Bioresource Technology: Sciencedirect
Bioresource Technology: Sciencedirect
Bioresource Technology: Sciencedirect
Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
G R A P H I C A L A B S T R A C T
A R T I C LE I N FO A B S T R A C T
Keywords: The traceability of conventional pollutants and 10 organic microcontaminants in the sludge line of a wastewater
Anaerobic digestion treatment plant (WWTP) was evaluated. The application of thermal hydrolysis (TH) as pre-treatment to anae-
Organic micropollutants robic digestion (AD) or as inter-treatment (between two AD stages) was considered and compared with the
Sewage sludge conventional digestion scheme. TH scenarios reduced the mass flow rate of biosolids (40–60%) as well as the
Traceability
ratio of solids (50–100%), organic matter (5–26%) and nitrogen (8–13%) destined to biosolids. Micropollutants
Thermal hydrolysis
showed a strong tendency to accumulate in the solid phase (more than 90% were sorbed) in spite of thermal and
dewatering processes, but TH scenarios exhibited greater removal efficiency (80%) in comparison to conven-
tional AD (50%), reducing the ratio of micropollutants destined to biosolids from a conventional 48% to 7–8%.
These findings reveal that TH could increase the value of biosolids from sewage sludge treatment because of
greater removal of pollutants and dewaterability.
1. Introduction and about 60% of the nitrogen. Apart from these conventional con-
taminants, emerging micropollutants have become the new challenge of
In WWTP, water is treated by physico-chemical and biological WWTP for their persistence, bioaccumulation and biological activity,
processes to remove undesirable pollutants to the water bodies, and and previous studies exhibit that the sludge line is the end point of most
sewage sludge is the resulting stream where the pollution ends; sludge of them (Gonzalez-Gil et al., 2016; Narumiya et al., 2013). The different
catches more than 90% of the solids, over 60% of the organic matter physical, chemical and biological unitary processes applied during
⁎
Corresponding author.
E-mail address: [email protected] (S.I. Pérez-Elvira).
https://doi.org/10.1016/j.biortech.2020.123028
Received 30 December 2019; Received in revised form 12 February 2020; Accepted 14 February 2020
Available online 15 February 2020
0960-8524/ © 2020 Elsevier Ltd. All rights reserved.
I. Díaz, et al. Bioresource Technology 305 (2020) 123028
sewage sludge treatment impact the fate of the different types of pol- sludge line, neither on the effect of the implementation of a thermal
lutants and the regulated destiny of the final biosolids. Among the unit (pre-, post- or inter-treatment) on the pollutants fractioning and
sludge treatment and valorisation alternatives, sewage sludge lines with fate to the final biosolids. When TH is implemented, whether before,
a core AD process followed by dehydration are extensively applied in after or between two AD stages, distribution of pollutants among phases
WWTP because of several benefits regarding organic matter removal, and streams is altered. In this sense, TH pre-treatment revealed a larger
biosolids stabilization, pathogens deactivation and nutrients separation solubilisation of polysaccharides and proteins (Donoso-Bravo et al.,
(Appels et al., 2011). However, high concentrations of heavy metals, 2011), which could result in a potential inhibition because of ammo-
industrial pollutants and sometimes pathogens might limit its applic- nium generation during AD (Zhuo et al., 2018). To optimize energy
ability (Liu et al., 2018; Singh and Agrawal, 2008), especially in those consumption for the application of ITH, the application of two thick-
countries where sludge is used as a fertilizer for agriculture. ening stages has been proposed (Ortega-Martinez et al., 2016); an initial
Regarding the performance of the AD, which is key from the dual stage to feed the first AD and second one to feed the ITH, hence an
objective of biogas production (energetic valorisation) and sludge re- additional liquid stream was generated.
