ELSEVIER

The Scienceof the Total Environment 206 (1997) l-15

A contribution to the study of the heavy-metal and nutritional element status of some lakes in the southern Andes of Patagonia (Argentina)
B. Markert aT*,F. Pedrozob, W. Geller, K. Friese, S. Korhammer, G. Bafficob, M. Diazb, S. W61fl
bCentro International Graduate School Zittau (IHI), Markt 23, 02763 Zittay Germany Argentina Regional Universitario Bariloche, Universidad National de1 Comahue, Quintrall250,8400 Bariloche, UFZ Centre for Environmental Research Leipzig/ Halle, Department for Inland Water Research Magdeburg, Germany Am Biedetitzer Busch 12,39114 Magdeburg,

Received 17 March 1997;accepted20 June 1997

Abstract Various nutrients and chemical elements, as well as other parameters, were to be measured by different methods in water and plankton samples from three Argentinian lakes in the Andes: Lake Nahuel Huapi, Lake Gutierrez and Lake Mascardi. The quality of the instrumental measurements was controlled by independent methods (TXRF and ICP/MS) and by using reference materials (NIST 1643~ and BCR/CRM 414). All the chemical concentrations were very low, which means that all the lakes can be classified as oligotrophic to ultra-oligotrophic. Slightly increased concentrations within the lakes investigated may be attributed to anthropogenic influences from the town of Bariloche in the case of Lake Nahuel Huapi or to the glacial influence of the Upper Manso River, which carries considerable amounts of dissolved salts and suspended particles from the Tronador glacier. The waters are very dilute solutions dominated by calcium, bicarbonates and dissolved silica. The ionic composition is largely below the world average given by Livingstone (1963, in: Home AJ, Goldman CR. Limnology, 2nd ed. USA: McGraw Hill, 1994576). The Andean-Patagonian lake waters showed concentrations of Cr, Sr, Zn, Cu, Co and Pb that were of the same order as the freshwater world average. The remaining elements (P, S, Si, Fe, Mn, Ni, Na, K, Mg, Ca, As, Cl and Cd) fall below or around the limit for the freshwater world average. With the exception of calcium, which is twice as high as in reference freshwater (Markert B. Inorganic chemical fingerprinting of the environment; reference freshwater, a useful tool for comparison and harmonization of analytical data in freshwater chemistry. Fresenius Z Anal Chem 1994;349:697-702), the element concentrations (S, Fe, Mg, Na, K and Sr) are lower than in reference freshwater. The phytoplankton biomass was mainly dominated by Dinophyceae in Mascardi and Gutierrez lakes and by Bacillariophyceae in Lake Nahuel Huapi. The phytoplankton shows greater accumulation of the minerals K and Ca, and the essential trace elements (Mg, Fe, Cu and Zn) than the zooplankton. Sulphur occurs in greater

* Corresponding author. 0048-9697/97/$17.00 0 1997Elsevier ScienceB.V. Ail rights reserved. PZZ SOO48-9697(97)00218-O

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concentrations in zooplankton than in phytoplankton, this could be due to higher protein contents. In the case 01 non-essential elements that are toxic at higher concentrations (As and Pb) it is noticeable that the levels are similar for phyto- and zooplankton. This indicates that these substances are taken up passively from the water and deposited in the organism. In general it can be said that the organisms accumulate all the elements by lOO- to lOOO-fold in relation of the surrounding environment. 0 1997 Elsevier Science B.V. Keywords: Lakes; Multi-element analysis; Heavy metals; Water; Plankton

1. Introduction When evaluating the productivity and trophic status of lakes it is essential to know of any factors that may limit the growth of phytoplankton and zooplankton. The notion that most lakes in the temperate zones are P-limited may indeed be regarded as a paradigm of limnology (Zaucke et al., 1992). This applies initially at the conceptual level of a classic ecosystem approach that is based on the abstract stage of the primary producers. But in reality phytoplankton communities are a complex mixture of species with highly individual life histories; this also applies to their nutritional requirements. In view of their biological diversity it is most unlikely that all phytoplankton populations in a community of organisms are limited by a single factor (Zaucke et al., 1992; Markert and Geller, 1994). This is already evident from the biochemical and metabolic fact that plant organisms require a considerable number of other macronutrients (C, H, 0, N, P, S, K, Ca and Mg) and micronutrients (Cl, Si, Mn, Na, Fe, Zn, B, Cu, Cr, MO and Co) in order to exist. Tropical water systems seem to differ from those of the temperate zones in that they have a greater variety of factors limiting the growth of algae (Zaucke et al., 1992). For example, evidence of P-limitation emerges from bioassays of blackwater systems in the Amazon region (Zaret et al., 1981) and various man-made lakes in Zimbabwe (Robarts and Southall, 1977). On the other hand, similar experiments conducted on tropical lakes tend to indicate N-limitation; such water bodies include various man-made lakes in Brazil (Henry and Tundisi, 19821, Lake Titicaca (Wurtsbauch et al., 1985) and whitewater systems of the Amazon region (Zaret et al., 1981; Grobelaar, 1983).

