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Waterborne metal levels in four freshwater lakes from Harmony Point, Nelson Island, Antarctica

Abstract

The aim of this study is to analyze the waterborne metal levels in four lakes (one endorheic and three exorheic) of Harmony Point, Nelson Island, Antarctica. Water samples were analyzed by using a quadrupole type inductively coupled plasma mass spectrometer and an inductively coupled plasma optical emission spectrometer. The levels of As, Cu, Mn, Mo, and V were significantly lower and those of Cr, Mg, Na, and Sr were significantly higher in the endorheic lake than in the other lakes. Most water samples presented levels of Ag, Be, Cd, Pb, Se, Tl, and U below the limit of quantification, while for Ba, Co, and Ni around half of the samples were below this limit. The waterborne metal levels were not significantly different between the exorheic lakes. Waterborne metal levels in the freshwater lakes from Harmony Point did not show any clear relationship with their levels in the soil of the region or with bird guano, and overall, their levels indicate an environment without anthropogenic influence. Apparently, the Na levels are influenced by salt spray from the ocean, as they are related to the distance of the lakes from the ocean.

Key words
hydrochemical; limnology; periglacial environments; salt spray

INTRODUCTION

Antarctic freshwater lakes are dependent on the melting of glacial ice habitats (Cantonati et al. 2020CANTONATI M ET AL. 2020. Characteristics, main impacts, and stewardship of natural and artificial freshwater environments: consequences for biodiversity conservation. Water 12. doi: 10.3390/w12010260.) and their area is continuously increasing due to climate warming (Rosa et al. 2022ROSA KK, OLIVEIRA MAG, PETSCH C, AUGER JD, VIEIRA R & SIMOES JC. 2022. Expansion of glacial lakes on Nelson and King George Islands, Maritime Antarctica, from 1986 to 2020. Geocarto Int 37(15): 4454-4464.). Several studies analyzed the limnology and anthropic impact on water channels and lakes from the Antarctic Peninsula: King George Island (Souza et al. 2012SOUZA JJLL, SCHAEFER CEGR, ABRAHAO WAP, MELLO JWV, SIMAS FNB, SILVA J & FRANCELINO MR. 2012. Hydrogeochemistry of sulfate-affected landscapes in Keller Peninsula, Maritime Antarctica. Geomorphology 155: 55-61., Nedzarek et al. 2014NEDZAREK A, TORZ A & DROST A. 2014. Selected elements in surface waters of Antarctica and their relations with the natural environment. Polar Res 33. doi: 10.3402/polar.v33.21417., Bueno et al. 2018BUENO C, KANDRATAVICIUS N, VENTURINI N, FIGUEIRA RCL, PEREZ L, IGLESIAS K & BRUGNOLI E. 2018. An evaluation of trace metal concentration in terrestrial and aquatic environments near Artigas Antarctic Scientific Base (King George Island, Maritime Antarctica). Water Air Soil Pollut 229: 398., Chu et al. 2019CHU ZD, YANG ZK, WANG YH, SUN LG, YANG WQ, YANG LJ & GAO YS. 2019. Assessment of heavy metal contamination from penguins and anthropogenic activities on Fildes Peninsula and Ardley Island, Antarctic. Sci Total Environ 646: 951-957. doi: https://doi.org/10.1016/j.scitotenv.2018.07.152.
https://doi.org/10.1016/j.scitotenv.2018...
, Lopes et al. 2021LOPES DV, SOUZA JJLL, SIMAS FNB, OLIVEIRA FS & SCHAEFER CEGR. 2021. Hydrogeochemistry and chemical weathering in a periglacial environment of Maritime Antarctica. Catena 197: 104959. doi: 10.1016/j.catena.2020.104959., Sparaventi et al. 2022SPARAVENTI E, RODRIGUEZ-ROMERO A, NAVARRO G & TOVAR-SANCHEZ A. 2022. A novel automatic water autosampler operated from UAVs for determining dissolved trace elements. Front Mar Sci 9. doi: 10.3389/fmars.2022.879953.), Seymour Island (Gargiulo et al. 2021GARGIULO JD, CHAPARRO MAE, MARIE DC & BOHNEL HN. 2021. Magnetic monitoring of anthropogenic pollution in Antarctic soils (Marambio Station) and the spatial-temporal changes over a decade. Catena 203. doi: 10.1016/j.catena.2021.105289.), James Ross Island (Lecomte et al. 2020LECOMTE KL, VIGNONI PA, ECHEGOYEN CV, SANTOLAYA P, KOPALOVA K, KOHLER TJ, ROMAN M, CORIA SH & LIRIO JM. 2020. Dissolved major and trace geochemical dynamics in Antarctic lacustrine systems. Chemosphere 240. doi: 10.1016/j.chemosphere.2019.124938.), Deception Island, Livingston Island (Toro et al. 2007TORO M ET AL. 2007. Limnological characteristics of the freshwater ecosystems of Byers Peninsula, Livingston Island, in maritime Antarctica. Polar Biology 30(5): 635-649., Centurion et al. 2022CENTURION VB, SILVA JB, DUARTE AWF, ROSA LH & OLIVEIRA VM. 2022. Comparing resistome profiles from anthropogenically impacted and non-impacted areas of two South Shetland Islands-Maritime Antarctica. Environ Pollut 304. doi: https://doi.org/10.1016/j.envpol.2022.119219.
