Atmospheric deposition in coniferous and deciduous tree stands in Poland

Accepted Manuscript Atmospheric deposition in coniferous and deciduous tree stands in Poland Anna Kowalska, Aleksander Astel, Andrzej Boczoń, Żaneta Polkowska PII:

S1352-2310(16)30203-5

DOI:

10.1016/j.atmosenv.2016.03.033

Reference:

AEA 14515

To appear in:

Atmospheric Environment

Received Date: 3 August 2015 Revised Date:

29 February 2016

Accepted Date: 12 March 2016

Please cite this article as: Kowalska, A., Astel, A., Boczoń, A., Polkowska, Ż., Atmospheric deposition in coniferous and deciduous tree stands in Poland, Atmospheric Environment (2016), doi: 10.1016/ j.atmosenv.2016.03.033. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Highlights Chemistry of rainfall depends on site, water amount, sea salt effect, and pollution Type of tree stand considerably influences the chemical composition of precipitation

Deciduous species raise pH of precipitation

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Coniferous species cause acidification of PRECIPITATION

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Chemistry of precipitation in the forests of Poland is typical of European countries

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Atmospheric deposition in coniferous and deciduous tree stands in Poland

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Anna Kowalskaa, Aleksander Astelb, Andrzej Boczońa, Żaneta Polkowskac

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[email protected] tel. +48 227150534, fax +48 227150507 (corresponding author)

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Arciszewskiego Str., 76-200 Słupsk, Poland

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(GUT), 11/12 G. Narutowicza Str., 80-233 Gdańsk, Poland

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Abstract

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Forest Research Institute, Sękocin Stary, 3 Braci Leśnej Str., 05-090 Raszyn, Poland

Pomeranian University in Słupsk, Institute of Biology and Environment Protection, 22a

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Department of Analytical Chemistry, Chemical Faculty, Gdansk University of Technology

The objective of this study was to assess the transformation of precipitation in terms of

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quantity and chemical composition following contact with the crown layer in tree stands with

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varied species composition, to investigate the effect of four predominant forest-forming

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species (pine, spruce, beech, and oak) on the amount and composition of precipitation

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reaching forest soils, and to determine the sources of pollution in atmospheric precipitation in

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forest areas in Poland.

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The amount and chemical composition (pH, electric conductivity, alkalinity, and chloride,

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nitrate, sulfate, phosphate, ammonium, calcium, magnesium, sodium, potassium, iron

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aluminum, manganese, zinc, copper, total nitrogen, and dissolved organic carbon contents) of

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atmospheric (bulk, BP) and throughfall (TF) precipitation were studied from January to

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December 2010 on twelve forest monitoring plots representative of Polish conditions. The

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study results provided the basis for the determination of the fluxes of pollutants in the forest

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areas of Poland and allowed the comparison of such fluxes with values provided in the

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literature for European forest areas. The transformation of precipitation in the canopy was

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compared for different tree stands. The fluxes of substances in an open field and under canopy

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were influenced by the location of the plot, including the regional meteorological conditions

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(precipitation amounts), vicinity of the sea (effect of marine aerosols), and local level of

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anthropogenic pollution. Differences between the plots were higher in TF than in BP. The

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impact of the vegetation cover on the chemical composition of precipitation depended on the

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ACCEPTED MANUSCRIPT region of the country and dominant species in a given tree stand. Coniferous species tended to

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cause acidification of precipitation, whereas deciduous species increased the pH of TF. Pine

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and oak stands enriched precipitation with components that leached from the canopy

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(potassium, manganese, magnesium) to a higher degree than spruce and beech stands.

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Keywords: bulk precipitation; throughfall enrichment; multivariate analysis; deciduous

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stands; coniferous stands; precipitation transformation

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1. Introduction

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In spite of considerable reduction in industrial emissions over the last 25 years, air pollutants

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still have an effect and are predicted to have an effect in the future on the structure and

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functioning of forest ecosystems in the territory of Poland (Hettelingh et al., 2012). The

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identification of the cause-effect relationship between air pollution and the state of the forest

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environment requires the determination of levels of compounds transported in the atmosphere

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and deposited in the forest areas. Ions of varied origin reach forest areas: from marine

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aerosols: sodium (Na), chloride (Cl-), sulfate (SO42-), potassium (K), magnesium (Mg), and

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calcium (Ca); from local soil dusts or dusts transported over large distances: Ca, Mg, and K;

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and from anthropogenic sources: ammonium (NH4+), nitrate (NO3-), and SO42- (Mosello et al.,

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2002; Balestrini et al., 2007).

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Precipitation reaching soils under tree canopies differs from atmospheric precipitation.

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Elements of the crown layer participate in processes that lead to enrichment or depletion of

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mineral and organic compounds in precipitation. The precipitation amount also changes as a

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result of, e.g., evaporation of part of the water from the surface of plants. The form of

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deposition, evaporation of precipitation from the surface of leaves/needles, washing out of

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dusts, gases, and aerosols from the surface of trees, and leaching from plant tissues all play a

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crucial role in the transformation of the composition of precipitation in contact with the

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canopy. The intensity of the processes depends on factors related to the following:

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- features of trees and tree stands such as species (Adriaenssens et al., 2011; Jung et al., 2011),

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crown geometry (Adriaenssens et al., 2012a), age of trees, canopy cover (Herrmann et al.,

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2006), leaf surface area, age of leaves, phenological phase (Staelens et al., 2005;

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Adriaenssens et al., 2011; Van Stan II et al., 2012),

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- meteorological conditions such as duration, intensity, and type of precipitation, duration of

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dry periods, wind velocity and direction (Starr and Ukonmaanaho, 2004; Wuyts et al., 2008;

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Van Stan II et al., 2012),

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- presence of sources of pollution, transport of pollutants, and their inflow to forests (Herrmann et al., 2006; Balestrini et al., 2007).

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Issues related to transformation of precipitation in the forest canopy are broadly described in

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the global literature, although research in Europe particularly covers spruce and beech stands

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(e.g., Oulehle and Hruška, 2005; Gandois et al., 2010). Other tree species, including pine and

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oak, important for the area of Poland, have been described considerably less often in both

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European and national works. The above factors indicate the need for the investigation of the

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transformation of the chemical composition of precipitation in tree stands caused by the main

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forest-forming species growing in varied habitat and anthropopressure conditions.

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The objective of this study was to identify the sources of pollutants in atmospheric

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precipitation in forest areas in Poland, to determine the degree of transformation of

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precipitation following contact with canopy, and to study the effect of the four main forest-

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forming species (pine, spruce, beech, and oak) on the amount and composition of

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precipitation reaching forest soils. To evaluate the hypothesis that deposition in the forests

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differs depending on species composition and level of atmospheric pollution, annual data

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from Polish forest monitoring plots were used to conduct the analysis.

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2. Methods

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2.1 Site description

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The study was conducted on twelve Level II plots (Table 1, Figure 1, Table 2) that belong to

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the Polish forest monitoring network. The national forest monitoring program forms a part of

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the Pan-European Programme based on the International Co-operative Programme on

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Assessment and Monitoring of Air Pollution Effects on Forests (ICP-Forests). The plots were

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located in mature pine, spruce, oak, and beech stands in numbers reflecting the species

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structure of the tree stands in the national forests.

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2.2. Sampling and laboratory methods

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ACCEPTED MANUSCRIPT The study plot was a rectangular area on the surface 1500 - 2500 m2. Throughfall water

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sample was collected into thirty 5 dm3 funnel-type throughfall (TF) water collectors with a

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diameter of 16 cm at CHO405 and 25 on the remaining plots The collecting surface was

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positioned 1 m above the ground level. In the winter season summer collectors were replaced

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with six 20 dm3 polypropylene-polyethylene (PP/PE) buckets with a diameter of 31.6 cm.