duction (agronomic valorisation), conventional AD of sludge lacks ef- Regarding organic micropollutants, no global study is reported on
ficiency. It requires long hydraulic retention times (HRT) to achieve their fractioning along the sludge line, and the studies about the bio-
high organic matter removal (typically less than 40% for a HRT over 30 transformation of organic micropollutants during AD and the effect of
d) as a consequence of the low hydrolysis rate of complex organic TH on their removal or bioavailability are contradictory. Although
material produced during the activated sludge process (Appels et al., extensively studied, there is no consensus on the fate of organic mi-
2008). Different approaches have been proposed and evaluated to op- cropollutants. Most of the authors agree that they are mainly sorbed to
timize AD of sludge, such as pre-treatments to solubilise the solid or- the solid phase of digested sludge (Gonzalez-Gil et al., 2016; Narumiya
ganic matter. Among them, the thermal hydrolysis process (TH), which et al., 2013). Some studies suggest that sludge pre-treatment can be
consists in heating the sludge over its boiling point under pressure used to improve micropollutants biotransformation by enhancing their
(typically by saturated steam injection), has shown to be a reliable pre- accessibility (Aemig et al., 2016; Gonzalez-Gil et al., 2018; Reyes-
treatment method to facilitate subsequent AD of sludge with a global Contreras et al., 2018; Zhang and Li, 2018), while others conclude that
positive energy balance; the energy required for the process can be TH does not substantially increase their biotransformation efficiency
recovered by the increase in biogas production during AD (Cano et al., during AD (Taboada-Santos et al., 2019). Consequently, the traceability
2015). This is evidenced by its growing implementation in WWTP, with of contaminants and possible route to the biosolids need to be assessed
75 full-scale facilities reported (Barber, 2016). in order to evaluate the risk of land application of the final biosolid
Apart from this TH pre-treatment configuration, novel schemes of obtained.
TH implementation in the sludge line have arisen from recent research, Therefore, the aim of this study is to evaluate the traceability of
such as a post-AD TH step (Yang et al., 2019), and the intermediate pollutants in a WWTP sludge line when TH is employed, whether as a
thermal hydrolysis (ITH), between two stages of AD, (Campo et al., pre-treatment or an inter-treatment between two stages of AD, and
2018; Shana et al., 2013). The application of ITH has shown to facilitate compared with the conventional AD. For this purpose, the concentra-
the degradation of recalcitrant chemical oxygen demand (COD) during tion and mass flow rate of macropollutants (total solids, volatile solids,
the second AD-step, with much lower energy requirement compared to COD, organic nitrogen and ammonium) as well as 10 micro-
the TH pre-treatment configuration, thus achieving a higher perfor- contaminants (methylparaben, ethylparaben, propylparaben, clofibric
mance of organic matter removal and biogas production (Ortega- acid, ibuprofen, salicylic acid, naproxen, triclosan, diclofenac, bi-
Martinez et al., 2016; Ruffino et al., 2019) and an enhanced dewatering sphenol A) were determined in the different solid and liquid streams
of the digestate. generated during sludge treatment.
There is no report on the traceability of organic contaminants in the
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2. Materials and methods 2.1.2. Thermal hydrolysis plant and operating conditions
The lab-scale TH plant consisted of a stainless-steel cylindrical batch
2.1. Experimental set-up reactor (PN25 DN100) with a working volume of 1 L (2 L total volume)
coupled to a steam boiler (ETE H-20, Spain) and a 35L stainless-steel
2.1.1. Scenarios flash tank. Sludge (fresh or digested, depending on the scenario to as-
Three scenarios of sludge treatment were evaluated (Fig. 1), sess) was manually fed to the reactor through a feeding cone and a ball
namely: valve, and then a saturated steam (16 bar) was supplied from the boiler
and regulated with a control valve (RTK MV 5211, Germany) to achieve
a) Conventional AD of thickened sludge and digestate dewatering (AD a temperature of 170 °C in the reactor. Every batch required 20 min to
scenario), achieve the desired temperature and this was maintained for an addi-
b) TH pre-treatment of thickened sludge followed by AD and digestate tional 20 min before a sudden decompression of the sludge, by opening
dewatering (TH + AD scenario), and the release valve (PRISMA PA15S, Spain), in the flash tank to atmo-
c) AD of thickened sludge followed by thickening and ITH of digestate, spheric pressure (steam explosion effect), while the process vapours
and subsequent AD of the hydrolysed digestate and final dewatering were released. These operating conditions were based on previous
(AD + TH + AD scenario). studies (Sapkaite et al., 2017), which reported optimal conditions for
sludge pre-treatment of 160–180 °C for 20–40 min and a sudden de-
Data from each scenario were experimentally obtained by per- compression to atmospheric pressure.
