ORIGINAL ARTICLE
Origin of nickel in water solution of the chalk aquiferin the north of France and influence of geochemical factors
Daniel Bernard Æ Jamal El Khattabi Æ Emilie Lefevre ÆHani Serhal Æ Sabine Bastin-Lacherez ÆIsam Shahrour
Received: 4 October 2006 / Accepted: 26 February 2007 / Published online: 21 March 2007
� Springer-Verlag 2007
Abstract In the north of France, high registers of nickel
are sometimes recorded within the chalk aquifer. In a
confined context, the presence of pyrite in the covering
clays or in the marcasite nodules encrusted in the clay may
constitute a natural source of trace metals. With an
objective of sanitary control, the limits of chemical con-
tents regulating the quality of water destined for human
consumption have been lowered by the European Frame-
work Directive in the field of water policy (2000/60/EC).
As a result, nickel limits have been reduced from 50 to
20 lg/l. The analyses, carried out on three water catchment
fields in our area of study, were centred on variable
parameters (Eh, O2(d), pH, Conductivity, T�), major ele-
ments (SO4, NO3) and metals (Fe, Ni, Mn, Co). The ac-
quired data enabled us to identify from one hand, the
conditions which are presented within the site, special
thanks to the evolution of nitrate and iron contents and on
the other hand, the natural origin (geological) of nickel for
two of the three sites studied based essentially on the
evaluation of the Nickel/Cobalt ratio. Thus, on the first site,
the evolution of nickel content and nitrate content showed
the influence of the phenomenon of denitrification on the
re-mobilisation of the nickel. Whereas on the second site, a
high variation of total iron content and oxygen dissolved in
solution highlighted a particular phenomenon of oxidation
of the pyrite through molecular oxygen. Finally, the cor-
relation with the sulphates clearly showed behaviour of the
nickel, once released, that was entirely dependent on the
phenomenon of adsorption on the iron and manganese
hydroxides.
Introduction
Nickel is present at the trace state in many minerals
(olivine, pyrites,...); it is also used in numerous alloys
thanks to its characteristics of hardness and corrosion
resistance. Its anthropogenic origin is related to mining
activities or surface treatment. In natural water, the pre-
valent shape of nickel is Ni [2+], which is adsorbed easily
by manganese and iron oxides. It is not common in surface
water because it is fixed on the sediments of the rivers. In
groundwater, according to conditions of pH and Eh, nickel
could exist in dissolved form (Valley 1999; Atteia 2005).
In the natural environment, underground water has
generally very low rates of nickel. In the region of
Northern France, the layer of chalk which supplies nearly
97% of water requirements is subjected to strong anthro-
pogenic stress (intensive agriculture, industrialisation,
D. Bernard � J. El Khattabi (&) � E. Lefevre �H. Serhal � S. Bastin-Lacherez � I. Shahrour
Laboratoire de Mecanique de Lille (CNRS UMR 8107),
Universite des Sciences et Technologies de Lille (USTL),
Polytech-Lille, Avenue Paul Langevin,
59655 Villeneuve d’Ascq Cedex, France
e-mail: [email protected]
D. Bernard
e-mail: [email protected]
E. Lefevre
e-mail: [email protected]
H. Serhal
e-mail: [email protected]
S. Bastin-Lacherez
e-mail: [email protected]
I. Shahrour
e-mail: [email protected]
123
Environ Geol (2008) 53:1129–1138
DOI 10.1007/s00254-007-0704-z
demographic growth,...) permanently threatening its quality
(Bernard 1979). It should also be noted that the omni-
presence of pyrite participates in its mineralization by
means of trace elements such as nickel and cobalt. For
sanitary control, the limits of chemical contents regulating
the quality of water destined for human consumption have
been lowered by the European Framework Directive in the
field of water policy (2000/60/EC). As a result, the nickel
limits dropped from 50 to 20 lg/l. The new policy leads to
the non-conformity of the quality of the water produced in
certain water catchment fields in the region. The origin
may be natural but it can also be associated with an
anthropogenic phenomenon of an industrial pollution type.
In the studied sites, the nickel may be present in the peat,
the clay of Landenian era (Cenozoic era) confining the
chalk aquifer (Cretaceous era). It is also found integrated in
the nodules of marcasite in the chalky Cenomanian for-
mations. The sources of nickel principally invoked in the
natural environment are iron sulphates through co-precip-
itation, iron and manganese (hydro)-oxides through co-
precipitation and especially through adsorption (Vallee
1999).