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Stemflow was measured at two beech plots: GDA116 and BIR804 but due to the frequent

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overflow the data have not been used in this work. Roughly estimated stemflow deposition

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amounted to at least 8% of total TF input at GDA116 and 3% at BIR804. The contribution of

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stemflow to the stand deposition is usually lower for coniferous and deciduous species other

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than beech, therefore stemflow was not measured at the 10 remaining plots. Open field

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precipitation (BP) was collected simultaneously in three 3 dm3 funnel collectors with a

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diameter of 15 cm located at distances from 150 m to 3 km from the TF plots. In winter,

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summer equipment was replaced with polyethylene buckets with a capacity of 10 dm3 with a

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diameter of 26 cm.

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Samples were collected monthly. The electric conductivity (EC) and pH was measured by

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means of the conductometric and potentiometric method, respectively. In samples with pH

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higher than 5.0, alkalinity (Alk) was measured by titration to two final points, pH 4.5 and 4.2.

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In separate samples after filtration through 0.45 µm membrane filters, the concentrations of

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Cl-, NO3-, SO42-, phosphate (PO43-,), and NH4+ were determined by the method of ion

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chromatography with suppression. The concentrations of metals (calcium (Ca), magnesium

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(Mg), sodium (Na), potassium (K), iron (Fe), aluminum (Al), manganese (Mn), zinc (Zn), and

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copper (Cu)) were measured by the method of emission spectrophotometry with inductively

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coupled plasma. Total nitrogen (TN) was determined by the chemiluminescence method and

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dissolved organic carbon (DOC) by the spectrophotometry method in infrared with NDIR

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detection. H+ concentration was derived from pH.

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Certified reference materials were used for quality control: SPS-SW2 by Spectrapure

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Standards and CRM No 409 by IRMM. Quality control tests such as ion balance, comparison

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of measured and calculated conductivity, ratio of sodium to chloride ions, and balance of

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nitrogen compounds were applied when the results of chemical analyses were completed. The

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methodology for the control tests and the criteria of assessment of the results were described

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in more detail by Mosello et al. (2005).

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ACCEPTED MANUSCRIPT 2.3. Data analysis

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Monthly values of concentration of BP and TF per plot and single period were obtained from

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volume weighted means for parallel collectors. BP and TF fluxes were calculated by

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multiplying concentrations by corresponding water fluxes. Enrichment ratios were determined

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by dividing medians of the monthly fluxes in TF by BP fluxes. Values less than one imply the

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retention of the elements in canopy while values greater than one imply the enrichment of the

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precipitation. The Wilcoxon signed-rank test was performed to test whether precipitation

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amount and ion fluxes were significantly different between BP and TF.

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Based on the results of research conducted within 12 months, statistical descriptive

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parameters were determined for BP and TF at twelve plots grouped by predominant species in

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tree stands. For each studied parameter in each type of precipitation separately, median values

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between the plots were compared by means of the non-parametric Kruskal-Wallis test,

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because most data were not normally distributed. Then, pairwise multiple comparisons of

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mean ranks were performed for all samples.

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Data were grouped into two periods: winter-spring (from January to May and December) and

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summer-autumn (from June to November). In the winter season, increased levels of

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atmospheric pollution usually occur. The identification of months with low temperatures thus

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allowed for the assessment of the effect of increased levels of pollutants, particularly those of

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anthropogenic origin, on the BP and TF fluxes. Months of the summer-autumn half-year are

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associated with increased biological activity of trees. In this half-year, the observation of the

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effect of the species composition of the tree stand on the TF fluxes was expected.

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To analyze the similarity of the plots in terms of parameters of precipitation and to perform a

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spatial division into regions with different anthropopressure levels (based on BP), as well as

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to verify similarities between tree stands differing in terms of species (based on TF),

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multivariate analysis was applied. The analysis was also performed for investigation of

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potential sources of pollutants at the plots (based on BP) and origin of components in TF (dry

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deposition, leaching from plant tissues, adsorption in canopy). Hierarchical agglomeration by

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the Ward method with squared Euclidean distance was applied as a measure of similarity

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among clusters. The Spearman rank correlation analysis was also applied for each type of

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ACCEPTED MANUSCRIPT water for the analysis of relationships between the variables, separately in the winter-spring

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and summer-autumn season and separately for each studied tree species.

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The STATISTICA version 10 software package (StatSoft, Inc., 2011) was used for the

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statistical calculations.

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3. Results and discussion

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Medians of precipitation variables were calculated separately for each type of tree stand

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(Table 3 and Table 4). The highest amounts of precipitation were at spruce plots (83.2 mm

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monthly, on the average) and beech plots (75.5 mm), resulting from their location. The annual

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precipitation at GDA116 (beech) and in southern Poland: (ZAW513 (pine), SZP701 (spruce),

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BIE801 (spruce), and BIR804 (beech) exceeded 1000 mm. In the remaining locations, the

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precipitation varied from 735 mm (KRU312) to 882 mm (CHO405).

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3.1. Chemistry of precipitation

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The lowest pH was recorded at spruce plots (BIE801, SZP701, and SUW203) and averaged

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4.9 in BP and 4.8 in TF (Table 3). Bulk precipitation at the pine stands had a relatively high

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pH (5.7), but under the canopy, the pH decreased to 5.3. Throughfall was less acidic at

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deciduous plots compared to coniferous plots. In bulk precipitation, the pH was 5.1-5.2, while

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under the canopy, pH increased to 5.9 in beech stands and even to 6.1 in oak stands.

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With few exceptions, the components analyzed had higher concentrations and higher fluxes in

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TF than in BP and differences were significant for most of the components (Table 3 and 4).

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3.2. TF enrichment

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Throughfall was the most substantially enriched with K and Mn (Figure 2). At spruce and

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beech stands, the fluxes of those ions in TF increased approximately six times, at pine and oak

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stands the enrichment index was approximately 8 for K and 12-21 for Mn. Mg, Fe, SO42- were

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enriched from 0.8 to 4.3 times on average, but similar to K and Mn, the enrichment index was

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higher at pine and oak stands than at spruce and beech plots. For numerous ions lower

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enrichment was observed at the beech stands than at the other stands.

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ACCEPTED MANUSCRIPT Fluxes of H+ were lower under the canopy of deciduous species than in the BP. The

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enrichment index was 0.1 at oak plots and 0.3 at beech plots. The opposite was observed at

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spruce and pine stands, where H+ fluxes in the TF increased by, respectively, 1.2 and 1.8

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times compared to BP. The literature provides evidence of the neutralization of acid

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precipitation by the canopy as well as of the acidification in the canopy. The former

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phenomenon predominantly concerns deciduous forests (Stachurski and Zimka, 2002;

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Adriaenssens et al., 2012a), as also confirmed by results of this study. In coniferous forests,

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no change in pH was observed (Stachurski and Zimka, 2002), TF was depleted of H+ (De

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Schrijver et al., 2004; Adriaenssens et al., 2012a), or pH was decreased (Walna et al., 2003).

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The results of this study seem to confirm the research by Walna et al. (2003), who observed

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also pH levels in TF similar to or higher than those of BP at deciduous (oak and beech)

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stands. Additionally, Jung et al. (2011) observed higher deposition of H+ in coniferous than in

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deciduous forests. The question remains, however, whether the same mechanisms that were

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identified by Jung et al. (2011) (i.e., higher interception of SO42-, lower adsorption of H+ in

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the canopy, and higher leaching of organic acids from plant tissues as a result of ion exchange

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at a coniferous rather than at a deciduous stand) account for the lower pH of TF at coniferous

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stands in Poland. The enrichment of SO42- and of DOC, with the latter being the main source

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of organic acids in TF, is different for spruce stands than for pine stands, with spruce stands

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having a similar level of enrichment as observed in oak stands.

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A net release of organic compounds in canopies was observed for all studied tree species.