forming continuous operation, periodic sampling and analysis of each
stream identified in Fig. 1, as described below. 2.1.3. Lab-scale anaerobic digestion: anaerobic digesters and biochemical
methane potential tests
2.1.1.1. Base scenario: conventional full-scale anaerobic digestion of sludge AD in the laboratory was performed in continuously-fed digesters
(AD scenario). The conventional full-scale AD of sludge (AD scenario) (20 L working volume) built in polyethylene (PE) and coated with an
performed in the WWTP of Valladolid (Spain) was considered the base electric resistance to maintain mesophilic conditions (35 °C). Sludge
scenario (Fig. 1a). In the WWTP, fresh mixed sludge (FM-a), composed was fed with peristaltic pumps (Watson-Marlow 323, UK) to achieve a
of sludge from the primary settler and waste activated sludge, is firstly residence time of 20 d, mixing was provided by sludge recirculation
thickened in centrifuges to increase the solids concentration for a (Watson-Marlow 530, UK) at a rate of 0.3 L min−1 and the biogas flow
suitable AD, thus obtaining the thickened mixed sludge (FM-b) and a rate was measured by liquid displacement at atmospheric pressure. The
return liquor (RET) which is returned to the water treatment line. FM-b continuous operation was kept in each scenario for 8 months, sampling
is anaerobically digested at 35 °C for 30 d producing biogas (BIOGAS) inlet and outlet twice a week for characterization.
and the digestate (DIG) is finally dewatered in centrifuges producing a In addition, BMP tests were performed in triplicate to evaluate
biosolid (BIOS) and a centrate (CENT) also returned to the water whether lab-scale digesters were close to the biodegradability potential
treatment line. Samples of FM-a, FM-b, RET, DIG, BIOS and CENT were of the sludge. 160 mL flasks were filled to a volume of 90 mL with a
collected, and the concentration of pollutants was determined to substrate-to-inoculum volatile solids (VS) ratio of 0.5 gVS gVS−1, sealed
evaluate their traceability. with a septum and a crimp and flushed with helium. Biogas production
was measured manually with a pressure transducer and the composi-
tion by collecting samples (100 µL) with a gas-tight syringe and sub-
2.1.1.2. Thermal hydrolysis pre-treatment followed by anaerobic digestion sequent injection in a gas chromatograph coupled to a thermal con-
(TH + AD scenario). When TH was applied as a pre-treatment (Fig. 1b), ductivity detector (GC-TCD). Details about the BMP tests are described
samples of FM-a were collected from the WWTP, concentrated by elsewhere (Donoso-Bravo et al., 2011).
centrifugation in the laboratory (10,000 rpm and 10 min) to produce
FM-b and a liquid stream (RET). FM-b was thermally pre-treated in a 2.2. Analytical procedures
lab-scale TH plant (170 °C and 20 min). Afterwards, the hydrolysed
sludge (TH) was fed to a lab-scale anaerobic digester and employed as 2.2.1. Characterization of conventional pollutants
substrate for biochemical methane potential (BMP) tests. Finally, the The concentration of total solids (TS), VS, COD, soluble COD, total
digestate (TH-DIG) was centrifuged for dewatering to obtain the CENT Kjeldahl nitrogen (TKN) and ammonium were determined by standard
and the BIOS. The concentration of pollutants was measured in FM-a, methods (APHA, 2012). The soluble phase of streams was attained by
FM-b, RET, TH, TH-DIG, BIOS and CENT. centrifuging samples (10,000 rpm and 10 min) in a Thermo Sorvall
Legend RT+ Refrigerated Benchtop Centrifuge (Madrid, Spain) and
2.1.1.3. Intermediate thermal hydrolysis between two stages of anaerobic subsequent filtration of the supernatant with a glass-fibre syringe filter
digestion (AD + TH + AD scenario). In this scenario (Fig. 1c), the initial (0.7 µm pore size).
