![A Reflected-light microscopy image of sample KLX_19A_428 consisting of granitoid base rock and calcite fracture filling material with the centric greenish contact zone. The µXRF scanned area is outlined in black. B µXRF manganese element mapping of the area marked in A). The growth generations one and two are marked with black numbers. The LA-ICP-MS scanned area is outlined in black. C LA-ICP-MS manganese element mapping of the area marked in B). Transects cutting the greenish contact zone are marked as white lines within the image (A′–A″, B′–B″). The spatially resolved profiles of Mn, Fe, Sr, La, Yb, Pb, Th, U and Ca are shown below. Trace elements contents are taken from LA-ICP-MS measurements. Calcium contents are calculated from cCacalcite=400,400ppm-cTEcalcite\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$c\left({Ca}^{calcite}\right)=\mathrm{400,400} \; ppm -c\left({TE}^{calcite}\right)$$\end{document}. D Cluster analysis of the LA-ICP-MS scanned area. Clusters are color coded. Mean trace elements contents of the cluster are displayed normalized to the upper continental crust. Cluster 1 and 2 are mainly found in calcite of the older overgrowth one, as marked in B), cluster 3, 5 and 6 are mainly found in the younger calcite of overgrowth two. Cluster 4 and 7 are part of the greenish contact zone](https://www.researchgate.net/publication/361954793/figure/fig4/AS:1179987344400386@1658342314850/A-Reflected-light-microscopy-image-of-sample-KLX-19A-428-consisting-of-granitoid-base_Q320.jpg)
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Environmental Earth Sciences (2022) 81:371
https://doi.org/10.1007/s12665-022-10462-1
THEMATIC ISSUE
LA‑ICP‑MS analysis oftrace andrare‑earth element distribution
incalcite fracture fillings fromForsmark, Simpevarp andLaxemar
(Sweden)
AnnemieKusturica1 · NeelevanLaaten1 · HenrikDrake2 · ThorstenSchäfer1
Received: 7 February 2022 / Accepted: 22 May 2022 / Published online: 11 July 2022
© The Author(s) 2022
Abstract
Concentrations and spatial distribution of trace elements in secondary minerals provide valuable information about mobil-
ity controlling processes in natural fractures. Important examples include rare-earth element contents that act as analogues
for the retention of trivalent actinides such as Am/Cm or Pu(III). The secondary phases (carbonates) investigated in this
study originate from exploration drilling bore cores of the Swedish Nuclear Fuel and Waste Management Company SKB
(Forsmark, Simpevarp and Laxemar, Sweden).
Here, high-resolution element analysis (Micro-X-rayFluorescence-Spectrometry (µXRF) and Laser Ablation-Inductively
Coupled Plasma-Mass Spectrometry (LA-ICP-MS)) is applied to scan for Na and the trace elements Mn, Fe, Sr, Pb, Th and
U as well as the rare-earth elements Y, La, Ce and Yb associated with carbonate fracture fillings. High resolution element
maps highlight growth zones and microstructures within the samples, which are not detected by the usual point and line
measurements. Evidence of phase-dependent partitioning is observed.
The partition coefficients, D, determined from formation water and carbonate data were compared to experimentally generated
coefficients and values derived from a 17-year precipitation experiment carried out at the Äspö Hard Rock Laboratory (HRL).
Distribution coefficients of the light rare-earth elements La and Ce have been found to be relatively high in the studied sam-
ples, whereas the coefficients of distribution of Sr and U are remarkably low.
Overall, the results of this work show that the secondary calcite formed in deep granitic fractures coprecipitated periodically
with significant amounts of radionuclide analogues (i.e., rare-earthelements).
Keywords LA-ICP-MS· Calcite· Trace element· Rare-earth element· Partitioning coefficient
Introduction
Ever since nuclear power plants have been part of the civil
energy mix, the responsible long-term disposal of the radi-
oactive waste and isolation from the biosphere has been
a major challenge. Even though radiotoxicity gradually
declines over geological time (Joyce 2017), the long per-
sistence of nuclear waste and its decay products require a
carefully selected concept for the long-term storage (Ojovan
etal. 2019). Crystalline rocks are widely discussed as one
suitable host rock formation for the deep geological disposal
of spent nuclear fuel (SNF). To this day, major investiga-
tion campaigns on crystalline host rock are carried out for
example at the Fennoscandian Shield of Sweden and Fin-
land (Andersson etal. 2013; Milnes etal. 2008), at Archean
granite-gneisses in Siberia (Laverov etal. 2016), or within
underground research laboratories such as the Grimsel Test
This article is part of a Topical Collection in Environmental Earth
Sciences on Deep Geological Disposal, guest edited by Thomas
Nagel, Wolfram Rühaak, Florian Amann, Guido Bracke, Stefan
Buske, Julia Kowalski, Sönke Reiche, Thorsten Schäfer, Traugott
Scheytt, Thorsten Stumpf, Holger Völzke, Florian Wellmann.
* Annemie Kusturica
annemie.kusturica@uni-jena.de
1 Applied Geology, Institute ofGeosciences, Friedrich
Schiller University Jena, Burgweg 11, 07749Jena, Germany
2 Department ofBiology andEnvironmental Science, Linnaeus
University, 39182Kalmar, Sweden
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Environmental Earth Sciences (2022) 81:371
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371 Page 2 of 28
Site (GTS, Switzerland, Quinto etal. 2017) and the Korean
Underground Research Tunnel (KURT, Korea) (Kwon etal.
2006). These site investigations contributed to the profound
understanding of retention and transport mechanisms in the
context of SNF disposal. In this context, fracture-fillings
are of special interest as they are expected to control radio-
nuclide (RN) mobility by sorption and/or incorporation
through solid solutions (OECD/NEA 2007).
Since the experimental verification of man-made RN
retention in fracture fillings through geological time scales
is not feasible, natural analogues like rare-earth elements
(REE) and their incorporation have been used in a well-
founded approach (Eisenbud etal. 1984; Johannesson etal.
1995; Smellie and Karlsson 1999; Dobashi and Shikazono
2008).
Due to their similar chemical behavior (i.e., 5p66s2 con-
figuration of the outermost atomic shell, lanthanoid and
actinoid contraction, mostly trivalent state under natural
conditions) REE can serve as natural analogue to estimate
the fate and mobility of actinides such as Pu(III), Am(III)
and Cm(III) (Krauskopf 1986; Bruno and Sandino 1987;
Zhong and Mucci 1995). Bruno and Sandino 1987 further-
more described the use of Th as analogue for tetravalent
actinides (Pa(IV), U(IV), Np(IV), Pu(IV)).
This study focuses on the fracture filling carbonates from
granitoid host rocks in Forsmark, Simpevarp and Laxemar,
Sweden. Forsmark is the planned spent fuel repository site,
whereas Simpevarp and Laxemar have been intensely stud-
ied in the siting process as one candidate area by Svensk
Kärnbränslehantering; SKB (Hedin 2006).
Trace element (TE) incorporation in carbonate fracture
fillings is highly sensitive to changes of the precipitation
environment, e.g., pH value, oxidation state, TE speciation,
temperature, salinity, precipitation rate, pressure and char-
acteristics of the precipitation solution, e.g., aqueous TE/
Ca ratio, adsorption–desorption equilibrium of TE at the
crystal surface and microbial activity (Lorens 1981; Zhong
and Mucci 1989; Rouff etal. 2005; Tang etal. 2008; Day
and Henderson 2013; Füger etal. 2019; Smrzka etal. 2019).
Hence, the study of the spatial trace element distribution
within the fracture filling minerals can help to reconstruct
the paleo-hydrogeological evolution of the site (Tullborg
etal. 2008; Milodowski etal. 2018; Mizuno etal. 2022).
In the context of SNF storage, these findings allow us to
estimate the potential TE retention under prospective hydro-
geologic and climatic changes.
At Forsmark, Simpevarp and Laxemar the fracture sys-
temof the granitoid bedrock is filled with assemblages of
hydrothermal, sedimentary and low temperature fracture
fillings formed at intermittent fluid flow events. Low tem-
perature carbonates in Forsmark, Simpevarp and Laxemar
show enrichments in REE and other elements, e.g., Mg, Mn,
Fe, Sr, Th and U (Landström and Tullborg 1995; Drake etal.
2012, 2018; Maskenskaya etal. 2015). TE analyses of these
fracture coatings have been carried out mainly on ground
and dispersed bulk samples or as point measurements on
intact rocks.
In contrast to previous works, this study aims to gain a
more detailed understanding of the structural incorporation
of TEs in calcite fracture-fill. High-resolution spatial dis-
tributions allow for a precise evaluation of the formation
conditions and their influence on element retention. In this
study, µXRF and LA-ICP-MS were used to examine the dis-
tribution patterns of the trivalent REEY, especially Y, La,
Ce and Yb in association with other common elements (Na,
Fe, Mn, Sr, Pb, Th, U). Comparing calcite compositions and
groundwater compositions from the same (or adjacent) bore-
hole sections enable calculation of apparent TE/Ca partition-
ing coefficients, which signify the role of solid solutions in
the mobility of RN under natural conditions. Based on these
results, precipitation rate and plausibility of the interpreta-
tions were estimated.
Geology
Simpevarp and Laxemar site is located ca. 320km southof
Stockholm at the Swedish east coast (Fig.1). The nuclear
power plant of Oskarshamn and the Äspö Hard Rock Labo-
ratory (HRL) are in close proximity to the site. The Fors-
mark site is located ca. 350km to the north of Oskarshamn,
adjacent to the Forsmark nuclear power plant (Fig.1). The
sites are situated in the Svecokarelian Orogen of the Fen-
noscandian Shield. The predominantly igneous bedrock
(ca. 1.91–1.75Ga) underwent numerous cycles of mostly
Proterozoic tectonic deformation and magma intrusions and
was uplifted later in time (Guenthner etal. 2017). The sites
belong to different tectonic units and were affected by early
ductile and later brittle deformation, i.e., Sveconorwegian
faulting, late- and post-Caledonian faulting, and Permian
extension (Hermansson etal. 2007; Viola 2008; Viola etal.