The presence of pyrite is frequent in the alluvial, peaty,
tertiary clay and secondary chalk levels. Its oxidation in-
duces an increase in the rate of sulphates and trace metals
in the aquifers (Mariotti 1994). This phenomenon occurs
frequently during the passage from the unconfined
groundwater to more confined condition. The former con-
stitutes good conditions for the flow of oxidant elements, in
particular the nitrates. The pyrite intervenes as an electron
exchanger in the overall de-nitrification reaction (Eq. 1)
following (Mariotti 1994):
5 FeS2 + 14 NO�3 + 4 Hþ
! 7 N2(g) + 10 SO2�4 + 5 Fe2þ + 2 H2O. ð1Þ
In the oxidising part, the ferrous iron is unstable in
solution and precipitates in the form of oxide or hydroxide.
In the presence of high contents of nitrates, the latter can
also be reduced depending on the overall reaction (Strebel
et al. 1990; Kolle et al. 1990):
5Fe2þþNO�3 þ7H2O! 5FeOOHþ 1
2N2ðgÞþ 9Hþ: ð2Þ
Moreover, the oxidation of the pyrite may also intervene
in the presence of molecular oxygen. The oxidation then
takes place according to the overall reaction (Kamei and
Ohmoto 2000):
FeS2 þ15
4O2 þ
7
2H2O! FeðOHÞ3ðsÞþ2SO2�
4 þ4Hþ: ð3Þ
The bacteria present in the environment need oxygen for
their metabolism and the oxianions (NO3, SO42–) constitute
their sources. The activation energies of the denitrification
and respiration are close and the reaction to denitrification
substitutes itself to the process of oxygen respiration by the
bacteria from a certain limit of solution dissolved oxygen
(0.01 < O2(d) < 0.7 mg/l (Matthes 1982).
The reduction of nitrates is produced by electron ex-
change with powerful reducers like pyrite (FeS2) organic
carbon. The chemical reduction phenomenon of the ni-
trates, producing the ammonium ions, is within the same
energy field as denitrification but it remains very minor in
relation to the biological reaction when in takes place (Sigg
et al. 2001).
Nevertheless, a sharp fall in the content of nitrates in
water can also be caused by a phenomenon of dilution
caused by old water with potentially lower redox (Edm-
unds et al. 1982). As a result, the use of hydrogeochemicals
is not a sufficient answer in the light of the phenomenon of
denitrification and a prior study of the hydrogeological
conditions is indispensable.
In order to better identify the origin of the nickel, its
behaviour can be compared to that of cobalt, which rep-
resents a very close atomic radius (Denis et al. 2000;
Laurent and Henry 1979) and similar adsorption properties
(Mendes and Martins 2004). Moreover, these two elements
only precipitate in very low proportions with iron
hydroxide (Vallee 1999; Cornell et al. 1992). In the pyritic
formations, several authors (Nielsen 1990; Aktor 1996;
Cornell and Giovanoli 1989) have observed a close cor-
relation between cobalt and nickel, which during dissolu-
tion in the pyritic phase, would pass into solution in the
same conditions, thus conserving the existing ratio of
concentration within the iron sulphate crystals.
The research presented in this paper concerns the causes
and conditions of the mobilisation of trace elements. It is
based on the use of the Ni/Co ratio, which gave good re-
sults through the influence of the marcasite on the
groundwater mineralization (Denis et al. 2000). This paper
presents the results of the identification of the nickel
solution origin in three water catchments fields destined for
human consumption in the north of France.
Study area
The study concerned three sites in the north of France
(Fig. 1) where the chalk of the upper Seno-Turonian rep-
resents the main aquifer. The groundwater exploited from
the study sites presents values above the standard toler-
ances in nickel sometimes reaching 100 lg/l.
For each water catchment field, the natural regime of the
chalk aquifer is confined under a cover of Tertiary clays
1130 Environ Geol (2008) 53:1129–1138
123
and alluvial deposit (Quaternary) (Fig. 2). However, the
exploitation of these water catchments fields at certain
times may lead to a drop of the piezometric level under the
chalk roof and so lead to a temporary disappearance of
the confined regime, provoking a brutal modification of
the redox conditions of the environment.
The water catchment field of Houplin-Ancoisne is
located in a valley covered in Quaternary deposits in which
a branch of the Seclin canal has been built (Fig. 2). The
groundwater run-offs are aligned in the axis of the valley in
a NW–SE direction. In the South West is a large water
catchment field inducing a piezometric depression likely to
increase a canal aquifer communication. Along this water
catchment field, a reduction in nitrate content can be ob-
served which could result from both denitrification and a
mixing of the chalk groundwater with the waters of the
alluvial groundwater (Simon 1986).