https://doi.org/10.1016/j.envpol.2022.11...
) and from the main Antarctic continent: Terra Nova Bay (Conca et al. 2017CONCA E, MALANDRINO M, GIACOMINO A, BUOSO S, BERTO S, VERPLANCK PL, MAGI E & ABOLLINO O. 2017. Dynamics of inorganic components in lake waters from Terra Nova Bay, Antarctica. Chemosphere 183: 454-470., Zelano et al. 2017ZELANO I, MALANDRINO M, GIACOMINO A, BUOSO S, CONCA E, SIVRY Y, BENEDETTI M & ABOLLINO O. 2017. Element variability in lacustrine systems of Terra Nova Bay (Antarctica) and concentration evolution in surface waters. Chemosphere 180: 343-355.), Enderby Land (Kakareka et al. 2019KAKAREKA S, KUKHARCHYK T & KURMAN P. 2019. Major and trace elements content in freshwater lakes of Vecherny Oasis, Enderby Land, East Antarctica. Environ Pollut 255. doi: https://doi.org/10.1016/j.envpol.2019.113126.
https://doi.org/10.1016/j.envpol.2019.11...
), Larsemann Hills (Nuruzzama et al. 2021NURUZZAMA M, RAHAMAN W & MOHAN R. 2021. Sources, distribution and biogeochemical cycling of dissolved trace elements in the coastal lakes of Larsemann Hills, East Antarctica. Sci Total Environ 764. doi: https://doi.org/10.1016/j.scitotenv.2020.142833.
https://doi.org/10.1016/j.scitotenv.2020...
), and Windmill Islands (Koppel et al. 2021KOPPEL DJ, PRICE GAV, BROWN KE, ADAMS MS, KING CK, GORE DB & JOLLEY DF. 2021. Assessing metal contaminants in Antarctic soils using diffusive gradients in thin-films. Chemosphere 269. doi: 10.1016/j.chemosphere.2020.128675.). Besides direct human contamination (Yin et al. 2006YIN XB, LIU XD, SUN LG, ZHU RB, XIE ZQ & WANG YH. 2006. A 1500-year record of lead, copper, arsenic, cadmium, zinc level in Antarctic seal hairs and sediments. Sci Total Environ 371(1-3): 252-257.), penguins, petrels, and gulls can also transport metals and contaminate lacustrine environments with their feces (Chu et al. 2019CHU ZD, YANG ZK, WANG YH, SUN LG, YANG WQ, YANG LJ & GAO YS. 2019. Assessment of heavy metal contamination from penguins and anthropogenic activities on Fildes Peninsula and Ardley Island, Antarctic. Sci Total Environ 646: 951-957. doi: https://doi.org/10.1016/j.scitotenv.2018.07.152.
https://doi.org/10.1016/j.scitotenv.2018...
, Chen et al. 2020CHEN YQ, GE JW, HUANG T, SHEN LL, CHU ZD & XIE ZQ. 2020. Restriction of sulfate reduction on the bioavailability and toxicity of trace metals in Antarctic Lake sediments. Mar Pollut Bull 151. doi: 10.1016/j.marpolbul.2019.110807., Castro et al. 2022CASTRO MF, MEIER M, NEVES JCL, FRANCELINO MR, SCHAEFER C & OLIVEIRA TS. 2022. Influence of different seabird species on trace metals content in Antarctic soils. An Acad Bras Cienc 94: e20210623 doi: 0.1590/0001-3765202220210623, Lopes et al. 2022LOPES DV, OLIVEIRA FS, SOUZA JJLL, MACHADO MR & SCHAEFER CEGR. 2022. Soil pockets phosphatization and chemical weathering of sites affected by flying birds of Maritime Antarctica. An Acad Bras Cienc 94: e20210595. doi: 10.1590/0001-3765202220210595.), since metal contamination occurs in coastal Antarctic areas (Potapowicz et al. 2020POTAPOWICZ J, SZUMINSKA D, SZOPINSKA M, BIALIK RJ, MACHOWIAK K, CHMIEL S & POLKOWSKA Z. 2020. Seashore sediment and water chemistry at the Admiralty Bay (King George Island, Maritime Antarctica) - Geochemical analysis and correlations between the concentrations of chemical species. Mar Pollut Bull 152. doi: 10.1016/j.marpolbul.2020.110888., Finger et al. 2021FINGER JVG, CORA DH, CONVEY P, SANTA CRUZ F, PETRY MV & KRUGER L. 2021. Anthropogenic debris in an Antarctic Specially Protected Area in the maritime Antarctic. Mar Pollut Bull 172. doi: 10.1016/j.marpolbul.2021.112921, Sparaventi et al. 2022SPARAVENTI E, RODRIGUEZ-ROMERO A, NAVARRO G & TOVAR-SANCHEZ A. 2022. A novel automatic water autosampler operated from UAVs for determining dissolved trace elements. Front Mar Sci 9. doi: 10.3389/fmars.2022.879953.).

