Evaluation of dispersal volcanic products of recent eventsin lichens in environmental gradient, Nahuel Huapi NationalPark, Argentina

Débora Bubach & Leandro Dufou &

Soledad Perez Catán

Received: 25 July 2013 /Accepted: 21 March 2014 /Published online: 23 April 2014# Springer International Publishing Switzerland 2014

Abstract The atmospheric transport of volcanic prod-ucts are subject to several variables, mainly the height ofthe eruption column and wind direction, thus elementsassociated with the ashes are deposited inmajor or lesserdegree depending on variables as latitude, wind andhumidity. The lichens are able to reflect the atmosphericfallout. The present work evaluated the correlation be-tween meteorological parameters, geographic locations,sulphur and other element concentrations in lichensgenus Usnea affected by Puyehue–Cordón Caulle com-plex (North Patagonia Andean Range) eruption of June4, 2011. Semiquantitative analyses of biological ele-ments by scanning electron microscope methods, sul-phur (S) by LECO and other elements by instrumentalneutron activation were evaluated by principal compo-nent analysis. Elements as antimony, arsenic, barium,bromine, calcium, caesium, potassium, rubidium, sele-nium, and uranium correlated with distance to volcano,also calcium and potassium with longitude while bro-mine, rubidium, and potassium with humidity. Those

results indicate that Usnea sp. is a good bioindicator ofthe atmospheric volcanic emissions in relation to envi-ronmental gradient.

Keywords Lichen . Sulphur . Volcanic eruption .

Elements . Humidity

Introduction

Volcanoes emit aerosols considerably enriched in majorcomponents such as water (H2O), carbon dioxide (CO2),sulphur dioxide (SO2), hydrogen sulphide (H2S), hydro-chloric acid (HCl), hydrofluoric acid (HF) and minorcomponents such as nitrogen gas (N2), rare gases, car-bon monoxide (CO), methane (CH4), hydrogen gas (H2)including many trace elements as alkali metals, alkali-earths, and transition metals (Pfeffer et al. 2006). Suchelement enrichments are always in gaseous emanationsfrom volcanoes worldwide, provided that magma tem-perature is high enough to ensure their volatilization.Trace elements are degassed from magmas as halides,sulphates, sulphides or metals, and are typically found inthe aerosol phase of the airborne plume (Moune et al.2010). Environmental effects on local, regional andglobal scales can be significant depending on the emis-sion distance prior to deposition. The impact is a conse-quence of chemical and physical factors (including sol-ubility and particle size), as well as weather and geo-graphical factors, i.e., wind, dry deposition, volcanolatitude and the maximum height of the erupted column(Pfeffer et al. 2006). However, the wind speed and

Environ Monit Assess (2014) 186:4997–5007DOI 10.1007/s10661-014-3754-1

Electronic supplementary material The online version of thisarticle (doi:10.1007/s10661-014-3754-1) contains supplementarymaterial, which is available to authorized users.

D. Bubach (*) : S. P. CatánLaboratorio de Análisis por Activación Neutrónica,Centro Atómico Bariloche, CNEA,Av. Bustillo km 9.5, 8400 Bariloche, Argentinae-mail: bubachd@cab.cnea.gov.ar

L. DufouGrupo de Separación Isotópica, Complejo TecnológicoPilcanilyeu, Centro Atómico Bariloche, CNEA,Av Bustillo 9.5, 8400 Bariloche, Argentina

precipitation influence is controversial. Fujita et al.(2003) have observed that the dispersion of SO2 canbe affected by the wind speed and rainfall; but otherstudies showed less or absent effects of these parameters(McGonigle et al. 2004). Compounds and elementalconcentrations in the atmosphere have been correlatedby lichens in several publications (Garty 2001, Contiand Cecchetti 2001). Many works such as Grasso et al.(1999) and Davies and Notcutt (1996), found, that nat-ural contamination from volcanic emissions werereflected in lichens. Differences of the element concen-tration were observed in relation to volcano source(Grasso et al. 1999). Mercury (Hg) contents in lichensshowed a major input from the active eruption sites ofKilauea volcano (Hawaii) but it was significantly mod-ified by wind patterns (Davies and Notcutt, 1996). Sul-phur compounds in lichens from volcanic emission havebeen rarely investigated. There are many studies ofanthropic impact areas in which the lichens reflectedthe sulphur (S) pollution (Fenn et al. 2007, Olszwskiet al. 2012; Suchara 2012). Atmospheric losses of vol-canic SO2 can be accomplished by dry deposition asSO2 and sulphur trioxide (SO3), and sulphuric acid(H2SO4) as wet deposition, which is the main compo-nent of acid rain. It has been observed that lichensrespond to the acidity increase with gypsum formation(CaSO4·2H2O) taking calcium (Ca) from calcite(CaCO3) present in the fallout dust (Garty and Garty-Spitz 2011). Also, liberation of potassium (K) fromlichens has been observed which was associated todamage in the cell membranes (Garty et al. 2002).

