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Journal of Applied Geophysics 59 (2006) 273 – 283

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Magnetic properties of soils from sites with different geological


and environmental settings
Hana Fialová a,*, Günter Maier b, Eduard Petrovský a, Aleš Kapička a,
Tetyana Boyko b, Robert Scholger b
MAGPROX Team
a
Geophysical Institute ASCR, Bočnı́ II/1401, 141 31 Prague 4, Czech Republic
b
Department of Geophysics, University of Leoben, Peter Tunner Str.25, A-8700 Leoben, Austria
Received 21 March 2005; accepted 26 October 2005

Abstract

Measurements of magnetic susceptibility of soils, reflecting magnetic enhancement of topsoils due to atmospherically deposited
magnetic particles of industrial origin, are used recently in studies dealing with outlining polluted areas, as well as with
approximate determination of soil contamination with heavy metals. One of the natural limitations of this method is magnetic
enhancement of soils caused by weathering magnetically rich parent rock material. In this study we compare magnetic properties of
soils from regions with different geological and environmental settings. Four areas in the Czech Republic and Austria were
investigated, representing both magnetically rich and poor geology, as well as point-like and diffuse pollution sources. Topsoil and
subsoil samples were investigated and the effect of geology and pollution was examined. Magnetic data including mass and volume
magnetic susceptibility, frequency-dependent susceptibility, and main magnetic characteristics such as coercivity (Hc and Hcr) and
magnetization (Ms and Mrs) parameters are compared with heavy metal contents. The aim of the paper is to assess the applicability
of soil magnetometry under different geological-environmental conditions in terms of magnetic discrimination of dominant
lithogenic/anthropogenic contributions to soil magnetic signature. Our results suggest that lithology represents the primary effect
on soil magnetic properties. However, in case of significant atmospheric deposition of anthropogenic particles, this contribution can
be clearly recognized, independent of the type of pollution source (point-like or diffuse), and discriminated from the lithogenic one.
Different soil types apparently play no role. Possible effects of climate were not investigated in this study.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Magnetic susceptibility; Heavy metals; Soils; Pollution; Atmospheric deposition; Lithology

1. Introduction approximate tool to detect and characterise environ-


mental pollution (e.g., Dearing et al., 1996; Kapička
The need for fast and cheap screening and monitor- et al., 1999, 2001a,b, 2003; Petrovský and Ellwood,
ing tools of industrial pollution caused that increased 1999; Hoffmann et al., 1999a,b; Magiera and Strzyszcz,
number of studies deal with magnetic methods as an 2000; Petrovský et al., 2000; Hanesch and Scholger,
2002; Schibler et al., 2002; Veneva et al., 2004, and
* Corresponding author. Tel./fax: +420 267 103 332. others). Measurements of magnetic susceptibility of
E-mail address: hfialova@ig.cas.cz (H. Fialová). soils proved to be suitable, under certain circumstances,
0926-9851/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jappgeo.2005.10.006
274 H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283

