Waste Management 102 (2020) 371–379

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Peracetic acid for conditioning of municipal wastewater sludge:

Hygienization, odor control, and fertilizing properties
Tero Luukkonen a,⇑, Hanna Prokkola b, Simo O. Pehkonen c
a
Fibre and Particle Engineering Research Unit, University of Oulu, Finland
b
Research Unit of Sustainable Chemistry, University of Oulu, Finland
c
H2OPrima, Vihurintie 11, FI-70780 Kuopio, Finland

a r t i c l e i n f o a b s t r a c t

Article history: Peracetic acid (PAA) is an environmentally friendly disinfectant and oxidizer used in several water and
Received 10 August 2019 wastewater treatment applications. In the present study, PAA was utilized for the conditioning of munic-
Revised 5 October 2019 ipal wastewater sludge before thickening and dewatering. It was shown that PAA can effectively prevent
Accepted 4 November 2019
odor formation (i.e., H2S and NH3) and provide hygienization (using E. coli and Salmonella as indicators).
Available online 12 November 2019
Phytotoxicity can be prevented by controlling the amount PAA-conditioned sludge that is mixed in the
soil to be fertilized. The required PAA dose for hygienization was relatively high (480 mg 100% PAA
Keywords:
per L sludge) but the results indicated that other sludge stabilization processes are not necessarily
Biosolids
Disinfection
required. Therefore, the proposed process involving PAA could be feasible in cases where limited land
Fertilizer area is available for sludge processing or quick conditioning of sludge is required.
Peracetic acid Ó 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
Odor control (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction it was recently shown that the repeated amendment of agricultural

soils with sewage sludge for 15 years did not accumulate Cu, Cr, Ni,
Municipal wastewater sludge generation in the EU is more than Pb, Zn, Cd, or Hg over the legislative limit values but some increase
10 Mt as dry matter annually (Bianchini et al., 2016). Biological in unregulated metal(loid)s (As, Co, Sb, Ag, Se, and Mn) was
sewage sludge, which is also known as biosolids after stabilizing observed (Marguí et al., 2016). Degradation of 72 different pharma-
treatment steps (Collivignarelli et al., 2019a), contains significant ceuticals and personal care products in sludge-soil mixtures
nutrient resources: typically approximately 3.3 and 2.3% nitrogen showed that their half-lifes varied from approximately 0.5 to
and phosphorus (of dry solids), respectively (Tchobanoglous, 10 years, while some (such as diphenhydramine, fluoxetine, thi-
Burton and Stensel, 2004). Especially phosphorus utilization from abendazole and triclocarban) showed no degradation over the
sludge is beneficial as phosphate rock deposits are depleting glob- three years observation period (Walters et al., 2010). However,
ally, and thus it has been listed as a critical raw material by the EU the accumulation of micropollutants or their transformation prod-
(Commission’s Communication, 2017). Sludge contains also other ucts (total 141) to vegetables was shown to be low (Sabourin et al.,
organic matter (Wijesekara et al., 2017) that would be beneficial 2012). Nevertheless, even though there is no clear evidence about
for soils since there has been a decline in the soil carbon content the harmfulness of the sludge land-application, the low public
(Heikkinen et al., 2013). Consequently, the utilization of sludge acceptance of sludge utilization can become an obstacle (Oberg
as a fertilizer or soil improver is important, and thus it is encour- (Öberg) and Mason-Renton, 2018).
aged by the Sewage Sludge Directive in the EU (Council Directive Typically, the sludge treatment process consists of thickening,
86/278/EEC, 1986). conditioning, dewatering, and stabilization stages, for instance,
Concentration of seven metals (Cu, Cr, Ni, Pb, Zn, Cd, and Hg) in but the order of the aforementioned processes may vary. Thicken-
the sludge to be utilized as fertilizer or soil conditioner are ing and dewatering are used for the sludge volume reduction,
controlled by the EU legislation (Council Directive 86/278/EEC, whereas stabilization aims for the reduction of pathogen numbers,
1986). However, there have been increasing concerns about odor elimination, and putrefaction inhibition. Possible options for
other potentially toxic elements, organic micropollutants, and stabilization are, for instance, alkaline treatment (i.e., increase of
microplastics in sludge. Regarding the potentially toxic elements, pH to 12 or higher), anaerobic or aerobic digestion, or composting
(Tchobanoglous, Burton and Stensel, 2004). In addition, some
chemical conditioning methods can be used: for instance, treat-
⇑ Corresponding author.
ment with sulfuric acid and hydrogen peroxide (at pH of 3–5) to
E-mail address: [email protected] (T. Luukkonen).