As for the water catchment field of Flers-en-Escrebieux,
it is located on the confined limit of the chalk aquifer. The
catchment area is well protected by a clayey argillous over-
lap (silt or Tertiary) in the Eastern part, which brings about
a supply from the West, a sector where the groundwater is
unconfined and so sensitive to pollution. Along the Esc-
rebieux River several infiltration zones pointed out, and the
supply part coming from river flow is not negligible at low
water level (Talbot and Tillie 1979). To the right of the
sampling points, the piezometric level is generally located
in the peaty alluvial covering the Tertiary clay area. The
passage of the confine zone is accompanied with a natural
de-nitrification phenomenon (Simon 1986).
Finally, on the Pecquencourt site, no nitrate traces were
detected. This absence is the consequence of a phenomenon
of denitrification operating upstream of the study sector.
Methodology
Two sampling operations were carried out in 31 drills. In
the Flers-en-Escrebieux sector, the two hydrogeologic
surveys were carried out in July and November; during this
period the groundwater decreased by about 2 m. On the
two other sites, a change in the rate of pumping on the
drills was operated between the two sampling operations.
In Pecquencourt, the sampling was conducted in May,
firstly during full rate pumping then after 4 days pumping
at low rate, which allowed a rise of a few metres of the
piezometric measurement. Finally, in Houplin-Ancoisne,
the first sampling operation was carried out after a reduc-
tion of the production of the water catchment field for
during 4 days, whereas the second was carried out 3 days
after the resumption of full rate production. This procedure
allowed a study of the influence of the piezometric fluc-
tuations on its mineralization.
The in situ parameters measured were: dissolved O2, the
redox potential (Eh), the pH, the temperature (T�) and the
Fig. 1 Site locations and geology
Fig. 2 Geological cross-
sections and localisation of
drills on the three study sites
Environ Geol (2008) 53:1129–1138 1131
123
conductivity (Cond). For the principal elements, the anal-
yses centred on nitrites (NO2), nitrates (NO3), ammonium
(NH4) and sulphates (SO4) were carried out according to
the international standard (ISO 13395 1996). For the NO2
the water samples were acidified and controlled by spec-
troscopy absorption. NO3 were determined by the same
method after reducing to nitrites by passage on cadmium
column. The NH4 was dosed by Colourimetry at Indo-
phenol blue. The SO4 were determined by an internal
method in continuous flow and by colourimetry.
The other analyses concern total organic carbon (TOC)
and trace metals (Fe, Ni, Mn, Co). TOC analysis was
realized according to the international standard (ISO 8245
1999) by oxidation with the potassium persulphate and
dosage of CO2(g) resulting by infrared analysis. Concern-
ing the trace elements, the water samples were filtered
through a 0.45 lm and stored at 4�C, or acidified to pH 2.
Measurements of the total metal concentrations were car-
ried out by Inductively Coupled Plasma Atomic Emission
Spectrometry (ICPAES) in axial mode.
Results and discussion
Results of analyses are summarized in Table 1. They were
interpreted thereafter by the realization of hydrogeochem-
ical profiles of the three sectors (Figs. 3, 4, 5).
Hydrogeochemical profiles
As the water is confined, the oxidant types are progres-
sively reduced in the direction of its confinement (Blum
et al. 2002). As the oxygen disappears from the environ-
ment, the microorganisms use various electron acceptors in
the following sequence: O2(d), NO3–, Mn2+, Fe2+, SO4
2– and
CO2. In the solution, it remains difficult to discern these
steps simply with the help of the oxygen reduction poten-
tial (Stumm and Morgan 1981). Nevertheless, the presence
of more or less oxidising or reducing enables the evaluation
of the environment conditions (Washington et al. 2004).
The redox gradient can be represented by a succession of
three different states (Champ et al. 1979; Groffman and
Crossey 1999):
• Oxidising zone where the oxianions O2 and NO3– are
mobile elements and iron and manganese remain
immobile in the form of hydroxide.
• Reducing zone Fe–Mn where the metals pass in soluble
ionic form following the consumption of oxidising
types. Certain transition metals like Ni, Co, Cu and Zn
may also appear in solution.
• High reducing zones where sulphur passes as sulphides.