for spatial delineation of polluted and unpolluted ceptibility in soil columns using new SM400 instru-
regions. This method is based on the assumption that ment (Petrovský et al., 2004). The effect of lithology
industrial processes, such as combustion of fossil fuel, and soil type on magnetic susceptibility of soils was
produce fly ashes with significant portion of magnetic studied by Hanesch and Scholger (2005). On the other
minerals (Flanders, 1994, 1999). These are transported hand, Magiera et al. (in press) analysed some 600
through atmospheric pathways and deposited on the vertical profiles of soil magnetic susceptibility and
ground. In soils, such particles penetrate downwards distinguished 7 main classes of profiles, independent
and accumulate in top layers, and their increased con- of lithology and soil type.
centration can be easily detected using surface magnetic In this study we examine the applicability of magnetic
measurements (e.g., Lecoanet et al., 1999). measurements of soils to discrimination of anthropogen-
In several studies, significant correlation between ic and lithogenic contributions in areas characterised by
magnetic susceptibility and heavy metal content in different geological and environmental settings. It is of
soils was found (e.g., Heller et al., 1998; Dearing et great importance to show that the same set of magnetic
al., 2001; Lecoanet et al., 2001; Hanesch et al., 2003; parameters and measurements can be applied under
Jordanova et al., 2003). Using geochemical analysis, various circumstances, and to provide certain general
additional data can be obtained, and in combination guidelines in interpreting magnetic data in terms of
with magnetic data, polluted areas can be well out- anthropogenic and lithogenic contributions to magnet-
lined and geologic/anthropogenic anomalies identified ic-mineral population in soil columns. In this way we
(Hanesch and Scholger, 2002). Lecoanet et al. (2003) intend to make further step towards standardization of
used magnetic parameters only in order to discriminate magnetic measurements of soils in terms of pollution
individual sources of soil contamination. Thus, mag- studies.
netic susceptibility can serve as an indicator of soil
contamination. 2. Methodology
However, only few studies attempted to solve the
main limitations of the soil magnetometry. Kapička et 2.1. Area description, field work and soil sampling
al. (2000, 2001a,b) studied stability of magnetic prop-
erties of fly-ash particles under different soil conditions. Based on large-scale magnetic mapping (with a
Possibilities of the method to be applied in relatively mesh of 10 km) within a 5FP EU RTD Project MAG-
clean areas were investigated (Kapička et al., 2003). PROX, four areas were selected, characterized by (mag-
Competition of different contributions to soil popula- netically) different underlying geology and by different
tion of magnetic minerals was studied using statistical environmental settings (Fig. 1). These areas were
analysis of large datasets (Dearing et al., 1996; Hanesch mapped in detail with a mesh of about 500 m. In the
et al., 2001; Hanesch and Scholger, 2002). Czech Republic, areas close to towns of Přı́bram (Cen-
In practical field measurements, lithogenic and an- tral Bohemia) and Ostrava (North of Moravia) were
thropogenic contributions can be assessed by in-situ studied (Fig. 1). In the Přı́bram area pollution due to
measurements of vertical distribution of magnetic sus- atmospherically deposited dust is relatively low, but this

5
Fig. 1. Location of the four investigated areas on the basis of MAGPROX topsoil magnetic susceptibility map (10 SI units, mesh of 10 km).
H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283 275

