Prepared by Xavier Lazzaro (BOREA/IRD)
Water quality time series of water quality every 30 min at 1-m depth from the HydroMet buoy during 2019-2022
This page presents the time series for the 1-m depth water quality parameters evolution during the 2019-2022 (in 2019-2020, 2019-2021, and 2019-2022 sequences). Then the first sub-page shows the last 2023-2024 time series for the 1-m depth water quality parameters evolution. The second sub-page shows the 1-10 m vertical profiles for the 2019-20220, and 2019-2021 sequences.
2019-2020 Temporary changes in water quality at 1 m depth
[file = SondeHourly_270619-060720.csv , n = 12.366 observations]
The data presented are validated raw data, with an acquisition frequency of 30 min.
Table 1 - Data variability over the observation year (06/27/2019 to 07/06/2020). Variables: Temp. = Temperature; Conductivity = Conductivity; ORP = Oxidation-Reduction Potential; DO = Dissolved Oxygen; Turbidity = Turbidity; RFU = Relative Fluorescence Unit; Chl-a = Chlorophyll-a, with 1 RFU = 4 µg/L; BGA PC = Cyanobacterial Phycocyanin, with 1 RFU = 1 µg/L; fDOM = fluorescent dissolved organic matter; Depth = depth of YSI EXO2 sonde, Statistics: Mean = Average; Max = Maximum; Min = Minimum; Median = Median; Stdev = Standard deviation; SE = Standard error (= Stdev/root(number of observations)). *pH sensor decalibrated during the first months. Replaced on 02/12/2019 as of which values are reliable. **Outlier ORP value. Reliable DO values as of October. ***Due to the fact that the YSI EXO2 sonde stayed more than 2 months at the bottom (~10 m), the average depth is 4.15 m, however the average is 0.97 m, i.e. corresponds to the 1.0 m programmed.
Figure 1 - Time evolution of the YSI EXO2 sonde immersion depth (programmed at 1 m depth to take measurements every 30 min) during the monitoring period. On several occasions, the sonde remained near the bottom (dammed by drifting fishing nets; or for unknown reasons). It is necessary to be attentive to send the sonde to the surface and program it to start the profiles again. Since June 2020, it did not happen anymore. Care must be taken to interpret the data.
Figure 2 - Temporal evolution of water temperature at 1 m depth (except for the periods during which it was at the bottom; see previous figure). The temperature follows a perfectly parabolic curve, with a maximum of 17 ºC at the end of January, and a minimum of 11ºC in July. Note: dates are presented as month/day/year format.
Figure 3 - Temporal evolution of conductivity (in µS/cm). On average, it remains at 1,455 µS/cm, except between October and November when the YSI EXO2 sonde was trapped at the bottom, reaching 1,176-1,258 µS/cm (not visible on the graph). This suggests the presence of fresher water at the bottom.
Figure 4 - Temporal evolution of pH. From June to November, we had a decalibrated sensor (its drift is observed) that was replaced by a new one on 0/12/2019, since when the measurements have been reliable. The pH fluctuated between 8.75 and 9.21, with an average of 9.00.
Figure 5 - Time evolution of the oxidation-reduction potential (ORP) in milli-volts. The sensor was recalibrated in October. However, the data are reliable from December onwards when they fluctuate between 190 and 270 mV, being 241 mV on average.
Figure 6 - Temporal evolution of the dissolved oxygen saturation percentage. The sensor was recalibrated in October. Since January, it fluctuated between 67 and 114%, with an average of 98%. This behavior represents a very good level of oxygenation, in equilibrium with the atmosphere. Cycles (oscillations) of 2-4 weeks are observed.
Figure 7 - Temporal evolution of dissolved oxygen concentration. For the same reason, the data are reliable from October onwards. From October to December it fluctuates between 8.5 and 11.0 mg/L. From January on, it fluctuates between 7.5 and 11.0 mg/L, with periods of 2-4 weeks. From March onwards, it gradually increases up to 12.0 mg/L in June. Corresponds to a good level of oxygenation, given the altitude of the lake.
Figure 8 - Temporal evolution of turbidity. In the dry period (until November) it remains between 0.1-0.4 NTU. It increases in the rainy period (December-February). From January on, it reached 1.1 NTU, then gradually decreased with oscillations until reaching 0.1-0.2 NTU at the end of March. From June onwards, it increased slightly. The average is 0.28 NTU, with fluctuations between 0.08 and 4.02 NTU. So the water was very clear. It can be noted that the pattern of turbidity evolution follows the pattern of chlorophyll-a concentration (Fig. 9). In other words, turbidity results mainly from phytoplankton biomass (not from suspended mineral particles).