Lichens of Usnea sp. were used to evaluate thevolcanic influence of Puyehue–Cordón Caulle complex(PCCc) event in 2011 (Bubach et al. 2012). Thisallowed identifying elements associated with particlematerial (PM) of geological origin, fine volcanic ashes,and volatile elements in the impacted sites in NahuelHuapi National Park, North Argentina, Patagonia. Thisarea covers a 200-km2 distance and is limited by thehigh peaks of the Western Andes and on the Easternside, by the Patagonic plateau. Consequently, it has astrong vegetation gradient from dense rainforests in theWest, to dry grasslands (ecotonal forest) in the East,associated with steep precipitation gradients in the im-pacted region. In this context, the aim of the presentwork was to evaluate the elemental concentration inrelation to geographical variables and weather condi-tions. That analysis included new sulphur determina-tions in the homogenates in entire thalli, biological

elements in cross-sections of lichens, and other elementconcentrations taken from Bubach et al. 2012.

Materials and methods

Study area

The sampling area belongs to Nahuel Huapi NationalPark (41° 43′ S, 71° 00′ W) located in Northwest Pata-gonia, Argentina, which was the most affected by pyro-clastic material dispersed by PCCc eruption. The impactregion was estimated (Fig. 1) from spatial variation ofthe plume as observed form satellite photographs andamount of ash fallen (Gaitán et al. 2011). Accordingly,eight sampling sites were selected within the impactedregion, along one scattered line from the volcanic sourceto the Southeast: Espejo Chico (ES), Correntoso (CO),West Traful (T1), Brazo Rincón (R); Brazo Huemul(HU), East Traful (T2), Dina Huapi (DH) and 50 kmfurther along the road to Pilcaniyeu town (PI). The othersampling sites selected were less-impacted zones toprovide baseline sites as: Moreno (PP) and (GP),Guillelmo (GU) and Mascardi (MA) (Fig. 1).

The area is characterised by a great diversity of lakesranging from large and deep glacially originated lakes tosmall and shallow ones. The weather is cold temperatecontinental, prevalent winds blow from West to East inNahuel Huapi National Park area. The region has a steepdecrease in rainfall from West to East. Mean annualrainfall decreases from eastwards, from more than3,000 mm next to the Andes, to less than 700 mm inca. 70 km. The moisture gradient is reflected in a West–East spatial succession of mountainous forest types, toxeric shrublands in the ecotone, before it gives way tothe steppe, in the East (Dezzotti and Sancholuz 1991;Veblen et al. 1992):

Sampling and analyses

The epyphytic fruticose lichen, Usnea sp., was selectedas a bioindicator due to its common distributionthroughout Nahuel Huapi National Park. The lichencollection was performed 2 months after the PCCceruption.

Pooled samples were made up from 10 lichen thallicollected from each site with similar development char-acteristics. Individual thalli were cleaned under micro-scope, using titanium and Teflon devices to remove

4998 Environ Monit Assess (2014) 186:4997–5007

substrate remains and external particulate and extrane-ous organic matter. Afterwards, the samples werewashed twice with ASTM grade-1 water, and then driedat room temperature in a laminar flow hood. This wasdone to reduce the effect of dilution on the elementalconcentration between sites due to the large amount ofashes fallen.

The geographical location as latitude, longitude, alti-tude and distance from the volcano, were obtained byGPS and Google Earth programme (2012 cnes/spotimage inav/Geosistemas SRL ® 2012 Mapcity). A hu-midity factor (Hum. F.) was estimated based on mea-sures of known rainfall taken from theWindguru (www.windguru.cz), Argentine National Weather Service(www.smn.gov.ar) (Table 1) as well as vegetationcharacteristics taken from references, which areshowed on Table 2. This Hum. F. takes values between1 to 5, according to increasing gradient of rain andvegetation development.

