Beskydy, 2011, 4 (2): 133146

Mendelova univerzita vBrn

ISSN: 1803-2451

Application of Mann-Kendall test and the Sens slope estimates for

trend detection in deposition data from Bl K (Beskydy Mts., the
Czech Republic) 19972010

K. Drpela , I. Drpelov

Doc.Ing.Karel Drpela, CSc., Institute of Forest Management, Faculty of Forestry and Wood Technology
(FFWT), Mendel University in Brno, Zemdlsk 3, 61300 Brno, Czech Republic. Tel.: + 420545134141,
e-mail: drapela@mendelu.cz
RNDr.Ida Drpelov, Institute of Forest Ecology, Faculty of Forestry and Wood Technology (FFWT), Mendel
University in Brno, Zemdlsk 3, 61300 Brno, Czech Republic, Tel.: + 420545134186, e-mail: idad@men-
delu.cz

Abstract: Drpela, K., Drpelov, I., 2011: Application of Mann-Kendall test and the Sens slope
estimates for trend detection in deposition data from Bl K (Beskydy Mts., the
Czech Republic) 19972010. Beskydy, 4 (2): 133146

Data from precipitation monitoring station located at Bl K in Beskydy Mts. were

analyzed in order to find out whether and how the decrease of emissions in the Czech
Republic and neighbouring countries is reflected in the composition of precipitation.
Statistically significant decrease of mean annual concentrations of Zn, Pb, Cd, Ni, Fe
in bulk precipitation and of H+, K+, Mg2+, Ca 2+, NO3-, SO42-, Cl- and conductivity in wet
only precipitation were found by applying Mann-Kendall test. No trend was found for
Na+, Mn, F- and for total wet deposition of potential acid. The decrease in deposition of
acidifying substances is accompanied by simultaneous decrease of Ca 2+ and Mg2+ what
can hinder the recovery from acidification. Cluster analysis has indicated the influence
of the sea spray at this upcountry site and the common source of Pb, SO42-, Cd.

Keywords: atmospheric deposition, pollution trends, Moravian-Silesian Beskydy Mts., trend

analysis, Mann-Kendall test, Sens slope estimates

Introduction forest decline in the region adjacent to the in-

Moravian-Silesian Beskydy Mts. is amoun-
tain range occupying the north-east part of the
Czech Republic along the border with the Slo-
vak Republic. This part of the West Carpathians
has been under the influence of air pollutants
coming from Ostrava (the Czech Republic),
Katowice, and Bielsko-Biala (Poland) industrial
regions for many years. The region situated
around the intersection point of Czech, Polish
and Slovakian borders can be called the Black
Triangle II analogically to the highly polluted
area known as Black Triangle Isituated around
the point where Germany, Poland and the Czech
Republic meet (Markert et al. 1996). The indus-
trial immission load was continuously increas-
ing until the end of 1980s in the region. The
dustrial centre of Ostrava emerged in the 1970s
(Kus, 1989) and in the 1990s the damaged area
grew broader (rmek et al. 2008). Long-term
impact of acidic deposition causes acidification
of surface waters and soils (Falkengren-Grerup
et al. 1987, Rodhe et al. 1995) alters the cycling
of important biogenic elements such as S, N, H,
Ca, Mg (Driscoll et al. 2001) and influences also
the state of toxic or potentially toxic elements as
heavy metals and Al. High load of nitrogen com-
pounds may bring about the changes in biodi-
versity and cause eutrophication of ecosystems.
Gases and dust particles released to the atmos-
phere from industrial combustion processes or
from motor vehicles contain also heavy metal
compounds which undergo complex chemical