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Nevertheless, the enrichment of DOC was higher in pine, spruce and oak stands (3.7, 3.0, and

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2.8 times, respectively) than in beech stands (1.3 times). Strong positive correlations (p ≤

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0.001) was found for DOC in TF and elements involved in canopy exchange: Ca, Mg, K in all

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stands and Al and Mn in coniferous stands, but, except for pine stands, no significant

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correlations were found between DOC and Na and Cl- of marine origin. The above results

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confirm findings of Arisci et al. (2012) that leaching processes play a dominant role in DOC

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enrichment of TF, and that forest type affects DOC concentrations and fluxes in TF.

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Nitrogen compounds were either depleted or enhanced in TF compared to BP depending on

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the ion type and tree species. Enrichment in TN and NH4+ was observed in the oak and spruce

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stands (1.1 – 1.4 times) while enrichment factors amounted to merely 0.7 – 0.9 in the pine and

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beech stands. The depletion of TF in NH4+ in the pine stands can be attributed to the sorption

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ACCEPTED MANUSCRIPT on the bark of the twigs, more pronounced than for beech and oak (Adriaenssens et al.,

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2012b). On the other side, foliage of deciduous species compared to the coniferous is more

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effective in sorption of NO3- than NH4+ (ibid.). This may explain the depletion of TF in NO3-

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in deciduous stands. The enrichment of TF in nitrates in coniferous stand by a factor of 1.2

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can be attributed to both: lower sorption of NO3- (ibid.) and higher efficiency in capturing dry

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deposition (Skeffington and Hill, 2012).

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3.3. Chemistry of precipitation in European and Polish forests

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The deposition of precipitation components at pine stands in this study (BIA212, STR206,

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KRU312, CHO405, and ZAW513) was usually typical of the European countries (Herrmann

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et al., 2006; Terauda and Nikodemus, 2007) (Figure 3). Higher fluxes of Mg, Na+ and Cl- in

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Germany (Herrmann et al., 2006) ) probably result from the higher impact of marine salt.

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For spruce stands (SUW203, SZP701, and BIE801), annual fluxes of components are within

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the range of values for numerous European countries (Adamson et al., 1993; Bäumler and

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Zech, 1997; Balestrini and Tagliaferri, 2001; Lochman et al., 2002; Moffat et al., 2002;

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Mosello et al., 2002; Piirainen et al., 2002; Oulehle and Hruška, 2005; Balestrini et al., 2007;

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Clarke et al., 2007; Berger et al., 2008; Gandois et al., 2010), but a number of components

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(e.g., Ca, Mg, Na, SO42-, Cl-) had fluxes lower than the fluxes recorded in Poland in earlier

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studies (Polkowska et al., 2005). Lower deposition, especially for SO42-, in this case can be

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accounted for by the reduction in atmospheric emission rates reported for Poland in the

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1990’s (Mill, 2006).

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At beech stands (GDA116 and BIR804), the fluxes of components are within ranges recorded

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in European countries (Skřivan et al., 1995; Mosello et al., 2002; Oulehle and Hruška, 2005;

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Balestrini et al., 2007; Berger et al., 2008; Gandois et al., 2010). In Poland, the higher fluxes

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of SO42- reported by Polkowska et al. (2005) probably result from higher emissions of SO2

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more than a decade before this study, as is the case for spruce stands.

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At two oak plots, KRO322 and LAC326, the fluxes of components of precipitation were close

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to those for plots in several European countries (Amezaga et al., 1997; Mosello et al., 2002;

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Herrmann et al., 2006), except for Na and Cl-, more abundant at European sites influenced by

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marine deposition. In reference to the conditions of Poland, pH was higher and deposition in

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ACCEPTED MANUSCRIPT the open field of Ca, Mg, Na, SO42-, and Cl- were lower than in the study by Polkowska et al.

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(2005) at the Jeziory site, located 15 km from urban agglomeration. The differences could

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have resulted from much lower risk of industrial pollution at sites reported here.

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3.4. Differences between plots

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Significantly higher fluxes of Na were observed in BP at plot situated in the coastal area

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(GDA116) (Table 5) than at the other plots located in central, northern and north-eastern

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Poland, where marine deposition inputs are low. Significant differences in terms of the

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components in BP were recorded between the three plots of the mountainous regions

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(SZP701, BIE801, and BIR804) and STR206 and BIA212. The latter two plots are located in

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the north eastern part of Poland, considered as the low pollution areas due to the low level of

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urbanization and industrialization. On the other hand, the differences in fluxes between plots

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located in southern and north-eastern Poland result partly from the differences in the amount

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of precipitation in those regions. Plots SZP701, BIE801, and BIR804 received 1496, 1649,

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and 1220 mm of precipitation in 2010, respectively, while SUW203 had 766 mm, and

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BIA212 had 850 mm.

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Differences between plots were more clearly seen in TF than in BP. Most frequently, the

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fluxes of components of TF were significantly different (p ≤ 0.05) at SZP701, BIE801, and

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ZAW513 from those of the remaining plots. Although those three plots represent different

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types of stands (spruce (SZP701 and BIE801) and pine (ZAW513)), no statistically significant

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differences were detected between them, but they all differed significantly from oak plots at

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KRO322 and LAC326, beech plot at GDA116, and pine plots at BIA212, KRU312. Within

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spruce plots in southern (SZP701 and BIE801) and northeastern Poland (SUW203),

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statistically significant differences were observed for H+, Mn at BIE801 and SUW203 and for

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H+, SO42-, and Al at SZP701 and SUW203.

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Beech plots GDA116 located in the coastal area of the Baltic Sea in northern Poland and

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BIR804 located in foothills of the Carpathian Mountains far from the sea in southern Poland

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differed significantly in terms of the deposition of Na (15.6 meq m-2 and 5.0 meq m-2,

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respectively).

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ACCEPTED MANUSCRIPT The components of TF for which differences were recorded between the plots can therefore

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be divided into three groups. The first small group includes ions of marine origin (Na+ and Cl-

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), the fluxes of which are related to the influence of sea salt aerosols. The components easily

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leaching from plant tissues such as H+, Mn, Al belong to the second group. The third group,

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consisting of SO42- and NO3- may be ascribed to the overall level of atmospheric pollution.

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3.5. Similarities between plots

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3.5.1. Bulk precipitation

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Groups of similar plots and groups of similar components of precipitation were isolated as a

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result of cluster analysis. According to the more restrictive significance criterion of Sneath’s

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index (1/3 Dmax), KRU312 formed a separate single-element group both in the winter-spring

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and summer-autumn seasons (Figure 4). Fluxes of TN, NH4+, PO43-, K, and alkalinity in

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precipitation were higher at that plot than in other locations (Table 6). Elevated levels of

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NH4+, PO43-, and alkalinity suggests contamination of samplers by birds (Erisman et al., 2003)

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at KRU312, which basically constrains any further credible analysis of the chemical

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composition of BP in this location.

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Among the remaining eleven plots, according to the more restrictive significance criterion of

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Sneath’s index (1/3 Dmax), BIE801 and SZP701 entered into one group in the summer-autumn

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season. In winter and spring, the same group included also ZAW513, BIR804, and GDA116.

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These plots, except for the coastal plot GDA116, were located in southern Poland and

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differed from the other plots in terms of higher precipitation amount and higher fluxes of

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SO42-, Cl-, DOC, and nitrogen compounds (Table 6).

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The agglomeration analysis showed three groups of similarities between the components for

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the winter-spring season and four groups for the summer-autumn season. Generally, the

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grouping results from the geographical location of plots (precipitation amount) and

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anthropogenic effects (SO42-, NO3-), aeolian effect (Ca, Mg), contamination by birds (K, PO43-

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, NH4+, TN, alkalinity), and marine impact (Na, Cl-). The correlations between components

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within the distinguished groups are confirmed by high (in absolute values) and significant

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(p ≤ 0.05) correlation coefficients in the summer-autumn and winter-spring season.