thickening and digestion steps match with those in the base scenario of
conventional AD, followed by the corresponding specific operation 2.2.2. Selection and characterization of organic micropollutants
scheme, which is parallel to the TH + AD scheme. In this case, the Organic micropollutants include a large number of compounds such
sludge sampled to be subjected to thickening, TH, subsequent AD and as pharmaceuticals and personal care products (PPCPs) used in daily
final dewatering was anaerobically digested sludge (DIG-a) collected life and usually found in sewage sludge (Pérez-Lemus et al., 2019). Ten
from the WWTP. DIG-a samples were centrifuged to generate a PPCPs were selected as target analytes and the choice was based on
concentrated digestate (DIG-b) and a return liquor (RET-2). DIG-b was their physicochemical properties (i.e., lipophilicity, solubility, vapour
thermally hydrolysed in the TH plant in the laboratory (170 °C and pressure, among others) and also the huge use of these PPCPs belonging
20 min). The hydrolysed digestate (TH) was then anaerobically digested to different categories (i.e., pharmaceuticals, preservatives, endocrine
in a lab-scale digester and employed for BMP tests, to obtain biogas disruptors, herbicides and antiseptics) and their presence in this type of
(BIOGAS 2) and the final digestate (TH-DIG), which was dewatered by environmental matrices. The PPCPs selected correspond to three pre-
centrifugation to obtain the CENT and the final BIOS. The concentration servatives, methylparaben (MP), ethylparaben (EP) and propylparaben
of pollutants was determined in DIG-a, DIG-b, RET-2, TH, TH-DIG, BIOS (PP); three anti-inflammatories, ibuprofen (IBP), naproxen (NPX) and
and CENT. In this scenario, the concentration and flow rates of the diclofenac (DFC); two endocrine disruptors, triclosan (TCS) and bi-
streams FM-a, FM-b, BIOGAS 1, RET were assumed to be those of the sphenol A (BPA); one herbicide, clofibric acid (CA); and one antiseptic,
conventional full-scale AD of sludge (AD scenario). salicylic acid (SA). In addition, these target analytes were suitable for
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analysis by gas chromatography- mass spectrometry (GC–MS). in each scenario were obtained from experimental operation (inlet and
The analysis of this type of complex samples consisted of direct outlet concentration values). The steam needed in the TH was experi-
immersion Solid-Phase MicroExtraction on-fibre derivatization-gas mentally obtained from dilution values (1.4 dilution factor) and biogas
chromatography-mass spectrometry (DI-SPME-on-fibre derivatization- in AD were calculated as mL CH4 gVSfed−1 and later converted to flow
GC–MS) (López-Serna et al., 2018). The work here presented used the (m3) with the corresponding VS fed mass flows.
