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and CO
3
2
according to the
German Standard Methods for pK
a
and pK
b
analysis (DEV 2005). The density of the water was cal-
culated under consideration of salinity, local pressure and temperature using the formula of CHEN and
MILLERO (1986) for natural waters and is expressed as
(S, T, Psurface)
(= density 1000 kg/m
3
); salinity was
calculated by the total ionic content. Oxygen concentration within the carbonate precipitates was deter-
mined using optical oxygen sensor of 2 mm with a Fibox 3 oxygen meter (PreSens, Germany). Water
samples were taken using a Ruttner water sampler (Hydrobios, Germany) at 78 m (9 samples in 178 m;
N 01811.4 W 782210.9) and 148 m depth (13 sample in 1148 m; N 01742.3 W 782126.7;
Fig. 2), portions of the water samples were filtered immediately, using 0.45 m cellulose-acetate filters
for cation and anion analyses. Water samples for chemical analyses were preserved by HNO
3
as well
as HCl (both at pH ~ 1), using HDPE bottles.
Gas sampling was done directly with GC vials at the lake shore and on Island Yerovi.
Samples of suspended material for Scanning Electron Microscopy was obtained by filtration of
250 mL lake water from the water sampler, immediately after sampling in the boat, using 0.4 m poly-
carbonate filters (Nuclepore). The wet polycarbonate filters were stored in plastic bags with taps soaked
with formaldehyde (37%) for preservation.
Sediment samples were collected by a sediment gravity corer, 5 cm with a sediment capturer. Sedi-
ment sampling was recognized to be very difficult due to only a thin sediment layer on the stony floor
and due to sediment oversaturation by gases, which led to the loss of sediments while degassing during
lifting of the equipment. Sediment samples were prepared using an HCl/HNO
3
acid digestion method
(VDLUFA 1991) and chemically analysed using the analytical methods mentioned below. Sedimentation
behaviour of seston was studied using 8 sediment traps, 8 cm , 50 cm length, which were exposed
in the western bay of the lake for two periods, each one for 2 weeks at depths of 15, 30, 50 and 70 m
(N 01815.3 W 782214.9). Samples were preserved with 4% glutaraldehyde solution for Scanning
Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS) analyses.
A SONY HCR-HC16E digital video camera was modified as an underwater camera and was pro-
tected by a purpose-built aluminium housing and equipped with 4 underwater lamps (NEMO 8C Xenon,
14 watt). With this camera, sediment type and gas emissions with sediment resuspension were regis-
106 G. GUNKEL and C. BEULKER
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.revhydro.com
tered as well as the penetration of the sediment core sampler into the sediment. During two campaigns,
divers were used for sampling and underwater filming, and the experiences of the divers were helpful
for further investigations.
Phytoplankton samples were collected from the water sampler (11 depths in 0145 m), preserved with
Lugols solution. Zooplankton was collected using a plankton net (55 m) with trapping mechanism (a
profile was made by 8 sections from 0145 m), and preserved with HANEY and HALL solution. Plants
were collected using a macrophyte anchor (KIERSCH et al., 2004) in 1998 within 6 profiles from the lake
surface down to 40 m. Sampling of the invertebrates was done by a fine sieve and a plankton net at
6 different positions in the littoral zone, surficial and down to a few meter water depth, preserved with
4% formaldehyde. Fish control was done by using a sonar (Garmin Fishfinder 250 C).
2.3. Chemical Analyses
Nitrite was determined using the Merck test (Aquaquant, 0.005 0.1 mg L
1
NO
2
) immediately after
the sample was collected. Chemical analyses for CO
2
, HCO
3
and CO
3
2
were undertaken on the sam-
pling day applying the German Standard Methods for pK
a
and pK
b
determination (DEV 2005). Oxygen
concentration was analysed using the WINKLER method, soluble reactive phosphorus (SRP), ammonia
and nitrate were analysed according to US APHA Methods (1998) in the Laboratory of Chemistry,
University Central, Quito, Ecuador. Water chemistry of the non-reactive cations and anions were carried
out in the laboratory of the Berlin University of Technology, Dept. of Water Quality Control, Germany,
using the acid-preserved water samples. Water samples for the determination of total amounts of ions
were digested in an autoclave under acidic conditions using K
2
S
2
O
8
(121 C, 1.3 bars for 2 h). Total
phosphorus and total nitrogen were analysed photometrically by flow injection analysis in accordance
with EN ISO 15681-1 (2004) and 11905-1 (1998), respectively (Foss Tecator FIAstar 5000) with a
detection limit of 0.005 g L
1
.
