Accepted Manuscript

Quantitative detection of powdered activated carbon in wastewater treatment plant

effluent by thermogravimetric analysis (TGA)

Therese Krahnstöver, Julia Plattner, Thomas Wintgens

PII: S0043-1354(16)30444-4
DOI: 10.1016/j.watres.2016.06.008
Reference: WR 12137

To appear in: Water Research

Received Date: 25 January 2016

Revised Date: 27 May 2016
Accepted Date: 3 June 2016

Please cite this article as: Krahnstöver, T., Plattner, J., Wintgens, T., Quantitative detection of powdered
activated carbon in wastewater treatment plant effluent by thermogravimetric analysis (TGA), Water
Research (2016), doi: 10.1016/j.watres.2016.06.008.

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to the oxidation of wastewater background matrix, which is mainly composed of biological material,
e.g. flocks of sewage sludge. Another relatively sharp mass decrease at 400 °C - 700 °C is caused by
the oxidation of powdered activated carbon. The specific temperature of this signal is found to vary
depending on the sample composition, but could be clearly identified in all cases. Finally, at
temperatures above 700 °C, the sample mass reaches a nearly constant value which corresponds to
the ash content o e sample. In the case of a constant temperature gradient, the temperature axis
can be directly correlated to a time axis. In order to take into account mass transport and reaction
kinetics and allow for the evaluation of the mass loss rate, the time axis is of particular interest for
analyzing a TGA curve.

ACCEPTED MANUSCRIPT

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Sample filtration TGA curve

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Sample mass [mg]

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Wastewater
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without activated
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carbon
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2
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1
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0
0 200 400 600 800
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Temperature [°C]
Wastewater
containing
activated carbon

Methods for sample preparation

Two methods tested for sample preparation, namely centrifugation and filtration, were compared
with regard to their practical feasibility and reproducibility. The ss of solids during the decanting,
centrifugation and drying procedure was found to be considerable: On average, the centrifugation of
2.2 L water yielded the same solid sample mass as the filtration of 1.0 L. This incomplete solid
separation increases the workload and calls for an additional, reliable determination of the sample's
solids content. In contrast, in the case of filtration, a complete removal of solids was achieved (Figure
3) and the separated solid mass correlated well with the TSS, making an additional determination
redundant. Furthermore, it was observed that the solid separation by centrifugation is not always
consistent for biological matrix and activated carbon. By qualitatively comparing the TGA curves
obtained with these methods, it was found that a significantly better reproducibility could be
achieved if the water samples were filtrated rather than centrifuged (Figure 4). If the water sample is
filtrated, the solid sample partly consists of filter material, which reduces the degree of sample
decomposition and causes a slight mass decrease above 700 °C. This did not directly affect the
analyzability of the TGA curve, but it must be considered that the additional filter weight could have
an impact on the method's detection limit.
 ACCEPTED MANUSCRIPT
Quantitative detection of powdered activated carbon in

wastewater treatment plant effluent by thermogravimetric

analysis (TGA)

Therese Krahnstövera, Julia Plattnera, Thomas Wintgensa*

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a
Institute for Ecopreneurship, School of Life Sciences, University of Applied Sciences and Arts

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Northwestern Switzerland, Gründenstrasse 40, 4132 Muttenz, Switzerland

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* Corresponding author. Tel. +41 61 467 44 59; fax: +41 61 467 42 90; e-mail:

thomas.wintgens@fhnw.ch

1 Abstract
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2 For the elimination of potentially harmful micropollutants, powdered activated carbon (PAC)
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3 adsorption is applied in many wastewater treatment plants (WWTP). This holds the risk of PAC

4 leakage into the WWTP effluent and desorption of contaminants into natural water bodies. In order to
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5 assess a potential PAC leakage, PAC concentrations below several mg/L have to be detected in the
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6 WWTP effluent. None of the methods that are used for water analysis today are able to differentiate

7 between activated carbon and solid background matrix. Thus, a selective, quantitative and easily
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8 applicable method is still needed for the detection of PAC residues in wastewater.
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9 In the present study, a method was developed to quantitatively measure the PAC content in wastewater
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10 by using filtration and thermogravimetric analysis (TGA), which is a well-established technique for

11 the distinction between different solid materials. For the sample filtration, quartz filters with a

12 temperature stability up to 950 °C were used. This allowed for sensitive and well reproducible

13 measurements, as the TGA was not affected by the presence of the filter. The sample's mass fractions

14 were calculated by integrating the mass decrease rate obtained by TGA in specific, clearly identifiable

