Application Note · PlasmaQuant 9100 Elite

Challenge
The precise determination of
trace elements while analyzing
bulk elements.

Solution
PlasmaQuant 9100 ICP-OES
series with its DualView Plus
option provides an extended
linear dynamic range from sub-
ppt level to percentage range.

Determination of Phosphorus and Other Critical Elements in Sewage Sludge

Introduction
Phosphorus and phosphorus compounds are essential for Sewage sludges originate from municipal wastewater
all living things. Without phosphorus, organisms cannot be treatment plants (WWTP), in which wastewater from
built up and function. In humans and animals, for example, private households and comparable facilities in particular are
this applies to DNA but also to bones and teeth. Plants stunt treated. They are considered as waste, but because of their
if they cannot absorb enough phosphates. Phosphorus is relatively high content of valuable nutrients (e.g., Ca, K, N)
irreplaceable for the production of fertilizers and helps to they have considerable resource potential. Depending on its
secure food supplies worldwide. levels of pollutants, sewage sludge can be used as fertilizer
Phosphorus was classified as a critical raw material by the on agricultural soils or in landscaping measures.
European Commission in the “List of Critical Raw Materials The European Union has passed several directives to be
for the European Union”[1]. In 2012, the German government adopted by the member states to regulate the application
also emphasized the need for sustainable management of of sewage sludge to land (e.g., „Sewage Sludge Directive
this material flow that is relevant to resource conservation. 86/278/EEC“[3]). They prohibit the use of sludge from
In addition, the German sewage sludge ordinance (GSSO, treatment plants unless the specified requirements (see
AbfKlärV)[2] includes the obligation to recover phosphorus Table 1) are fulfilled. The GSSO regulates in particular the
from 2029 or 2032 respectively (depending on the pollutant requirements for the utilization of sewage sludge
size of the wastewater treatment plant). To meet GSSO for fertilizer purposes on agriculturally used soils. In order
requirements, phosphorus must be recovered if a sewage to ensure the unrestricted usability of the soils intended
sludge contains 20 grams or more per kilogram of dry for sewage sludge application, the ordinance provides
matter. for regular pollutant tests of these soils and standardizes
pollutant limit values (see Table 1) in this respect, which
2 Determination of Phosphorus and Other Critical Elements in Sewage Sludge

may not be exceeded. As an overall consequence, levels of Table 1: Limits of European and German sewage sludge directives
nutrients (e.g., P) and pollutants (e.g., Cd, Hg, Pb) in sludges
from urban and industrial wastewater treatment need to be 86/278/EEC German Sewage
controlled on a regular base. Element Sludge Ordinance
Due to its multi-element determination capability, high
[mg/kg] [mg/kg]
dynamic linear range, and sensitivity, inductively coupled
plasma-optical emission spectrometry (ICP-OES) is widely Cd 20‒40 10

used for the analysis of soil and sludge. The application Cr - 900
is described in standard procedures such as EPA methods
3050B and 6010C, DIN EN 16174:2012-11, and the ISO Cu 1000‒1750 800

standard ISO 11885:2007. Hg 16‒25 8

In this study, a high-resolution ICP-OES, the
PlasmaQuant 9100 Elite, was used for the analysis of major, Ni 300‒400 200

minor, and trace elements in different sludge samples.

Pb 750‒1200 900
The exceptionally high resolution in combination with the
DualView Plus option allows for interference-free analysis Zn 2500-4000 2500
of all investigated analytes ranging from sub-ppb to
percentage range. The sample preparation was performed
according to EN 13346:2000. The accuracy of the method
was investigated using the standard reference material
NIST 2781 and a sewage sludge sample, which was part of
a national round robin test. Additionally, analyte recovery
and long-term stability tests were performed to verify
the suitability of the analytical method and instrument
performance.

