Chemical Papers 68 (8) 10151021 (2014)

DOI: 10.2478/s11696-014-0555-5

ORIGINAL PAPER

Comparison of digestion methods for determination

of total phosphorus in river sediments
Jitka Mal*, Marcela Lagov
Department of Chemistry, Faculty of Civil Engineering, Brno University of Technology,
Veveri 331/95, 602 00 Brno, Czech Republic
Received 4 October 2013; Revised 7 January 2014; Accepted 18 January 2014

In this study, four digestion methods used to determine total phosphorus in river sediments,
including Na2 CO3 fusion, the H2 SO4 and H2 SO4 + H2 O2 methods and the SMT protocol were
investigated. Interference eects of iron, calcium and organic matter in river sediments, and the
substances contained in the digestion agents on the photometric determination of the phosphates
were analysed. The digestion methods were tested on ten river sediment samples. Statistical analysis
of the results showed signicant dierences between sample treatments relating to the mean total
phosphorus concentration.
c 2014 Institute of Chemistry, Slovak Academy of Sciences


Keywords: sediments, total phosphorus, digestion methods, photometric determination, interferences

Introduction
Phosphorus is recognised as one of the key factors responsible for the eutrophication of fresh water
and a key element in biogeochemical cycles in river
ecosystems (House, 2003). Dissolved phosphorus compounds usually comprise only a small fraction of the
total phosphorus (TP) in bodies of water, hence they
occur in river waters at low concentrations. Phosphorus accumulates in sediments in both inorganic and
organic forms: it is physically adsorbed onto sediment
surfaces, chemically bonded in minerals and is biologically assimilated in cells and in the detritus originating
from biota (House et al., 2002).
Assessment of the TP content in sediments entails
decomposition of the sediment matrix followed by determination of the released phosphates. The method
most commonly used for the determination of phosphates is a spectrophotometric method with ammonium molybdate. The phosphates react with ammonium molybdate in the acidic medium to form a
heterocomplex of phosphomolybdic acid. This heterocomplex is further reduced in the presence of

Sb3+ ions. The resulting molybdenum blue is suitable

for spectrophotometric evaluation. Sodium sulphite,
tin(II) chloride, 1-amino-2-naphtol-4-sulphonic acid,
hydrazine sulphate, ferrous salt and ascorbic acid can
be used as reducing agents. Interferences in the analysis of phosphorus may be expected from compounds in
the sediment that also react with molybdate (e.g. silicates, arsenates, etc.) or aect the reduction of phosphomolybdic acid (e.g. Fe2+ /Fe3+ ) or from extraction
reagents that alter the pH of the acid medium (e.g.
HCl, H2 SO4 , NaOH, NH4 OH) (Maly, 1985).
Decomposition of the sediment matrix can be
achieved in various ways, usually based on methods
using strong acids or bases along with thermal degradation (Pardo et al., 1998).
The oldest methods of determining TP in soils
were developed by soil scientists and were only later
adopted by environmental researchers. Among these
methods, sodium carbonate fusion and perchloric acid
digestion, both introduced by Jackson (1958), are of
particular importance. Carbonate fusion is regarded
as one of the most eective digestion methods because
it also extracts the phosphorus which forms part of in

*Corresponding author, e-mail: mala.j@fce.vutbr.cz

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the matrix of silicate minerals (Kovar et al., 2009).