2009; Saintot etal. 2011; Tillberg etal. 2020, 2021). Sim-
pevarp and Laxemar belong to the Transscandinavian Igne-
ous Belt (TIB) which was formed ca. 1.85–1.66Ga ago
(Högdahl etal. 2004) in the context of the volcanic activ-
ity related to the subduction alongside the Svecokarelian
orogeny, to which Forsmark belongs (Wahlgren 2010). The
TIB consists of granite to quartz monzodiorite to diorite
gabbros. These areas experienced further major periods of
igneous activity viz. the granitic magmatism ca. 1.45Ga ago
linked to the Hallandian orogeny and the intrusion of doler-
ite dykes (ca. 0.9Ga) in the TIB due to the Sveconorwegian
orogeny (Söderlund etal. 2005; Wahlgren etal. 2007). The
long-term uplift of the region enabled the manifestation of
a sub-Cambrian unconformity followed by several cycles of
loading and unloading. Present regoliths are assumed to be
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Environmental Earth Sciences (2022) 81:371
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deposited by the end of the last glaciation and after deglacia-
tion (Lundin etal. 2004; Tröjbom and Söderbäck 2006; SKB
2008; Nyman etal. 2008; Brydsten and Strömgren 2010).
During the Quaternary, periods of glaciation, glacial
reboundand shoreline displacements shaped the area. Along
with the glacial waters, a range of meteoric, lacustrine,
brackish, marine, and fresh water, so called end members,
infiltrated into deeper aquifers. The paleo-hydrogeological
setting has been influenced by the mixing processes of these
end members with deep saline waters (Laaksoharju 2004;
Laaksoharju etal. 2008a, 2008c; Gómez etal. 2014).
As a result of the complex groundwater evolution in com-
bination with upwelling hydrothermal fluids multiple gen-
erations of fracture fillings developed. At both sites, a set of
hydrothermal fracture fillings is followed by two younger
generations of fracture fillings of low-temperature ground-
water precipitates (Generation 3/4 in Forsmark, generation
5/6 in Simpevarp and Laxemar). In this study, low tempera-
ture carbonates were investigated (see e.g., Drake etal. 2006,
2009b; Sandström etal. 2008 for detailedoverviews of the
fracture filling generations).
Fig. 1 Map of the study sites
Simpevarp, Laxemar and
Forsmark
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Methods
Calcite crystal samples were hand-picked from drill cores
taken at the SKB test sites Simpevarp, Laxemar and Fors-
mark and named according to borehole number and depth in
meter (Table1). Formationwater samples were taken from
the nearest possible sampling location in the same borehole
(Table1). The hydrogeochemical data of the formation water
samples were provided by the SKB (Table2) (Laaksoharju
etal. 2008b, 2009).
Calcite samples of < 3cm length were impregnated in
Araldite 2020 epoxy resin (Huntsman Corporation, Salt Lake
City, Utah, USA) and polished to create a planar surface. For
characterization via Polarized TransmittedLightMicroscopy
(PTLM), thin sections were polished to a thickness of 30μm.
Images were generated using the VHX-6000 Keyence digital
microscope (Keyence Corporation, Osaka, Japan) and the
research microscope Zeiss Axioplan 2 (Carl Zeiss AG,
Oberkochen, Germany).
Micro-X-ray Fluorescence-Spectrometry (µXRF)
(M4TORNADOPLUS µXRF, Bruker Corporation, Bill-
erica, Massachusetts, USA) was used to generate spatially
resolved element map scans of the planar sample surfaces.
Map scans were measured in one cycle with overlapping
spots (spot size 20μm, spot distance 10μm) under vacuum
condition (20mbar). The acceleration voltage was 40keV at
130,000 cps, the time per pixel 15ms and the energy devia-
tion between 0.4–0.8meV. Samples with well-distinguished
zonation were selected for further analysis.
Laser Ablation-Inductively Coupled Plasma-Mass
Spectrometry (LA-ICP-MS) analysis were carried out
with a LSX-213 C2 + Laser Ablation System (Teledyne
Table 1 Overview on samples with according research site, bore hole number, depth and prepared section and origin of the associated formation
water
Site Boreholes At borehole
length [m] Wall rock Formation water sampling
Forsmark KFM04A 233 Granitic gneiss Same section
Simpevarp KSH01A 205 Fine-grained diorite Same section
212
Laxemar KLX04 669 Granite to quartz monzodiorite, generally porphyritic 150m shallower
KLX19A 414 Quartz monzonite to monzo-diorite, equigranular to weakly
porphyritic
100m shallower
428 100m shallower
Table 2 Hydrogeochemical
data of formation water samples
from drillings KFM04A
in Forsmark, KSH01A in
Simpevarp and KLX04,
KLX15A and KLX19A in
Laxemar, Sweden
The samples were taken in close proximity to the fracture fillings listed in Table2. * Additional groundwa-
ter data from (Laaksoharju 2004) were added for drilling KSH01A Section150–200m
n.a. no data available, < LOD data below limit of detection
Site Forsmark Simpevarp Laxemar
Bore hole KFM04A KSH01A KLX04 KLX15A KLX19A
Elevation SecMid (m) − 199.83 − 243.59 − 150–200 − 486.52 − 467.22 − 413.86
pH (field) 6.74 n.a n.a n.a n.a n.a
pH (lab) 7.19 n.a 7.24* 7.83 n.a 8.22
Na (mg/l) 1910 2610 1610* 691 2080 962
Ca (mg/l) 1480 1220 692* 234 1540 152
Fe (mg/l) 1.99 0.611 n.a 0.09 0.537 0.0707
FeTOT (mg/l) 2.13 0.604 1.6* 0.104 0.556 0.084
Fe2+ (mg/l) 2.15 0.584 n.a 0.082 0.548 0.074
Mn (mg/l) 3.15 0.626 0.72* 0.109 0.549 0.068
Sr (mg/l) 15.5 21.3 0.72* 4.67 27.7 2.65
Y (µg/l) 1.42 0.422 n.a 0.0877 0.397 0.0533
La (µg/l) 0.296 0.137 n.a 0.139 < LOD 0.0225
Ce (µg/l) 0.315 0.0966 n.a 0.175 < LOD 0.0266
Yb (µg/l) < LOD < LOD n.a < LOD < LOD < LOD
U (µg/l) 27.8 0.074 n.a 0.253 0.144 0.0806
Th (µg/l) < LOD < LOD n.a 0.356 < LOD < LOD
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Environmental Earth Sciences (2022) 81:371
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Technologies Inc., Thousand Oaks, California, USA) and
XSeries 2 Quadrupole ICP-MS (Thermo Fisher Scientific
Inc., Waltham,Massachusetts,USA). For single line scans, a
spot size of 30µm and 80% energy were used, for area scans
a spot size of 20µm and 80% energy were used. Tuning
of the ICP-MS was performed using NIST SRM 612 glass
standard (National Institute of Standards and Technology,
Gaithersburg, Maryland, USA) and USGS MACS-3 was
used as an external carbonate calibration standard (United
States Geological Survey, Reston, Virginia, USA). Scan
Speed was 10μm/s, energy fluence 10J/cm2. Due to the
destructive character of the method, direct measurement rep-
etition on the same sample spot is not possible. However, the
measurement of the MAC-S 3 standard prior to and after
each calcite scan ensured homogeneity and comparability of
the measurements. Element specific detection limit (LOD)
ranges within one map scan are given exemplarily in the
Appendix, Table9.
The LA-ICP-MS data were processed with the data analy-
sis software Iolite v3 (School of Earth Science, University
of Melbourne, Melbourne, Australia) running in IGOR Pro
6 (WaveMetrics Inc., Oregon, USA). Single line scans were
hand processed based on a similar approach with Microsoft
Excel 2016 (Microsoft Corporation, Washington, USA).
Calcium contents were determined by calculating the dif-
ference between the stoichiometric values of Ca minus the
cumulative trace elements content (Eq.1):
Element maps and single line scans allowed the iden-
tification of generations of overgrowth. To clearly assign
each measurement point of the mappings to a growth zone,
multivariate analyses were performed using the software R
(version 3.6.1) and RStudio® (version 1.2.5019) with basic
packages as well as ggplot2 and psych. Only elements for
which a zonation was visible in the element map (Mn, Fe,
Sr, Y, La, Ce, Yb, U) were included and the data were log-
transformed and auto scaled prior to any multivariate calcu-
lations. First, a principal component analysis was performed
for each sample. In a next step, only principal components
whose scores showed a (spatial) zonation were included in a
k-means cluster analysis of the corresponding principal com-
ponent scores. Different numbers of k were chosen and for
each of them the cluster analysis was calculated ten times.
The solution to work with was chosen based on a combina-
tion of a reasonable number for k (zones not spatially con-
nected should be separate clusters) and the most frequent
solution of the ten repetitions.
For single line scans, the contents of the outermost over-
growth were extracted from the hand processed data as the
mean of the ten outermost laser spots (100µm). For map
scans, the module profile points of the software Iolite was
(1)
c(
Ca
calcite)
=400, 400 ppm −c(ΣTE
calcite)
used to extract data points alongside the youngest over-
growth with an estimated thickness of several tens µm.
The REE fractionation was calculated based on the Chon-
drite normalized La and Yb content of the calcite and the
Chondrite normalization factors taken from McDonough and
Sun 1995. For sample KSH01A_212, the REE fractionation
was evaluated based on Chondrite normalized La/Y ratios as
for this sample, no Yb contents were measured.
The partition ratios of trace elements between the for-
mation water and the youngest overgrowth were calculated
based on the Henderson-Kracek division coefficient DTE
(Eq.2), (Henderson and Kracek 1927):
whereas η is the molar amount of the subscripted element in
the superscripted phase.
The precipitation rate RP was calculated based on Eq.3
(DePaolo 2011). Experimentally driven TE/Ca partitioning
ratios of this work, the equilibrium partition coefficient Keq
and the forward partition coefficient Kf taken from DePaolo
2011 and the calcite dissolution rate Rb adapted from (Chou
etal. 1989) were applied to Eq.3:
Results anddiscussion
Morphology, overgrowth, zonation ofthecarbonate
fracture fillings
Single calcite crystals from Forsmark and Simpevarp show
euhedral crystal habitus. The habitus of the single growth
zones at the samples KSH01A_205_A/B, that consist of sev-
eral concentric, accordant growth zones, changes between
elongated c-axis (c ≈/ > a) and elongated a-axis (c < a).