Materials and Methods

Samples preparation
All laboratory equipment was washed with deionized The sample preparation was performed in accordance
(DI) water from a PURELAB system (18.2 MΩ-cm, ELGA with EN 16174:2012 (Method B), which requires a
LabWater, High Wycombe, England). Chemicals were of microwave-assisted acid digestion step. Before taking
analytical reagent grade. All multi-element stock solutions each triplicate to be analyzed, the contents of the sample
were made up using single element and multi-element bottles were homogenized by shaking the bottle upside
standard solutions (Merck, Sigma-Aldrich, CPAchem, down. Afterwards, approximately 0.5 g of homogenized
Inorganic Ventures). The working standards were prepared sample were accurately weighed (0.0001 mg) and added
by serial volume/volume dilution in polypropylene tubes to a digestion vessel (DAP60). Successively, 0.5 mL of DI
of the stock solutions using 1% (v/v) HNO3. Yttrium (Y) water, 6 (± 0.1) mL HCl, and 2 (± 0.1) mL HNO3 were
was added on-line to all blanks, standards, and samples added. The mixture was swirled carefully and left standing
as internal standard. The artificial sewage sludge solution for at least 15 minutes before the vessel was closed.
for determining the long-term stability was prepared from Subsequent heating (175 °C, 10 min) was performed in a
single and multi-element standard solutions and contained speedwave XPERT microwave digestion system. Afterwards
the following analyte concentrations: 0.1 mg/L (Hg), the vessels were allowed to cool to room temperature (RT) to
0.5 mg/L (Ag, As, Cd, Cr, Cu, Mn, Ni, Pb, Se, Zn), 50 mg/L avoid foaming and splashing. The solutions were transferred
(Mg), 150 mg/L (Al, Fe, P, S), 300 mg/L (Ca). to a graduated polypropylene tube, diluted to 50 mL with DI
The sample list consisted of one standard reference material water, and centrifuged (1125xg, 10 min). The supernatants
(SRM), Domestic Sludge NIST 2781, and a sewage sludge were immediately submitted to the analysis. The analysis
sample, which was part of a national round robin test (RRT) results were not related to the dry mass, but to the initial
(“Phosphorus determination in sewage sludge” (2021) by weight of the sample.
the Federal Institute for Materials Research and Testing
(Bundesanstalt für Materialforschung und -prüfung, BAM).
3 Determination of Phosphorus and Other Critical Elements in Sewage Sludge

Calibration
Calibration levels for each element were chosen based on the expected concentration ranges. At least three calibration points
were used for each element, as described in Table 2. Selected calibration curves are shown in Figure 1.

Table 2: Concentration of calibration standards

Element Unit Cal. 0 Std. 1 Std. 2 Std. 3 Std. 4 Std. 5 Std. 6 Std. 7

As, Hg mg/L 0 0.01 0.1 - - - - -

Cd mg/L 0 0.01 0.1 1.0 - - - -

Ag, Ni, Se mg/L 0 - 0.1 1.0 - - - -

Cr, Pb mg/L 0 - 0.1 1 10 - - -

Cu mg/L 0 - - 1 10 - - -

Mg mg/L 0 - - - - 10 50 200

Ca mg/L 0 - - - - 40 200 1000

K mg/L 0 - - - - 4 20 100

Fe, P, S mg/L 0 - - - - 20 100 500

Mn, Na, Zn mg/L 0 - - - - 1 5 25

Figure 1: Selected calibration functions

4 Determination of Phosphorus and Other Critical Elements in Sewage Sludge

Instrument settings Table 3: Instrument settings

The analysis was performed on a PlasmaQuant 9100 Elite
ICP-OES. The sample introduction components as well as the
Parameter
instrumental settings were selected to achieve a high level of
sensitivity for trace elements in possibly high-salt containing Plasma power 1350 W

matrices. In conjunction with this instrument, a Teledyne Plasma gas flow 14 L/min
CETAC ASX-560 Autosampler was used. An internal standard
mixing kit was also used to introduce a 10 mg/L yttrium Auxiliary gas flow 0.5 L/min

internal standard solution on-line, resulting in approximately Nebulizer gas flow 0.6 L/min
1mg/L final concentration. A summary of individual settings
and components is given in Table 3. Nebulizer Concentric, SeaSpray, 2.0 mL/min, Borosilicate

Spray chamber Cyclonic spray chamber, 50 mL, Borosilicate

Outer tube / Inner tube Quartz/Quartz

Injector Quartz, ID: 2 mm

Sample tubing PVC (red/red)

Internal standard tubing PVC (green/orange)

Pump rate 1.00 mL/min

Fast pump 4.00 mL/min

Measuring delay / Rinse time 45 s/15 s

Torch position -1 mm

Method and evaluation parameters

The analysis was performed on a PlasmaQuant 9100 Elite ICP-OES. The sample introduction components as well as the
instrumental settings were selected to achieve a high level of sensitivity for trace elements in possibly high-salt containing
matrices. In conjunction with this instrument, a Teledyne CETAC ASX-560 Autosampler was used. An internal standard
mixing kit was also used to introduce a 10 mg/L yttrium internal standard solution on-line, resulting in approx. Method
parameters are shown in Table 4.