Sulphur contents were measured by LECO method(HF-100 Induction Furnaces model 777-400 SN 675) inentire thalli.

Semiquantitative analyses of biological elements inlichen cross sections were evaluated in cortex–medulla(C) and axis (A). The element concentrations analysed(Ca), magnesium (Mg), K and iron (Fe) were identifiedwith chemical symbol and C and A according to thecross section; e.g., CaC, in cortex–medulla and CaA, inaxis as it is shown in Fig.2. These analyses were per-formed by scanning electron microscopy with energydispersive spectrometer (SEM-EDS; SEM-EDAX Phil-ip 505 equipment). SEM-EDS provide micro-chemicalanalysis of spot samples; semiquantitative results arepresented in weight percentage (wt) relative to totaldetected elements.

Other elements in entire thalli, as antimony (Sb),arsenic (As), barium (Ba), bromine (Br), caesium (Cs),cobalt (Co), mercury (Hg), selenium (Se), thorium (Th),

Fig. 1 Puyehue–Cordón Caulle volcanic complex, North Patago-nia Andean Range. The dark cone is the region impacted by thedispersion of pyroclastic materials in the volcanic eruption of June

4, 2011, and thereafter, estimated from satellite photographs con-sidering the variations of the plume position according to winddirection

Environ Monit Assess (2014) 186:4997–5007 4999

uranium, (U), zinc (Zn), calcium (Ca), iron (Fe), potas-sium (K), sodium (Na); hafnium (Hf), rubidium (Rb),scandium (Sc), strontium (Sr), tantalum (Ta), and rareearth elements (REE) as cerium (Ce), europium, (Eu),lanthanum (La), lutetium (Lu), neodymium (Nd), sa-marium, (Sm), terbium (Tb), and ytterbium (Yb) wereanalysed by instrumental neutron activation analysis(INAA). The INAA measure procedures, analytical

quality and preliminary data can be found in Bubachet al. (2012).

The element contents, geographical parameters andHum. F. were evaluated by principal componentanalysis (PCA) using XLSTAT (7.5) programme.The missing data matrix was eliminated by thisanalysis. The statistical significance level was takenas p<0.05.

Table 1 Geographic coordinates and rainfall of areas that include the sampling sites

Areas Sampling sites Precipitation(mm/year)

Author Years

Geographic coordinates

East Traful 40° 40′ 47″ S 71° 2′ 23″ W T1 800 Nuñez et al., 2009

Bariloche 40° 41′ 58″ S 71° 15′ 49″ W HU 823 SMN 1995–2012

Brazo Machete 40° 48′ 47″ S 71° 40′ 28″ W ES-CO-R-T2 1,707 www.windguru.cz 1995–2012

Brazo Huemul 40° 56′ 24″ S 71° 22′ 12″ W HU 836 www.windguru.cz 2009–2012

Pto. Blest 41° 2′ S 71° 49′ W ES-CO-R-T2 3,000 Chimner et al., 2011

Llao Llao 41° 3′ S 71° 32′ W GP 1,500 Chimner et al., 2011

San Ramón 41° 3′ 32″ S 71° 1′ 36″ W DH-PI 600 Chimner et al., 2011

Bariloche 41° 7′ 48″ S 71° 18′ 36″ W HU 1,205 www.windguru.cz 2006–2012

Moreno 41° 6′ S 71° 28′ 48″ W PP-GU 895 www.windguru.cz 2006–2012

Gutierrez 41° 10′ 12″ S 71° 23′ 24″ W MA 1,205 www.windguru.cz 2010–2012

SMN Servicio Metereológico Nacional (Argentino)

Table 2 Sampling sites according to distance to the volcano, geographic coordinates, vegetation types and humidity factor (Hum. F.)