The cations Ca
2+
, Na
+
, Mg
+
, K
+
, As
2+
and Fe
3+
were analysed by flame AAS (GBC Scientific Equip-
ment, Pty. Ltd. Victoria, Australia), lower concentrations of Li
+
, Fe
3+
and Mn
2+
(< 0.1 mg L
1
) were ana-
lysed by graphite furnace ASS (Varian Spectra A-400). The anions Cl
, SO
4
2
and NO
3
were analysed
using an ionic chromatograph (AS 50 Dionex) with CD 20 detector, GD 50 gradient pump and an AS
11 column for separation. Boron was determined photometrically in accordance with DIN 38405-D17
(DEV 1981; Dr. LANGE LCK 307). Analyses of the gases CO
2
, CO, O
2
, N
2
, N
2
O, and CH
4
were carried
out using a GC with FID and TCD detectors at the Leibniz-Institute of Freshwater Ecology and Inland
Fisheries, Berlin, Germany.
14
C-analyses of soils were carried out by the Leibnitz Institute for Applied
Geosciences, Hannover, Germany.
2.4. Biological and Microscopic Analyses
The determination of seston (bacteria, precipitations, detrital flocs) was done by Scanning Electron
Microscopy as with Energy Dispersive Spectroscopy. For SEM-EDS analyses the wet polycarbonate
filters were fixed on a bracket, air dried and then sputtered with gold or carbon. A SEM-EDS Hitachi
S 2700 electron microscope was used with an acceleration voltage of 20 kV and an IDFix hardware
and software from SAMx for analysis.
Phytoplankton was determined qualitatively using a Zeiss Laboval 4 and quantitatively according
to the Utermhl method (DEV 2007) using a Olympus microscope CK30, about up to 5 transects of
the Utermhl chamber (2 to 50 ml) were counted for quantitative determination, for the calculation of
the biovolume 20-100 cells were measured in the Zeiss using an ocular with a reticle. The biovolume
was calculated using related geometrical bodies (PADISK and ADRIAN, 1999). Diversity, abundance and
biovolume were determined for each of the 11 sampling depths.
Determination of macroinvertebrates was carried out by Dr. CORREOSO, Catholic University of
Quito.
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2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.revhydro.com
3. Results
3.1. Lake Formation and Morphometry
The strato volcano Cotacachi was active during the middle Pleistocene period up to
630 000 years ago (INECEL 1983), which documents the end of volcanic activities. Cui-
cocha, a parasitic volcano of the Cotacachi, began its activity with a series of eruptions
45003000 years BP followed by the collapse of the dome and a caldera was formed.
Final eruptions took place more or less simultaneously about 14501330 BP and led to
the formation of four domes within the caldera, nowadays the islands of Yerovi and Wolf
(GRUPE et al., 2008; Fig. 1), and the differentiation of the caldera into two main basins of
different depth. Following the extinction of the Cuicocha volcano, the caldera was partly
filled with sediment from the catchment area; fine grained and clay material sealed existing
fissures and fractures within the caldera and after the end of the colmation process, lake
water accumulation began, probably a few hundred years ago.
Nowadays Lake Cuicocha is situated about 3072 m a.s.l. and has a maximum water depth
of 148 m, a mean depth of 72 m; the volume amounts to 0.28 km
3
and the lake surface
3.78 km
2
(Table 1). The lake morphometry is determined by the caldera flanks with steep
inclinations, and in some parts of the crater rim, a water depth of 100 m is reached only 20 m
from the shore line. The bathymetric map (Fig. 2) was developed on the basis of 1250 data
points and shows two lake basins, one with a maximum depth of 148 m extending east of
the islands, and the other with a depth of 78 m, situated in the western area of the lake.
