Keywords

Highlights

  • Scientific interest in the issue of presence of pollutants in Antarctica steadily increasing since 1960.

  • In various samples from Antarctica a variety of harmful pollutants were identified.

  • The analytic methods, which are dedicated to determine POPs and metals in different matrices, need to be developed.

  • Antarctica is prone to storage of POPs, which may also undergo remobilization processes.

1 Introduction

The term “Antarctica” is used to define both the Antarctica continent itself as well as the Southern Ocean that surrounds the continent and the islands of this ocean. Antarctica is the most isolated continent; however, its specific location does not protect this area from negative impact of human activities (Aronson et al. 2011). A broad belt of the Southern Ocean’s waters constitutes a barrier, which makes it difficult to transport pollutants this way. Therefore, volatile and semi-volatile chemical compounds may reach Antarctica together with air masses moving in this direction (long-range atmospheric transport—LRAT) (Corsolini 2009). However, more and more attention has been recently paid to the determination of the size of the locally emitted contamination impact on Antarctic environment (Bengtson Nash et al. 2011).

The first information on the occurrence of anthropogenic pollutants comes from the 1960s and it pertains to the presence of dichlorodiphenyltrichloroethane (DDT) in sea organisms (Bargagli 2008). Further research pertained to chemical composition of samples of water, snow and ice and it included metal and ion determination. Since the 1960s, research on the presences of pollutants from the group of persistent organic pollutants (POPs), e.g. hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), aldrin, endrin, heptachlor and other pollutants in samples of living and non-living matter collected in Antarctica has been undertaken (Bargagli 2008; Corsolini 2009).

However, due to difficult climatic conditions, research pertaining to pollution analysis in this area was conducted on irregular basis. In recent decades, there has been a growing interest in the problems of pollutants present in samples from various elements of Antarctica’s ecosystem. Figure 1 presents milestones of events influencing the development of research on Antarctica (including ones influenced development of chemical research).

Fig. 1
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Milestones of events connected with the development of Antarctic research (Köler 2013; SCAR Information; Dastidar and Ramachandran 2008; Dodds 2010)

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Urbanised areas, especially those with intensive agriculture, as well as tropical and subtropical regions, where spraying is used for disease vector control, are the main sources of POPs and heavy metals in the Southern Hemisphere. The increase in the usage of many POPs has been observed in the 1990s in Asian countries and Southern Pacific islands (Bargagli 2008). Some large amounts of polychlorinated biphenyls (PCBs) used in older electrical devices were also deposited as landfill in some developing countries. The heaviest user of DDT, toxaphene and lindane, has historically been in South America. A comprehensive report by UNEP in 2002 gives more precise data on air levels of POPs in the Southern Ocean and Antarctica (Bargagli 2008).

A critical comparison and discussion of results of the research conducted over decades is not easy, as over a period of more than 50 years, methods and techniques used for research have undergone continuous changes. Moreover, while conducting research on such a complex ecosystem, it is necessary to frequently verify any possible changes by comparing the data acquired during different research projects and at different times. However, this task often cannot be practiced as the results may be achieved with the use of analytical techniques which present extremely different degrees of accuracy and sensitivity (Magi and Tanwar 2014).

The study presents information on the dynamics of the development of polar research (covering main groups of pollutants) both in terms of its methodology and the scope of research on Antarctica (diversity of tested samples and analytes) conducted over the past decades by members of teams working at polar research stations.

2 The Presence of Pollutants in Antarctica’s Environment

Polar ecosystems consist of several key species. Mutual relationships between individual elements of the environment are closely connected; therefore, the presence of pollutants in one of elements of the ecosystem may have a significant influence on the functioning of the other ones. To become familiar with the influence of pollutants on the functioning of Antarctica’s ecosystem, research is conducted on both abiotic and biological samples.

2.1 Abiotic Environment

Abiotic environmental media (fresh water and seawater, precipitation, glaciers, soils, etc.), as well as all processes and phenomena connected with changes occurring in individual elements of the environment (meteorological, geological, geochemical processes, etc.), play a significant role in transporting pollutants in Antarctica (Cipro et al. 2012). Elements of abiotic environmental media, such as snow, glaciers and polar catchment areas are sources of water for all organisms living in Antarctica. Antarctica’s ecosystem has a very simple structure, therefore, even a small amount of pollution present in abiotic elements of nature may constitute a significant hazard for any individual plant and animal species because of absence of advanced detoxification mechanisms (Bengtson Nash et al. 2011).

2.1.1 Air

The atmosphere plays an important role in transport of pollutants to polar areas. Over the past decade, a range of research has been conducted to determine mechanisms, which contribute to the presence of pollutants in Antarctica, as well as to distinguish between local sources of pollution and long-range atmospheric transport.

Information about Antarctica’s air pollutants mostly comes from research conducted during cruises near Antarctica (Bengtson Nash et al. 2011) and is predominantly based on short-term (weeks–month) atmospheric monitoring (Kallenborn et al. 2013). Some of these data have been included in the assessment of global distribution of numerous POPs. However, due to the limited number of samples and non-continuous measurement periods, it is difficult to compare the results of air sample research conducted in Antarctica with the results of sample research from the Arctic region. A long-term atmospheric pollution monitoring in the polar regions is a significant scientific tool for assessing anthropogenic influences on the environment on a global scale. It enables the control or even changes of international legal regulations (Kallenborn et al. 2013).