15 peak areas. A two-step TGA heating method consisting of N2 and O2 atmospheres led to a good

16 differentiation between PAC and biological background matrix, thanks to the reduction of peak

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17 overlapping. A linear correlation was found between a sample's PAC content and the corresponding

18 peak areas under N2 and O2, the sample volume and the solid mass separated by filtration. Based on

19 these findings, various wastewater samples from different WWTPs were then analyzed by TGA with

20 regard to their PAC content. It was found that, compared to alternative techniques such as

21 measurement of turbidity or total suspended solids, the newly developed TGA method allows for a

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22 quantitative and selective detection of PAC concentrations down to 0.1 mg/L. The method showed a

23 linearity coefficient of 0.98 and relative standard deviations of 10% , using small water sample

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24 volumes between 0.3 and 0.6 L.

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25 Keywords: Micropollutants, Wastewater, Powdered Activated Carbon, Thermogravimetric Analysis

26 Introduction

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27 An increasing range of chemicals and degradation products is being detected in our water bodies

28 (Bolong, et al., 2009). These substances, referred to as micropollutants, are present in very low
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29 concentrations, but may still pose a risk to the aquatic environment (Magdeburg, et al., 2014, Leusch,

30 et al., 2014). As surface and ground water bodies often serve as sources for drinking water, negative
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31 effects on public health cannot be ruled out (Bolong, et al., 2009, Pasquini, et al., 2014). One of the
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32 most important entry paths of micropollutants into surface waters are effluents from wastewater

33 treatment plants (WWTP). Several anthropogenic pollutants can pass existing conventional WWTPs
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34 and may enter natural water bodies (Zietzschmann, et al., 2014, Bolong, et al., 2009). For this reason,

35 additional treatment steps in WWTPs will have to be developed and implemented in the near future
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36 (Zietzschmann, et al., 2014, Snyder, et al., 2003, Jekel, et al., 2013). For instance, in 2014 Switzerland
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37 has revised its Water Protection Ordinance that now demands an upgrade of around 100 WWTPs to

38 reduce their emission of micropollutants by 80% until 2040 (Eidgenössisches Departement für

39 Umwelt, Verkehr, Energie und Kommunikation, 2015). According to several studies, ozonation and

40 activated carbon adsorption are the most feasible and effective process options for the removal of

41 micropollutants from aqueous solutions (Bolong, et al., 2009, Löwenberg, et al., 2014, Margot, et al.,

42 2013). Activated carbon is able to adsorb and thus remove micropollutants from water (Zietzschmann,

43 et al., 2014) and can be applied either in its granular form or as a fine powder with a particle size of
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44 10-150 µm. Powdered activated carbon (PAC) can be dosed with a high flexibility in relation to the

45 water volume and its degree of contamination and is commonly applied in doses of 10 to 20 mg/L

46 (Böhler, et al., 2012, Löwenberg, et al., 2016). Once the dosed PAC is loaded, it has to be separated

47 from the WWTP effluent in order to prevent desorption of pollutants into natural water bodies

48 (Löwenberg, et al., 2014, Metzger, et al., 2011, To, et al., 2008). With increasing adsorption efficiency

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49 and decreasing filter retention, the amount of micropollutants adsorbed to leaking PAC can make up a

50 substantial part of the pollutants released from the WWTP. It was estimated in the here presented

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51 study that at an adsorption rate of 80% and a PAC retention of 90%, the PAC release can contribute to

52 almost one third of the micropollutants present in the effluent.There are currently several approaches

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53 to separate powdered activated carbon from wastewater and retain it in the treatment plant. Deep bed

54 filtration is a widely used method, but also ultrafiltration has been proposed for PAC retention

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(Löwenberg, et al., 2014, Snyder, et al., 2007, Altmann, et al., 2015a, Altmann, et al., 2015b). In any
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56 case, the PAC retention of a separation step has to be examined in order to assess the PAC leakage

57 into the effluent. Several authorities and institutions are currently proposing limit values for the
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58 emission of PAC into natural water bodies (Vu, et al., 2012, Abegglen and Siegrist, 2012). For this
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59 purpose, PAC concentrations below several mg/L have to be detected and quantified in WWTP
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60 effluents.

