Accepted Manuscript

Bioavailability of Pb, Zn, Cu, Cd, Ni and Cr in the sediments of the Tessa River : A
mining area in the North-West Tunisia

Abdelaziz Sebei, Mohamed Amine Helali, Walid Oueslati, Chiraz Abdelmalek-

babbou, Fredj Chaabani

PII: S1464-343X(17)30355-2

DOI: 10.1016/j.jafrearsci.2017.09.005

Reference: AES 3006

To appear in: Journal of African Earth Sciences

Received Date: 09 June 2016

Revised Date: 04 September 2017

Accepted Date: 04 September 2017

Please cite this article as: Abdelaziz Sebei, Mohamed Amine Helali, Walid Oueslati, Chiraz
Abdelmalek- babbou, Fredj Chaabani, Bioavailability of Pb, Zn, Cu, Cd, Ni and Cr in the sediments
of the Tessa River : A mining area in the North-West Tunisia, Journal of African Earth Sciences
(2017), doi: 10.1016/j.jafrearsci.2017.09.005

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 ACCEPTED MANUSCRIPT

Highlights

Geochemical analysis, pollution and toxicity were determined in Tessa River.

Enrichment levels of heavy metals are recorded in eighteen sediments samples.

Chemical speciation and Enrichment factor were used to assess pollution in Tessa River.

Bioavailable fraction of some heavy metals is upper 45%, which represent some risk of toxicity.
 ACCEPTED MANUSCRIPT

Bioavailability of Pb, Zn, Cu, Cd, Ni and Cr in the sediments of the Tessa River : a mining area
in The North-West Tunisia

Abdelaziz SEBEI, Mohamed Amine HELALI*, Walid OUESLATI, Chiraz ABDELMALEK-

BABBOU, Fredj CHAABANI
Laboratory of Mineral Resources and Environment, Department of Geology, Faculty of Sciences of
Tunis, University of Tunis El Manar, 2092 El Manar II, Tunis, Tunisia.

Corresponding author: he.amine@gmail.com

Abstract

Tessa River is seen as one of the important rivers in Tunisia. Its catchment is known for its agricultural
and mining activities, especially the Bougrine and Fedj Lahdhoum mines. Eighteen (18) surface
sediments and five (5) water samples were collected from the Tessa River, near these two mining sites.
Sediments are essentially sandy (> 80 %), the most important mineral is quartz (20 to 73 %), then
calcite (41 %) and dolomites (4 %). Heavy metal contents are relatively high near the mining sites,
356 g g-1 for Pb, 3000 g g-1 for Zn, and 5 g g-1 for Cd. These values are lower downstream due to
watercourse dilution effects. Other heavy metals: Cu, Ni and Cr, are low, and values are relatively
constant in all the studied samples, even near the mining sites. The metals originate from natural
sources and not from mining activities. This trend is confirmed by the enrichment factor (EF) where
EFNi, EFCu and EFCr are lower or equal to 1, unlike EFPb, EFZn or EFCd where values are much higher
(> 20). Chemical speciation of these metals does not show any spatial variation. Except for cadmium
which is bound to the residual fraction and in the carbonates; all other heavy metals are bound to the
five sediment chemical fractions: the residual fraction (> 52 %), followed by the oxyhydroxides
fraction (21 %) and carbonates (16 %), and finally bound to the organic matter and to the
exchangeable fraction (< 10 %). The bioavailable fraction of the studied heavy metals exceeds 45 %,
which present risk of toxicity.

Keywords: Tessa River; mining sites; bioavailability; enrichment factor; heavy metals; chemical
speciation