The following sections are devoted to the initial results of a sampling campaign carried out on Argentinean lakes in the Andes; this campaign was intended as a pilot project for further investigations. As part of the work described, samples were taken from three different lakes to give a rough idea of: 1. The nutrient and heavy-metal content of the water; and 2. The composition of the phytoplankton and zooplankton. The objective of this and subsequent series of tests is to use such unpolluted lake systems as reference or baseline systems for comparative analyses of more polluted lakes, especially in the northern hemisphere. 2. Study area The lakes are located at 41s 71W (Fig. 1). The morphometric characteristics are given in Table 1. Although most of the lakes are set in a mountainous landscape where glacial geomorphology predominates, surrounded by well-developed forests, some, including Nahuel Huapi, may reach the fringe of the Patagonian Steppe on their eastern edges. The climate has been characterized as moderately continental (INTA, 1982), ranging from cold temperate near the Andes Mountains to arid and warmer (desertic) on the Patagonian Plateau (41% 68W). The prevaiIing westerlies lose most of their moisture over the Andes, resulting in a strong west-to-east precipitation gradient. At stations on the ArgentineChilean border (1020 m.a.s.1.) precipitation is 2700

B. Marker? et nl. /The Science of the Total Environment 206 (1997) l-15

-.e!?::::. ..2%: ... ARGENTINA ::c .:. .--:):/: -aI+% :/,:

?-

ril

Gutierrez LakeA y

20 Km

Fig. 1. Location of the sampling sites in the Patagonian lakes. Table 1 Morphometric characteristics of Andean-Patagonian given by Quiros and Drago (1985) Lake Area (kn?) Volume (hm3)

lakes

Z mean Z max (m) (m) 157 80 111 464 111 218 118 218

Nahuel Huapi 557 87 449 Gutierrez 16.4 1307 Mascardi 39.2 4213 Mascardi (Tronador arm> Mascardi (Catedral arm)

mm year- ; 50 km further east, at the extreme eastern point of Lake Nahuel Huapi (800 m.a.s.l.1, where the Patagonian Plateau begins, precipitation is 500 mm year-l. In respect of vegetation, the dominant stand in the area is a mixed forest of Nothophagus sp., Fitzroya cupressoides and Austrocedms chilensk, whereas undergrowth cover is dominated by bamboo-like canes (Chusquea sp.) and some shrubs (Berbeti sp.1. The region is

dominated by a mixture of crystalline igneous, volcanic and plutonic rocks. Pyroclastic rocks are of secondary importance, while metamorphic and sedimentary rocks occur in minor quantities. Valleys are dominated by glacial drift and alluvial outwash deposits. During the Pleistocene epoch this area was glaciated extensively and repeatedly (Flint and Fidalgo, 1964). The lakes are very dilute and tend to be silica-dominated (Pedrozo et al., 1993); most of them are of ultra-oligotrophic or oligotrophic status. Andean lakes have been classified by Quiros and Drago (1985) as warm monomictic, bearing a period of summer stratitication.
3. Materials &d methods

Three Patagonian lakes around Bariloche City were sampled for water and plankton analysis on 25 and 26 November 1993 (Fig. 1). Lake Mascardi

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was sampled at two sites: the Tronador and Catedral arms. Lake Guterriez was sampled at its extreme northern point, while Lake Nahuel Huapi was sampled off Puerto Paiiuelo and off Bariloche City, an area of low pollution on the coast (only samples for heavy-metal analysis were collected at this site). The Upper Manso River, the main tributary of Lake Mascardi, was also sampled. The sampling of these lakes was done during the snow melt period and it is representative of the end of water column mixing period (Fig. 2). Spring is a season with increase of light and water temperature, and accumulation of nutrients. Under these high availability of resources an algal maximum biomass is expected. The temperature profile was established using YSI equipment. Conductivity and pH, adjusted to 25C were measured with potentiometric equipment. Dissolved oxygen was measured by Winklers method, in Lake Nahuel Huapi only.