The results of research on long-term monitoring of POPs were published in 2013 and focused on the concentrations of long-range transported contaminants (POPs) in the Antarctic environment. The research has revealed that the atmospheric long-range transport of polluted air masses is considered as the main source for the POPs monitored at Norwegian Troll station in Dronning Maud Land (Kallenborn et al. 2013). In the discussion about the presence of more volatile substances in Antarctica, as a source of it, long-range atmospheric transport is considered, while the presence of less volatile substances, which occur occasionally in Antarctic’s air, may rather indicate influence of local sources (Kallenborn et al. 2013). A particular impact of local sources is shown in the analysis of compounds from the polybrominated diphenyl ethers (PBDEs) group. Due to the fact that neither plastics nor PBDE manufacturing occur in Antarctica, the substantial indoor PBDE residues are likely to originate from losses of imported flame retarded plastic and electronic products. There are plenty of electronic devices in the research stations, but at the same time there is not much space for them. Moreover, the material transport to Antarctica is expensive (Hale et al. 2008). The first atmospheric measurement, which was constructed as a part of a new continuous monitoring effort, was presented in one of Australia’s all-year research station—Casey Station (66°17′ S 110°3′ E). The results suggest a potential local source of the currently produced, involatile, decabrominated PBDE congener 209, which contributes to PBDE profiles in all the samples (Bengtson Nash et al. 2011).

These discussions prove that it is necessary to take additional precautions in order to stop further deterioration of the pristine air status in Antarctica caused by the human presence in this region.

2.1.2 Snow and Ice

In polar areas chemicals like POPs have been observed in seasonal snowpack and in older layers of firn and ice, providing accumulation time series (Herbert et al. 2006b).

During long-range atmospheric transport, pollutants may undergo decomposition and deposition processes, depending on the physicochemical properties of individual compounds.

The mechanisms of exchange of trace organic contaminants between the atmosphere and snow (both falling snow and standing snowpack) depend on the major processes like scavenging (vapour and particle) by falling snow, vapour sorption/desorption to the snow’s surface, and diffusion of chemicals both into and out of the snowpack (Herbert et al. 2006b). These processes dictate the quantities of chemical compounds available to meltwater and in deeper areas (permanent snow and ice). Additionally, processes occurring after deposition, e.g. snow settling (fresh snow is gradually transformed into firn and then in a glacier layer, the volume of which becomes gradually reduced) are of importance. The snow-settling process is the first stage, during which compounds, e.g. from the polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) group, are adsorbed on snowflakes. These compounds due to their physicochemical properties are classified as semi-volatile compounds, may become released back to the gaseous phase during seasonal snowmelt or diffused into deeper snow layers (Wania 1997). This process inter alia depends on solubility (concentration of a given compound), the snow-air partitioning properties and the temperature gradient. The snow-air partitioning properties not only depend on the vapour pressure but also on the surface properties of the snow flakes/snow pack. These properties largely determine the sorption and diffusion processes (Herbert et al. 2006b).

Based on experimental diffusivities for a volatile tracer of sulfur hexafluoride in snowpack it was concluded that in the low-wind (up to 3 m/s) scenario the migration of sulfur hexafluoride in the snowpack can be largely attributed to diffusive transport, while at high wind speeds (up to 9 m/s) the chemical migration is largely due to advective transport (Albert and Shultz 2002). Snow and firn metamorphism processes depend on the temperature fluctuations. Grain growth may occur, which, in turn, increases the firn permeability. As a result of global migration of a broad range of compounds towards higher latitudes, they become accumulated in polar regions (Kozak et al. 2013). Systematic compound accumulation contributes to the formation of a pollutant reservoir. A large part of the pollutant load is stored in snow and ice. Chemical compounds, which may be trapped in polar areas, can constitute a long-term hazard due to the possibility of their subsequent release into the environment—the so-called reemission into the environment may occur (Herbert et al. 2006a). Quantities of pollutants released during the spring snowmelt could have significant influence on the quantities of pollutants present in both freshwater and marine system (Herbert et al. 2006b). This hypothesis is named “spring pulse” and currently researchers are working on the creation of snowmelt models concerning quantitative transport of pollutants from snow to other abiotic environmental media (Burniston et al. 2007; Herbert et al. 2006b; Wania et al. 1999).

2.1.3 Soil and Permafrost

For the study of air transported pollutants, soil samples are worthy of note materials because of their direct contact with the atmosphere. Antarctica’s soil may become polluted as a result of wet and dry deposition (LRAT) and accidental release of pollutants into the environment (oil spills) (Curtosi et al. 2007; Webster et al. 2003; Aisable et al. 2004).

The concentration limits of compounds in soil depend on the type of soil. Antarctica’s soil variability is mainly due to parent material, differences in land-surface age (range: from a few thousand to millions of years), topographic position and local climate (Aisable et al. 2004).

In general approach to the presence of pollutants in soil, permafrost and an active soil layer play an important role in migration of compounds in soil (Curtosi et al. 2007). An active soil layer and permafrost presence is a unique characteristic of polar areas. It is known that repeated freeze/thaw cycles occur in areas with an active layer of permafrost, as a result of which soil particles may undergo a slow process of screening. Small particles may migrate from the surface layer into deeper layers, while stones have a tendency to migrate from deeper layers to the surface. Pollutants are adsorbed mostly from the surface of particles with a smaller diameter. Research results show that the percentage (quantity) of small particles and their dynamics in the soil matrix are the key factors in determining the fate and degradation of pollutants, e.g. PAHs in Antarctic soil. In this way, thawing of the upper layer of the permafrost, which may be caused by global warming, will have widespread influence on the distribution of pollutants in this environment (Curtosi et al. 2007).

2.1.4 Catchment Areas

There are lakes and small streams, which thaw in the summer in small areas of Antarctica which are free from ice. Open water lakes in Antarctica are very rare due to low temperatures. However, the accumulation of pollutants also occurs in lakes and lake sediments. Much higher concentrations (as compared to concentrations of the same analytes in soil samples) of some compounds, e.g. HCH in lake sediments are probably determined by the nature of Antarctic lakes. Antarctic’s lakes are formed from melting ice water, which is rich in atmospheric particles (trapped in it during formation) (Fuoco et al. 2009a; Vandal et al. 1998).

