Study of aluminium concentration and speciation of surface water in four catchments in the Limousin region (France)

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  • Journal of Inorganic Biochemistry 97 (2003) 1625www.elsevier.com/ locate / jinorgbio

    S tudy of aluminium concentration and speciation of surface water in fourcatchments in the Limousin region (France)

    * Gilles Guibaud , Cecile GauthierLaboratoire des Sciences de lEau et de lEnvironnement, Faculte des Sciences et Techniques, 123 Avenue Albert Thomas, 87 060 Limoges Cedex,

    France

    Received 31 March 2003; received in revised form 6 June 2003; accepted 6 June 2003

    Abstract

    `This study highlights the contamination of the upstream catchment of several rivers (Vienne, Gartempe, Vezere) in the Limousin(France) by aluminium in the absence of atmospheric pollution. The presence of acid soils on a granitic platform is a natural factor whichcontributes to the presence of protons and aluminium in water. In the Limousin, it seems that the presence of aluminium in surface wateris due to a combination of natural factors: poor acid soils, numerous wet moors and peat bogs. It is currently difficult to evaluate the realimpact of intensive cultivation of coniferous trees on the aluminium concentrations found in water in this area. In water, the concentrationin total aluminium increases with a decrease in pH and an increase in organic matter. Despite, high concentrations of total aluminium atlow pH (close to or lower than 6), the monomeric toxic forms of aluminium, computed with a speciation software, are always inferior tothe toxic values for fish. Under such conditions, the concentration in aluminium recorded in some upstream catchments of the Limousinrivers may not cause damage to aquatic life. 2003 Elsevier Inc. All rights reserved.

    Keywords: Aluminium; Water quality; Organic matter; Forest; Runoff water

    1 . Introduction geological platform, the size of the catchment area, thebuffer capacity of the soils and stream water also influence

    In the northern hemisphere, since the 1970s, the quality the quality of natural water [8]. The formation of organicof natural water with weak buffer capacity has decreased matteraluminium complexes allows aluminium to be[1,2]: acidification, increase in nitrate and sulphate con- maintained in soluble forms in spite of unfavourablecentrations or in metal elements such as aluminium [3]. physicochemical conditions [9]. Several studies haveSeveral factors of natural or anthropic origins have been shown that the aluminium concentrations in surface wateridentified as being responsible for this deterioration. Acid are in direct relationship to pluviometry [1012]. This soilrains and atmospheric deposits have produced a decrease or water denaturation produces toxic aluminium (Al)in pH and a rise in the concentrations in nitrogen or effects on trees, fauna and aqueous flora [1315].sulphur compounds in the soils and natural water [4] and Al is present in the environment in various forms, withthe intensive cultivation of several tree species, such as very different toxicities, that can interact with the com-spruce and fir, are at the origin of the increase in the ponents of the soil and bedrock. The predominant toxic

    31concentrations in protons and aluminium in the rivers forms are known to be the monomeric ones [i.e., Al ,

    21 1 2neighbouring these forests [3,5]. These two phenomena are Al(OH) , Al(OH) and Al(OH) ]. The biological avail-2 4accentuated when they occur on poor, acid brown earth ability of aluminium is influenced by various substancessoils [6,7]. In certain areas subjected to air pollution and such as silicon: silicic acid can react with Al to formwith acid soils (the Vosges, France), it was shown that the hydroxyaluminosilicates (HASs), thereby decreasing the

    toxic effects of Al [16,17]. Organic matter (OM), of a veryheterogeneous composition, also plays a major role in Al

    *Corresponding author. Tel.: 1335-55-45-7428; fax: 1335-55-457- bioavailability [18].223.As for aquatic life, it was demonstrated that bothE-mail addresses: gguibaud@unilim.fr (G. Guibaud),

    c.gauthier@netcourrier.com (C. Gauthier). oligomeric silica and humic acid influence Al bioavail-

    0162-0134/03/$ see front matter 2003 Elsevier Inc. All rights reserved.doi:10.1016/S0162-0134(03)00254-X

  • 17G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 1625

    ability of the freshwater snail Lymnaea stagnalis [19]. and Grande Creuse rivers is due to a diffuse pollution fromThus external conditions play a major role in aluminium agriculture (extensive breeding of bovines) and that ob-