133
134 K. Drpela , I. Drpelov

reactions in the atmosphere and fall to the
earth as wet or dry deposition. The chemicals
can be transported long distances from their
sources influencing ecosystems far away from
the sources. After deposition, heavy metals can
be accumulated in the environmental compart-
ments and in tissues of living organisms (Sein-
feld, Pandis 1998).
Within the last two decades adistinct decrease
in emissions in the Czech Republic, Slovakia
and Poland has been achieved (see Tab. 1) due to:
improvement of heat and power production
technology,
implementation of measures aimed at redu-
cing sulphur emissions from power stations
that use brown coal,
increased use of low-sulphur fuels in private
households,
emission control at national and European
level.
The decrease in emission should be reflected
in the improvement of air and precipitation
quality in formerly highly polluted Beskydy
region. Air pollution and precipitation qual-
ity monitoring in the Czech Republic is carried
out by the Czech Hydrometeorological Institute
(CHMI). At the beginning, i.e. in the 1960s, the
monitoring was focused on sulphur dioxide and
aerosol particles. Later, when causes of forest
dieback were investigated (since 1980), the at-
tention started to be aimed to monitoring other
acidifying substances and also ground ozone
levels which are believed to bring about tree
damages by synergic action (De Vries et al., 2000,
Thomson, Nelleman, 1994, Klap et al. 2000).
The network of monitoring stations is rela-
tively dense today and some of the stations are
included in international air quality monitoring
networks such as EUROAIRNET, IRIS, AMS-
SRS, EMEP or GAW: air quality monitoring
was performed at more than 200 localities and
precipitation sampling at about 48 localities
throughout the Czech Republic in 2009 (CHMI
2010a). One of these stations is situated at Bl
K in Moravian Silesian Beskydy Mts..
The aim of this study is to reveal the informa-
tion stored in the published datasets of annual
concentrations of various substances in precipi-
tation at Bl K station by means of statistical
methods and evaluate the trends in inputs of
acidifying and other air polluting substances.

Tab. 1: C
 ontribution of the Czech Republic, Slovakia and Poland to the emissions of sulfur and nitrogen oxides, ammonia
and primary particulate matter with particles smaller than 10mm (further PM 10) in chosen years during 19902007.
Data were taken from EEA 2009.

Emissions in Gt Decrease in %
SO x in 1990 SO x in 1995 SO x in 2000 SO x in 2007 19952007
Czech Republic 1876 1095 264 217 80
Slovakia 526 246 127 14 94
Poland 3210 2376 1202 1131 52
NO x in 1990 NO x in 1995 NO x in 2000 NO x in 2007 19952007
Czech Republic 742 430 397 284 34
Slovakia 222 178 109 45 75
Poland 1280 1120 838 885 21
NH4 in 1990 NH4 in 1995 NH4 in 2000 NH4 in 2007 19952007
Czech Republic 156 86 74 60 30
Slovakia 65 40 30 32 20
Poland 512 380 322 292 23
PM10 in 1990 PM10 in 1995 PM10 in 2000 PM10 in 2007 20002007
Czech Republic NA NA NA 35 NA
Slovakia NA NA 40 34 15
Poland NA NA 281 269 4
NA: data not available
 Application of Mann-Kendall test and the Sens slope estimates for trend detection
in deposition data from Bl K (Beskydy Mts., the Czech Republic) 19972010
Material and Methods
The monitoring station is situated in the top
part of the Moravian-Silesian Beskydy Mts. in
the Czech Republic at an altitude of 890m. The
geographical coordinates of the site are 49 30
9,396 N latitude and 18 32 18,816 E longitude
(see Fig. 1). The open area with the station is
surrounded by young spruce forests. The rep-
resentativeness of the station is regional within
the range of tens to hundred kilometres (CHMI
2010b). The station is apart of Automatic Imis-
sion Monitoring network and is included in
international EUROAIRNET and IRIS imission
monitoring networks. The site is also included
in precipitation quality monitoring network and
is equipped with an automatic wet-only sampler
and abulk precipitation sampler. Water was an-
alysed weekly. Conductivity, pH, Na+, K+, NH4+,
Mg2+, Ca2+, NO3- , Cl- and SO42- concentrations
were determined in wet-only precipitation sam-
ples. Mn, Zn, Pb, Cd, Ni and Fe were determined
in bulk precipitation samples. Mean annual val-
ues of all variables were taken from CHMI web
site (CHMI 2010a). Details of sampling proce-
dures and the list of all monitored variables with
analytical methods used for their determination
can be found at CHMI web site (CHMI 2010c).
Fig.1: Location of the monitoring station at Bl K in the Moravian-Silesian Beskydy Mts.
Part of the deposition of Na+, K+, Mg2+, Ca2+,
Cl- and SO42- originates in the sea spray (see e.g.
Draaijers et al. 1997a, Draaijers et al. 1997b). To
estimate what fraction of this ions is of non-sea-
salt origin, correction factors have been derived
based on the composition of seawater (Pilson
135
1998). It is assumed that Na+ originates from sea
spray and that the ratio between the concentra-
tion in sea spray for the component to be cor-
rected and Na+ is the same as in bulk seawater.
The corrected concentration of component X
(corX) can subsequently be calculated as:
X = Xf X Na+ (1)
cor
where X is the uncorrected concentration of
the component X,
f X is the correction factor for the compo-
nent X,
Na+ is the concentration of Na.
Total wet deposition of potential acid TWDpa
was calculated according to Draaijers et al. (1998)
using equation (2)
[TWDpa] = 2[corSO4] +[NO3] +[NH4]
2[corMg] 2[corCa] [corK]  (2)
where data in square brackets quote depositions in
mol ha-1 yr-1 calculated from mean annual concentra-
tions of individual ions and precipitation totals in cor-
responding year. Prefix cor denotes that for this ion
non-sea salt concentration was used.
The series of annual values of electrical
conductivities, pH, ion concentrations (both
original and sea-salt corrected) and of calculated
variable TWDpa were analysed for monoto-
nous increasing or decreasing trends with the
non-parametric Mann-Kendall test and Sens
136 K. Drpela , I. Drpelov

method for slope estimates (Salmi et al. 2002). E(S) = 0(5)

