Such organic matter cannot remove the isotopically light iron
from the ground water and therefore would not result in isotopically
heavy composition like it was the case for the other ores.
The second aspect is the spread in the data from ore-field1. In this
ore, the influence of organic matter can only to some extent explain the
spread in the data. The LOI of its samples has to be smaller than in all
other samples because most of them are quartz and feldspar, which
could not be removed. In this area of the deposit, the sand might also
have altered the isotopic composition of the Fe hydr (oxides). During
growth of goethite, silicates block some of the sites, on which dissolved
Fe ions adsorb. Therefore, growth of the mineral is limited but this also
makes adsorption more selective for the heavier isotopes as they will
preferentially oxidize due to the stronger bonding environment
(Wiederhold et al., 2007; Wu et al., 2011). Fractionation caused by this
process does not seem as strong as the one caused by organic matter. An
intermediate isotopic composition, with respect to samples with low
and high content of organic matter might be expected, as it is the case
in the data from the Eyller Bruch (Fig. 3). Further, the LOI of one ore
nodule is as high as of the ores from other sites of the deposit. It must be
assumed, that the isotopically heaviest compositions (esp. ore-field1-4)
results from a mixture of both processes.
5.2. Smelting experiment
All materials from the smelting experiment or at least their bulk
59
Journal of Archaeological Science 101 (2019) 52–62
samples yielded identical isotopic compositions within analytical pre-
cision. This strengthen the previous discussion in Milot (2016) and
Milot et al. (2016) concluding absence of Fe isotope fractionation from
ore to metal.
Nevertheless, deviations from the slightly negative δ 56Fe value of all
smelting materials can be seen in the ore and the roasted ore and always
show isotopically heavier compositions. Because the whole ore is used,
these heterogeneities will level each other out, resulting in the isotopic
composition of the bulk sample. Nonetheless, they have to be discussed.
For the ore this was already done together with the other ore samples.
Concerning the roasted ore, the bulk analysis gave an isotopic compo-
sition well within the variation of the other materials obtained in the
smelting experiment. The sample from the dark red material is clearly
isotopically heavier and the isotopic difference between the dark red
and the light red areas indicate isotopic heterogeneity within the
roasted ore. It seems very unlikely that the phase transformation from
goethite to hematite during roasting (Rzepa et al., 2016) provoked an
isotopic fractionation through translocation. We therefore suggest that
the heterogeneity is inherited from the bog iron ore. As was shown
above, a high content of organic matter seem to correlate with an iso-
topically heavier composition. The texture of the roasted ore is similar
to the one of ARC762, indicating a formation in close contact to plants.
We therefore suggest that the different isotopic composition result from
different proportions of organic matter and that the dark red material
has a higher proportion of organic matter than the light red material,
resulting in a distinctly heavier isotopic composition.
5.3. Application potentials of Fe isotopes in archeometallurgy
5.3.1. Fe isotopes as provenance tracer for Fe artifacts
The Fe isotope compositions of bog iron ores from the Eyller Bruch
ore field spread only over a per mil, if individual samples with ‘extreme’
isotopic compositions (ARC762-2, ARC762-3, ore-field2-2) are not
taken into account (Fig. 6). For ARC762 it was shown in the previous
chapter that such strongly positive values like the ones from the both
excluded data only occur at very small scales and have negligible in-
fluence on the bulk composition of the ore piece. And ore-field2-2
shows a strongly negative isotope composition due to weathering pro-
cesses and therefore cannot be assumed as representative for the iso-
topic composition of this bog iron ore.
The spread of one per mil is similar to the variation of primary
hematite ore from the Schwarzwald region (Markl et al., 2006). It is
considerably larger than the variation in ores from the Montagne Noire
and the Departement Tarn (Milot, 2016; Milot et al., 2016), and ores
from the Gaosong deposit (Cheng et al., 2015).