    `reactivity and toxicity. It was shown that between pH 5.0 served in the Vienne at Royere is due to the presence ofand 6.0, when toxicity appears to be most acute, conditions several small towns and low level agricultural pollutionare favourable for Al polymerisation [20]. Growth of Al (extensive breeding of bovines).polymers on the surface of fish gills and increased mucus The four upstream catchments are located on a similarsecretion cause severe clogging of the interlamellar spaces. geological platform but their covering vegetation is differ-The interaction of mucus (mollusc, Lymnaea stagnalis) and ent. The percentages of the surface with coniferous trees

    `Al has also been studied [21]: it is suggested that gel- are, respectively, 8 and 38% for Gartempe and Vezereforming extracellular glycoconjugates plays a crucial role catchments. The Gartempe catchment is characterised byin preventing the diffusion of Al into biological systems. the presence of numerous peat bogs and wet moors which

    In France, many studies have been carried out on are also present on the catchments of Vienne at `experimental catchments of the Vosges and the Ardennes Peyrelevade and the Vezere but their surfaces are smaller

    [7] but few data are available on the acidification and the than that of the Gartempe.pollution of waters by aluminium in other areas. In the Rainfall is high on the catchments sampled and in-Vosges and Ardennes, concentrations in protons and creases from west to east for the sampling points.aluminium in natural waters are greatly influenced by thepresence of acid rain and atmospheric deposits whereas in 2 .2. Sampling and analysesthe Limousin, soils have developed mainly on a graniticplatform and are naturally acidic Acid rain and atmos- Six to 12 samples per year were collected from eachpheric deposits have not been recorded in this area [22] but point over the period May 1998 to March 2003. They werethe surface covered with coniferous trees increases by 18 stored at 4 8C in Nalgen bottles and analysed as soon as

    2 21km year [23]. In this area, studies have shown how possible (less than 2 days).soils under Douglas plantations have been modified [24]. The pH, conductivity (at 25 8C) and dissolved oxygenbut few studies are available on the state of contamination were measured with WTW devices on collection.of the rivers of the Limousin. Only one has been carried Before analyses, the samples were filtered through 0.45-

    21 21 1 1out using data on aluminium concentrations in Limousin mm membranes. The major cation (Ca , Mg , Na , K )

    2 2 22rivers collected over a period of 2 years [25] and it pointed and anion (Cl , NO , SO ) concentrations were de-3 4out the contamination of some rivers by aluminium with termined by ion chromatography, Dionex Dx-100 [27].

    21concentrations greater than 110 mg l . The phosphate and ammonium concentrations were de-

    The objective of this study was to characterise, in four termined, respectively, by ammonium Molybdate and theupstream catchments in the Limousin area, aluminium, Nitroprussiate colorimetric methods [27]. The silica con-organic matter and proton concentrations in water. The centrations were determined according to the AFNORrelationships between these three parameters were studied colorimetric method [27], and total aluminium concen-using data collected over 5 years. The natural water trations using a Varian Zeeman ASS 800 correctioncontamination by aluminium in a region with no acid rain graphite furnace. Total organic carbon (TOC) analysesinfluence or acid deposits is discussed. An evaluation of were carried out with a Dorhman Phoenix 8000 COT-the risk of toxicity for aquatic life is carried out by the meter and the concentrations in TOC were used to evaluatecomputation of aluminium speciation. the organic matter concentration in river waters.

    2 .3. Computation of Al speciation2 . Materials and methods

    In order to determine the toxic aluminium concen-31 21 12 .1. Characteristics of studied catchments trations [monomeric species: Al , Al(OH) , Al(OH)2

    2and Al(OH) ], aluminium speciation was carried out for4

    This study was carried out on upstream catchments of some water samples according to the literature [2830].1the four major rivers in the Limousin area: the Vienne, Mineql version 4.07 was used to compute aluminium

    `Vezere, Gartempe and the Grande Creuse. There are two speciation. Equilibria assumed to be involved in thepoints located on the river Vienne. Fig. 1 shows the five speciation of aluminium are given in Table 2.sampling points and Table 1 presents the major charac- The speciation of aluminium was performed with the

    2 32 22teristics of the four catchments studied. following species: OH , PO , SO , Si(OH) and or-4 4 4To determine the general quality of water the French ganic matter (as mol equiv. of carbon from fulvic acid).