Figure 9 - Temporal evolution of total chlorophyll-a concentration (in RFU). In the dry period, it remained between 0.2-1.0 RFU (according to the calibration with the FluoroProbe bbe probe presented in Annex 5 of the 5th Quarterly Report, it is necessary to multiply the NTU x 8 to obtain the µg/L), i.e. equivalent to 1.6-8.0 µg/L (oligotrophic to mesotrophic). In the rainy period in January-February (due to nutrient inputs from river wastewater, in addition to atmospheric inputs from aerosols) it increases between 0.5-2.8 RFU, i.e. equivalent to 4.0-22.4 µg/L (predominantly mesotrophic-eutrophic). During the annual cycle, chlorophyll-a fluctuated between 0.10 and 2.78 NTU (i.e. 0.80 and 22.24 µg/L), with an average of 0.69 NTU (i.e. 5.52 µg/L). In comparison, during 1979-1980, for the entire Minor Lake, chlorophyll-a concentrations did not exceed 0.5 µg/L in the dry period and 2.0 µg/L in the rainy period, with a maximum of 5.0 µg/L (Lazzaro, 1981).
Figure 10 - Temporal evolution of phycocyanin concentration (photosynthetic pigment of cyanobacteria). In this period it remained below 0.35 RFU, with a maximum of 1.72 RFU. According to the manufacturer's calibration YSI, 1 RFU = 1 µg/L phycocyanin. The average was 0.14 RFU (=0.14 µg/L) which is a very low concentration. The concentration was highest in January, and increased gradually from April onwards.
Figure 11 - Temporal evolution of the fluorescent dissolved organic matter (fDOM) concentration. During the dry period it varied between 0.8-1.4 RFU. It increased slightly during the rainy period from January 2020, up to 1.8 RFU. This increase in January and February resulted from organic matter inputs from the rivers, particularly from the Katari basin, via the Cohana and Sehuenca rivers joining to form the Cumana lagoon, which flows into Cumana Bay. As of March, it stabilized around 1.3 RFU.
2019-2021 Temporal evolution of water quality at 1 m depth
[file = SondeHourly_270619-230721.csv , n = 26.097 observations]
The data presented are validated raw data, with an acquisition frequency of 30 min. In order to make inter-annual comparisons, we have overlaid the data for the 2nd half of 2019, the 1st and 2nd semesters of 2020 and the 1st half of 2021 on a time scale from January (E) to December (D).
Table 1 - Variability of data over two years of observations (06/27/2019 to 07/23/2021). Variables: Temp. = Temperature; Conductivity = Conductivity; ORP = Oxidation-reduction potential; DO% = % saturation in dissolved oxygen; DO = Dissolved Oxygen; Turbidity = Turbidity; RFU = Relative Fluorescence Unit; Chl-a = Chlorophyll-a, with 1 RFU = 8 µg/L; BGA PC = Cyanobacterial phycocyanin, with 1 RFU = 1 µg/L; fDOM = fluorescent dissolved organic matter; Depth = depth of YSI EXO2 probe, Statistics: Mean = Average; Max = Maximum; Min = Minimum; Median = Median; Stdev = Standard deviation; SE = Standard error (= Stdev/root(number of observations)). *pH sensor decalibrated during 2021. Replaced on 02/12/2019 as of which values are reliable. **ORP outlier. Reliable DO values as of October. ***Due to YSI EXO2 sonde occasionally staying on the bottom (~10 m), average and median depths are 1.28 m, however close to 1.0 m programmed.
Figure 1 - Time evolution of the immersion depth of the YSI EXO2 sonde (programmed to stay at 1 m depth to take measurements every 30 min) during the two years of monitoring. On several occasions the sonde stayed close to the bottom (dammed by drifting fishing nets; by the depth gauge control; or by unknown causes; we fixed the problem in 2021 when it was much less frequent). So, care must be taken to consider these events in interpreting the data.
Abbreviations: E (Enero) = January; F (Febrero) = February; M (Marzo) = March; A (Abril) = April; M (Mayo) = May;
Figure 2 - Temporal evolution of water temperature at 1 m depth (except for some periods during which it was at the bottom; see previous figure). The temperature followed a perfectly parabolic curve, with a maximum of 17.7 °C from January to March, and a minimum of 10.3 °C in June-July. The average for the period was 14.2 ºC and the median 14.4 ºC. During the 1st semester the temperature was slightly higher (≤ 1 ºC) in 2020 relative to 2021.
Figure 3 - Temporal evolution of conductivity (in µS/cm) at 1 m depth. On average it has remained at 1,455 µS/cm, except between October and November when the YSI EXO2 sonde was trapped at the bottom, reaching 1,176-1,258 µS/cm (not visible on the graph). This could suggest the presence of fresherwater at the bottom. From January to April, conductivity was higher in 2021 relative to 2020 during the same period. We do not know the cause of this phenomenon: would it be higher evaporation, lower rainfall and/or lower water level in 2021?
Figure 4 - Temporal evolution of pH at 1 m depth. From June to November 2019, we had a decalibrated sensor (its drift is observed) that was replaced by a new one on 10/12/2019, from when the measurements were reliable. The pH fluctuated between 8.75 and 9.21, with an average of 9.00 during 2020. However, from February 2021 onwards, the sampler became decalibrated again and it was not possible to calibrate it at all. So since February 2021 we have no pH data (nor ORP data for that matter). A new sensor was ordered; however, due to the shortage of components during the pandemic, it only just arrived on September 28, 2021. It will be installed in October.