61 Due to its low concentration, the detection of PAC in WWTP effluent was found to be challenging and
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62 an easily applicable, quantitative method is still needed (Abegglen and Siegrist, 2012). In several

63 studies, turbidity measurements have been performed in order to estimate the PAC concentrations in
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64 wastewater. The results were found to be qualitatively comparable, but the measurements were close
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65 to the detection limit and no quantitative evaluation was possible (Metzger, et al., 2011). DIN 38 409

66 describes the measuring of total suspended solids (TSS) as an alternative method, but experiments

67 showed that measurements below 5 mg/L are of only limited validity (Metzger, et al., 2011). Metzger

68 et al. assessed the PAC concentrations by filtrating water samples with membrane filters and then

69 visually comparing the color of the filter with previously defined reference filters (Metzger, et al.,

70 2011). This method was able to detect PAC concentrations down to 0.05 mg/L. However, it is a highly

71 subjective method which provides qualitative rather than quantitative results. All proposed methods
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72 have in common that they do not differentiate between activated carbon and other solids contained in

73 the wastewater, e.g. biological matrix. However, as in many cases only the PAC leakage is of

74 particular interest, a material specific method is more favorable.

75 A well-established technique that allows for the distinction between different solid materials is

76 Thermogravimetric Analysis (TGA). TGA is used in industrial and scientific applications to evaluate

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77 the purity and properties of e.g. pharmaceutical and petrochemical materials. With this method,

78 changes in the mass of a solid sample are studied while the sample is subjected to a controlled heating

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79 program. The obtained TGA curves provide information relating to certain physical or chemical

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80 phenomena, such as thermal decomposition and oxidative degradation (Coats and Redfern, 1963,

81 Brown, 2001). Due to their different physico-chemical properties, sewage sludge and carbon show

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82 significant differences in their TGA curves (Folgueras, et al., 2003, Otero, et al., 2007, Otero, et al.,
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83 2008). Samples taken from WWTP effluent will thus exhibit an intermediate behavior between these

84 two, so that it will be possible to evaluate their composition. This approach was confirmed in a study
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85 where the detection of activated carbon in activated sludge was performed by TGA (Vu, et al., 2012,

86 Vogel, 2013). However, the referenced study does only focus on the composition of the analyzed
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87 solids obtained by vaporisation. In contrast, the here presented study aimed at quantifying the absolute
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88 PAC concentration in mg/L in the analyzed water sample by calculating an overall mass balance.

89 Thus, a sample preparation method was needed that yields a complete and quantifiable recovery of
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90 suspended solids, and sample centrifugation and filtration were tested for this purpose in the here

91 presented study. Furthermore, the method proposed by Vu et al. (2012) relies on a comparative
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92 measurement of a PAC-free reference sample consisting of background matrix only. This drawback
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93 can only be overcome by clearly differentiating between the fractions of PAC and background matrix

94 in one single TGA curve. As this differentiation was not possible using the mass decrease curve under

95 O2 atmosphere only, a combined heating method under N2 and O2 was developed, and the mass

96 decrease rate was analyzed rather than the absolute mass decrease.

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97 This method was then applied to a variety of wastewater samples from different WWTPs and the

98 results were compared with those of reference methods in order to assess the TGA method's sensitivity

99 and reliability.

100 Materials and methods

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101 Method development

102 In the first stage of this study, for method development purposes, wastewater samples were taken from

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103 the municipal WWTP Ergolz 1 in Sissach (Switzerland) (Table 1). PAC-free samples were taken in

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104 the supernatant of the secondary sedimentation. In order to simulate various PAC concentrations in

105 wastewater, these samples were spiked with defined, specific amounts of PAC later on in the

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106 laboratory. By doing so, measurement series with PAC concentrations CPAC between 0 and 2 mg/L
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107 were performed in triplicates in order to standardize and validate the TGA method.

108 As TGA can only be applied to solid samples, all water samples had to be concentrated and dried
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109 before the measurement. Two different methods were tested for sample preparation, namely

110 centrifugation and filtration. In the case of centrifugation, a defined water volume in the range of 5-20
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111 L, depending on its estimated solids concentration, was filled into 50 mL conical falcon tubes and then
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112 centrifuged at 4'000 rpm for 10 minutes (Eppendorf, 5810 R). The solid-rich phase was dried at 80 °C

113 in a nitrogen atmosphere for 8 hours (Techne, Dri-Block DB-3D). The weighed and ground solids
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114 were then used for TGA measurement. Alternatively, a defined sample volume V in the range 0.3-0.6

115 L was filtrated with a pre-dried quartz fiber filter (Macherey-Nagel, MN QF-10, temperature stable up
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116 to 950 °C) in a vacuum filtration unit with an active filtration area of 1 cm2. The filter with a layer of
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117 separated solids on top was carefully removed and dried at 105 °C for 24 hours. From weighing the

118 filter in the dry state before and after usage, the mass of separated solids mtot was calculated. The filter

119 together with the solid layer on top was then used for TGA measurements.

