1
Atmospheric deposition chemistry in Italian forested sites Atmospheric deposition chemistry in Italian forested sites S. Arisci, M. Rogora, A. Marchetto & R. Mosello S. Arisci, M. Rogora, A. Marchetto & R. Mosello CNR Institute of Ecosystem Study -28922 Verbania Pallanza – Italy www.ise.cnr.it and www.idrolab.ise.cnr.it Corresponding author: [email protected] This work was partially funded by the European Union under Regulation (EC) 2152/2003 (“Forest Focus”) and programme LIFE+ 07/ENV D 000218 “FutMon” (Further Development and Implementation of an EU-level Forest Monitoring System) and by the Italian National Forest Service. Open field depositions were sampled weekly using three continuously exposed collectors in each area. For both open field and throughfall, samples are pooled together and an aliquot sent to the laboratory for the chemical analysis (Tartari et al. 2002). For throughfall sampling, 16 rain collectors were distributed at regular intervals in the plot. 1 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Protection Stemflow collectors Throughfall collectors Snow collectors The mean values of the period 2009- 2010 for bulk open field and throughfall concentration are shown in these two plots, with the main cations in the upper part of each plot, and the main anions in the lower part. 9 In spite of the remote location of many sites, atmospheric deposition carries high amounts of anthropogenic ions. 9 Great variability in the bulk ion concentration is due to the marine contribution, as shown by the wide range of chloride and sodium levels. 9 For base cations (calcium and magnesium) there is a strong latitudinal gradient. Most of these ions derive from the long range transport of Saharan dust, which is more important at the southernmost sites. Base cations buffers the acidity of deposition, so that the mean annual acidity is very low at all the sites. 9 Throughfall concentration in all the sites is higher than the respective bulk value (please note the different scale). The difference between bulk and throughfall mainly regards alkalinity and the major ions. Exceptions are NH 4 + and NO 3 - , which in several stations show lower values in throughfall samples, indicating a possible foliar uptake. Picea abies – Norway spruce Fagus sylvatica - Beech Quercus cerris – Turkey oak Quercus ilex - Holm oak Q. robur and Q. petraea – European and sessile oak Bulk open field Bulk throughfall Under the EU-funded Forest Focus and FUTMON Life+ Programme, deposition acidity and ionic content were analysed in 1998-2010 in forested sites in Italy distributed over the whole country. Temporal trends of ion concentration and precipitation amount were evaluated in 10 sites. Finally, critical loads for nutrient nitrogen were used to calculate exceedance and identify the areas most sensitive to N enrichment. Open field Abies alba and Q. Cerris Silver fir and oak -450 -300 150 0 150 300 450 FRI2 BOL1 LOM1 TRE1 VAL1 PIE3 EMI1 VEN2 LAZ1 MAR1 ABR2 ABR1 CAL1 CAM1 PIE1 VEN1 PUG1 TOS1 SAR1 TOS2 LAZ2 K + Na + Mg ++ Ca ++ NH 4 + H + Alk SO 4 = NO 3 - Cl - Picea abies Larix decidua Fagus sylvatica Q. ilex Q. cerris/ robur/petraea 900 600 300 0 300 600 900 FRI2 BOL1 LOM1 TRE1 VAL1 PIE3 EMI1 VEN2 LAZ1 MAR1 ABR2 ABR1 CAL1 CAM1 PIE1 VEN1 PUG1 TOS1 SAR1 TOS2 LAZ2 K Na + Mg ++ Ca ++ NH 4 + H + Alk SO 4 = NO 3 - Cl - Abies alba and Q. Cerris Level of significance: ** p<0.01 *** * p<0.001 p<0.05 Temporal trends in precipitation chemistry were tested with the Seasonal Kendall Test (Hirsch et al. 1982) applied to monthly bloscks of data for the period 1998-2010. SKT has been identified as a suitable method for the analysis of water quality data, and is applied in a number of monitoring programmes, including ICP Waters and ICP Integrated Monitoring (Stoddard et al. 1999; Forsius