Water for nutrient analyses was collected using a Van Dorn bottle at depths of 5 m and 40 m. Samples for heavy-metal analyses were collected using a Hydro-Bios collector (MERCOS 436 252 model). The samples were immediately transferred to pre-cleaned polypropylene flasks sterilized with 1 ml of ultra-pure nitric acid. Phytoplankton samples were collected at depths of 5, 10, 20 and 40 m, then integrated to form one sample and preserved with acetic Lug01 solution. Chlorophyll concentration was measured in subsurface samples (N 0.50 m) extracted with 90% acetone (APHA, 1985). Eight hundred litres were pumped from a depth of 3-5 m with a peristaltic pump and passed through a 63-pm sieve and a 25-pm plankton net. For the purposes of this article the 63-pm fraction will be termed the zooplankton fraction and the 25-pm fraction the phytoplankton fraction. Both fractions were concentrated on a 0.45~pm membrane filter for

Temperature
5 6 7 6 9 IO

(C)
11 12 13 14

-30 --

-35 .-

-40 --

r
-+a
tb -c -cl 1

.Fig. 2. Temperature profiles of the Patagonian lakes: (a) Mascardi (Tronador arm); (b) Mascardi (Catedral arm); (c) Gutierrez; and td) Nahuel Huapi.

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heavy-metal analysis. A second aliquot of the 63-pm fraction was fixed with sugar-formalin (final concentration 4% volume) for zooplankton analyses including analyses of large ciliates. Nutrients and major ions were determined in the chemical laboratory of the Centro Regional Universitario Bariloche as follows: soluble reactive phosphorus (SRP) by molybdate blue, ascorbic acid reduction; total phosphorus (TP) by persulphate oxidation and SRP analysis; nitrates plus nitrites by cadmium column reduction and diazoic complexion. Ammonia was determined by the indophenol-blue method, calcium and magnesium by microtitration (EDTA), sodium and potassium by flame photometry, sulphates by turbidimetry and alkalinity by titration. All the above standard analytical methods were performed according to the recommendations of Standard Methods (API-IA, 1985). Dissolved inorganic nitrogen (DIN) was considered to be the sum of nitrates + ammonia + nitrites. Heavy-metal analyses were performed at UFZ with a commercial total reflection X-ray fluorescence spectrometer (TRFX, EXTRA II A, Atomika Instruments Ltd., OberschleilJheim/ Munich, F.R.G.) including Si(Li) detector (resolution 168 eV at 5.9 keV), electronics and a data processing system. Both MO-tube and W-tube excitation were used for analysis, with tube settings of 50 kV and lo-38 mA. The measuring time was uniformly 1000 s for MO-excitation and 2000 s for W-excitation, Details are given in Reus et al. (1993) and Friese et al. (1997). In addition, samples were measured with an Elan 5000 device from the Perkin Elmer/Sciex company. Rhodium was used as a response element so that matrix influences could be taken into account in the measurements. The samples were measured in diluted (1:lO) and undiluted form. Further details are given in Markert (1996). To decompose the plankton samples, 100 mg of the dried sample were measured into quartz vessels (30 ml) and mixed with 2 ml nitric acid. The samples were then enclosed in a high-pressure asher (HPA) after KNAPP in Markert (1996). Tri-distilled water was added to the decomposition solutions to make a final volume of 50 ml (Marker& 1996).

The quality of the heavy-metal analysis was controlled by independent methods (TXRF and ICP/MS) and by using standard reference materials (NIST 1643~ and BCR/CRM 414). The phytoplankton was counted using an inverted Hydro-Bios microscope. The diversity index was calculated by the Shannon-Weaver method. Crustaceans, rotifers and ciliates were counted in Bogorov-chambers with an inverted microscope at a 40 X and 100 X magnification, respectively. The abundance of the large, coloured ciliates of the genus Stentor was determined in parallel with the rotifers. Furthermore, Stentor was counted on the filters (5 m and 40 m) according to WSlfl (1995). The determination of the biomass of ciliates, rotifers and crustaceans follows the methodology given in detail by Wijlfl (1995).
4. Results and discussion 4.1. Water temperature

On the sampling days the lakes showed a water-temperature profile typical of the beginning of the stratification period (Fig. 2). Lakes Gutierrez and Nahuel Huapi showed the smallest difference between surface and deeper waters, while the Catedral arm of Lake Mascardi exhibited stratification with the thermocline between 12 and 28 m. Other physical characteristics (pH, conductivity, transparency, depth, geochemical composition) are given in Tables 2 and 3.
4.2. Quality control 4.2.1. By use of standard reference materials

A comparison of measured and certified values for the standard reference materials investigated is given in Table 4.
4.2.2. By comparison of different analytical methods

Figure 3 shows the relationship between standard and TXRF methods applied to the analysis of K, Ca and S. Although the replication is low,