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1 1. Introduction
2
3 Pollution assessment of heavy metals in soils and sediments depends on their total contents and also
4 on the association of the metals to the different carrier fractions in the sediments (Tessier et al., 1979;
5 Added, 1981; Tessier, 2012; Helali et al., 2013). Therefore it is necessary to determine their mobility,
6 bioavailability and to estimate their toxicity. The solid phase of soils and sediments is heterogeneous,
7 composed of different mineral and organic compounds, which can bound metallic elements through
8 various retention sites, such as the reactive surface groups in silt and clay sediments whose behaviour
9 is similar to that of a weak acid. The sorption phenomena (absorption or adsorption) are reversible,
10 metal elements "sorbed" on soil or sediment is therefore bioavailable and potentially toxic. This
11 toxicity in the natural environments is dependent on the changes of the physicochemical parameters
12 such as salinity, pH and Eh (Forstner, 1993; Leleyter and Probst, 1999; Abollino et al., 2002).
13
14 Many experimental techniques exist to estimate the bioavailability of heavy metals in soils and
15 sediments, especially there exist a chemical speciation technique proposed in different variants by
16 several authors (Chao, 1972; Tessier et al., 1979; Added, 1981; Sposito et al., 1982). According to
17 some authors, the type of extracted solution is not selective for a specified mineral, and the extraction
18 efficiency depends on the studied element (Martin et al., 1987). In addition, some authors have
19 observed that there is a metal transfer phenomenon from one fraction to another during the extraction
20 procedure. The sequential extraction used in this study was performed according to the protocol
21 developed by Tessier (1979), according to which the heavy metal concentration was determined in five
22 phases: (1) exchangeable fraction, (2) bound to carbonates, (3) bound to oxyhydroxides, (4) bound to
23 organic matter and sulfides and (5) bound to residual fraction. As a result of using this technique, the
24 estimation of bioavailability of heavy metals is appropriate in the case of soils and sediments subjected
25 to industrial and mining effluents, such as the Tessa River and its tributaries (Fig.1) a region hitherto
26 characterized by mining activities in the north of Tunisia.
27
28 The aims of this study are to (i) determine the impact of tailings of the disused Fej Lahdhoum and
29 Bougrine mines on the waters of the Tessa River, and to (ii) determine the chemical form in which
30 heavy metals are fixed and transported and their bioavailability in the Tessa River and its tributaries.
31 These results will provide important informations on the accumulation and toxicity of heavy metals in
32 sediments, soils and watercourses in this mining areas.
33
34 2. Geological setting of the study area
35
36 The Tessa River catchment is located in Tunisian Tell Atlas. It is known for agricultural and mining
37 activities and is drained by the Tessa river which has a length of 143 km (Rodier et al., 1981). (Fig. 2).

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38 The main geological outcrops in the region consist of Triassic and Post-Triassic formations. The
39 Triassic rocks are composed of gypsium, dolomite, marls and breccias whereas the Post-Triassic
40 outcrops are formed of limestone and marl.
41
42 The mineralization that was mined at Fedj Lahdhoum and Boujabeur mines was hosted within
43 limestone and breccia located in the Triassic contact series (Perthuisot, 1981; Rouvier et al . 1985,
44 Boussen et al., 2010, Souissi et al., 2012). Most of these mines have stoped production and the tailings
45 accumulated over the years are the source of heavy metals and contaminate the water and soils of this
46 region (Moldenhauer et al., 2007) and marine environments of northern Tunisia (Essoni 1998; Helali
47 et al., 2013; Helali et al., 2016).
48 The area is characterised by a semi-arid climate (Moldenhauer et al., 2007). Rainy season is
49 characterised by temperatures in the range 6-13 C, whereas for the dry season the temperature varies
50 from 18 to 27 C. The average rainfall is around 540 mm / year. Evaporation is important and often
51 exceeds precipitation. The estimated average water deficit in the study area is 650 mm year-1.
52
53 3. Sampling and analytical methods
54
55 The 18 surface sediment samples were taken using sediment grab and stored at 4 C for physical and
56 chemical analysis. Handling and analysis of samples were carried out in a clean laboratory using
57 plastic labware. Sediments were sieved using a 63-m nylon mesh to collect the finer fraction and
58 oven-dried at 50 C. Minerals were analysed by X-ray PANALYTICAL X'PERT PRO diffractometer.
59 The sediment samples were digested by adding a mixed solution of concentrated 20 mL HClO4, 10
60 mL HF, and 20 mL HNO3 to 1 g of sediment in Teflon bombs. The dissolution of the major elements
61 was performed by alkaline fusion with lithium metaborate. The resulting digestates were analysed for
62 Cr, Cu, Co, Ni, Pb, Zn, Cd, Ca, Mg, Na and K, by flame atomic absorption spectrometry (FAAS
63 SOOLAR). The accuracy of the analytical procedures employed for the heavy metal analysis was
64 checked using the BCR-032 certified reference material, which yielded values in good agreement with
65 the certified values. Relative Standard Deviations (RSDs) were typically < 9.8 % (Table 1). The
66 granulometric analysis was carried out by wet process on AFNOR Mesh. CaCO3 contents were
67 determined by calcimetry technique.
68
69 The sequential extraction procedure applied in this work was developed by Tessier et al. (1979) and
70 consists of extractions in the following order with associated chemical reagents and conditions to a 1 g
71 of sediment:
72 (1). Exchangeable fraction : 8 mL of MgCl2 (1M) adjusted to pH 7.0 with ammoniac +
73 continuous agitation for 1 hour;