https://doi.org/10.1016/j.wasman.2019.11.004
0956-053X/Ó 2019 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
372 T. Luukkonen et al. / Waste Management 102 (2020) 371–379

induce Fenton reactions with Fe2+ present in sludge (Schaum et al., 2.2. Sludge conditioning experiments
2008).
One alternative sludge conditioning chemical could be peracetic Sludge samples were homogenized with an overhead stirrer using
acid (PAA, CH3COOOH). PAA is an environmentally friendly water 500 rpm mixing speed for 30 mins. Then, commercially available PAA
and wastewater disinfectant and an oxidizer with a low tendency solution (tradename ProxitaneÒ WW-12, composition as w/w: 12%
to form harmful by-products (Domínguez Henao et al., 2018a,b). PAA, 20% hydrogen peroxide, 20% acetic acid, and 0.5–1% sulfuric acid,
It has been used at full scale or studied for the disinfection of Solvay, Finland) was dosed into 1.0 L sludge samples at 0, 60, 120, 240,
municipal wastewaters, sewer overflows, industrial effluents, pota- or 480 mg of 100% PAA/L of sludge and mixed for 15 mins (500 rpm).
ble water, ballast water, aquaculture systems, and for the oxidation The PAA doses correspond to ratios of 0, 1/2000, 1/1000, 1/500, and
of recalcitrant organic compounds in advanced oxidation processes 1/250 as kg PAA solution/kg of sludge, respectively, or approximately
(Liu et al., 2016; Luukkonen and Pehkonen, 2017). For sludge treat- 0, 1/108, 1/54, 1/27, and 1/14 as kg PAA solution/kg dry matter in
ment, the research involving PAA is relatively scarce. The inactiva- sludge, respectively. After the PAA dosing, the sludge samples were
tion of Salmonella and beef tapeworm (Taenia saginata) in sludge centrifuged (using Jouan C412 centrifuge, 2000 rpm, 5 min) to simu-
has been reported to occur at PAA doses of 250–1000 mg/L (as late thickening/dewatering. Centrifuging increased the dry matter
100% PAA) (Baldry and Fraser, 1988; Fraser, Godfree and Jones, content of the sludge from an average of 5.4 to 9.6%. Homogenized cen-
1984). PAA treatment is beneficial before anaerobic digestion, as trifuged sludge was mixed to low-nutrient soil at 1, 5, or 10 vol%. The
it can improve organic matter solubilization and sludge disintegra- low-nutriend soil was prepared by mixing 20 wt% of quartz sand and
tion leading to increased biogas production (Appels et al., 2011; 80 wt% of commercial soil product (Kekkilä Viljelyseos, Finland, which
Sun et al., 2018; Zhou et al., 2017). Furthermore, pre-oxidation of contains sphagnum peat and sand, has pH of 6.0, conductivity of
sludge with PAA decreased the sludge volume and improved dewa- 20 mS/m, water-soluble nitrogen, phosphorus, and potassium of
tering due to the degradation of extracellular polymeric substances 300, 70, and 700 mg/kg dry solids, respectively).
(Zhang et al., 2016). Sludge volume decrease with advanced chem-
ical, biological, thermal, or electrochemical techniques can have a 2.3. Analysis and calculation methods
significant impact on the sludge treatment costs (Collivignarelli
et al., 2019b). It was recently estimated that if such methods are Conductivity and pH were measured from sludge samples
applied to larger than 500,0000 population equivalent wastewater before dewatering using a Hach-Lange HQ40D multi-parameter
treatment plants in the EU, that alone could decrease sludge meter with SPC401 and PHC101 electrodes, respectively.
amount (as mass of dry matter) by approximately 25% Reduction-oxidation (redox) potential of sludge samples before
(Collivignarelli et al., 2019b). Furthermore, PAA can be applied to centrifuging was measured with an EZ-7200 multiparameter probe
treat biological foaming (also known as sludge bulking or swelling) (EZDO, Taiwan) equipped with a Pt test electrode and a Ag/AgCl
in an active sludge process (Maunuksela and McIntyre, 2000). The reference electrode. Conductivity and pH of sludge-soil mixtures