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ACCEPTED MANUSCRIPT In research by Balestrini et al. (2007) at Italian tree stands, high-mountain (Alpine) plots,

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similar to the plots of southern Poland discussed in this paper, had a higher amount of

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precipitation and higher alkalinity, as well as lower concentrations of Ca, Mg, Na, NO3-, SO42,

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and Cl- and alkalinity than the plots in areas with lower precipitation and in the lowlands. In

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reference to NO3- and SO42-, the low contribution of dry deposition in high-mountain regions

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was attributed by the authors to a lower level of anthropopressure in areas located above 1000

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m. a.s.l. In Poland in 2010, in spite of low concentrations of pollutants, precipitation at

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BIR804, SZP701, and BIE801 showed the highest total deposition among the twelve intensive

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monitoring plots (according to the monitoring data for forests in Poland). The results of the

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FRAME model of deposition of S-SO4, N-NO3, and N-NH4 show that the mountain areas of

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southern Poland receive the highest loads of pollutants, mainly as a result of long-distance

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atmospheric transport, high precipitation, and the seeder-feeder effect (Kryza et al., 2013). As

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a result of similar factors, the mountain regions of Great Britain received higher acid

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deposition (sulfur and nitrogen compounds) than other areas (Kryza et al., 2012). In spite of

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high deposition, the mountain regions of Poland are at low risk of eutrophication and

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acidification caused by atmospheric pollution (Mill, 2006; Pecka and Mill, 2012). The

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sensitivity of ecosystems to these unfavorable phenomena depends – according to the theory

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of critical loads – on water flow in the soil, i.e., indirectly on the precipitation amount (ibid.).

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3.5.2. Throughfall

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Pine plot ZAW513 and two spruce plots SZP701 and BIE801 were separated in the winter-

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spring season according to both of the applied significance criteria of Sneath’s index (1/3

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Dmax and 2/3 Dmax) as a single group, the least similar to the remaining nine plots (Figure 5).

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Components of TF in the winter-spring season were divided into two main groups (Figure 5).

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The first group included precipitation amount, SO42-, NO3-, Cl-, NH4+, TN, DOC, and trace

312

metals. Apart from precipitation amount, DOC, NH4+, and Al, these components are not

313

significantly involved in canopy exchange processes. A number of correlations were recorded

314

between these components in the winter-spring season (e.g., Cl--SO42-, Cl--Al, Cl--Fe, Cl--Zn)

315

that were absent in the summer-autumn season. Deposition of those components usually

316

increases in winter as a result of an increase in emissions and stronger winds. The components

317

had considerably higher fluxes in TF of the winter-spring season at the coniferous plots in

318

southern Poland (ZAW513, SZP4701, and BIE801) than at the second group of plots (Table 11

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ACCEPTED MANUSCRIPT 6), which can be ascribed to at least two reasons. First, ZAW513 is located in Upper Silesia,

320

in a region with the highest population density and industrialization in the country. An

321

increase in deposition and concentrations of pollutants in precipitation is often observed in

322

forest areas in industrialized and urbanized regions (Balestrini et al., 2007), particularly in

323

winter (Hansen, 1996). High deposition in mountains (SZP701 and BIE801) was discussed

324

earlier in section 3.5.1. Second, total deposition of ions under coniferous species is usually

325

higher than under deciduous species growing in similar habitat conditions (Skeffington and

326

Hill, 2012) due to the higher filtering effectiveness of dry and gaseous deposition, particularly

327

of acidic ions (Jung et al., 2011; Skeffington and Hill, 2012).

328

The second group of components in the winter-spring season includes those for which the

329

concentration in TF is related to a higher degree to exchange processes in the canopy and/or

330

the biological contamination of samples, i.e., Mn, K, Mg, PO43-, and alkalinity. Fluxes of

331

those components were similar for both groups of plots, indicating low biological activity of

332

trees in the dormant season.

333

Two deciduous plots (beech GDA116 and oak KRO322) formed one group, eight plots (pine

334

(BIA212, STR206, CHO405, KRU312, and ZAW513), oak (LAC326), beech (BIR804), and

335

fertile spruce plot SUW203) entered second group, and the remaining two mountain spruce

336

plots (BIE801 and SZP701) were included in the third group in the summer-autumn season. In

337

spruce stands at BIE801 and SZP701, throughfall precipitation and fluxes of H+, SO42-, NO3-,

338

Na and Cl- were considerably higher than at the remaining locations (Table 6), similar to the

339

winter-spring season.

340

The analysis of similarities between components of precipitation in the summer-autumn

341

season indicates three main groups to which potential sources of origin can be ascribed. The

342

first group includes Na and Cl- of marine origin, trace metals, SO42- and nitrogen compounds

343

of anthropogenic origin. Al and DOC from leaching from the canopy belong to the second

344

group. The third group includes mainly those components that are involved in exchange

345

processes in the canopy and/or indicate biological contamination (Mg, K, PO43-, Mn and

346

alkalinity). Significant correlations were recorded within this group between DOC and Al

347

(Rs = 0.63, p ≤ 0.05) as well as between PO43- and alkalinity (Rs = 0.69, p ≤ 0.05).

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12

ACCEPTED MANUSCRIPT The composition of TF differed considerably between the groups of plots. Third group of

349

plots (BIE801 and SZP701) differed from the two remaining groups in terms of the

350

components included in the first group, i.e., components of marine and anthropogenic origin.

351

Both first and second group of plots had higher fluxes of the components exchangeable in

352

canopy (third group of the components) than the third group of plots. The processes of ion

353

exchange are intensive in the vegetative season, leading to an increase in deposition of cations

354

(K, Ca, Mg) both in deciduous and coniferous stands (Hansen, 1996; Piirainen et al., 2002;

355

Staelens et al., 2005; Adriaenssens et al., 2012a).

356

The composition of TF depended, especially in the summer-spring season, on the type of tree

357

stand, as suggested by differences between plots in fluxes of substances exchanged in the

358

canopy. Pine stands in summer and autumn developed a uniform (in terms of species

359

dominant in the tree stand) group of plots with a high similarity of components of TF. Pine,

360

beech, and oak plots were more similar to each other in terms of composition of TF than to

361

mountainous spruce plots. This effect, however, can be partly explained by the amount of

362

precipitation. The differences between the tree stands are manifested in, e.g., enrichment of

363

TF in components such as K, Mg, and Mn. A higher leaching of these ions from the canopy

364

was observed in pine and oak stands than in spruce and beech stands.

365

4. Conclusions

366

The fluxes of components in precipitation in the forest areas of Poland were usually typical of

367

European countries. Differences in the fluxes between plots located in southern Poland and

368

other plots representative of Polish conditions partly resulted from decreasing emissions

369

between 1990’s and 2010. The effect of anthropogenic pollutants was the most evident at sites

370

located in southern Poland, in Silesia and at two mountainous plots.

371

The analysis of differences and similarities between the intensive monitoring plots shows that

372

the type of tree stand considerably influences the deposition. At most of the studied plots, the

373

majority of components of precipitation had higher fluxes under the canopy than in open

374

fields. The impact of the tree stand on the composition of precipitation, however, depended on

375

the region of the country and on the dominant species in the tree stand. Coniferous species

376

(pine and spruce) caused acidification of TF, whereas deciduous species (oak and beech)

377

increased the pH of TF. Precipitation was enriched in substances from exchange in the canopy

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13

ACCEPTED MANUSCRIPT (e.g., K, Mn, and Mg) to a higher degree in pine and oak stands than in spruce and beech

379

stands.

380

The geographical location of the plots also influenced the composition of TF, as reflected,

381

e.g., in fluxes of ions originating from marine salts: Na+ and Cl- (impact of marine aerosols in

382

the vicinity of the sea on the composition of precipitation), precipitation amount (high

383

precipitation amounts in the mountains and the related high fluxes of substances in

384

precipitation), and degree of anthropopressure.