Figure 5 - Time evolution of the oxidation-reduction potential (ORP) in milli-volts at 1 m depth. The sensor was recalibrated in October 2019. However, the data were only reliable from January 2021 when they fluctuated between 190 and 270 mV, being 241 mV on average. In 2021, the data has to be discarded. The sensor will be replaced in October 2021.
Figure 6 - Temporal evolution of the percentage of dissolved oxygen saturation at 1 m depth. The sensor was recalibrated in October 2019. As of January 2020, it fluctuated between 67 and 114%, with an average of 98%. This behavior represents a very good level of oxygenation, in equilibrium with the atmosphere. Cycles (oscillations) of 2-4 weeks are observed. Higher oxygenation of up to 20% more was observed during 2020 relative to 2021, except from October-December 2020 when oxygenation was lower by up to 20% to 2019 oxygenation. Higher oxygenation may also result from higher micro-algal biomass due to higher photosynthetic intensity.
Figure 7 - Temporal evolution of dissolved oxygen concentration at 1 m depth. Of course, it follows the same pattern as the % saturation in dissolved oxygen (%DO) in Fig. 6. For the same reason, the data are reliable as of October 2019. From October to December 2019 it fluctuated between 8.5 and 11.0 mg/L. From January 2020 it ranged between 7.5 and 11.0 mg/L, with periods of 2-4 weeks. From March 2020, it gradually increased to 12.0 mg/L in June. This corresponds to a good level of oxygenation, given the altitude of the lake. The concentration in dissolved oxygen was higher in 2020 by up to 2 mg/L relative to 2021, except from October to December when dissolved oxygen was lower than in 2019. As for %DO it may result from higher biomass/photosynthesis of micro-algae.
Figure 8 - Temporal evolution of turbidity at 1 m depth. In the dry period (until November) it remained between 0.1-0.6 NTU. It increased in the rainy period (December-February). From January 2020, it reached 1.1 NTU, then gradually decreased with oscillations until reaching 0.2-0.4 NTU at the end of April 2020. From June onwards, it increased slightly. The average is 0.34 NTU and the median is 0.32 NTU, with fluctuations between 0.08 and 4.02 NTU. In other words, the water was very clear. It can be noted that the pattern of turbidity evolution followed the pattern of chlorophyll-a concentration (Fig. 9). This means that the turbidity mainly reflects the phytoplankton biomass (but not suspended mineral particles).
Figure 9 - Temporal evolution of total chlorophyll-a concentration (in RFU) at 1 m depth. During the dry period, it remained between 0.2-1.0 RFU (according to the calibration with the FluoroProbe bbe probe presented in Annex 5 of the 5th Quarterly Report, one has to multiply NTU x 8 to obtain µg/L), i.e. equivalent to 1.6-8.0 µg/L (oligotrophic to mesotrophic). In the rainy period in January-February (due to nutrient inputs from river wastewater, in addition to atmospheric inputs from aerosols) it increased between 0.5-2.8 RFU, i.e. equivalent to 4.0-22.4 µg/L (predominantly mesotrophic-eutrophic). During the annual cycle, chlorophyll-a fluctuated between 0.1-3.0 NTU (i.e. 0.8-24.0 µg/L), averaging 0.34 RFU (i.e. 2.72 µg/L). In comparison, during 1979-1980, for all of Lake Minor, chlorophyll-a concentrations did not exceed 0.5 µg/L in the dry period and 2.0 µg/L in the rainy period, with a maximum of 5.0 µg/L (Lazzaro, 1981). This means that, compared to 1979-1980, the current Chl-a concentration is up to 16 times higher during the dry period, and up to 11 times higher during the rainy period, compared to 40 years ago. This demonstrates the significant increase in the biomass of micro-algae in response to the combination of the effects of climate change with several decades of massive inputs of nutrients from pollution from the urban area of El Alto through the Katari watershed.
Figure 10 - Temporal evolution of phycocyanin concentration (photosynthetic pigment of cyanobacteria) at 1 m depth. During this 2-year period, phycocyanin remained below 0.4 RFU, with a maximum of 2.9 RFU. According to the manufacturer's YSI calibration, 1 RFU = 1 µg/L of phycocyanin. The average was 0.78 RFU (=0.78 µg/L) which is a relatively low concentration. The concentration was slightly higher during the 2nd half of 2020 relative to 2019. It was slightly higher during the 1st half of 2021 relative to 2020, with a delayed peak at the beginning of March 2021 (0.4 RFU) prolonged to the beginning of April 2021, relative to the peak of 0.32 RFU only during January 2020. This suggests poorer water quality during the 2021 rainy period, as well as a gradual increase in the contribution (~doubling) of cyanobacterial biomass from 2019 (≤ 0.2 RFU) to 2021 (≤ 0.4 RFU). Meanwhile, the ratio of cyanobacteria biomass to total phytoplankton biomass dropped slightly from 0.15/0.5 = 30% in 2019 to 0.2/1.0 = 20% in 2021. However, we need the data for 3 full years to confirm this calculation. A ratio of 20-30% is quite high. It suggests keeping a high and permanent vigilance, because if conditions become favorable, cyanobacteria can quickly proliferate and generate blooms that can become recurrent every year. The damage (mortality of fish, frogs and waterfowl) would be irreparable and repeated in the long term, since cyanobacterial blooms would be impossible to control in Lake Titicaca. In fact, Lake Titicaca has no herbivorous organisms (neither fish nor zooplankton) capable of grazing them effectively, nor wastewater treatment plants (WWTPs) capable of retaining the nutrients used by the algae for their growth. Even if Totora are natural biological filters of nutrients and pollutants, alone in the absence of WWTPs, they are not capable of controlling the biological discharges of a population of 1.2 million inhabitants of the urban area of El Alto. To have beneficial effects, Totora (and wetlands in general) must be associated as a complementary treatment to WWTPs, as is universally practiced throughout the world.