analytical method developed by López-Serna et al. (2018) with some
modifications to achieve a resulting methodology which highlights 3. Results and discussion
environment safety, short time consumption and an increase of SPME
fibre lifespan. Analytical method development and optimization for 3.1. Traceability of conventional contaminants
sewage and sludge samples was carried out by López-Serna et al. (2018)
and the information concerning the analytical methodology was in- 3.1.1. Effect of TH on the physico-chemical characteristics of sludge streams
cluded by the authors in the experimental section of the publication. Table 1 presents the results of the characterization, which generally
Some examples of chromatograms obtained from water and sludge agree with those previously reported (Appels et al., 2011; Fernández-
samples after the application of the optimized method were also re- Arévalo et al., 2017; Ortega-Martinez et al., 2016). The values exhibit a
ported in the same publication. general change among scenarios in the characteristics of all the streams,
The methodology for the solid phase consisted of the following from the thickened feeding (FM-b) to BIOS and return liquors (RET and
steps: 1) A volume of 180 mL of the homogeneous sewage sludge was CENT). In the schemes with TH, the feeding to the TH unit (FM-b for
centrifuged at 10,000 rpm for 10 min. The solid phase was collected TH + AD and DIG-b in AD + TH + AD) was concentrated to nearly
and stored at −20 °C in darkness. 2) The frozen samples were freeze- 11%TS (compared to 4%TS in conventional AD), due to the need to
dried and stored in the dark at −20 °C until analysis. 3) ~800.0 mg of reduce the amount of water to the thermal unit for energy sustainability
freeze-dried sample was placed in a vessel and spiked with 200 µL of a reasons. Cano et al. (2015) reported that sludge concentration is the key
mixture of the all isotopically labelled internal standards at 2 mg L−1 in parameter for energy integration and economic sustainability of TH
acetone and remained overnight for the solvent evaporation. 4) A vo- plants. It is also remarkable the decrease of all the parameters in the TH
lume of 24 mL of MilliQ® water/MeOH mixture, 95/5 (v/v) at pH 9 and outlet (TH) compared to the inlet, due to the dilution (1.4 factor) of the
100.0 mg of activated alumina (Al2O3 at 100 °C for 48 h) were added steam used to heat the sludge. Regarding the biosolids, the final con-
for in-situ matrix clean-up, which were then vortex-stirred for 1 min. 5) centration achieved in terms of solids (and therefore in the rest of
The sample was subjected to Microwave Assisted Extraction (MAE) for parameters) with respect to AD biosolids was 50% and 100% higher for
30 min at 110 °C in a Milestone START-D Microwave Digestion System TH + AD and AD + TH + AD schemes, respectively. The reason is the
(Madrid, Spain). 6) Afterwards, the extract was centrifuged at enhanced dewaterability of the sludge when suffering a thermal pre-
10,000 rpm for 10 min and the supernatant was collected and trans- treatment, which favours getting a more concentrated cake. All these
ferred to a 25 mL glass beaker. 7) The resulting supernatant was satu- results match with previously reported laboratory pre and post- TH
rated with NaCl at 36% (weight/volume) and was also adjusted at pH 3 characterization values (Wang et al., 2018, Ortega-Martinez et al.,
with hydrochloric acid (HCl). 8) Finally, the extract was filtered 2016, Ruffino et al., 2019).
through a 0.7 µm glass-fibre syringe filter and 17.0 mL of the resulting
solution was collected in a 20.0 mL SPME glass vial for the analysis for 3.1.2. Influence of TH on anaerobic digestion of mixed or digested sludge