Metals thus precipitate in insoluble sulphides form.
Analysis of the spread of the various types indicates that
drills F1, F2, F6 and F5 in Flers-en-Escrebieux as well as
those F10, F11 and F13 in Houplin-Ancoisne (2) are in
oxidising phase. Concomitant O2(d) and NO3 ions can be
found. In the two sites, a phenomenon of denitrification
occurs during this phase and leads to a progressive
reduction in the ion NO3 content along the flow axis
(Lefevre 2005).
The highest nitrate concentration encountered in Houplin-
Ancoisne ([NO3–]avg = 59 mg/l) indicates greater oxidising
conditions than at Flers-en-Escrebieux ([NO3–]avg = 17 mg/l).
This variation is also detected within the potential redox
values (EhHouplin = 399 and EhFlers = 255 mV).
The absence of NO3 as well as the highly dissolved iron
values measured on the drills F7 and F8 (325–882 lg/l) in
Flers-en-Escrebieux and all the drills at Pecquencourt
(55 lg/l at 3,640 lg/l) (Fig. 5) indicate a reducing envi-
ronment. The potential reduction values and the variety of
Fe content from the two hydrogeologic surveying (low and
high water levels) indicate the presence of two groups: on
one hand, the drills F15, F16, F17, F18 and F19 for which
the potential values vary between 300 and 400 mV and on
the other hand, drills F21 and F24, for which the potential
values are no greater than 300 mV. In the first group, the
maximum dissolved iron concentration varies greatly from
one surveying to another: [Fe]avg = 95 lg/l in high water
level and 358 lg/l in low water level. As for the second
group, the iron level remains high. However, these contents
seem to be less sensitive to the variations of the water level,
which indicates a more stable reducing environment.
It is important to note the intermediary water type of
drill F12 (Houplin-Ancoisne) and F6 (Flers-en-Escrebieux)
for which the presence of NO3 is associated with that of
Fe solution. As a result, the hydrochemical type of drill
F12 varies significantly with the overall profile (Fig. 4),
which could be explained by its position on the opposite
bank of the Seclin canal where the presence of a fault can
be remarked along this canal (Fig. 2). This latter may
contribute to the creation of a hydraulic and hydrogeo-
logical discontinuity within the chalk aquifer. Conse-
quently, this batch could beneficiate from a specific type
of supply compared with the rest of the water catchment
field. As for drill F6 in Flers-en-Escrebieux (Fig. 4), it can
be identified in the transition oxidising phase/reduction
phase of the profile.
Search for the origin of the Ni
The maximum contents of nickel were detected at Flers-en-
Escrebieux during the transition oxidising phase/reduction
phase, to the right of the drills F5 and F6 where the con-
centrations approach 40 lg/l. The contents increase when
the concentration in NO3 decreases, which suggests that the
1132 Environ Geol (2008) 53:1129–1138
123
denitrification could be involved in the nickel solution
formation. However, in Houplin-Ancoisne, the nickel re-
mains constant throughout the profile: it does not seem to
be affected by the denitrification and show no link with the
total Fe concentration in the water. The maximum content
is recorded in F12.
Finally, in Pecquencourt, the presence of nickel inter-
venes in the least reducing and stable of the profile.
For all of the sites, the hydrochemical profiles show the
disappearance of soluble nickel in the stable reducing
phases of the profiles (F7 and F8 at Flers-en-Escrebieux,
F24 and F27 in Pecquencourt).