Figure 11 - Temporal evolution of fluorescent dissolved organic matter (fDOM) concentration at 1 m depth. During the dry period it varied between 0.9-1.5 RFU. It increased slightly during the rainy period from 1.7 RFU in February 2020 to 2.1 RFU in November 2020. This increase in February and November resulted from organic matter inputs from the rivers, particularly from the Katari watershed, via the Cohana and Sehuenca rivers joining in the Cumana Lagoon, which flows into Cumana Bay. Counter-intuitively to what was thought about the pandemic and quarantine period in 2020, the concentration of organic matter (fDOM) was much higher in 2020 compared to the 2nd half of 2019 and the 1st half of 2021. In fact, the population did not stop contributing to the organic pollution of rivers and lakes. Contrary to what the press wanted to convince us, no significant improvement in the water quality of the Lago Menor was observed in 2020. Even if the discharges of organic matter were completely stopped in 2020 (impossible situation), the organic matter already deposited for decades with the polluted sediments would not have disappeared in one year with the action (= mineralization) of the microbial loop. In conclusion, it is essential to maintain permanent long-term monitoring, since without the implementation of new WWTPs, there are no mechanisms to eliminate such massive discharges of nutrients and organic matter that benefit microalgae blooms.
2019-2022 Evolution of water quality parameters from 06/27/19 to 05/01/22 (34 months) at the HydroMet buoy site at 1m depth
[file = SondeHourly_270619-050122.csv , n = 354,528 observations]
The data presented cover the entire deployment period of the HydroMet buoy, from 06/27/19 to 05/01/22, and correspond to the file [SondeHourly Cellular Sounding Buoy 270619-010522.csv]. They are organized in 29,544 lines (date-time) x 12 parameters* = 354,528 data. We removed all data corresponding to depths between 2 and 10 m (see section 1, below), in order to only keep the data corresponding to the surface (1 m).
Parameters: Temperature = Temp (ºC) | Specific conductivity**= SpCond (µS/cm) |pH and pH (mV) | Oxidation-reduction potential = ORP (mV) | Dissolved oxygen = DO (%) and DO (mg/L) | Turbidity = Turbidity (NTU) | Chlorophyll- a = Chl-a (RFU) | Phycocyanin = Phycocyanin (RFU) | Fluorescent dissolved organic matter = fDOM (RFU) | Depth = Depth (m). **The specific conductivity takes into account the surface area of the electrodes (µS/cm) so that the measurement of the current flowing through the water is as accurate as possible.
Since > 3 months, the EXO2 sonde is not profiling, and the buoy is not transmitting data remotely due to an accumulation of unforeseen events, causing 8 missions to the Buoy from December to April:
a) On 01/12/21, a colony of seagulls had settled on the buoy platform, completely fouling it with droppings. In the morning we untied it from its two anchorages. We towed it ashore with the Catari's Inti boat. To avoid damage, we disassembled the EXO2 sonde and removed the EXO Link that connects the sonde with the profiler cable to the datalogger. By unscrewing the retaining ring of the EXO Link, we broke one of the 12 pins. We dragged the buoy to the Catari beach at Huatajata. We cleaned it thoroughly with a high-pressure cleaner (Kärcher), including the two hulls covered with a biofilm of microalgae. At the end we tried to re-attach the buoy to its moorings. However, the wind and waves were so strong that we abandoned, returned the buoy ashore, and returned to La Paz. There, a technician (micro-) soldered the plug and two others that were loose.
b) On 03/12/21, we towed the Buoy and re-tied it to its moorings. We re-attached the EXO Link to the sonar and the profiler cable. However, the weld was unsuccessful. From this point on, we could not initiate a vertical profile, nor could we have remote data transmission.
c) As a commercial gesture, Eng. Pierre Sterling ordered another EXO Link free of charge. On 02/23/22, we received it via DHL, sent by Cynthia Marrot (BASEFLOW) from Miami.
d) On 03/03/22, after hours of trying, we connected the new EXO Link to the profiler cable. It would not connect because the pins were not aligned with their holes by 1 mm. By rotating the 1 mm base, the pins were aligned, allowing the EXO Link to be screwed onto the cable. However, it did not work either. With the serial-USB cable we manually downloaded the data from the sonde and weather station. To maintain data acquisition, we submerged the battery-powered sonde to 1m. We put it in deployment position, to acquire data every 30 min.