Both methods were used in their basic forms:
the Mann-Kendall test is suitable for cases with
monotonous trends and no seasonal or other 1
VAR ( S ) = n ( n 1) ( 2n + 5 )
cycles in the data. One advantage of this test is 18
that the data need not conform to any particu-
p =1 t p ( t p 1) ( 2t p + 5 )
q
lar distribution. The second advantage of the
test is its low sensitivity to abrupt breaks due to
inhomogeneous time series (Tabari et al. 2011).
Sens method uses alinear model to estimate the (6)
slope of the trend and the variance of the residu- where q is the number of tied groups
als should be constant in time (Salmi et al. 2002). tp is the number of data values in the pth group.
Mann-Kendall test (M-K) The standard test statistic Zis computed as
By M-K test, we want to test the null hypoth- follows
esis H0 of no trend, i.e. the observations xi are
randomly ordered in time, against the alterna- S 1
tive hypothesis, H1, where there is an increasing if S >0
or decreasing monotonic trend. The data values VAR ( S )
are evaluated as an ordered time series. Each
data value is compared with all subsequent data
Z = 0 if S =0
values. If adata value from alater time period S +1
is higher than adata value from an earlier time if S <0
period, the statistic Sis incremented by 1. On VAR ( S )
(7)
the other hand, if the data value from alater time
period is lower than adata value sampled ear- The presence of astatistically significant trend
lier, Sis decremented by 1. The net result of all is evaluated using the Zvalue. Apositive (nega-
such increments and decrements yields the final tive) value of Zindicates an upward (downward)
value of S (Shahid 2011). The M-K test statistic trend. To test for either an upward or downward
Sis calculated using the formula: monotone trend (atwo-tailed test) at level of
significance, H0 is rejected if the |Z| > Z1-/2, where
S = k =1
n 1 n Z1-/2 is obtained from the standard normal cu-
j = k +1
sgn ( x j xk ) (3)
mulative distribution tables.
Sens slope estimator
+1 if If alinear trend is present in atime series, then
x j xk > 0
the true slope (change per unit time) can be esti-
sgn ( x j xk ) = 0 if x j xk = 0 mated by using asimple nonparametric proce-
1 if x j xk > 0
dure developed by Sen (1968). This means that
(4) linear model f (t) can be described as