area is well known for uranium and lead ore mining in All four investigated areas were examined using the
the past. Geology is rich on iron oxides, with basaltic same strategy for topsoil magnetic susceptibility mapping
rocks such as granodiorites and gabbros. The Ostrava developed in frame of the MAGPROX-project (Schibler
region is well known for intense coal mining and et al., 2002; Boyko et al., 2004). Field measurements of
related heavy industry (e.g. power plants, steel works) topsoil volume magnetic susceptibility were performed
and thus belongs to the most polluted areas in the Czech with Bartington-MS2D probe. Each measured point repre-
Republic. From geological point of view this region is sents a spot of about 4 m2, where about 15–30 measure-
poor in Fe-bearing rocks; there are only sedimentary ments were taken and averaged. In case of large data
rocks like sandstones. The Přı́bram area was 10 by 15 scatter, more readings were performed. However, our
km large and 42 soil profiles were investigated, while experience shows that increasing the number of readings
the Ostrava area was 6 by 10 km large and 29 soil above 20 does not improve standard deviation signifi-
profiles were examined (Fialová, 2004). For the pur- cantly. Geographic positions of all measured soil profiles
pose of this paper, 6 and 8 most representative vertical were determined by the GPS Total Station 4700. Maps of
profiles from the Přı́bram and Ostrava regions, respec- topsoil magnetic susceptibility of investigated areas with
tively, were analysed in detail. From pedological point surface measurements and soil profile positions of all
of view (according worldwide soil classification system regional studies are shown in Fig. 2. These contour plots
of FAO/UNESCO), the Přı́bram region contains mostly were created by Surfer 8.0 (Golden Software).
dystric and euric cambisols, dystric planosols, euric Vertical distribution of selected typical profiles was
cambisols and euric gleysols. The Ostrava region con- measured by Bartington MS2F stratigrafic sensor in the
tains mostly albogleyic luvisols, euric gleysols and field. In addition, soil cores were collected for further
gleyic fluvisols (Němeček, 2001). laboratory measurements using MS2C coil sensor. Then
The studied areas in Austria (Fig. 1) are situated samples from upper and lower part of the cores were
around Linz and around Breitenau (Maier and Schol- prepared for detailed laboratory investigation. These
ger, 2004). The city of Linz (capital of Upper Austria) samples were selected in order to represent magnetically
is a highly industrialized region, which is known for enhanced topsoil (top 5 cm) and the bottom-most part of
steel production and processing, chemical industry, the core (depth of at least 25 cm). All collected soil
etc. In addition to that, Linz is an important traffic samples are from forest areas, covered mostly by needle
junction for cars as well as for railway. As the region trees (mainly spruce or pines). In this study, soil cores
is situated in the lowlands, mixed influence of several were measured in laboratory. At present, sensitive and
pollution sources can be expected. The main geolog- fast in-situ measurements are available using new de-
ical units of the area are metamorphites (migmatites) vice, described by Petrovský et al. (2004).
and granitoides. The studied area covers 10 by 15 km.
The area of Breitenau is situated in a narrow mountain 2.2. Laboratory analyses
valley in Styria with a suspected point emission source
caused by magnesite production and processing which The low- and high-frequency magnetic susceptibility
plays an important role in the ecological situation of (nlf and nhf) was measured by Bartington MS2B probe,
the climatically nearly closed narrow valley. In this expressed as mass-normalised susceptibility mlf and
case it could be expected that the area is nearly mhf, respectively, and the corresponding frequency-de-
separated from pollution influences outside the valley pendent susceptibility was calculated as difference per-
and that the pollution impact was dominated by a centage jfd = (nlf nhf)/nlf. This parameter enables
strong single source. The two main geological units assessment of significance of ultrafine superparamag-
of the area are schists, limestones, dolomites, gneisses netic magnetite grains (Dearing et al., 1996). Coercive
and amphibolites. The investigation area stretches over force (Hc), coercivity of remanence (Hcr), saturation
5 by 12 km. Prevailing soil types in the Linz area are magnetization (Ms) and saturation remanent magneti-
lime-free cambisols and brown podzols, derived from zation (Mrs) were measured using a Princeton Vibrating
crystalline rocks, while soils in the Breitenau area Sample Magnetometer VSM MicroMag 2900. Maxi-
mostly lime-free cambisols, derived from schists, mum applied field was 0.5 T. Heavy metal contents was
weathered para-gneiss, or amphibolites. From the analysed using Atomic Absorption Spectrometry
Linz area, 5 out of 17 vertical soil profiles are exam- (AAS) after dissolution in 2 M HNO3. Correlation
ined. From the Breitenau region, previously studied by between magnetic susceptibility and heavy metals (Fe,
Maier and Scholger (2004), 10 profiles out of 27 are Pb, Mn, Zn, Cd, Cu, Ni, Cr) was studied for each
analysed in detail in this study. investigated area.
276
H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283
Fig. 2. Contour plots of spatial distribution of topsoil volume magnetic susceptibility (10 5 SI) of the four studied areas. Small dots mark locations of the measured sites, big labeled dots mark
locations where vertical soil profiles were collected (shown in Fig. 4), dashed line delimits the city boundaries.
H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283 277

Scanning electron microscopy (SEM) with wavelength


dispersive spectroscopy (WDS) was performed on mag-
netic concentrates obtained from raw soil samples using
hand-magnet separation in ultrasonic bath.