Another factor, which influences the level of pollutants in freshwater environment, is the transport of persistent chemicals by seabirds biovector. Higher concentration of POPs has been recorded in aquatic organisms from a seabird-affected lake. This is a proof that seabird-transported contaminants have been entering freshwater and thereby local food webs (Michelutti et al. 2010; Xie and Sun 2008). As long as detailed mechanism of pollution transfer by seabird’s vectors are not widely described, further researches should be applied in this direction.

2.1.5 Ocean, Seas and Bottom Sediments

Oceans and seas plays a significant role in the circulation and removal of pollutants. Within Antarctica, the Antarctic Convergence Zone (also called the Antarctic Polar Front) is distinguished. It runs between 47°S and 62°S. It separates cold and less saline Antarctic waters from subantarctic waters. The zone may be the barrier for pollutants transported by sea (Bengtson Nash et al. 2011).

Relatively much attention was devoted to research targeted at estimating the degree of exchange of pollutants between the seawater surface (inter-phase) and the atmosphere and the role of seawater in the process of transporting chemical compounds to polar regions. The sea surface consists of layers, out of which the sea surface microlayer (SML) has been researched most broadly (0.1–0.001 mm). This is a place where pollutants, atmospheric particles and microorganisms accumulate. However, the majority of research projects focusing on measurements of pollutant content in SML samples were conducted using samples collected in coastal environments. There is very little data from open ocean samples (Fuoco et al. 2009a).

Another element of abiotic environmental media in the pollutant transportation process is bottom sediments. More hydrophobic organic compounds may undergo sorption on solid particles and microorganisms. Dead particles of organic matter and solid particles settle on the bottom and, thus, pollutants adsorbed on them accumulate in bottom sediments (Boutron et al. 1990). Pollutants present in bottom sediments may be re-emitted as a result of activity of bottom organisms and ocean currents. Thus, the bottom sediments can become secondary source of pollution.

2.2 Biotic Environment

Anthropogenic pollutants have an adverse effect on living organisms. Antarctic biota (e.g. seals and penguins) are particularly sensitive to contaminants. The natural stress on wildlife in extreme polar environments is often more severe than in temperate regions. Hence Antarctic species can be more vulnerable to the effects of pollutants in comparison with species which come from temperate regions (Schiavone et al. 2009a). Moreover, due to very simple structures of polar ecosystems, relationships between individual organisms are important in terms of pollution transfer. Mutual connections between individual species determine the way, in which pollutants are transported (Cipro et al. 2012).

2.2.1 Plants

Mosses and lichens are the main components of the terrestrial flora of Antarctica’s ecosystem. Bryophytes are predominantly useful for monitoring the atmospheric pollution (metals and organochlorine compounds) because they have no protective waxy cuticles and no root system (Borghini et al. 2005). The content of pollutants present in samples of these plants largely depends on precipitation. Thus, they can play a very important role of biomonitors, i.e. indicators of long-term pollutant deposition (Fuoco et al. 2009a).

As mentioned above, pollutants present in the air may undergo dry or wet deposition, thus getting into Antarctica’s environment. Plants absorb pollutants from the atmosphere (through their above-ground parts, especially leaves) or/and from the soil (through the roots). For compounds with strong hydrophobic properties, transport through solids seems to have little significance. Literature data may be the basis for concluding that the main mechanism of collecting pollutants from the environment is absorption from the surrounding air into the leaf surface of pollutants in the gaseous phase or the solid phase (through particles settled on plant surfaces) (e.g. Borghini et al. 2005; Mão de Ferro et al. 2014; Poblet et al. 1997; Wu et al. 2014; Yogui and Sericano 2008; Yogui et al. 2011). Pollutants get into plants through stomata or leaf epidermis. Furthermore, the process of “assimilating pollutants” into plants is influenced by a range of physicochemical factors (e.g. partial pressure of water vapour, the numerical value of the octanol/water partition coefficient and the water/octanol partition coefficient), environmental factors (e.g. the temperature, precipitation, wind speed) and plant properties (e.g. the species, fat content, leaf morphology) (Yogui and Sericano 2008; Yogui et al. 2011).

2.2.2 Crustaceans, Benthic Organisms and Fishes

Antarctica’s ecosystem has a very simple structure. Organisms at higher levels of the trophic chain depend on several key species, such as the Antarctic silverfish (Pleuragramma antarcticum) and the Antarctic krill (Euphausia superba). The Antarctic silverfish and the Antarctic krill are the main sources of food for many maritime species of birds and mammals. As a result of the mutual relationship between the size of the krill and silverfish populations and the size of the populations of other species, a decrease in the krill and silverfish population size may have a negative impact on the entire environment of Antarctica’s marine ecosystem (Corsolini et al. 2002b). As a result of close relationships between individual species, POPs are present in every level of the trophic chain (Corsolini et al. 2002b). The phenomenon of biomagnification plays a more important role than bioaccumulation itself in the case of Antarctic fish. Lower pollutant concentrations are observed in samples of fish, for which krill is the staple food. Values of harmful compound concentrations increase if invertebrates or other fish are the main source of food (Weber and Goerke 2003).

In pelagic fish a downward trend in concentrations of some persistent organic pollutants (e.g. HCB, dieldrin) is visible (Van den Brink et al. 2011). It contrasts distinctly with steady or increasing concentrations levels in benthic organisms. Transfer of contaminants between Antarctic pelagic and benthic food webs is associated with seasonal sea-ice dynamics and thus with different climatic conditions. This fact may hinder the predictability of future trends of emerging compounds in the Antarctic ecosystem (e.g. the brominated compounds). The discrepancy in trends between pelagic and benthic organisms still remains the question whether the total environmental burden of contaminants in the Antarctic ecosystem is declining or increasing (Van den Brink et al. 2011).