The sample KFM04A_233 and KSH01A_205_B show
inclusions of Fe-oxides/-hydroxides. The sample aliquots
of KFM04A_233 and KSH01A_205_A/B consist of single
euhedral crystals, whereas the others are healed fracture
fillings. The samples KLX04_669 and KLX19A_414/428
display calcite fracture-fill attached to wall rock and dis-
play aggregates of anhedral carbonate crystals. Sample
KLX04_669 shows traces of wall rock alteration. The frac-
ture wall is rimmed by the oldest generation of euhedral
quartz followed by calcite (Fig.2A andB). Samples from
Laxemar (KLX19A_414/428, Fig.2C and D) show a green-
ish contact zone (GCZ) within the fracture filling calcite. At
(2)
D
TE =
𝜂
Calcite
TE /
𝜂
Calcite
Ca
𝜂Fluid
TE /
𝜂Fluid
Ca
(3)
D
TE =
K
f
1+Rb
R
p
+R
b
(Kf
K
eq
−1
)
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371 Page 6 of 28
a depth of 414m, the fracture filling shows anhedral growth
with a sudden change of crystal habitus approximately in
the center of the fracture (at the GCZ). At 428m below
the surface, the greenish contact zone is expanded to about
3–5mm with a more symmetrical structure of the growth
zones on both sides.
Trace elements composition
Simpevarp
The two samples of the borehole KSH01A, Sect.205m,
show analogue overgrowths with similar element assem-
blage but different absolute contents.
At least seven distinct periods of precipitation, with
growth zone1 being the oldest overgrowth, were identi-
fied by morphology and trace element assemblage. Based
on the qualitative element content, the strictly statistically
generated cluster analyses revealed seven and eight clusters
shown in Fig.3. These are, however, not to be confused
with the growth zones which were interpreted based on ele-
ment content, morphology and mineralogy of the fracture
fillings. Overall, sample B shows lower TE contents. In both
samples, enrichment patterns of light rare-earth elements
(LREE) follow the opposite trend as Fe and Mn. At intervals,
distribution patterns of Sr are congruent with Mn and Fe.
Uranium is strongly enriched in the two youngest growth
zones. Within sampleA, similar distribution patterns for Pb,
Th and U are apparent. Growth zone4 of sample A shows
signs of face dependent partitioning. The growth zone5
shows a gradual decline in Na, Mn, Fe, Sr and heavy rare-
earth elements (HREE), but increase in LREE. The degree
of fractionation of REE differs throughout the samples and
reaches highest ratios in zone2 (median Chondrite normal-
ized ratio: 58.27 for sample A and 5.45 for sample B) and
the youngest part of zone5 (median Chondrite normalized
ratio: 236.68 for sample A and 68.79 for sample B). Further
similarities are evident for zone2 and the youngest part of
zone5, e.g., both show strong enrichment in LREE.
The third analyzed sample of borehole KSH01A origi-
nates from a depth of 212m and contains two growth zones.
As Yb contents are often below detection limit in this sam-
ple, the La/Y ratio is used as indicator of REE fractionation.
The older, Fe, Sr and REE enriched zone1 is subdivided into
zone 1a with high TE contents (see Appendix, Figure9) and
zone1b with decreasing TE contents and REE fractionation
in favor of LREE (La/Y ca.1—12.5). Within the adjoined
zone 2, TE contents are generally low. The La/Y ratio
decline to < 1. The crystal is surrounded by a rim enriched
in TEs and REE. La/Y ratios reach values up to > 100.
In general, the observed calcite TE contents are higher
compared to sample measurements performed by Drake and
Tullborg (2009a), Drake etal. (2012) and Maskenskaya etal.
(2015) from comparable depths. Only Th and U contents are
Fig. 2 A Polarized transmitted
light microscopic image of sam-
ple KLX04_669 under parallel
polarized light. The white frame
marks the detail displayed in
picture B. B Polarized transmit-
ted light microscopic image of
the wall rock/fracture filling
contact of sample KLX04_669
under crossed polarized light.
The white arrow points at a
quartz overgrowth. C Image
of sample KLX19A_414 with
the greenish contact zone. D
Polarized transmitted light
microscopic image of the
greenish contact zone at sample
KLX19A_428 under crossed
polarized light. The black arrow
in C and D marks the greenish
contact zone
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lower than expected values based on the former study. The
fact that the number of growth zones varies with the depth
might be related to a later opening of the deeper fracture
or fewer events of fracture reactivation. Model calculations
identified a change of groundwater types at approximately
200m depth at the site (Laaksoharju 2004). It is therefore
proposed, that the samples precipitated from different for-
mation waters.
The combination of high Mn content, relatively low Sr
content and Chondrite normalized La/Yb, respectively La/Y
ratios of the samples from Simpevarp (Table3) indicates the
affiliation of the fracture fillings from drill core KSH01A
with generation5a or 5b/6 calcites, as described by Drake
and Tullborg 2009a. This generation has been dated to max.
age of ~ 160Ma (Drake etal. 2017; Ivarsson etal. 2020).
REE adsorption on highly reactive surfaces such as
colloids (Ozaki etal. 2006; Pourret etal. 2009) and clay
Fig. 3 Trace elements distribution pattern of calcite fracture fillings
from bore hole KSH01A (205m) from Simpevarp. Upper continental
crust (UCC) normalized (Wedepohl 1995) mean element contents of
sample KSH01A_205_A (A) and KSH01A_205_B (B) are visualized
based on cluster analyses. The clusters are color-coded at the sample
maps on the left
Table 3 Comparison of Mn and Sr content and Chondrite normalized
La/Yb ratios (McDonough and Sun 1995), respectively La/Y ratios
of calcite fracture fillings from Simpevarp and Late Palaeozoic frac-
ture fillings (Generation5a and 5b/6) from Laxemar and Simpevarp
described by Drake and Tullborg 2009a
Site Simpevarp Simpevarp/Laxemar
Depth 205 212 0–686m 0–686m
Sample A B Gen. 5a Gen. 5b/6
Mn (ppm) Ø 8298 Ø 5800 Ø 2714 147–1980ppm at KSH01A around 200m, decreasing with depth from ca. 3000–12,000ppm
to < 100ppm
Sr (ppm) Ø 141 Ø 12 Ø 130 ca. 50–75ppm
La/Yb Ø 53.1 Ø 18 Ø 70.3 Highly variable REE content, mostly flat Chondrite normalized profile Highly variable REE content,
significant LREE enrich-
ment
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minerals (Kretzschmar and Schäfer 2005; Bouby etal. 2008;
Norrfors etal. 2016) is widely observed in ground waters.
The complexation of REE with organic ligands in particular
enables the transport of REE with infiltrating waters and
leads to an overall increase in the formation water (Torres
and Choppin 1984; Xiong 2011). Natural calcites with a
Chondrite normalized REE curve depleted in heavy rare-
earth elements (HREE) have been linked to precipitation
from organic-rich waters under low-temperature conditions
in contrast to flat REE profiles which trace back to compl-
exation by inorganic HCO3− (Tullborg etal. 2008). Mathurin
etal. 2014 applied speciation modeling to show, that the
REEs in meteoric groundwaters are strongly bound to humic
substances.
It is therefore proposed, that infiltrating surface waters
loaded with organic complexes contributed remarkably
to the formation waters of overgrowth 2 and 5a at sample
KSH01A_205A/B. (see Appendix, Figure10and Table4).
Laxemar
The area scan of sample KLX04_669 from borehole KLX04
reveals a series of four precipitation events. Along the frac-
ture wall, secondary euhedral quartz of ca. 30–50µm formed
followed by three generations of calcite overgrowth. The
oldest calcite (zone 1) contains especially high REE contents
and relatively high contents of Pb, Th and U. It is disrupted
by growth zones 2 and 3 which indicates the disruption of
the fracture. The calcite growth zone2 contains particularly
high median Mn and Fe contents. The zone is crossed by
numerous micro-veins (calcite growth zone 3), with local
accumulations and lamination perpendicular to the growth
direction. Parallel and perpendicular fractures in relation to
the precipitation front have been linked to crystallization
pressure (Noiriel etal. 2010). In comparison to the gen-
eration 2 calcite, the micro-veins are enriched in REE with
median Chondrite normalized La/Yb ratios of 43.48. Chon-
drite normalized REE contents reveal an LREE enrichment
within the zones1 and the vein filling carbonate and a flat
profile for zone 2. Based on the overall low REE concen-
tration and flat Chondrite normalized profile (see Appen-
dix, Figure11, Table6), it is concluded, that the calcites of
zones2 precipitated from formation water with minor share
of typically organic-rich surface waters (Torres and Choppin
1984; Xiong 2011).
Samples from borehole KLX19A consist of two genera-
tions of calcite. Within the older growth zone 1, TEs are
homogeneously distributed. At 414m, TE contents are
elevated along the wall rock/fracture filling contact (most
prominent for Na, Th). Within this sample, interspaces
between the calcite crystals of growth zone 1 are filled with
secondary calcites that are enriched in U but depleted in
REE, Sr and Th (see Appendix, Figure12, Table7).
Generation 1 calcites are overgrown by large, euhedral
calcite crystals, which indicate prolonged and slow pre-
cipitation. The µXRF element mapping shows TE incor-
poration is irregular throughout the growth zone (Fig.4B).
Two crystal-types with clear REE fractionation were iden-
tified at 414m. Type1 carbonates are enriched in LREE
(median Chondrite normalized La/Yb ratio: 26.33) associ-
ated with Pb and Th, whereas HREE associated with Mn
and Fe are preferentially incorporated in type 2 carbonates
(median Chondrite normalized La/Yb ratio: 0.66). At 428m
(Fig.4A), cluster analysis of the LA-ICP-MS scanned area
show three cluster within growth zone 2 with highly differ-
ing Fe, Sr, REE, Pb, Th and U contents (Fig.4D).
The fracture filling generations are divided by a ca.
1-mm-thin greenish contact zone (GCZ) with strongly trace
elements enriched rims (Fig.4C). Low Ca contents indi-
cate other mineral phases than calcite. Maximal difference
between LREE and HREE is reached within the rims of the
GCZ with median Chondrite normalized La/Yb ratios of 5.5
at 414m and up to 300 at 428m.
Deposition of clay minerals and adsorbed TEs seems to
be a likely scenario to explain the extremely high TE con-
tents. LREE and TEs such as Th and U predominantly bind
on organic ligands and clay minerals. However, in present
day fracture waters from bore hole KLX19A, DOC concen-
trations of 1.5–2.2mg/l were measured in the correspond-
ing depth. Analogue to present day concentrations, organic
ligands have been presumably low in this depth in the past
(Laaksoharju etal. 2008b, 2009). The fractionation in asso-
ciation with organic ligands in the formation water seems
therefore less probable.
A more likely scenario is the former presence of biofilms.
At the Laxemar and Simpevarp sites, paleo-biofilms of esti-
mated Late Pleistocene age were described by Heim etal.