3. Results and discussion

3.1. Magnetic mapping and vertical profiles

Spatial distribution of surface magnetic suscepti-


bility of the four areas in concern (mesh of about 500
m) is outlined as in Fig. 2. Measured data were collected
only from forest soils, mostly in pine woods. Hand-
magnet separation from topsoil samples (top 5 cm)
revealed clearly Fe-rich spherules, typical for particles
of anthropogenic origin, derived from combustion of
fossil fuel (Flanders, 1994, 1999; Maier and Scholger,
2004; Fialová, 2004). Representative spherules, ob-
served in topsoil from the Ostrava region, are shown
in Fig. 3. Contrary to topsoils, bottom soils were lacking
these spherules. In the Breitenau area, lithogenic crystals
and anthropogenic spherules were found frequently in
both top- and subsoils (Maier and Scholger, 2004).
Typical vertical profiles of magnetic susceptibility
are shown in Fig. 4. In the Přı́bram area, dominant
lithogenic contribution is assumed to control the in-
crease of magnetic susceptibility with depth. Contrary
to that, Ostrava and Linz profiles show dominant an-
thropogenic contribution, reflected by significant en-
hancement of magnetic susceptibility in the top 10 cm,
followed by rapid decrease of susceptibility with depth.
The Breitenau area represents a mixture of both types.
Anthropogenic contribution is dominant in profiles col-
lected in the narrow valley of this region, while several
profiles from the upper parts of the valley show signif- Fig. 3. SEM image of a Fe-rich spherule (top, grain-size of about
icant lithogenic contribution (Maier and Scholger, 80 Am), found in topsoil layer in the Ostrava region, and cross-sections
2004). Large set of vertical soil profiles of magnetic of two spherules with elemental analysis (middle: grain-size about
susceptibility was recently collected, discussed and clas- 40 Am, FeO 91%, Al2O3 0.8%, SiO2 0.2%; bottom: about 50 Am,
sified by Magiera et al. (in press). FeO 83%, Al2O3 8.4%, SiO2 2,2%, MgO 0.3%).

3.2. Laboratory magnetic measurements (standard deviation of the mean) and SD denotes stan-
dard deviation of the dataset (Tukey, 1977). Thus, dot
In order to analyse magnetic properties, mass-spe- in the plot represents the mean (central tendency), large
cific susceptibility mlf, frequency-dependent suscepti- box represents the mean F SE and whiskers represent
bility jfd, saturation remanence Mrs, saturation the mean F standard deviation. Note that different scal-
magnetization Ms, coercivity of remanence Hcr and ing for the value axes is intentionally used in Fig. 5. In
coercive force Hc were measured in laboratory on soil this way, we can compare trends in data distribution
samples prepared from the collected soil cores, and the from topsoils and subsoils for each respective area
data were analysed using box-whisker-plots (Fig. 5). studied. Absolute values could be compared as well,
The box-whisker plots summarize the distribution of a but in this case they are less important then the general
variable by three components. In this study, we used the tendency/behaviour and relative comparison of the
mean/SE/SD mode, where SE stands for standard error measured data.
278 H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283

Fig. 4. Magnetic susceptibility of vertical soil profiles collected from the investigated areas. Dominant lithogenic contribution in Přı́bram and some
Breitenau profiles is reflected by significant enhancement of magnetic susceptibility with depth. Ostrava, Linz and some Breitenau profiles show
dominant anthropogenic influence in the top 10 cm.

Mass-specific magnetic susceptibility shows the same the assumed significant lithogenic contribution, dominat-
tendency for the Ostrava, Linz and Breitenau areas. Large ing the soil profile, no significant difference between the
box-whisker-plots are typical for topsoil samples and top-and subsoil was observed, both showing box-whis-
very narrow ones for subsoils. In the Přı́bram area, with kers corresponding to large data scatter. There seems to
H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283 279

Fig. 5. Box-whisker plots of measured magnetic parameters of samples prepared from the top and subsoils from the investigated areas. Dot—Mean,
Box—Mean F SE, h – — Mean F SD, dots outside the box-whiskers represent outliers and are not included in the evaluation. Note that different
scales are used for the value axes in order to compare relative trends rather than absolute values. Left-hand sided and right-hand sided box-whiskers
on each plot represent the topsoil and subsoil samples, respectively. Numbers inside each plot are ratios of the topsoil and subsoil mean values of the
corresponding parameters.