Table 4: Method parameters

Element Line Plasma View Integration Read Time Evaluation

[nm] [s] Pixel Baseline Fit Poly. Deg.

Y 371.030 axial/radial Peak 1/1 3 ABC1 auto

Ag 328.068 axial Peak 1 3 ABC auto

As 188.979 axial Peak 10 3 ABC auto

Ca 315.887 att. radial2 Peak 1 3 ABC auto

Cd 228.802 axial Peak 3 3 ABC auto

Cr 267.716 axial Peak 3 3 ABC auto

Cu 327.396 axial Peak 1 3 ABC auto

Fe 259.940 att. radial Peak 1 3 ABC auto

Hg 184.886 axial Peak 10 3 ABC auto

K 766.491 radial Peak 1 3 ABC auto

Mg 285.213 radial Peak 1 3 ABC auto

5 Determination of Phosphorus and Other Critical Elements in Sewage Sludge

Table 4 (continued): Method parameters

Element Line Plasma View Integration Read Time Evaluation

[nm] [s] Pixel Baseline Fit Poly. Deg.

Mn 257.610 att. radial2 Peak 1 3 ABC1 auto

Na 589.592 radial Peak 1 3 ABC auto

Ni 231.604 axial Peak 3 3 ABC auto

P 214.914 axial Peak 1 3 ABC auto

Pb 220.353 axial Peak 3 3 ABC auto

S 182.565 axial Peak 1 3 ABC auto

Se 196.028 axial Peak 3 3 ABC auto

Zn 206.200 axial Peak 1 3 ABC auto

1
Automated Baseline Correction
2
 ttenuated radial observational view extends linear dynamic range into the percentage range
A

Results and Discussion

Analyte recovery and accuracy
The accuracy of the developed method was investigated by analyzing the standard reference material NIST 2781. Table 6 shows
certified values and recovery rates for the tested reference material. All recoveries were within ± 9% of the certified value.

Table 5: Comparison of the reference values with the determined mass fractions for NIST SRM 2781 (Domestic sludge)

Element NIST SRM 2781 (Domestic Sludge)

Reference value Uncertainty Measured mass RSD1 Recovery

fraction

[mg/kg] [mg/kg] [mg/kg] [%] [%]

Ag 86.3 ± 1.7 83.9 1.5 97.2

As 7.81 ± 0.67 7.98 0.6 102.2

Ca 36 440 ± 1 830 36 190 0.8 99.3

Cd 11 ± 2 10.8 0.9 98.2

Cr 143 ± 14 134 1.5 93.7

Cu 601 ± 16 576 0.9 95.8

Fe 24 300 ± 2 100 24 973 1.8 102.8

Hg 3.68 ± 0.14 3.46 1.4 94.0

Mg 4 850 ± 290 4 780 2.0 98.6

Mn 745 ± 33 751 0.6 100.8

Ni 72.3 ± 6.3 67.1 0.3 92.8

P 24 300 ± 400 22 580 0.4 92.9

Pb 183 ± 15 167 0.3 91.3

Se 16.0 ± 1.5 15.1 0.6 94.4

Zn 1 120 ± 34 1 140 1.6 101.8

1
Relative standard deviation based on the measurement of three independent replicates
6 Determination of Phosphorus and Other Critical Elements in Sewage Sludge

Additionally, spiking experiments were carried out to illustrate the applicability of the analytical method. ISO 11885 requires
that the recovery of the spiked analyte concentration must be within ± 20% of the concentration equivalent added to the
sample for matrix effects to be considered negligible. To evaluate that, the RRT sample was spiked after the digestion
step with the desired elements. Table 6 shows the analyte recoveries which all were within a ± 14% range illustrating the
applicability of the analytical method.