2012. They too linked the accumulations of LREE and TEs
(Mg, Al and Fe) to the complexation with organic matter,
but also associated them with the transport of Fe-rich col-
loids (Heim etal. 2012 and references therein). Authigenic
clay-minerals, as they are accumulated along the rims of the
GCZ, have been proposed to be part of fossilized microbial
mats (Sallstedt etal. 2019).
Furthermore, cogenetic calcite and pyrite have been
found related to microbial activity (Tullborg etal. 1999;
Drake etal. 2015; Drake etal. 2018b). Pyrite precipitation
consumes free Fe2+ cations in formation waters and could
be an explanation for low Fe contents in proximity of the Fe
enriched rim of the GCZ at sample KLX19A_428. Coge-
netic pyrite has been described as characteristic for genera-
tion 5/6 calcites as defined by Drake etal. 2009b. This fact
supports the assumption, that calcites investigated in this
work precipitated under low-temperature conditions at max.
160Ma ago (Drake etal. 2017, 2018; Ivarsson etal. 2020).
Thus, the results show that
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• REE fractionation is highly variable. Chondrite normal-
ized La/Yb ratios reach outliers of < 1 and > 100. How-
ever, preferential LREE incorporation is predominating.
• The calcites investigated from Simpevarp (205–212m
depth) presumably belong to generation5/6 fracture fill-
ings as defined by Drake etal. (2009b).
• The GCZ is a feature of fracture fillings below 400m at
the Simpevarp and Laxemar sites. The zone stands out
by extremely high TE contents. The origin of those might
result from a combination of coprecipitating minerals in
association with biofilms, and the sorption of TEs on
inorganic ligands.
• Th contents often lie below the detection limit. In areas
where both elements are sufficiently enriched, Th and
U follow the same distribution patterns. As a result,
uranium which is commonly above detection (mean
Fig. 4 A Reflected-light
microscopy image of sample
KLX_19A_428 consisting of
granitoid base rock and calcite
fracture filling material with
the centric greenish contact
zone. The µXRF scanned area
is outlined in black. B µXRF
manganese element mapping
of the area marked in A). The
growth generations one and
two are marked with black
numbers. The LA-ICP-MS
scanned area is outlined in
black. C LA-ICP-MS manga-
nese element mapping of the
area marked in B). Transects
cutting the greenish contact
zone are marked as white
lines within the image (A′–A″,
B′–B″). The spatially resolved
profiles of Mn, Fe, Sr, La, Yb,
Pb, Th, U and Ca are shown
below. Trace elements contents
are taken from LA-ICP-MS
measurements. Calcium
contents are calculated from
c(
Cacalcite
)
= 400,400 ppm −c
(
TEcalcite
)
.
D Cluster analysis of the LA-
ICP-MS scanned area. Clusters
are color coded. Mean trace
elements contents of the cluster
are displayed normalized to the
upper continental crust. Cluster
1 and 2 are mainly found in
calcite of the older overgrowth
one, as marked in B), cluster 3,
5 and 6 are mainly found in the
younger calcite of overgrowth
two. Cluster 4 and 7 are part of
the greenish contact zone
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371 Page 10 of 28
of ~ 0.01–0.21ppm in calcite, ~ 10–24ppm in GCZ) can
be used as a reference for the Th retention capacity in
calcites. The similar behavior indicates that Th and U are
both present in tetravalent state and therefore coprecipi-
tated in near equilibrium Th/U ratios.
• Throughout this study, REE could be detected in
high abundances with values up to 112,233ppm Y,
283,154ppm La, 862,177ppm Ce and 5068ppm Yb.
The retention of trivalent actinides is estimated to be
analogously high under comparable hydrogeochemical
conditions.
Forsmark
One central line scan and five perpendicularly arranged
line scans were carried out at the sample KFM04A_233.
The element maps indicate at least one major change in the
hydrochemical properties of the formation water. An early
generation of highly TE-loaded calcite is followed by a gen-
eration with fluctuating TE content. The spatially resolved
results show, that the younger growth zone is divided into
at least two subzones. Mn and Yb are of higher abundances
in closer proximity of growth zone1. At the center of this
overgrowth, light rare-earth elements (LREE) are enriched.
Towards the outer rim of zone2, LREE decrease whereas
other TEs such as Fe, Yb, Pb, Th and U reach higher con-
tents (Appendix, Figure8). However, this study emphasizes
the necessity of detailed element mappings to describe the
element incorporation precisely and draw differentiated con-
clusions. Further studies on sample materials from Forsmark
are therefore foreseen.
Face‑dependent partitioning
The concentric growth zone 4 of sample KSH01_205_A
shows areas of distinct TE enrichment (Fig.5A). These dis-
tinctions can be found exclusively within this sample but
not at the equivalent growth zone of the same geochrono-
logic episodes within sample KSH01_205_B. This find-
ing indicates sector related zoning as described by Reeder
and Paquette (1989) rather than a change in precipitation
environment. Within growth zone 4 at least five sectors are
visible (Fig.5A). The statistical analysis confirms the het-
erogeneity within the growth zone. A cluster analysis of TE
contents in the sample assigned the sectors a and b as well as
sector B belong to the same cluster, whereas sector A has a
uniform signature as growth zone 5a and sector C the same
as growth zone 5b (Fig.5B).
Sector b contains enrichment of the TEs Mn, Fe and Sr,
whereas the other TEs compared in this study (Na, Y, La,
Ce, Yb, Pb, Th, U) are relatively enriched in sector a. Ana-
logue to growth zone 4, sector B of growth zone 5 stands
out by enrichment of divalent TEs. However, sectors A and
C do not follow the same pattern. While HREE and U are
enriched in sector A, Na, LREE, Pb and Th are enriched in
sector C.
Fig. 5 A Element mappings of
the sample KSH01A_205_A
based on LA-ICP-MS data.
Within the Lanthanum map,
the concentric growth zones
1–7 are marked. The areas A, B
and C as well as a and b mark
sectors within the same distinct
growth zone. The differentia-
tion of the sectors is based on
the trace elements content.
B Microscopic image of the
sample KSH01A_205_A. C
Average trace elements content
of sector a and sector b and
sector A, sector B and sector
C of growth zone 4, sample
KSH01_205_A. Sector A and B
show mostly alike composition
with slightly increased U and
REE (Y, La, Ce, Yb) contents in
sector A. Sector C stands out by
strong LREE (La, Ce), Pb and
Th enrichment. The discrep-
ancy in trace elements contents
between sector a and b is most
distinguished for LREE (La,
Ce) and U
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The observations are congruent with the studies of
Reeder and Paquette (1989) on synthetic and natural calcite
crystals, who found Mn, Fe and Sr to be enriched in the
same sector within one growth zone. In addition to these
findings, our data suggest, that all other TEs investigated in
this study are relatively enriched in the remaining sectors.
This observation leads us to the conclusion, that differences
in partitioning regarding nonequivalent crystal faces (face
dependent partitioning) applies to those elements as well.
The structural separation between Mn, Fe, Sr and the triva-
lent REE (Y, La, Ce and Yb) suggest, that Mn and Fe must
be in divalent form. Studies of Elzinga etal. (2002) and
Withers etal. (2003) on synthetically grown single-crystal
REE-doped calcite show that HREE occur in a six-fold coor-
dination, whereas the incorporation of LREE in the Ca site
in calcite requires a sevenfold coordination. The seven-fold
coordination, however, leads to disruption of local structures
and charge disequilibrium. As one possible mechanism of
charge compensation, Elzinga etal. (2002) and Marques
Fernandes etal. (2008) refer to co-substitution of Ca2+ with
monovalent cations, e.g., Na+ + REE3+ as it is most distinct
in sector C. From the similar behavior of Pb with LREE and
U with HREE it can be reasoned that site-specific partition-
ing occurs in dependence of the ionic radius.
The face dependent partitioning observed in this study
gives strong evidence, that.
• REE (Y, La, Ce, Yb) and divalent cations (Mn, Fe, Sr)
do not coprecipitate in the same sector.
• HREE/LREE partitioning might occur. Pb and Th are
thereby associated with LREE, U with HREE.
Plausibility assessment oftrace element partitioning
Fracture fluids exhibit a unique, depth-dependent composi-
tional fingerprint of the different infiltrating and hydrother-
mal mixing waters (Gimeno etal. 2008; Drake etal. 2012;
Gómez etal. 2014). To allow for the estimation of DTE ratios
in natural systems, bulk formation water data are commonly
used under the assumption, that the analyzed physicochemi-
cal parameters are identically with those of the precipitation
solution of the calcites (outermost growth zones of calcites
fracture fillings at Laxemar (Drake etal. 2015) have been
dated to an age of Late Miocene by Ivarsson etal. (2020).
This assumption simplifies not only the temporal fluctua-
tions since the precipitation of the outermost calcite growth
zones, but also the spatial disparities between the forma-
tion waters in single fractures. However, this approach is
still a meaningful addition to laboratory and field derived
experiments.
Here, partition coefficients DTE between TE concentra-
tion of the formation water and TE content of the outermost
overgrowth of single calcite crystals are discussed regarding
their plausibility in comparison to laboratory-derived par-
tition coefficients (Curti 1999 and references therein) and
previous field studies conducted at the Äspö HRL (Drake
etal. 2018 Fig.6). The latter field studies were carried out
on recent precipitated calcites (i.e., 17years growth period)
and recent formation water in bore holes at more than 400m
depth (pH 7.4–7.7, 14°C) (Drake etal. 2018).
At Simpevarp and Laxemar, two recent groundwater types
are dominant in borehole KSH01A (Laaksoharju 2004). The
transition between the freshwater type and the underlying
brackish groundwater type is located at ca. 200m. Therefore,
data from the formation water of the same borehole section
and freshwater type groundwater data taken between 150
and 200m depth were used to calculate DTE ratios for the
samples KSH01A _205_A/B (Table2, Laaksoharju 2004).
Overall, DTE ratios based on formation water data
from < 200m depth fit best with previously found ratios
calculated by Drake etal. (2018) based on 17-year precipi-
tation experiment carried out at the Äspö HRL. Partition-
ing coefficients of Mn and Fe are comparably higher and
lower for Sr when calculated based on formation water data
from > 200m dept h. DNa coefficients are in good agreement
with field-derived data and at the lower end of laboratory-
derived data. REE and U concentrations are only available
for formation water > 200m. The discrepancies of Y uptake
between samples from the same site in Simpevarp is striking,
as the ratios in 205m depth match with laboratory-derived
ratios while those from 212m depth correspond with field
observations from the area. Partition coefficients for La, Ce
and U are in good agreement with laboratory experiments
and high in comparison with previous field studies at the
Äspö HRL.