The bog iron ores from the Eyller Bruch do not differ significantly in
their isotope composition from the selected and compared deposits,
although the examples represent a wide variety of mineralization types
(primary and altered ores from different types of hydrothermal de-
posits, where the data from Markl et al. (2006) are from various de-
posits in the Schwarzwald region). Based on their very limited variety
and significance, the reconstruction of ore provenance based on Fe
isotopes alone would therefore be misleading, as the method has no
discriminating potential as the geochronological isotope systems have,
and as the available analyses have shown so far.
Even their use as a first approach as suggested by Milot et al. (2016)
is not viable considering the large variety of ore types with comparable
and almost homogeneous isotopic compositions (Fig. 6). The applica-
tion could lead to matches without archeological sense. A good negative
example for such a misleading application would be the Eyller Bruch
matching by analysis result with the Roman semi products of Les
Saintes-Maries-de-la-Mer (SM9-99.242., this study; Milot et al., 2016;
Milot, 2016). This would clearly be a misjudgment as Baron et al.
(2011) and Coustures et al. (2006) on the one hand conclude from other
methods than the iron isotopes that the iron for these objects originated
from the Montagne Noir and on the other hand no Roman mining
T. Rose et al.
activity is known for the Eyller Bruch. This is a strong example that Fe
isotopes should not be used as a provenance tracer. This also holds true
on a more local scale as the strong overlap between the deposits from
the Montage Noire and the Departement Tarn and from the different
mines from the Schwarzwald shows (Fig. 6, Supplement A1).
One of the major roots on the Fe isotope composition of bog iron
ores should be the iron source, whose isotopic signal was presumably
altered during dissolution of the iron. Although no other isotopic data
than the results from this study are available for bog iron ores yet, it is
thinkable that bog iron ores from other occurrences might have dif-
ferent isotopic compositions, if their different iron sources does. As was
shown in the data from Eyller Bruch, also other influences might shift
the isotope signal towards heavier compositions (organic components,
pH-level, etc.). These mechanisms and the full isotopic range of bog
iron ores and other mineralizations must be investigated before Fe
isotope compositions of iron ores could again be discussed for use in
archeometry.
As a positive result, one preliminary trend can be deduced. Ores
from the Eyller Bruch, the Montagne Noire and the Departement Tarn
can be clearly separated from Lahn-Dill ores and ores from Bassar
(Fig. 6), with the latter two deposits showing a strongly positive iron
isotope signature. Based on the present data it seems that very distinct
ore formation processes and depositional influences might lead to dif-
ferent iron isotope signatures in the ores. As the Lahn-Dill-study was a
case study and does not represent the complete ore district, it cannot be
assumed that the available data show the full isotopic spread of this ore
type. Quartz veins in one of the ore pieces indicate hydrothermal al-
teration and Markl et al. (2006) present evidence for Fe isotope frac-
tionation through hydrothermal alteration. As the extent of hydro-
thermal alteration was not investigated, it must remain unclear whether
the measured isotopic composition represent unaltered or completely
altered ore or, most likely, something in between.
5.3.2. Intra-deposit variation as tool for environmental reconstructions?
Data from the Eyller Bruch indicate an influence of environmental
parameters on the isotopic composition of bog iron ores (esp. content of
organic matter and silicates). This could point towards an isotopic
subdivision within bog iron ore deposits.
If a bog iron ore occurrence is identified by other methods as ori-
ginal ore source, this might allow to narrow down the particular mining
area within a deposit, which was exploited during a particular time
period. Such an approach would be similar to the use of copper isotopes
to reconstruct the exploitation history of a deposit (Klein et al., 2010).
Another potential application of iron isotopes relates to intra-de-
posit variation. As they are influenced by environmental parameters,
bog iron ores might yield some information about the appearance of the
bog iron ore deposit or its underlying substrate even if its location can
no longer be reconstructed. Consequently, they might contribute to the
reconstruction of past landscapes.