B. Markert et al. / The Science of the Total EnvironrPtent 206 (1997) l-15

Table 2 Physical and chemical characteristics of the surface water of Andean-Patagonian Lake Nahuel Huapi Gutierrez Mascardi (Catedral arm) Mascardi (Tronador arm) a At 5-m depth. Date 26 25 25 25 November November November November 1993 1993 1993 1993 Time 10.00 h 19.30 h 10.00 h 13.30 h PH 7.01a 7.48 7.37 7.39

lakes Transparency Cm) 15 13 15 4 Depth (m) in sampling site 307 100 300 90

Conductivity ($4 cm-) 30 47 43 42

the fit is good for Ca and S, while it is rather poor for K. The microtitration method used to estimate calcium seems to be very effective at the low levels typically found in Andean-Patagonian waters. For sulphates the turbidimetry method with barium chloride is reliable up to approximately 1 mg SOi- 1-i. The concentration of sulphates in Andean-Patagonian waters is close to the detection limit; the fit against TXRF was therefore lower than for calcium. For potassium the figure shows a very slight gradient, suggesting that flame photometry is unsuitable for the very low concentrations characteristic of AndeanPatagonian lakes. It is quite apparent that the TXRF method increases the sensitivity and discriminating power of the analysis.

4.3. Comparison of the element concentrations in relation to water depth Table 5 summarizes the results of the chemical measurements obtained by standard methods (API-IA, 1985) and Table 6 the multielemental composition ascertained by TXRF and ICP. In Lake Nahuel Huapi, neither of the methods revealed differences between the two depths. The only exception was the iron content determined by TXRF, which was higher at 40 m than at 5 m. The sample taken from a polluted site showed a significantly higher concentration of Fe and Zn than those from unpolluted sites. This may be due to the input of contaminants from Bariloche City.

Table 3 Main elementary composition (%) of rocks from Nahuel Huapi, Mascardi and Gutierrez lakes Lakes Rocks Gutierrez + Mascardi + Nahuel Huapia Plutonic Metamorphic Grandodioritic Amphibolites 67.57-70.48 0.43-0.89 14.85-16.22 3.62-4.99 0.28-0.95 3.01-4.03 0.03-0.086 1.06-1.49 4.21-5.5 1.98-2.76 0.11-0.19 52.67-59.86 0.46-0.87 17.05-18.85 7.34-9.81 4.03-5.25 0.13-0.20 3.53-5.22 7.21-9.79 2.78-3.84 0.31-0.76 0.10-0.19 Nahuel Huapib Pyroclastic tuffs Nahuel Huapib Volcanic basalts, andesites, dacites 49.86-69.43 0.41-1.17 14.49-18.06 1.80-5.73 0.71-3.90 0.12-0.19 0.52-5.36 1.19-7.99 3.14-3.91 0.84-3.88 0.05-0.25

SiO, TiO,
%03

Fe0 MnO NO CaO Naz W pzos a Data from Dalla Salda et al. (1991). b Data from Spaletti et al. (1982).

FeA

62.66-74.96 0.17-0.90 12.21-17.57 0.67-3.02 0.07-2.04 0.02-0.22 0.34-1.17 0.45-2.60 1.90-5.45 0.45-4.75 0.02-0.10

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Table 4 Comparison of measured and certified values of the standard reference materials analyzed NET 1643~ As Ca Cd
co 82.1

K WV)
450 '400 350 300 250 . 200 150 100 50 0 0 100 200 300 -----.
l .

.
.
l . .

ICP/MS
81.6

TXRF
86.7

BCR/CRM
414a 6.82 (65000)

ICP/MS
6.88 68420 0.347 1.48 2.5 28.8 1853 272 19.7 3.3 250 105

12.2
23.5

12.8
24.1 17.8 22.8 26.4 17.2 23.2 105.6 36.3 60.7 36.5

Cr
CU

19
22.3 106.9

Fe Mn Ni Pb Sr Zn

35.1
60.6 35.3

33.8
62.8 35.9

0.383 (1.43) 23.8 29.5 1850 299 18.8 3.97

y = 0.0842x+ 320.35 R'= 0.0112 400

/ 500

TXRF

W
9000 T

Ca (pg.f) 6000J, .

73.9

79.5

82.5

261
112

a Was not measured by TXRF. Values are given in pg g- (ppm) for BCR/CRM 414 on a dry wt. basis and in pg 1-i (ppb) for NIST 1643~. Figures in brackets give indicative values (not certified).
0 2000 4000 6000 6000 10000

The TXRF analysis of Lake Gutierrez (Table 6) showed differences between 5 m and 40 m for sulphur only (10% higher at 5 m). This result coincides with the difference ascertained by turbidimetry (Table 5). The TXRF analysis produced similar values at both depths for potassium, but flame photometry revealed a difference of 67%. This is probably an error of the flame method resulting from the low K content of the lake water. For magnesium, the titration method showed a difference of 30% between the two depths. However, since the concentration of most elements is similar at both depths, the difference in magnesium content is more likely to be artificial. In the Catedral arm of Lake Mascardi the differences in ion content in terms of percentages were greater at 40 m than at 5 m, with the exception of Si and K. The differences are: HCO,, 8%; Ca, 15%; SO,, 22%; Na, 44% and Mg, 240%. Such differences were also detected by TXRF: S, 88%; K, 114%; Ca, 101% and Sr, 98%, although the reason for the different concentration at these depths is not clear. The possibility of sample contamination can be rejected, since we used different glassware for each method. The TXRF