385

Acknowledgments

386

Installation of the 11 intensive monitoring plots and data collection on all 12 plots in 2010

387

were performed under the project LIFE 07 ENV/D/000218 “Further Development and

388

Implementation of an EU-level Forest Monitoring System (FutMon)” with the financial

389

contribution of the EU and the Polish National Fund for Environmental Protection and Water

390

Management. Data analysis was carried out within project No. 240801 with the financial

391

support of the Polish Ministry of Science and Higher Education. The authors express their

392

gratitude to the National Forest Service for granting access to the plots and help in organizing

393

field work. Thanks are due to all the people involved in the field and laboratory work for their

394

efforts in handling several thousand deposition samples. Special thanks to Robert Hildebrand

395

for providing a map for the manuscript.

396

References

397

Adamson, J.K., Hornung, M., Kennedy, V.H., Norris, D.A., Paterson, I.S., Stevens, P.A.,

398

1993. Soil solution chemistry and throughfall under adjacent stands of Japanese larch and

399

Sitka spruce at three contrasting locations in Britain. Forestry 66 (1), 51–68.

400

Adriaenssens, S., Hansen, K., Staelens, J., Wuyts, K., De Schrijver, A., Baeten, L., Boeckx,

401

P., et al., 2012a. Throughfall deposition and canopy exchange processes along a vertical

402

gradient within the canopy of beech (Fagus sylvatica L.) and Norway spruce (Picea abies (L.)

403

Karst). Sci. Total Environ. 420, 168–182.

AC C

EP

TE D

M AN U

SC

RI PT

378

14

ACCEPTED MANUSCRIPT Adriaenssens, S., Staelens, J., Wuyts, K., Samson, R., Verheyen, K., Boeckx, P., 2012b.

405

Retention of dissolved inorganic nitrogen by foliage and twigs of four temperate tree species.

406

Ecosystems, 15(7), 1093–1107.

407

Adriaenssens, S., Staelens, J., Wuyts, K., De Schrijver, A., Wittenberghe, S., Wuytack, T.,

408

Kardel, F., et al., 2011. Foliar nitrogen uptake from wet deposition and the relation with leaf

409

wettability and water storage capacity. Water Air Soil Pollut. 219 (1-4), 43–57.

410

Amezaga, I., Gonzalez Arias, A., Domingo, M., Echeandia, A., Onaindia, M. 1997.

411

Atmospheric deposition and canopy interactions for conifer and deciduous forests in northern

412

Spain. Water Air Soil Pollut. 97 (3-4), 303–313.

413

Arisci, S., Rogora, M., Marchetto, A., Dichiaro, F., 2012. The role of forest type in the

414

variability of DOC in atmospheric deposition at forest plots in Italy. Environ. Monit. Assess.

415

184, 3415–25.

416

Astel, A., Tsakovski, S., Barbieri, P., Simeonov, V. 2007. Comparison of self-organizing

417

maps classification approach with cluster and principal components analysis for large

418

environmental data sets. Water Res. 41, 4566-4578.

419

Balestrini, R., Arisci, S., Brizzio, M.C., Mosello, R., Rogora, M., Tagliaferri, A., 2007. Dry

420

deposition of particles and canopy exchange: Comparison of wet, bulk and throughfall

421

deposition at five forest sites in Italy. Atmos. Environ. 41 (4), 745–756.

422

Balestrini, R., Tagliaferri, A., 2001. Atmospheric deposition and canopy exchange processes

423

in alpine forest ecosystems (northern Italy). Atmos. Environ. 35 (36), 6421–6433.

424

Bäumler, R., Zech, W., 1997. Atmospheric deposition and impact of forest thinning on the

425

throughfall of mountain forest ecosystems in the Bavarian Alps. For. Ecol. Manag. 95 (3),

426

243–251.

427

Berger, T.W., Untersteiner, H., Schume, H., Jost, G., 2008. Throughfall fluxes in a secondary

428

spruce (Piceaabies), a beech (Fagus sylvatica) and a mixed spruce–beech stand. For. Ecol.

429

Manag. 255 (3-4), 605–618.

AC C

EP

TE D

M AN U

SC

RI PT

404

15

ACCEPTED MANUSCRIPT Clarke, N., Wu, Y., Strand, L.T., 2007. Dissolved organic carbon concentrations in four

431

Norway spruce stands of different ages. Plant Soil 299 (1-2), 275–285.

432

De Schrijver, A., Nachtergale, L., Staelens, J., Luyssaert, S., De Keersmaeker, L., 2004.

433

Comparison of throughfall and soil solution chemistry between a high-density Corsican pine

434

stand and a naturally regenerated silver birch stand. Environ. Pollut. 131 (1), 93–105.

435

Erisman, J.W., Möls, H., Fonteijn, P., Geusebroek, M., Draaijers, G.P.J., Bleeker, A., Van der

436

Veen, D., 2003. Field intercomparison of precipitation measurements performed within the

437

framework of the Pan European Intensive Monitoring Program of EU/ICP Forest. Environ.

438

Pollut. 125 (2), 139–155.

439

Gandois, L., Tipping, E., Dumat, C., Probst, A., 2010. Canopy influence on trace metal

440

atmospheric inputs on forest ecosystems: Speciation in throughfall. Atmos. Environ. 44 (6),

441

824–833.

442

Hansen, K., 1996. In-canopy throughfall measurements of ion fluxes in Norway spruce.

443

Atmos. Environ. 30 (23), 4065–4076.

444

Herrmann, M., Pust, J., Pott, R., 2006. The chemical composition of throughfall beneath oak,

445

birch and pine canopies in Northwest Germany. Plant Ecol. 184 (2), 273–285.

446

Hettelingh, J.-P., Posch, M., Slootweg, J., Le Gall, A.-C., 2012. Assessing Effects of the

447

Revised Gothenburg Protocol, pp. 13-20 [In:] Posch, M., Slootweg, J., Hettelingh, J.-P. [Eds.]

448

Modelling and Mapping of Atmospherically-induced Ecosystem Impacts in Europe. CCE

449

Status Report 2012.

450

Jung, K., Chang, S.X., Arshad, M.A.C., 2011. Effects of canopy-deposition interaction on H+

451

supply to soils in Pinus banksiana and Populus tremuloides ecosystems in the Athabasca oil

452

sands region in Alberta, Canada. Environ. Pollut. 159 (5), 1327–1333.

453

Kryza, M., Werner, M., Dore, A.J., Błaś, M., Sobik, M., 2012. The role of annual circulation

454

and precipitation on national scale deposition of atmospheric sulphur and nitrogen

455

compounds. J. Environ. Manag. 109, 70–79.

AC C

EP

TE D

M AN U

SC

RI PT

430

16

ACCEPTED MANUSCRIPT Kryza, M., Mill, W., Dore, A.J., Werner, M., Błaś, M., 2013. Calculation of sulphur and nitrogen

457

deposition with the Frame model and assessment of the exceedance of critical loads in Poland. Ecol.

458

Chem. Eng. S, 20 (2), 279–290.

459

Lochman, V., Bíba, M., Fadrhonsová, V., 2002. Air pollution load of forest stands in Vojiřov

460

and the impact on soil and run-off water chemistry. J. For. Sci. 48 (7), 292-309.

461

Lorenz, H. (Ed.), 2005.Atlas Klimatu Polski. IMGW, Warszawa (in polish)

462

Małek, S., Astel, A., 2008. Throughfall chemistry in a spruce chronosequence in southern

463

Poland. Environ. Pollut. 155, 517–527.

464

Mill, W., 2006. Temporal and spatial development of critical loads exceedance of acidity to

465

Polish forest ecosystems in view of economic transformations and national environmental

466

policy. Environ. Sci. Policy 9 (6), 563–567

467

Mosello, R., Amoriello, M., Amoriello, T., Arisci, S., Carcano, A., Clarke, N., Derome, J., et

468

al., 2005. Validation of chemical analyses of atmospheric deposition in forested European

469

sites. J. Limnol. 64 (2), 93–102.