Samplingsites

Distance to thevolcano (Km)

Geographic coordinates Vegetation types Hum. F. Author

R 31 40° 42′ 34″ S 71° 47′ 15.8″ W N. dombeyi forest 5 Veblen et al., 1992

ES 34 40° 43′ 15″ S 71° 47′ 53.7″ W N. dombeyi forest 5 Veblen et al., 1992

CO 41 40° 44′ 13″ S 71° 40′ 24.7″ W N. dombeyi forest 5 Veblen et al., 1992

T1 47 40° 37′ 1″ S 71° 32′ 39″ W N. dombeyi forest 5 Veblen et al., 1992

HU 61 40° 56′ 17″ S 71° 24′ 30″ W Shrubland 2 Dirección de bosques, 2003

T2 70 40° 41′ 58″ S 71° 15′ 49″ W Austrocedrus Forest 3 Veblen et al., 1992

GP 71 43° 3′ 19″ S 71° 33′ 42″ W N. dombeyi forest and shrubland 4 Dirección de bosques, 2003

PP 73 41° 4′ 22″ S 71° 31′ 26″ W N. dombeyi forest and shrubland 4 Dirección de bosques, 2003

VE 87 40° 40′ 47″ S 71° 2′ 23″ W Austrocedrus Forest 3 Veblen et al., 1992

MA* 96 41° 18′ 44″ S 71° 29′ 34″ W N. dombeyi forest 4 Dirección de bosques, 2003

DH 97 41° 3′ 3″ S 71°9′ 6″ W Shrubland 2 Dirección de bosques, 2003

PI 102 41° 42′ 3″ S 71° 6′ 31″ W Shrubland and gramineousand shrubland

1 Texeira et al, 2010

GU 105 41° 24′ 45″ S 71° 29′ 32″ W N. dombeyi forest and shrubland 4 Dirección de bosques, 2003

R Brazo Rincón, ES Espejo Chico, CO Correntoso, T1 West Traful, HU Brazo Huemul, T2 East Traful, GP and PP Moreno, VE Valleencantado, MAMascardi, DH Dina Huapi, PI road to Pilcaniyeu town, GU Guillelmo

*Outside the plume

5000 Environ Monit Assess (2014) 186:4997–5007

Results and discussion

Figure 3 shows the PCA biplot of thalli for each sitesampling, the elemental contents, weather and geo-graphical parameters. The variation explained by prin-cipal component 1 (PC1) and principal component 2(PC2) was of 73 %. The correlation matrix is shown onTable 3. This result shows a group of elements includingAs, Cs, Ce, Eu, La, Lu, Nd, Sb, Sm, Tb, Yb, Fe, Hf, Na,Sc, Se, Ta, Th and U which correlate with each other(R=0.59 to 0.99, p<0.05; Table 3). There are significantnegative correlations of the As, Br, Cs, Rb, Se, U, Sband Ba with the distance from the volcano (R=−0.56 to−0.72, p<0.05; Fig. 3, Table 3).

The relationship between those element concentra-tions and distance is an indication of the ash contribu-tion, in addition to geological source. In our previouswork (Bubach et al. 2012), the same elements wereidentified as PM of geological source due to a linearcorrelation with Sm (geochemical tracer) as well as Asand Cs were also associated with permanent geothermalemissions from PCCc.

In order to assess the elements behaviour not associ-ated to PM, a second PCAwas made with the followingelements: S, Br, Ca, Zn, Sr, Hg, K, Rb and Zn whichcomponents are shown in the Fig. 4 (the concentrationsare on Table 1, complementary data). The variationexplained between PC1 and PC2 was of 60 %. Allgeographical parameters and Hum. F. correlated witheach other (R=0.66 to 0.81; p<0.05). The Hum. F. andlongitude relationship, follows the humidity gradient,which decreases from West to East. Bromine and Rbshowed a negative correlation with the distance (R=−0.84, −0.63; p<0.05) and a positive one with Hum.F. (R=0.76, 0.68; p<0.05) (Table 3), which could be anindication of possible dissolution with rainfall. The Rbwas identified as a volatile component of volcanic emis-sions byMoune et al. (2010) and Symonds et al. (1987).The Br and Rb correlation suggests that both elementscame from PCCc volatile emissions.

Sulphur, geographical parameters and Hum. F.showed no significant correlations (p>0.05), as it wasreported by McGonigle et al. (2004). However, the Svalues were somewhat higher in areas close to the PCCc(1.2–1.4 %) than in the sites considered as baselines(1.0–1.2 %), the difference was of approximately 20 %(Table 1, Complementary data). Pfeffer et al. 2006found that the atmospheric SO2 losses corresponded toa SO4