For sample KSH01A_212, mean DTE ratios of Mn, Fe
and Sr are below or at the low end of the range of laboratory
driven values. The low Sr uptake is contrary to previously
found ratios at the Äspö area, which even exceed laboratory-
derived ratios. Partition coefficients for La and Ce are in
good agreement with laboratory experiments and high in
comparison with previous field studies. DNa and DU are in
good agreement with field-derived coefficient range.
For sample KFM4A_233 (Forsmark), DTE ratios of Mn,
Fe, Sr and U diverge significantly from laboratory and field
driven ratios (Fig.6). Only La and Ce partitioning is in the
expected range.
Based on these results, the comparison with partition
ratios generated under laboratory conditions should be
treated with caution as they are conducted under well-
known, abiotic conditions (i.e.;
p=1atm
,
T=25◦C
, defined
aqueous speciation, supersaturation conditions, competing
cation and others) and therefore represent only a rough
approximation of natural systems. Under laboratory condi-
tions, most elements exist in free cationic state, complexa-
tion on the other hand is common in the formation waters.
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371 Page 12 of 28
Sr for example is mostly available as Sr2+, Fe mainly as
Fe2+ and with increasing depth as FeHS+ (Laaksoharju etal.
2009). Mn is available as Mn2+, still a large portion of the
element is bound as MnHS+, MnCO3, MnHCO3+ (Laakso-
harju etal. 2009; Kalinowski and Swedish Nuclear Fuel and
Waste Management Co., Stockholm 2009). The presence of
Mn-reducing microorganisms (Drake etal. 2009; Ivarsson
etal. 2020) might lead to local Mn enrichments which could
explain the elevated levels in proportion to recent ground
waters. With increasing depth (below 250m), complexation
is less relevant due to decreasing HCO3− and TOC (total
organic carbon) concentrations in the formation water (Laak-
soharju etal. 2009).
As mentioned above, it is unlikely that physiochemical-
properties remained comparable since the point of precipi-
tation. However, even with constant trace element concen-
tration, other parameters such as temperature T, pH value
and precipitation rate RP can limit or benefit the TE incor-
poration. DePaolo (2011) described the influence of these
parameters mathematically in Eq.3. The equation was used
in this work, to back-calculate TE/Ca ratios of precipita-
tion solutions and compare them to recentgroundwater data.
The example of Sr/Ca and Mn/Ca ratios of the precipitation
Fig. 6 Partition ratio of the
trace elements Na, Mn, Fe,
Sr, Y, La, Ce and U between
fracture water and outer most
growth zone of calcite crystals
from bore hole KFM04A
(233m) and KSH01A (205m
and 212m). For comparison,
partition ratios from laboratory
experiments carried out at 25°C
and 1atm (Curti 1999 and refer-
ences therein) and field-driven
experiments carried out at the
Äspö HRL (Drake etal. 2018)
were added. Missing data are
marked in the diagram
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solution as a function of log RP under defined T and pH is
given in Fig.7. The pH values of the recent formation waters
range from 7.19 in Forsmark to 7.24 in Simpevarp. We
therefore used equilibrium TE/Ca partitioning coefficients
of Keq = 0.035 for strontium and Keq = 60 for manganese and
forward kinetic fractionation factor for TE/Ca in the precipi-
tation reaction is Kf = 0.24, Rb = 7 × 10–7mol/m2/sec (values
taken from DePaolo (2011) used for experimental data of
Lorens (1981) obtained at T = 25°C, pH≈7.4, P = 1atm).
Under these assumptions, the best fit between recalcu-
lated TE/Ca ratios of the precipitation solution and recent
ground waters could be found for sample KSH01A_212 and
waters from above 200m under medium to fast precipita-
tion rates (logRp ≈-5). Even though, Sr/Ca ratios areslightly
lower than expected from groundwater data (Fig.7). For
the samples KSH01A_205_A/B and groundwaters above
200m, Sr/Ca ratios fit with a logRP ≈ − 7, whereas Mn/Ca
ratios would be rather high in comparison to recent ground-
waters (power of ten above). However, Mn rich waters are
not uncommon at the site (Tullborg etal. 1999). Especially
through microbial activity, local Mn enrichments can occur.
For groundwater data below 200m, logRp < − 8 is reason-
able. The results of KFM04A show, under the given T and
pH values, precipitation solution and recent groundwater TE
chemistry differ largely.
Overall, these results show, that the partitioning ratios as
generated in this and many otherstudies should be handled
with caution. The interrelation between DTE, respectively,
TE/Ca and RP given in Fig.7 shows, that even slight changes
of the precipitation environment can influence significantly
the trace element incorporation into the calcite crystal lattice
during the secondary phase formation and retention.
Conclusions
The high-resolution maps created in the course of this work
allow for the detection of zonation and microstructures
within the samples. Local enrichment and variability of
elementcontents measured by LA-ICP-MS are in many cases
not detectable with µXRF. Thus, it becomes clear, that single
point measurements or line scans reveal a limited view of the
sample which could lead to misinterpretations. Especially
face-dependent partitioning, as it was found at our samples,
cannot be covered by point measurements.
From the change of paleo-hydrogeological conditions
determined by trace elements, it can be concluded that the
retention of rare-earth elements in calcite is high even with
fluctuating precipitation conditions. Special attention should
be given to the greenish contact zone found in samples from
Laxemar at approximately 410–430m, where clay mineral
rims are incorporated into a calcite-dominated aggregate
growth. The particularly high trace elements contents in this
area are promising in terms of understanding the increased
uptake of trace elements.
Taken that lanthanides and trivalent actinides show a sim-
ilar chemical behavior, and that the observed concentrations
and apparent partitioning of the lanthanides in the studied
calcites are high, the retention potential of radionuclides in
calcite facture fillings in crystalline rock environments for
deep geological disposal of radioactive waste should be con-
sidered to be promising.
Appendix
1. Spatially resolved trace element content
inppm
See Figs.8 and 9.
Fig. 7 Datapoints mark the recalculated Sr/Ca, respectively Mn/Ca
ratios of the precipitation solution in dependency of the precipitation
rate RP as proposed by DePaolo (2011). Calculations are based on the
median solid solution Sr/Ca, respectively Mn/Ca ratios of the outer-
most calcite zones obtained by LA-ICP-MS measurements of samples
from bore hole KSH01A (Simpevarp) and KFM04A (Laxemar). pH
and T dependent Kf,Sr = 0.24, Kf,Mn = 5, Rb = 7 × 10 7 mol/m2/sec and
Keq,Sr = 0.035 and Keq,Mn = 60 were applied
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Fig. 8 Spatially resolved
element content of sample
KFM04A_233 of the line scans
H3 and V based on LA-ICP-
MS measurements. For better
visualisation moving averages
(Period 10) were applied if
possible
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Fig. 9 Spatially resolved
element content of sample
KSH01A_212 of line scan V
based on LA-ICP-MS measure-
ments. For better visualisation
moving averages (Period 10)
were applied if possible
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2. Mean trace‑element content based
onLA‑ICP‑MS analysis classied bycluster
analysis
See Figs.10, 11, 12 and 13; Tables4, 5, 6, 7 and 8.
Fig. 10 Reflected-light
microscopy image of sample
KSH01_205_A on the left and
KSH01A_205_B on the right.
Cluster are colour coded on the
sample maps next to the image
Fig. 11 Reflected-light
microscopy image of sample
KLX4A_669. Cluster are colour
coded on the sample maps next
to the image
Fig. 12 Reflected-light
microscopy image of sample
KLX19A_414. Cluster are col-
our coded on the sample maps
next to the image. The cluster
WR describes Ca rich wall rock
minerals. Consequently, for this
sample, calcite cluster 1 starts
with a red colour code
Fig. 13 Reflected-light
microscopy image of sample
KLX19A_428. Cluster are col-
our coded on the sample maps
next to the image
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Table 4 Trace element contents of sample KSH01A_205_A based on LA-ICP-MS measurement
Cluster N Total Mean(ppm) SD Min. (ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
Na 1 2250 544.6 2186.6 0.4 37.9 53.0 85.1 43,143.2
2 3304 464.4 2402.1 0.1 22.8 38.8 62.2 71,311.0
3 1179 880.4 3831.2 0.0 10.1 24.3 144.5 76,984.5
4 1583 521.8 2195.5 0.2 21.7 38.0 62.0 38,864.8
5 3189 507.5 2071.0 0.1 26.0 41.3 66.0 39,084.2
6 4611 571.9 2455.5 0.1 32.8 54.5 81.7 56,013.3
7 2539 682.1 3322.5 0.0 20.4 46.4 92.3 71,585.6