Nelson Island has 164.8 km2 and is in the middle of the South Shetland Islands, located in Maritime Antarctic. Most of this island (95%) is covered by a permanent ice cap, and chemical analysis of the surface snow made around 30 years ago indicated detectable human influence (Rin et al. 1995RIN JW, QIN DH, PETIT JR, JOUZEL J, WANG WT, LIU C, WANG XJ, QIAN SL & WANG XX. 1995. Glaciological studies on Nelson Island, South-Shetland Islands, Antarctica. J Glaciol 41(138): 408-412.). From 1989 to 2020, Nelson Island registered 8.4% glacier area loss and 190% increase in lake area (Rosa et al. 2022ROSA KK, OLIVEIRA MAG, PETSCH C, AUGER JD, VIEIRA R & SIMOES JC. 2022. Expansion of glacial lakes on Nelson and King George Islands, Maritime Antarctica, from 1986 to 2020. Geocarto Int 37(15): 4454-4464.). Harmony Point, located in the southwest of the island, is an ice-free area (Rin et al. 1995RIN JW, QIN DH, PETIT JR, JOUZEL J, WANG WT, LIU C, WANG XJ, QIAN SL & WANG XX. 1995. Glaciological studies on Nelson Island, South-Shetland Islands, Antarctica. J Glaciol 41(138): 408-412.) whose lakes start to thaw in October, become completely thawed in February, and freeze again in March (Rosa et al. 2020ROSA CN, BREMER UF, PEREIRA W, SOUSA MA, KRAMER G, HILLEBRAND FL & JESUS JB. 2020. Freezing and thawing of lakes on the Nelson and King George Islands, Antarctic, using Sentinel 1A synthetic aperture radar images. Environ Monit Assess 192. doi: https://doi.org/10.1007/s10661-020-08526-5.
https://doi.org/10.1007/s10661-020-08526...
). The area of the lakes in Harmony Point increased 56-100% from 1988 to 2020 (Rosa et al. 2022ROSA KK, OLIVEIRA MAG, PETSCH C, AUGER JD, VIEIRA R & SIMOES JC. 2022. Expansion of glacial lakes on Nelson and King George Islands, Maritime Antarctica, from 1986 to 2020. Geocarto Int 37(15): 4454-4464.). Analysis of the soils of this region demonstrated phosphatization associated with guano accumulation but that there is low anthropic impact (Rodrigues et al. 2019RODRIGUES WF, OLIVEIRA FS, SCHAEFER C, LEITE MGP, GAUZZI T, BOCKHEIM JG & PUTZKE J. 2019. Soil-landscape interplays at Harmony Point, Nelson Island, Maritime Antarctica: Chemistry, mineralogy and classification. Geomorphology 336: 77-94., 2021a,b). Nevertheless, despite being a protected area, several kinds of anthropic debris (charcoal, rubber, plastic, and metal) were found recently (Finger et al. 2021FINGER JVG, CORA DH, CONVEY P, SANTA CRUZ F, PETRY MV & KRUGER L. 2021. Anthropogenic debris in an Antarctic Specially Protected Area in the maritime Antarctic. Mar Pollut Bull 172. doi: 10.1016/j.marpolbul.2021.112921). However, the contamination by metals in the freshwater lakes of this region has not been investigated. Therefore, the aim of this study is to analyze the waterborne metal levels in four lakes of Harmony Point to determine if human contamination has affected the freshwater of a protected Antarctic environment.

MATERIALS AND METHODS

Study area

Harmony Point is an area of Nelson Island whose lakes remain thawed in summer (Rosa et al. 2020ROSA CN, BREMER UF, PEREIRA W, SOUSA MA, KRAMER G, HILLEBRAND FL & JESUS JB. 2020. Freezing and thawing of lakes on the Nelson and King George Islands, Antarctic, using Sentinel 1A synthetic aperture radar images. Environ Monit Assess 192. doi: https://doi.org/10.1007/s10661-020-08526-5.
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), and they contain very low levels of chlorophyll, electrical conductivity, and turbidity (Rosa et al. 2021ROSA CN, PEREIRA W, BREMER UF, ANDRADE AMD, KRAMER G, HILLEBRAND FL & JESUS JB. 2021. The limnology and spectral behaviour of a freshwater lake at Harmony Point, Nelson Island, Antarctica. Antarctic Sci 33: 479-492.). This area consists of the tip of the island which is surrounded by the Bransfield Strait to the southeast and Drake Passage. To the northeast, there is a place where there is predominantly the island’s ice cap. The predominant rocks in Harmony Point are altered volcanic rocks, andesitic and dacite lavas, basalts of grayish to greenish dark colors interbedded with volcanic breccias, agglomerates, conglomerates, and tuffs, of Mesozoic to Cenozoic age (Smellie et al. 1984SMELLIE JL, PANKHURST RJ, THOMSON MRA & DAVIES RES. 1984. The geology the South Shetland Islands, VI. Stratigraphy, geochemistry and evolution. British Antarctic Survey Reports 87, 83 p., Machado 1997MACHADO A. 1997. Petrologia, geoquímica e geologia estrutural da Península Fildes. Ilha Rei George, Antártica (M.Sc. thesis). Brazil: Federal University of Rio Grande do Sul, 182. (Unpublished)., Rodrigues et al. 2019RODRIGUES WF, OLIVEIRA FS, SCHAEFER C, LEITE MGP, GAUZZI T, BOCKHEIM JG & PUTZKE J. 2019. Soil-landscape interplays at Harmony Point, Nelson Island, Maritime Antarctica: Chemistry, mineralogy and classification. Geomorphology 336: 77-94.). The drier areas are covered by carpets of the mosses Sanionia uncinate and Polytrichastrum alpinum and wetter regions contain Sanionia georgicouncinata and Warnsdorfia spp. Other mosses present are Andreaea gainii and Andreaea depressinervis. Several species of lichens are common in this area: Acarospora macrocyclus, Caloplaca spp, Himantormia lugubris, Ochrolechia frigida, Psoroma hypnorum and Cladonia spp. (Rodrigues et al. 2019RODRIGUES WF, OLIVEIRA FS, SCHAEFER C, LEITE MGP, GAUZZI T, BOCKHEIM JG & PUTZKE J. 2019. Soil-landscape interplays at Harmony Point, Nelson Island, Maritime Antarctica: Chemistry, mineralogy and classification. Geomorphology 336: 77-94.). This site is an Antarctic Specially Protected Area (ASPA 133) because it is the breeding ground for several seabird species in the region, among them the southern giant petrel (Macronectes giganteus) (Krüger 2019KRÜGER L. 2019. An update on the Southern giant petrels Macronectes giganteus breeding at Harmony Point, Nelson Island, Maritime Antarctic Peninsula. Polar Biol 42: 1205-1208.), the Antarctic shag (Leucocarbo bransfieldensis) (Oosthuizen et al. 2020OOSTHUIZEN WC, KRUGER L, JOUANNEAU W & LOWTHER AD. 2020. Unmanned aerial vehicle (UAV) survey of the Antarctic shag (Leucocarbo bransfieldensis) breeding colony at Harmony Point, Nelson Island, South Shetland Islands. Polar Biol 43: 187-191.), and penguins (Pygoscelis sp) (Rodrigues et al. 2021bRODRIGUES WF, OLIVEIRA FS, SCHAEFER CEGR, LEITE MGP & PAVINATO PS. 2021b. Phosphatization under birds’ activity: Ornithogenesis at different scales on Antarctic Soilscapes. Geoderma 391. doi: https://doi.org/10.1016/j.geoderma.2021.114950.
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).