2− conversion in a 53 and 42 % to dry deposition,and 5 % to lateral transport from the prevalent plumedirection, in samples taken 70 km away from activeIndonesian volcanoes. Studies on the surface waterchemistry after Mt. Hekla’s eruption indicated that theH2SO4 contamination depended on time and place(Flaathen and Gislason 2007). Volcanic eruptions dur-ing winter at high latitudes with low oxidation rate (lowsolar radiation) result in S contamination relatively highat global level and low at local scale. The PCCc, locatedat 41 ° South latitude, erupted at the end of autumn; thelichens were taken according to the low solar radiationperiod (NASA 2011). This fact, together with a dryperiod (16–39 total millimetres fallen between June 4and September 4, http://www.windguru.cz), probably

Fig. 2 Micrograph of cross-section Usnea sp. thallus. Cortex–medulla (a) and axis (b) obtained by SEM-EDS analyses

Latitude

Long

it.

Distance

Hum

. F

SbAsS Ba

Br

Ca

CeCs

Zn

CoEu ScSr

HfFe

Yb

LaLuHg

Na

Nd

K

SmSe

TaTbTh

U

-3

-2

-1

0

1

2

3

-3 -2 -1 0 1 2 3

Pri

nci

pal

Co

mp

on

ent

2 (1

6 %

) --

>

Principal Component 1 (58 %) -->

CO DH ES GP GU HU MA PI PP R T1 T2 VE

Fig. 3 Principal component analysis of all measured elements,geographical parameters and Hum. F. in the thalli

Environ Monit Assess (2014) 186:4997–5007 5001

Tab

le3

Correlatio

nmatrixof

theelem

ents,geographicalp

aram

etersandHum

.F.inlichenthalli

Distance

Hum

.F.

Sb

As

SBa

Br

Ca

Ce

Cs

Zn

Co

Eu

ScSr

Hf

Latitu

de0.74

−0.28

−0.73

−0.71

−0.46

−0.57

−0.58

0.39

−0.72

−0.82

0.19

−0.17

−0.73

−0.51

0.72

0.65

Longitude

−0.81

0.71

0.51

0.34

−0.12

0.58

0.75

−0.63

0.21

0.47

0.14

0.12

0.16

0.040

−0.20

0.20

Altitude

0.31

−0.25

−0.080

0.080

−0.16

0.14

−0.16

0.19

0.18

0.10

0.10

0.68

0.10

0.45

0.36

0.12

Distance

1.00

−0.66

−0.72

−0.56

−0.24

−0.63

−0.84

0.75

−0.49

−0.69

0.090

−0.12

−0.46

−0.23

0.60

−0.44

Hum

.F.

1.00

0.38

0.28

−0.21

0.37

0.76

−0.49

0.060

0.31

0.45

0.070

0.070

−0.17

−0.23

0.040

Sb1.00

0.92

0.51

0.90

0.84

−0.54

0.76

0.93

0.040

0.35

0.76

0.66

−0.45

0.85

As

1.00

0.35

0.85

0.71

−0.36

0.88

0.94

−0.020

0.56

0.89

0.82

−0.37

0.94

S1.00

0.21

0.23

−0.22

0.39

0.46

−0.08

−0.14

0.35

0.42

−0.38

0.39

Ba

1.00

0.77

−0.45

0.65

0.83

0.15

0.52

0.65

0.62

−0.22

0.79

Br

1.00

−0.68

0.49

0.74

0.18

0.17

0.49

0.33

−0.46

0.59

Ca

1.00

−0.33

−0.42

0.12

−0.02

−0.31

−0.07

0.68

−0.31

Ce

1.00

0.87

−0.22

0.52

0.98

0.87

−0.44

0.87

Cs

1.00

−0.060

0.52

0.84

0.81

−0.45

0.87

Zn

1.00

−0.22

−0.17

−0.23

0.41

−0.20

Co

1.00

0.45

0.73

0.12

0.54

Eu

1.00

0.82

−0.47

0.88

Sc1.00

−0.15

0.87

Sr1.00

−0.39

Hf

1.00

Fe Yb

La

Lu

Hg

Na

Nd

K Rb

Sm Se Ta Tb

Th

U

FeYb

La

Lu

Hg

Na

Nd

KRb

Sm

Se

TaTb

Th

U

Latitu

de−0

.61

−0.63

−0.65

−0.61

−0.40

−0.66

−0.70

0.010

−0.38

−0.67

−0.80

−0.50

−0.68

−0.63

−0.74

Longitude

0.32

0.070

0.13

0.040

−0.41

0.31

0.19

0.060

0.71

0.18

0.27

0.020

0.18

0.12

0.42

Altitude

0.080

0.30

0.28

0.31

0.29

−0.22

0.22

0.17

0.10

0.23

0.15

0.47

0.24

0.35

0.16

5002 Environ Monit Assess (2014) 186:4997–5007

Tab

le3

(contin

ued)