2.2.3 Seabirds

Marine birds are another link in the food chain, where penguins constitute the most numerous group. They belong to key-species in Antarctica’s ecosystem. Penguins feed mainly on krill and also on fish (depending on krill’s accessibility). Researchers have reported that predators may be a sink for chemicals (special for volatile and toxic ones) and this may pose an important environmental problem (Corsolini et al. 2007).

Penguins (Adèlie and Emperor) spend their whole life in the Southern Ocean, while marine bird species, such as migrating snow petrel, south polar skua, brown skua are species migrating all over Antarctica. In both cases, results of samples researched from these species could reflect the condition of their ecosystems (Corsolini et al. 2011). The aforementioned bird species rely on all krill species and the Adèlie penguin eats the most krill (Corsolini et al. 2011). The Emperor penguin also eats a lot of fish as well as crustaceans and cephalopods. The south polar skua feeds on penguins’ eggs and chicks and it also eats Antarctic silverfish krill (over 80 %). In the nesting season, on the other hand, skuas depend on food found on land. The brown skua also relies on sea food (Corsolini et al. 2011). Moreover, the research results concerning detection of POPs in seabirds’ eggs (including penguin and south polar skua eggs) proved the transfer of POPs from mothers to eggs (Corsolini et al. 2002a).

The most important link between Antarctic marine, freshwater and terrestrial ecosystems constitutes seabirds. In fact, they maintain the development of terrestrial flora due to the high amount of nutrients deposited by seabirds on the land (e.g. by guano). Seabirds usually transport loads of pollution. Unfortunately, endocrine mechanisms are still poorly investigated in free-living organisms, despite the fact, that contaminants have endocrine disrupting properties. In the scientific literature there is surprisingly only few data on the effect of age on contaminant levels, despite the fact that long-lived organisms are thought to be highly sensitive to pollution. Therefore, it is not clear if seabirds accumulate POPs with increasing age (Tartu et al. 2015).

Comparing research results concerning pollution in birds’ tissues from other areas of the world, shows that POPs concentrations in penguins are relatively low (Corsolini et al. 2007). In relation to species and sex, different chemical accumulation patterns are observed. Penguins are showing low detoxifying capacities and therefore studies on their xenobiotic metabolism should be carried out (Corsolini et al. 2007).

2.2.4 Marine Mammals

During the evaluation of contamination presence in the marine mammals’ tissues scientists should bear in mind the migratory habits of these organisms. Some species of marine mammals (including cetaceans) exist in Antarctica’ seawaters in summer time and then go northward during winter, while other species, e.g. some seals, spend their entire life cycles in the Southern Ocean and on the Antarctic coasts. In migrating organisms what may affect the amount of pollution in Antarctic organisms is the forage or breed during summer, as well as exposition to pollutants in more contaminated areas during winter. Species and individuals staying in anthropized areas during migration contribute to greater exposure to contamination compared with those that stay in Antarctica all year round. Furthermore, pollution (like POPs) accumulation in marine mammals depends on some other factors including metabolism (Corsolini 2009).

Marine mammals differ from the land ones with a high lactation transfer of all lipophilic substances (including pollutants) to young animals (Schiavone et al. 2009a; Trumble et al. 2012). This mostly results from an increased fat content in the mother’s milk (Schiavone et al. 2009a). For cetacea and pinnipeds a vast majority (approx. 90 %), of the total amount of chloroorganic pollutants occurring in newborns are transferred in the mother’s milk (Cipro et al. 2012). Due to the position of mammals in the trophic chain of the marine environment, a relatively long life and an increased demand for energy, the pinniped species can be treated as an indicator (reference) species for the examination of harmful effects of pollutant bioaccumulation in organisms (Cipro et al. 2012).

Marine mammals have been exposed also inter alia to heavy metals. Scientists are devoting particular attention to mercury because of its toxicity as well as the fact that it is widespread within the environment, and can be biomagnified in marine food chains. Very important is also the fact that Hg is available mainly because of human activities (e.g. Jerez et al. 2011). However, data of concentrations of Hg in seals and other vertebrates of Antarctica’s are sparse (Szefer et al. 1993). Moreover, most of the attention in marine mammals’ research is devoted to the identification of organic contaminants. Some reports lead even to observation of an increasing trend of PCBs and chlorinated pesticides: HCB, HCHs, chlordanes (CHLs), DDTs in minke whales (Balaenoptera bonaerensis) feeding on Antarctic krill between 1984/1985 and 1992/1993 (Aono et al. 1997). Concentration of DDTs, PCBs and HCB have been reported in various species of marine mammals during last decades. However, data on the presence of other POPs (including new emerging ones, like poly- and per fluorinated organic compounds (PFCs)), even if it was reported in oceanic and lake water samples (Cai et al. 2012), in marine mammals tissues are still scarce (Corsolini 2009).

Only a few of the hundreds of thousands of different industrial chemicals produced on a world scale have been studied and reported in the Antarctic environment. Antarctica’s trophic chains are relatively simple and short and therefore understanding the detailed information on the levels of pollutants in different parts of the environment (including abiotic part) is very important. Animals at the top of the food webs depend on a few key species. Therefore affecting one of these key species could have a devastating impact on the whole ecosystem.