From the catchment area, water inflow into the caldera occurred until recently, however,
the watershed is small (18.2 km
2
) with a surrounding factor of only 5.9. Additional hydro-
thermal water has been entering into the caldera and mainly influences the water chemistry.
The lakes water conductivity clearly points to a significantly increased ionic content com-
pared with the inflow water of the catchment, and a rough estimate shows in total about
30% hydrothermal water, based on rain water inflow and recent hydrothermal water quality
(see below).
3.2. Lake Stratification and Mixing Processes
Lake Cuicocha is a weakly thermal stratified lake with a monomictic cycle, and overturn
occurs during the windy dry period from July to October (Fig. 3). The epilimnion stretches
down to 40 m. Temperature differences between surface waters (approx. 1618 C) and the
deep water body were small and amounted to about 2 C during stratified periods. The stabil-
ity of the stratification in Lake Cuicocha was further reduced due to nocturnal cooling and
deep lake mixing, the so called atelomixis, which was analysed in detail in the nearby Lake
San Pablo (GUNKEL and CASALLAS, 2002, 2002a). During a 24 hour period in March during
stratification period (Fig. 4), heating occurred in the upper water body of 50 m, mainly as
a consequence of daily radiation input; and in the deeper water layer of 70 to 100 m depth
a decrease in temperature was registered due to convection currents which occurred during
the night after cooling of the surface layer.
An input of hydrothermal water was detected in the 78 m lake basin, and near the lake
bottom both temperature and conductivity increased significantly (T = about 0.04 C;
Cond = about 25 S cm
1
; Fig. 5), resulting in a decreasing density of
(S,T)
= 0.00915 kg m
3
(P < 0.0001) in the 70 m water depth compared to the 55 m depth. In the whole lake density
of the water increased from the surface ( = 999.0191) to the ground ( = 999.2731 in 78 m
depth, = 999.2986 in 148 m depth), but no chemocline was build up and the hydrothermal
water was quickly mixed with the lake water. The inflow of hydrothermal water at the lake
floor could not be quantified. Well known is the hydrothermal water inflow at the shore line
108 G. GUNKEL and C. BEULKER
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.revhydro.com
of Island Yerovi, which was used for water chemical analyses, in 2005 an additional inflow
of hydrothermal water was observed near the Island Yerovi in 510 m water depth.
The conductivity profile in the 148 m lake basin showed no increase, and an inflow of
hydrothermal water must be excluded.
In the western basin of Lake Cuicocha, at 78 m depth, a permanent emission of CO
2
took
place detected by sonar and few gas bubbles reached the lake surface. The composition of
the gas (see below) clearly pointed to the volcanic origin. The emission of the gas led to a
resuspension of sediments proved by sonar and underwater filming and to a partial mixing
of the water body by billows during upraising of gas bubbles.
Figure 1. Lake Cuicocha with domos Yerovi (left) and Wolf (right).
Table 1. Morphometric data of Lake Cuicocha.
Parameter Lake Cuicocha
Lake coordinates
NorthSouth N0 18 49.9 W78 21 40.1 N0 17 32.6 W78 21 28.8
WestEast N0 18 22.1 W78 22 33.1 N0 18 03.9 W78 20 52.8
Watershed (km
2
) 18.2
Surrounding factor 5.9
Lake water level (m a.s.l.) 3,072
Length (m) 3,238
Width (m) 2,232
Shore line without islands (km) 10.14
Shore line with islands (km) 14.43
Shore line development without islands 2.9
Shore line development with islands 4.2
Surficial area (m
2
) 3,781,012
Maximum depth (m) 148
Mean depth (m) 72
Relative depth (%) 3.3
Volume (m
3
) 282,053,575
Volume of the islands underwater (m
3
) 103,648,907
Volume of Jerovi above water line (m
3
) 9,011,699
Volume of Wolf (m
3
) above water line (m
3
) 29,381,720
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2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.revhydro.com
3.3. Water Chemistry and Post-Volcanic Activities
Gas analyses showed that the main composition was CO
2
(51%) and N
2
(23%) with
smaller amounts of O
2
(3.0%) CH
4
(1.7%) and CO (0.3%). Gaseous emissions of boron
compounds led to increased BO
4
3
concentrations in the lake water, a typical component of
volcanic gases.