Combinations of the acids H2 SO4 + HF or HClO4 +
HF have similar eects.
Another method for determining phosphorus concentrations has been proposed by the Commission of
the European Communities within the framework of
the Standards, Measurements and Testing Programme
(SMT protocol). This protocol was designed to determine ve phosphorus fractions (inorganic P, organic
P, apatite P, non apatite inorganic P and TP) in sediments, and is based on the Williams method (Williams
et al., 1980, Ruban et al., 1999).
Other scientists, such as Blikov (1992), used sulphuric acid as the digestion agent. Decomposition by
sulphuric acid can be accelerated by adding potassium
or ammonium persulphate (Hupfer, 1995) or hydrogen
peroxide (Zwirnmann, 1999).
Ostrofsky (2012) compared the eciency of four
selected digestion methods: the combustion method
(similar to but not identical with the SMT protocol), the persulphate (K2 S2 O8 ) method, the HClO4 +
HNO3 method and the H2 SO4 + H2 O2 method, on a
collection of sediments from six lakes. He found no signicant dierences between the methods with regard
to the mean TP concentrations. However, the persulphate method exhibited greater variability than the
other three methods. He explained that this resulted
from the lower eciency of the persulphate method in
oxidising organic-bound phosphorus to reactive phosphates in samples with a higher organic content (Ostrofsky, 2012).
It is obvious that the accuracy of the TP determination depends not only on the eciency of decomposition of the sediment matrix but also on the potential interfering eects of the reagents used in the
decomposition reaction, as well as the substances released in the course of the decomposition of the sediment. The current study sought to compare four different commonly used digestion methods using spectrophotometric determination of the phosphates released.

Experimental
The following analytical reagent-grade chemicals:
sulphuric acid (Penta, CO); hydrochloric acid, hydrogen peroxide, sodium and ammonium hydroxides, sodium hydrogen carbonate, ammonium molybdate, ascorbic acid (Penta, Czech Republic), sodium
carbonate (Mach, Czech Republic), silica (Sigma
Aldrich, Czech Republic), potassium antimonyl tartrate, ferric ammonium sulphate (Merck, Czech Republic) were used. 2,4-dinitrophenol (Aldrich, Czech
Republic, 97 mass % purity) was also used
All glassware was cleaned ve times with tap water
prior to use. Impurities were removed with a clean
brush used only for this purpose. Next, the glassware
was washed once using deionised water before being

immersed into an ultrasonic bath lled with deionised

water for 10 minutes.
The eect on the photometric determination of
phosphates of the reagents used in the digestion and
certain substances which can be released from the
sediment was examined, using a concentration of P,
1
c(PO3
. Each determination was car4 ) = 0.5 mg L
ried out in 10 replicates. The dierences between a set
of control samples and a set of samples with the tested
substance were investigated using the Student t-test at
a 5 % signicance level. The statistical analyses were
performed using the R software (R Development Core
Team, 2009).
The digestion methods were tested on ten sediment
samples collected from three brooks in the Morava
river basin, Czech Republic: Troubsky (TRB) 3 sampling sites, Leskava (LES) 4 sampling sites and
an un-named stream near the village of Hartmanice
(HAR) 3 sampling sites. Wet sediments were passed
through a nylon sieve to separate the fractions smaller
than 100 m, then these fractions were dried at 105 C
to constant mass and manually crushed into powder.
The sediments were characterised by the organic matter contents, expressed as the loss on ignition (Czech
Oce for Standards, 2007), and calcium and iron contents determined using a Prodigy ICP optical emission spectrometer (Teledyne Leeman Labs, USA) in
accordance with respective methods (Czech Oce for
Standards, Metrology and Testing, 2009).
In all the digestion methods tested the phosphorus
contained in the samples was converted to soluble reactive phosphorus, which was then measured using the
molybdenum blue method proposed by Murphy and
Riley (1962), using ascorbic acid as reduction agent.
The optical density was measured at a wavelength of
710 nm using a Cecil CE 2021 spectrophotometer. The
detection limit of this method is c(PO3
4 ) = 0.005 mg
L1 and the calibration curve is linear up to c(PO3
4 )
= 0.8 mg L1 .
The rst digestion method tested was the sulphuric
acid method described by Blikov (1992). Unfortunately, the author did not provide a detailed account
of the parameters used. Accordingly, the following
conditions were used: a 100 mg sediment sample was
digested with 4 mL of concentrated sulphuric acid
at 440 C for 70 min in a 100 mL Kjeldahl ask in
a Digesdahl digestion apparatus (HachLange). This
was sucient time for the sample to become almost
clear. After cooling, the sample was transferred into
a 200 mL volumetric ask, diluted with deionised water, then 2,4-dinitrophenol was added and the sample
neutralised with concentrated ammonium hydroxide
to attain pH 5. The ask was then made up to 200 mL
with deionised water and, once the sediment settled,
an aliquot of the clear supernatant was analysed.
Several modications of the SMT protocol have
been reported; the method described by Pardo et al.
(2003) was used in this study. A 200 mg sediment sam-