120 Table 1: Characteristics of the WWTPs for water sampling and PAC quantification

WWTP Location Population Origin PAC PAC separation Plant type DOC

equivalents municipal dosage concentration in

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: the influent to the

industrial PAC treatment

Ergolz 1 Sissach 40'000 100 : 0 12 mg/L Flocculation + Technical scale 6.7 mg/L

deep bed filtration

Flotation + Pilot scale 6.7 mg/L

surface filtration

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Bachwis Herisau 35'000 50 : 50 15 mg/L Sedimentation + Full scale 13.2 mg/L

deep bed filtration

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Basel Basel 250'000 90 : 10 15 mg/L Membrane Pilot scale 11.6 mg/L

filtration

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121 For sample analysis, a thermogravimetric analyzer with a top-loading balance was used (PerkinElmer,

122 TGA4000). Depending on the sample preparation, either pure solid samples or pieces of the solid-

123
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containing filters were weighed into ceramic sample pans. Sample masses were around 5-10 mg and
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124 the initial weight of the sample was registered before starting the thermogravimetric heating method.

125 As was reported by Vogel et al. (2012), sample analysis under O2 does not allow for a clear
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126 differentiation between PAC and background signals. Therefore, a preceding heating step under N2
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127 atmosphere was inserted, for selectively removing the background matrix prior to oxidation (Table 2).

128 The resulting two-stage method was compared to the conventional approach during method
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129 development, and was then applied for sample analysis during the method application stage.
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130
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131 Table 2: Temperature programs of the TGA heating methods

O2 method N2/O2 method

Step Temperature Atmosphere Step Temperature Atmosphere

Heat from 30 °C to Heat from 30 °C to 350 °C

1 20 mL/min oxygen 1 20 mL/min nitrogen
900 °C with 5 °C/min with 5 °C/min

Constant at 350 °C for

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2 Cool down to 30 °C 20 mL/min oxygen 2 20 mL/min nitrogen
300 min

3 Cool down to 30 °C 20 mL/min nitrogen

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Constant at 30 °C for
4 20 mL/min oxygen
300 min

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Heat from 30 °C to 900 °C
5 20 mL/min oxygen
with 5 °C/min

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6 Cool down to 30 °C 20 mL/min oxygen
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132 The sample weight msample and temperature T were digitally logged during the whole TGA

133 measurement and were then analyzed with the TGA software (PerkinElmer, Pyris Software, version
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134 2009). For method development purposes, the sample degradation was assessed using both the curve

135 msample vs. temperature and its time-derivative ṁsample vs. temperature, in order to compare both
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136 options. During method application, the samples were analyzed using the derivative curve.
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137 Calculation of the PAC content of a sample

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138 In order to quantitatively assess the PAC content of a sample, the curve ṁsample vs. time during

139 combined N2 and O2 treatment was used. The mass loss was calculated by integration of the clearly
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140 identifiable mass decrease peaks in the specific time interval. A dimensionless variable XTGA was then
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141 defined as an indicator for the sample's PAC fraction:

mPAC
XTGA = (1)
mPAC + mMatrix, O2 + mMatrix, N2

142 with mPAC being the mass decrease caused by PAC oxidation, while mMatrix, O2 and mMatrix, N2 are the

143 background mass decreases under O2 and N2, respectively. While the pyrolytic mass decrease is

144 entirely caused by background matrix:

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mMatrix, N2 = mN2 , (2)

145 the oxidative mass decrease is composed of both activated carbon oxidation and the oxidation of

146 background matrix (Figure 4):

mPAC + mMatrix, O2 = mO2 . (3)

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147 If

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mMatrix, O2
FMatrix = (4)
mMatrix, N2

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148 is the known ratio of oxidative and pyrolytic decomposition of background matrix and with

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mO2
FTGA = (5)
mO2 + mN2
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149 being a quantitative variable that can be obtained from the TGA curve analysis, the sample's PAC
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150 content can be expressed by inserting (2)-(5) into (1), which yields the linear equation:
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XTGA = 1+FMatrix  · FTGA - FMatrix . (6)

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151 On the other hand, with regard to the sample preparation, the sample's theoretical PAC content XSample

152 can be calculated as:

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CPAC · V
Xsample = (7)
mtot
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153 with CPAC being the concentration of powdered activated carbon in the water sample, V the filtrated

154 water volume and mtot the mass of solids separated by filtration. Based on a mass balance, it is

155 postulated that the TGA parameter XTGA correlates with the PAC content Xsample in a water sample:

Xsample = XTGA · FDegr , (8)

156 where FDegr is a measure for the degree of sample degradation during TGA. Hence, by inserting (6) and

157 (7) into (8), a water sample's PAC concentration can be calculated from a TGA curve as:

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FPAC · mtot
CPAC = · 1+FMatrix  · FTGA - FMatrix  (9)
V

158 The values for FDegr and FMatrix were obtained by measuring several samples of known composition, as

159 described in the results and discussion section.