where xj and xk are the annual values in years j f ( t ) = Qt + B

 (8)
and k, j > k, respectively.
If n < 10, the value of |S| is compared directly where Q is the slope
to the theoretical distribution of Sderived by B is aconstant.
Mann and Kendall (Gilbert, 1987). The two- To derive an estimate of the slope Q, the slopes
tailed test is used. At certain probability level H0 of all data pairs are calculated
is rejected in favour of H1 if the absolute value
of Sequals or exceeds aspecified value S/2, x j xk
where S/2 is the smallest Swhich has the prob- Qi = , i = 1, 2, ... N , j > k
ability less than /2 to appear in case of no trend.
jk (9)
Apositive (negative) value of Sindicates an up-
If there are n values xj in the time series we get
ward (downward) trend (Salmi et al 2002, Luo et
as many as N = n(n-1)/2 slope estimates Qi .
al. 2008).
The Sens estimator of slope is the median
For n 10, the statistic Sis approximately nor-
of these N values of Qi. The N values of Qi are
mally distributed with the mean and variance as
ranked from the smallest to the largest and the
follows
Sens estimator is
 Application of Mann-Kendall test and the Sens slope estimates for trend detection
in deposition data from Bl K (Beskydy Mts., the Czech Republic) 19972010
Q N +1 if N is odd
2
Q=
1 increased too drastically. This results groups in
Q N + Q N + 2 if N is even
2 2 2 Although clustering results may be sensitive to
(10)
A 100(1-)% two-sided confidence interval
about the slope estimate is obtained by the non-
parametric technique based on the normal dis-
tribution. The method is valid for n as small as
10 unless there are many ties (Salmi et al. 2002).
At first we compute
C = Z VAR ( S ) ,
1 tions and graph creation. STATISTICA Cz 9.0 by
2 (11)
where VAR (S) has been defined in equation (6),
Z1-/2 is obtained from the standard normal
distribution.
Next M 1 = ( N - C )/2 and M2 = ( N + C )/2 are
computed. The lower and upper limits of the
confidence interval, Qmin and Qmax, are the
M 1th largest and the (M 2 +1)th largest of the N
ordered slope estimates Qi. If M1 and/or M 2 are
not awhole numbers, the respective limits are
interpolated.
To obtain an estimate of B in equation (8) the
n values of differences xi Qti are calculated. The
median of these values gives an estimate of B
(Sirois 1998). The estimates for the constant B
of lines of the 99% and 95% confidence inter-
vals are calculated by asimilar procedure. Data
were processed using an Excel macro named
MAKESENS created by Salmi et al. (2002).
Cluster analysis
In order to uncover the groups of sources
influencing the chemical composition of pre-
cipitation at the site, the studied element and
ion fluxes were subjected to the correlation and
cluster analysis.
In cluster analysis (CA), Wards method was
used. Ward (1963) proposed avery general hi-
erarchical cluster method known as Wards
method or the minimum variance method.
The Wards method calculates the distance
between two clusters as the sum of squares
between the two clusters added up over all the
variables. At each generation, the within-cluster
sum of squares is minimized over all partitions
obtainable by merging two clusters from the pre-
vious generation. The main difference between
this method and the other linkage methods con-
sists in the unification procedure. This method
does not put together groups with smallest dis-
tance, but it joins groups that donot increase
137
too much agiven measure of heterogeneity.
The aim of the Ward method is to unify groups
such that the variation inside these groups is not
clusters that are as homogeneous as possible.
the chosen method (e.g. average-linkage as op-
posed to Ward), e.g. Blashfield (1976) found that
the Wards method clearly obtained the most
accurate solutions among the four hierarchical
methods he tested and recommended it. Among
hierarchical clustering approaches, Wards
method has the tendency to build not too many
clusters and of similar size.
Microsoft Excel 2007 was used for calcula-
StatSoft Inc. was used for statistical analysis.
Results and Discussion
Annual volume weighted means of conduc-
tivities and ion concentrations for the studied
period are summarized in Tab. 2. Calculated
variables, i.e. sea-salt corrected concentrations
of K+, Mg2+, Ca2+, Cl-, SO42- and TWDpa are shown
in Tab. 3. While comparing the data in Tab. 2 and
Tab. 3, it becomes apparent that the concentra-
tion decrease of corCl- during the studied period
is more distinct than the decrease of uncor-
rected Cl- concentration. This can be ascribed to
the decrease of brown coal mining (the decrease
of about 23.8% is reported between 1997 and
2010 on the web site of the Ministry of Industry
and Trade of the Czech Republic 2011) and con-
sumption because brown coal burning is one
of the anthropogenic sources of Cl- in the air.
Mean annual concentrations of anions, cations
and heavy metals in precipitation collected at
Bl K for the period of 19972010 are de-
picted in the Fig. 2. Annual values of total wet
deposition of potential acid for the same period
are shown in Fig. 3. Results of trend analysis are
summarized in Tab. 4. The prevailing anion in
precipitation was SO42- followed by NO3- and
Cl- as is shown in Fig. 2. The difference between
SO42- and NO3- concentrations has been decreas-
ing throughout the studied period. Among base
cations the highest concentrations (in equiva-
lents per litre) belonged alternatively to Ca2+ (7
years) or Na+ (7 years).
The statistically significant decreasing trend
was observed for conductivity of precipita-
tion and for annual mean concentration of all
studied elements and ions with the exception
of Na+, NH4+, Mn, F- and TWDpa (Tab. 4, Fig. 2).
Total wet deposition of potential acid does not
show any decreasing tendency in spite of the
138 K. Drpela , I. Drpelov
fact that the concentration of hydrogen ions
(measured as pH) and concentrations of acidi-
fying substances, namely SO42- and NO3-, have
been significantly decreasing. This is caused
by simultaneous decrease of basic precipita-
tion components, such as Mg2+, Ca2+ and K+ ions
which play their part in the formula for TWDpa
calculation (equation 2). The amount of acidi-
fying substances in precipitation is gradually
decreasing but the recovery from acidification
is being decelerated by concurrently decreasing
content of basic ions in the rain water. When the
natural acidity of rainwater is taken to be pH 5.6,
which is that of pure water in equilibrium with
the global atmospheric concentration of CO2
(Seinfeld, Pandis 1998), we can still consider the
precipitation at Bl K to be acid. Mean annual
values of pH of bulk precipitation sampled dur-
ing 2008 and 2009 at the 10 intensive monitoring
plots throughout the Czech Republic within the
ICP Forest Programme were within 4.65.8 and
4.75.2, respectively (Bohov et al. 2010) and
these ranges can serve as acomparison for val-
ues measured at Bl K at the background site
also surrounded by forest in the same years (4.72
and 4.55, respectively).
For F- ion released into the atmosphere
mostly by coal burning processes surprisingly
no significant trend was found for the period
of 19972011 though the relative decrease cal-
culated from the first (19971999) and the last
(20082010) three years averages (see Tab. 2)
was about 30%. This can be explained by the fact
that concentrations of F- must have been very
low, close to the detection limit of the analytical
method which was ion exchange chromatogra-
phy (SN 1995) and relatively high inevitable
error could have distorted the results of the sta-
tistical analysis. For this reason F- was excluded
from multivariate statistical analysis.
Highly significant decreasing trend was de-
tected for Zn, Pb, Cd and Ni. This positive devel-
opment can be attributed not only to the ban of
leaded gasoline in the Czech Republic in 2001
and to general restructuralization of Czech in-
dustry but also to the improving condition in the
neighbouring states and in the whole Europe
(according to Ilyin et al. 2009 only about 30% of
Cd and less than 20% Pb of anthropogenic Cd
and Pb deposition in the Czech Republic came
from national sources in 2007). The decrease
in Cu, Zn, Pb and Cd deposition was observed
already between19942002 in Central Bohemia
region (Vach et al. 2004) and decreasing trends
of heavy metal deposition were demonstrated
on the basis of moss analysis for the period
19902005 for example in Bulgaria and Switzer-
land (Thoeni et al. 2011).
An attempt to disclose mutual relationships
among rainwater components was undertaken
by applying of correlation and cluster analysis.
The resulting correlation matrix is shown in
Tab. 5. The anthropogenic acidifiers SO42- and
NO3- are correlated and correlate also with Cl-
and Pb, Cd and Ni (in case of Ni the correlation
was not statistically significant but the correla-
tion coefficient was rather high) what can be
explained by easier transition of metals into the
solution in more acidic environment. Two of
the examined elements, the Mn and NH4+, dont
significantly correlate with any of the other ex-
amined elements and ions. Highest correlation
coefficients for Mn were found for Ca2+, Mg2+
and Fe, which are typical lithogenic elements,
may mark the natural sources of Mn (soil parti-
cles and mineral dust from weathered rock). The
main source of NH4+ is undoubtedly agriculture
(Kopek, Vesel, 2005) and the pollution with
NH4+ might have been influenced mainly by
local pollution sources in contrast to other ele-
ments. Significant mutual correlation of Pb, Cd,
Ni, Fe and Zn documents the impact of common
anthropogenic sources of these metals which
are mining, industrial production (foundries,
smelters, oil refineries, petrochemical plants,
pesticide production, and chemical industry),
untreated sewage sludge and diffuse sources
such as metal piping, traffic and combustion by-
products from coal-burning power stations. All
these metals are introduced in the atmosphere
mainly in the form of fine to coarse particulate
matter. Na+correlates with Cl- (the highest cor-
relation coefficient) and also with K+, Mg2+ and
NO3-. The significant correlation with Cl-, K+ and
Mg2+ suggest presence of significant amounts
of sea spray over the locality. This fact we have
taken into account and recalculated annual con-
centration of corCl-, corK+, corMg2+ and corSO42- are
therefore presented in Tab. 2.
Information on relationships among the
deposition components can be extracted also
from the cluster analysis result shown in the Fig.
4. Three basic clusters were distinguished: (Na+,
Cl-), (Ca2+, Fe, Zn), and (Pb, SO42-, Cd). The first
cluster clearly associates the sea spray elements
and the third one elements from industrial pol-
lution. The second cluster contains elements
which can partly come from resuspended soil
dust and partly from industrial sources.
We can conclude that, by applying Mann-Ken-
dall test, we were able to prove statistically signif-
icant decrease of mean annual concentrations of
Tab. 2: P recipitation totals and annual means of conductivities and ion concentrations for wet-only (indexed with w) and bulk (indexed wih b) precipitation samples from CHMI station at Bl
K, Beskydy Mts. for the time period of 19972010. Date retrieved from CHMI web site http: portal.chmi.cz files portal docs uoco isko tab_roc tab_roc_CZ.html 20.6.2011.