470

Mosello, R., Brizzio, M.C., Kotzias, D., Marchetto, A., Rembges, D., Tartari, G., 2002. The

471

chemistry of atmospheric deposition in Italy in the framework of the National Programme for

472

Forest Ecosystems Control (CONECOFOR). J. Limnol. 61 (Suppl. 1), 77–92.

473

Moffat, A.J., Kvaalen, H., Solberg, S., Clarke, N., 2002. Temporal trends in throughfall and

474

soil water chemistry at three Norwegian forests, 1986–1997. For. Ecol. Manag. 168 (1-3), 15–

475

28.

476

Oulehle, F., Hruška, J., 2005. Tree species (Picea abies and Fagus sylvatica) effects on soil

477

water acidification and aluminium chemistry at sites subjected to long-term acidification in

478

the Ore Mts., Czech Republic. J. Inorg. Biochem. 99 (9), 1822–1829.

479

Pecka, T., Mill, W., 2012. Modelling of atmospheric nitrogen deposition effects to Polish

480

terrestrial ecosystems for various emission scenarios. Environ. Prot. Eng. 38 (3), 133-143

AC C

EP

TE D

M AN U

SC

RI PT

456

17

ACCEPTED MANUSCRIPT Piirainen, S., Finér, L., Starr, M., 2002. Deposition and leaching of sulphate and base cations

482

in a mixed boreal forest in eastern Finland. Water, Air, Soil Pollut. 131 (1-4), 185–204.

483

Polkowska, Ż., Astel, A., Walna, B., Małek, S., Mędrzycka, K., Górecki, T., Siepak, J., et al.,

484

2005. Chemometric analysis of rainwater and throughfall at several sites in Poland. Atmos.

485

Environ. 39 (5), 837–855.

486

Skeffington, R.A., Hill, T.J., 2012. The effects of a changing pollution climate on throughfall

487

deposition and cycling in a forested area in southern England. Sci. Total Environ. 434, 28–38.

488

Skřivan, P., Rusek, J., Fottová, D., Burian, M., Minařik, L., 1995. Factors affecting the

489

contenst of heavy metals in bulk atmospheric precipitation, throughfall and stemflow in

490

central Bohemia, Czech Republik. Water, Air, Soil Pollut. 85 (2), 841–846.

491

Stachurski, A., Zimka, J.R., 2002. Atmospheric deposition and ionic interactions within a

492

beech canopy in the Karkonosze Mountains. Environ. Pollut. 118 (1), 75–87.

493

Staelens, J., De Schrijver, A., Van Avermaet, P., Genouw, G., Verhoest, N.E.C., 2005. A

494

comparison of bulk and wet-only deposition at two adjacent sites in Melle (Belgium). Atmos.

495

Environ. 39 (1), 7–15.

496

Starr, M., Ukonmaanaho, L., 2004. Levels and characteristics of TOC in throughfall, forest

497

floor leachate and soil solution in undisturbed boreal forest ecosystems. Water, Air, Soil

498

Pollut: Focus 4 (2-3), 715–729.

499

StatSoft, Inc., 2011. STATISTICA (data analysis software system), version 10.

500

www.statsoft.com.

501

Terauda, E., Nikodemus, O., 2007. Sulphate and nitrate in precipitation and soil water in Pine

502

forests in Latvia. Water, Air, Soil Pollut: Focus 7 (1-3), 77–84.

503

Van Stan II, J.T., Levia, D. F., Inamdar, S.P., Lepori-Bui, M., Mitchell, M.J., 2012. The

504

effects of phenoseason and storm characteristics on throughfall solute washoff and leaching

505

dynamics from a temperate deciduous forest canopy. Sci. Total Environ. 430, 48–58.

AC C

EP

TE D

M AN U

SC

RI PT

481

18

ACCEPTED MANUSCRIPT Walna, B., Polkowska, Ż., Małek, S., Mędrzycka, K., Namieśnik, J., Siepak., J., 2003.

507

Tendencies of change in the chemistry of precipitation at three monitoring stations 1996-

508

1999. Pol. J. Environ. Stud. 12 (4), 467-472.

509

Ward, J.H. Jr., 1963. Hierarchical grouping to optimize an objective function. J. Am. Stat.

510

Assoc. 58, 236-244.

511

Wuyts, K., Verheyen, K., De Schrijver, A., Cornelis, W.M., Gabriels, D., 2008. The impact of

512

forest edge structure on longitudinal patterns of deposition, wind speed, and turbulence.

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Atmos. Environ. 42 (37), 8651–8660.

AC C

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ACCEPTED MANUSCRIPT Table 1. Description of research plots, stand volume in 2009, * in 2005.

Gdańsk GDA116

180

Stand No of % of Volume Forest type age in trees trees of [m3 ha-1] 2010 per ha domina [years] nt tree species European beech 94 561 76 590 Galio odorati-Fagetum

Suwałki UW203 Strzałowo STR206 BiałowieżaBIA212 Krucz KRU312

240 145 140 64

Norway spruce Scots pine Scots pine Scots pine

70 63 78 73

421 773 758 1241

90 79 57 100

428 505 563 332

Krotoszyn KRO322 Łąck LAC326 Chojnów CHO405 Zawadzkie ZAW513 Szklarska Poręba SZP701 Bielsko BIE801

166

Sessile oak

87

576

79

385

Endogleyic Dystric Arenosol Tilio-Carpinetum Haplic Cambisol Tilio-Carpinetum Haplic Lixisol Calamagrostio-Piceetum Epidystric Arenosol Leucobryo-Pinetum Thapto Arenosolic Epidystric Arenosol Galio-Carpinetum Acric Eutric Stagnosol

108 108 230

Sessile oak Scots pine Scots pine

100 72 63

431 1164 814

97 75 100

381 285 406

Tilio-Carpinetum Epidystric Arenosol Querco roboris-Pinetum Dystric Arenosol Querco roboris-Pinetum Dystric Arenosol

1000 Norway spruce 75

457

100

267

958

Norway spruce 68

451

Bircza BIR804

450

European beech 102

467

Calamagrostio villosae- Skeletic Cambic Umbrisol Piceetum Abieti–Piceetum Endogleyic Hyperdystric Regosol Dentario glandulosaeClayic Luvisol Fagetum

EP AC C

SC

M AN U 464*

70

385

TE D

91

Soil type

RI PT

Site name and code Elev Dominant tree ation species a.s.l. [m]

ACCEPTED MANUSCRIPT Table 2. Location of the study plots with specification of climatic factors and potential sources of pollutants in precipitation. Annual precipitation, mean annual temperature and prevailing wind directions are given according to climate data from the years 1970-2000 (Lorenz, 2005). Potential Sources of Pollutants

forest complex 10 km WNW of a large urban agglomeration (Gdańsk-Gdynia-Sopot)

urban agglomeration, road transport, refining, shipbuilding, and fish processing industries

SUW203 500-600 mm / 6.5-7.5C / W

agricultural and forest areas, 20 km NNW of a medium-sized city (Suwałki)

no substantial sources of industrial pollution, low level of pollution

STR206

600-700 mm / 6.5-7.5C / SW

forest areas approx. 20-30 km from the largest tourist towns

roads with medium traffic, agriculture, no local sources

BIA212

500-600 mm / 6.5-7.5C / W

forest areas 10 km from a small town (Hajnówka)

no local sources except for households

KRU312

500-600 mm / 7.5-8.5C / W

forest areas 50 km NW of a large city (Poznań), minimum distance from national roads, 30 km

agriculture, no local sources

KRO322

500-600 mm / 7.5-8.5C / W

1.2 km into a dense forest complex surrounded by agricultural areas, 11 km NE of a medium-sized city (Krotoszyn)

agriculture

LAC326

500-600 mm / 7.5-8.5C / W

approx. 700 m into a forest complex, surrounded by agricultural areas; 6 km from a medium-sized city (Płock)