foaming is caused by the presence of filamentous bacteria or extra- were measured according to standard methods (SFS-EN 13038:
cellular polymeric substance, of which the latter was found to cor- en, 2011; SFS-EN 13037:en, 2011): measurements were conducted
relate well with the aeration/non-aeration regimes and using a sludge-soil mixture to distilled water ratio of 1:2.5 (V/V).
temperature (Collivignarelli et al., 2017). The effect of PAA on the The CO2 production of sludge-soil mixtures (containing 0, 1, 5,
prevention of foaming is caused by the oxidation of extracellular or 10 vol% of sludge treated with 0, 120, or 240 mg/L of PAA) was
polymeric substances and the destruction of flocs held together measured by placing the sample in a closed bottle, incubating at
by mycelium (Maunuksela and McIntyre, 2000). +37 °C for 24 h, and determining the gas evolution with an infrared
In the present study, PAA was used for the conditioning of analyzer (Itävaara et al., 2010). The CO2 evolution rate (mg CO2-C/g
sludge collected from primary sedimentation and activated sludge VS/d) can be calculated with Eq. (1):
process (i.e., before thickening or dewatering). After the PAA- V p  CO2  M C  t  T NTP
treatment, sludge was centrifuged in laboratory and mixed with CO2 ev olution rate ¼ ð1Þ
T  V NTP  mn  kan  VSn  tx
low-nutrient soil. The goals of the study were to: (1) find adequate
PAA dose for sludge hygienization; (2) determine the amount that where Vp = volume of the test bottle (mL), CO2 = CO2 concentration
PAA-treated sludge can be mixed with soil without causing a phy- (%/100), MC = atomic weight of carbon (12.01 g/mol), t = time (24 h),
totoxic effect (i.e., plant growth prevention); and (3) observe the TNTP = temperature at the NTP conditions (273.15 K), T = tempera-
effect of PAA-treatment on the macro nutrient levels in the ture (K), VNTP = volume of ideal gas at the NTP conditions (22.42
sludge-soil mixtures. L/mol), mn = weight of the sample (g), kan = dry weight of the sam-
ple (%/100), VSn = volatile solids in the sample (%/100), t = time from
the beginning of the measurement (h).
Biological oxygen demand (BOD) with an allylthiourea addition
2. Materials and methods
was measured using the OxiTop manometric respirometric method
under the OECD 301F standard conditions. The BOD measurements
2.1. Sludge sampling
were conducted from sludge samples before centrifuging.
Phytotoxicity (i.e., plant growth prevention) was measured
Sludge samples were collected from the Taskila (Oulu, Finland)
according to the method by Itävaara et al. (2006). In the test, 100
municipal wastewater treatment plant (WWTP) with 174 200 pop-
cress (Lepidium sativum) seeds were planted to the sludge-soil mix-
ulation equivalent capacity and approximately 50,000 m3/d dis-
tures (similar amount of sludge and PAA as with the CO2 produc-
charge. The main unit processes of the Taskila WWTP and the
tion experiment) and to a reference soil, watered, and allowed to
sludge sampling point are shown in Fig. 1. Sludge samples were
grow for 14 d. Then, seedlings were cut, counted, and weighed
collected on seven occasions during a winter season (November–
after drying at 70 °C for 1 d. The growth index (Eq. (2)) less than
January). Sludge retention time (SRT) during the sampling was
80% indicates phytotoxicity.
approximately 5 d.
Sludge treatment experiments were performed on the same day weight of seedlings in sludge  soil mixture ðgÞ
Growth index ¼  100%
as the sampling was performed. Typical properties of sludge after weight of seedlings in reference soil ðgÞ
sampling are shown in Table 1. ð2Þ
 T. Luukkonen et al. / Waste Management 102 (2020) 371–379 373

Fig. 1. Schematic presentation of the main unit processes of the Taskila wastewater treatment plant and the sludge sampling point.