Decrease
Variable Unit 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
%
rainw mm 1625.4 1336.6 1185.2 1428.6 1519.7 1274.9 1050.3 1214.3 1581.7 1392.0 1413.7 1268.5 1524.6 2128.0
-1
condw S cm 21.22 23.50 24.77 18.92 21.53 21.00 24.40 22.43 19.60 19.10 19.20 16.53 15.24 14.10 34
pHw - 4.59 4.47 4.47 4.61 4.54 4.60 4.61 4.52 4.62 4.67 4.66 4.72 4.55 4.71 -3
Na+w g l-1 140 160 160 150 130 100 170 183 166 106 168 139 101 63 34
K+w g l-1 100 120 120 120 110 70 78 91 70 69 137 76 63 52 44
NH4+w g l-1 540 580 540 470 540 610 865 521 566 643 572 662 547 558 -6
2+ -1
Mg w
g l 50 50 50 50 40 30 43 40 34 30 32 38 22 20 47
Ca 2+w g l-1 420 310 310 240 210 280 235 156 167 193 163 276 142 165 44
Mnb g l-1 6.3 4.5 4.7 10.1 3.5 4.1 5.9 4.2 2.9 5.3 2.8 7.7 4.1 3.3 3
-1
Znb g l 46.9 41.4 25.4 20.2 18.2 18.1 18.5 14.5 16.2 15.1 13.2 12.8 9.2 5.9 75
Pbb g l-1 5.7 5.9 5.1 4.6 4.5 3.5 4.7 3.3 3.0 4.3 1.9 1.8 1.6 1.4 72
Cdb g l-1 0.3 0.3 0.4 0.3 0.3 0.3 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 79
Nib g l-1 2.4 1.3 4.7 2.2 2.5 2.1 0.7 0.6 2.0 0.5 0.5 0.9 1.0 0.1 76
Feb g l-1 90 50 60 40 30 30 36 24 24 37 26 32 24 36 54
F--w g l-1 20 20 10 10 10 20 44 26 21 16 18 14 11 9 32
- -1
Cl w g l 480 450 460 400 320 290 479 488 363 312 372 300 229 175 49
NO3-w g l-1 1640 1960 2210 1650 1660 1730 2257 1820 1690 1746 1638 1659 1465 1257 25
in deposition data from Bl K (Beskydy Mts., the Czech Republic) 19972010
Application of Mann-Kendall test and the Sens slope estimates for trend detection