3 Types of Pollutants Present in Antarctica’s Environment

Anthropogenic pollutants in Antarctica may come from global (LRAT) and local sources. Global sources include industrialised sites situated all over the Southern Hemisphere, from which pollutants are transported to Antarctica by various routes (Bargagli 2008). Local sources, on the other hand, include, amongst other things, scientific activities which are connected with the use of waste incineration plant, fuel consumption, sewage production, developing tourism and related intensification of ship transport (Cincinelli et al. 2009). The most polluted areas include areas around historic bases and polar stations where soil is often polluted by fuel remains, solid waste and household sewage (Negri et al. 2006; Webster et al. 2003). Anthropogenic pollutants are present in various elements of the environment in Antarctica. Because of their specific (also hazardous) properties POPs and heavy metals are described in this article in detail. However, authors do not include any chapter about general sources, properties and toxicity of pollutant groups determined in various types of samples collected from the Antarctic environment. This information has been given in other literature sources (e.g. Aisable et al. 2004; Borghesi et al. 2008; Cincinelli and Dickhut 2011; Corsolini 2009; Fuoco et al. 2012; Houde et al. 2011; Ma et al. 2014; Planchon et al. 2002; Vecchiato et al. 2015).

Despite the fact that environmental studies represent only a small part of scientific research in Antarctica (Magi and Tanwar 2014), polar explorers are increasingly also interested in chemical research. Figure 2 shows a group of chemical compounds that are of interest to researchers in Antarctica (after Walton et al. 2001).

Fig. 2
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The group of chemical compounds identified in Antarctica

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In the discussion on the presence of organic compounds in the Antarctic environment, scope of interest is mainly focused on POPs like HCB, PCBs, DDTs, PBDE and PAHs. Over the past decades, sporadic research also pertained to identification and determination of compounds such as: CHL, dioxins, dioxin-like compounds (DLCs), PFCs, pesticides (dieldrin, mirex, heptachlor, endosulfan), aliphatic hydrocarbons, n-alkanes and cumulative parameters such as total organic carbon (TOC) in various environmental samples.

The presence of metals in remote Antarctica is not, as it was thought previously, limited only to lead and copper, but also other includes metallic elements, metalloids and radioactive elements, such as: V, Cr, Mn, Zn, Co, Ag, Cd, Ba, Bi, U, Pt, Ir, Rh, Mo, Tl, As, Sb (Hong et al. 2012; Soyol-Erdene et al. 2011).

4 Detailed Information Pertaining to Analytical Research in Antarctica

For a long time Antarctica was not available to scientists mainly because of the specificity of its location. Initial research was aimed at getting to know geological properties of the area. With time, also meteorological, magnetic and botanic research was undertaken and in recent years, chemical research was also conducted. The implementation of this research requires enormous involvement and determination on the part of scientists, mostly due to very difficult weather conditions (Köler 2013).

4.1 History of Research on the Chemical Composition of Samples from Antarctica

Research conducted in Antarctica has always been interdisciplinary. One area of research includes actions connected with determining the chemical composition of biotic and abiotic samples. Initially, it was research using classical analytical techniques; however, the scope of determined compounds has been expanded over time. Table 1 presents the historical calendar pertaining to the development of the scope of analytical research of the Antarctic environment conducted up to the end of 1989.Footnote 1

Table 1 Historical calendar pertaining to the development of the scope of analytical research of the Antarctic environment conducted up to the end of 1989
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4.2 Pollution Concentration Levels Over Decades

The scope of analytical researches conducted over individual decades is differentiated both in respect of the place of research and types of samples and analytes which are determined in them. Monitoring of the environment allows for reliable observation changes and information contained in publications pertain to individual parts of the Antarctic ecosystem and various groups of pollutants. At present, scientists devote a lot of attention to research on pollutant levels in Antarctica’s environment; however, there are still areas which have not been researched in this respect. Figure 3 shows the percentage of most commonly studied regarding the presence of contaminants in the environment of Antarctica up to end of 2014.

Fig. 3
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The percentage of areas most commonly studied regarding the presence of contaminants up to end of 2014 in the Antarctic environment

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In this article, the authors pay particular attention to the research on determination of persistent organic compounds and heavy metals in different samples from Antarctica because of the toxic properties and the threat which is associated with their presence in the polar environment. Table 2 presents general information on xenobiotics determined in samples collected from various parts of the Antarctic ecosystem.

Table 2 Summary of literature data on results of analytical research on various types of (a) abiotic and (b) biotic samples collected in Antarctica in three time periods
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In the discussion pertaining to the presence of pollutants in Antarctica, it is very important to become familiar with accurate levels of concentration present in individual elements of both, biotic and abiotic, environments. Table 3 (A, B, C) data referring to levels of detected contamination present in the whole Antarctic environment and Fig. 4 presents a summary of POPs and heavy metals concentration levels determined in various elements of Antarctica’s environments during three time periods (up to end of 2014).

Table 3 Detailed literature data on results of analytical research on (a) main POPs; (b) remaining organic compounds; (c) heavy metals in various types of biotic and abiotic samples collected in Antarctica in three time periods
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Table 3b Detailed literature data on results of analytical research on (a) main POPs; (b) remaining organic compounds; (c) heavy metals in various types of biotic and abiotic samples collected in Antarctica in three time periods
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Table 3c Detailed literature data on results of analytical research on (a) main POPs; (b) remaining organic compounds; (c) heavy metals in various types of biotic and abiotic samples collected in Antarctica in three time periods
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Fig. 4
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Contamination concentration levels during three time periods: (a) POPs in abiotic samples, (b) POPs in biotic samples, (c) heavy metals in abiotic samples, (d) heavy metals in biotic samples