be a contradiction between relatively narrow box-whisker volume magnetic susceptibility, measured by Bartington
plot for subsoils in the Breitenau area (Fig. 5) as com- MS2C, and mass-specific susceptibility. In the former
pared to the vertical profiles of magnetic susceptibility, case, susceptibility values are much more affected by
shown in Fig. 4. This is caused by bincompatibilityQ of variations in density, especially considering the fact, that
280 H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283

in the case of soil cores with the diameter of 3.5 cm, Coercivity of remanence and coercive force do not
small effective volume was measured. show any significant differences between the top and
Frequency-dependent magnetic susceptibility is sup- subsoil samples and even any significant differences
posed to reflect the significance of ultrafine SP parti- between individual areas. Although the reliability of the
cles. Large grains of magnetite (e.g. produced by two parameters can be discussed due to low maximum
combustion processes) are practically insensitive to magnetic field applied, our data suggest that, in terms of
change in the frequency of the applied magnetic field discrimination between the anthropogenic and litho-
used. Therefore, such samples exhibit small jfd, usu- genic contributions in soil samples, these parameters
ally less than 2%. Our data show, that only in the alone can be considered as of negligible importance.
Ostrava and Linz topsoil, very narrow box-plots are Moreover, ratios of magnetic parameters, which are
observed, suggesting single type of grain-size distribu- used as granulometric indicators for the construction
tion rather than SP/SD/MD mixture. Low absolute of the Day plot (Day et al., 1977), seem to be quite
(mean) value suggests that presence of SP particles, similar for top and subsoils from the four regions, and
resulting mostly from pedogenic processes, can be are, therefore, less significant for the discrimination of
practically excluded. One single extreme value, ob- the lithogenic and anthropogenic contributions. How-
served in Ostrava bottom-soil sample, can be attributed ever, as shown by Fialová (2004), samples dominated
to measurement error due to very low susceptibility by anthropogenic contribution only (topsoils from the
value, on the sensitivity limit of the Bartington probe. Ostrava region), are clustered more densely within the
In such case, apparently high frequency-dependent sus- pseudo-single domain area of the Day plot, while the
ceptibility may be an artefact, resulting from rounding samples with significant lithogenic contribution span
off by the instrument. This data point was not included over much larger interval.
in our evaluation. This instrument effect is most proba-
bly responsible also for high mean value for the Ostrava 3.3. Correlation with heavy metals
subsoil samples, although in these samples one can
expect also presence of higher portion of smaller parti- Relationship between magnetic susceptibility and
cles, which are able to migrate downwards from the concentration of heavy metals was evaluated using
topsoil. However, since susceptibility values are ex- the coefficient of determination r 2 (Table 1) of linear
tremely low, we assume that the instrument error is fit of bi-plots (examples of such bi-plots are shown in
more significant. Relatively high jfd for Breitenau top- Fig. 6). Due to availability of AAS geochemical analy-
soils (almost 5%), calculated with sufficient reliability sis, only samples from representative vertical profiles
(j values of around 50) may suggest the presence of were selected and analysed. It seems that significant
relatively more SP magnetite of pedogenic origin, com- correlation is observed between susceptibility and con-
pared to other localities. However, threshold values for centration of Pb in polluted areas (Ostrava, Breitenau
jfd, related to significance of SP magnetite, are not and Linz topsoils). However, it seems that this relation-
that clear. ship strongly depends on the leaching method used.
Saturation remanence values of the subsoil samples This effect will be subject of our future study. In case of
from both the Ostrava and Linz areas are very low and Fe, apparently contradictory correlation was found.
show practically no scatter. Saturation magnetization While it seems to be missing in the Přı́bram and
shows more or less the same tendency like saturation Ostrava regions, reasonably high values of the r 2 coef-
of remanence, with a small aberration in the Přı́bram ficient were found for the Linz and Breitenau regions.
samples and much larger irregularity in the case of This is striking especially for the Ostrava region, where
Breitenau samples. no lithogenic contribution is assumed, and Fe is sup-

Table 1
Coefficient of determination r 2 of linear fit between mass-specific magnetic susceptibility (m3 kg 1
) and heavy metal content (ppm) in soils
Number of samples Fe Pb Mn Zn Cd Cu Ni Cr
PŘÍBRAM 6 0.00a 0.02a 0.14 0.02 0.14 0.02 0.21 0.04
OSTRAVA 8 0.01a 0.72a 0.22 0.69 0.40 0.64 0.41 0.72
LINZ 12 0.59 0.29 0.10 0.55 b.d.l. 0.29 0.23 0.33
BREITENAU 16 0.69 0.78 0.02 0.01 0.67 0.14 0.05 0.17
b.d.l.—below detection limit.
a
16 samples.
H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283 281