et al. 2001). At most of the sites, total N deposition is close to the estimated critical loads of nutrient N, while in part of the Po Plain (i.e. stations PIE1 and EMI1) and at TOS1 and CAL1 the critical values have been exceeded during the study period. In a smaller number of sites (PIE1, PIE3, BOL1, TRE1, FRI2, ABR2 and LAZ1), runoff water was sampled weekly even if precipitation did not occur during the week. The watercourses are fairly small streams, but not so small to be dry for more than 3-4 months during the year. * *** *** ** NH 4 + ** * *** *** *** *** *** *** SO4 = *** ** Cl - ** ** * NO 3 - * K + *** ** Na + *** * *** *** * Mg ++ * *** * * *** *** Ca ++ *** ** Cond. CAM1 CAL1 LAZ1 TOS1 EMI1 FRI2 BOL1 TRE1 PIE1 kg ha -1 y -1 μeq L -1 μeq L -1 Throughfall *** ** * NH 4 + *** *** *** *** *** *** *** SO4 = *** * * Cl - * ** NO 3 - ** ** *** *** ** *** ** K + *** Na + *** ** *** *** Mg ++ *** * *** *** Ca ++ *** * * *** * Cond. CAM1 CAL1 LAZ1 TOS1 EMI1 FRI2 BOL1 TRE1 PIE1 y = 1.3549e 0.0293x R 2 = 0.399 0 5 10 15 20 25 30 35 40 30 55 80 105 Inorganic N deposition (meq m -2 y -1 ) NO3 in runoff (μeq L -1 ) PIE1 PIE3 ABR2 FRI2 LAZ1 TRE1 BOL1 Results show significant decreasing trend for SO 4 = for most of the plots, both for open field and throughfall deposition. A significant decrease, for both the sample typologies, also emerges for calcium, magnesium and potassium, but in a smaller number of plots. A negative trend was detected for inorganic nitrogen only at few plots in bulk open field samples, while for throughfall at CAL1 a positive trend for ammonia was found. Significant negative trends were also found for chloride at TOS1, TRE1 and EMI1. Hirsch R.M., Slack J.R., Smith R.A. 1982 - Techniques of trend analysis for monthly water quality data. Water Res. Res., 18: 107– 121. Stoddard J.L., Jeffries D.S., Lükewille A., Clair T.A., Dillon P.J.,Driscoll C.T., Forsius M., Johannessen M., Kahl J.S., Kellogg J.H., Kemp A., Mannio J., Monteith D., Murdoch. S., Patrick S., Rebsdorf A., Skjelkvåle B.L., Stainton M.P., Traaen T., Van Dam H., Webster K.E., Wieting J., Wilander A. 1999 - Regional trends in aquatic recovery from acidification in North America and Europe. Nature, 401: 575– 578. Forsius M., Kleemola S., Vuorenmaa J., Syri S. 2001 - Fluxes and trends of nitrogen and sulphur compounds at Integrated Monitoring Sites in Europe. Water Air Soil Pollut., 130: 1641-1648. Tartari G.A., S. Arisci, M.C. Brizzio, A. Marchetto, R. Mosello & A. Pranzo, 2002 - Programma Nazionale Integrato per il Controllo degli Ecosistemi Forestali (CON.ECO.FOR.): Studio della chimica delle deposizioni atmosferiche. Manuale per le operazioni di campionamento. C.N.R., Institute of Ecosystem Study, Verbania Pallanza: 35 pp. Lower deposition values were detected at the Central-Southern sites where total nitrogen deposition in bulk open field samples are lower than 13 kg N ha -1 y -1 , while at Northern sites the range is 8-18 kg N ha -1 y -1 . In throughfall samples, total nitrogen deposition increases, with maximum of 25 and 28 kg N ha -1 y -1 at EMI1 and VEN1, respectively. 0 5 10 15 20 25 30 0 5 10 15 20 25 30 N deposition kg ha -1 y -1 N Critical Load kg ha -1 y -1 Exceedance In this figure, mean NO 3 concentration (2009-2010) measured in runoff water at 7 sampling sites are plotted against nitrogen deposition values (sum of NH 4 and NO 3 ). A relationship between the variables can be observed, with increasing NO 3 leaching when the critical value of 10 kg N ha -1 y -1 of N deposition (71 meq m -2 y -1 ) is exceeded (Dise and Wright 1995). Dise NB, Wright RF (1995) Nitrogen leaching in European forests in relation to nitrogen deposition. Forest Ecol. and Manage. 71: 153-162 Negative trends are in red, positive trends in blue Larix decidua - Larch ABR1 ABR2