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As is showed in Fig. 4 studies on the determination of the pollutants concentrations in biotic and abiotic samples over the decades are irregular. It makes presentation of concentrations trends very difficult. However, as a main source of air contamination the LRAT from Africa, South America or Australia (Negoita et al. 2003) is administered. Nevertheless, the year-round operation of stations and activities of tourists and scientists can result in the detectable contaminants (PBDE, PFAS) in most stations’ areas in Antarctica (Cai et al. 2012). Every part of the abiotic environment (as well as Antarctica’s atmosphere and reservoirs: soil and snow) are currently closely coupled. These parts, affecting each other, have a tendency for re-volatilization of POPs to the atmosphere. These are so called secondary sources of pollution. However it is not known to what extent this remobilization is a part of a seasonal cycle with volatilization during summer and deposition during winter (Cabrerizo et al. 2013). Glacial melt may carry pollutants to nearby lakes and the adjacent coastal marine areas, thereby spreading the contamination and increasing its impacts (Majer et al. 2014). Glacier meltwater can be a current source of pollution to Antarctica’s marine food web as a result of an unexpected consequence of climate change (Geisz et al. 2008). Therefore the monitoring and remediation of this scenario is essential. The active layer/permafrost transition zone was revealed to be a low-permeability barrier to downward migration of chemical compounds (Curtosi et al. 2007). Near Antarctica’s stations exhibiting PAHs contamination in soils, this behaviour highlights the risk for coastal marine environments (Curtosi et al. 2007). An analysis of stations’ emissions and transect sampling of abiotic matrices are carried out. The research provides indication as to the significance of research stations as local sources of POPs contamination (Bengtson Nash et al. 2010). Only few studies have determined PCB and organochlorine pesticides (OCP) concentrations in sediments in Antarctica (Zhang et al. 2013). Pollution in marine sediments are the end result of a long term accumulation and this is not directly correlating with activities on land. Unfortunately, pollutants in sediments will persist for many years to come (Kim et al. 2006), hence it is necessary to control the levels of pollution in every part of abiotic environment including sediments.

Referring to abiotic research the monitoring programs need to be extended to facility points far from major bases, assessing the extent of contamination in order to prevent local pollution episodes. This kind of studies should verify the hypothesis of a decline of PCBs in the last decade in Antarctica (Vecchiato et al. 2015).

In the discussion of biological research, what is important is using organisms for monitoring. Atmospheric monitoring of POPs using conventional instrumental methods is expensive and difficult. Scientists can overcome this limitation using biomonitoring methods and thereby provide reliable information assessing the impact of pollutants on the biota and various ecosystems. Most popular in Antarctica is using mosses to define the relationship between the concentrations of POPs in Antarctic environment and in the atmosphere (Wu et al. 2014). It should be noted, based on PBDEs studies, that mosses can accumulate more POPs than lichens (Yogui et al. 2011).

Equally important is the transport of pollution between organisms. Collected data can be useful to notice that the high concentrations of POPs encountered in the brown skua is certainly correlated to its migratory habits as well as its high trophic level position (Taniguchi et al. 2009). A useful tool to trace migration behaviour of seabirds and marine mammals can be the research of POPs levels in tissues (Kallenborn et al. 2013). Moreover, the transfer of contaminants between Antarctica’s pelagic and benthic organisms is associated with seasonal sea-ice dynamics (Van den Brink et al. 2011). The concentrations of organochlorines in penguin eggs may be toxicologically insignificant, but more studies are needed to assess the real health risks associated with these levels of pollutants because Antarctica’s seals and penguins are more sensitive to contaminants than those living in temperate regions (Schiavone et al. 2009b).

In a comprehensive approach to the issue of the presence of pollutants in Antarctica, it is also very important to become familiar with accurate levels of heavy metals in this environment. In a discussion of heavy metals in abiotic environment, the geochemical characteristics of the area should be further investigated, in particular, the transport of metals as particulate or soluble fraction from the terrestrial to the marine environment (Vodopivez et al. 2015). Based on lead isotopic data, Southern South America is an important source of dust deposited in Antarctica’s ice (Vallelonga et al. 2010). Moreover, based on results of research on ice cores, anthropogenic activities have become the most important source of heavy metals in Antarctica (Yin et al. 2006). Antarctica is a kind of a sink for heavy metals (e.g. Hg). Considering long atmospheric lifetime and the ability to deposit and be re-emit from soil and oceans, the ability of heavy metals to bioaccumulate suggests that their deposition would indeed have a serious effect for environment (Sprovieri et al. 2002).

Referring to heavy metals present in biological samples, particular attention should be paid to the biomagnification process which depends upon the food web (high trophic level animals have a higher content than lower trophic level ones) (Moreno et al. 1997). The presence of potentially toxic elements (such as Cd and Hg) in penguins suggest, that the accumulation of elements depends on the geochemical characteristics of the area, age of individuals and also on their diet (mainly krill) (Smichowski et al. 2006). Moreover, the results of research indicated, that a slight increase in Mn and Cr levels in Antarctica could be related mainly to human presence (usage of combustibles and oil contamination). Other studies indicate common sources of pollution (such as Cr, Ni, Pb, Mn, Cd or As), which are correlated with anthropogenic activities (plane and ship trips related to the tourism industry) (Jerez et al. 2013a). Feathers can be an important identifiers of the absorbed heavy metals (e.g. Pb) in penguins (Jerez et al. 2013b). For a better understanding of spatio-temporal trends feathers of Antarctic penguins, put together with other penguin tissues, are useful tools for long-term monitoring of trace elements in Antarctic marine environment (Jerez et al. 2011).