FeYb

La

Lu

Hg

Na

Nd

KRb

Sm

Se

TaTb

Th

U

Distance

−0.51

−0.33

−0.40

−0.29

0.14

−0.54

−0.47

0.070

−0.63

−0.44

−0.56

−0.21

−0.44

−0.35

−0.65

Hum

.F.

0.19

−0.12

−0.050

−0.15

−0.25

0.23

0.010

0.060

0.68

0.020

0.28

−0.21

0.010

−0.060

0.25

Sb0.92

0.69

0.72

0.66

0.20

0.88

0.74

0.19

0.55

0.71

0.74

0.62

0.71

0.74

0.89

As

0.98

0.85

0.87

0.83

0.35

0.86

0.86

0.18

0.36

0.85

0.83

0.79

0.85

0.89

0.94

S0.37

0.38

0.38

0.38

0.29

0.41

0.39

0.090

0.19

0.34

0.20

0.40

0.35

0.40

0.43

Ba

0.86

0.60

0.64

0.59

0.090

0.83

0.63

0.40

0.62

0.61

0.68

0.57

0.61

0.67

0.81

Br

0.70

0.36

0.42

0.33

0.020

0.71

0.47

0.14

0.77

0.45

0.57

0.29

0.45

0.41

0.67

Ca

−0.37

−0.15

−0.27

−0.12

0.24

−0.34

−0.34

0.050

−0.50

−0.35

−0.47

−0.12

−0.34

−0.19

−0.43

Ce

0.85

0.97

0.99

0.96

0.49

0.64

1.00

−0.020

0.17

0.99

0.84

0.87

0.99

0.94

0.87

Cs

0.90

0.82

0.84

0.80

0.35

0.78

0.85

0.12

0.50

0.83

0.83

0.79

0.83

0.88

0.97

Zn

−0.090

−0.28

−0.25

−0.28

−0.22

−0.020

−0.26

0.68

0.52

−0.24

−0.14

−0.29

−0.26

−0.22

−0.090

Co

0.55

0.61

0.60

0.62

0.18

0.25

0.53

0.010

0.040

0.53

0.51

0.75

0.54

0.71

0.64

Eu

0.85

0.94

0.97

0.93

0.50

0.69

0.97

0.020

0.14

0.98

0.85

0.81

0.98

0.90

0.83

Sc0.83

0.95

0.92

0.96

0.54

0.59

0.89

0.11

0.86

0.66

0.99

0.88

0.98

0.84

0.84

Sr−0

.32

−0.31

−0.37

−0.28

−0.35

−0.40

−0.45

0.26

−0.22

−0.45

−0.65

−0.21

−0.45

−0.28

−0.37

Hf

0.97

0.88

0.88

0.88

0.48

0.89

0.87

0.21

0.25

0.86

0.76

0.85

0.86

0.90

0.85

Fe1.00

0.83

0.85

0.83

0.32

0.89

0.83

0.19

0.32

0.82

0.75

0.80

0.82

0.87

0.90

Yb

1.00

0.99

1.00

0.56

0.61

0.97

−0.010

0.060

0.96

0.76

0.94

0.97

0.97

0.83

La

1.00

0.98

0.50

0.62

0.99

0.00

0.11

0.99

0.81

0.92

0.99

0.96

0.86

Lu

1.00

0.57

0.60

0.96

0.00

0.030

0.96

0.74

0.94

0.96

0.97

0.82

Hg

1.00

0.29

0.50

−0.070

−0.040

0.50

0.48

0.53

0.51

0.49

0.23

Na

1.00

0.62

0.35

0.39

0.60

0.63

0.54

0.60

0.64

0.72

Nd

1.00

−0.030

0.16

1.00

0.82

0.88

1.00

0.94

0.85

K1.00

0.49

−0.030

0.010

0.040

−0.040

0.060

0.10

Rb

1.00

0.14

0.32

0.070

0.14

0.14

0.40

Sm1.00

0.84

0.87

1.00

0.93

0.83

Se1.00

0.69

0.83

0.78

0.81

Ta1.00

0.88

0.98

0.83

Tb

1.00

0.93

0.83

Th

1.00

0.91

U1.00

Inbold,significant

values

(exceptd

iagonal)atalpha=

0.05

(two-tailedtest)

Environ Monit Assess (2014) 186:4997–5007 5003

contributed to a low oxidation of SO2 spreading outsidethe study area (NASA 2011). The SO2 oxidised totrioxide SO3, could react with gaseous water and pro-duce sulphuric acid aerosols, droplets small enough toremain in the stratosphere for years (Bailey et al. 2002).This could prove to be another reason for the lack ofcorrelation of S concentration and distance.