CHO405

500-600 mm / 7.5-8.5C / W

380 m into a forest complex, 25 km from the center of a large urban agglomeration (Warsaw)

SC

RI PT

Location

GDA116

Precipitation / temperature / wind direction 600-700 mm / 7.5-8.5C / W

refining and chemical industry, road transport, agriculture urban agglomeration, road and railway transport, large waste dump approx. 3 km away, industrial plants

M AN U

Code of Plot

forest complex surrounded by urban agglomerations and industrial areas at a distance of 30 km (Katowice, Opole)

extractive industry, mining, heavy industry, road transport

SZP701

> 800 mm / 6.57.5C / W

mountain forest areas in the Sudety Mountains, neighboring industrial areas in the Czech Republic; 35 km E of a brown coal mine and fossil-fuel power station

cross-border pollutants, mining, energy industry, road transport

BIE801

> 800 mm / 6.57.5C/W

mountain forest areas in the Beskid Śląski, 12-15 km from medium-sized tourist centers an industrial city

machine and automobile industry, heat and power plants, road transport, household

BIR804

> 700 mm / 6.57.5C/S

dense forest complex in low mountains, areas with the highest forest cover in Poland, low population density

household furnaces

AC C

EP

TE D

ZAW513 600-700 mm / 6.5-7.5C / W

ACCEPTED MANUSCRIPT Table 3. Median of monthly precipitation amount (water), alkalinity (Alk) and components in open field precipitation (BP) and throughfall (TF). Monthly sum of precipitation in mm, concentration in µeq dm-3, DOC in mg dm-3. Median absolute deviation given in parentheses. Pine

Spruce

Beech

Oak

BIA212, STR206, KRU312, CHO405, ZAW513

SUW203, SZP701, BIE801

GDA116, BIR804

KRO322, LAC326

83 4.9 13 23 4.8 8.0 5.2 43 38 36 9.5 0.97 1.0 0.48 0.12 0.31 1.0 2.0 2.1 120

BP (49) (0.50) (11) (10) (2.7) (5.3) (0.0) (18) (14) (14) (5.4) (0.0) (0.0) (0.17) (0.07) (0.15) (0.24) (2.0) (0.96) (46)

72 4.8 118 37 11 12 27 55 50 45 17 0.97 1.0 0.75 0.79 0.14 1.2 0.0 5.0 131

TF (41) (0.32) (16) (17) (5.8) (4.9) (13) (23) (21) (15) (6.7) (0.0) (0.0) (0.18) (0.5) (0.0) (0.32) (0.0) (2.6) (46)

EP

76 5.2 7.3 24 5.8 9.5 5.2 44 40 34 13 2.2 1.0 0.51 0.29 0.14 1.0 4.0 2.0 118

BP (41) (0.6) (6.7) (8.2) (2.3) (6.9) (0.0) (21) (15) (15) (6.6) (1.3) (0.0) (0.33) (0.17) (0.0) (0.27) (4.0) (0.55) (31)

49 5.9 1.2 42 11 11 32 36 47 41 19 3.8 1.0 0.54 2.0 0.30 1.1 27 4.1 106

TF (25) (0.59) (0.94) (9.0) (4.1) (7.9) (15) (20) (16) (17) (12) (2.8) (0.0) (0.21) (1.3) (0.17) (0.31) (27) (1.4) (24)

59 5.1 7.8 30 5.5 8.4 5.2 56 41 38 14 0.97 1.0 0.45 0.25 0.32 1.0 0.0 3.0 120

BP (34) (0.58) (7.0) (6.9) (1.3) (5.8) (0) (22) (13) (11) (8.5) (0.0) (0.0) (0.23) (0.14) (0.15) (0.3) (0.0) (1.3) (40)

48 6.1 0.80 48 25 11 65 85 64 40 20 19 2.3 0.91 4.2 0.34 1.1 49 8.7 202

TF (26) (0.41) (0.52) (12) (7.3) (3.9) (38) (49) (18) (14) (8.5) (16) (1.3) (0.28) (2.7) (0.2) (0.35) (49) (2.7) (90)

RI PT

(27) (0.53) (4.7) (17) (8.6) (4.8) (24) (39) (27) (21) (12) (4.4) (1.4) (0.23) (1.9) (0.15) (0.31) (22) (4.4) (57)

TE D

48 5.3 5.4 53 23 15 56 59 58 34 25 5.4 3.8 0.86 3.5 0.37 1.4 22 13 129

SC

TF

(33) (0.71) (1.7) (11) (2.5) (4.7) (0.0) (23) (13) (12) (6.6) (0.0) (0.0) (0.24) (0.09) (0.15) (0.38) (25) (1.1) (57)

AC C

59 5.7 1.9 33 6.7 7.4 5.2 52 40 33 11 0.97 1.0 0.45 0.17 0.29 1.3 25 2.8 123

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BP water pH H+ Ca Mg Na K NH4+ SO42NO3ClPO43Al Fe Mn Cu Zn Alk DOC TN

ACCEPTED MANUSCRIPT Table 4. Mean annual precipitation amount (water, in mm) and fluxes of alkalinity (Alk) and components in open field (BP) and throughfall (TF). Mean annual flux in meq m-2, for DOC in g m-2. P-values from Wilcoxon signed rank test of paired samples for monthly values in BP and TF. Pine

Spruce

Beech

Oak

BIA212, STR206, KRU312, CHO405, ZAW513

SUW203, SZP701, BIE801

GDA116, BIR804

KRO322, LAC326

EP AC C

TF

1112 13 27 5.8 11 6.8 54 42 34 14 3.7 1.4 0.5 0.3 0.3 1.1 16 2.3 130

814 6.6 32 10 10 49 42 35 29 16 15 1.1 0.5 2.3 0.2 1.0 45 3.2 98

p-value, n = 24 0.000*** 0.003** 0.015* 0.000*** 0.162 0.000*** 0.009** 0.003** 0.007** 0.407 0.110 0.001*** 0.361 0.000*** 0.034* 0.440 0.004** 0.010* 0.000***

BP

TF

784 8.7 21 4.4 6.0 4.7 47 34 28 9.2 3.2 1.0 0.4 0.4 0.2 0.9 12 2.0 103

679 3.7 31 16 7.3 54 71 42 25 13 23 1.2 0.6 3.2 0.2 0.7 62 6.5 126

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BP

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p-value, n = 36 1226 0.185 24 0.232 42 0.003** 13 0.000*** 15 0.177 34 0.000*** 58 0.888 67 0.006** 50 0.003** 23 0.000*** 3.5 0.954 2.4 0.310 0.9 0.106 1.5 0.000*** 0.3 0.044* 1.4 0.802 16 0.741 5.7 0.000*** 147 0.593 TF

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p-value, BP n = 59 671 water 855 0.000*** 1304 + 6.7 6.5 H 0.187 19 28 36 Ca 0.001*** 34 6.5 14 Mg 0.000*** 6.6 6.5 9.4 Na 0.000*** 11 9.5 42 K 0.000*** 7.2 49 NH4+ 86 0.546 56 232 42 SO4 0.006** 48 23 28 NO3 0.141 39 9.1 17 Cl0.000*** 13 315 6.1 PO4 0.369 4.1 1.0 2.5 Al 0.000*** 1.8 0.4 0.5 Fe 0.007** 0.7 0.1 2.4 Mn 0.000*** 0.2 0.2 0.2 Cu 0.030* 0.4 1.0 0.9 Zn 0.315 1.4 62 30 Alk. 0.789 19 2.5 8.7 DOC 0.000*** 3.1 189 104 TN 0.394 152 *** p ≤ 0.001. ** p ≤ 0.01. * p ≤ 0.05. BP

p-value, n = 34 0.001*** 0.000*** 0.002** 0.000*** 0.110 0.000*** 0.230 0.002** 0.019* 0.001*** 0.001*** 0.290 0.014* 0.000*** 0.092 0.007** 0.018* 0.000*** 0.278