TXRF

s bK3.1)

500

1000

1500

2000

S(TXRF)

Fig. 3. Comparison of the results for S, Ca and K between standard methods (APHA, 1985) and TXRF.

method seems to bring an improvement in the detection level and supports the results obtained by standard methods. The different concentration at the two depths may be explained by the dilution of surface waters caused by the input of rain and melted snow. The beginning of the stratification period prevents mixing with epilimnetic waters. In the Tronador arm of Lake Mascardi the concentrations ascertained by the TXRF method were higher at 5 m than at 40 m (Table 6) for S, 33%; Fe, 33%; Zn, 33%; K, 38%; Ca, 36% and

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Table 5 Major ion concentration (PM) of Andean-Patagonian Lake Nahuel Huapi Difference % (40 m/S m) Gutierrez Difference % (40 m/5 m) Mascardi (Catedral arm) Difference % (40 m/5 m) Mascardi (Tronador arm) Difference % (40 m/5 m) Patagonian lake (average) Freshwater world averagea 5 40 5 40 5 40 Depth SiO, 169.17 158.67 -6 186.00 184.30 -1 159.83 160.33 0 164.27 169.10 3 168.96 Na+ 69.60 69.60 0 69.60 82.65 19 39.15 56.55 44 60.90 60.90 0 63.62

lakes analyzed by standard methods (APHA, 1985) K+ 7.67 7.67 0 7.67 12.79 67 7.67 7.67 0 Mg2+ 28.80 28.80 0 41.14 53.49 30 20.57 69.94 240 Ca2+ 72.36 74.85 3 182.14 194.61 7 117.27 134.73 15 137.23 144.71 5 132.24 374.25 HCO,93.44 90.16 -4 250.82 236.07 -6 157.38 170.49 8 150.82 155.74 3 163.11 960.66 20.03 CI14.10 SO,2-12.50 12.50 0 27.08 30.21 10 21.88 28.13 22 30.21 30.21 0 24.09 1419 1414 Sum Z+ 279.58 284.57 523.83 591.63 322.50 473.57 411.41 418.15 Sum A132.55 115.16 304.99 296.48 221.15 226.74 225.25 216.15

(m)
5 40

10.23 32.92 10.23 28.80 0 -13 8.95 58.83 38.06 168.69

14.02

16.05

200.00 273.91

220.01 116.67

a From Livingstone (1963) in Home and Goldman (1994).

Sr, 38%. On the other hand, standard methods (Table 5) only showed differences in Mg concentration (12% higher at 5 m). The Upper Manso River influences the upper layer of the Tronador arm, as is apparent from the higher sulphur, iron and calcium contents. The Upper Manso River conveys a considerable amount of dissolved salts and suspended particles from the Tronador glacier.
4.4. Transparency, chlorophyll and nutrients

Water transparency was high (13-15 m); this was to be expected in view of the low chlorophyll content, which ranged from 0.10 to 0.24 mg rne3. Only in the Tronador arm of Lake Mascardi was the transparency relatively low (4 m) due to the influence of suspended solids from the Upper Manso River. All forms of measured nutrient concentrations were very low too (Table 71, and within the range for oligotrophic or ultraoligotrophic lakes of the northern hemisphere according to the OECD (1982). The DIN/TP ratio was higher (Table 8) in Lake Nahuel Huapi (6.8-9.9) than in Lake

Gutierrez (1.2-5.0) and in the two arms of Lake Mascardi (0.6-1.9). This correlates with the higher percentage of Cyanophytes in Lake Mascardi (mainly in the Tronador arm) and Lake Gutierrez (Table 9). Cyanophytes are better competitors under conditions of low N/P ratios, i.e. below 7:l (Smith, 1983). The Fe/SRP ratio ranged between 0.6-1.8 in Nahuel Huapi, 2.2-3.0 in Lake Gutierrez and 4.2 in the Catedral arm of Lake Mascardi (Table 8). In the Tronador arm of Lake Mascardi the Fe/SRP ratio was noticeably higher (11.3-14.3). The main tributary of Lake Mascardi is the Upper Manso River, which discharges into the Tronador arm and brings in a heavy load of glacial sediment rich in Fe and S. The influence of this input is apparent in the sulphur concentration of the Tronador arm, which is similar to that of the Upper Manso River but about twice that of the Catedral arm. It has been suggested (Brand, 1991) that the Fe/PO, ratio of the nutrient inputs influences the ratio of procaryotes to eucaryotes in marine phytoplankton communities, with high Fe/PO, ratios favouring procaryote growth. The cyanophyte density in the Tronador arm of Lake