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74 (2). Bound to carbonates: 8 mL of NaOAc (1M) adjusted to pH 5.0 with acetic acid + agitation
75 for 6 hours;
76 (3). Bound to Fe and Mn oxides 20 mL of NH2OH.HCl (0.04 M) in 25 % (HOAc) heated for 6
77 hours at 95 C with occasional agitation;
78 (4). Bound to organic matter: 3 mL of NH4OAc + 5 mL of 30 % H2O2 adjusted to pH =2 with
79 HNO3, samples were heated to 85 C for 2 hours with occasional agitation + a second 3 mL
80 aliquot of (30 % H2O2) were added and the samples were heated to 85 C for 3 hours with
81 occasional agitation, after cooling, samples were diluted to 20 mL and agitated continuously
82 for 30 minutes;
83 (5). Residual fraction: HF + HClO4 total digestion.
84
85 After each extraction, a separation was performed by centrifuging the suspension at 3000 rpm for 15
86 minutes. The supernatant liquid was then separated with a micropipette. The sediment was washed
87 with 10 mL of deionized water and again centrifuged and the wash water discarded. The metal
88 concentrations were determined by FAAS.
89
90 The sampling of flowing river water was performed using a clean polypropylene bottle (0.5L), pH was
91 immediately measured in-situ with a 82862 Weilheim WTW pH-meter. Water was filtered, in-situ,
92 using a Minisart NML syringe filter with 0.45 m pore size previously washed with 2.5 % HNO3, and
93 water samples was acidified (2.5 %) with HNO3 and then dissolved metals are measured by ICP-MS
94 Ultima-C.
95
96 4. Results
97
98 4.1. Water characterisation of the Tessa River
99 The waters of the Tessa River are characterised by a constant and pH (7.3 7.8), except near the Fedj
100 Lahdhoum mine where pH = 6.47 (Table 2). These pH values are essentially the result of the
101 dissolved carbonates, the most abundant geological outcrop in the Tessa catchment. Values of the
102 dissolved heavy metals are high near the mining sites especially the Fedj Lahdhoum mine where
103 results show 1.25 mg l-1 for Pb and 3.86 mg l-1 for Zn. Downstream of the mining sites, values are
104 lower, and in accordance with the Tunisian standards NT 0914 (Table 2).
105
106 4.2. Sediment characterisation of the Tessa River
107 Sediments of the Tessa river are mostly sandy (92 % at some locations) and the fine fraction
108 represents less than 15 % (Table 3). The chemical analysis results show that carbonate contents vary
109 considerably from 24 % at the T1 station to 57 % at T13 station. The carbonate values are low near the
110 mining site of Bougrine (28 to 31 %) and much greater near the Fedj Lahdhoum mine site where the