In Pecquencourt, following the piezometric fluctua-
tions, the hydrochimical profiles (Fig. 6) indicate strong
variations of the total iron contents (between low and
high waters) on drillings F24 ([Fe]T = 184 – 440 lg/l),
F15 ([Fe]T = 60.9 – 777 lg/l) and F16 ([Fe]T = 61.9 –
512 lg/l). This variation of Iron is accompanied by that
of dissolved oxygen, which evokes an oxidizing disso-
lution (case of oxygen increase). The evolution of the
contents manganese and nickel in comparison with the
dissolved iron concentrations makes it possible to better
differentiate the campaigns from the low and high levels
of the groundwater. Indeed, the high groundwater level
Table 1 Description of water points used in the present study and selection of samples for Fig. 2
Water catchment field Drills Sampling date T (�) O2(d) pH Eh Cond SO42– NO2
– NO3– NH4
+ FeT MnT Ni Co TOC
Flers-en-Escrebieux F1 18/07/03 11.62 1.3 7.08 407 858 99 0.04 24 0.04 4 6.3 14.9 0.9 2.6
18/11/03 11.27 0.72 6.99 247 797 95 0.05 15 0.04 4 8.6 17 1.3 3.2
F2 18/07/03 11.54 3.2 7.25 394 856 86 0.04 39 0.04 4 0.4 9 0.9 1.8
18/11/03 11.39 3.38 7.16 196 843 82 0.04 34 0.04 4 2.4 10 0.9 2.4
F3 18/07/03 – – – – – 90 0.05 27 0.04 4 4.9 22 2.5 1.8
F4 18/11/03 11.23 5.81 7.21 191 833 95 0.04 18 0.13 4 7 31 3.2 1.8
F5 18/07/03 11.62 2.03 7.08 396 873 96 0.07 16 0.04 14 10.5 34.4 5.1 1.6
18/11/03 11.01 3.37 7.09 197 818 87 0.04 24 0.12 4 10.4 33 4.8 1.8
F6 18/07/03 12.03 1.2 7.5 328 861 116 0.06 10 0.04 59 12.1 43.2 5.2 1.6
18/11/03 11.42 2.8 7.06 218 904 122 0.04 6.6 0.04 10 12.6 33 4.7 1.7
F7 18/07/03 11.76 1.24 7.15 306 910 128 0.04 3.2 0.04 325 14.3 8.7 1.5 1.8
18/11/03 11.45 4.96 7.01 77 880 104 0.04 0.04 0.11 607.8 15.2 6 1.2 1.8
F8 18/07/03 11.63 3.26 7.15 96 852 112 0.04 0.04 0.04 882 12.2 1.9 0.9 1.9
Houplin-Ancoisne F10 15/05/03 11.1 7.34 6.87 411 1,220 132 0 88 0 7.6 0 13 1 2.5
19/05/03 11.07 4.44 6.92 409 1,086 128 0 82 0 15 2.9 12 0.9 2.4
F11 15/05/03 11.01 7.19 6.94 405 1,229 134 0 80 0 15.1 0 13 1 2.2
19/05/03 11.15 3.21 6.93 402 1,080 147 0 81 0 20.9 3.6 12 0.9 2.3
F12 15/05/03 10.98 1.4 6.83 390 1,248 201 0 16 0.19 222 23.1 26 8 2.7
19/05/03 11.01 0.66 6.95 374 1,123 198 0.16 15 0 624 133 25 10 2.4
F13 15/05/03 11.41 1.89 7.01 399 1,179 183 0 46 0 0 0 12 0.9 2.5
19/05/03 11.23 4.68 6.91 389 1,160 235 0 32 0 25.2 9.4 12 0.9 2.8
F14 15/05/03 – – – – – 142 0 72.8 0 44.7 2.3 8 0.9 2.4
Pecquencourt F15 13/05/03 11.82 0.9 7.05 319 735 38 0 0 0 777 10.2 28 7 1.4
21/05/03 11.41 0.35 7.07 391 723 39 0 0 0 60.9 8.8 31 8 1.8
F16 13/05/03 11.48 0.39 6.98 320 753 44 0 0 0 512 11.4 47 11 1.4
21/05/03 11.39 0.16 6.89 395 766 55 0 0 0 61.9 8.9 39 9 1.8
F17 13/05/03 11.39 0.52 6.92 337 804 66 0 0 0 103 10.2 47 10 1.5
21/05/03 11.29 0.17 6.89 396 832 62 0 0 0 81.2 7.6 28 6 2.1
F19 13/05/03 11.91 0.53 7.05 341 869 98 0 0 0.25 232 10.2 35 8 1.4
21/05/03 11.59 0.18 6.83 349 928 90 0 0 0 85.9 8.3 26 6 2.3
F21 13/05/03 11.7 0.38 6.84 368 813 53 0 0 0.25 166 6.5 12 3 1.3
21/05/2003 11.77 0.24 6.90 366 803 51 0 0 0.10 144 5.5 6 2 1.9
F24 13/05/03 12.09 0.29 7.12 271 747 60 0 0 0.25 184 4.9 0 0 1.4
21/05/03 11.99 0.57 7.13 275 757 72 0 0 0.1 440 6.1 0 0 1.8
F27 13/05/03 11.52 0.38 6.98 283 963 106 0 0 0.35 213 8.1 0 0 1.5
21/05/03 11.7 0.42 7.06 312 967 96 0 0 0.25 55.2 79.7 0 0 1.9
Environ Geol (2008) 53:1129–1138 1133
123
shows that the contents of Mn and Ni evolve contrary to
those of Fe (Fig. 6). With the exception of drillings F24
and F27 in the absence of nickel (in spite of the strong
iron concentrations in F24), overall, the fall of the pie-
zometric level with Pecquencourt causes an increase in
the nickel contents in water. The reduction in the con-
tents of iron dissolved at the right of drillings F15 and
F16 is associated with a significant fall of the nickel
content at the right of drillings F16, F17 and F19 (up to
19 lg/l of difference for F17). The correlation Fe/Ni is
very satisfactory and almost linear in high groundwater
level; this result indicates that dissolved iron acts on the
mobilization of nickel. It appears clearly that a modifi-
cation intervenes following the piezometric fluctuations
and that it distorts the balances presented within the
context.