Furthermore mercury and its transformation products (e.g. methylmercury), because of their high bioaccumulation properties, should be investigated more precisely. A quantitative understanding of pathways and mechanisms that affect the transport of mercury from sources to ecosystems as well as the conversion of mercury to methylmercury, and their bioaccumulation in food webs are fundamental to evaluating and managing human and wildlife health risks in a local and global scale (Driscoll et al. 2013). The observations that have been made in polar marine ecosystems showed progressive increase in mercury concentrations in the food web (Bargagli et al. 1998). The role of Antarctic coastal ecosystems as sink in the global mercury cycle can be enhanced by the global warming and the possible change in the ice coverage together with increasing anthropogenic emissions of gaseous mercury in countries of the Southern Hemisphere (Bargagli et al. 2007). It clearly demonstrates the need for understanding how climatic variability and anthropogenic disturbances (e.g., increases of population, perturbations to food chains, changes in other air pollutants) affect mercury and methylmercury concentrations in Antarctic ecosystems (Driscoll et al. 2013; Bargagli 2008). Research data on pollutant levels has been enhanced during last two decades. Figure 5 presents information on the proportion of various types of analytical research in a general number of studies aimed at getting to know the degree of pollution of the Antarctica’s environment during the last two decades.

Fig. 5
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Classification of analytical research according to types of environmental samples collected in the years 2000–2014

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The most popular research locations were the areas of the Antarctic Peninsula (including South Shetland Islands) and Ross Sea. A little more attention (55 % of contemporary research) is paid to tests of biological samples, mostly due to the interest in the actual influence of pollutants on Antarctica’s ecosystem and becoming familiar with new directions of pollutant movement in the food web. Research on the chemical composition of inorganic samples (45 % of contemporary research), is equally important, as elements of abiotic environmental media are the first link in the pollutant movement process in Antarctica.

4.3 Analytical Techniques in the Study of the Antarctic Environment

Together with the development of science and instruments, various analytical procedures and techniques were used in analytical practice to test environmental samples (abiotic and biotic) collected in Antarctica.

Nowadays, Antarctica’s researchers have gained access to many different analytical techniques of scope detection, power and robustness, which they couldn’t even dream of some decades ago (Caroli 2001). For the chemical elements they can use: atomic absorption spectrometry (AAS) with flame or electrothermal (another name—graphite furnace (GF)) atomisation, inductively coupled plasma—atomic emission spectrometry (ICP-AES), inductively coupled plasma—optical emission spectrometry (ICP-OES), atomic fluorescence spectrometry (AFS), mass spectrometry (MS) with different ionization sources (e. g. ICP), X-ray fluorescence spectrometry (XRF), neutron activation analysis (NAA), ion-selective electrodes and isotope dilution mass spectrometry (IDMS). For organic substances, depending on properties of organic substances, analysts can choose one of the following techniques: gas chromatography (GC), high performance liquid chromatography (HPLC), thin layer chromatography (TLC), supercritical fluid chromatography (SFC) and gel permeation chromatography (GPC) with several detection systems (electron capture (EC), flame ionization (FI)), thermal conductivity (TC), flame photometry (FP), infrared spectroscopy (IR), UV absorption spectrophotometry, fluorescence (F), capillary zone electrophoresis (CZE) and MS (Caroli 2001). To determine ionic compound concentration the analysts use ion chromatography (IC) with various types of detection (e.g. conductometry detector (CD), ICP).

Applications with impressively high-resolution and full scan performances were made possible by modern instrumental configuration, that is hybrid mass spectrometers. Quantification of highly polar organic pollutants without derivatization, lower than the ppt level (nanogram per liter or per kilogram of matrix) in environmental samples, is possible by the use of tandem mass spectrometry combined with liquid chromatography. The measurement of emerging contaminants in environmental analysis are performed using the achievements of liquid chromatography—mas spectrometry (LC-MS) like the more recent advancements in triple quadrupole (QqQ), linear ion trap, time of flight analyzer (TOF) and Orbitrap mass spectrometers (Magi and Tanwar 2014).

Generally, the analysts are warned of pushing the instrumental method beyond its intrinsic limits, in terms of limits of detection, optimal working range and applicability to specific groups of substances. Otherwise, the rapid increase in the overall uncertainty associated with the experimental date will be observed soon (Caroli 2001).

Polar regions are an excellent place to study some natural phenomena as well as historical trends mostly due to the large distance between them and anthropogenic emissions sources. The concentration of micro-constituents or micro-pollutants in polar regions is rather low and therefore it is necessary to develop some analytical methods of high sensitivity.

The chemical specification of such a variety of samples requires scientific experience and skills from different areas of science. The wide choice of analytical techniques, from the classical to the most innovative ones, which are available nowadays, offers the scientists an opportunity to face challenging qualitative and quantitative determinations. What is more, some more precise chemical information can be achieved by developing hyphenated methodologies, which means the combination of different instrumental techniques (Magi and Tanwar 2014).

Nowadays the most useful analytical tool seems to be the mass spectrometry, which was designed for determining a wide range of compounds present in environmental samples. In combination with such techniques as gas or liquid chromatography, it creates the possibility of specifying the organic (GC-MS, LC-MS) as well as inorganic compounds (ICP-MS) with a large degree of sensitivity and selectivity. Another advantage of such an analytical solution is the fact that MS provides more chemical information using a minimum amount of sample than any other analytical method (Gasparics and Marıa 2000; Magi and Tanwar 2014; Planchon et al. 2001).

Determination of organic contaminants in various matrices is usually performed using chromatographic techniques (Płotka et al. 2013). Actual trend in chromatography is development of multidimentional approaches (e.g. Ouyang et al. 2015; Seeley and Seeley 2013). Multidimensional chromatography is a technique for isolating and identifying volatile (GC) and semi-volatile (GC and LC) organic compounds present in complex mixtures during one analytical cycle. Hence this techniques coupled with mass spectrometry can provide an important tool in a future monitoring of organic chemicals in Antarctica. Therefore, because of a low concentration of chemical compounds in complex matrices (feathers, leathers and internal organs of organisms) (Magi and Tanwar 2014), Antarctica poses a real challenge of developing innovative analytical approaches as well as improving MS instrument performances.