Table 1 emission spectrometer (Thermo Electron IRIS Intrepid II XDL

Typical properties of the sampled sludge. Duo) according to the standard (SFS-EN ISO 11885, 2009).
Property Value Potentially toxic elements were analyzed as total concentra-
pH 6.72 ± 0.10
tions from solid samples (sludge-soil mixtures) by first dissolving
Conductivity 2390 ± 500 lS/cm the sample with a microwave-assisted acid digestion method
Redox potential 171 ± 18 mV (U.S. EPA, 2007) and then quantifying the metal(loid) concentra-
Total solids 5.4 ± 0.6% tions with an optical emission spectrometer similarly as described
Biological oxygen demand (30 d) 3500 ± 80 mg/L
above.
Temperature 8–10 °C
Total solids content of sludge samples was determined by evap-
orating at 105 °C until a constant weight was achieved.

The PAA concentration during the decomposition experiment

was measured with a pre-calibrated handheld photometer (Che- 2.4. Odor control experiment
metrics, V2000) and the K-7913 cuvettes for PAA concentration
(Chemetrics). The analysis is based on the addition of an excess Septic-condition sludge was placed in airtight glass bottles (vol-
of potassium iodide, which reacts with PAA to form iodine. Iodine ume of sludge was 200 mL). Samples were mixed well, the bottle
then oxidizes N,N-diethyl-pphenylenediamine into a pink-colored was opened, and after 10 s, gaseous H2S and NH3 were measured
species from which absorbance is determined. The method is suit- from the opening with a Dräger X-am 5000 gas detector equipped
able for the 0–5.00 mg/L PAA range and thus the samples were with H2S and NH3 sensors (DrägerSensor XXS H2S and XXS NH3
appropriately diluted before measurement using distilled water. with measuring ranges of 0–200 ppm and 0–300 ppm, respec-
The values of the first order kinetic rate law (Eq. (3)) parameters tively). Redox potential was also measured at the same time. PAA
were obtained with the non-linear regression using the Microsoft was dosed to samples with incremental increases (with 10 s effec-
Excel Solver tool (GRG nonlinear). tive mixing in a closed bottle between each dose), until zero read-
ing of H2S was reached.
C ¼ ðC 0  DÞ  ekt ð3Þ
3. Results and discussion
where C = PAA concentration at time t (mg/L), C0 = initial PAA con-
centration (mg/L), D = initial PAA demand (mg/L), k = rate constant 3.1. pH, conductivity, and redox potential of sludge and sludge-soil
(mg/(L  min)), and t = time (min). mixtures
E. coli and Salmonella were determined from the PAA-treated
sludge samples before centrifuging by applying the NMKL 125 The sludge pH decreased approximately 0.004 units per 1 mg/L
(NMKL 125, 2005) and the VIDASÒ (Bird et al., 2013) methods, of dosed PAA and, consequently, the largest applied PAA dose
respectively. (480 mg/L) decreased pH by approximately 1.7 units (Fig. 2A). As
For nutrient (NH+4, NO3 , P, Ca, K, Mg, and S) analyses, sludge-soil a comparison, in secondary or tertiary effluents, PAA has been
samples (similar amount of sludge and PAA as with the CO2 pro- reported to decrease pH by 0.02–0.03 unit per 1 mg/L PAA
duction experiment) were air-dried, passed through a 2-mm sieve, (Cavallini et al., 2013; Koivunen and Heinonen-Tanski, 2005). The
and extracted with a 0.5 M ammonium acetate and 0.5 M acetic clearly lower impact of PAA on the sludge pH could be caused by
acid solution (pH = 4.65) for 1 h using a 1:10 (V/V) sludge-soil to a higher buffering capacity, that is, ammonium, carbonate, and
solution ratio (Vuorinen and Mäkitie, 1955). NH+4 and NO 3 were volatile fatty acids (e.g., acetic, propanoic, and butyric acids) equi-
determined by using a flow injection analyser (Fiastar 5000, librium (Procházka et al., 2012). When PAA-conditioned and cen-
Foss-Tecator) according to standard methods (SFS-EN ISO 13395, trifuged sludge was mixed with soil, pH of the mixture remained
1996; SFS-EN ISO 11732, 2005). P was determined colorimetrically constant 6.2–6.3 regardless of the sludge amount (Fig. 2B).
by a molybdenum blue method with stannous chloride as the The conductivity of the sludge increased as a function of the
reducing agent. Ca, K, Mg, and S were determined with an optical PAA dose due to the introduction of hydroxyl (OH) and acetate
374 T. Luukkonen et al. / Waste Management 102 (2020) 371–379