The source composites
In the aquifer fields, the nickel may be present in the peat,
the clay confining the chalk aquifer or incrusted in the
nodules of marcasite in the Cenomanian chalk formations.
Its concentration within these nodules can reach 400 mg/kg
(Vallee 1999).
In pH < 10 solution, the dominant form of the nickel is
the ionic state (Ni2+). It is likely to co-precipitate with the
ferruginous composites (goethite, hematite, pyrite),
because its atomic scale (0.0690 nm) is close to that of Fe
(0.0645 nm). It could also substitute the iron in the goe-
thite up to 0.055 mol/mol (Cornell et al. 1992). Above this
concentration, it is adsorbed at the surface of the goethite
or precipitates in the form of Ni(OH)2. The nickel sources
principally invoked in the natural environment are thus
iron sulphides through co-precipitation, iron hydroxides
and manganese through co-precipitation and especially
adsorption.
Furthermore, nickel behaviour is closely associated to
that of cobalt. Therefore, the study carried out in the north
of France and Belgium on various carbonated aquifers af-
fected by the dissolution of pyrite (Denis et al. 2000) show
the existence of a correlation between these two elements,
which determine their origin. The latter is geological
(natural) when the nickel/cobalt ratio has an average of
five; but anthropogenic when the ratio exceeds ten.
0
2
4
6
8
O2(
d) e
n m
g/l
Low water level High water level
0
20
40
60
[NO
3] (
mg/
l)
0
100
200
300
400
500
Eh
(mV
)
0
200
400
600
800
1000
[Fe]
T (
µg/l
)
0
20
40
60
0 200 400 600
Length (m) following the flow axis
[Ni]
(µg
/l)
F1 F6
F5
F7 F8F2 F4F3
Fig. 3 Hydrochemical profile of Flers-en-Escrebieux
0
2
4
6
8
10
O2(
d) m
g/l
Low water level High water level
0
20
40
60
80
100
[NO
3] (
mg/
l)
370
390
410
Eh
(mV
)0
200
400
600
800
[Fe]
T (
µg/l)
0
10
20
30
0 500 1000 1500 2000 2500
Length (m) following the flow axis
[Ni]
(µg
/l)
F13F12F11F10F9
Fig. 4 Hydrochemical profile of Houplin-Ancoisne
1134 Environ Geol (2008) 53:1129–1138
123
Evaluation of the Ni/Co ratio
On the Flers-en-Escrebieux site (Fig. 7), a strong correla-
tion exists between the content of nickel and cobalt with a
Ni/Co ratio close to six. The distinction between the two
groups of drills enables us to find the best correlations. On
the one part the Ni/Co ratios were found to vary between
5.8 and 8.3 for the F5, F6 and F7 drills. These values are
thus compatible with a geological origin. Moreover, the Ni/
Co ratios of drills F2 and F1 vary between 10 and 16.6
suggesting an anthropical influence for the nickel.
For the Houplin-Ancoisne site, three out of four drills
have identical behaviour. The content of Nickel and Cobalt
are very close and their Ni/Co ratio is about 13; the F12
drill appears completely isolated and presents a ratio of 2.5.
As a result, apart from this last drill, the Ni/Co ratio indi-
cates an anthropogenic origin for the complete set of cap-
ture fields for Houplin-Ancoisne.
On the Pecquencourt site, a strong correlation exists
between the Nickel and Cobalt of drills (R2 = 0.99).
Moreover, an average value of four for the Ni/Co ration
indicates strongly a geological origin. The nickel is not
detected in drills F24, F27 and F16bis.