Furthermore, we expected a correlation between Sand Ca as consequence of Gypsum product due to aneutralisation effect as mentioned by Garty et al. (2002),but this was not observed. However, Ca showed apositive correlation with distance and negative with thelongitude (concentration increase towards to steppe,Fig. 4 and Table 3) which may be an indication of otherCa source, masking the S–Ca dependence.

Several processes besides direct nutrient supply fromthe atmosphere, such as windblown soil dust, canopythrough fall and uptake of elements from soil water,have been found to affect metal concentrations in bio-monitor pseudotissues (Godinho et al., 2008). Wind cantransport soil and falling over the lichens, which incor-porate Ca in this way. The soil may be an extra source ofCa for the lichens of this area given that, the PI and theMA and GU soil surrounding areas (see Fig. 1) aremainly mollisols (Cruzate et al. (2006a, b)),characterised by a granular structure with high Ca dom-inance (Baikey 1987). The East sampling area (DH, PI)is a steppe (Barthelemy et al. 2008) characterised bylower vegetal cover with more wind and dust storms

exposure than MA and GU sites. Consequently, theseplaces have a higher contribution to particulate than thesites located to the West. In addition, Monaci et al.(2012) reported significant variation in elemental con-centrations, included Ca, in Usnea sp. lichens located inrainforest region (>5,000 mm per year) compared toarea that included grassland and temperate forest(5,000 to 100 mm per year) in SW Chilean Patagonia(46–47 ° S and 72–73 ° W). The grassland and temper-ate forest from Chilean study has a rain fall rangecoincident with lichens analysed in this work; into thisprecipitation range (3,000 to 700 mm per year) differ-ences in Ca content were not significant in both studies.Consequently, the hypothesis of an additional Ca sourcefor lichens located in DI, PI and also places consideredas baseline, GU and MA, is solid supported.

Calcium and Sr have the same chemical propertiesand, their behaviours are similar in biological matrices(Wasserman 1998, Fitter and Hay 2002), both showedpositive correlation with distance. Relevant informationof Sr in lichens was not found.

The SEM-EDS element concentrations in differentparts of the cortex–medulla and axis lichen samples areshown in Table 2 and Table 3, complementary data. ThePCA results of these data are presented in Fig. 5. Thevariation explained between PC1 and PC2 was of 65 %.The correlation matrix is presented on Table 4. Thelichens samples are grouped mainly by the environment:ES-Co; Hu-DH and PI-T2. The relationship between

LatitudeAltitude

DistanceCaBr

AsS Hg

Zn

SrK

-3

-2

-1

0

1

2

3

-3 -2 -1 0 1 2 3

Pri

nci

pal

Co

mp

on

ent

2 (2

0 %

) --

>

Principal Component 1 (40 %) -->

CO DH ES GP GU HU MA PI PP R T1 T2 VE

Fig. 4 Principal component analysis of element not associated toparticle material of geological origin (PM), geographical parame-ters and Hum. F in the thalli

LatitudeLongit.

Altitude

Distance Hum. F

NaC

NaA

MgC

KCKA

CaCCaA

FeA

-2

-1,5

-1

-0,5

0

0,5

1

1,5

2

-2 -1,5 -1 -0,5 0 0,5 1 1,5 2

Pri

nci

pal

Co

mp

on

ent

2 (2

4 %

) --

>

Principal Component 1 (43 %) -->

CO DH ES HU PI T2

Fig. 5 Principal component analysis of biological elements withgeographical parameters and Hum. F. in cortex–medulla and axis