Admittedly, such information might be gathered only from the ore
itself and not from metallurgical by-products or the metal. Besides the
general positive inference, that the overall Fe isotope composition is not
altered during smelting, isotopic differences within the ore seem to be
homogenized and information about the deposit might be erased in the
objects. There is one chance for use if pronounced intra-deposit zona-
tion occurs and ores from different zones are not mixed but result in
isotopically distinct furnace charges. Subsequently isotopically distinct
metal objects from the different zones could result, which were in-
formative for the deposit. If they are previously provenanced by other
methods such as trace elements or osmium isotopes, the structure of the
bog can be reconstructed. Or vice versa, combining Fe isotope data
from local bog ores found in the archeological record with methods for
landscape reconstruction might allow to infer the location of past
mining areas. To implement these applications, future studies must
confirm such distinctive intra-deposit variations and must link specific
isotope fractionations to distinct environmental parameters.
60
Journal of Archaeological Science 101 (2019) 52–62
For all three aspects, the reconstruction of ore sources, the ex-
ploitation history of bog iron ore deposits, and the reconstruction of
past landscapes it is highly desirable to have more iron isotope analyses
of iron ores from various deposits and mineralizations around the
world. In combination with a sound mineralogical description they are
crucial to understand the influences on and the behavior of iron iso-
topes within the different kinds of deposits and to draw further con-
clusions about their potential for archeological research. Additionally,
other methods like trace elements should be used to reveal if there
might be other methods capable to differentiate between and/in within
bog iron ore deposits.
6. Conclusions
Data from two sites of the historically mined bog iron ore deposit
Eyller Bruch (Germany) provide an example for the influence of en-
vironmental parameters on the Fe isotope signature of iron ores and
suggest an intra-deposit zonation controlled by these factors. Materials
from a smelting experiment conducted with bog iron ore from this
deposit verify the conclusions of Milot (2016) and Milot et al. (2016)
that Fe isotopes do not fractionate in metallurgical processes. Even
isotopic variation within the ore seems to become homogenized during
smelting since it was still detectable in the roasted ore but not in the
bloom or slag.
The isotopic variation of the Eyller Bruch is comparable with the
range of other deposit types and largely overlaps with most of them;
even with those that are entirely unrelated both geologically and re-
gionally. Since Fe isotopes are sensitive to redox processes, this is to be
expected. Although the scarcity of Fe isotope studies from iron ore
deposits other than banded iron formation impedes the assessment of Fe
isotopes as an additional tool rather than as being similar to the lead
isotope application in archeometry. The iron isotope system clearly
shows a lack in discriminatory power necessary for a widely applicable
provenance tracer, as it is predictable from geochemical knowledge.
Our results also emphasizes the importance of the historical and ar-
cheological context for provenance reconstructions.
Further studies should thus address the Fe isotopic variation of other
bog iron ore deposits. If the variation turns out to be even larger than
observed in this study this would finally fully exclude the use of Fe
isotopes as a provenance tracer. Data from the Eyller Bruch provided
positively first indications that Fe isotope compositions of bog ores can
be used for the reconstruction of past bog landscapes and the ex-
ploitation history of a mine and might even help to localize past mining
areas.
Acknowledgements
The Deutsches Bergbau-Museum Bochum and the Institut für
Geowissenschaften of the Goethe Universität Frankfurt are thanked for
funding the analytical work of Thomas Rose's Master thesis. The
Hermann-Willkomm-Stiftung thankfully financially supported the
travel of T. Rose to Lyon. We thank Luc Long for the allowance to
sample and analyze the Roman semi-product. T. Rose is grateful for the
support of Maria Arians-Kronenberg and Guntram Gassmann during
fieldwork. We thank our colleagues Katrin Westner and Eveline
Salzmann for fruitful discussions and Chiara Girotto for improvement of
the language. The helpful comments of the anonymous reviewers are
gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data related to this article can be found at https://
doi.org/10.1016/j.jas.2018.11.005.
T. Rose et al.
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