Fig. 2. pH of (A) sludge before dewatering and (B) sludge-soil mixtures. Conductivity of (C) sludge before dewatering and (D) sludge-soil mixtures. (E) Redox potential of
sludge before dewatering.

(CH3COO) ions to the sludge (Fig. 2C). When PAA-conditioned and potential might indicate that the sludge sample becomes tem-
centrifuged sludge was mixed with soil, the conductivity of the porarily saturated with dissolved oxygen (Luukkonen et al.,
mixture increases linearly from 4 to 6 mS/cm at sludge amounts 2014). The redox potential behavior has important implications
of 0–10 vol% of soil, respectively (Fig. 2D). The sludge contains sev- for odor control. The initial redox potential (171 mV) of sludge
eral water-soluble ionic species affecting the conductivity when indicated an anoxic situation, in which the generation of odors
mixed into the soil but also the solubilization of sludge organic can take place: for instance, bacterial reduction of sulfate (SO2
4 )
matter by PAA (Zhang et al., 2016) could have contributed to the to hydrogen sulfide (HS) begins at redox potentials lower than
increased conductivity. The conductivity of soil between 2.5 and 50 mV (Boon, 1995) and mercaptans (a general structure of
10 mS/cm is classified as ‘‘high” in the Finnish recommendations R-SH, in which R = carbon chain) can also be formed (Gostelow,
for agricultural soils (Eurofins Viljavuuspalvelu Oy, 2019). When Parsons and Stuetz, 2001). The odor control potential of PAA dosing
conductivity of soil is >10 mS/cm, it can affect water balance of is discussed in the next section (see Section 3.2).
crops detrimentally and actions should be taken to decrease it
(Eurofins Viljavuuspalvelu Oy, 2019). However, it is typical that 3.2. Odor control
the conductivity of soil is temporarily high after applying a
fertilizer. Odours in wastewater or sludge are formed as a result of several
Redox potential of sludge increased steeply as PAA was dosed chemical and biochemical reactions but a general feature leading
up to 240 mg/L (Fig. 2E). The increase is a result of PAA and hydro- to the malodour formation is the development of anaerobic or
gen peroxide decomposition and a subsequent release of dissolved septic conditions (i.e., no molecular oxygen or oxidized nitrogen
oxygen. When the dose of PAA is further increased, redox potential species present) (Boon, 1995). One of the most common sources
levels off at approximately +100 mV. The stabilization of redox of odor, dihydrogen sulphide (H2S), is formed as sulfate reducing
 T. Luukkonen et al. / Waste Management 102 (2020) 371–379 375

Fig. 3. Redox potential and odor (NH3 and H2S) concentrations in air of septic
Fig. 4. E. coli and Salmonella amounts of sludge samples (before centrifuging) as a
municipal wastewater sludge as a function of the PAA dose.
function of the PAA dose. For the PAA dose 480 mg/L, the results were <10 CFU/g.