SO42-w g l-1 2480 2400 2390 1840 2010 2190 2395 1853 1700 1848 1721 1690 1365 1300 40
139
 140

Tab. 3: I on concentrations corrected for the sea-salt, and total wet deposition of potential acid (TWD pa) at CHMI station at Bl K, Beskydy Mts. for the time period of 19972010.

Decrease
Variable Unit 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010
%

cor
K+ g l-1 95 114 114 114 105 66 72 84 63 65 131 71 59 50 44

cor
Mg2+ g l-1 25 23 23 24 18 13 17 14 10 13 9 16 7 9 54
2+ -1
cor
Ca g l 415 304 304 234 205 276 229 149 161 188 157 271 138 163 44

cor
Cl- g l-1 229 163 173 131 87 110 174 160 65 122 70 50 48 62 72

cor
SO42- g l-1 2445 2360 2350 1802 1977 2165 2352 1807 1658 1822 1679 1655 1340 1284 40
kmol
TWDpa 1.323 1.233 1.113 1.042 1.260 1.145 1.242 1.029 1.303 1.242 1.144 1.025 1.107 1.437 3
ha-1 yr-1
K. Drpela , I. Drpelov

Decrease (last column in tables) was calculated from differences of the first (19971999) and the last (20082010) three years averages.
 Application of Mann-Kendall test and the Sens slope estimates for trend detection 141
in deposition data from Bl K (Beskydy Mts., the Czech Republic) 19972010

60

50
-1
l-1 l
eqeq

40
concentration in in
Concentration

30

20

10

0
1996 1999 2002 2005 2008 2011
SO 2-
SO42-
4
SO42-
corSO42-
cor
NO
NO3-
3
-
Cl
Cl-- Cl-
corCl-
cor
dif (SO42-, NO
dif(SO42-, -
NO3-)
3
)

12

10
eql-1l-1

8
concentrations inineq
Concentration

0
1996 1999 2002 2005 2008 2011
Cl
Na+-
K
K+
+
cor
K+
corK+ Mg2+
Mg2+ Mg2+
corMg2+
cor
Ca
Ca2+
2+
Ca2+
corCa2+
cor