    Water Agencies uses only parameters dealing with N, P or The calculation was done at the temperature of the water2C pollution and parameters such as aluminium or pes- recorded on the sampling day. The F concentration was

    ticides are not take into account. At Peyrelevade the not measured in the samples. According to Stumm and21

    `quality of the Vezere and the Vienne water is very good. Morgans results [31], a concentration of 10 mmol l isThe reduction in water quality observed in the Gartempe chosen for all samples. But no significant fluorine con-

  • G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 162518

    Fig. 1. Location of the studied rivers and characteristics of their catchments.

    centrations were recorded in water in the region studied by physicochemical parameters recorded from May 1998 tothe French Ministry of Health. March 2003 at the five sampling points studied.

    `The Vezere and Vienne at Peyrelevade present lowmineralization and an acidic pH due to the geology of theareas crossed by the rivers (Table 1). The buffer capacities

    3 . Results of these waters are low and high pH peaks can be noted.`The Vienne at Royere, Gartempe and the Grande Creuse

    `3 .1. General quality of river waters sampling points show higher conductivity than Vezere andVienne at Peyrelevade due to lower pollution from sewage

    Table 3 shows the minimal and maximal values of and agriculture. These kinds of pollution are a source of

  • 19G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 1625

    T able 1Location of the studied rivers and characteristics of their catchment

    `River name La Vezere La Vienne La Vienne La Grande Creuse La Gartempe`Sampling point location Bugeat Royeres Peyrelevade Clairavaux Maisonnises

    Km from spring 24 89 4 4.5 42Size of catchment (km ) 70.61 1442.8 14.58 14.425 6.35

    Geology Granite as biotite Migmatites Granite as Migmatites andor 2 micas and granites 2 micas granites Granite asbiotite

    aVegetation Forest, moor, End of woody Peat bog, Grassland, forest Lot of peat bog,peat bog area, grassland moor, forest moor, forest

    aTotal area with forest (%) 45 30 30 35 30aTotal area in resinous trees (%) 38 23 25 23 8

    bQuality Very good Good Very good Very good/good Very good/goodAverage rainfall between 1998

    21and 2002 (mm year ) 1898 1260 1560 1440 1410a According to the Atlas du Limousin [26].b According to French Water agency criteria (only C, N, P pollution parameters used).

    alkalinity, phosphorous and ammonium (Table 3) and as a minium and organic matter vary greatly over the samplingconsequence, the pH increases close to neutral. period (by about a factor of 4 minimum). The aluminium

    For each catchment studied, the concentrations in alu- and organic matter concentrations recorded are very differ-

    T able 2Reaction assumed to account for the speciation of aluminium (from Boudot and co-workers [13,29]; Maitat [30])Species Log K

    Monomeric species31 31Al Al

    21 31 21 1AlOH Al 1H OAlOH 1H 2521 31 1 1Al(OH) Al 12H OAl(OH) 12H 210.12 2 2

    31 1Al(OH) Al 13H OAl(OH) 13H 216.83 2 32 31 2 1Al(OH) Al 14H OAl(OH) 14H 222.74 2 4

    1 31 22 1AlSO Al 1SO AlSO 3.54 4 42 31 22 2Al(SO ) Al 12SO Al(SO ) 54 2 4 4 2

    21 31 2 21AlF Al 1F AlF 71 31 2 1AlF Al 12F AlF 12.72 2

    31 2AlF Al 13F AlF 16.83 32 31 2 2AlF Al 14F AlF 19.44 422 31 2 22AlF Al 15F AlF 20.65 532 31 2 32AlF Al 16F AlF 20.66 6

    31 32Al(PO ) Al 1PO Al(PO ) 17.284 4 41 31 32 1 1AlH(PO ) Al 1PO 1H AlH(PO ) 19.754 4 4

    21 31 32 1 21AlH (PO ) Al 1PO 12H AlH (PO ) 22.652 4 4 2 421 31 2 21AlOSi(OH) Al 1H SiO 1OH AlOSi(OH) 22.383 4 4 3

    31 32AlFulvate Al 1Org AlOrg 8.381 31 32 1 1AlHFulvate Al 1Org 1H AlHOrg 13.1

    22 31 32 32 1 22AlH(PO )Fulvate Al 1PO 1Org 1H AlH(PO )Org 28.834 4 422 32 1 22HFulvate Org 1H HOrg 5.942 32 1 2H Fulvate Org 12H H Org 11.602 2