Atmospheric deposition chemistry in Italian forested sites · 2018. 11. 15. · PIE1 TRE1 BOL1 FRI2 EMI1 TOS1 LAZ1 CAL1 CAM1 y = 1.3549e0.0293x R2 = 0.399 0 5 10 15 20 25 30 35 40

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Page 1: Atmospheric deposition chemistry in Italian forested sites · 2018. 11. 15. · PIE1 TRE1 BOL1 FRI2 EMI1 TOS1 LAZ1 CAL1 CAM1 y = 1.3549e0.0293x R2 = 0.399 0 5 10 15 20 25 30 35 40

Atmospheric deposition chemistry in Italian forested sitesAtmospheric deposition chemistry in Italian forested sitesS. Arisci, M. Rogora, A. Marchetto & R. MoselloS. Arisci, M. Rogora, A. Marchetto & R. Mosello

CNR Institute of Ecosystem Study -28922 Verbania Pallanza – Italywww.ise.cnr.it and www.idrolab.ise.cnr.it Corresponding author: [email protected]

This work was partially funded by the European Union under Regulation (EC) 2152/2003 (“Forest Focus”) and programme LIFE+ 07/ENV D 000218 “FutMon”

(Further Development and Implementation of an EU-level Forest Monitoring System) and by the Italian National Forest Service.

Open field depositions were sampled weekly using three continuously exposed

collectors in each area.

For both open field and throughfall, samples are pooled together and an aliquot

sent to the laboratory for the chemical analysis (Tartari et al. 2002).

For throughfall sampling, 16 rain collectors were distributed at regular intervals in the plot.

1 2 3 4

5 6 7 8

9 10 11 12

13 14 15 16

Protection

Stemflow collectors

Throughfall collectors

Snow collectors

The mean values of the period 2009-2010 for bulk open field and throughfall concentration are shown in these two plots, with the main cations in the upper part of each plot, and the main anions in the lower part.

In spite of the remote location of many sites, atmospheric deposition carries high amounts of anthropogenic ions.

Great variability in the bulk ion concentration is due to the marine contribution, as shown by the wide range of chloride and sodium levels.

For base cations (calcium and magnesium) there is a strong latitudinal gradient. Most of these ions derive from the long range transport of Saharan dust, which is more important at the southernmost sites. Base cations buffers the acidity of deposition, so that the mean annual acidity is very low at all the sites.

Throughfall concentration in all the sites is higher than the respective bulk value (please note the different scale). The difference between bulk and throughfall mainly regards alkalinity and the major ions. Exceptions are NH4

+ and NO3- ,

which in several stations show lower values in throughfall samples, indicating a possible foliar uptake.

Picea abies – Norway spruceFagus sylvatica - BeechQuercus cerris – Turkey oakQuercus ilex - Holm oakQ. robur and Q. petraea –European and sessile oak

Bulk open field

Bulk throughfall

Under the EU-funded Forest Focus and FUTMON Life+ Programme, deposition acidity and ionic content were analysed in 1998-2010 in forested sites in Italy distributed over the whole country.

Temporal trends of ion concentration and precipitation amount were evaluated in 10 sites. Finally, critical loads for nutrient nitrogen were used to calculate exceedance and identify the areas most sensitive to N enrichment. Open field

Abies alba and Q. Cerris Silver fir and oak

-450

-300

150

0

150

300

450

FRI2

BO

L1

LOM

1TR

E1

VAL1

PIE3

EMI1

VEN

2LA

Z1

MAR

1

ABR

2AB

R1

CAL

1

CAM

1PI

E1

VEN

1PU

G1

TOS1

SAR

1

TOS2

LAZ2

K+

Na+

Mg++

Ca++

NH4+

H+

AlkSO4

=

NO3-

Cl-

Picea abies

Larix decidua

Fagus sylvatica Q. ilexQ. cerris/ robur/petraea

900

600

300

0

300

600

900

FRI2

BO

L1

LOM

1TR

E1

VAL1

PIE3

EMI1

VEN

2LA

Z1M

AR1

ABR

2

ABR

1

CAL

1C

AM1

PIE1

VEN

1PU

G1

TOS1

SAR

1

TOS2

LAZ2

KNa+

Mg++

Ca++

NH4+

H+

AlkSO4

=

NO3-

Cl-

Abies alba and Q. Cerris

Level of significance:

** p<0.01 *** *p<0.001 p<0.05

Temporal trends in precipitation chemistry were tested with the Seasonal Kendall

Test (Hirsch et al. 1982) applied to monthly bloscks of data for the period 1998-2010.

SKT has been identified as a suitable method for the analysis of water quality

data, and is applied in a number of monitoring programmes, including ICP Waters and ICP Integrated Monitoring

(Stoddard et al. 1999; Forsius et al. 2001).