8 3397 741.3 3427.0 0.1 28.0 52.6 117.2 107,285.8
Mn 1 2324 7926.5 1795.7 1882.2 6766.4 7907.0 9077.7 15,163.4
2 3558 12,190.7 2531.1 5113.3 10,701.3 11,998.7 13,354.7 44,023.3
3 2255 14,435.1 3637.8 5877.1 12,561.7 14,013.0 15,616.7 61,702.4
4 1992 14,372.0 2609.4 7150.7 12,691.0 14,110.0 15,690.5 37,214.2
5 3761 9591.5 1789.9 4291.7 8387.3 9331.8 10,544.5 20,171.8
6 5308 8558.1 1714.4 3524.6 7481.0 8344.8 9328.3 22,485.0
7 3207 11,274.6 3009.2 4761.7 9264.5 11,042.7 12,961.9 44,325.8
8 4185 8298.2 1644.6 2703.3 7143.8 8170.5 9278.2 15,859.1
Fe 1 2324 1312.9 406.1 293.4 1064.7 1275.4 1516.1 4937.5
2 3558 1763.0 544.1 544.6 1455.0 1705.4 1979.8 10,454.1
3 2255 2061.8 760.6 757.1 1625.6 1983.3 2355.0 21,197.8
4 1992 3178.4 714.9 1114.8 2742.4 3150.0 3549.6 9817.7
5 3761 2265.8 498.9 764.7 1929.5 2232.7 2543.4 7054.6
6 5308 1830.5 408.7 526.6 1551.8 1810.4 2071.1 4854.9
7 3207 4024.9 2129.6 1253.7 3170.5 3741.3 4526.8 74,181.1
8 4185 2603.1 658.8 952.6 2185.6 2534.6 2922.5 8935.8
Sr 1 2324 154.2 52.0 21.2 117.2 150.9 184.1 624.3
2 3558 79.9 18.9 12.6 67.8 78.5 90.1 213.9
3 2255 72.0 18.5 18.9 59.4 70.7 82.8 150.7
4 1992 191.4 60.4 48.5 165.2 189.2 214.6 2087.7
5 3761 174.9 219.6 72.9 146.5 165.3 186.1 12,748.9
6 5308 121.8 45.6 44.1 100.3 116.8 137.6 2502.2
7 3207 140.9 46.8 26.4 109.2 133.8 166.7 524.3
8 4185 141.4 43.4 26.0 113.4 137.5 163.6 967.2
Y 1 2324 93.44 32.39 20.83 75.56 88.03 102.80 508.76
2 3558 65.72 29.06 13.52 46.33 61.98 79.17 353.60
3 2255 289.40 121.32 55.59 178.59 288.50 375.51 831.91
4 1992 124.23 41.51 45.40 95.20 112.79 144.24 341.24
5 3761 259.79 63.33 89.41 218.63 257.56 295.68 945.36
6 5308 157.09 40.54 67.67 128.71 151.71 179.75 469.96
7 3207 188.25 63.30 42.52 143.16 182.33 224.15 581.64
8 4185 242.69 75.15 41.86 190.64 232.31 284.51 666.86
La 1 2324 106.11 83.86 8.12 35.79 86.49 146.90 745.50
2 3558 43.78 21.08 4.38 31.96 42.89 51.74 368.71
3 2255 54.83 22.95 10.68 40.10 53.60 65.53 247.39
4 1992 37.57 27.69 5.95 18.64 27.01 52.68 351.84
5 3761 66.45 44.89 15.19 37.67 50.00 80.81 614.03
6 5308 445.13 150.87 126.20 333.14 446.31 548.06 1160.17
7 3207 56.82 26.68 5.14 37.05 53.49 72.00 202.08
8 4185 124.35 70.36 16.65 73.86 110.11 157.29 823.59
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Table 4 (continued)
Cluster N Total Mean(ppm) SD Min. (ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
Ce 1 2324 70.24 47.62 9.72 29.88 61.38 95.56 509.77
2 3558 35.65 16.77 3.13 26.62 34.91 42.54 404.00
3 2255 47.70 18.94 7.16 37.41 46.77 55.39 410.40
4 1992 29.31 17.30 1.25 17.59 24.24 37.22 220.76
5 3761 54.56 26.76 10.60 37.84 47.62 63.10 504.90
6 5308 263.83 97.65 77.59 196.42 258.90 318.70 2680.64
7 3207 40.13 21.46 2.63 24.51 37.41 52.23 486.04
8 4185 84.16 43.04 12.56 55.51 75.48 102.37 708.92
Yb 1 2324 0.62 0.31 0.00 0.43 0.58 0.77 2.57
2 3558 0.53 0.27 0.00 0.34 0.50 0.70 2.63
3 2255 2.61 1.13 0.60 1.67 2.50 3.34 10.44
4 1992 0.89 0.42 0.00 0.60 0.83 1.12 6.59
5 3761 2.28 0.75 0.56 1.78 2.19 2.69 11.17
6 5308 1.35 0.50 0.12 1.00 1.28 1.63 5.09
7 3207 1.03 0.48 0.00 0.71 0.96 1.29 5.14
8 4185 1.59 0.69 0.23 1.08 1.47 1.98 8.00
Pb 1 1676 0.1209 0.5618 0.0000 0.0177 0.0369 0.0799 14.1917
2 2491 0.1229 1.0366 0.0000 0.0158 0.0326 0.0633 45.9084
3 1636 0.1962 2.0710 0.0000 0.0163 0.0334 0.0651 63.2961
4 1382 0.0681 0.2330 0.0000 0.0145 0.0285 0.0506 4.0762
5 2672 0.1645 2.1400 0.0000 0.0149 0.0306 0.0570 72.5722
6 3623 0.6349 21.3543 0.0000 0.0149 0.0302 0.0570 1170.6850
7 2364 0.6834 15.0233 0.0000 0.0161 0.0367 0.0817 533.0561
8 3119 0.1520 1.2351 0.0000 0.0186 0.0385 0.0841 47.2930
Th 1 401 0.0228 0.0357 0.0071 0.0134 0.0157 0.0234 0.6043
2 837 0.0242 0.0558 0.0081 0.0138 0.0161 0.0224 1.1525
3 1180 0.0279 0.0199 0.0066 0.0157 0.0201 0.0346 0.2124
4 215 0.0192 0.0106 0.0079 0.0137 0.0161 0.0189 0.1003
5 293 0.0245 0.0252 0.0069 0.0140 0.0164 0.0272 0.3077
6 1512 0.0203 0.0156 0.0067 0.0135 0.0156 0.0220 0.2259
7 409 0.0307 0.0524 0.0076 0.0129 0.0159 0.0290 0.7120
8 839 0.0238 0.0310 0.0065 0.0128 0.0157 0.0253 0.4468
U1 2324 0.0130 0.0583 0.0002 0.0002 0.0002 0.0048 1.2695
2 3558 0.0107 0.0452 0.0002 0.0002 0.0002 0.0002 0.8862
3 2255 0.0153 0.0602 0.0002 0.0002 0.0002 0.0065 1.4816
4 1992 0.0028 0.0114 0.0002 0.0002 0.0002 0.0002 0.1505
5 3761 0.0024 0.0074 0.0002 0.0002 0.0002 0.0002 0.1517
6 5308 0.0127 0.0583 0.0002 0.0002 0.0002 0.0049 2.3589
7 3207 0.2170 0.1627 0.0002 0.1204 0.1944 0.2786 4.2371
8 4185 0.1543 0.2327 0.0002 0.0674 0.1166 0.1897 10.0763
Given are mean, standard deviation (SD), minimum (min.), 1stquartile (Q1), median, 3rdquartile (Q3) and maximum (max.)
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Table 5 Trace element contents of sample KSH01A_205_B based on LA-ICP-MS measurement
Cluster N Total Mean(ppm) SD Min.(ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
Na 1 3228 141.0 929.3 0.0 3.6 9.0 30.2 29,879.3
2 2239 141.1 841.9 0.0 3.8 8.8 27.8 18,733.2
3 4553 110.8 723.5 0.0 3.2 7.1 16.8 21,654.9
4 3776 170.1 1454.1 0.0 4.3 10.4 35.0 66,508.3
5 2563 179.2 1178.0 0.0 5.1 11.0 28.5 31,391.9
6 8762 93.2 618.0 0.0 11.4 22.7 47.8 34,207.4
7 5698 115.2 1603.7 0.0 6.1 12.5 22.8 90,881.6
Mn 1 5052 681.6 483.3 0.1 394.5 544.8 799.7 9363.8
2 2943 1143.6 575.1 0.0 744.9 1187.9 1555.3 4836.8
3 6743 5989.1 2273.4 524.9 4694.4 5957.6 7263.3 18,991.3
4 5799 7984.2 5628.6 223.4 4551.1 6672.3 9700.0 63,456.6
5 3253 3443.7 2107.9 0.1 2033.6 3264.5 4493.8 19,247.0
6 9702 5799.5 4296.3 77.9 3642.7 4947.7 6658.9 78,510.1
7 6854 5321.4 2796.5 62.2 3319.0 5335.2 7090.2 30,392.6
Fe 1 5047 45.8 108.6 0.9 18.5 27.0 43.8 3213.4
2 3354 367.8 699.3 0.8 87.1 158.7 280.2 12,739.7
3 6742 888.0 413.8 56.8 620.3 845.5 1090.8 4327.5
4 5799 1697.5 1165.2 33.2 1031.9 1461.5 2060.3 12,130.8
5 3294 1093.9 1342.4 56.2 660.8 888.6 1196.4 28,162.8
6 9702 2305.3 1676.1 83.1 1437.3 1948.5 2642.8 48,978.7
7 6853 1515.4 840.0 40.4 898.9 1446.0 2058.3 8054.7
Sr 1 5050 4.3 3.1 0.3 2.5 3.4 5.1 63.6
2 3359 10.4 16.6 1.1 5.8 9.3 13.0 900.7
3 6742 6.5 3.6 0.4 4.4 5.5 7.3 38.2
4 5799 17.5 18.9 1.9 10.9 14.9 20.0 1175.1
5 3294 14.3 10.4 3.5 8.7 11.5 15.9 134.7
6 9702 12.1 7.1 2.0 7.5 10.5 14.5 160.5
7 6853 8.3 5.5 0.5 4.8 6.6 10.8 210.8
Y 1 5040 0.71 0.50 0.01 0.39 0.61 0.88 5.92
2 3355 2.95 4.39 0.07 1.08 1.75 2.60 56.50
3 6742 3.61 1.99 0.30 2.19 3.23 4.54 18.88
4 5799 10.15 5.76 0.34 5.91 9.25 13.20 45.57
5 3294 9.80 9.04 1.30 5.98 8.24 11.27 199.79
6 9702 15.56 7.14 0.57 10.70 14.24 18.85 76.39
7 6854 6.06 3.39 0.33 3.29 5.76 8.27 22.06
La 1 4904 0.13 0.19 0.00 0.04 0.07 0.14 4.04
2 3357 4.42 4.78 0.05 1.66 3.21 5.30 43.79
3 6741 2.13 1.37 0.06 1.18 1.97 2.72 14.39
4 5793 2.95 2.01 0.06 1.50 2.47 3.91 15.94
5 3294 23.71 16.95 2.10 11.35 19.24 33.08 283.65
6 9702 7.40 8.24 0.58 3.10 4.67 7.81 109.61
7 6852 2.04 1.63 0.02 1.05 1.68 2.57 16.86
Ce 1 5035 0.46 0.50 0.01 0.20 0.34 0.55 11.60
2 3359 7.75 7.16 0.27 3.40 5.97 9.22 67.22
3 6742 4.78 2.75 0.14 2.80 4.60 6.16 27.66
4 5798 6.87 4.15 0.17 3.93 6.10 8.73 33.12
5 3294 38.00 25.53 5.81 19.93 32.26 49.61 399.35
6 9702 13.82 12.50 1.05 6.78 9.93 15.45 163.64
7 6854 4.31 3.18 0.15 2.21 3.67 5.52 40.95
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Table 5 (continued)
Cluster N Total Mean(ppm) SD Min.(ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
Yb 1 2991 0.04 0.07 0.01 0.01 0.03 0.04 2.93
2 3077 0.07 0.10 0.01 0.02 0.04 0.07 1.22
3 6653 0.09 0.05 0.01 0.05 0.07 0.11 0.48
4 5358 0.27 0.27 0.02 0.15 0.23 0.35 16.25
5 3227 0.23 0.19 0.01 0.13 0.19 0.28 3.22
6 9564 0.28 0.15 0.03 0.18 0.25 0.35 1.95
7 6733 0.11 0.07 0.01 0.06 0.10 0.15 0.53
Pb 1 3124 0.0204 0.1132 0.0000 0.0029 0.0056 0.0125 2.6266
2 2179 0.0141 0.1045 0.0000 0.0022 0.0046 0.0092 4.4098
3 4868 0.0122 0.1083 0.0000 0.0020 0.0040 0.0074 3.9167
4 4379 0.0890 4.0783 0.0000 0.0033 0.0060 0.0118 267.8140
5 2395 0.0184 0.1522 0.0011 0.0029 0.0053 0.0104 5.0264
6 6956 0.0201 0.1395 0.0000 0.0034 0.0061 0.0131 9.2314
7 5134 0.0123 0.1015 0.0000 0.0020 0.0040 0.0077 3.8232
Th 1 172 0.0050 0.0069 0.0011 0.0018 0.0029 0.0055 0.0701
2 260 0.0032 0.0032 0.0011 0.0018 0.0021 0.0034 0.0257
3 1107 0.0026 0.0017 0.0011 0.0017 0.0020 0.0031 0.0224
4 663 0.0047 0.0060 0.0013 0.0021 0.0033 0.0052 0.1076
5 633 0.0044 0.0091 0.0012 0.0019 0.0023 0.0041 0.1352
6 1939 0.0063 0.0119 0.0010 0.0021 0.0036 0.0060 0.3338
7 984 0.0038 0.0136 0.0008 0.0018 0.0021 0.0036 0.3851
U1 640 0.0095 0.0223 0.0004 0.0011 0.0030 0.0099 0.4338
2 442 0.0194 0.0213 0.0005 0.0031 0.0115 0.0291 0.1078
3 23 0.1120 0.0879 0.0333 0.0521 0.0905 0.1438 0.4009
4 247 0.0967 0.1167 0.0096 0.0535 0.0816 0.1190 1.7233
5 92 0.1007 0.1496 0.0035 0.0227 0.0521 0.0950 0.9158
6 9702 0.0274 0.0256 0.0003 0.0069 0.0223 0.0396 0.3889
7 6854 0.0143 0.0174 0.0003 0.0010 0.0053 0.0243 0.1156
Given are mean, standard deviation (SD), minimum (min.), 1stquartile (Q1), median, 3rdquartile (Q3) and maximum (max.)