Table 6: Quantitative results and analyte spike recoveries for different sewage sludge samples

Element Sewage Sludge SRM NIST 2781

Measured conc. Spiked conc. Recovery Measured conc. Spiked conc. Recovery

[mg/L] [mg/L] [%] [mg/L] [mg/L] [%]

Ag 0.017 0.5 93 0.858 0.5 97

As 0.050 0.5 93 0.075 0.5 91

Ca 869 200 97 366 200 103

Cd 0.010 0.5 98 0.104 0.5 89

Cr 0.309 0.5 90 1.33 0.5 96

Cu 4.88 0.5 96 5.84 0.5 97

Fe 312 100 99 257 100 100

Hg 0.003 0.05 111 0.035 0.05 111

K 25.9 20 103 28.7 20 102

Mg 89.5 50 101 49.3 50 105

Mn 3.94 5 100 7.39 5 107

Na 5.69 5 103 9.93 5 103

Ni 0.248 0.5 86 0.600 0.5 92

P 251 100 99 221 100 100

Pb 0.396 0.5 87 1.67 0.5 95

S 106 100 108 137 100 102

Se 0.031 0.5 93 0.151 0.5 88

Zn 7.70 5 106 10.8 5 104

Long-term stability
Long term stability was investigated by monitoring the results of an artificial sewage sludge sample for ten hours resulting
in recoveries in the range of ± 7% (see Figure 2). Relative standard deviations below 1.65% (for analytes) and 1.05%
(for internal standards, Figure 3) indicate a highly stable performance of the instrumentation throughout the 10 hours of
measurement.
7 Determination of Phosphorus and Other Critical Elements in Sewage Sludge

130

120
Recovery [%]

110

100

90

80

70
0 2 4 6 8 10
Time [h]

Ag As Ca Cd Cr Cu
Fe Hg K Mg Mn Na
Ni P Pb S Se Zn

Figure 2: Percentage recoveries of the analytes throughout a 10-hour sequence. RSD values were below 1.65% for all elements.

130

120
Recovery [%]

110

100

90

80

70
0 2 4 6 8 10
Time [h]

Y371.030 Axial Y371.030 Radial

Figure 3: Percentage recoveries of the internal standard (yttrium) throughout a 10-hour sequence. RSD values were below 1.05% for both
observational views.

External quality control – Round robin test (RRT)

The overall aim of the RRT organizers was to evaluate the equivalence of different methods for phosphorus determination
permissible according to German “sewage sludge ordinance“ (GSSO, AbfKlärV). To demonstrate the PlasmaQuant 9100
Elite’s performance and the applicability of the analytical method for phosphorus analysis, the application lab of Analytik
Jena’s headquarters took part in this test. The organizer of the RRT specified the approved analytical methods and
the corresponding regulations for sample preparation. Nineteen laboratories submitted results obtained by ICP-OES
measurements and sample preparation using a closed microwave digestion system. The results of the RRT are displayed in
Table 7.
8 Determination of Phosphorus and Other Critical Elements in Sewage Sludge

Table 7: Quantitative results for round robin test sample

Element Sewage Sludge Sample

RRT Mean CVr* Measured CVr,L* z-score*

[g/kg] [%] [g/kg] [%]

Mn 257.610 att. radial

2
Peak 1 3

*C
 alculation was performed in accordance to ISO 5725-2

Sensitivity and spectral resolution

According to ISO 11885, the limits of detection (LODs) are calculated following the equation 1:
LOD = 3 x s0
where s0 is the standard deviation of 10 replicates of the blank. The instrumental and method detection limits, which
consider the dilution factor of the digestion step, are shown in Table 8.

Table 8: Instrumental detection limits (IDLs) and method detection limits (MDLs) for analytical lines utilized

Element Line Plasma View IDL MDL

[nm] [µg/L] [mg/kg]

Ag 328.068 axial 0.21 0.02

As 188.979 axial 0.49 0.05

Ca 315.887 att. radial1 3.29 0.33

Cd 228.802 axial 0.10 0.01

Cr 267.716 axial 0.20 0.02

Cu 327.396 axial 0.24 0.02

Fe 259.940 att. radial 1.18 0.12

Hg 184.886 axial 0.41 0.04

K 766.491 radial 22.7 2.27

Mg 285.213 radial 0.40 0.04

Mn 257.610 att. radial 0.20 0.02

Na 589.592 radial 4.72 0.47

Ni 231.604 axial 0.18 0.02

P 214.914 axial 3.69 0.37

Pb 220.353 axial 0.59 0.06

S 182.565 axial 9.75 0.97

Se 196.028 axial 1.61 0.16

Zn 206.200 axial 0.17 0.02

1
Attenuated radial observational view extends linear dynamic range into the percentage range
9 Determination of Phosphorus and Other Critical Elements in Sewage Sludge