ACCEPTED MANUSCRIPT Table 5. Between plot comparison of median for fluxes in bulk precipitation (BP) and throughfall (TF) (Kruskal-Wallis ANOVA and median test for all samples, 12 months, TF n = 144, BP n = 143, p ≤ 0.05). Only components in BP (upper right part of the table) and in TF (bottom left part of the table) that were significantly different (p ≤ 0.05) between the plots are presented. Na sodium, Cl – chlorides, Mn – manganese, H – protons, NO3 – nitrates, SO4 – sulfates, Fe – iron, Al – aluminum, Alk – alkalinity, PO4 – phosphates, TN – total nitrogen. GDA116

SUW203 STR206

BIA212

KRU312

KRO322

LAC326

CHO405

ZAW513

SZP701

BIE801

BIR804

Bulk Precipitation -

Na, Cl

Na, Cl, Mn

H

-

BIA212

-

NH4

H

H, Na, SO4, NO3, Cl

PO4

PO4

-

Na

-

M AN U

Throughfall

-

CHO405

H

SO4, NO3, Cl

ZAW513

SO4, Al

SO4

SZP701

H, SO4, NO3, Al, Alk

H, SO4, Al

H, SO4, H, SO4, SO4, NO3, Fe, NO3, TN, NO3, Fe Alk Alk

BIE801

Mn

H, Mn

NO3

BIR804

Na

Cl, Al

H, NO3, Alk

H, NO3, Zn

H

H, Mn

AC C

EP

TE D

H, NO3, Mn

Al

H, SO4, NO3, Cl, Fe, Alk

SO4, NO3

H

Fe H

-

SO4, Cl

H

Na, NO3, H, Cl, Al Cl

Cl

KRU312

LAC326

Na

-

STR206

KRO322

Na

SC

SUW203

Na, Cl, Mn

RI PT

GDA116

H -

ACCEPTED MANUSCRIPT Table 6. Mean monthly water amount (mm) and fluxes (meq m-2, DOC in g m-2) in groups of plots.

86 0.53 2.7 0.49 0.38 0.55 3.7 2.6 2.0 0.55 0.38 0.10 0.03 0.01 0.02 0.09 2.3 0.20 8.2

91 0.46 1.6 0.55 0.58 1.7 17 3.6 2.6 1.0 3.9 0.09 0.03 0.02 0.01 0.10 13 0.24 28

147 2.0 2.5 0.47 0.79 0.77 5.5 4.5 3.5 0.92 0.41 0.19 0.08 0.02 0.03 0.17 1.6 0.20 13

49 0.69 2.3 0.93 0.73 2.1 3.7 3.3 2.5 1.1 0.43 0.13 0.03 0.19 0.02 0.06 1.7 0.36 8.31

93 3.0 3.7 1.0 1.2 2.1 6.2 7.8 5.0 2.2 0.16 0.34 0.07 0.10 0.03 0.12 0.15 0.52 16

69 0.06 3.1 1.5 1.0 7.5 7.2 2.9 1.9 1.7 3.7 0.08 0.05 0.23 0.01 0.10 9.1 0.58 12

SC

92 0.43 2.3 0.65 0.95 0.56 4.2 2.8 2.2 1.2 0.39 0.10 0.04 0.05 0.02 0.10 1.9 0.19 8.9

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47 0.42 2.0 1.2 1.4 2.4 25 4.6 2.4 1.7 5.7 0.06 0.03 0.02 0.03 0.07 21 0.30 66

TE D

53 0.54 2.3 0.45 0.58 0.41 4.2 2.5 2.0 0.73 0.42 0.08 0.03 0.01 0.02 0.06 2.3 0.18 9.1

EP

95 1.9 2.0 0.42 1.0 0.50 4.6 4.1 3.5 1.4 0.22 0.13 0.05 0.02 0.04 0.09 0.31 0.27 14

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water H+ Ca Mg Na K NH4+ SO42NO3ClPO43Al. Fe Mn Cu Zn Alk DOC TN

RI PT

Bulk precipitation Throughfall Winter-spring Summe-autumnr Winter-spring Summe-autumnr Group 1 Group 2 Group 3 gr1, n=2 gr2,n=7 gr3,n=1 gr4,n=2 gr1,n=9 gr2,n=3 gr1,n=2 gr2,n=8 gr3,n=2 GDA116 SUW203 KRU312 GDA116 SUW203 KRU312 SZP701 GDA116 ZAW513 GDA116 SUW203 SZP701 ZAW513 STR206 LAC326 STR206 BIE801 SUW203 SZP701 KRO322 STR206 BIE801 SZP701 BIA212 BIA212 STR206 BIE801 BIA212 BIE801 KRO322 KRO322 BIA212 KRU312 BIR804 LAC326 CHO405 KRU312 LAC326 CHO405 ZAW513 KRO322 CHO405 BIR804 LAC326 ZAW513 CHO405 BIR804 BIR804

64 0.24 3.3 1.3 0.67 4.7 3.7 2.7 2.0 1.2 0.87 0.17 0.05 0.25 0.01 0.08 4.1 0.76 7.63

148 1.8 4.0 1.0 1.8 4.1 5.9 6.5 4.6 2.7 0.37 0.22 0.10 0.06 0.03 0.17 0.85 0.64 14

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Figure 1. Forest plots of the intensive forest monitoring network in Poland.

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Figure 2. Throughfall enrichment as a ratio of median monthly fluxes of components in TF to BP.

25

5

20

4

15

3

10

2

5

1

0

0 PO43-

Mg DOC Al

spruce

Ca

beech

Fe Na SO42- NO3- NH4+ TN

oak

EP

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pine

Cl-

Zn

Cu

SC

K

AC C

Mn

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H+ water

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Figure 3. Range (whiskers), median values (short horizontal lines) and individual values of annual fluxes of compounds in bulk precipitation (hollow symbols) and throughfall (filled symbols). Ps = Pinus sylvestris stands, Pa = Picea abies stands, Fs = Fagus sylvatica stands, Qsp = oak species stands. Circles stand for concentrations in European countries (Ps Herrmann et al., 2006; Terauda and Nikodemus, 2007; Pa - Adamson et al., 1993; Bäumler and Zech; 1997; Balestrini and Tagliaferri, 2001; Lochman et al., 2002; Moffat et al., 2002; Mosello et al., 2002; Piirainen et al., 2002; Oulehle and Hruška, 2005; Balestrini et al., 2007; Clarke et al., 2007; Berger et al., 2008; Gandois et al., 2010; Fs – Skřivan et al., 1995; Mosello et al., 2002; Oulehle and Hruška, 2005; Balestrini et al., 2007; Berger et al., 2008; Gandois et al., 2010; Qsp - Amezaga et al., 1997; Mosello et al., 2002; Herrmann et al., 2006). Triangles stand for concentrations in Poland (Pa - Polkowska et al., 2005; Małek and Astel, 2008; Fs and Qsp - Polkowska et al., 2005). Values, if necessary, are calculated by multiplying precipitation amount and concentrations and converted into meq m-2 year-1.

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Figure 4. Groups of similarities between plots (upper part) and components of bulk precipitation (bottom) in winter-spring (left) and summer-autumn (right) season. Grouping by Ward’s method with squared Euclidean distance for grouping of plots and 1-r Pearson distance for BP components. Dashed line indicates groups resulting from the Sneath’s 1/3 Dmax criterion and dotted line indicates groups resulting from the Sneath’s 2/3 Dmax criterion (Astel et al., 2007).

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Figure 5. Groups of similarities between plots (upper part) and components of throughfall (bottom) in the winter-spring (left) and summer-autumn (right) seasons. Other details are the same as in Figure 4.

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