Fig. 6. Examples of bi-plot correlation between selected heavy metals and magnetic susceptibility. Data of Mn concentration are divided by a factor
of 10.

posed to be solely in the form of industrially produced illustrate basic geochemical meaning of the magnetic
Fe-oxides. Obviously, the leaching agent used (2 M parameters analysed.
HNO3) is not effective, especially in the case of large
particles with Fe-oxides embedded in Al–Si matrix. 4. Conclusions
This effect is subject of our further study and will be
published later on elsewhere. Anthropogenic spherules Top- and bottom-soil samples from four areas, char-
could be dissolved by HCl or by total dissolution acterised by different geological and environmental
(HNO3 + HF + H2O2), but with the latter one paramag- settings, were analysed. The four areas are charac-
netic minerals can be also dissolved and the data will be terised, in terms of significance of anthropogenic vs.
biased. lithogenic contributions to magnetic-mineral population
Our results suggest that, in the areas studied, Pb, Cu in soils, as anthropogenically dominated (Ostrava and
and Cr are elements with significant correlation with Linz), mixed with dominant lithogenic contribution
magnetic minerals in anthropogenically affected (pol- (Přı́bram) and mixed with sites showing either anthro-
luted) areas, while in the case of Mn and Ni no signifi- pogenic, or lithogenic prevalence (Breitenau). Although
cant correlation was found. Zn is not of typically climatic effects are not a subject of this study, the areas
lithogenic origin. It can be found in topsoils affected investigated do not differ practically in terms of climatic
by specific industrial sources, and is characterised by conditions. Regarding possible pedogenic contribution
high mobility (Karczewska, 1996). In our samples, Zn to population of magnetic minerals in the soils con-
correlates well with magnetic susceptibility in the in- cerned, frequency-dependent magnetic susceptibility
dustrial regions around Ostrava and Linz. indicates practically insignificant portion of ultra-fine
Contrary to that, Ni and Fe can be considered, in the superparamagnetic magnetite. Our data suggest that if
investigated areas, as elements of typically lithogenic the lithogenic contribution is dominant, this effect is of
origin. However, as mentioned above, the anthropo- primary significance also for topsoil magnetic suscep-
genic/lithogenic character of Fe is quite dubious due tibility measurements, and the anthropogenic contribu-
to variable efficacy of leaching methods. tion cannot be that easily assessed. Contrary to that, in
Since it is known from linear regression theory that soils from areas with negligible lithogenic contribution
the ideal number of observations is 20 for one inde- of strongly magnetic minerals, mass specific magnetic
pendent variable, and the minimum is 5, and that the susceptibility alone is reliable in discriminating mag-
number of observations determines the threshold for netically enhanced topsoils from the unaffected bottom
the r 2 coefficient in terms of significance, we are well soils. Data of magnetic susceptibility are in accordance
aware of the fact that our data in Table 1 have with concentration-dependent saturation magnetization,
different meaning in terms of significance. However, and thermomagnetic analysis of magnetic phases is not
we do not aim at detailed analysis of relationship necessary. In areas, where both anthropogenic and
between magnetic properties and geochemistry of the lithogenic contributions are significant, magnetic sus-
soils studied. These data are presented only in order to ceptibility and saturation magnetization cannot serve
282 H. Fialová et al. / Journal of Applied Geophysics 59 (2006) 273–283

for reliable discrimination of the two soil layers, and a Anorg. Chemistry, Acad. Sci. Czech Rep., for fruitful
combination of more magnetic parameters have to be discussion and help with chemical analysis, and to Ms.
used. In this case, comparison with concentration of T. Dolecková from the Geophysical Inst., Acad, Sci.
heavy metals of presumably anthropogenic origin (e.g. Czech Republic, for great help with laboratory mea-
Pb) can validate magnetic data and enable discrimina- surements. The authors also thank Dr. W. Krainer from
tion between anthropogenically affected topsoils and the Styrian Agricultural Laboratory for his help and
lithologically controlled bottom soils. advice.
Based on our results, and provided that the signifi-
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