bacteria (SRB) use sulfate as an electron acceptor to form hydrogen sludge hygienization experiments, it was found that only the
sulfide (HS). At pH < 7, H2S becomes the dominant species and is largest studied dose, 480 mg/L PAA, was able to reach these tar-
easily volatelized (Park et al. 2014). get values (Fig. 4). The results are in agreement with earlier
To demonstrate the odor control with PAA in sludge condition- studies, in which the required PAA dose for Salmonella elimina-
ing, a septic sludge sample (i.e., initial redox potential  350 mV) tion in sludge has been 250–500 mg/L (Baldry and Fraser, 1988;
was studied (Fig. 3). The addition of PAA (and hydrogen peroxide in Fraser et al., 1984). The relatively high required PAA dose is
the solution) prevents the formation of H2S odors by directly oxi- explained by the protection of microbes by the presence of large
dizing HS and H2S and by supplying dissolved oxygen (i.e, amounts of suspended solids as summarized in (Luukkonen and
increasing redox potential). When pH is between 6 and 9 (as in Pehkonen, 2017). It is likely that the effective solubilization of
the present study), the oxidation of H2S and HS by hydrogen per- organic matter and the destruction of extracellular polymeric
oxide can be presented with Eq. (4) (Bonani, 1998). In the case of substances, which offer protection to microbes, occurs between
PAA, the exact reaction with H2S or HS has not been reported 50 and 100 mg/L PAA dose as indicated by a significant decrease
but it likely occurs via similar kind of direct oxidation or formation of microbes in this dosing region.
of hydroxyl and other radicals as a first step. A complete removal of
H2S emissions was observed at 24 mg/L PAA dose coinciding with
the redox potential higher than approximately 200 mV (Fig. 3), 3.4. Microbial respiration and phytotoxicity of sludge-soil mixtures
which is in agreement with earlier literature (Delgado et al., 1999).
The CO2 production and phytotoxicity of soil amended with dif-
H2 S(aq) + HS (aq) + 2H2 O2 (aq) ! zS0 (aq) + Sx Oy (aq) + aO2 (aq) + bH2 O(l) ferent amounts of PAA-treated sludge was measured to evaluate
ð4Þ (1) how much sludge could be mixed into soil without introducing
In addition, the formation of ammonia (NH3) odors were also excessive microbial activity or inhibition of plant growth and (2)
diminished as a result of PAA dosing. One possible explanation is how the PAA concentration affects microbial respiration or plant
the shift in the equilibrium of NH+4–NH3 (pKa = 9.23 at 25 °C) growth of soil-sludge mixtures.
towards the direction of ammonium (NH+4) due to the slight Conventionally, the CO2 production test is used as an indication
decrease of pH (see Fig. 2A) according to Eq. (5). of the compost maturity (i.e., nontoxicity and the release of nutri-
ents) as it measures the microbial respiration, and thus, indirectly,
NH4 þ (aq) $ NH3 (aq) + Hþ (aq) ð5Þ the availability of easily biodegradable carbon sources (Itävaara
et al., 2010). A CO2 production value less than 3 mg CO2-C/g VS/d
However, PAA does not react directly with ammonium (Fraser (VS = volatile solids) indicates sufficiently low microbial respira-
et al., 1984), which was also confirmed in the present study (see tion (Itävaara et al., 2010). Based on the results, sludge amounts
supporting information). However, it has been reported that a rel- more than 1 vol% cause clearly too high CO2 production values
atively slow reaction between aqueous ammonia and OH radicals when using a constant PAA dose of 120 mg/L (Fig. 5A). This is
is possible (Huang et al., 2008). PAA and hydrogen peroxide can due to the organic matter present in raw sludge. Moreover, the
generate OH radicals in the sludge matrix as there are transition CO2 production of sludge samples appears to be independent of
metal catalysts present. Therefore, the observed ammonia odor the applied PAA dose in the range of 0–240 mg/L (Fig. 5A). This is
abadement is likely a combination of the aforementioned two an expected result since PAA is not usually able to decompose
effects. organic matter present in wastewaters into CO2 but in fact
increases total organic carbon (TOC) or chemical oxygen demand
3.3. Hygienization of sludge (COD) due to the introduction of acetic acid (Luukkonen et al.,
2014; Lazarova et al., 1998; Cavallini et al., 2013). The effect of dif-
One of the most important goals in municipal wastewater ferent PAA doses (0–240 mg/L) on microbial respiration of sludge
sludge stabilization is to decrease the amount of pathogenic samples (before centrifuging and mixing into soil) was confirmed
microbes to safe levels. Conventional indicators for sludge by using another analysis method: biological oxygen demand
microbial quality are E. coli and Salmonella. In Finland, for (see supporting information, Fig. S2). In this test, sludge samples
sludge to be used as a fertilizer, their levels should be 1000 treated with 0–240 mg/L of PAA behaved identically in terms of
colony forming unit (CFU) per g (or 100 if used in green- oxygen consumption for the first approximately 100 h followed
houses) for E. coli and not detectable per 25 g for Salmonella by a slight variation between samples which is, however, likely
(Ministry of Agriculture and Forestry of Finland, 2011). In the due to inhomogeneity of samples.
376 T. Luukkonen et al. / Waste Management 102 (2020) 371–379