online direct immersion Solid-Phase MicroExtraction on-fibre derivati- In agreement with literature, the introduction of a TH step before
zation-gas chromatography-mass spectrometry (DI-SPME-on-fibre de- AD, enhanced the performance of the digestion by increasing the solids
rivatization-GC–MS). The liquid phase of the centrifuged sludge sam- removal and subsequent methane production. These findings are also
ples, and those corresponding to liquor streams (RET, RET-1, RET-2 and reported for full-scale facilities (Cambi, Biothelys, Exelys). An increase
CENT), were also determined by following the steps 7) and 8). of VS removal from 35% (in conventional AD) to 40% in the TH + AD
In addition, the solid and liquid phases were quantified (mass and scheme was observed, together with an improvement in the methane
solids content) and analysed independently in triplicate. Precision, productivity from 281 ± 17 mL CH4 gVSfed−1 for fresh mixed sludge,
corresponding to the overall method repeatability, was calculated as 402 ± 12 mL CH4 gVSfed−1 for hydrolysed mixed sludge. In the case of
the relative standard deviation (% RSD) of equal samples in triplicate. the intermediate digestion (AD + TH + AD), an extra 26% removal of
The % RSD results obtained in the same time (intra-day precision) were VS was obtained when performing TH and AD to the digested sludge,
lower than 10% and the % RSD results obtained in different days (inter- joint to an additional methane productivity of 281 ± 7 mL CH4
day precision) were below 21%. gVSfed−1 for the hydrolysed digested sludge. These results are in
agreement with those reported elsewhere, for TH of mixed sludge and
2.3. Calculations (mass balances) for digested sludge (Ortega-Martinez et al., 2016; Sapkaite et al., 2017,
Mehari et al., 2018). From the values reported in Table 1 for the di-
Although the results for pollutants traceability were expressed as a gested streams (DIG) and centrate (CENT) it must be noted that TS, VS,
percentage with respect to the sludge inlet, the mass basis chosen to TCOD, TKN and ammonium concentrations were higher for the TH
perform the calculations was 1000 ton of mixed sludge (FM-a) feeding. schemes. This was not only due to the enhanced thickening step for TH,
This value is approximately equivalent to the daily sludge production of but also indicated the release of non-biodegradable TCOD and ammo-
230,000 equivalent inhabitants or a WWTP treating a flow rate of nium, as a consequence of the hydrolysis and solubilisation that the
wastewater of 50,000 m3 d−1. solid matter suffered during the thermal treatment. The increase was
The initial characterization of this feeding is presented in Table 1, especially remarkable for the TKN and N-NH4+ parameters (5-fold
and corresponds to a typical fresh mixed sludge (63%VS/TS, 9% SCOD/ higher) than for solids and COD (which duplicates or triplicates), in
TCOD, 1.8 TCOD/VS). Total mass balances were first performed to accordance with other authors (Keymer et al., 2013; Souza et al., 2013,
identify the total flow of each stream, and then the fractioning of each Suschka and Grübel, 2014).
pollutant was calculated incorporating to the calculation the corre-
sponding concentration value (shown in Tables 1 and 3). The density of 3.1.3. Influence of TH on the traceability of conventional pollutants through
all streams was considered to be constant (1000 kg m−3). the sludge line
For the thickening and dewatering, mass fractioning into thickened The traceability of conventional contaminants through the sludge
stream and liquor was calculated by mass balances according to the line in the three schemes and an estimation of the biogas production