e) We imagined that we had forgotten to deposit Bs 2 in the ENTEL account (guaranteeing the activity), because we had a balance of ≥ Bs 700. Pierre Sterling (XYLEM), with the LoggerNet application (Campbell), we tried in vain to restart the data transmission and profiling, but without success. The weather station stopped transmitting on 03/03/22, unrelated to the failure of the EXO Link, the modem, or the server.
f) On 03/14/22, we tried again to restart communication with the sonde. It was raining hard. We disconnected the equipment from the Buoy for 10 sec and reconnected it, without success. With a voltmeter we checked that the battery was only delivering 12.2 V instead of ≥ 13.5 V. After 3 years without failure, due to weeks of cloudy weather, we discovered that the solar panels had not charged it sufficiently. In La Paz we charged the battery one night and it recovered to 100% up to 13.6V.
g) Due to our 1st workshop with the social actors on 03/17/22 in Quehuaya, only on 03/22/22/22 we were able to reinstall the battery in the buoy and try to restart the system. The voltmeter indicated that no voltage was reaching the sonde through the EXO Link, there was no communication from the datalogger to the sonde, so it was not profiling.
h) On 05/04/22, with the equipment plugged in, the battery voltage fluctuated from 13.2-13.3V in the morning to 13.8-14.5V in the sunny afternoon, which is excellent. We manually downloaded all the data.
j) On 28/04/22, three divers from CIBA, the Centro de Instrucción de Buceo en Altura, replaced all the ropes and shackles of the two anchors of the Buoy, which were badly damaged (about to break) after almost 3 years of windy events and swell.
As a consequence, we lost some data series between the months of February and April 2022.
1.- Measuring depth of the YSI EXO2 multiparameter sounder
Figure 1 - The data presented here correspond exclusively to surface data at 1.0 m depth (range 0.8-1.2 m). The acquisition frequency is 30 min. Every 2 hours, the profiler (guincho) vertically profiles the EXO2 probe from 1 m to 10 m. It performs a measurement every meter, at the end of the 1 minute dwell time (to stabilize the conditions for the sensors). Each down and up cycle takes ~15 min, so it does not affect the next 1 m measurement. However, we have observed numerous occasions when the EXO2 sonde stays several days (most often 1-2 days, exceptionally up to 5 days) at 10 m**.
**NOTE: This intriguing situation was clarified on 28/04/22 when the divers of CIBA (Centro de Instrucción de Buceo en Altura, Tiquina) replaced all the mooring lines of the buoy, worn by 3 years of storms and waves, about to break, including some shackles badly worn by friction. The GoPro camera video revealed long stretches of damaged and abandoned fishing nets wrapped around the concrete blocks and bottom mooring anchors. Therefore, one can imagine that the EXO2 sonde gets caught in these nets and takes a long time to free itself and ascend.
Although we can detect these situations remotely on the LoggerNet (Campbell Scientific Inc.) screen of our DELL laptop, we do not always have the time, the service vehicle or the budget to drive to the lake, rent the boat, hoping to solve the problem by manually lifting the sonde. Then, we just have to let the swell and the Buoy's movements free the probe from these nets. In fact, the winch of the profiler has a safety device to avoid forcing the electric motor in case of excessive resistance of the cable.
The presence of these abandoned nets reveals the intense artisanal fishing activity in the Buoy area. Of course, it would be ideal if fishermen would retrieve their damaged nets instead of letting them drift and thus pose a danger to the outboard motor propellers, the buoy sounder, and especially to the fish communities (considering that frogs are scarce), as they continue to fish and kill fish uselessly. Obviously, it is not always easy to avoid losing nets. However, environmental education (e.g. with a primer) in this regard could reduce this problem.
2. Water temperature
Figure 2a - Water temperature evolution at 1 m depth (date format mm/dd/yy). This graph illustrates the effect of the seasonal cycle of solar radiation on water surface temperature. The sinusoidal curve has a large amplitude with maxima (≤ 18 ºC) in summers (November to February) and minima (≥ 10 ºC) in winters (June to August). At first glance the oscillation is regular with no apparent difference between years. Blanks in the data correspond to periods when the EXO2 sonde remained at 10 m depth (corresponding data were removed). Mean +/- standard error = 14.247 +/- 0.009 ºC.
Figure 2b - Comparison of seasonal temperature evolution between years 2019 (blue), 2020 (red), 2021 (green) and 2022 (purple) (m/dd date format). The seasonal patterns are similar between years and overlap. Perhaps, the water warmed slightly faster and more (~+0.5 °C) in September-October 2021. However, it does not seem significant.
3. Specific conductivity (µS/cm)
Figure 3a - Evolution of specific conductivity. In 2019-2020 it started around 1,510 µS/cm. It increased in the rainy seasons of 2020 (≥ 1,550 µS/cm) and 2021 (≥ 1,650 µS/cm) and decreased in the dry season of 2021 (≤ 1,490 µS/cm), which may seem counter-intuitive. Throughout the study period it has a tendency to increase, although not statistically significant. Mean +/- standard error = 1526.584 +/- 0.357 µS/cm.