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ple was combusted in a porcelain crucible at 450 C

for 3 h. After cooling, 20 mL of 3.5 mol L1 HCl was
added and the suspension shaken for 16 h. Finally, the
suspension was centrifuged at 5000 min1 for 10 min
and an aliquot of the supernatant was analysed.
The third procedure tested was the sodium carbonate fusion method, performed as described by Kovar et al. (2009). A 1000 mg sample of sediment was
melted with 4 g of Na2 CO3 in a platinum crucible.
After melting, the mixture was heated using the full
power of the burner for 20 min in an oxidising atmosphere, then the contents of the crucible were dissolved
in 30 mL of 4.5 mol L1 H2 SO4 . The crucible and the
lid were then placed in 25 mL of 1 mol L1 H2 SO4
and brought to the boil. Both solutions were transferred into a 250 mL volumetric ask and the ask
lled with deionised water. After allowing the sediment to settle, a 2 mL aliquot of the clear supernatant
was analysed. The pH of the aliquot was adjusted to
5 with 5 mol L1 NaOH, using 2,4-dinitrophenol indicator.
The H2 SO4 + H2 O2 method has been used in our
research centre for several years for TP analyses of
samples of both water and sediments. The method has
been applied under various reaction conditions. For
example, Hupfer digested 510 mg of sediment with
a mixture of 2 mL of 5 mol L1 H2 SO4 , 2 mL of 30
mass % H2 O2 and 20 mL of distilled water at 150 C for
16 h (Hupfer et al., 2004). The same author later used
the same parameters but reduced the digestion time
to 8 h (Hupfer et al., 2009). Kleeberg used a reaction
time of 3 h at two temperatures (120 C and 160 C)
(Kleeberg et al., 2010). Ostrofsky digested a 510 mg
sediment sample with 2 mL of 5 mol L1 H2 SO4 and
2 mL of 30 % H2 O2 , with no added water at 120 C for
8 h (Ostrofsky, 2012). In the present study, the conditions were changed so that the reaction time could
be substantially reduced. A 100 mg sediment sample
was digested with 3 mL of concentrated sulphuric acid
in a 100 mL Kjeldahl ask at 440 C in a Digesdahl
digestion apparatus (Hach Lange), until white fumes
appeared. After heating for a further 5 min, 17 mL
of 30 % H2 O2 was added drop-wise through a capillary funnel and the mixture was heated for a further
5 min. After cooling, the volumetric ask was lled to
the 100 mL with deionised water and, once the sediment settled, an aliquot of the clear supernatant was
analysed.
All TP determinations were performed using three
replicates. The mean TP concentrations and coecients of variation were calculated for each method
and sediment sample. Both data sets were analysed
and no obvious violation of normality or homogeneity
and no obvious relationship between group mean and
variance were found. In order to compare the mean TP
concentrations, the analysis of variance was conducted
separately for each stream, with the sampling site as
a blocking factor. This procedure is recommended by

Table 1. Reagents used during decomposition methods tested

c/(mol L1 ) Na2 CO3 fusion SMTP H2 SO4 H2 SO4 + H2 O2
Na2 CO3
NaOH
HCl
H2 SO4
NH4 OH
H2 O2

0.15
a

0.64

3.5

0.37
a

0.55

1.65

a) These reagents are added in small amounts to adjust pH of

the nal solutions.