Fig. 5. (A) CO2 production and (B) phytotoxicity of sludge-soil mixtures as a function of conditioned sludge amount in soils using a constant 120 mg/L PAA dose and as a
function of PAA dose using a constant sludge amount of 1%.

Phytotoxicity is caused by the presence of organic or inorganic

toxic compounds in soil hindering the plant growth (Itävaara et al.,
2010). Typically phytotoxicity decreases as a result of sludge stabi-
lization processes, such as aerated composting, resulting the
decomposition of some of the toxic organic compounds (Itävaara
et al., 2010). The phytotoxicity test results (Fig. 5B) indicated that
up to approximately 3 vol% of sludge treated with 120 mg/L of PAA
could be added without inhibiting plant growth. It was observed
that phytotoxicity decreased slightly when the PAA dose was
increased (up to 240 mg/L, keeping sludge amount constant 1 vol
%). These effects were likely mainly caused by organic compounds
of the sludge (the amount of potentially toxic metal(loid)s were
found to be low, see supporting information, Table S1), which were
increasingly oxidized as the PAA dose was increased.

3.5. Decomposition of PAA in sludge

Fig. 6. Decomposition of PAA (C0  100 mg/L) in the sludge matrix modelled with
The decomposition of PAA in the sludge matrix closely followed the modified first order kinetic model taking into account the initial PAA
the modified first-order kinetic rate law taking into account the consumption. Dashed lines correspond to 95% confidence intervals of fitting the
model to the experimental data.
initial PAA consumption (Fig. 6). The obtained rate constant
(k = 0.0181 1/min) was approximately in the same range as with
primary, secondary, or tertiary wastewaters (Falsanisi et al.,
the half-life of PAA is short in the studied sludge matrix with a
2006; Dell’Erba et al., 2004; Luukkonen et al., 2015). However,
large amount of suspended solids (5.4%): half-life was approxi-
the observed initial decomposition (D = 33.4 mg/L) was relatively
mately 15 min in this case.
high although a value of D = 19.4 mg/L has been reported earlier
for primary wastewater (Falsanisi et al., 2006). The initial con-
sumption reflects the instantaneous reactions taking place when 3.6. Macronutrient and potentially toxic element amounts in sludge-
PAA is dosed: for instance, the oxidation of reduced species such soil mixtures
as sulfides (see section 3.2). The values of rate constant and initial
consumption increase as the suspended solids and organic matter Macronutrient (N, P, K, Ca, Mg, and S) amounts in sludge-soil
amounts increase (Domínguez Henao et al., 2018a,b). Therefore, mixtures using different sludge amounts (1, 5, and 10 vol%) and
 T. Luukkonen et al. / Waste Management 102 (2020) 371–379 377

Fig. 7. Nutrient amounts in sludge-soil mixtures containing different amounts of sludge as a function of the PAA dose. The dashed horizontal lines refer to the reference
sample with 0% of sludge and 0 mg/L PAA.