5004 Environ Monit Assess (2014) 186:4997–5007

geographical parameters and Hum. F. observed inFigs. 3, 4, is also shown in this analysis. The mostsignificant correlations are KA with distance (R=−0.93, p<0.05), KC-CaC (R=0.84, p<0.05) and CaC-CaA (R=0.83, p<0.05) (Table 4). Alkaline elements areof high mobility, soluble, being mainly involved inwater regulation in plants (Salisbury and Ross 1991).Calcium oxalate and K play an important role in thehydration in lichens (Bennet 2008). Potassium effluxand Ca influx in damaged lichens have been observedin polluted environment, especially by SO2 (Bennet,et al. 1997 and Garty et al. 2002). Lichens affected byMount St. Helens emissions showed significant reduc-tions in internal K, without SO2 differences compared tocontrol areas (Moser et al. 1983) as our results show.Wethink that the Ca-K balance mechanism could be aphysiological response to volcanic emissions and thiscould explain the positive Ca correlation with distance.However, there is no evidence that this response is dueto sulphur pollution.

Conclusions

The PCA improves the interpretations of volcanic effectof PCCc on element concentrations in lichens. Thisallowed to identify elements from PM (As, Cs, Ce, Eu,

La, Lu, Nd, Sb, Sm, Tb, Yb, Fe, Hf, Na, Sc, Se,Ta, Th and U) and those related to ash addition asAs, Cs, Rb, Se, U, Sb and Ba. The humidity factorand longitude correlation confirmed the humidity gradi-ent according to principal wind direction, from West toEast.

Br and Rb were the only elements positively relatedwith humidity. These elements were identified as possi-ble volatile volcanic contribution owing to their rela-tionship and chemistry characteristics.

Sulphur concentrations were 20 % higher in areasnear the volcano; however, this element did not correlatesignificantly with any variable.

In the sections of the thalli, Ca showed a positivecorrelation with the distance to PCCc and negative withthe longitude (concentration increase towards to steppe).The lack of correlation of this element with S, likely dueto masking by other sources of Ca, did not allow us toexplain the impact of S emission from PCCc.

Potassium was the only element that showed somerelation with both geographical and meteorological var-iables (distance, longitude and Hum. F.). This fact,together with the Ca correlation in both tissues, couldsuggest a physiological response due to the damagecaused by PCCc volcanic emissions. Although, thisbalance of Ca-K needs further research to be used asearly biomarkers for contamination damage.

Table 4 Correlation matrix of the biological elements. geographical parameters and Hum. F. in cortex–medulla (C) and axis (A)

Distance Hum. F. NaC NaA MgC MgA KC KA CaC CaA FeC FeA

Latitude 0.83 −0.85 −0.73 0.55 −0.20 0.37 0.53 −0.62 0.62 0.75 −0.25 0.40

Longitude −0.97 0.92 0.10 −0.46 −0.08 −0.75 −0.26 0.97 −0.34 −0.46 −0.30 −0.59Altitude 0.45 −0.38 0.38 0.56 0.00 0.13 −0.18 −0.49 −0.52 −0.44 0.26 0.87

Distance 1.00 −0.91 −0.30 0.56 0.00 0.71 0.23 −0.93 0.31 0.52 0.08 0.57

Hum. F. 1.00 0.27 −0.47 −0.04 −0.48 −0.60 0.81 −0.55 −0.57 −0.27 −0.65NaC 1.00 −0.32 0.32 0.02 −0.32 0.01 −0.48 −0.68 0.74 0.11

NaA 1.00 −0.73 0.01 0.01 −0.51 −0.11 −0.12 −0.42 0.76

MgC 1.00 0.34 0.06 0.03 0.03 0.26 0.61 −0.25MgA 1.00 −0.22 −0.80 0.13 0.44 0.25 0.00

KC 1.00 −0.07 0.84 0.56 0.26 0.25

KA 1.00 −0.20 −0.32 −0.26 −0.56CaC 1.00 0.82 0.13 −0.12CaA 1.00 −0.07 −0.21FeC 1.00 0.19

FeA 1.00

In bold, significant values (except diagonal) at alpha=0.05 (two-tailed test)

Environ Monit Assess (2014) 186:4997–5007 5005

Acknowledgements The authors wish to express their gratitudeto Ricardo Sanchez for the sampling and sample preparation,María Arribére for her critical reading and suggestions, the reactorRA–6 operation staff for their assistance in sample analysis andCarolina Ayala (Grupo de Caracterización de Materiales delCentro Atómico Bariloche) for the SEM analysis.

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