Thus, the application of the Ni/Co index on the study
sites indicates a geological origin for the nickel in the
following drills:
• F15, F16, F17, F19 and F21 in Pecquencourt,
• F5, F6 and F7 for Flers-en-Escrebieux,
• F12 in Houplin-Ancoisne.
Evaluation of the Ni/SO4– ratio
The study of Nickel/Sulphates correlation is based on the
data presented earlier and the sanitary data of the Pec-
quencourt and Flers-en-Escrebieux drills offered by the
Departmental Direction of the Sanitary Socials Affairs
between 1987 and 2003.
Sector of Flers-en-Escrebieux
Analysis of the water data of the Flers-en-Escrebieux
catchment field indicates the presence of a detectable
content of nickel directly in the drills F1, F2, F3, F4, F5,
F6, F7 and F8. Although the origin of the nickel is sup-
posed to be pyritical, the nickel/sulphates correlation is
mediocre: the best correlations (R2 = 0.45) were obtained
for drills F2 and F6 drill (Fig. 8).
Similar tendencies were observed for the variation of the
nickel and sulphate in the drills. This observation is
coherent with the diffusion of nickel through pyrite dis-
solution. In the same way, the high content of the nitrate in
the site indicates the presence of iron and manganese
hydroxide formation. This can explain the absence of sig-
nificant correlations between nickel and sulphates, indi-
cating an influence of nickel adsorption phenomenon at the
surface of iron and manganese hydroxide. These phenom-
0
1
O2
(d)
(mg/
l)Low water level High water level
F21F19F17F15 F24 F27
0
50
100
150
[SO
42-]
en m
g/l
0
200
400
600
800
1000
[Fe]
(µg
/l)
0102030405060
0 200 400 600 800 1000 1200 1400
Relative length (m) between several boreholes
[Ni]
(µg
/l)
F16
Fig. 5 Hydrochemical profile of Pecquencourt
0.00
5.00
10.00
15.00
0.00 200.00 400.00 600.00 800.00
[Fe]T ( g/l)
[Mn]
T(
g/l)
H.W.L
0.00
10.00
20.00
30.00
40.00
50.00
60.00
0.00 200.00 400.00 600.00 800.00
[Fe]T (mg/l)
[Ni] T
(mg/
l)
Low water level High water level
Low water level High water level
H.W.L
Fig. 6 Evolution of the contents iron, nickel and manganese
dissolved in the Pecquencourt groundwater
Environ Geol (2008) 53:1129–1138 1135
123
ena contribute to the modification of Ni concentrations in
the water masking the nickel/sulphate ratio.
Pecquencourt sector
In the Pecquencourt sector, good correlations between the
two elements can be observed in drills F15 to F19. Drills
F15 and F16 are distinguished by logarithmic type rations
(Fig. 9). Indeed, a strong increase can be observed in the Ni
content in SO4 contents of 20 to 55 mg/l followed by a
joint increase in the two parameters.
This type of evolution indicates an important influence
of adsorption and desorption, which creates a storage of
nickel and then leaching an unvaried washing of the sul-
phate content (Fig. 10).
The Ni and SO4 content of drills F17 to F19 present
linear correlations (Fig. 11), more compatible with a sim-
ple dissolution phenomenon of pyrite without nickel
adsorption. This weaker effect of the adsorption phenom-
enon is probably due the conditions of the environment,
which are less favourable to the formation of iron and
manganese hydroxides. Some points however, vary from
this tendency on the F17 and F19 drills which present
nickel content close to the analytic detection limit (5 lg/l
for standard analyses for sanitary control) associated with
high sulphate content (these points were not taken into
account in the calculation of regression coefficient).
The comparison of Ni/SO4 correlations of these drills
with the straight line of theoretical dissolution of marcasite
(Fig. 12) show relatively high nickel content in the water.
These contents may correspond to the supplementary
addition of nickel stored through adsorption or to a transfer
of an initial concentration of nickel in the water originating
from drills F15 and F16 for instance.