    32 1H Fulvate Org 13H H Org 14.223 3

    Solids31 1Al(OH) amorphous Al 13H OAl(OH) 13H 210.383 2 331 32AlPO amorphous Al 1PO AlPO 20.304 4 431 1Gibbsite natural Al 13H OAl(OH) 13H 28.772 331 1Allophanes Al 1H SiO 13H OAl(OH) SiOH(OH) 13H 27.14 4 2 3 3

    31 1Proto-imogolite 2Al 1H SiO 13H OAl O SiOH(OH) 16H 213.34 4 2 2 3 331 1Imogolite 2Al 1H SiO 13H OAl O SiOH(OH) 16H 212.504 4 2 2 3 3

    31 22 1Jurbanite Al 1SO 1H OAlSO (OH)1H 3.234 2 431 22 1 1Alunite 3Al 12SO 1K 16H OKAl (SO ) (OH) 16H 1.354 2 3 4 2 631 22 1Basaluminite 4Al 1SO 110H OAl (OH) SO 110H 222.74 2 4 10 4

    31 1 1Boehmite Al 14H OAlOOH 13H 28.58231 1Kaolinite 2Al 12H SiO 1H OAl Si O (OH) 16H 25.734 4 2 2 2 5 4

  • G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 162520

    T able 3Minima and maxima values of different parameters recorded between May 1998 and March 2003

    ` `Vezere Vienne (Royeres) Vienne (Peyrelevade) Grande Creuse GartempeMin Max Min Max Min Max Min Max Min Max

    3 21Daily average flow (m s ) 0.3 7.2 5.7 99.3 0.04 0.96 0.09 0.82 0.03 0.2421Aluminium (mg l ) 45.2 146.4 18.4 78 31.5 130.5 9.2 141.2 8.7 274.8

    21Aluminium (mmol l ) 1.67 5.42 0.68 2.89 1.17 4.83 0.34 5.23 0.32 10.1821TOC (mg C l ) 2.8 10.2 2.3 7.1 2.4 8.5 1.8 4 4.9 16.2

    21TOC (mmol C l ) 233 850 192 592 200 709 150 334 408 1350Absorption at 254 nm 0.106 0.464 0.114 0.256 0.093 0.404 0.071 0.212 0.229 0.79pH 5.6 6.8 6.3 7.2 5.7 6.8 6.5 7.4 6.2 7

    2 21AlkalinityHCO (mg l ) ,5 6 8 17 ,5 7 10 18 10 23321Conductivity (mS cm ) 17 26 41 62 21 31 48 68 52 76

    2 2 21NO (NO mg l ) 1.0 2.9 2.9 6.7 1.1 2.9 2.7 6.8 1.4 3.63 31 1 21NH (NH mg l ) ,0.02 ,0.02 ,0.02 0.07 ,0.02 0.03 ,0.02 ,0.02 ,0.02 0.034 4

    32 32 21PO (PO mg l ) ,0.03 0.15 0.03 0.12 ,0.02 0.08 ,0.02 0.15 0.02 0.314 422 21Si (SiO mg l ) 7 23 9 13 8 22 16 18 18 273

    21 21Ca (mg l ) 1.0 1.7 2.4 3.9 1.1 1.6 2.5 4.6 2.9 5.121 21Mg (mg l ) 0.2 0.6 0.9 1.5 ,0.5 0.8 1.0 1.7 0.9 1.51 21Na (mg l ) 1.7 2.5 3.4 5 2.3 3.3 4.4 5.4 4.6 7.31 21K (mg l ) 0.4 0.7 0.9 1.8 ,0.5 1.0 0.9 1.4 1.1 3.0

    ent from one catchment to another, the river Gartempe In a general way, the Limousin river water studied ishaving the highest contents in organic matter (due to the less acidic than the water of the river presented in thepresence of numerous peat bogs) and aluminium and the Table 4. This is due to the absence of acidic deposits orGrande Creuse river having low ones. acid rains in the Limousin region.