concentration of TS measured. The performance of the TH and the AD (from the biogas productivity reported in Section 3.1.2) were calculated
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Table 1
Conventional contamination parameters of sludge in the three scenarios.
TS VS TCOD SCOD TKN N-NH4+
(g L−1) (g L−1) (g L−1) (g L−1) (g L−1) (g L−1)
Sludge feeding FM-a 12.8 ± 0.2 8.1 ± 0.1 14.6 ± 0.1 1.3 ± 0.2 0.93 ± 0.02 0.22 ± 0.1
AD (Conventional Anaerobic Digestion) RET 0.8 ± 0.1 0.5 ± 0.1 1.4 ± 0.1 0.4 ± 0.1 0.33 ± 0.01 0.06 ± 0.01
FM-b 39.9 ± 0.2 25.2 ± 0.2 44.4 ± 0.5 3.3 ± 0.2 2.27 ± 0.05 0.57 ± 0.04
DIG 24.8 ± 0.1 16.2 ± 0.1 27.9 ± 0.2 1.4 ± 0.1 2.06 ± 0.03 0.53 ± 0.01
CENT 2.5 ± 0.1 1.4 ± 0.1 2.0 ± 0.1 1.1 ± 0.1 0.35 ± 0.01 0.30 ± 0.01
BIOS 200.0 ± 1.5 134.0 ± 1.2 232.5 ± 1.3 3.4 ± 1.1 15.49 ± 0.05 2.36 ± 0.03
TH + AD (Thermal Hydrolysis Pre-treatment) RET 0.8 ± 0.1 0.5 ± 0.1 1.4 ± 0.1 0.4 ± 0.1 0.30 ± 0.01 0.07 ± 0.01
FM-b 109.6 ± 0.2 69.2 ± 0.2 121.2 ± 0.4 8.8 ± 0.2 5.98 ± 0.03 1.39 ± 0.02
TH 77.3 ± 0.1 47.4 ± 0.1 86.6 ± 0.3 26.4 ± 0.2 4.45 ± 0.02 0.85 ± 0.01
TH-DIG 45.7 ± 0.2 28.6 ± 0.1 44.4 ± 0.2 3.4 ± 0.2 4.07 ± 0.05 2.46 ± 0.3
CENT 5.3 ± 0.1 3.3 ± 0.1 5.1 ± 0.1 3.1 ± 0.1 1.62 ± 0.02 1.34 ± 0.2
BIOS 305.0 ± 1.6 190.0 ± 1.4 296.7 ± 1.1 5.0 ± 1.2 22.01 ± 0.05 9.59 ± 0.04
AD + TH + AD (Thermal Hydrolysis Inter-treatment) RET-1 0.8 ± 0.1 0.5 ± 0.1 1.4 ± 0.1 0.4 ± 0.1 0.33 ± 0.01 0.06 ± 0.01
FM-b 39.9 ± 0.2 25.2 ± 0.1 44.4 ± 0.3 3.3 ± 0.2 2.27 ± 0.03 0.57 ± 0.01
DIG-a 24.8 ± 0.1 16.2 ± 0.1 27.9 ± 0.1 1.4 ± 0.1 2.06 ± 0.02 0.53 ± 0.01
RET-1 2.5 ± 0.1 1.4 ± 0.1 2.8 ± 0.1 0.7 ± 0.1 0.28 ± 0.01 0.05 ± 0.01
DIG-b 111.4 ± 0.2 73.5 ± 0.2 125.6 ± 0.5 4.1 ± 0.1 8.95 ± 0.05 2.38 ± 0.03
TH 78.5 ± 0.1 53.8 ± 0.1 91.6 ± 0.3 29.6 ± 0.2 7.06 ± 0.04 1.36 ± 0.02
TH-DIG 66.7 ± 0.1 39.8 ± 0.1 63.5 ± 0.2 5.9 ± 0.1 6.85 ± 0.03 3.79 ± 0.02
CENT 6.8 ± 0.1 3.8 ± 0.1 7.0 ± 0.1 4.5 ± 0.1 1.96 ± 0.01 1.39 ± 0.01
BIOS 395.0 ± 1.5 243.0 ± 1.1 373.6 ± 1.4 13.3 ± 1.3 33.63 ± 0.05 16.95 ± 0.04
Table 2
Traceability of conventional contaminants and organic micropollutants for the three scenarios.
ton (m3) kg TS kg TCOD kg TKN kg N-NH4+ g micropollutant
from values in Table 1 (Table 2). In order to get a general approach and 35%. Biosolids contained 54%, 55% and 58% of TS, TCOD and TKN of
compare the results of the three scenarios more easily, the values pre- the inlet, respectively, while the huge flow of liquor (96% in mass re-
sented in Table 2 were treated to get relative values with respect to the spect inlet) returned 10% of TS and COD and 35% of TKN.
feeding (FM-a) in terms of: (i) return liquors (RET from thickening and When introducing a pre-treatment step before the digester
CENT from dewatering), (ii) removal (to BIOGAS), and (iii) biosolids (TH + AD scenario) the balances changed to a smaller quantity of
(BIOS). biosolids (2.1% vs 3.5% in AD, due to the enhanced dewaterability) and
A general overview on the flow and main contaminants along the a higher removal efficiency in terms of TS and COD, resulting in a
sludge line can be observed in Fig. 2. A quick view of the results for a smaller fraction derived to biosolids (50% of TS and 43% of TCOD). The
conventional sludge line, confirms that the double objective followed of return liquors increased however the amount returned to the WWTP,
mass reduction and stabilisation was achieved. Biosolids accounted for especially in terms of COD (from 10 to 12% due to the solubilisation of
only 4% of the fresh sludge inlet, and TS and COD were removed by non-degradable COD) and nitrogen (from 35% to 49%, mainly as
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Fig. 2. Fate of conventional contaminants from the inlet to biosolids, removal or return liquors, calculated for the three scenarios.