Crawley (2007); otherwise analysis of pooled data with

an auto-correlated structure (streams) results in biased p-values. If a signicant dierence was detected
among the treatments, the Tukey test for multiple
comparisons was performed. Analyses were performed
using the R software (R Development Core Team,
2009).
All the procedures were veried by analysis of a
certied reference material BCR
-684 river sediment (European Commission, Joint Research Centre,
Institute for Reference Materials and Measurements).
In BCR
-684, the concentrated HCl-extractable P is
certied. The expanded uncertainties of the dierence
between the results obtained and the certied value
(U ) were calculated and compared with the absolute
dierences between the mean measured values and the
certied value (m ) (Linsinger, 2010). Standard deviations of the measurements were used as rough estimates of measurement uncertainties.

Results and discussion

The reagents used in the various decomposition
methods are listed in Table 1. Table 2 shows the concentrations of the reagents that were veried by the
procedure described above as not interfering with the
photometric determination of phosphates (error of less
than 1 %). In addition, Table 2 also lists SiO2 and
Fe3+ since they are common components of the sediments. When assessing the possible impact of these
substances on photometric determination, both the dilution of the extract prior to the photometric determination, as well as the chemical transformations of
reagents during decomposition, must be considered.
The H2 SO4 method only uses sulphuric acid, at a
concentration in the leachate of 0.37 mol L1 . Prior to
photometric analysis, the sample is diluted and neutralised with NH4 OH to pH 5, hence the H2 SO4 does
not interfere with the determination of phosphates.
The SMT protocol uses combustion followed by extraction using hydrochloric acid. The HCl concentration in the leachate is 3.5 mol L1 . So that the acidity
does not interfere, the maximum permitted concentration of HCl is 200 mmol L1 .Hence, the leachate
sample to be photometrically assessed must be diluted
at least 17.5 times or neutralised.

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Table 2. Concentrations of selected compounds that do not interfere with photometric determination of phosphates
Compound
NaHCO3
NaOH
HCl
H2 SO4
NH4 OH
H2 O2
Fe3+
SiO2

c/(mmol L1 )

Error/%

P-value of the Student t-test

10
40
200
120
30
0.88
1.5
0.13

0.7
0.3
0.7
0.8
0.6
0.4
0.1
0.7

0.084
0.531
0.201
0.269
0.203
0.509
0.917
0.085

Fig. 1. Mean TP concentrations ( SD) in sediments obtained by the four analytical methods of decomposition tested.

The Na2 CO3 fusion includes a 25-fold dilution of

the leachate sample prior to photometric determination and neutralisation of the acidic sample by the
addition of NaOH. There is uncertainty as to whether
the acidication of the sample in the process of dissolving the solidied melt removes all of the carbonates in the form of CO2 . If not, residual hydrogen
carbonates could be present in the solution and interfere via their buering capacity. However, at the
recommended dilution, the concentration of hydrogen carbonates cannot exceed the critical value of
10 mmol L1 . The advantage of this method is that,
unlike the other methods tested, it extracts phosphorus from apatite inclusions or those that are part of
the matrix of silicate minerals (Syers et al., 1967). The
silicates released have negligible interfering eect on
the photometric determination at the recommended
dilution.
In the leachate obtained by the H2 SO4 + H2 O2
method, the concentration of sulphuric acid is
0.55 mol L1 . This means that, in order to full the
acidity conditions, the leachate must be either diluted
4.6 times or neutralised prior to photometric determination. Hydrogen peroxide interferes even at very low
concentrations. Given the reaction time required, how-

ever, the H2 O2 is fully decomposed during digestion

of the sediment.
Interference by Fe3+ was observed at concentrations higher than 1.5 mmol L1 . Since sample portions of 100200 mg were used and large dilutions of
the leachates obtained, the concentrations of iron were
substantially lower than this value, even in case of sediments rich in iron.
Having demonstrated that neither sediment constituents nor reagents interfered with the analysis of
phosphorus, it was possible to compare the eciencies
of the 4 extraction techniques.
The mean TP concentrations found in the sediments using the four digestion methods are shown in
Fig. 1.
The results ranged from 0.52 mg g1 to 2.80
mg g1 . Fig. 1 shows that the results obtained by the
various digestion methods dier from each other, but
the order of the results is not the same for all the sediment samples. The variance calculated for each stream
separately, with the sampling site as a blocking factor,
showed a signicant dierence among the treatments
of the LES and TRB samples (LES: F = 2.23, P =
0.002; TRB: F = 10.70, P = 0.008). In the case of
samples from HAR, the dierence between the meth-