Lake Titicaca is slightly saline, presenting a TDS value ≤ 1,000 µSi/cm. Specific conductivity (SpCond) correlates with total dissolved solids (TDS, mg/L). Significant changes in conductivity can be due to natural flooding, evaporation or anthropogenic pollution and can be very detrimental to water quality. Therefore, a sudden increase or decrease in conductivity in a water body may indicate pollution. Agricultural runoff or a sewage discharge may be the main cause of increased conductivity due to additional chloride, phosphate and nitrate ions. In fact, the highest conductivity values correspond to the rainy season (November-February) when the Katari and Sehuenca rivers overflow with domestic and industrial wastewater.
Figure 3b - Comparison of the seasonal evolution of specific Sp conductivity between 2019, 2020, 2021 and 2022. What jumps out is: a) Lower conductivity in January-May 2020; b) Higher conductivity in February (≤ 1,570 µS/cm) and December 2021 (≤ 1,650 µS/cm); and c) The highest conductivity in January 2022 (≤ 1,630 µS/cm).
4. pH
Since 2021 we have had measurement problems with the integrated pH/ORP sensor, despite successful calibrations with the standard solutions (pH 4.0, 7.0 and 10.0). So the pH data are not reliable, most often around 8.60. The captor ended up not responding in November 2021. We could not buy another one, because of the high cost and delay in delivery, due to the lack of electronic components after COVID-19. Therefore, we only show the comparative Fig. 4a.
Figure 4 - Comparison of seasonal pH evolution between 2019, 2020, 2021 and 2022. What jumps out is: a) EYE: 2019 (blue) and 2021 (green) values are not reliable; b) pHs are high (> 8.6), with a tendency to increase from January (8.7-9.0) to December (9.2-9.3) in 2020, in case it is not a sensor drift.
5. Oxidation-Reduction Potential, ORP (mV)
Figure 5a - Evolution of the oxidation-reduction potential, ORP. As the ORP sensor is integrated to the pH sensor, the measurements were reliable until September 2020, around +240 mV. Average +/- standard error = 241.977 +/- 0.445 mV.
The Oxidation-Reduction Potential (ORP) measures the ability of a lake to cleanse itself or break down waste products, such as pollutants and dead plants and animals. When the ORP value is high, there is plenty of oxygen present in the water. This means that the bacteria that break down dead tissues and pollutants can work more effectively. In general, the higher the ORP value, the healthier the lake. In healthy waters, the ORP should be high, between 300 and 500 mV. Low ORP is expected in waters that receive inputs of wastewater or industrial wastes, such as Cohana Bay, Cumana Bay and South Cojata Island. For more information see: Horne & Goldman (1994), Wetzel (1983).
In Fig. 5, the ORP of +240 mV, reliable until September 2020, is slightly lower than the ≥ 300 mV that could be expected for healthy waters. From February 2021 the ORP is very high (up to ≥ 1,100 mV) which is good, plus it fluctuates a lot (up to ≤ 300 mV). It corresponds with the period in which the oxygen concentration is high (DO% ≥ 90%; DO ≥ 9 mg/L). In the meantime, it may not be reliable because the pH sensor is out of service.
Figure 5b - Comparison of the seasonal evolution of ORP between 2019, 2020, 2021 and 2022. What jumps out is: a) EYE: the values from January to May 2021 (green; from June onwards unreliable) and January 2022 (purple; from February onwards unreliable) are the highest (280-400 mV). b) The 2019 (blue) and 2020 (red) values are relatively stable between 280 and 200 mV, at the lower limit of healthy waters. c) Two periods of higher values are observed: December 2021 (300-550 mV) and January 2022 (300-400 mV). As it is a sensor that integrates pH (defective) and ORP measurements, there is a doubt that the ORP measurement may not be very reliable (as in 2021).
6.- Percentage of saturation in dissolved oxygen = DO (%)
Figure 6a - Percent saturation in dissolved oxygen fluctuated between ≤ 70% (December 2021) and ≥ 115% (January 2020). As a trend it is higher during the dry period (June-July) and lower at the end of the dry period (November-December). It is highlighted that it remained high (≤ 110%) throughout the confinement period (March-September 2020), due to the good water quality in the absence of most of the inputs from polluting human activities, low turbidity, strong insolation (low cloudiness), intense vertical mixing during the windy period (July-June), among others. Average +/- standard error = 89.248 +/- 0.054 %.
The higher dissolved oxygen saturation during the confinement period (March-September 2020) suggests a higher photosynthetic activity of phytoplankton and/or a more intense vertical mixing of the water column due to the wind. However, the concentration of chlorophyll-a is the lowest in this period, and the windy period corresponds to August, which is not reflected in the profile that remains between 100 and 110%. Perhaps, it is more related to the low temperatures (6 ºC less) which induces a higher dissolution of oxygen in the water, as is also noted in 2021.