    A wide range of Al concentrations have been reported The upstream catchments of some rivers in the Limousin `for surface waters. Elevated concentrations of Al have (Vezere, Gartempe, Vienne) are contaminated part of the

    generally been found in acidic surface waters in regions year by aluminium, if we compare the concentrationsreceiving high acidic input. In order to compare the values recorded to the ones presented in Table 4. In the absencefor aluminium concentration recorded in the rivers studied of acid rain in the area [22], the presence of acid soils and(a region with no acidic atmospheric pollution), some significant presence of coniferous trees may be two factorsvalues reported in the literature are presented in Table 4. at the origin of the contamination of river waters by

    T able 4Different values of total or monomer aluminium, pH recorded in different polluted or unpolluted sites in Europe and the USA

    Ref. Sampling area Total Al Monomer Al pH Remarks21 21(mg l ) (mg l )

    21 21(mmol l ) (mmol l )Maitat [30] Vosges (France) 62.165.4 5.4560.05 Atmospheric pollution

    212.3 6 0.2 TOC: 0.03 C mg l

    Lawlor and Tipping [32] Northern England 811194 5.17.1 Atmospheric pollution3 44.2

    Kopacek et al. [33] Czech Republic 540 (271080) 189 (27540) 3.846.30 Acid rain;2120 (1 40) 7 (1 20) TOC: 6.5 (0.629.9) (C mg l );

    21Conductivity 40.3 (15.974.2) mS cm

    Christophersen et al. [4] Birkenes II (Norway) 110 4.65.0 Acid rain4.1

    Birkenes I (Norway) ,1 5.07.2 No atmospheric pollution,0.03

    Linthurst et al. [34]; Adirondack (USA) 137.7 (8.1756) 43.2 (0324) 6.3 (4.29.4) Three acid sensitive regionsSposito [35] 5.1 (0.3 28)

    Maine (USA) 81 (8.1810) 14 (0270) 6.9 (4.38.4)3 (0.3 30)

    Florida (USA) 89.1 (8.11350) 21 (0432) 6.3 (3.89.0)3.3 (0.3 50)

  • 21G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 1625

    aluminium. All the catchments studied are on a granitic The highest aluminium concentrations are recorded inplatform and as a consequence the soil and the natural descending order on the upstream catchments of Gartempe,

    `waters are acidic. The geology of the area influences Vezere and Vienne (Peyrelevade). The percentages ofmineralization, the pH and the aluminium concentration of surfaces with coniferous trees are, respectively, 8, 38 andthe rivers in the catchments studied whereas the effect of 25% on these three upstream catchments. The Gartempethe cultivation of coniferous trees is difficult to evaluate. catchment has a lot of peat bogs and wet moors which giveThe percentage of the surface of the catchment area water very rich in organic matter according to the TOCcovered in coniferous trees seems insufficient to explain values recorded (Table 3). Several studies have shown thatthe aluminium concentrations. By comparing the charac- the organic matter, by forming complexes with aluminium,teristics of the catchment and the composition of water, we allows the aluminium in the soil to migrate towards thecan make assumptions about the factors influencing the rivers [36]. The presence of peat bogs and wet moorswater quality. seems to have a strong influence on this. For the upstream

    `Fig. 2. Relation between total dissolved aluminium and pH or organic matter (expressed as total organic carbon) for the Vezere river (with a 99%confidence interval).

  • G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 162522

    `Vezere and Vienne catchments (Peyrelevade) the presence influence the dissolved aluminium concentration and theof some peat bogs and wet moors could be at the origin of dissolved aluminium concentration increases with the pH.part of the concentrations in aluminium and organic matter It seems that the pH and the organic matter do not controlfound in the water of these two rivers. These results seem the aluminium concentrations recorded in the Grandeto be confirmed by the quality of water of the Grande Creuse upstream catchment. The very low concentrations

    21Creuse in its upstream catchment. This river has a low of aluminium recorded (between 15 and 40 mg l ) can beorganic matter and aluminium concentration and its catch- explained by such results (under solubility concentration).ment is characterised by a high percentage of coniferous The pH values and the organic matter concentrationstrees (23% of the surface of the catchment), but the peat greatly influence the dissolved aluminium concentrationsbogs and wet moors are absent. recorded in water of the studied rivers. For the same

    catchment area (Vienne), if we study two distant points`3 .2. Relations between aluminium concentration and pH (Peyrelevade, Royere, about 85 km apart), the change in

    or organic matter concentration the physicochemical conditions [increase in pH, anddissolved ions (conductivity)] produces a reduction in the