100 6
90
5
80
70
4
Concentration in eq-1l-1

60
concentration in g l-1
concentration in g l

50 3
40
2
30
20
1
10
0 0
1996 1999 2002 2005 2008 2011
Fe Zn Ni Cd Pb

Ni, Cd and Pb concentration reading on the right axis

Fig. 2: MeanFig. 2:annual concentrations

Mean annual concentrations of anions,
of anions, basicbasic
cationscations
and heavyand
metalsheavy metalscollected
in precipitation in precipitation
at Bl
collected at Bl K,
K,Beskydy
BeskydyMts. Prefix cor denotes non sea-salt concentrations of ion.
Mts. Prefix cor denotes non sea-salt concentrations of ion.
142 K. Drpela , I. Drpelov

1.50
1.45
1.40
Deposition in kmol ha-1
1.35
1.30
1.25
1.20
1.15
1.10
1.05
1.00
1996 1999 2002 2005 2008 2011

TWD
TWDpa
pa

Fig. 3: Annual values of total wet deposition of potential acid (TWDpa) of precipitation collected at Bl
K during 19972010.

Tab. 4: T
 rends in total wet deposition of potential acid and in element and ionic concentrations of precipitation
collected at CHMI station at Bl K, Beskydy Mts. for the time period of 19972010. Trend analysis
with non-parametric Mann-Kendall test (Sens slope estimate and significance of Mann-Kendall test).

Variable Slope estimate Significance

condw 0.657 **
H+w 0.692 **
Na+w 3.625 NS
K+w 4.318 **

cor
K+w 4.176 *
NH4+w 3.220 NS
Mg2+w 2.308 ***

cor
Mg2+w 1.353 ***
Ca 2+w 14.566 **

cor
Ca 2+
w
14.426 **
Mnb 0.117 NS
Znb 1.625 ***
Pbb 0.350 ***
Cdb 0.024 ***
Nib 0.137 **
Feb 2.000 *
F-w 0.400 NS
Cl-w 19.000 **

cor
Cl-w 10.463 **
NO3-w 30.100 **
SO4 2-
w
80.000 ***

cor
SO42-w 79.835 ***
TWDpa 0.003 NS
*** for p < 0.001, ** for p < 0.01, * for p < 0.05, NS for p 0.1, index w denotes wet only deposition,
index b denotes bulk deposition, prefix cor denotes sea salt corrected values.
Tab. 5: Correlation matrix of the element and ion annual concentrations in precipitation sampled at the Bl K site. (n =14).

cond H+ Na+ K+ NH4+ Mg2+ Ca 2+ Mn Zn Pb Cd Ni Fe Cl- NO3- SO42-

cond 1.00 0.67 0.67 0.51 0.23 0.74 0.45 0.01 0.58 0.79 0.72 0.49 0.34 0.85 0.89 0.89
H+ 0.67 1.00 0.40 0.46 0.29 0.53 0.26 0.16 0.50 0.58 0.62 0.56 0.26 0.53 0.53 0.53
Na+ 0.67 0.40 1.00 0.61 0.09 0.68 0.13 0.13 0.34 0.38 0.23 0.22 0.06 0.86 0.65 0.46
K+ 0.51 0.46 0.61 1.00 0.33 0.69 0.31 0.15 0.48 0.48 0.53 0.42 0.30 0.59 0.36 0.46
+
NH4 0.23 0.29 0.09 0.33 1.00 0.06 0.03 0.04 -0.11 0.04 0.15 0.35 -0.12 0.10 0.49 0.26
Mg2+ 0.74 0.53 0.68 0.69 0.06 1.00 0.69 0.52 0.76 0.82 0.76 0.57 0.61 0.85 0.64 0.78
2+
Ca 0.45 0.26 0.13 0.31 0.03 0.69 1.00 0.42 0.85 0.68 0.71 0.54 0.87 0.47 0.35 0.78
Mn 0.01 0.16 0.13 0.15 0.04 0.52 0.42 1.00 0.22 0.30 0.29 0.13 0.32 0.25 0.13 0.19
Zn 0.58 0.50 0.34 0.48 0.11 0.76 0.85 0.22 1.00 0.83 0.67 0.44 0.84 0.65 0.38 0.80
Pb 0.79 0.58 0.38 0.48 0.04 0.82 0.68 0.30 0.83 1.00 0.84 0.53 0.66 0.72 0.64 0.89
Cd 0.72 0.62 0.23 0.53 0.15 0.76 0.71 0.29 0.67 0.84 1.00 0.80 0.59 0.53 0.55 0.82
Ni 0.49 0.56 0.22 0.42 0.35 0.57 0.54 0.13 0.44 0.53 0.80 1.00 0.48 0.35 0.40 0.53
Fe 0.34 0.26 0.06 0.30 0.12 0.61 0.87 0.32 0.84 0.66 0.59 0.48 1.00 0.46 0.22 0.64
Cl- 0.85 0.53 0.86 0.59 0.10 0.85 0.47 0.25 0.65 0.72 0.53 0.35 0.46 1.00 0.75 0.77
-
NO3 0.89 0.53 0.65 0.36 0.49 0.64 0.35 0.13 0.38 0.64 0.55 0.40 0.22 0.75 1.00 0.77
SO42- 0.89 0.53 0.46 0.46 0.26 0.78 0.78 0.19 0.80 0.89 0.82 0.53 0.64 0.77 0.77 1.00