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Table 6 Trace element contents of sample KLX4A_699 based on LA-ICP-MS measurement
Given are mean, standard deviation (SD), minimum (min.), 1stquartile (Q1), median, 3rdquartile (Q3) and maximum (max.)
Cluster N Total Mean (ppm) SD Min. (ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
Na 1 179,374 1558.7 18,307.5 0.0 28.3 72.9 207.4 1,556,408.0
2 57,724 1126.4 17,372.3 0.0 21.8 53.8 141.3 1,411,154.0
3 126,150 1408.1 19,437.1 0.0 31.3 80.6 231.4 2,374,618.0
Mn 1 261,863 9941.5 2955.2 23.3 8713.5 9962.1 11,196.6 210,957.6
2 97,587 16,198.9 5387.7 187.5 12,012.4 16,334.0 20,603.5 50,093.2
3 179,999 14,103.7 5245.5 239.4 11,103.0 14,017.4 17,358.5 154,409.0
Fe 1 261,863 1619.9 32,899.1 5.4 205.2 250.3 289.6 2,657,032.0
2 97,587 518.7 4154.1 5.7 308.4 433.9 646.9 733,298.8
3 179,999 1070.9 26,207.3 2.5 246.7 348.3 460.9 3,657,005.0
Sr 1 261,863 83.0 647.2 4.6 52.1 61.9 73.9 171,011.6
2 97,587 59.8 287.4 12.6 46.9 53.4 61.4 80,826.7
3 179,999 76.0 427.3 9.2 50.3 61.1 75.1 83,773.7
Y 1 261,863 387.06 715.88 1.07 178.58 411.21 510.92 99,470.52
2 97,587 2.49 2.60 0.01 0.96 1.92 3.28 179.83
3 179,999 10.65 12.48 0.01 4.58 7.63 12.82 1054.96
La 1 261,863 110.20 347.00 0.01 61.14 88.91 124.25 46,948.44
2 97,587 0.12 0.50 0.01 0.01 0.01 0.20 68.81
3 179,999 7.93 35.34 0.01 0.64 1.28 3.01 3362.55
Ce 1 261,863 248.32 796.27 0.73 153.56 220.57 284.23 113,734.10
2 97,587 0.50 1.60 0.01 0.01 0.26 0.59 153.48
3 179,999 12.19 50.80 0.01 1.35 2.55 6.14 11,659.80
Yb 1 261,863 16.56 15.45 0.02 9.70 17.14 22.04 1617.16
2 97,587 0.16 0.58 0.02 0.02 0.02 0.02 77.11
3 179,999 0.55 3.00 0.02 0.02 0.02 0.77 1159.52
Pb 1 164,859 3.2094 211.2490 0.0294 0.2164 0.3820 0.7653 75,060.7300
2 47,577 2.1294 59.0699 0.0365 0.1896 0.3151 0.6160 8008.3330
3 106,501 2.6189 66.5567 0.0646 0.2202 0.4026 0.8327 9234.1390
Th 1 6423 1.2970 21.5727 0.0487 0.1426 0.1863 0.3071 1190.7100
2 1199 0.2548 0.4103 0.0668 0.1364 0.1772 0.2769 12.2309
3 3084 0.3172 0.8533 0.0230 0.1431 0.1822 0.2736 27.8616
U1 261,863 0.1422 2.7903 0.0026 0.0026 0.0026 0.0026 1037.2400
2 97,587 0.0882 0.7332 0.0026 0.0026 0.0026 0.0026 52.7842
3 179,999 0.1092 1.0516 0.0026 0.0026 0.0026 0.0026 200.9853
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Table 7 Trace element contents of sample KLX19A_414 based on LA-ICP-MS measurement
Cluster N Total Mean (ppm) SD Min. (ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
Na 1 49,355 341.3 1471.5 0.0 25.8 51.4 124.1 49,582.5
2 6788 6307.2 45,117.8 0.9 159.2 402.5 1342.4 1,484,690.0
3 43,360 272.9 1611.1 0.0 18.9 35.6 72.2 116,980.3
4 30,546 352.8 3998.0 0.0 13.8 28.4 68.3 597,453.1
5 30,787 298.2 2138.5 0.0 23.7 46.1 100.7 208,988.3
Mn 1 52,433 8879.2 2027.9 191.5 7564.4 8639.5 9882.8 31,302.0
2 6793 7736.7 7365.4 144.0 4152.5 5942.2 8470.5 122,462.7
3 46,767 19,463.0 4294.0 3270.3 16,678.6 19,388.1 21,993.7 61,692.8
4 34,631 10,331.0 3060.2 168.8 8544.7 10,098.8 11,635.4 226,878.0
5 32,704 7253.0 2524.5 0.7 5848.4 7011.2 8286.8 28,183.7
Fe 1 52,433 283,4 474.7 30.7 154.2 193.2 269.4 18,657.5
2 6793 220,578.6 428,424.7 611.1 22,655.1 71,421.7 215,467.6 5,254,798.0
3 46,767 890.5 757.5 95.9 705.7 843.2 983.1 51,364.6
4 34,631 413.5 844.8 75.7 253.2 327.2 402.8 75,736.3
5 32,704 421.5 1277.7 1.5 135.3 183.3 291.7 54,111.4
Sr 1 52,433 75.7 37.3 16.5 56.5 69.7 87.1 1702.2
2 6793 190.0 905.8 19.9 64.2 89.2 139.0 36,749.5
3 46,767 129.3 301.9 24.6 81.9 109.4 148.6 35,029.3
4 34,631 147.2 703.8 17.8 94.3 118.1 152.7 59,820.5
5 32,704 44.8 22.7 0.2 32.9 41.6 52.2 1466.7
Y 1 52,433 100.64 32.71 27.92 80.48 96.03 115.49 1014.07
2 6793 94.99 100.22 0.02 43.09 66.06 105.47 1922.18
3 46,767 189.99 109.45 28.85 147.86 186.84 223.54 7770.80
4 34,631 118.25 91.49 23.75 82.99 105.83 136.11 4393.30
5 32,704 57.49 19.04 0.02 45.34 57.26 69.06 719.42
La 1 52,433 65.25 33.70 4.24 42.22 58.73 80.90 986.69
2 6793 139.30 343.77 4.02 36.46 64.84 133.99 14,626.27
3 46,767 22.85 16.95 1.24 12.09 18.60 28.04 399.42
4 34,631 511.58 282.69 9.53 425.36 502.69 575.04 11,520.36
5 32,704 33.55 29.85 0.02 17.99 27.08 40.53 1609.16
Ce 1 52,433 130.63 97.91 12.68 84.72 112.99 151.73 4425.83
2 6793 358.76 958.51 13.74 90.53 160.15 333.12 36,508.47
3 46,767 66.02 62.74 7.09 37.44 54.28 77.03 4672.30
4 34,631 966.25 810.19 69.04 753.71 892.49 1046.27 45,309.46
5 32,704 75.39 149.57 0.03 42.44 60.04 84.22 14,847.84
Yb 1 52,433 13.20 5.53 2.07 10.16 12.55 15.44 713.64
2 6793 11.38 12.08 0.03 4.76 8.01 13.24 173.45
3 46,767 20.40 19.99 2.63 14.50 19.24 24.58 2836.88
4 34,631 13.76 8.25 0.03 10.00 12.97 16.60 1140.40
5 32,704 8.23 3.38 0.03 5.92 7.94 10.20 44.29
Pb 1 49,647 1.4669 29.4332 0.0000 0.3357 0.6023 0.9996 3470.3650
2 6735 11.0752 180.5259 0.0000 0.9064 2.2339 6.2994 14,657.2400
3 46,035 1.9944 21.0512 0.0000 0.4635 1.0466 1.9766 2921.2440
4 33,376 3.3967 113.1067 0.0000 0.3785 0.6663 1.1090 19,262.4000
5 27,124 1.6299 46.7071 0.0000 0.1612 0.3246 0.5976 6707.7360
Th 1 30,040 0.5272 4.8306 0.0591 0.1401 0.2483 0.4321 652.1945
2 6644 70.9911 278.0068 0.0366 2.2604 9.1753 41.1631 7153.8940
3 11,002 0.5505 19.6045 0.0621 0.1234 0.1407 0.2458 2025.9940
4 6565 3.9655 36.9164 0.0671 0.1308 0.1513 0.2867 1393.6960
5 14,567 0.4422 4.9485 0.0415 0.1260 0.1748 0.3330 486.4583
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Given are mean, standard deviation (SD), minimum (min.), 1stquartile (Q1), median, 3rdquartile (Q3) and maximum (max.)