The pH of Lake Cuicocha in the epilimnic water (040 m) was weakly alkaline, the pH
was raised to 8.3 as a consequence of loss of CO
2
from the oversaturated water to the atmos-
phere and primary production. The hypolimnion (> 40 m) exhibited neutral conditions with
a pH down to 7.0 (Fig. 6), caused by CO
2
input from volcanic gases from the lake floor in
the western basin (GUNKEL et al., pers. com.).
The carbon dioxide concentrations were elevated in the whole water column with the
highest concentrations in the deep water layers > 60 m, a consequence of the hypolimnic
gas input in the shallow basin, combined with high wind-induced horizontal water cycling
between the different parts of the lake. In the deep water, an oversaturation of CO
2
of up
to 78 times, compared with the atmosphere and the local pressure was observed, this cor-
responded to a CO
2
concentration of 40 mg L
1
or 31 mL CO
2
per litre water. Nevertheless,
the in situ CO
2
saturation of the hypolimnic water was low, due to the high pressure of
the water column in the deep water, where great quantities of CO
2
are soluble. Taking into
consideration the partial pressure of the gas, leaving the volcano (xi = 0.39%), the in situ
saturation of CO
2
in the bottom-near water layers amounted to only 0.08%.
Figure 2. Bathymetric map of Lake Cuicocha, = sampling points, 1 = cascades, 2 waterfall.
110 G. GUNKEL and C. BEULKER
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.revhydro.com
Figure 3. Temperature isopleths of Lake Cuicocha, based on 10 profiles.
Figure 4. Temperature profiles and temperature differences over a 1 day period during lake stratifica-
tion period, Lake Cuicocha, 148 m depth position, 30/31.3.2004.
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The dissolved ionic concentration of Lake Cuicocha resulted in a conductivity of about
810 S cm
1
; this was elevated compared with the water inflow of the cascades ( 260 S
cm
-1
) and a nearby rain water-filled caldera lake, Lake Mojanda (mean 43 S cm
1
). Thus the
Cuicocha lake water must be influenced significantly by the input of hydrothermal water.
Lake Cuicocha is a sodium hydrogen carbonate water (60.6 mg L
1
Na
+
, 189 mg L
1
HCO
3
,
PO
4
3
.
In Lake Cuicocha the trophic level is very low, and a median phosphorus concentration of
12 g L
1
P
total
was observed. The nitrogen concentrations were also shown to be low (mean
96 g L
1
N
total
). The N/P ratio (median = 10.0, mass basis) for most data showed P limita-
tion. Due to the volcanic origin of the lake, the siliceous concentration (median = 21 mg L
1
SiO
2
) was very high and exceeded the normal range in natural lakes.
Pelagic calcium concentration varied between 39.856.1 mg L
1
(5- and 95-percentile),
and the epilimnic Ca saturation index of + 0.75 (030 m) showed a slight oversaturation.
Nevertheless, precipitation of calcium carbonate was registered at the shore line of Lake
Cuicocha. These precipitations were continuously built up by epilithic algae and cyanobac-
teria (see below), leading to CaCO
3
crusts of about 1 cm in thickness, which reached down
deep into the epilimnion. Wave action partly destroyed these crusts, forming fine carbonate
debris, which sank to the lake bottom, where dissolution of the CaCO
3
precipitates occurred
under conditions of negative Ca saturation index (S = 20.2 at 45135 m, see Fig. 8). An
up-welling of hypolimnic water by the lake floor heating (see 3.2.) led to an internal calcium
cycle.
Figure 5. Increases in temperature and conductivity with decrease of the density near the lake bot-
tom in the 78 m lake basin; (n = 107; variances R
2
for temperature = 0.8298, conductivity = 0.8913,
density = 0.8297).
112 G. GUNKEL and C. BEULKER
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.revhydro.com
The inflow of hydrothermal water was analysed at the shore of Island Yerovi. The water
was of relatively low temperature (2326 C), rich in sodium (247 mg L
1
Na
+
), calcium
(120 mg L
1
Ca
2+
) and iron (7.4 mg L
1
Fe
3+
) as cations and sulphate (193 mg L
1
SO
4
2
),
chloride (171 mg L
1
Cl