B. Markert et al. /The Science of the Total Environment 206 (1997) 1-15

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Nr? 00 vv WC-4 dd vv

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Mascardi was higher than in the Catedral arm; this coincided with a high Fe/SRP ratio and the low N/P ratio mentioned above.
4.5. Chemical classi@ation of the lakes investigated

and HCO, > SO;- > Cl-

Table 2 shows that the lake waters have a neutral or slightly alkaline pH (7.01-7.48) as the vast majority of Andean-Patagonian lakes around Bariloche (Pedrozo et al., 1993). Table 3 gives the main elementary composition (%) of rocks from Nahuel Huapi, Mascardi and Gutierrez lakes. The waters are very dilute solutions (conductivity between 30 and 46.6 $S cm-) dominated by calcium, bicarbonates and dissolved silica. The ionic composition is largely below the world average given by Livingstone (19631, in: Horne and Goldman (1994). The relative significance ( peq 1-l ) of the major cations and ions is: Ca2+ > Mg2+ > < Naf > K+
Table 7 Mean element composition ( pg 1-l) of Andean-Patagonian and Lake Constance As Ca Cd < 0.2 0.2 0.2-0.5 O-10 7800 0.005-0.01

Major ions show an excess of cations in the charge balance, ranging from 19 to 36%. These percentage differences were calculated according to Lesack et al. (1984) as:

This ionic imbalance cannot be explained by the SiO, concentration because silicates are ionized as H,SiO; at high pH values (Drever, 1982). Dissolved silica is below the world average (Table 7). These features of Andean-Patagonian lakes can be attributed to the dominant igneous rock (Pedrozo et al., 1993). The Andean-Patagonian lake water (LWP,,,) showed concentrations of Cr, Sr, Zn, Cu, Co and

lakes compared with reference freshwater, world average freshwater Cl co Cr < l- < 2 1 0.1-1.4 CU < 0.5-2.6 3 0.83-15 5600 10 0.32-0.95 Fe 18.8 500 K 361 2000

Mg 925 4000

Patagonian lakes (avg> nd-< 1.2 5298 Reference freshwater (Markert, 1994) 0.5 2000 Fresh water world average (Margalef, 1983) 1.7-3.0 (Livingstone, 1963) Lake Constance (Sigg, 1985) 15 000

569 < 0.2 8000 0.5 0.02-0.6 o-2 0.8

6.3-60 1.5-33 - 40 2300 4100

Table 7 (Continued) Mn Patagonian lakes (avgl Reference freshwater (Markert, 1994) Fresh water world average (Margalef, 1983) (Livingstone, 1963) Lake Constance (Sigg, 1985) <l-<4 5 35 Na 1463 5000 6300 0.04-0.010 Ni < 0.5- < 1 0.3 O-10 P 8 20 Pb nd- < 2.2 3 o-2 5973 S 1063 4000 Si 4731 4000 5600 6000 Sr 18 50 6.3-60 Zn 2.9 5 1.5-33 10 0.65-1.96

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11

Table 8 Nutrient and chlorophyll concentrations in Patagonian lakes Lake Nahuel Huapi Gutierrez Mascardi (Catedral arm) Depth NNO, + NNO,

(m)
5 40 5 40 5 40

CpgNl-1

NNHh+ (,qNl-l) 20 25 8 10 6 3 8 9

DIN/TX :gPI-1 5 5 10 15 5 7 7 9 :;;P1-) 3 3 3 2 1 2 2 2 $gFel-) 3 8 10 11 13 52 35 9.9 6.8 5.0 1.2 1.4 0.6 1.4 1.9

Fe/SRP 1.1 3.2 3.9 5.4 7.6 25.8 20.3

29 9 43 9 2 2 3 8

Chlorophyll aa (mgCh1 a rnm3) ___~-__ 0.12 0.24 0.10 0.14

Mascardi 5 (Tronador arm) 40 a Taken at 0.5 m.

Pb (Table 7) that were of the same order as the freshwater world average (FWW,,) given by Margalef (1983). The remaining elements fall below or are around the limit for the FWW,,. It is surprising that the Cu, Zn, Pb and Cd levels in Andean-Patagonian lakes are similar to or higher than those given by Sigg (1985) for Lake Constance, that receives far more contaminants. However, as far as these heavy metals are concerned, the waters of the AndeanPatagonian lakes and those of Lake Constance were close to the lower range of FWW,,. The Fe and Ca concentrations in reference freshwater (REFW) are the only two that differ greatly from the FFWaVg given by Horne and Goldman (1994). It is instructive to look at the difference between the average lake-water composition of Andean-Patagonian waterbodies (LWP& and REFW (Markert, 1994). With the exception of calcium, which is twice as high as in REFW, the element concentrations (S, Fe, Mg, Na, K and Sr) are lower than in REFW. 4.6. Phytoplankton composition