Correlation coefficients evaluated as statistically significant (p < 0.05) are written in bold italic script.
in deposition data from Bl K (Beskydy Mts., the Czech Republic) 19972010
Application of Mann-Kendall test and the Sens slope estimates for trend detection
143
 144 K. Drpela , I. Drpelov

Mn K+ Cl- Zn Ca 2+ SO42- Mg2+ H+

NH4+ NO3- Na+ Fe Cd Pb Ni

Fig.4: Results of cluster analysis for mean annual element concentrations at Bl K site during
Fig.4: Results of cluster analysis for mean annual element concentrations at Bl K site
19972010.
during 19972010.

Zn, Pb, Cd, Ni, Fe in bulk precipitation and also Vortelov, L. 2010: Forest Condition Monitoring
We can conclude
statistically significantthat, by
decrease applying Mann-Kendall
of mean annual in the test,
Czechwe were [Annual
Republic. able to prove
reportstatistically
ICP For-
concentrations of H+, K+, Mg2+, Ca2+, NO3-, SO42-, ests/ Forest Focus 2008 and 2009.] Jlovit-
significant decrease of mean annual concentrations of Zn, Pb, Cd, Ni, Fe in bulk precipitation
Cl- and conductivity in wet only precipitation at Strnady, VLHM, 157 pp.
andthealso
Blstatistically
K monitoringsignificant
station decrease
for the of mean
period CHMI annual
2010a:concentrations of H+, K+Divi-
Air Quality Protection , Mg2+,
2+ - 2- -
Ca of, 19972010.
NO3 , SO4No, Cl trend and
was conductivity
found for theintotal
wet only
sionprecipitation at theOverview.
Annual Tabular Bl Khttp://por-
monitoring
station for the period
wet deposition of 19972010.
of potential acid in spite No trend was
of the found for the total wet deposition of
tal.chmi.cz/files/portal/docs/uoco/isko/
potential
fact thatacid in spite of the
the concentrations fact that sub-
of acidifying the concentrations of acidifying substances were
tab_roc/tab_roc_EN.html
stances were decreasing. The cause of this ap- CHMI 2010b: TBKRB Bl K. Stav vroce
decreasing. The cause of this apparent
parent contradiction consist in the fact that the
contradiction consist in the fact that the decrease in
2010. (TBKRB Bl K. State in 2010.) http://
deposition of acidifying substances
decrease in deposition of acidifying substances is accompanied by simultaneous decrease of Ca 2+ and
portal.chmi.cz/files/portal/docs/uoco/isko/
2+
Mgis accompanied
deposition. Wards method was
by simultaneous suitable
decrease of for dividing the deposition components into
tab_roc/2010_enh/cze/pollution_locality/
several groups
Ca2+ and Mg2+regarding
deposition. probable sources was
Wards method of theseloc_TBKR_CZ.html).
elements (or ions).
suitable for dividing the deposition components CHMI 2010c: TBKRB Bl K. Stav vroce
into several groups regarding probable sources 2009. (TBKRB Bl K. State in 2009.)
Acknowledgement
of these elements (or ions). http://por tal.chm i.cz/files/por tal/docs/
The authors thank M. Matjk for creating the mapuoco/isko/tab_roc/2009_enh/cze/precipita-
(Fig. 1). The study was supported by
MSM 621 564
Acknowledgement
8902 project. tion_locality/loc_TBKR.html.
SN ISO 10304-1 (757391) 1995: Water quality
The authors thank M. Matjk for creating the Determination of dissolved fluoride, chloride, ni-
map (Fig. 1). The study was supported by MSM trite, orthophosphate, bromide, nitrate and sulfate
6215648902 project. ions using liquid chromatography of ions - Part
1 : Method for water with low contamination. In
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