PAA doses (0, 120, and 240 mg/L) are shown in Fig. 7. The nutrient The amount of nitrogen (i.e., NH+4 and NO 3 ) correlated poorly
amounts are reported as mg/L in the extraction solutions used in with the added sludge amount (Fig. 7A and B) but there is a sub-
the test (see Section 2.3 for details) and are compared to the stantial increase compared to a reference sample (with 0% of
Finnish recommendations (Eurofins Viljavuuspalvelu Oy, 2019; sludge and 0 mg/L PAA). Moreover, the amount of NH+4 varied con-
The Finnish Association of Landscape Industries, 2019) in the siderably when applying different PAA concentrations even though
below discussion. The Finnish nutrient level recommendations NH+4 does not react with PAA (Fraser et al., 1984). Ammonium
for agricultural soils have been developed based on the data (NH+4), as a readily adsorbable species, might have been partially
collected in the course of over 50 years (Keskinen et al., 2016). associated with particulates rather than being present as a
378 T. Luukkonen et al. / Waste Management 102 (2020) 371–379

dissolved species resulting variation when dosing sludge to soil. PAA-conditioned sludge that could be mixed with soil were 3
The weight ratio of NO3-N/NH4-N was 0.1–0.6 (should be prefer- and 1 vol% in terms of phytotoxicity and CO2 production values,
ably greater than 1) in the present study indicating a low level of respectively. The macronutrient (N, P, Ca, K, Mg, S) amounts or
biodegradation (Itävaara et al., 2010). Some of the phytotoxicity availability in soil were not detrimentally affected by PAA. The
observed in Fig. 5B could have been caused by ammonium chemical cost of PAA treatment was 74–81 €/t of dry solids, which
(Itävaara et al., 2010). Nevertheless, the observed soluble nitrogen can be competitive against other conventional treatment options.
(i.e., NH+4 and NO3 ) amounts (14–53 mg/L) are within the Finnish On the basis of this study, PAA could be considered as a sludge
recommendation (15–100 mg/L) for plant substrates (The Finnish treatment option in locations with a limited space (since no other
Association of Landscape Industries, 2019). conditioning methods might be required) and requirement for
Phosphorus amount increases in a consistent manner with dif- quick treatment. Furthermore, the promising odor prevention
ferent PAA doses as a function of sludge amount (Fig. 7C). The mea- results indicate that PAA-based treatment could be feasible for
sured phosphorus amounts are higher than in the reference soil wastewater treatment plants located near residential areas.
without sludge and PAA (dashed line in Fig. 7C). The observed val-
ues (16–35 mg/L) are largely within the recommendations for Declaration of Competing Interest
plant substrate (5–30 mg/L) (The Finnish Association of Landscape
Industries, 2019) and agricultural soil (less than 20–35 mg/L The authors declared that there is no conflict of interest.
depending on the soil type) (Eurofins Viljavuuspalvelu Oy, 2019).
The amounts of Ca, K, Mg, and S appear to be unaffected by the Acknowledgements
increasing sludge dose (Fig. 7D–G). Their amounts are approxi-
mately similar as the reference sample without sludge and PAA, Mr. Teuvo Kekko and the whole staff of the former PAC-Solution
that is, the studied sludge sample appears to be a poor source for Oy are acknowledged for providing this interesting research topic
these nutrients. Their amounts are within the ‘‘good” or ‘‘high” lim- and co-operation during the study. The authors wish to also thank
its (depending on the soil type) according to the Finnish recom- M.Sc. Ville Kaikkonen for aiding in some of the laboratory experi-
mendations (Eurofins Viljavuuspalvelu Oy, 2019). ments. This work was supported by the Academy of Finland (grant
The concentration of potentially toxic elements (As, Ba, Cd, Co, #315103).
Cr, Cu, Mo, Ni, Pb, Hg, Sb, V, and Zn) were determined from the
sludge-soil mixtures with 1% of sludge treated with 0, 120, or Appendix A. Supplementary material
240 mg/L of PAA and from soil without sludge (see Supporting
information, Table S1). The mixing of 1 vol% of sludge to soil did Supplementary data to this article can be found online at
not increase significantly the levels of the studied metal(loid)s https://doi.org/10.1016/j.wasman.2019.11.004.
compared to the background (i.e., soil without sludge). Further-
more, there are no significant changes in the metal(loid) amounts
when PAA dosing is increased from 0 to 240 mg/L. However, since
PAA is known to destroy extracellular polymeric substances and References
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