160 Method application

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161 In the second stage of this study, wastewater samples from three Swiss WWTPs were analyzed in

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162 triplicates using TGA and comparative methods (Figure 1). All of these plants comprise a mechanical

163 pre-treatment, a biological sludge treatment and a secondary clarification followed by a PAC

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164 adsorption step. The PAC processes of these plants mainly differ in their volume flow capacity, the

165 origin of the treated wastewater and the method used for PAC separation (Table 1). The PAC dosage

166 was at 12-15 mg/L in all cases.

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167 Several alternative techniques were applied in order to assess the suspended solids content of
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168 wastewater samples and to validate and compare the TGA method developed in this study. Turbidity

169 measurements were performed in glass vials with a portable turbidimeter (WTW, Turb 355 IR/T) and
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170 the concentration of particles (>1 µm) was measured with an online particle counter (PAMAS,
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171 OLS50P). The amount of total suspended solids was determined according to DIN 38 409-2 using

172 cellulose nitrate filters (Macherey-Nagel, PORA NC) and a precision scale (Mettler Toledo, XS 205).
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173 Additionally, the filter color after filtration and drying was visually compared to reference filters, as

174 proposed by Metzger et al. (2011).

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175
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176
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177 Figure 1: Flow schemes of the PAC processes on WWTPs Ergolz 1 (A), Bachwis (B) and Basel (C)
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178 with sampling points (grey)

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179 Results and Discussion

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180 Qualitative evaluation of TGA curves

181 The TGA with a heating step in oxygen atmosphere showed a characteristic curve that is in accordance
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182 with the results of previous studies (Vu, et al., 2012, Otero, et al., 2008). The behavior of a sample
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183 exposed to a TGA heating method is characterized by decreases in sample mass msample, which each

184 correspond to a peak of the mass loss rate ṁsample (Figure 2). In many cases, the sample mass decreases

185 slightly during the first minutes of measurement at temperatures lower than 150 °C. This effect is

186 related to residual moisture in the filter and can be clearly differentiated from any other mass

187 decreases at higher temperatures. A significant decrease is observed in the temperature range 200 °C -

188 400 °C. This can be explained by the volatilization and subsequent oxidation of wastewater

189 background matrix. Wastewater background matrix consists of carbohydrates, proteins and fatty acids
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190 which are characterized by a high fraction of volatiles. Thermal treatment results in a decomposition

191 of macromolecules into smaller volatile molecules (Basu, 2010). Evaporation of these molecules is

192 detected as a mass loss in the TGA curve. Another sharp mass decrease at 400 °C - 700 °C is caused

193 by the oxidation of powdered activated carbon. Activated carbon consists of a network of carbon rings

194 and contains negligible amounts of volatiles, thus oxidation reactions are governed by solid-gas

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195 reactions (Marsh and Rodríguez-Reinoso, 2006). At temperatures below 500 °C, the reaction rate is

196 kinetically controlled by a high activation energy (Luo and Jean-Charles, 2006). It is assumed that, at

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197 600-700 °C, reaction kinetics increase rapidly and are then controlled by in-pore oxygen and carbon

198 monoxide diffusion which, however, increases at progressing burn-off. The specific temperature of

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199 this mass decrease is found to vary depending on the sample composition, but could be clearly

200 identified in all cases. Finally, at temperatures above 700 °C, the sample mass reaches a nearly

201
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constant value which corresponds to the ash content of the sample. In the case of a constant
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202 temperature gradient, the temperature axis can be directly correlated to a time axis. In order to take

203 into account mass transport and reaction kinetics and allow for the evaluation of the mass loss rate, the
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204 time axis is of particular interest for analyzing a TGA curve.