At most of the sites, total N deposition is close to the estimated critical loads of nutrient N, while in part of

the Po Plain (i.e. stations PIE1 and EMI1) and at TOS1 and CAL1 the critical values have been exceeded

during the study period.

In a smaller number of sites (PIE1, PIE3, BOL1, TRE1, FRI2, ABR2 and LAZ1), runoff water was sampled weekly even if precipitation did not occur during the week. The watercourses are fairly small streams, but not so small to be dry for more than 3-4 months during the year.

*********NH4+

*********************SO4=

*****Cl-

*****NO3-

*K+

*****Na+

***********Mg++

************Ca++

*****Cond.

CAM1CAL1LAZ1TOS1EMI1FRI2BOL1TRE1PIE1

kg ha-1 y-1

µeq L-1

µeq L-1

Throughfall

******NH4+

*********************SO4=

*****Cl-

***NO3-

*****************K+

***Na+

***********Mg++

**********Ca++

*********Cond.

CAM1CAL1LAZ1TOS1EMI1FRI2BOL1TRE1PIE1

y = 1.3549e0.0293x

R2 = 0.3990

5

10

15

20

25

30

35

40

30 55 80 105Inorganic N deposition (meq m-2 y-1)

NO

3 in

runo

ff

(µeq L-1)

PIE1

PIE3ABR2

FRI2LAZ1

TRE1

BOL1

Results show significant decreasing trend for SO4

= for most of the plots, both for open field and throughfall deposition. A

significant decrease, for both the sample typologies, also emerges for calcium,

magnesium and potassium, but in a smaller number of plots.

A negative trend was detected for inorganic nitrogen only at few plots in bulk open field

samples, while for throughfall at CAL1 a positive trend for ammonia was found. Significant negative trends were also

found for chloride at TOS1, TRE1 and EMI1.

Hirsch R.M., Slack J.R., Smith R.A. 1982 - Techniques of trend analysis for monthly water quality data. Water Res. Res., 18: 107–121.

Stoddard J.L., Jeffries D.S., Lükewille A., Clair T.A., Dillon P.J.,Driscoll C.T., Forsius M., Johannessen M., Kahl J.S., Kellogg J.H., Kemp A., Mannio J., Monteith D., Murdoch. S., Patrick S., Rebsdorf A., Skjelkvåle B.L., StaintonM.P., Traaen T., Van Dam H., Webster K.E., Wieting J., Wilander A. 1999 -Regional trends in aquatic recovery from acidification in North America and Europe. Nature, 401: 575– 578.

Forsius M., Kleemola S., Vuorenmaa J., Syri S. 2001 - Fluxes and trends of nitrogen and sulphur compounds at Integrated Monitoring Sites in Europe. Water Air Soil Pollut., 130: 1641-1648.

Tartari G.A., S. Arisci, M.C. Brizzio, A. Marchetto, R. Mosello & A. Pranzo, 2002 - Programma Nazionale Integrato per il Controllo degli EcosistemiForestali (CON.ECO.FOR.): Studio della chimica delle deposizioni atmosferiche. Manuale per le operazioni di campionamento. C.N.R., Instituteof Ecosystem Study, Verbania Pallanza: 35 pp.

Lower deposition values were detected at the Central-Southern sites where total nitrogen deposition in bulk open field samples are lower than 13 kg N ha-1 y-1, while at Northern sites the range is 8-18 kg N ha-1 y-1. In throughfall samples, total nitrogen deposition increases, with maximum of 25 and 28 kg N ha-1 y-1

at EMI1 and VEN1, respectively.

0

5

10

15

20

25

30

0 5 10 15 20 25 30

N deposition kg ha-1 y-1

N C

ritic

al L

oad

kg

ha-1

y-1

Exceedance

In this figure, mean NO3concentration (2009-2010) measured in runoff water at 7 sampling sites are plotted against nitrogen deposition values (sum of NH4 and NO3). A relationship between the variables can be observed, with increasing NO3 leaching when the critical value of 10 kg N ha-1

y-1 of N deposition (71 meq m-2

y-1) is exceeded (Dise and Wright 1995).

Dise NB, Wright RF (1995) Nitrogen leaching in European forests in relation to nitrogen deposition. Forest Ecol. and Manage. 71: 153-162

Negative trends are in red, positive trends in blue

Larix decidua - Larch

ABR1ABR1ABR1ABR2