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DOI: 10.2478/s11696-014-0555-5
ORIGINAL PAPER
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
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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
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0.15
a
0.64
3.5
0.37
a
0.55
1.65
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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/%
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.
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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
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
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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
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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