Interference-free detection of trace signals is a prerequisite on HR ICP-OES. The spectra of an instrument with average
for reliable and accurate monitoring of sewage sludge. Trace spectral resolution (left) reveals an insufficient separation
signals can easily be interfered by matrix components. In of the Cd line at 228.802 nm and the surrounding matrix
this regard, high spectral resolution provides well separated peaks, which makes it impossible to use this line for
peaks of high definition and therefore circumvents the reliable quantification. In this case, using an alternative,
risk of spectral interferences in sewage sludge analysis. less sensitive line is inevitable with the consequences of an
Figure 4 displays a comparison of spectra on the example increased MDL as well as inferior precision and accuracy at
of cadmium (Cd). Since sewage sludge often contains high the limit concentration. In contrast to the average resolution,
concentrations of iron (Fe), the sensitive quantification of the high spectral resolution of the PlasmaQuant 9100 Elite
Cd with ICP-OES can be very challenging. The two most provides a baseline-separated signal for Cd at 228.802 nm.
sensitive lines of Cd at 226.502 and 214.441 nm are prone Thus, the sensitive quantification of Cd remains accessible
to Fe interferences. Using an ICP-OES with medium to low resulting in a lowest possible MDL and highest reliability
spectral resolution can easily result in overestimation of Cd in of the obtained results. The high spectral definition also
such Fe-rich samples. Therefore, the user is forced to switch contributes to an improved sensitivity since it results in larger
to Cd at 228.802 nm to enable at least a less sensitive peak heights and increased readings for a basic three-pixel
analysis. Since sewage sludge frequently contains relatively peak evaluation as commonly applied in ICP-OES.
high amounts of arsenic, this analytical line is only usable

Cd228.802 (PQ 9100, 6 pm @ 200 nm) Cd228.802 (PQ 9100 Elite, 2 pm @ 200 nm)

Figure 4: Comparison of PlasmaQuant 9100 (6 pm @ 200 nm) and PlasmaQuant 9100 Elite (2 pm @ 200 nm) illustrating the application
advantage of high-resolution spectra (red: sample, blue: blank, green: baseline correction (ABC)).
10 Determination of Phosphorus and other critical Elements in Sewage Sludge

Conclusion
The presented method describes the capabilities of the
PlasmaQuant 9100 OES series (standard configuration)
for the analysis of sewage sludge samples. The method
validation was performed by analyzing a certified reference
material and several spiked sludge samples, as well as long-
term stability analysis demonstrating the suitability of the
PlasmaQuant 9100 Elite ICP-OES system for the elemental
analysis of sewage sludge matrices.
The major challenge of this application includes analyzing
elements over a large concentration range (low μg/L to high
mg/L) in a single run. Trace elements (e.g., Cd, Hg) are to be
analyzed together with nutrients (e.g., Ca, K, Mg, P), which
is successfully demonstrated by the DualView Plus feature
of the PlasmaQuant 9100 OES. Besides the common radial
and axial plasma observation modes it offers axial plus and
radial plus, which attenuates the signal in the respective
observation mode. The described method uses radial and Figure 5: PlasmaQuant 9100 series

attenuated radial plasma observation to measure high levels

of minerals alongside trace levels of toxic elements in a
single measurement run. Running several dilutions to cover
the entire concentration range is therefore avoided.
It could be demonstrated that the requirements in terms of
sensitivity, stability, and accuracy to perform the analysis
of sludge samples can be met with the here proposed
setup. The use of the PlasmaQuant 9100 OES series allows
laboratories to perform the entire elemental screening on
one instrument. Both, toxic elements and future critical
nutrients, such as phosphorus can be analyzed in parallel
side by side without compromising precision.

References
[1] Communication from the Commission to the European Parliament, the Council, the European Economic and Social Committee and the Committee of
the Regions, Brussels, 2020
[2] Verordnung über die Verwertung von Klärschlamm, Klärschlammgemisch und Klärschlammkompost (Klärschlammverordnung - AbfKlärV), Revision
2017.
[3] 86/278/EEC Council Directive on the protection of the environment, and in particular of the soil, when sewage sludge is used in agriculture, 1986

This document is true and correct at the time of publication; the information within is subject to change. Other documents may supersede this document, including technical modifica-
tions and corrections.

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