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205
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206 Figure 2: Typical TGA curves of samples with varying composition (centrifuged, O2 method)

207 Methods for sample preparation

208 In the studies performed by Vu et al. (2012) and Vogel (2013), the solids were concentrated from

209 sewage sludge samples by evaporation. However, those samples contained around 10 g/L solid matter,

210 while in the here presented study, the solids content of the water samples was always below 0.1 g/L. In

211 preliminary experiments, it was found that vaporization does not allow for the complete recovery and
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212 mass balance of solid matter in this concentration range. Thus, two alternative methods were tested for

213 sample preparation, namely centrifugation and filtration, and were then compared with regard to their

214 practical feasibility and reproducibility. The loss of solids during the decanting, centrifugation and

215 drying procedure was found to be considerable: On average, the centrifugation of 2.2 L water yielded

216 the same solid sample mass as the filtration of 1.0 L. This incomplete solid separation increases the

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217 workload and calls for an additional, reliable determination of the sample's solids content. In contrast,

218 in the case of filtration, a complete removal of solids was achieved and the separated solid mass

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219 correlated well with the TSS, making an additional determination redundant. Furthermore, it was

220 observed that the solid separation by centrifugation is not always consistent for biological matrix and

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221 activated carbon. By qualitatively comparing the TGA curves obtained with these methods, it was

222 found that a better reproducibility could be achieved if the water samples were filtrated rather than

223
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centrifuged (Figure 3). If the water sample is filtrated, the solid sample partly consists of filter
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224 material, which reduces the degree of sample decomposition and causes a slight mass decrease above

225 700 °C. However, at this temperature, the mass decrease attributed to activated carbon and biological
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226 background matrix is already completed. This means that the oxidation of filter material can be clearly
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227 differentiated from the sample oxidation and that the presence of the filter during analysis does not
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228 affect the analyzability of the TGA curve.

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230 Figure 3: TGA curves of triplicates prepared by centrifugation (A) and filtration (B) (2 mg/L PAC, O2

231 method)

232 TGA heating methods

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233 For the analysis of solid samples, two different TGA methods were applied. The O2 method, in which

234 the sample is exposed to only one heating step in oxygen atmosphere, was found to be relatively

235 robust. In the corresponding TGA curves, all mass decreases related to water, background matrix and

236 activated carbon could be identified. Nevertheless, due to overlapping effects, it was impossible to

237 specifically and quantitatively determine the PAC fraction. For this reason, the N2/O2 method was

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238 developed, which leads to partial pyrolysis in a first step under N2. Due to its chemical composition,

239 PAC is not expected to decompose at the applied conditions (Marsh and Rodríguez-Reinoso, 2006),

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240 which was verified by the present experiments (Figure 4 A). The mass decrease caused by pyrolytic

241 reactions can therefore be selectively attributed to the decomposition of water background matrix. In

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242 contrast, the simultaneous oxidation of biomass and PAC results in an overlapping mass decrease

243 under O2 atmosphere (Figure 4 B). Still, the mass decrease in this second heating step can be used as a

244
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measure for the amount of oxidable solids in the TGA, including both background matrix and PAC.
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245 This allows to differentiate between the solids extracted from the original water sample and the filter

246 material, which does not degrade under these conditions. If both heating steps are taken into account,
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247 the combined N2/O2 heating method allows for the identification of filter material, background matrix
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248 and PAC, and for the quantification of the sample's composition by simply determining the pyrolytic
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249 and oxidative mass decreases during TGA.

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251 Figure 4: TGA curves of samples analyzed with the combined method under N2 (A) and O2 (B)

252 (filtrated)

253 Quantitative assessment of mass fractions

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254 As shown in the materials and methods section, based on a TGA curve, the PAC content of a water

255 sample can be calculated as:

FPAC · mtot
CPAC = · 1+FMatrix  · FTGA - FMatrix  (9)
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256 with FTGA being obtained from the TGA curve analysis, mtot and V being parameters of the sample

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257 preparation step and FDegr and FMatrix being dimensionless characteristics of PAC and background

258 matrix, respectively. The values obtained from several samples of known composition were found to

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259 correlate with a linear trendline (n=19). If this trendline is assumed to satisfy equation (9) with

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260 mtot ∙ 1+ FMatrix  being the slope and − m ∙ F being the Y-intercept, it is possible to

261 calculate the values (Figure 5):

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FMatrix = 0.55 and
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263 FDegr = 0.60 .
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264 In order to validate the developed method, CPAC was calculated for samples with known PAC

265 concentrations between 0 and 2 mg/L and compared to the actual PAC dosage (Figure 6). The method
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266 repeatability was assessed on the basis of the standard deviations of triplicate measurements at each
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267 concentration. The average standard deviation was ±0.04 mg/L, which corresponds to 10% of the