Table 7 (continued)
Cluster N Total Mean (ppm) SD Min. (ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
U 1 52,433 0.1559 1.3073 0.0034 0.0034 0.0034 0.0910 228.8494
2 6793 10.4823 24.2576 0.0034 0.5963 2.1258 8.5917 433.2345
3 46,767 0.1516 0.9016 0.0034 0.0034 0.0034 0.0920 65.0613
4 34,631 0.2019 1.1074 0.0034 0.0034 0.0034 0.0901 56.4890
5 32,704 0.2033 1.3179 0.0034 0.0034 0.0034 0.0985 177.2760
Table 8 Trace element contents of sample KLX19A_428 based on LA-ICP-MS measurement
Cluster N Total Mean (ppm) SD Min. (ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
Na 1 40,712 334.0 1830.4 0.0 70.5 117.6 213.0 117,444.1
2 39,543 466.5 2966.1 0.0 72.4 128.5 259.0 399,525.2
3 36,162 282.7 1733.1 0.0 62.7 100.9 168.1 129,777.3
4 16,374 4513.7 37,490.4 0.2 139.1 261.3 665.3 1,196,845.0
5 13,442 276.8 4081.8 0.0 51.3 77.5 114.6 294,990.5
6 23,717 563.3 8896.8 0.1 59.0 93.0 151.2 1,016,395.0
7 3622 2965.1 34,102.9 0.2 124.7 207.9 335.0 888,626.4
Mn 1 42,932 7508.1 2822.3 648.4 5543.2 7552.2 9309.4 27,515.3
2 42,996 10,113.5 3060.3 1756.4 8201.9 9821.3 11,674.4 42,310.8
3 38,944 9781.1 3036.8 1942.6 7778.9 9525.4 11,400.7 37,162.5
4 16,662 7465.2 6344.9 319.9 4064.6 6443.9 9526.2 304,030.3
5 14,934 20,467.0 5946.4 2496.0 16,939.9 20,892.0 24,137.2 72,418.6
6 26,546 16,819.3 4895.7 2573.6 13,719.8 16,317.7 19,310.4 117,181.3
7 3705 2715.9 3413.5 0.4 821.1 1129.1 2536.7 26,857.4
Fe 1 42,932 140.9 285.1 0.0 69.3 98.0 139.8 15,423.0
2 42,996 192.4 290.0 0.0 105.2 145.3 207.6 25,411.7
3 38,944 190.1 315.9 0.0 98.6 151.0 221.5 29,853.4
4 16,662 18,620.4 77,476.6 9.5 695.3 2405.2 9669.0 2,417,278.0
5 14,934 584.7 2107.1 13.5 378.9 560.3 703.1 252,379.3
6 26,546 558.0 1197.4 31.0 343.1 446.4 554.7 102,633.5
7 3705 330.4 2668.2 0.0 7.5 25.7 81.8 90,355.7
Sr 1 42,932 41.5 18.7 4.8 30.7 38.4 47.9 567.7
2 42,996 71.7 52.2 11.2 48.7 61.0 79.6 3133.8
3 38,944 33.8 14.6 3.6 23.2 31.6 42.0 193.3
4 16,662 175.9 583.6 15.5 53.6 73.7 120.4 20,186.4
5 14,934 57.3 54.2 6.9 44.7 54.4 66.3 4760.1
6 26,546 147.0 419.2 22.1 87.2 120.6 169.4 40,252.5
7 3705 77.4 286.3 0.0 38.8 55.7 75.8 9259.0
Y 1 42,932 37.74 15.89 2.44 26.73 35.41 46.21 170.60
2 42,996 90.80 216.99 13.33 54.23 71.08 95.33 22,083.24
3 38,944 60.14 30.06 4.35 39.61 55.95 75.08 962.17
4 16,662 240.45 1834.94 6.50 55.07 80.23 132.13 112,233.10
5 14,934 53.30 25.47 0.96 34.73 50.90 69.03 244.11
6 26,546 144.33 288.80 13.22 96.27 125.18 169.24 21,643.54
7 3705 8.23 10.07 0.00 2.41 4.75 9.05 115.33
La 1 42,932 71.62 43.74 4.24 42.20 63.67 90.92 2177.05
2 42,996 159.52 437.41 12.85 71.71 102.60 149.67 21,485.14
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Given are mean, standard deviation (SD), minimum (min.), 1stquartile (Q1), median, 3rdquartile (Q3) and maximum (max.)
Table 8 (continued)
Cluster N Total Mean (ppm) SD Min. (ppm) Q1 (ppm) Median (ppm) Q3 (ppm) Max. (ppm)
3 38,944 27.60 14.17 1.22 17.38 25.15 35.18 252.44
4 16,662 823.58 5121.17 9.90 109.65 205.53 446.66 283,154.80
5 14,934 7.26 4.72 0.02 3.80 6.52 9.72 55.75
6 26,546 26.49 18.05 2.95 16.43 22.17 30.23 512.12
7 3705 36.49 55.05 0.02 12.46 25.59 42.06 2265.17
Ce 1 42,932 123.77 79.93 7.49 76.73 110.30 154.09 7314.40
2 42,996 294.89 1081.84 23.00 129.72 180.11 262.80 96,359.86
3 38,944 56.45 26.93 3.94 37.42 52.16 70.82 478.12
4 16,662 1812.04 14,126.97 24.80 207.25 384.21 848.42 862,177.70
5 14,934 16.92 9.52 0.02 9.62 15.80 22.68 227.20
6 26,546 63.39 34.80 11.10 41.79 56.59 75.73 984.77
7 3705 61.18 69.11 0.02 20.90 44.68 72.52 939.34
Yb 1 42,932 5.11 2.76 0.03 3.12 4.68 6.61 34.17
2 42,996 12.23 26.97 0.75 7.54 10.27 13.95 2848.13
3 38,944 9.68 9.98 0.61 6.27 8.81 12.06 1618.43
4 16,662 18.98 93.58 0.03 5.10 8.68 14.13 5067.90
5 14,934 4.71 2.83 0.03 2.64 4.25 6.31 30.44
6 26,546 13.46 20.59 0.03 8.57 11.85 16.16 2243.89
7 3705 0.60 0.89 0.03 0.03 0.03 0.96 11.13
Pb 1 31,813 1.0587 27.0439 0.0705 0.2415 0.4266 0.7112 3547.2460
2 37,487 1.2172 9.6752 0.0983 0.3971 0.7012 1.1743 939.1515
3 26,510 0.7564 3.4037 0.0645 0.2436 0.4224 0.7219 212.0463
4 15,686 7.8645 66.7598 0.1132 0.7134 1.5044 3.7996 7580.7270
5 11,660 0.7723 7.6163 0.0939 0.2581 0.4864 0.8063 806.8278
6 25,691 3.1291 51.2807 0.1093 1.0681 2.0290 3.3756 7650.1890
7 1692 1.2533 7.0501 0.0892 0.2378 0.3575 0.6717 146.2635
Th 1 17,945 0.4392 1.1754 0.0587 0.1920 0.2524 0.4370 70.2832
2 22,743 0.6362 1.9338 0.0947 0.2352 0.3619 0.6289 106.6625
3 10,403 0.3782 1.3379 0.0626 0.1936 0.2435 0.3865 74.4016
4 14,961 121.1233 1695.0840 0.1073 1.3290 4.6241 15.3572 85,290.4800
5 1989 0.3545 1.5402 0.0283 0.1918 0.2241 0.2733 63.9064
6 5950 0.4303 1.1068 0.0985 0.2097 0.2492 0.4017 47.9916
7 516 1.9994 5.5256 0.0881 0.2374 0.3649 1.1651 54.3225
U 1 42,932 0.1230 1.6656 0.0000 0.0000 0.0000 0.0000 214.3815
2 42,996 0.0084 0.1224 0.0000 0.0000 0.0000 0.0000 13.3082
3 38,944 0.0559 0.6415 0.0000 0.0000 0.0000 0.0000 34.8827
4 16,662 24.1402 220.4716 0.0000 0.6672 2.4482 8.1514 11,006.2100
5 14,934 0.0546 0.9132 0.0000 0.0000 0.0000 0.0000 87.3487
6 26,546 0.0520 0.4885 0.0000 0.0000 0.0000 0.0000 21.5119
7 3705 0.2044 1.0103 0.0000 0.0000 0.0000 0.0000 27.3483
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3. Example: limit ofdetection
See Table9.
Acknowledgements The authors would like to thank the Swedish
Nuclear Fuel and Waste Management Company SKB for providing
samples and data. We want to thank Sandra Urban and Frank Linde for
preparation of the thin sections and polishing as well as Arno Märten
for his supervision on the use of µXRF and LA-ICP-MS.
Author contributions All authors contributed to the study conception
and design, however the first conceptualization was provided by TS
and HD. Sample collection and water analysis were carried out by HD.
Solid sample preparation, data collection and analysis were performed
by AK and NvL. TS and HD provided oversight to data collection and
interpretation. The first draft of the manuscript was written by AK and
all authors commented on previous versions of the manuscript. All
authors read and approved the final manuscript.
Funding Open Access funding enabled and organized by Projekt
DEAL. This research was founded by the Crafoord fund (20210524),
the Swedish Research Council (contract 2017-05186 and 2021-04365)
and Formas (contract 2020-01577) all to HD.
Data availability All relevant data are included. Please contact the
authors for further access to data and images.
Code availability Not applicable.
Declarations
Conflict of interest The authors declare that they have no competing
interests.
Open Access This article is licensed under a Creative Commons Attri-
bution 4.0 International License, which permits use, sharing, adapta-
tion, distribution and reproduction in any medium or format, as long
as you give appropriate credit to the original author(s) and the source,
provide a link to the Creative Commons licence, and indicate if changes
were made. The images or other third party material in this article are
included in the article's Creative Commons licence, unless indicated
otherwise in a credit line to the material. If material is not included in
the article's Creative Commons licence and your intended use is not
permitted by statutory regulation or exceeds the permitted use, you will
need to obtain permission directly from the copyright holder. To view a
copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/.
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