The % saturation in dissolved oxygen decreases in a negative exponential manner with increasing altitude. However, the oxygen saturation values in the lake are higher than the theoretical values as a function of altitude. Thus, at 3,809 m asl the % saturation should be < 66% (Table 1), although in the lake the percentages are > 70%. Therefore, photosynthesis processes contribute significantly.
Table 1 - Calibration values for various atmospheric pressures and altitudes. Source: XYLEM Technical instructions: https://www.ysi.com/File%20Library/Documents/Technical%20Notes/DO-Oxygen-Solubility-Table.pdf
Figure 6b - Comparison of the seasonal evolution of dissolved oxygen saturation (DO, %) between 2019, 2020, 2021 and 2022. What jumps out is: a) Better DO% saturation in January 2020 (> 110%), relative to the other years; b) Higher saturation (up to > 100%) than the other years, during confinement (March-September 2020); and c) Bad saturations in December 2021 (≤ 70%).
7.- Dissolved oxygen concentration = DO (mg/L)
Figure 7a - The dissolved oxygen concentration follows the behavior of the percent saturation in dissolved oxygen in Fig. 6. Mean +/- standard error = 9.126 +/- 0.006 mg/L.
As for the % saturation, the concentration in DO is higher during the coldest periods (March-September). However, it has a tendency to decrease over the three years. This is not good news, as it highlights that the eutrophication process is intensifying and is already beginning to affect the central part of the northern region of Lake Menor where the HydroMet buoy is located, not only concentrated in the littoral regions affected by the Katari River wastewater.
Figure 7b - Comparison of the seasonal evolution of dissolved oxygen concentration (DO, mg/L) between the years 2019, 2020, 2021 and 2022. What jumps out is: a) Logically, the DO patterns (mg/L) are similar to DO patterns (%) (see Fig. 6b).
8. Turbidity
Figure 8a - Evolution of turbidity. Average +/- standard error = 0.226 +/- 0.002 NTU.
Turbidity increases during the windy season (August) due to vertical mixing of the water column, which re-suspends bottom sediments. It is highest at the end of the rainy season (January-February), up to 1.8 NTU, most likely due to the contribution of fine sediment-laden water from the Katari and Sehuenca river floods. During the period of confinement, human activities were largely suspended. In particular, with the cessation of dredging of the quarries in the Seke and Seco rivers, the contribution of fine sediment to the lake was cut off.
Figure 8b - Comparison of the seasonal evolution of turbidity between 2019, 2020, 2021 and 2022. What jumps out is: a) The lowest values during confinement (March-June 2020); b) The exponential increase in turbidity from October to November 2021; and c) The maintenance of higher values (up to 0.6 NTU) in April 2022.
9. Chlorophyll-a
Figure 9a - Evolution of chlorophyll-a concentration. Mean +/- standard error = 0.875 +/- 0.003 RFU.
Chlorophyll-a is the main photosynthetic pigment of plants (plants and phytoplankton). In aquatic ecology and limnology, the concentration of chlorophyll-a serves as a bioindicator of the biomass of phytoplankton microalgae, thus of the level of eutrophication. The EXO total algae sensor contains two excitation beams: a blue one (470 nm) that directly excites the chlorophyll molecule, and an orange one (590 nm) that excites phycocyanin, the accessory pigment found in cyanobacteria. Measurements of chlorophyll-a and phycocyanin concentrations are expressed in RFU (Relative Fluorescence Unit) and µg/L. The conversion factors are: 1 RFU = 6 µg/L according to the manufacturer (YSI) and 1 RFU = 8 µg/L when using the Fluoroprobe BBE Moldaenke fluorimetric probe (own experimentation, when we simultaneously submerged our YSI EXO and Fluoroprobe BBE probes to the same depth (X. Lazzaro, own experimentation). Then, on average chlorophyll-a reaches values of 5.3 to 7.0 µg/L, with maxima of 15 to 20 µg/L in the 2019 and 2020 rainy seasons, and 21 to 28 µg/L in the 2021 rainy season. As a comparison, chlorophyll-a concentrations (acetone extraction method) did not exceed 3 µg/L in Lake Minor in 1979-1980 (Lazzaro 1981). That is, at present, the maximum surface concentrations in the center of the northern region can reach values 5 to 9 times higher... in spite of the intense sub-surface solar radiation (visible and ultraviolet) that inhibits photosynthesis.
According to the open classification (i.e. overlapping ranges of state values) of the OECD (1982), 0.3-4.5 µg/L corresponds to an oligotrophic state, 3.0-11 µg/L to a mesotrophic state, and 2.7-78 µg/L to a eutrophic state. Thus, whereas Lake Minor was characterized by an oligotrophic state in 1979-1980, it now oscillates seasonally between mesotrophic and eutrophic states. Together with the other parameters, this confirms the rapid progress of eutrophication.
Figure 9b - Comparison of the seasonal evolution of chlorophyll-a concentration between 2019, 2020, 2021 and 2022. What jumps out is: a) In relation to the other years, the confinement period (March-October 2020, red) exhibits the lowest chlorophyll-a concentrations; b) The 2021 rainy season (September-December, green) exhibits the highest chlorophyll-a concentrations.