268 actual concentration, and it was observed that the relative deviation decreased with increasing PAC
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269 concentration. Taking the background noise into account, the method's detection limit was estimated

to be around 0.1 mg/L. The average recovery of PAC was 83.8%, which indicates a satisfactory
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271 method accuracy. However, the accuracy was notably influenced by the sample preparation step,
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272 where the complete and reproducible separation of solids is the determining factor. It is expected that

273 the increase of the sample volume and the optimal selection and conditioning of the filter could

274 increase the PAC recovery in the sample preparation step in particular. The calculation of FTGA from

275 TGA peak areas was found to be relatively robust, even in the case of slight variations in TGA curves

276 due to sample inhomogeneities. The calculations based on the fitted values for FMatrix and FDegr

277 correlated well with the known sample composition (R2=0.959) and showed a Parson correlation

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278 coefficient of 0.98, indicating a good method linearity. However, it should be noted that the fitted

279 parameters could vary for effluents from different WWTPs, e.g. depending on the nitrogen content of

280 the sewage sludge (Gómez-Rico, et al., 2005). It is thus recommended for future measurements on

281 different WWTPs to first determine FMatrix and FDegr before applying the calculation method to TGA

282 curves.

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283

284 Figure 5: FTGA and Xsample obtained from samples of known composition, fitted to a linear correlation
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285
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286 Figure 6: PAC detection by TGA (CPAC measured) in samples that contained a known amount of PAC

287 (CPAC dosed)

288 Method application for PAC retention assessment

289 The TGA method was applied to assess and compare the PAC retention of four different separation

290 technologies (Figure 1). The results give an outlook on the targeted application of the developed

291 method and on the range of PAC concentrations in WWTP effluents. The PAC removal of the final
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292 separation stage was above 99% in all cases, resulting in effluent concentrations close to the detection

293 limit (Figure 7).

294 On WWTP Ergolz 1, two process options for PAC removal were compared. It was found that by

295 applying flotation, the PAC concentration can only be reduced to 0.4 mg/L. Thus, in this case, an

296 additional final filtration step is necessary to achieve the same effluent quality as by deep bed

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297 filtration. The PAC removal was above 99% for both process options (Figure 7 A).

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298 On WWTP Bachwis, the PAC separated in the sedimentation step is fed back into the biological

299 treatment and discharged together with the waste activated sludge (Figure 1). However, it was found

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300 that some PAC residues pass through the secondary clarifier, resulting in a PAC concentration of 0.5

301 mg/L in the secondary effluent. As on WWTP Ergolz 1, the effluent still contains PAC in

302
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concentrations close to the detection limit, corresponding to a PAC removal of above 99% (Figure 7
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303 B).
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304 The secondary effluent on WWTP Basel is first treated in a pilot scale ozonation unit before entering

305 the PAC stage. In the adsorption reactor, a PAC concentration of 17.5 mg/L was measured, which is
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306 nearly consistent with the targeted PAC dosage of 15 mg/L. The ultrafiltration unit ensured a full PAC
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307 removal to values below the limit of detection (Figure 7 C).

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308

309 Figure 7: Characterisation of wastewater samples taken from the WWTPs Ergolz 1 (A), Bachwis (B)

310 and Basel (C) by N2/O2 TGA (n=3)

311 Method evaluation and comparison

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312 In order to compare the developed TGA method to reference methods, the wastewater samples from

313 several WWTPs with PAC treatment were analyzed not only by TGA, but also by particle counting,

314 turbidity and TSS measurements, as well as visually after Metzger, et al. (2011) (Figure 8).

315 The visual analysis of laboratory filters showed no blackness at all, which corresponds to the absence

316 of PAC according to Metzger, et al. (2011). This was the case for all sampled PAC stage effluents

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317 (Figure 8), indicating that the visual method is not sensitive enough to detect PAC traces in

318 wastewater. The results are considered semi-quantitative and of limited accuracy, so that this method

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319 is not recommended for PAC detection in WWTP effluents.