Places of collection

The water samples were collected in 50 mL Falcon tubes in February 2019, from four Antarctic lakes in an ice-free area, located at Harmony Point (Figure 1). The samples were transported by ship at ambient temperature to Brazil. The transportation took two months. According to the landscape description of this area by Rodrigues et al. (2021a)RODRIGUES WF, OLIVEIRA FS, SCHAEFER CEGR, GAUZZI T & LEITE MGP. 2021a. Geochemistry of Antarctic periglacial soils from Harmony Point, Nelson Island. Environ Earth Sci 80(12): 430. doi: 10.1007/s12665-021-09713-4., all four lakes are in the upper platform, and therefore, within the same geomorphological context. The spatial distribution of the sampling stations was performed in accordance with the spatial characteristics and accessibility of each lake. These samples were taken at a depth of 15 cm.

Figure 1
The lakes sampled at Harmony Point, Nelson Island, Antarctic Peninsula.

Lake 1 is endorheic (Figure 2a). The ocean is located at 530 m to the northwest, 1500 m to the east, and 800 m to the southeast of the lake. Perimeter samples were collected at 2 m from the edge and consisted of 12 equidistant samples taken approximately 52 m from each other. The sampling of the central area of the lake was performed using a boat, and it consisted of three samples. The remaining three lakes are exorheics and interconnected. They were labeled as lakes 2, 3, and 4 (Figures 2b, c, and d) according to the water flow, which is headed west. Therefore, Lake 2 corresponds to a high course at 830 m from the coastline, the third lake represents the medium course at 690 m from the coastline, and the fourth is a low course at 540 m from the coastline. These lakes were sampled only at their outskirts, and two samples were collected on each lake at distances of approximately 60 m from each other (Table I). Lake 1 is inserted in landform patterned ground and the others in cryoplanated platform, following the classification in the platform map of Rodrigues et al. (2019)RODRIGUES WF, OLIVEIRA FS, SCHAEFER C, LEITE MGP, GAUZZI T, BOCKHEIM JG & PUTZKE J. 2019. Soil-landscape interplays at Harmony Point, Nelson Island, Maritime Antarctica: Chemistry, mineralogy and classification. Geomorphology 336: 77-94.. Based on the same authors, the area of the lakes has permafrost affected soils at a depth between 30 - 38 cm, parent material volcanic tuff and is somewhat poorly drained. The vegetation is mainly composed of rocky mosses Andreaea spp and Sanionia uncinata.

Figure 2
General view of lakes 1 (a), 2(b), 3(c), and 4(d) at Harmony Point, Nelson Island, Antarctic Peninsula. 3c also shows the collection of samples.
Table I
Location of the sampling points in the four Antarctic lakes located at Harmony Point, Nelson Island, Antarctic Peninsula.

Instrumentation

Water samples were analyzed at Universidade Federal de Santa Maria (Brazil) by using a quadrupole type inductively coupled plasma mass spectrometer (Perkin Elmer Sciex, Model ELAN DCR II, Canada) and an inductively coupled plasma optical emission spectrometer (model SpectroCiros, CCD, Spectro Analytical Instruments, Germany). The inductively coupled plasma mass spectrometer is equipped with a quartz torch (quartz injector tube of 2 mm i.d.) and a concentric nebulizer fitted to a colonic baffled spray chamber. The inductively coupled plasma optical emission spectrometer is equipped with a cross-flow nebulizer coupled to a Scott double-pass type spray chamber. Argon (99.998% purity) was used for plasma generation. The operational parameters of the ICP-MS and ICP OES instruments are shown in Supplementary Material - Table SI.