10. Phycocyanin
Figure 10a - Evolution of phycocyanin concentration. Average +/- standard error = 0.208 +/- 0.001 RFU.
Phycocyanin is the main and specific photosynthetic pigment of cyanobacteria. Therefore, the EXO total algae sensor allows to detect the importance of the contribution of cyanobacteria (as harmful organisms able to proliferate, dominate the biomass and create blooms, or Blooms, some of which can generate (neuro- or hepato-) toxins), in the total biomass of phytoplankton microalgae. For this reason, cyanobacteria are of great interest in eutrophication studies in anticipation of blooms. According to the manufacturer YSI, 1 RFU = 1 µg/L phycocyanin.
The average phycocyanin concentration over the entire study period only reached 0.2 µg/L, or 0.7 to 1.4 % of the total phytoplankton biomass. It may not seem much, but the mere presence of cyanobacteria is worrisome, because they can develop exponentially as soon as environmental conditions (increased nutrient inputs, N:P ratio, nitrogen limitation, among others) become favorable. In addition, a trend of increasing average concentrations (x 3, from 0.1 to 0.3 µg/L) can be noted during the three years, although this trend is not significant.
Figure 10b - Comparison of the seasonal evolution of phycocyanin concentration between 2019, 2020, 2021 and 2022. What stands out is: a) The increase in concentration during the end of 2021 and the beginning of 2022, i.e. the transition period at the end of the dry season (September-October) and the rainy season (November-January), with a doubling of values.
11.- Fluorescent Dissolved Organic Matter, fDOM (RFU)
Figure 11a - Evolution of fluorescent dissolved organic matter (= chromophoric). Mean +/- standard error = 1.868 +/- 0.007 RFU.
Fluorescent dissolved organic matter (fDOM) is a product of decaying matter. It refers to the fraction of CDOM (colored dissolved organic matter) that is fluorescent. CDOM is largely a subset of the DOM, or Dissolved Organic Matter. Decomposition releases organic substances, also called tannins, which stain waters and can have effects on light absorption and other aspects of water quality. Basically, this decomposing organic matter is Dissolved Organic Carbon (DOC). Classically, fDOM is used as a surrogate for CDOM, and is one of the ways in which it is possible to track Dissolved Organic Matter (DOM) in waters. In addition to contributing to light absorption, fDOM can also help fuel bacterial respiration, due to the large amounts of carbon, nitrogen and phosphorus it carries. This can indirectly contribute to eutrophication. Along with turbidity and chlorophyll-a, CDOM is important in determining light attenuation in a water body. Also, conductivity can increase or decrease as a function of CDOM levels. In general, high absorption of infrared and red wavelengths of light occurs which significantly heats the first meter of water. Low concentrations of CDOM greatly increase ultraviolet absorption. However, at higher concentrations, this absorption is complete in less than one meter of water. DOC is related to mercury and methylmercury levels, because both tend to form complexes with organic carbon.
During the study period, an increase in average fDOM is observed from 2019 (1 RFU) to 2022 (x 3; 3 RFU), especially with a peak in the rainy period of 2021 (up to 5 RFU in December-January). It is also a symptom of eutrophication.
Figure 11b - Comparison of the seasonal evolution of fDOM concentration between 2019, 2020, 2021 and 2022. What jumps out is in relation to the average value (1.3 RFU): a) The increase of fDOM with maximum values in March-May 2021 and January 2022 (up to 4.8 RFU) in relation to the other years, and b) Its low values from July to December 2019, from January to December 2020, in June-July 2021, and in April 2022. It could result from the resumption of gravel extraction activities (in January 2021) in the Seke and Seco river quarries, heavy rains and/or the diversion of the Katari river towards Chojasivi, with heavy flooding of crops in Cohana Bay, all of which contribute to diffuse inputs of nutrients and dissolved organic matter (DOM). This clearly initiates a jump in the water quality status of the northern region of Lesser Lake. This should be carefully observed, because it may favor the proliferation of certain groups of micro-algae, in particular the harmful cyanobacteria.
12.- Conclusions regarding the state of the northern region of Lago Menor
Most of the biophysical parameters (related to each other) measured by the YSI EXO2 multiparameter sonde show a significant increase in the level of eutrophication in the central part of the northern region of Lake Menor, where the HydroMet buoy is located, in only 3 years. In particular, such as: the increase in conductivity, pH, ORP, chlorophyll-a, phycocyanin and its proportion in the phytoplankton biomass, fDOM; as well as the reduction of DO% and DO. The evolution of the taxonomic and functional composition of the phytoplankton community (cf. studies by V. Cruz & G. Lanza) confirms this.
This condition of Lago Menor, which is deteriorating faster than could be imagined, is quite worrying, especially in the absence of measures to control eutrophication and pollution by reducing point and diffuse inputs. That is, in the combination of wastewater treatment plants (WWTPs) with artificial wetlands (e.g., phytoremediation with cattails) at the mouths of each river (all being polluted with wastewater). Additionally, the improvement of conditions during confinement illustrates the importance of human activities in the eutrophication process.