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Table 3
Characterization of organic micropollutants in solid and liquid phases of mixed and digested sludge, fresh or thermally pre-treated.
Fresh mixed (FM) Fresh digested (DIG) Hydrolysed (TH) Hydrolysed and digested (TH-DIG)
Table 4
Quantification of organic micropollutants in streams of the three scenarios.
Feed AD TH + AD AD + TH + AD Return liquors
MP 64 31 26 13 17 17 0 9563
CA 167 87 11 6 15 10 349 634
EP 17 7 3 1 0 0 0 0
IBP 98 39 15 6 5 6 0 5221
PP 45 20 12 6 16 16 0 0
SA 544 220 188 107 162 186 927 152
NPX 33 10 11 3 0 0 813 12
TCS 383 199 95 53 88 96 0 0
DCF 52 22 23 11 17 19 0 0
BPA 194 100 97 49 34 31 43 2960
TOTAL 1596 736 480 255 355 380 2132 18,542
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I. Díaz, et al. Bioresource Technology 305 (2020) 123028
Fig. 6. Fate of organic micropollutants from the inlet to biosolids, removal and return liquors, calculated for the three scenarios.
CRediT authorship contribution statement Pedrazzani, R., Bertanza, G., Lema, J.M., Carballa, M., 2016. Is anaerobic digestion
effective for the removal of organic micropollutants and biological activities from
sewage sludge? Water Res. 102, 211–220. https://doi.org/10.1016/j.watres.2016.06.
Israel Díaz: Writing - original draft, Writing - review & editing, 025.
Formal analysis, Resources, Visualization, Supervision. Alina Díaz- Higgins, M.J., Beightol, S., Mandahar, U., Suzuki, R., Xiao, S., Lu, H.W., Le, T., Mah, J.,
Curbelo: Writing - original draft, Writing - review & editing, Pathak, B., DeClippeleir, H., Novak, J.T., Al-Omari, A., Murthy, S.N., 2017.
Pretreatment of a primary and secondary sludge blend at different thermal hydrolysis
Investigation, Visualization. Nereida Pérez-Lemus: Methodology, temperatures: impacts on anaerobic digestion, dewatering and filtrate characteristics.
Validation, Writing - original draft, Writing - review & editing, Water Res. 122, 557–569. https://doi.org/10.1016/j.watres.2017.06.016.
Investigation. Fernando Fdz-Polanco: Conceptualization, Keymer, P., Ruffell, I., Pratt, S., Lant, P., 2013. High pressure thermal hydrolysis as pre-
treatment to increase the methane yield during anaerobic digestion of microalgae.
Methodology, Funding acquisition. Sara Isabel Pérez-Elvira: Bioresour. Technol. 131, 128–133. https://doi.org/10.1016/j.biortech.2012.12.125.
Conceptualization, Methodology, Formal analysis, Resources, Writing - Liu, T., Liu, Z., Zheng, Q., Lang, Q., Xia, Y., Peng, N., Gai, C., 2018. Effect of hydrothermal
original draft, Writing - review & editing, Visualization, Supervision, carbonization on migration and environmental risk of heavy metals in sewage sludge
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Project administration, Funding acquisition.
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This study was supported by the Government of Spain (MINECO- org/10.1016/J.TALANTA.2018.04.099.
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León and the European Union through EU-FEDER (CLU 2017–09 and The effect of thermal hydrolysis pretreatment on the anaerobic degradation of non-
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