Sample analyses

All samples were collected in precleaned 50 mL polypropylene flasks (Sarstedt, Germany) and stored at -20 oC. Before analysis, the samples were thawed to ambient temperature. Ag, As, Ba, Be, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Se, Sr, Tl, U, and V were determined by inductively coupled plasma mass spectrometry (ICP-MS) and Ca, K, Mg and Na by inductively coupled plasma optical emission spectrometry (ICP OES). All analysis was done without any previous treatment or dilution. SRM 1640a was analyzed by ICP-MS and ICP OES in the same form as the samples. The accuracy of the results obtained by ICP-MS and ICP OES for the SRM 1640a water sample was checked at the 95% confidence level (using the t-test).

Reagents and solutions

Ultrapure water (resistivity of 18 MΩ cm) was obtained by a Milli-Q system (Millipore Corp., USA) and was used for material cleaning and solution preparation. Concentrated HNO3 (65% m m-1, Merck, Germany) was purified in a sub-boiling system (Milestone, Model Duopur, Italy). Multi-elemental reference solutions containing 10 mg L-1 (SCP 33MS, SCP Science, Canada) and 1000 mg L-1 (Certipur Merck IV, Merck, USA) were used for calibration in ICP-MS and ICP OES, respectively. The calibration curves and other solutions were prepared in 5% HNO3 (v v-1). Standard reference material (SRM 1640a, Trace Elements in Natural Water, National Institute of Standards & Technology, USA) was used to check the accuracy of the method.

Statistical analysis

Normality and homoscedasticity of data were checked with Bartlett and Levene tests, respectively. Data from all lakes that fulfilled the requisites (Ba, Ca, Cr, K, Mg, Na, and Sr) were analyzed by one-way Anova and the Tukey test, while non-parametric data (As, Cu, Mn, Mo, Ni, and V) were compared by Kruskal-Wallis and Dunn’s test. As lakes 2, 3, and 4 are interconnected and waterborne metal levels were not significantly different between them (see results), the mean of these lakes was also compared with Lake 1 by t-Student or Mann-Whitney tests (P<0.05). All data were expressed as mean ± standard deviation (SD).

RESULTS

The results obtained for the trace elements in natural water – SRM 1640a by ICP-MS and ICP OES and the limits of quantification (LOQ) of the methods are in Table II. The LOQ was calculated according to recommendations of the International Union of Pure and Applied Chemistry and considered the blank value and the standard derivation of 10 consecutive measurements of the blank (LOQ = B + 10s, where B is the blank value and s is the standard deviation).

Table II
Limit of quantification (LOQ) and results obtained for analysis of the SRM 1640a Trace Elements in Natural Water by ICP-MS and ICP OES. Values are the mean and standard derivation (1SD) for n = 3.

As can be observed, there were no significant differences (t-test, 95% confidence level) between certified and determined values obtained from the SRM 1640a. Therefore, both ICP OES and ICP-MS methods are considered accurate for the determination of these elements in the water samples.

Waterborne levels of Ag, Be, Cd, Pb (almost all samples), Se, Tl, and U were below LOQ, while for Ba half of the samples from lake 1, for Co two thirds of the samples from lake 1, all of the lakes 2 and 3, for Cr one lake 1 sample, and for Ni half of the lake 1 samples were below the LOQ. Waterborne levels of Mg were significantly lower in lakes 2 and 3 than in lake 1, and those of Na and Sr were significantly lower in lake 2 than in lake 1. The waterborne levels of As, Mo, and V were significantly higher in lake 4 than lake 1. The waterborne metal levels were not significantly different between lakes 2, 3, and 4. Considering the mean of waterborne levels in lakes 2, 3, and 4, the levels of As, Cu, Mn, Mo, and V were significantly higher and those of Cr, Mg, Na, and Sr were significantly lower than in lake 1 (Table III and Figure 3).

Figure 3
The concentration of the main elements in four Antarctic lakes located at Harmony Point, Nelson Island, Antarctic Peninsula. The values are the mean ± SD. # Significantly different from Lake 1 (considering only samples above the limit of quantification) by one-way Anova and the Tukey test or by Kruskal-Wallis and Dunn’s test (P<0.05).
Table III
The concentration of elements in four Antarctic lakes located at Harmony Point, Nelson Island, Antarctic Peninsula. Results were obtained from the analysis of water samples by ICP-MS and ICP OES. The values are the mean ± SD when the concentration of more than one sample was above the limit of quantification (each sample was measured in triplicate).