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320 The TSS removal of the studied processes was between 76% and 91% and always lower than the

321 corresponding PAC removals (Figure 7, Figure 8). On WWTP Ergolz I, the TSS and turbidity

322
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measurements qualitatively confirmed that the flotation and subsequent surface filtration yields a
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323 similar effluent quality as the deep bed filtration with direct PAC dosage. However, only 2% of the

324 solids leaking through the filter were attributed to PAC (Figure 8A). In the deep bed filtration of
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325 WWTP Bachwis, comparable reductions of TSS (72 %) and of turbidity (67 %) were observed with
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326 regard to the sedimentation effluent, while the TGA method revealed a PAC retention by almost 95%

327 (Figure 7, Figure 8B). As the filtration step on WWTP Basel was realized by ultrafiltration the TSS
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328 concentration of 3.8 mg/L in the filtration effluent was surprisingly high (Figure 8C). However, no

329 PAC was detected on the permeate side of the membrane unit. In all separation processes, the
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330 percentage removal value of TSS was found to be lower than that of PAC. This shows clearly that the
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331 determination of standard parameters such as TSS or turbidity is not sufficient to assess PAC leakage
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332 into WWTP effluent. The main disadvantage of the reference methods is that they represent the total

333 concentration of solids in the water without differentiating between PAC and background matrix.

334 However, combining TGA and TSS results reveals that the leaking solids on WWTP Ergolz 1 and on

335 WWTP Bachwis are partially composed of PAC, while the effluent of the pilot plant on WWTP Basel

336 contains no PAC at all. This example shows very well that conventional parameters are no suitable

337 indicators for PAC in wastewater, and that the PAC specificity of the developed TGA method is an

338 important contribution to assessing the PAC retention of filtration processes.

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339 TGA curves obtained from samples of different WWTPs showed the same characteristic behavior and

340 intervals of mass losses, indicating that the TGA measurement was not affected by the origin or the

341 characteristics of the sampled wastewater or the applied PAC product. However, variations of FDegr

342 and FMatrix may explain the slightly higher standard deviations in Bachwis and Basel compared to

343 WWTP Ergolz I, the water of which was used for method development.

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344
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345 Figure 8: Characterisation of wastewater samples taken from the WWTPs Ergolz 1 (A), Bachwis (B)

346 and Basel (C) by different methods (n=3)

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347 From a practical point of view, the developed method was found to be well workable under laboratory
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348 conditions. It takes around 18 hours to carry out one measurement, which is mainly due to filter drying
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349 (minimum 12 hours, e.g. over night) and TGA analysis (5.5 hours). However, laboratory staff is only

350 required for sample filtration, filter weighing and TGA curve analysis, which add up to an effective

351 workload of 15-20 minutes. In the development stage, the proposed method required visual peak

352 interpretation which, however, most likely can be automized once more data sets are available.

353

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354

355 Conclusion

356 In the present study, a method was developed to quantitatively measure the PAC content in wastewater

357 by using thermogravimetric analysis (TGA). Prior to TGA, the samples were filtered using a quartz

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358 filter with a temperature stability of up to 950 °C, so that the separated solids could be analyzed by

359 TGA without the measurement being affected by the presence of the filter. Based on the conducted

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360 laboratory experiments, a mathematical correlation was found for the calculation of a sample's PAC

361 content from the corresponding TGA curve. In comparison to alternative methods, such as measuring

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362 turbidity, suspended solids or particle concentration, the developed method combining vacuum

363 filtration and TGA is able to selectively differentiate between PAC and background particle matrix,

364
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which allows for assessing the retention of processes with regard to PAC in particular. Different
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365 separation processes were shown to achieve PAC removals between 95% and 100%. The TGA

366 method yields quantitative results with a detection limit around 0.1 mg PAC/L. One measurement
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367 requires small sample volumes around 0.5 L and an effective workload of less than 20 minutes. Given
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368 the incomplex sample preparation and relatively low TGA system prices, it seems manageable to

369 include the analysis of PAC concentration by the proposed method in the regular monitoring routine of
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370 WWTPs equipped with PAC stages for advanced treatment.

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371 Acknowledgement

372 The authors express their gratitude towards the Swiss Federal Office for the Environment for funding
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373 this study under contract number UTF 450.06.13/ IDM 2004.2423.391. Special thanks go to Felix
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374 Thiele, Antje Langbein and Jan Stemann for their helpful collaboration and valuable advice.

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Quantitative detection of powdered activated carbon in

wastewater treatment plant effluent by thermogravimetric

analysis (TGA)

Therese Krahnstövera, Julia Plattnera, Thomas Wintgensa*

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Highlights:

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- TGA is a suitable technique for differentiating PAC from biological background matrix.
- Temperature stable quartz filters were found suitable for sample preparation and TGA.

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- TGA accuracy was improved by using a heating method consisting of N2 and O2 atmospheres.
- A correlation was found to calculate a sample's PAC content based on its TGA curve.
- A detection limit below 0.1 mg PAC/L was reached with sample volumes as low as 0.5 L.

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