    Fig. 2 presents an example of the linear correlations, dissolved aluminium concentration. These results are in `obtained for the Vezere, between aluminium and organic accordance with Lukewille and Van Breemen [37].

    matter concentration (TOC), or with pH. Table 5 presents Guibaud et al. [25] showed that the concentration ofthe parameters of linear correlations for the five catch- aluminium in the rivers of the Limousin varied during thements studied: n (number of sample), r coefficient of year, the highest concentrations were recorded in wintercorrelation (sign of the slope of the linear regression line is and the lowest at the end of the summer. The results of thein front of coefficient of correlation), S.D. (standard correlations carried out between the aluminium concen-deviation) and P significance (significant correlation if trations and pH or the organic matter concentration showP,0.05). divergent points from the average line. The evolution in

    ` `For the Vezere, Vienne at Peyrelevade, Royere and the organic matter concentrations and the pH do not followGartempe, the dissolved aluminium concentrations in- the evolution in the aluminium concentration in the rivers.crease with an increase in the organic matter concentration The quantity of organic matter in water can be influenced(Table 5). The organic matter can bind aluminium and the by leaf fall in the autumn and low level domestic ororganic matter /aluminium complex does not precipitate agricultural pollution. Likewise, the pH can be affected bydespite unfavourable pH conditions for aluminium in the the metabolism of micro-organisms, the temperature ofsoluble form [9]. water and photosynthetic activity. Due to the weak buffer

    `For the river with a very low mineralization (Vezere and capacity of the water, the pH can be greatly affected.Vienne at Peyrelevade), the dissolved aluminium con- Such variations in aluminium concentrations, organiccentrations increase with the decrease in pH. These results matter or pH can produce toxic effects on aquatic life.are in agreement with the literature [4,7,9]. The acidic pHvalues increase the soluble forms of aluminium and 3 .3. Aluminium speciationprevent its precipitation as Al(OH) . For the Gartempe and3

    `Vienne at Royere, no significant correlations are obtained One of the main reasons for studying metals in thebetween aluminium concentration and pH. It may due to a stream waters of upland catchments is to assess the toxichigher buffer capacity and a pH range variation close to threat they pose to terrestrial and freshwater organisms.neutral. Although most environmental quality standards are set in

    The results obtained for the Grande Creuse are different terms of total concentration (e.g., concentration of dis-(Table 5). The organic matter concentration does not solved metal), it is now recognised that in many cases

    T able 5Parameters of linear correlation relation between total dissolved aluminium and pH or organic matter (in total organic carbon) for the rivers studied (sign ofthe slope of the linear regression line is in front of the coefficient of correlation, rin bold significant correlation if P,0.05)

    ` `Vezere Vienne (Royere) Vienne (Peyrelevade) Grande Creuse Gartempen (sample) 43 57 28 28 33

    Al5f(pH) r 20.36 20.06 20.53 0.53 20.26S.D. 28.1 18.1 21.4 8.9 42.9P 0.018 0.660 0.003 0.004 0.158

    Al5f(TOC) r 0.53 0.34 0.71 0.01 0.4S.D. 25.5 17.8 18.5 10.5 40.8P 0.001 0.015 0.001 0.980 0.023

  • 23G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 1625

    toxic effects depend upon the chemical speciation of the dangerous for aquatic life according to the results pre-metal in question, with the free ion activity or con- sented in Table 6 even if the concentrations of fluoridecentration being a key variable. were not measured. Indeed, the sum of the value of toxic

    Table 6 presents various values of aluminium for fish at aluminium and aluminium bound to fluoride was alwaysdifferent pH values to take into account the tendency of inferior to the toxic aluminium concentrations.toxic concentrations to fall with increasing pH.