DISCUSSION

As expected, waterborne metal levels in the freshwater lakes of Harmony Point were lower (except As) than those detected by Souza et al. (2012)SOUZA JJLL, SCHAEFER CEGR, ABRAHAO WAP, MELLO JWV, SIMAS FNB, SILVA J & FRANCELINO MR. 2012. Hydrogeochemistry of sulfate-affected landscapes in Keller Peninsula, Maritime Antarctica. Geomorphology 155: 55-61. and Nedzarek et al. (2014)NEDZAREK A, TORZ A & DROST A. 2014. Selected elements in surface waters of Antarctica and their relations with the natural environment. Polar Res 33. doi: 10.3402/polar.v33.21417. in streams and lakes of King George Island, one of the most populated areas of the maritime Antarctic Peninsula, and lakes close to human settlements in Deception Island (South Shetland Islands) (Sparaventi et al. 2022SPARAVENTI E, RODRIGUEZ-ROMERO A, NAVARRO G & TOVAR-SANCHEZ A. 2022. A novel automatic water autosampler operated from UAVs for determining dissolved trace elements. Front Mar Sci 9. doi: 10.3389/fmars.2022.879953.) and Vecherny Oasis, Enderby Land, East Antarctica (Kakareka et al. 2019KAKAREKA S, KUKHARCHYK T & KURMAN P. 2019. Major and trace elements content in freshwater lakes of Vecherny Oasis, Enderby Land, East Antarctica. Environ Pollut 255. doi: https://doi.org/10.1016/j.envpol.2019.113126.
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) (Table IV). Areas with anthropogenic contamination usually present high waterborne Cu, Mo, Ni, Sr, Pb and Zn levels (Nedzarek et al. 2014NEDZAREK A, TORZ A & DROST A. 2014. Selected elements in surface waters of Antarctica and their relations with the natural environment. Polar Res 33. doi: 10.3402/polar.v33.21417., Kakareka et al. 2019KAKAREKA S, KUKHARCHYK T & KURMAN P. 2019. Major and trace elements content in freshwater lakes of Vecherny Oasis, Enderby Land, East Antarctica. Environ Pollut 255. doi: https://doi.org/10.1016/j.envpol.2019.113126.
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), which was not registered in the lakes of Harmony Point (only Zn was not quantified in the current study). The levels of metals measured in the lakes of Harmony Point are lower or similar to those observed by Conca et al. (2017)CONCA E, MALANDRINO M, GIACOMINO A, BUOSO S, BERTO S, VERPLANCK PL, MAGI E & ABOLLINO O. 2017. Dynamics of inorganic components in lake waters from Terra Nova Bay, Antarctica. Chemosphere 183: 454-470. and Zelano et al. (2017)ZELANO I, MALANDRINO M, GIACOMINO A, BUOSO S, CONCA E, SIVRY Y, BENEDETTI M & ABOLLINO O. 2017. Element variability in lacustrine systems of Terra Nova Bay (Antarctica) and concentration evolution in surface waters. Chemosphere 180: 343-355. in the lakes of Terra Nova Bay, and by Toro et al. (2007)TORO M ET AL. 2007. Limnological characteristics of the freshwater ecosystems of Byers Peninsula, Livingston Island, in maritime Antarctica. Polar Biology 30(5): 635-649. in lakes from Byers Peninsula (Livingston Island), other Antarctic protected areas, as well as in unpolluted lakes of Vecherny Oasis (Kakareka et al. 2019KAKAREKA S, KUKHARCHYK T & KURMAN P. 2019. Major and trace elements content in freshwater lakes of Vecherny Oasis, Enderby Land, East Antarctica. Environ Pollut 255. doi: https://doi.org/10.1016/j.envpol.2019.113126.
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) (Table IV). The only exception is Cu, because lakes 2, 3 and 4 have higher levels than the lakes from Terra Nova Bay (Conca et al. 2017CONCA E, MALANDRINO M, GIACOMINO A, BUOSO S, BERTO S, VERPLANCK PL, MAGI E & ABOLLINO O. 2017. Dynamics of inorganic components in lake waters from Terra Nova Bay, Antarctica. Chemosphere 183: 454-470., Zelano et al. 2017ZELANO I, MALANDRINO M, GIACOMINO A, BUOSO S, CONCA E, SIVRY Y, BENEDETTI M & ABOLLINO O. 2017. Element variability in lacustrine systems of Terra Nova Bay (Antarctica) and concentration evolution in surface waters. Chemosphere 180: 343-355.). The waterborne As and Cu levels in lakes 2, 3 and 4 of Harmony Point are also the only levels higher than those from the coastal lakes of Larsemann Hills, East Antarctica (Nuruzzama et al. 2021NURUZZAMA M, RAHAMAN W & MOHAN R. 2021. Sources, distribution and biogeochemical cycling of dissolved trace elements in the coastal lakes of Larsemann Hills, East Antarctica. Sci Total Environ 764. doi: https://doi.org/10.1016/j.scitotenv.2020.142833.
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).

Table IV
The concentration range of elements in four lakes (this study) and soil from horizon A + horizon C of upper platform from Harmony Point (data of Rodrigues et al. 2021), surface snow from the top of Nelson Island (data of Qin et al. 1993QIN DH, MAYEWSKI PA, WAKE CP & YANG QZ. 1993. Anions and cations in a snow pit on the top of Nelson Ice Cap, the Southern Shetland Islands, Antarctica. Chinese Sci Bull 38(4): 312-316.), lakes from Byers Peninsula (Livingston Island) (data of Toro et al. 2007TORO M ET AL. 2007. Limnological characteristics of the freshwater ecosystems of Byers Peninsula, Livingston Island, in maritime Antarctica. Polar Biology 30(5): 635-649.), and from Vecherny Oasis, Enderby Land, East Antarctica (data of Kakareka et al. 2019KAKAREKA S, KUKHARCHYK T & KURMAN P. 2019. Major and trace elements content in freshwater lakes of Vecherny Oasis, Enderby Land, East Antarctica. Environ Pollut 255. doi: https://doi.org/10.1016/j.envpol.2019.113126.
https://doi.org/10.1016/j.envpol.2019.11...
).

The differences observed in some waterborne metal levels of lake 1 and lakes 2, 3, and 4 may be associated with the geographic context in which the lakes are located. Lake 1, endorheic, contains lower Cu data than the other lakes, which are exorheic. In this sense, it is noteworthy that lake 1 did not have snow/ice in its catchment area and is a lentic environment, while the other lakes were under snow/ice melting conditions in their hydrographic basin, configuring themselves as a semi-lentic. Therefore, they received water from meltwater and were subject to metal contamination due to leaching from the soils and from the meltwater itself.