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111 highest values observed are 38 to 57 %. The mineralogical composition of the studied sediments
112 varies significantly from stations T1 to T18 . In all cases calcite and quartz are the most abundant
113 minerals (respectively 25 to 80 % and 20 to 73 %). Feldspar and dolomite are present in lower
114 contents (0 to 4 and 0 to 8 %). Sediments are rich in carbonates, and also are sandy, which explains the
115 quartz and carbonate abundance in the mineralogical composition of the sediments (Table 4).
116
117
118 4.3. Major elements
119 The mineralogical analysis shows that SiO2 is the most abundant mineral in the studied sediments
120 followed by CaO. SiO2 values vary from 25 to 58 % (Table 5) while CaO contents generally ranged
121 from 18 to 32 %. Aluminum and iron contents are lower than CaO (Table 5). Al2O3 varies from 2.35
122 to 6.4 % (average of 4.41 %) and Fe2O3 varies from 1.8 to 3.8 % (average of 2.9 %).
123 As expected, the highest values of iron are observed near the Bougrine and Fedj Lahdhoum mining
124 sites respectively 3.12 % in T3 and 3.9 % in T12 samples (Table 5).
125
126 4.4. Heavy metal contents
127 The heavy metals analysed in this study comprise Pb, Zn, Cd, Cr, Cu and Ni (Fig. 3).
128
129 4.4.1. Lead
130 Lead contents in the sediments of the Tessa River are summarized in Figure 3. Minimum values for Pb
131 are about 17 g g-1 and they are located far away from the mining sites of Bougrine and Fedj
132 Lahdhoum; whereas the maximum values of 356 and 322 g g-1 are in located near the two mining
133 sites respectively. In general, Pb contents are high near the mining sites: samples T4 to T6 and T11 to
134 T14 (Grey area in Fig. 3). In all these sediment samples, Pb contents are higher than 200 g g-1.
135
136 4.4.2. Zinc
137 The same trends observed for Pb are observed for Zn (R = 0.98) (Table 6), where the maximum values
138 occur near the mining sites of Bougrine (350 g g-1) and Fedj Lahdhoum (2500 g g-1) as shown in
139 sediment samples T3 and T10, respectively. But, the Zn contents are much lower (about 100 g g-1) in
140 the upstream regions far away from the mining site (samples T1 and T2 )( Fig. 3).
141
142 4.4.3. Cadmium
143 The concentrations of Cadmium vary from 1 to 5 g g-1 (mean of 2 g g-1) in sediments near the
144 mining sites (samples T3 to T6 and T11 to T14) (Fig. 3). Upstream of the mining sites (T1 and T2
145 samples), the cadmium content is very low (below the detection limit). This is also the true
146 downstream of the mining sites in the samples T15 to T18 (Fig. 3).
147

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148 4.4.4. Chromium

149 Chromium contents in the sediments are between 39 and 90 g g-1 (mean of 73 g g-1). In contrast to
150 Pb and to Zn, the highest values (samples T4 and T11) are not located near the mining sites. In fact,
151 the spatial distribution of Chromium, upstream and downstream of the mining sites, does not show any
152 particularity, and the contents are unchanged.
153
154 4.4.5. Copper
155 Copper contents vary from 8 to 50 g g-1, in sample stations T17 and T5 respectively. Despite the fact
156 that the highest values are located in samples collected near the Bougrine mining site, the impact of
157 the mining activity is not evident and the behavior is similar to that of chromium, where there is no
158 particular trend in the spatial distribution of Copper from sample stations T1 to T18 (Fig.3).
159
160 4.4.6. Nickel
161 The Nickel concentrations vary from 16 to 89 g g-1 with an average of 48 g g-1. In contrast to Pb (R
162 = -0.71) and Zn (R = -0.72) (Table 6), the spatial distribution of Ni is independent of mining
163 activities in the catchement of the Tessa river and its tributaries (Fig.3). The highest concentration of
164 Nickel is found in samples located near the Fedj Lahdhoum mine (sample T12 ), but also upstream of
165 the mining areas; for example in sediment samples T1 and T2 whose Ni contents are 61 and 65 g g-1,
166 respectively (Fig.3).
167
168 5. Discussions
169
170 5.1. Enrichment factor (EF)
171 The enrichment factor for each heavy metal is calculated in accordance to the aluminum content as Al
172 is a conservative element, unaffected by human activity, therefore it is considered as the detrital
173 fraction of the sediment. The EF is calculated by normalizing metal levels in comparison to those of
174 aluminum (Zoller et al., 1974; Hakanson, 1980; Alvarez-Iglesias et al., 2003; Maanan et al., 2004).
175 The formula used is as follows (Salamons and Frstner, 1984):

( )
Me
Al
sample
176 =

( )

177 In this study, we calculated the EF using heavy metals contents in sample T1 , which corresponds to
178 the natural values of the background, except for cadmium where the NASC value is used (0.09 g g-
179 1).