    In order to estimate the risk of toxicity for aquatic life inthe upstream catchment of the rivers studied, Table 7 4 . Conclusionpresents the value of total aluminium concentrations, thepH, the concentration in organic matter measured and the This study points out the contamination by aluminium ofaluminium speciation computed in some characteristic

    some Limousin rivers in their upstream catchment. Thesamples collected at different dates for each river studied. Limousin region is not affected by acid rain or atmospheric(32n)1The Al(OH) concentration is the sum of the con-n pollution but the presence of acid soils developed on acentration of the toxic monomer forms of aluminium [i.e., granitic platform is a natural factor which contributes to31 21 1 2Al , Al(OH) , Al(OH) and Al(OH) ]. The Al-OM2 4 the presence of protons and aluminium in water.concentration is the concentration of aluminium bound to It seems that in the Limousin the presence of aluminiumthe organic matter according to Driscolls triprotic model in surface water is due to a combination of natural factors:(32m)1(Table 2). The Al(F) concentration is the sum of allm poor acid soils, presence of wet moors and peat bogs and italuminium fluoride complexes. According to Stumm and is difficult to evaluate the real impact of the intensiveMorgan results [31], a concentration in fluoride of 10

    cultivation of coniferous trees on the aluminium con-21mmol l is chosen for all the samples.

    centrations found in the water in this area.According to the speciation calculation, aluminium `For the Vienne,Vezere and Gartempe, the organic matter32 22

    complexes with PO , SO , Si(OH) , are present at very4 4 4 concentration has a great influence on the aluminium215 21low concentrations, about 10 mol l ,due to the lowconcentration and speciation in the water. Aluminium32 22

    concentrations of PO , SO . The concentrations of these4 4 concentration decreases with an increase in pH and with akinds of complexes are not discussed due to their minor decrease in organic matter concentration.importance. Despite high aluminium concentrations recorded for aFor the rivers studied, the fluoride concentration seems part of the year at a pH lower than 6, the concentration ofto have a minor influence on aluminium speciation. With

    toxic forms computed were always inferior to the toxic21an estimated concentration of 10 mmol l of fluoride, the

    concentrations for fish. In such a case, the aluminiumaluminiumfluoride complex is present at a very low

    concentration recorded in the upstream catchments of someconcentration.

    rivers may not cause damage to aquatic life. ` `For Vezere, Vienne at Peyrelevade and Royere, and

    Gartempe, the aluminium in water is mainly bound toorganic matter (more than 98%) but for the Grande Creuse,perhaps due to the low concentration of aluminium re- A cknowledgementscorded, concentrations of organic forms of aluminium aresmaller. Dissolved Al(OH) could be present as a signifi- This study was carried out with the financial support of3

    cant percentage. These results are in accordance with the the Conseil Regional du Limousin. The authors thankresults obtained with the correlation shown in Table 5. The Frederic Gisclard, Dominique Lagorce, Patrick Bouillon,organic matter concentrations seem to have a large in- Patrick Fayard, Bruno Moine of the DIREN Limousin forfluence on aluminium speciation in the rivers studied. their technical assistance and Yoann Bacque, Sophie

    The concentrations of toxic aluminium forms computed Bidegorry and Nicolas Tixier for the assistance brought to1

    with Mineql were very low and do not appear to be the data processing.

    T able 6Some values of toxic aluminium concentration for fish

    Ref. Species pH TOC Al monomer Al total21 21 21(C mg l ) (mmol l ) (mmol l )

    Roy and Campbell [38] Juvenile salmon 4.75.0 0.2 (free metal ion)

    Kroglund and Finstad [15] Atlantic salmon 5.8 Low concentration 0.150.30 (inorganic form)

    Probst et al. [39] Fario trout ,5.35.6 6.67.4

  • G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 162524

    T able 7(32n)1Computation of aluminium speciation for some water samples; Al(OH) is the sum of aluminium toxic formsn

    (32n)1 (32n)1Date Variable Al pH OM Al(OH) Al-OM Al(F) Al(OH)Total n n 3 dissolved `Vezere