Within the determined metal values, Ba, Cu, and V are trace elements with higher concentrations in the soil of the coastal domain from Harmony Point (Rodrigues et al. 2021aRODRIGUES WF, OLIVEIRA FS, SCHAEFER CEGR, GAUZZI T & LEITE MGP. 2021a. Geochemistry of Antarctic periglacial soils from Harmony Point, Nelson Island. Environ Earth Sci 80(12): 430. doi: 10.1007/s12665-021-09713-4.) (Table IV), which could explain the presence of Cu and V in the lakes. However, waterborne Ba levels in the lakes were comparatively low, which reduces the possibility of soil origin for these metals. Another possibility to explain the waterborne Cu and Sr levels would be the guano from different seabird species that occur in the region. Nevertheless, the guano of giant petrels, which have several active nests in Harmony Point (Krüger 2019KRÜGER L. 2019. An update on the Southern giant petrels Macronectes giganteus breeding at Harmony Point, Nelson Island, Maritime Antarctic Peninsula. Polar Biol 42: 1205-1208.), as well as of gentoo penguins (Pygoscelis papua) and kelp gulls (Larus dominicanus) contains 2-4-fold higher concentrations of Mn than Cu and Sr (Castro et al. 2022CASTRO MF, MEIER M, NEVES JCL, FRANCELINO MR, SCHAEFER C & OLIVEIRA TS. 2022. Influence of different seabird species on trace metals content in Antarctic soils. An Acad Bras Cienc 94: e20210623 doi: 0.1590/0001-3765202220210623), and waterborne Mn levels are 8-15-fold lower than Cu and Sr levels, but the same authors did not find any relationship between Mn content in the soils and bird guano. Apparently, the levels of As in the soil of Harmony Point, determined by Rodrigues et al. (2021a)RODRIGUES WF, OLIVEIRA FS, SCHAEFER CEGR, GAUZZI T & LEITE MGP. 2021a. Geochemistry of Antarctic periglacial soils from Harmony Point, Nelson Island. Environ Earth Sci 80(12): 430. doi: 10.1007/s12665-021-09713-4., also showed a relationship with the waterborne levels, as other metals such as Co and Pb presented higher levels in the soil (Rodrigues et al. 2021aRODRIGUES WF, OLIVEIRA FS, SCHAEFER CEGR, GAUZZI T & LEITE MGP. 2021a. Geochemistry of Antarctic periglacial soils from Harmony Point, Nelson Island. Environ Earth Sci 80(12): 430. doi: 10.1007/s12665-021-09713-4.) and waterborne levels close to LOQ. The lower levels of waterborne As in surface waters of King George Island (Nedzarek et al. 2014NEDZAREK A, TORZ A & DROST A. 2014. Selected elements in surface waters of Antarctica and their relations with the natural environment. Polar Res 33. doi: 10.3402/polar.v33.21417.) than in the lakes of Harmony Point are in disagreement with the hypothesis of anthropic origin of this metal. The waterborne metal levels in the freshwater lakes from Harmony Point, with exception of Cu in lakes 2, 3 and 4, indicated that the waters of these lakes are indicative of high ecosystem integrity according to United Nations University (2016)UNITED NATIONS UNIVERSITY. 2016. International Water Quality Guidelines for Ecosystems. and are below the limits established by the EPA (2022a, b) for aquatic life and human health. The increase of snow melting that has been occurring in the last years in Nelson Island (Rosa et al. 2022ROSA KK, OLIVEIRA MAG, PETSCH C, AUGER JD, VIEIRA R & SIMOES JC. 2022. Expansion of glacial lakes on Nelson and King George Islands, Maritime Antarctica, from 1986 to 2020. Geocarto Int 37(15): 4454-4464.) probably contributed to the low waterborne metal levels in the lakes compared to the soil in Harmony Point, as the snow in unpolluted sites has very low metal levels (Qin et al. 1993QIN DH, MAYEWSKI PA, WAKE CP & YANG QZ. 1993. Anions and cations in a snow pit on the top of Nelson Ice Cap, the Southern Shetland Islands, Antarctica. Chinese Sci Bull 38(4): 312-316., Kakareka et al. 2020KAKAREKA S, KUKHARCHYK T & KURMAN P. 2020. Study of trace elements in the surface snow for impact monitoring in Vecherny Oasis, East Antarctica. Environ Monit Assess 192(11): 725. doi: 10.1007/s10661-020-08682-8.) (Table IV). Despite the water of these lakes from Harmony Point having low levels of waterborne metals, before any consideration regarding use for human consumption, it is important to determine phosphate (or phosphorus) and nitrate levels as well as bacterial diversity, as these factors are influenced by the occurrence of birds (Mindl et al. 2007MINDL B, ANESIO AM, MEIRER K, HODSON AJ, LAYBOURN-PARRY J, SOMMARUGA R & SATTLER B. 2007. Factors influencing bacterial dynamics along a transect from supraglacial runoff to proglacial lakes of a high Arctic glacier. Fems Microbiol Ecol 59(2): 307-317., Villaescusa et al. 2013VILLAESCUSA JA, CASAMAYOR EO, ROCHERA C, QUESADA A, MICHAUD L & CAMACHO A. 2013. Heterogeneous vertical structure of the bacterioplankton community in a non-stratified Antarctic lake. Antarctic Sci 25(2): 229-238., Zhu et al. 2015ZHU RB, SHI Y, MA DW, WANG C, XU H & CHU HY. 2015. Bacterial diversity is strongly associated with historical penguin activity in an Antarctic lake sediment profile. Sci Rep 5: 17231. doi: 10.1038/srep17231.), and this region is the breeding ground for several seabird species (Krüger 2019KRÜGER L. 2019. An update on the Southern giant petrels Macronectes giganteus breeding at Harmony Point, Nelson Island, Maritime Antarctic Peninsula. Polar Biol 42: 1205-1208., Oosthuizen et al. 2020OOSTHUIZEN WC, KRUGER L, JOUANNEAU W & LOWTHER AD. 2020. Unmanned aerial vehicle (UAV) survey of the Antarctic shag (Leucocarbo bransfieldensis) breeding colony at Harmony Point, Nelson Island, South Shetland Islands. Polar Biol 43: 187-191., Rodrigues et al. 2021bRODRIGUES WF, OLIVEIRA FS, SCHAEFER CEGR, LEITE MGP & PAVINATO PS. 2021b. Phosphatization under birds’ activity: Ornithogenesis at different scales on Antarctic Soilscapes. Geoderma 391. doi: https://doi.org/10.1016/j.geoderma.2021.114950.
https://doi.org/10.1016/j.geoderma.2021....
).