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Table 3. P-values of simultaneous tests for linear hypotheses

concerning mean TP concentrations
Linear hypotheses

LES

TRB

HAR

H2 SO4 + H2 O2 H2 SO4 = 0
0.361
0.028
SMTP H2 SO4 = 0
0.069
Na2 CO3 fusion H2 SO4 = 0
0.002
SMTP H2 SO4 + H2 O2 = 0
Na2 CO3 fusion H2 SO4 + H2 O2 = 0 0.006
0.926
Na2 CO3 fusion SMTP = 0

0.237
0.034
0.007
0.423
0.064
0.444

0.927
0.267
0.517
0.517
0.268
0.048

Table 4. Main characteristics of sediments analysed

Sediment Loss on ignition/% Fe/(mg g1 ) Ca/(mg g1 )
LES8
LES9
LES10
LES12
TRB1
TRB4
TRB7
HAR2
HAR3
HAR4

10.5
7.1
8.1
6.1
3.9
3.9
3.3
9.6
6.5
7.1

1.1
0.7
0.8
0.6
0.4
0.4
0.3
1.0
0.7
0.7

13.8
10.4
14.3
10.1
24.4
23.6
24.4
31.1
30.4
25.1

1.8
1.4
1.9
1.3
3.2
3.1
3.2
4.0
4.0
3.3

2.9
2.5
2.4
4.2
8.7
2.3
17.8
11.4
11.2
9.0

0.2
0.2
0.1
0.3
0.5
0.1
1.1
0.7
0.7
0.5

ods was just above the level of signicance (F = 4.22,

P = 0.063). Accordingly, the Tukey test for multiple
comparisons was performed on the data from all three
brooks. The results are shown in Table 3.
Dierences in the results can be explained by the
relatively large diversity of the sediments, which differed in their composition. The details are shown in
Table 4. The values measured in the three brooks are
typical for river/brook sediments. Similar data were
reported by House et al. (2002).
Statistical analysis suggested that, for the LES
samples, the SMT protocol detected signicantly
lower levels of TP than the H2 SO4 + H2 O2 and H2 SO4
methods. In addition, the Na2 CO3 method detected
signicantly lower levels of TP than the H2 SO4 +
H2 O2 method. The LES samples were rich in organic
matter and had low iron and calcium contents. The
H2 SO4 method, which is thought to be ineective in
consistently oxidising all organic-bound phosphorus to
reactive phosphates, especially in samples that are rich
in organic matter (Ostrofsky, 2012), was shown to be
suciently eective up to loss on ignition of 10.5 %
(sample LES8).
Like the TRB samples, which contained little
organic material and medium amount of iron, the
SMT protocol and the Na2 CO3 fusion provided lower
amounts of phosphorus than the H2 SO4 method. No
statistically signicant dierence was found between
the H2 SO4 and H2 SO4 + H2 O2 methods. However,
more detailed analysis of the results showed that comparable results were measured only for the TRB4