4.4 Impact of Research Station Activities on Pollution Levels

Research stations are and will be an inseparable element of the Antarctic environment. Individual polar stations have a different nature. A detailed description of the operations of polar stations is presented in Table 4. The influence that each station can have on Antarctic environment is related with length of time it has been operated or/and number of people present at station etc. This information is given regularly each year by Council of Managers of National Antarctic Program (COMNAP) on its webpage (e.g. COMNAP Information). It is also important that the development of research (the use of the station and the construction of new facilities) should not additionally contribute to environmental pollution. There are numerous ways of operating stations without polluting the environment. The Princess Elisabeth Antarctica Station is an example of a station that virtually has no impact on the environment. At this station, electricity is produced using photovoltaic panels, solar collectors and wind turbines. The use of renewable sources of energy in Antarctica in the twenty-first century should not be a sign of modernity in this area, but a necessity. Reduction of potential anthropogenic pollution sources to a minimum allows to obtain reliable research results, in particular in research on long-range atmospheric transport of pollutants (Polar Foundation Information). The results of work on the design process of a photovoltaic (PV)-wind power system were recently published. This system could be installed in very challenging ambient conditions. This work has been done in the French-Italian Antarctic Base (Concordia Base). Work in this scope should be continued in other polar bases. Pollution can affect important research activities in this area (e.g. astronomical observations, studies of physics of atmosphere and Earth science). The ambient conditions significantly affect the quality of the research results. Usage of renewable energy leads to reduce usage of diesel generator and thereby leads to preserve an ecosystem, which is mandatory for heritage of the humanity (Boccaletti et al. 2014).

Table 4 Characteristics of polar stations operating in Antarctica (SCAR Information)
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5 Summary and Conclusions

The environment of polar regions is characterised by the lowest pollution levels in the world. However, the growing number of studies on the presence of a broad range of chemical compounds in various elements of the Antarctic environment may indirectly indicate the scale of the problem of growing symptoms of global human influence in this area.

Over the past decade, the scope of tested samples has been extended; however, the type of pollutants identified in individual samples (in the years 2000–2014) differs from the previous decades, inter alia is enhanced to new emerging pollutants. Most of the information about the presence of pollutants in biotic samples pertains to samples of Antarctic mosses krill, molluscs and invertebrates, various fish species and maritime birds—mostly penguins. Research of biotic samples have a special value as more and more attention is devoted to the phenomenon of bioaccumulation and its consequences within one plant or animal species as well as to biomagnification in the food chain. Research data about pollutants detected in abiotic samples are also important mainly due to direct and continuous contact with Antarctic biota.

A significant part of research is targeted at the occurrence of POPs compounds in the environment (Fuoco et al. 2009a, b). A possibly exhaustive list of information pertaining to POPs present in Antarctica’s environment is possible only for several groups of compounds (HCB, PCB, DDTs, PBDE and PAHs). Their presence may largely result from the activity of research stations and the development of tourism. Over the past decades, sporadic research also pertained to identification and determination of compounds, such as: CHL, dioxins, DLC, PFCs, pesticides (dieldrin, mirex, heptachlor, endosulfan), aliphatic hydrocarbons, n-alkanes and cumulative parameters such as TOC in various environmental samples. In the future emerging pollutants exhibiting characteristics of persistence comparable to POPs should also be considered in long term monitoring.

Heavy metals are global pollutants and can reach almost any location on Earth. They come from natural, volcanic or geological sources, or as a result of anthropogenic activities. Accordingly with increasing human presence in Antarctic region the presence of metals in this area is becoming an issue that needs to be more investigated. Especially issues like: understanding of pathways and mechanisms that affect the transport of mercury from sources to ecosystems, the conversion of mercury to methylmercury, and its bioaccumulation state in food webs should be continuously studied.

Regrettably, data on pollutants in Antarctica’s environment are dispersed in many magazines. It is worth mentioning that over the years different methods of POPs quantification have been used. Often information is scarce or lacking on the biology of the sampled species (age, sex, nutritional status, reproductive status, etc.). This makes data difficult to compare (Trumble et al. 2012). The fact that research results are presented in various units (g/g wet wt, g/g dry wt., etc.) is a further inconvenience, as it also makes it difficult to compare results of studies conducted in various areas of Antarctica. To overcome this problem, some of scientists have presented their results expressed in multiple units (Court et al. 1997; Yogui et al. 2011); unfortunately very few researchers have done so.

Research on the influence of research stations on the pollution levels in the surrounding environment is also important. Detailed research in this areas leads to differentiate sources of pollutants between influence of local sources and global sources (LRAT). Additionally polar stations should implement usage of renewable energy in whole possible areas. This kind of solution of energy production leads to reduced usage of diesel generators and thereby lead preservation of the polar ecosystem.

The analysis of available information allows for concluding that human activity on a local and global scale leads to affecting and/or degradation of Antarctic ecosystems. The basic direction for contemporary Antarctic research pertaining to pollutants should be:

  • carrying out the long term atmospheric monitoring for main POPs and new emerging pollutants coupled with meteorological data,

  • carrying out the long-term monitoring of man-made chemicals (as well as new emerging pollutants monitoring) in Antarctic abiotic environment and endemic species in order to follow the future trends of global contamination,

  • the detailed description of remobilization processes and “second sources” (e.g. melting glaciers) of pollutant in polar areas,

  • the enlargement of research using non-invasive samples (like feathers and preen oil) as a useful tool to POPs and heavy metals monitoring,

  • the determination of reaction and tolerance individual pollution levels for Antarctica’s fauna and flora towards individual anthropogenic chemicals (examination of the toxicological sensitivity of Antarctic key species),

  • the detailed description of environmental fate (including biotic and abiotic environment) and negative effects on Antarctic ecosystem of anthropogenic compounds,

  • the development of innovative analytical approaches improving the limits of detection of chemical compounds in various abiotic and biological matrices.