180 EF = [Me/Al]sample / [Me/Al]T1

181

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182 MeT1: Al = 4.75 mg g-1 ; Zn = 102 g g-1; Cr = 72 g g-1; Ni = 61 g g-1; Cu = 13 g g-1; Cd = 0.09 g
183 g-1; Pb = 17 g g-1.
184 Enrichment is a natural process, which has been observed to be high in soils and sediments affected by
185 human activities, especially near mining areas where the production of some metals is high. The
186 results of this study show that Pb, Zn and Cd are the most enriched metals in the sediments especially
187 near the Bougrine and Fedj Lahdhoum mines where EF ranges from 8 to 20 for Pb, 3 to 31 for Zn and
188 3 to 9 for Cd (Fig.4). Except of EFCu in the Bougrine mining site, where values are relatively high
189 (2.75 to 6.6) and in the Fedj Lahdhoum mine (EFCu = 1.5 to 2.5) the enrichment factor of Cu is low in
190 the rest of the sediments. In the two mining areas, the enrichment factors of Cu Ni and Cr are in
191 general much lower than those of Pb, Zn and Cd, especially far away from the mine sites where the
192 calculated Enrichment factors are lower than 1 (sediment samples T2, T3 and T15 to T18) (Fig.4).
193 Clearly, the mining activities in the North-West Tunisia are an important source of heavy metal in the
194 Tessa River and its tributaries, which are then dispersed into the Mejerda River (connected to Tessa
195 River) and probably into the rest of the Gulf of Tunis (outlet of the studied catchment) as reported in
196 other studies (Helali et al., 2013; Essoni, 1998).
197
198 5.2. Chemical speciation
199 There is not significant variation in the distribution of the metals between the five chemical fractions.
200 All results presented in Figure 5 are the average of the 18 anlaysed samples which contrary to to the
201 total contents of each metal, their chemical speciation does not show any spatial variation.
202
203 5.2.1. Lead
204 Chemical speciation shows that lead is bound to all the sediment fractions. Despite Pb being bound
205 essentially to the residual fraction (average of 52 %), it is also moderately sequestrated in the sediment
206 whereas 3 and 9 % are bound to exchangeable fraction and to carbonates respectively, and the rest to
207 the oxyhydroxides and organic material (Fig. 5). Lead is therefore the most toxic and polluting metal
208 in the Tessa Rivers sediments.
209
210 5.2.2. Zinc
211 Simailarly to Pb, zinc is bound to the five fractions of the sediments (Fig. 5). It is bound to residual
212 fraction (53 %), then to the oxyhydroxides (reaching 26 %). Zn-clays and Zn-oxyhydroxides
213 association in sediments has previously been reported by other authors (e.g. Fernex et al., 1986;
214 Tessier et al., 1979) and is also observed in the suspended particulate material and surface sediments
215 in the Gulf of Tunis (Helali et al., 2013 and Helali et al., 2016).
216
217 5.2.3. Cadmium