similar phytoplankton biomass (134 mg mw3), but the densities were very different (1136 cells ml- in the Tronador arm and 288 cells ml- in the Catedral arm>. Lakes Gutierrez and Nahuel Huapi also showed a higher biomass level (N 300 mg rne3) than Lake Mascardi, but the density was very different (2256 and 170 cells ml-, respectively). Chlorophyceae and Prymnesiophyceae groups dominated in density in the Tronador arm, but their contribution to the total biomass was low. Dinophyceae was the dominant group in the biomass (54%). The Catedral arm was dominated by Cyanophyceae and Prymnesiophyceae in respect of density, but the group that contributed most to the biomass was Dinophyceae (60%). Bacillariophyceae were dominant both in density and biomass in Lake Nahuel Huapi and were absent from the Tronador arm of Lake Mascardi. Lake Gutierrez showed Cyanophyceae to be the dominant group in terms of density, but the most significant group in respect of biomass was Dinophyceae (51%). 4.7. Zooplankton composition

Phytoplankton density ranged from 170 to 2256 cells ml-, while phytoplankton biomass ranged from 134 to 312 mg m -3 (Table 9). The greatest divergence (H= 3.23) was ascertained for the Catedral arm of Lake Mascardi, and the lowest value (H = 0.78) was estimated for Lake Gutierrez. The two arms of Lake Mascardi showed

Zooplankton, including crustaceans, rotifers and large ciliates, from Lake Mascardi (Tronador, Catedral) and Lake Gutierrez were counted quantitatively. Due to the filtering procedures, densities of rotifers and ciliates were most probably underestimated. The zooplankton diversity (crustaceans, rotifers)

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Table 9 Phytoplankton of Lakes Mascardi, Gutierrez and Nahuel Huapi Mascardi Tronador D B Cyanophyceae Anabaena sp.
Chrococcus minor Dactilococopsis raphidioides Gomphosphaeria aponina Merismopedia gIauca

Mascardi Catedral D B 27 6 44 16 93
0.5

Guttierrez D

Nahuel Huapi D B

302 302 31 373 404

9.1 9.1 3.1

0.1 1.3 2011 0.2 2.1 2011 20.1 20.1

24 24

0.7 0.7

Total Chlorophyceae
Cholorococal spheric Elakatoti gelatinosa Geminella sp. Scenedesmus ecomis

0.3 37.3 40.4 0.4 0.7

11 11 1 1

1.1 11 1.1 0.9 0.9 11 1.1 1.1

Total Zygophyceae cosmarium sp. Total Cryptophyceae

C?yptomonas Rodhomonas erosa lacustris

Total Chtysophyceae
Dinobvon divetgens Mallomonas sp. Ochromonas sp.

4 22 26

0.2 2.0 2.2

6 35 41

0.4 3.2 3.6

1 25 26 44

0.1 2.3 2.3 83.6 0.1 0.1 83.8 2.1 2.1 136.0 22.5 158.5 7 14 73 38 132 170 2.27 55.3 11.2 189.8 36.9 293.2 298.9 2 1 3 3.8 0.1 3.9

40 40
parva

1.2 1.2 8.9 8.9 72.0 72.0

cysts Total Prymnesiophyceae

Chlysochromulina

1 16 9 26 91 91 10 10 3 6 3 8 20

0.2 0.5 0.9 1.6 2.3 2.3 80.0 80.0 23.7 4.8 7.8 7.8 44.1 134.4

3 1 48 84 84 17 5 22

Total Dinophyceae
Gymrwdinium Peridinium

355 355 9 9

sp. sp.

Total Bacillariophyceae
Aulacoseira granulata Cyclotella stelligera Rhizosolenia eriensis Synedra acus

50 3 53 2256 0.78

40.0 2.9 42.9 311.7

Total 1136 Diversity index Notes: D, density (cells ml-); 2.07 B, biomass (mg mv3). 133.8

288.0 3.23

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Table 10 Zooplankton of Lakes Mascardi, Gutierrez and Nahuel Huapi Species Mascardi Tronador D Nauplia (calanoid)
Boeckella gracilipes

Mascardi Catedral D 0.8380 0.0026 0.0013 0.0013 0.0013 1.5100 2.35 16 B 0.1620 0.0042 0.0018 0.0017 0.0013 0.0021 0.17 1.2000

B 0.6230 0.0670 0.0050 0.0019 0.0077 0.0160 0.0035 0.72

Gutierrez D 0.200

B 0.040

3.1150 0.1580 0.0380

Cl-C5 Male
Mesocyclops Cl-C.5 longisetus

Male
Bosmina

sp.