The higher waterborne levels of Na and Mg (but not Ca) in Lake 1 compared to the other lakes may be due to salt spray from the ocean, as Lake 1 is closer to the ocean than lakes 2 and 3. In comparison, the distance of the lakes from the seashore affected more deeply the levels of Na, Ca, Mg, and K in Byers Peninsula, Livingston Island, with the ones closer to the ocean having 16-55-fold higher levels (Toro et al. 2007TORO M ET AL. 2007. Limnological characteristics of the freshwater ecosystems of Byers Peninsula, Livingston Island, in maritime Antarctica. Polar Biology 30(5): 635-649.) (Table IV). The low Mg/Ca ratio determined in the lakes of Harmony Point (0.818-1.275) is also an indication of the low influence of salt spray, because lower values are registered in lakes more distant from the sea (Abollino et al. 2004ABOLLINO O, ACETO M, BUOSO S, GASPARON M, GREEN WJ, MALANDRINO M & MENTASTI E. 2004. Distribution of major, minor and trace elements in lake environments of Antarctica. Antarct Sci 16: 277e291., Kakareka et al. 2019KAKAREKA S, KUKHARCHYK T & KURMAN P. 2019. Major and trace elements content in freshwater lakes of Vecherny Oasis, Enderby Land, East Antarctica. Environ Pollut 255. doi: https://doi.org/10.1016/j.envpol.2019.113126.
https://doi.org/10.1016/j.envpol.2019.11...
). Higher Na levels were observed in soils of Harmony Point closer to the ocean, but Mg and Ca levels were similar (Rodrigues et al. 2019RODRIGUES WF, OLIVEIRA FS, SCHAEFER C, LEITE MGP, GAUZZI T, BOCKHEIM JG & PUTZKE J. 2019. Soil-landscape interplays at Harmony Point, Nelson Island, Maritime Antarctica: Chemistry, mineralogy and classification. Geomorphology 336: 77-94., 2022). The levels of Na, Ca, Mg, and K are higher in soils affected by flying birds and penguins in Snow Island (Antarctic Peninsula) (Lopes et al. 2022LOPES DV, OLIVEIRA FS, SOUZA JJLL, MACHADO MR & SCHAEFER CEGR. 2022. Soil pockets phosphatization and chemical weathering of sites affected by flying birds of Maritime Antarctica. An Acad Bras Cienc 94: e20210595. doi: 10.1590/0001-3765202220210595.), but if there was enough leaching from ornithogenic soils to affect the levels of these ions in the lakes, this leaching was similar between lakes, as no significant difference in Ca and K levels were detected.

CONCLUSIONS

In conclusion, waterborne metal levels in the freshwater lakes from Harmony Point present low levels, as observed in lakes of other Antarctic unpolluted sites. There was no clear relationship of waterborne metals with their levels in the soil of the region or with bird guano, and overall, their levels indicate an environment without anthropogenic influence. However, these levels may be associated with the geographic context in which the lakes are located, because lake 1, endorheic, shows some significant differences compared to the exorheic lakes (2, 3, and 4). The Na levels are apparently influenced by salt spray from the ocean, as they are related to the distance of the lakes from the ocean, but the influence of the salt spray in these levels is much lower than observed in other Antarctic lakes. Therefore, these lakes can be used as reference sites for the analysis of environmental perturbations. As Harmony Point is a place with high occurrence of petrels, penguins, and gulls, future studies should investigate waterborne levels of phosphate, nitrate, uric acid, and bacteria.

ACKNOWLEDGMENTS

B. Baldisserotto, W. Pereira Filho, Dressler, V. L. received research fellowships from Conselho Nacional de Desenvolvimento Tecnológico (CNPq, Brazil). This research received funding from CNPq.

SUPPLEMENTARY MATERIAL

Table SI

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Publication Dates

  • Publication in this collection
    26 Aug 2024
  • Date of issue
    2024

History

  • Received
    11 Oct 2023
  • Accepted
    04 July 2024
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