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218 Cd is the only heavy metal bound to two fractions, first to the residual fraction (60 %) and then to
219 carbonates (40 %) (Fig. 5). Cd is one of the most toxic metals in this area, its contents are low
220 compared to the other studied heavy metals, but it is one of the most bioavailable metals, since 40 %
221 of Cd is bound to carbonates. This association is clearly limited to the surface sediments of the Tessa
222 River. It was not observed in the suspended particulate mtter of the Mejerda River (connected to Tessa
223 River) or in the Gulf of Tunis (outlet of the studied catchment) where Cd it is bound only to the
224 residual fraction (Helali et al., 2013 and Helali et al., 2016).
225
226 5.2.4. Nickel, Copper and Chromium
227 Chemical speciation shows that these elements are also bound to the five fractions of the sediment
228 (Fig.5). First, they are bound to the residual fraction (55 % for Cr, 52 % for Cu and 43 % for Ni), then
229 to the oxyhydroxides (30 % for Cr, 17 % for Cu and 24 % for Ni), and to the organic matter (17 % for
230 Cu, 8 % for Cr and 9 % for Ni). Ni, Cu and Cr are also bound to the exchangeable fraction and to
231 carbonates, (21. 9 and 4 %, respectively) which makes these heavy metals bioavailable and therefore
232 potentially toxic.
233
234 5.3. Bioavailability of heavy metals
235 The chemical speciation of all the heavy metals is summarized in the Figure 6. Results are grouped in
236 two categories; bioavailable metals which designate the average (%) of metals bound to the
237 exchangeable + carbonates + oxyhydroxides + organic matter, and the average (%) of metals bound to
238 the residual fraction (Table 7). The exchangeable fraction is the lowest fraction to which heavy metals
239 are bound (average of 3%). Copper is the most bound metal to this fraction, then Pb, Zn and finally Ni
240 and Cr. Cadmium is the only metal which is not bound to the exchangeable fraction (Fig.6). In the
241 carbonates fraction, the most abundant metal is cadmium, then Ni, Zn and Pb. (Fig.6).
242
243 Heavy metals are generally bound to the residual fraction (> 50 %) except for nickel. This element is
244 mainly bound to the labile fraction (43 %): exchangeable + carbonates + oxyhydroxydes + Organic
245 matter (mean of 43 %) as shown in Figure 6. In this case, heavy metals present in the mining activities
246 are deeply sequestrated in the river sediments. They are probably transported to the outlet of the Tessa
247 River, and then to the Mejerda River in association with the residual fraction. But an important part of
248 these metals, especially the most toxic (Pb, Zn and Cd), are bound to the labile fraction. These metals
249 are bioavailable and present a risk of toxicity. According to the total contents of these metals, the
250 toxicity is then limited to the neighboring zones of the mining areas of Bougrine and Fedj Lahdhoum.
251 Moreover, the sandy nature of the sediments of the Tessa River limits the risk of toxicity and the
252 accumulation of heavy metals in this river. Heavy metals are probably transported to the rest of the
253 catchment (to Mejerda River and then to the Gulf of Tunis) associated with the fine fraction. Recent

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254 studies have reported this type of association in the sediments and in suspended particulate matters in
255 the gulf of Tunis (Helali et al., 2013 and Helali et al., 2016).
256
257
258 6. Conclusion
259
260 Mining activities in Tessa River catchment date back to the 19th and 20th century and many of the
261 mines, such as Fedj Lahdhoum and Bougrine are closed and now discharge of minewater containing
262 heavy metals into watercourses, soils, and sediments. Therefore the characterisation of
263 physicochemical properties of abandoned tailings is important to assess the risk of potential mobility
264 of heavy metals and their toxicity.
265 The results of this study shows that Tessa River is highly contaminated by heavy metals Pb, Zn and
266 Cd. However, contamination is located at some restricted areas corresponding to mining sites of
267 Bougrine and Fedj Lahdhoum which is confirmed by the enrichment factor trend where Pb, Zn and Cd
268 are the most enriched metals in the studied sediments close to the mining areas and the enrichment
269 decreases downstream probably due to the dilution effects.
270
271 The chemical speciation shows that Cd is one of the most bioavailable metals, since 40 % of it is
272 bound to carbonates. Pb, Zn, Ni, Cu and Cr are essentially bound to residual fraction of the sediment
273 (up to 50 %). However, these metals are also bound to oxyhydroxides. In the case of Pb and Zn, the
274 exchangeable fraction and carbonates are an important carrier fractions. This suggests that a some
275 percentages of these metals are toxic because they are bioavailable. Based on the findings of the
276 study, it is demonstrated that there is no important chemical processes observed during the transport or
277 sedimentation by the rivers contrary to the observed phenomena mentioned in the Mejerda Outlet.
278 This is probably due to the sandy nature (> 85 %) of the river sediment.
279
280 7. References
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351 Sposito, G., Lund, J., Change, A.C., 1982. Trace metal chemistry in arid-zone filed soils
352 amended with sewage sludge: Fractionation of Ni, Cu, Zn, Cd and Pb in solid phases. Soil Sci. Soc.
353 Am.J., pp. 260-264.
354
355 Tessier, A., Campbell, P.G.C., Bisson, M., 1979. Sequential extraction procedure for
356 speciation of particulate trace metals. Anal. Chem., Vol. 51, pp. 884-851.
357
358 Tessier, E., 2012. Diagnostic de la contamination sedimentaire par les metaux/metalloids dans
359 la rade de Toulon et Mecanismes controlant leur mobilit. Thse Chimie de l'environnement.
360 Universit du Sud Toulon Var (291 pp.)
361
362 Zoller, W.H., Gladney, E.S., Gordon, G.E., Bors, J.J., 1974. Emissions of trace elements from
363 coal fired power plants. In: Hemphill, D.D. (Ed.)Trace Substances in Environmental Health 8.
364 University of Missouri, Colombia, Rolla, pp. 167172.