Rotifera
Stentor araucanus Stentor amethstinus

0.0130 0.0130 0.0150 0.2500 3.6000

Total
Stentor sp. on filters 5 m: Stentor araucanus 5 m: Stentor amethystinus 40 m: Stentor araucanus 40 m: Stentor amethystinus

0.520 0.700 24 19 44.42 150 73 3

0.520 0.008 1.800 1.420 3.79 11.250 5.4700 0.2200

6 2 B, biomass (mg mm3).

0.4500 0.1500

Notes: D, density (cells ml-);

in Lake Mascardi and Lake Gutierrez was low, which is typical for oligotrophic north Patagonian lakes (Wiilfl, 1995). Whereas in Lake Mascardi only calanoid (Boeckellu grucilipes) and one cyclopoid copepod (Mesocyclops longisetus) were registered. In Lake Gutierrez only calanoid nauplia were found. In both lakes, Bosmina represented the only cladoceran species. The most important rotifers in Lake Mascardi were Keratella cochlearis, Polyatihra sp., Ascomo?pha sp.,
Collotheca pelagica, Trichocerca pocillum, Lecane luna, Synchaeta sp. and Keratella cochlearis, Polyurthra sp. in Lake Gutierrez, respectively.

The zooplankton community of the two sampling stations of Lake Mascardi were quite similar in species composition, densities (2.35, 3.60 Ind 1-i) and biomass (0.72-0.17 pg C 1-l). The density and biomass of crustaceans and rotifers in Lake Gutierrez fall in the same range as those in Lake Mascardi. In contrast to Lake Mascardi, the zooplankton community in Lake Gutierrez was dominated by high abundance and biomass of Chlorella-bearing, large ciliates (Stentor aruucanus, S. amethystinus). Stentor is a common inhabitant of many (ultra)oligotrophic, north Patag-

onian lakes reaching a high proportion of zooplankton biomass (Wolf?, 1995; Geller et al., 1996). In Lake Gutierrez, Stentor amounted for 3.22 pg C L- or 85% of total zooplankton biomass. This value, calculated from net samples, probably underestimated the biomass of Stentor. The densities of the ciliate concentrated on filter are about five times higher than the net samples (Table 10). In comparison with Lake Mascardi, the zooplankton biomass in Lake Gutierrez was approximately 5-20 times higher. As the filter samples from Lake Mascardi show, Stentor was present in this lake in small concentrations, too. It is likely, that Stentor is an important component of the zooplankton community of the lake.
4.8. Chemical composition of the phytoplankton and zooplankton

Table 11 summarizes the element concentrations in the phytoplankton and zooplankton of Lake Mascardi at two different sites (Catedral and Tronador). It is noticeable that in all cases the phytoplankton shows greater accumulations of the minerals potassium and calcium and the

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Table 11 Element content of phytoplankton and zooplankton (P and Z) in Lake Mascardi at two different sites in mg kg- dry wt. Sample M. Tronador P M. Tronador Z Ratio P/Z M. Catedral P M. Catedral Z Ratio P/Z .-__ As 7.9 7.8 1.0 7.3 7.4 1.0 Ca 1194.0 392.0 3.0 933.0 88.0 10.6 CU 20.4 2.0 10.2 29.8 1.7 17.5 Fe 3807.2 291.2 13.1 741.2 69.2 10.7 K 455.5 198.5 2.3 293.5 74.5 3.9 Mn 145.6 14.0 10.4 30.6 4.7 6.5 Pb 61.7 64.7 1.0 49.7 66.7 0.7 S 158.5 221.5 0.7 230.5 1232.5 0.2 Sr 7.5 2.6 2.9 5.0 0.6 9.0

essential trace elements (manganese, iron, copper and zinc) than the zooplankton. An exception is sulphur, that occurs in greater concentrations in zooplankton. The reason would seem to be the higher protein content of the zooplankton. In the case of the non-essential elements that are toxic at higher concentrations (arsenic and lead) it is noticeable that the levels are more or less similar for phytoplankton and zooplankton. This indicates that these substances are mainly taken up passively from the stream of water and deposited in the cell bodies of the individual organisms. In general it can be said that the organisms acctmmlate all the elements loo-fold to lOOO-fold in relation to the surrounding medium (see Table 6). 5. Conclusion These first results on biological and chemical compositions clearly reflect the oligotrophic to ultra-oligotrophic status of the Argentinean lakes. These lake systems can be used as reference or baseline systems for further comparative studies of more polluted lakes, especially in the northern hemisphere. Acknowledgements We wish to thank Mr Pablo Gonzalez and Mr Walter Lopez for their help in collecting the samples and Lit. Pedro Temporetti, Bioq. Lucia Resseli and Lit. Patricia Satti for the laboratory analyses. M. Mages and C. Hoffmeister performed the TXRF and ICP-MS measurements, respectively. Mrs Marion Brasse, Buchholz, F.R.G., is thanked for polishing the English of the manuscript.

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