Origin of nickel in water solution of the chalk aquifer in the north of France and influence of...

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. Lefevre


H. Serhal


S. Bastin-Lacherez


I. Shahrour


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


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)



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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