1019

sample, which diered from the remaining two samples in its low calcium content. In the case of the
TRB1 and TRB7 samples, the results of the H2 SO4
+ H2 O2 methods were lower. It can be assumed that,
in the case of the samples with a high content of calcium (possibly phosphorus bound in apatite), a larger
dose of sulphuric acid and a longer contact time for
the H2 SO4 method in comparison with the H2 SO4 +
H2 O2 methods would be more eective than the addition of a strong oxidising agent (H2 O2 ).
For the HAR samples, a signicant dierence was
found only between the SMT protocol (the highest
TP concentrations measured) and the Na2 CO3 fusion
(the lowest TP concentrations measured). These sediments were rich in phosphorus, with the HAR2 sample
having the highest concentration of all the sediments
tested. The HAR samples also had the highest concentrations of iron, calcium and medium-to-high concentrations of organic matter.
From these results, it may be concluded that the
H2 SO4 and H2 SO4 + H2 O2 digestion methods were
ecient for all of the sediments analysed. At higher
concentrations of organic substances, the H2 SO4 +
H2 O2 method was more appropriate due to the addition of an oxidising agent.
The SMT protocol was most ecient for the HAR
samples, where it gave results comparable with the
H2 SO4 and H2 SO4 + H2 O2 methods. The HAR sediments diered from the other samples in their high
calcium and iron contents. During its retention in bed
sediments, P is initially adsorbed, particularly on the
surfaces of Fe oxides, edges of calcite and calcium carbonate surfaces of calcareous sediments, and can be
released to the water phase again (Jalali et al., 2013).
Hence, it can also be easily desorbed by the extraction
procedure.
Although the alkaline melting is undoubtedly a
very eective digestion method, especially because of
the decomposition of the silicate matrix, for this set of
sediments analysed, the Na2 CO3 fusion gave low results. This was probably the result of the experimental
design in which the melting apparently decomposed
the organic matter. Phosphorus compounds were most
probably converted to phosphates, which, at the high
temperatures, may have reacted with other components, such as iron and calcium, to form poorly soluble phosphorus compounds which were not dissolved.
Another possible explanation is that the phosphates
released were adsorbed on the silicic acid precipitate.
The mean coecients of variation of the methods
tested were 7.70 % (Na2 CO3 fusion), 6.27 % (H2 SO4 ),
11.64 % (SMT protocol) and 6.15 % (H2 SO4 + H2 O2 ).
According to one-way ANOVA, there was no signicant statistical dierence between the methods with
regard to the coecients of variation (F = 1.69, P =
0.182). This suggests that there was no signicant difference in relative variability of the results obtained
by the methods tested.

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Table 5. TP in BCR
-684. Comparison of measurement results with a certied value (concentrated HCl extractable P)
Measurement
Certied value
H2 SO4
H2 SO4 + H2 O2
Na2 CO3
SMTP

TP/( g g1 ) m /( g g1 ) U /( g g1 )
1373
1316
1342
1329
1467

35
18
33
19
38

31
44
57
94

96
80
78
200

Table 5 shows the results of verication of all the

procedures by analysis of a certied reference material
BCR
-684 (three parallel determinations).
As m U for all the procedures tested, no
signicant dierences were found between the measurement results obtained and the value certied for
BCR
-684.
From a comparison of the digestion methods, the
H2 SO4 + H2 O2 method is recommended for analysing
TP in sediments. This method, using the present experimental design (i.e. concentrated sulphuric acid
and a high digestion temperature), is simple, safe and
time-ecient (total sample decomposition takes approximately 15 minutes). The basic laboratory safety
principles need to be observed. Sulphuric acid must
be present in the digestion ask when the hydrogen
peroxide is added, and the ask must be placed behind a safety shield during digestion (the shield is part
of the DigesdahlHachLange apparatus). Attention
must be paid to the quality of the hydrogen peroxide. Some producers use phosphoric acid to stabilise
this highly unstable compound. However, this chemical must not be used. Furthermore, a portion of at
least 100 mg of the sediment sample is recommended
for use in all the methods tested. Even if the sediment
is homogenised, the use of an extremely small sample
portion extends the variability of the results.

Conclusions
Statistically signicant dierences were found between the digestion methods tested (the Na2 CO3 fusion, the H2 SO4 method, the H2 SO4 + H2 O2 method
and the SMT protocol) used for TP analyses in river
sediments. This implies that the digestion methods
are not universal, and the composition of the sediment
should be taken into account when choosing an appropriate method. The H2 SO4 + H2 O2 method, which
was eective for most of the analysed sediments, is
recommended for use.
Acknowledgements. This research was financially supported
by the Ministry of Education, Youth and Sports of the Czech
Republic, grant no. FAST-S-11-14/1161.

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