As for drills F21, F22, F23, F24 and F27 the nickel
content is lower than the previous drills with some
y = 4.3879x - 0.5821R2 = 0.9897
y = 8.3525x - 3.4121
R2 = 0.9356
0
10
20
30
40
50
60
121086420
Co (µg/l)
Ni (
µg/l)
Houplin-Ancoisne
Pecquencourt
Flers-en-Escrebieux
Anthropic origin Natural origin (geological)
Ni/Co = 10
Fig. 7 Correlations of nickel
and cobalt content samples
Drill F6R2 = 0.44
0
10
20
30
40
50
60
70
0 50 100 150 200
[SO42-] mg/l
0 50 100 150 200
[SO42-] mg/l
[Ni]
µg/
l
Drill F2 R2 = 0.45
0
5
10
15
20
25
[Ni]
µg/
l
Fig. 8 Correlations between
the nickel and sulphate content
of the waters on drills F2 and F6
at Flers-en-Escrebieux
F15
R2 = 0.67
0
20
40
60
80
100
120
0 50 100 150 200 250
[SO4²-] mg/l0 50 100 150 200 250
[SO4²-] mg/l
[Ni]
µg/
[Ni]
(µg
/l)l
F16
R2 = 0.54
0102030405060708090
100Fig. 9 Nickel and sulphate
content of drills F15 and F16
at Pecquencourt
1136 Environ Geol (2008) 53:1129–1138
123
exceptions, which stand out, indicating an episodic influ-
ence of previous drills. Finally, the search for correlations
between nickel and sulphate content show the complexity
of the phenomenon of Ni propagation in a natural envi-
ronment. The Pecquencourt sector gives good results,
which allow locating drills with dominant adsorption–
desorption phenomena (F15 and F16). The results of the
Flers-en-Escrebieux sector remain very average, doubtless
because of the duality of oxidising conditions/bacteria
denitrification.
Conclusion
Analyses confirm the interest of the nickel/cobalt ratio
as an indicator of the natural or anthropical origin of
the nickel in chalk aquifers such as those in the north
of France. This indicator allowed the detection of the
anthropic origin for the Houplin-Ancoisne site and the
geological origin of Flers-en-Escrebieux and Pecquencourt
sites.
The use of hydrochemical profiles showed that nickel
appears in solution following the diffusion of oxidising
elements like NO3 or atmospheric O2 in a confined and
semi-confined environment. Analysis of the process of
oxidising of pyrite shows that the nitrate pollution consti-
tutes a determining factor. In Flers-en-Escrebieux, the
nitrates seem to be clearly involved in the phenomenon of
the dissolution pyrite, which constitutes an additional
argument for the campaign for the reduction of this type of
pollution.
Despite the pyritic origin of the nickel in the sectors of
Flers-en-Escrebieux and Pecquencourt, the correlations
between Ni and SO4 content are less significant, this result
could be attributed to adsorption reactions of the nickel at
the surface of Fe and Mn hydroxides. The phenomenon of
F2 : R2 = 0,54
F1 : R2 = 0,67
0
20
40
60
80
100
0 50 100 150 200 250
[SO42-] mg/l
[Ni]
µg/
l
Drill F15 drill F16
Straight line of pyrite dissolution at 400 ppm of Nickel
Desorption component of nickel
Fig. 10 Theoretical affects
induced by the phenomena of
dissolution and desorption and
comparison with the evolutions
of nickel and sulphate content in
drills F15 and F16
F17
R2 = 0.69
0
20
40
60
80
100
0 50 100 150 200
[SO4²-] mg/l [SO4²-] mg/l
[Ni]
µg/
l
[Ni]
µg/
l
F18
R2 = 0.79
0
20
40
60
80
-10 10 30 50 70 90 110 130 150
F19R2 = 0.59
0
10
20
30
40
50
0 20 40 60 80 100 120 140
[SO4²-] mg/l
[Ni]
µg/
l
Fig. 11 Evolution content in
nickel and sulphate content
of drills F17, F18 and F19
Environ Geol (2008) 53:1129–1138 1137
123
nickel adsorption contributes to the modification of the
concentration of this metal in the water and masks the Ni/
SO4 ratio.
The results have enabled the identification of the origins
and causes of fluctuations in trace element content, in
particular, nickel. These results constitute a valuable basis
to improving the hydrogeologic survey for the water
quality according to new European Framework Directive.
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0
20
40
60
80
0 20 40 60 80 100 120 140 160 180 200
[SO42-] mg/l
[Ni]
µg/
l
Drill F18 Drill F17 Drill F19
Straight line of pyrite dissolution at 400 ppm of
Nickel
Straight line of pyrite dissolution at400 ppm of Nickelwith an initial nickel
provision of 20 µg/linitial de nickel de 20 µg/l
Component of pyrite dissolutionwith adsorption of nickel
Fig. 12 Straight lines of
theoretical dissolution of pyrite
in water devoid of nickel and an
initial concentration of 20 lg/l
and the comparison of the
analyses of drills F17, F18 and
F19
1138 Environ Geol (2008) 53:1129–1138
123
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