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List of figures

Figure 1. Study area and sampling sites.

Figure 2. Geological map of the study site (Moldenhauer et al., 2007).

Figure 3. Heavy metals content (g g-1) in sediment samples from T1 to T18. (Grey area
corresponding to Bougrine and Fedj Lahdhoum Mines).

Figure 4. Enrichmet factor in the sediments of the Tessa River and its effluent Bougrine and Fedj-
Lahdhoum (grey areas).

Figure 5. Chemical speciation of heavy metals Pb, Zn, Cd, Cr, Cu and Ni in the Tessa Rivers
sediments.

Figure 6. Labile fraction and bioavailability of heavy metals (F1 : Exchangeable, F2 : Carbonates, F3
: Oxyhydroxides, F4: organic matter, F5: Residual).

List of tables

Table 1. Accuracy of heavy metal analysis (%).

Table 2. pH and dissolved heavy metals in the waters of Tessa River (N.T : Tunisian standards (NT
0914).

Table 3. Fine fraction and sandy fractions (%) in different samples.

Table 4. Mineralogy composition (%) of the studied sediments.

Table 5. Major contents (%) in the sediments of the Tessa River. (Bold text correspond to mining
sites).

Table 6. Correlation matrix (R) of major and trace elements.

Table 7. Residual and labile fraction of heavy metals (mean of all sediments).

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Fig. 1. Study area and sampling sites.

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Fig. 2. Geological map of the study site (Moldenhauer et al., 2007).

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400 Bougrine Pb Fedj Lahdhoum

300
200
100
0
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T13 T14 T15 T16 T17 T18

4000 Zn
3000
2000
1000
0
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T13 T14 T15 T16 T17 T18

6 Cd

0
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T13 T14 T15 T16 T17 T18

100 Cr
80
60
40
20
0
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T13 T14 T15 T16 T17 T18

60 Cu
40

20

0
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T13 T14 T15 T16 T17 T18

100 Ni
80
60
40
20
0
T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T13 T14 T15 T16 T17 T18

Fig. 3. Heavy metals content (g g-1) in sediment samples from T1 to T18. (Grey area corresponding
to Bougrine and Fedj Lahdhoum Mines).
Enrichment factor ACCEPTED MANUSCRIPT

100
Bougrine Fedj Lahdhoum

10

0.1
T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T13 T14 T15 T16 T17 T18
Statio
Pb Zn Cd n

Fig. 4. Enrichment factor in the sediments of the Tessa River and its effluent Bougrine and Fedj-
Lahdhoum (grey areas).
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1
1
1
1
1
1
0
0
0
0
0
Pb Zn Cd Cr Cu Ni

Fig. 5. Chemical speciation of heavy metals Pb, Zn, Cd, Cr, Cu and Ni in the Tessa Rivers Sediments (
Exchangeable, Carbonates, Oxyhydroxides, OM, Residual).
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60

50

40

30

20

10

0
F5 F4 F3 F2 F1

Fig. 6. Labile fraction and bioavailability of heavy metals (F1 : Exchangeable, F2 : Carbonates, F3 :
Oxyhydroxides, F4: organic matter, F5: Residual).
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Table. 1
Accuracy of heavy metal analysis (%)
BCR-032 This study RSD (%)
(g g-1) (g g-1)
Cd 20,8 22 5.77
Cr 257 251 2.33
Co 0,59 0,57 3.39
Cu 33,7 33,9 0.59
Zn 253 250 1.19
Ni 34,6 31,2 9.83

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Table. 2
pH and dissolved heavy metals in the waters of Tessa River (N.T : Tunisian standards (NT 0914).