    219 /17 /99 Conc. (mmol l ) 5.35 5.59 849 0.002 5.346 0.000 % 0.0 100 0.0

    2111/1 /98 Conc. (mmol l ) 5.35 5.98 389 0.007 4.093 0.019 % 0.1 99.3 0.4

    219 /15 /99 Conc. (mmol l ) 2.08 6.59 309 0.052 1.986 0.010 % 2.5 95.5 0.5

    217 /13 /00 Conc. (mmol l ) 3.40 6.54 353 0.059 3.289 0.015 % 1.7 96.8 0.5

    213 /6 /01 Conc. (mmol l ) 5.22 5.81 249 0.010 5.157 0.052 % 0.2 98.8 1.0

    214 /1 /01 Conc. (mmol l ) 3.42 5.96 281 0.008 3.384 0.0229 % 0.2 99.1 0.7

    2111/1 /02 Conc. (mmol l ) 5.01 6.1 533 0.010 4.990 0.0145 % 0.2 99.5 0.3

    `Vienne (Royere)2110/13/98 Conc. (mmol l ) 1.64 6.5 590 0.014 1.616 0.005

    % 0.9 98.4 0.3 2112/15/99 Conc. (mmol l ) 2.08 6.43 358 0.019 2.049 0.006

    % 0.9 98.3 0.3 2112/6 /00 Conc. (mmol l ) 2.77 6.42 441 0.020 2.733 0.007

    % 0.7 98.6 0.3 215 /14 /01 Conc. (mmol l ) 1.71 6.26 250 0.013 1.677 0.013

    % 0.7 98.3 0.8 213 /1 /02 Conc. (mmol l ) 2.51 6.72 250 0.104 2.293 0.009

    % 4.1 90.5 0.4 2111/1 /02 Conc. (mmol l ) 3.41 6.67 492 0.061 3.286 0.007

    % 1.8 96.5 0.2

    Vienne (Peyrelevade)2109/17/99 Conc. (mmol l ) 4.38 5.7 693 0.002 4.342 0.031

    % 0.1 99.2 0.7 2106/13/00 Conc. (mmol l ) 3.85 6.29 373 0.022 3.800 0.020

    % 0.6 98.7 0.5 2108/22/00 Conc. (mmol l ) 4.83 6.13 613 0.009 4.800 0.018

    % 0.2 99.4 0.4 2103/01/02 Conc. (mmol l ) 2.72 5.88 258 0.006 2.684 0.023

    % 0.2 98.9 0.8 2108/01/02 Conc. (mmol l ) 2.76 6.44 283 0.038 2.690 0.017

    % 1.4 97.4 0.6 2112/01/02 Conc. (mmol l ) 4.04 5.75 467 0.003 4.013 0.025

    % 0.1 99.3 0.6

    Grande Creuse217 /22 /98 Conc. (mmol l ) 0.696 6.9 274 0.098 0.524 0.003 0.070

    % 14.1 74.9 0.4 10.1216 /16 /99 Conc. (mmol l ) 1.54 7.05 177 0.544 0.629 0.005 0.358

    % 35.3 40.8 0.3 23.3219 /12 /00 Conc. (mmol l ) 0.498 6.86 234 0.064 0.385 0.002 0.046

    % 12.9 76.7 0.5 9.3216 /1 /02 Conc. (mmol l ) 0.698 6.58 183 0.027 0.6488 0.006 0.016

    % 3.9 93 0.8 2.32112/1 /02 Conc. (mmol l ) 1.32 6.8 283 0.067 1.1696 0.004 0.078

    % 5.0 88 0.3 5.9

    Gartempe218 /19 /98 Conc. (mmol l ) 6.03 6.62 496 0.112 5.832 0.019

    % 1.9 96.7 0.3 217 /19 /99 Conc. (mmol l ) 5.1 6.17 1191 0.006 5.084 0.009

    % 0.1 99.7 0.2 215 /13 /00 Conc. (mmol l ) 9.64 6.58 1128 0.052 9.540 0.009

    % 0.5 99.0 0.1 213 /6 /01 Conc. (mmol l ) 3.31 6.54 474 0.036 3.238 0.007

    % 1.1 98.0 0.2 219 /1 /02 Conc. (mmol l ) 6.08 6.83 1033 0.091 2.922 0.004

    % 1.5 94.1 0.1 2112/1 /02 Conc. (mmol l ) 5.21 6.47 842 0.024 5.170 0.007

    % 0.5 99.1 0.1 213 /1 /03 Conc. (mmol l ) 2.8 6.8 392 0.106 2.561 0.006

    % 3.8 90.8 0.2

  • 25G. Guibaud, C. Gauthier / Journal of Inorganic Biochemistry 97 (2003) 1625

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    Study of aluminium concentration and speciation of surface water in four catchments in the LIntroductionMaterials and methodsCharacteristics of studied catchmentsSampling and analysesComputation of Al speciation

    ResultsGeneral quality of river watersRelations between aluminium concentration and pH or organic matter concentrationAluminium speciation

    ConclusionAcknowledgementsReferences

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