Samples pH Cd Cr Cu Fe Ni Pb Zn
(g l-1) (g l-1) (g l-1) (mg l-1) (g l-1) (g l-1) (mg l-1)
OT1 7,58 <0,5 <5 <5 0,68 <5 0,16 <0,01
OT2 7,56 <0,5 <5 <5 0,58 <5 0,16 <0,01
OT3 7,84 <0,5 <5 <5 0,59 <5 0,16 <0,01
OT4 6,47 <0,5 <5 <5 4,10 <5 1,25 3,86
OT5 7,49 <0,5 <5 <5 0,71 <5 0,31 0,64
BD1 7,56 <0,5 <5 <5 0,15 <5 0,16 <0,01
BD2 7,37 <0,5 <5 <5 0,26 <5 0,15 <0,01
BD3 7,57 <0,5 <5 <5 0,27 <5 0,15 <0,01
BD4 7,74 <0,5 <5 <5 0,13 <5 0,15 <0,01
N.T (mg l-1) 6,5- 8,5 0,005 0,01 0,5 1 0,2 0,1 5

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Table. 3
Fine fraction and sandy fractions (%) in different samples.

Station T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 T11 T12 T13 T14 T15 T16 T17 T18
>63m (%) 87 85 90 88 90 90 88 89 89 88 91 86 86 91 92 87 86 90
<63 m (%) 13 15 10 12 10 10 12 11 11 12 9 14 14 9 8 13 14 10

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Table. 4
Mineralogy composition (%) of the studied sediments

Sample Quartz Calcite Dolomite Feldspath

T1 73 25 0 2
T2 51 44 0 5
T7 20 80 0 0
T5 23 77 0 0
T13 44 52 4 0
T14 28 64 0 8
T16 48 44 3 5
T17 43 55 0 6
Min. 20 25 0 0
Max. 73 80 4 8

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Table. 5
Major contents (%) in the sediments of the Tessa River. (Bold text correspond to mining sites)

Sample CaO SiO2 Fe2O3 Al2O3

T1 29,36 34,25 3,21 4,75
T2 21,66 40,27 2,99 6,40
T3 27,65 38,25 3,12 4,50
T4 29,39 38,17 2,21 3,78
T5 31,25 36,25 2,61 2,81
T6 22,20 51,60 2,31 2,35
T7 32,56 34,58 1,80 2,78
T8 18,02 58,25 2,21 2,63
T9 28,28 31,62 2,35 4,65
T10 26,85 27,56 3,72 5,55
T11 30,80 24,82 3,43 4,91
T12 25,20 34,24 3,86 6,23
T13 24,36 35,60 3,52 4,33
T14 30,20 27,36 3,43 4,91
T15 27,30 33,17 2,35 4,53
T16 27,95 35,80 3,18 4,60
T17 27,86 29,96 3,43 4,72
T18 27,72 30,82 2,94 4,96
Min 18,02 24,82 1,80 2,35
Max 32,56 58,25 3,86 6,40
Moy. 27,14 35,70 2,93 4,41

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Table. 6
Correlation matrix (R) of major and trace elements

Ca Si Fe Al Pb Zn Cd Cr Cu Ni
Ca 1.00 -0.51 -0.74 -0.72 -0.26 0.17 -0.51 0.34 0.71 -0.6
Si 1.00 -0.74 -0.68 0.61 0.64 -0.82 -0.14 0.76 -0.6
Fe 1.00 0.91 -0.54 -0.62 0.80 -0.53 -0.88 0.81
Al 1.00 -0.33 -0.45 0.75 0.00 -0.84 0.8
Pb 1.00 0.98 0.4 0.65 0.54 -0.73
Zn 1.00 0.3 0.54 0.65 -0.72
Cd 1.00 0.4 -0.81 0.41
Cr 1.00 -0.31 -0.72
Cu 1.00 -0.54
Ni 1.00

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Table. 7
Residual and labile fraction of heavy metals (mean of all sediments)

Pb Zn Cd Cr Cu Ni
Labile fraction (%) 48 47 41 45 49 57
Residual fraction (%) 52 53 59 55 51 43