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Live fast, die young: Optimizing retention times in high-rate contact stabilization for maximal recovery of organics from wastewater. Francis A. Meerburg, Nico Boon, Tim Van Winckel, Koen T. G. Pauwels, and Siegfried E Vlaeminck Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b01888 • Publication Date (Web): 02 Aug 2016 Downloaded from http://pubs.acs.org on August 7, 2016
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Live fast, die young: Optimizing retention times in high-rate contact stabilization
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for maximal recovery of organics from wastewater.
3 4 5 6
Francis A. Meerburga, Nico Boona, Tim Van Winckela, Koen T. G. Pauwelsa and
7
Siegfried E. Vlaemincka,b,*
8 9 10 11 12 13 14
a
Center for Microbial Ecology and Technology (CMET), Ghent University, Coupure
Links 653, 9000 Gent, Belgium b
Research group of Sustainable Energy, Air and Water Technology, University of
Antwerp, Groenenborgerlaan 171, 2020 Antwerpen, Belgium *Corresponding author: Phone: +32 3 265 36 89; Fax: +32 3 265 32 25; E-mail:
[email protected].
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Abstract
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Wastewater is typically treated by the conventional activated sludge process, which suffers
17
from an inefficient overall energy balance. The high-rate contact stabilization (HiCS) has
18
been proposed as a promising primary treatment technology to maximize redirection of
19
organics to sludge for subsequent energy recovery. It utilizes a feast-famine cycle to select
20
for bioflocculation and/or intracellular storage. We optimized the HiCS process for organics
21
recovery and characterized different biological pathways of organics removal and recovery.
22
Eight HiCS reactors were operated at 15°C at short solids retention times (SRT; 0.24-2.8 d),
23
hydraulic contact times (tc; 8 and 15 min) and stabilization times (ts; 15 and 40 min). At an
24
optimal SRT between 0.5-1.3 d, tc of 15 min and ts of 40 min, the HiCS system oxidized only
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10% of influent chemical oxygen demand (COD) and recovered up to 55% of incoming
26
organic matter into sludge. Storage played a minor role in the overall COD removal, which
27
was likely dominated by aerobic biomass growth, bioflocculation onto extracellular
28
polymeric substances and settling. The HiCS process recovers enough organics to potentially
29
produce 28 kWh of electricity per population equivalent per year by anaerobic digestion and
30
electricity generation. This inspires new possibilities for energy-neutral wastewater treatment.
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TOC/Abstract art
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Keywords 2 ACS Paragon Plus Environment
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Environmental Science & Technology
Biosorption, Carbon capture and redirection, F/M ratio, High-rate activated sludge (HRAS), Sewage
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1. Introduction
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Conventional activated sludge (CAS) – in various process configurations – is by far the
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most commonly applied technology to treat municipal wastewaters. Decades of optimization
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have made it a reliable and efficient technology to remove organic matter and nutrients from
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wastewater, although centralized CAS treatment suffers from disadvantages such as high
43
operational costs and dependency on continuous external electricity supply. Urged by
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economic and societal pressure, innovation efforts focus on achieving energy neutrality and
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sustainable recovery of resources; a term which can be coined as ‘wastewater mining’. A
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typical CAS plant requires an annual energy input in the order of 27 kWh per population
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equivalent (PECOD110),1 which corresponds to up to 1% of the electrical energy consumption
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in developed countries.2 Yet, in the case of domestic sewage, the chemical energy content
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exceeds the required energy to operate a CAS plant by at least a factor nine.3 Anaerobic
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digestion (AD) of excess sludge is the most viable option to recover energy from wastewater
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in the form of methane, except in limited cases where mainstream AD of raw wastewater is
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feasible.4 To achieve energy-neutral or even energy-positive wastewater treatment, it is
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necessary to minimize respiration losses to CO2, and maximize sludge production in an
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advanced primary treatment step combined with AD. Subsequently, secondary treatment
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technologies should be optimized to polish residual organic matter and nutrients in an energy-
56
conservative manner.5
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A straightforward way to increase sludge production in wastewater treatment plants is
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chemically enhanced primary treatment (CEPT) with iron and aluminum coagulants.
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Removal efficiencies of particulate organics are as high as 85%,6 but the overall energy
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recovery potential of CEPT may be unsatisfactory if the wastewater has a large fraction of
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dissolved organics. The chemicals commonly used in CEPT, such as ferric chloride, alum
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and organic polymers, have been reported to inhibit biogas production during AD.7, 4 ACS Paragon Plus Environment
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Alternatively, high-rate activated sludge (HRAS) processes may be used to increase primary
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sludge production by combining a very short solids retention time (SRT) – typically several
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hours to two days – with a high sludge-specific organic loading rate (SLR) – typically 2 to 10
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kg biodegradable chemical oxygen demand (bCOD) per kg of volatile suspended solids
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(VSS) per day.6 At this short SRT, only fast-growing microorganisms are retained, and
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sludge losses by grazing microorganisms and other secondary consumers can be avoided.9
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The high SLR minimizes sludge losses through cell decay and endogenous respiration.6
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HRAS processes produce sludge with a higher anaerobic digestibility than CAS sludge,10, 11
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which makes their application suitable for energy recovery. HRAS systems are generally
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used as a stand-alone process,12 as the A-stage of the Adsorptions-Belebungsverfahren (AB)
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process,9 or as high-rate membrane bioreactor (MBR) systems.13-15
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Conventional HRAS processes (i.e., HRAS processes with a conventional process
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configuration) struggle with the trade-off between minimizing respiration losses by lowering
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the SRT and maximizing effluent quality and bioflocculation performance by raising the
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SRT.12,
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optimization efforts should therefore primarily focus on enhancing bioflocculation and
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intracellular storage of organic matter at short SRT. To this purpose, high-rate contact
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stabilization (HiCS) was proposed as a novel HRAS technology.17 The HiCS process subjects
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the sludge to a feast-famine regime: return sludge is aerated in a stabilization phase (famine)
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before it is brought into contact with wastewater under anaerobic conditions (feast).
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To redirect a maximal amount of incoming organics into the sludge stream,
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Applying a feast-famine regime is a strategy to selectively favor bioflocculation18, 19 and
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production of storage polymers,20, 21 and its combination with high loading rates and short
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SRT in the HiCS process is hypothesized to raise organics recovery percentages further
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compared to conventional HRAS processes.17, 22 Bioflocculation, which occurs at the level of
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the extracellular polymeric substances (EPS) of sludge flocs, may be more influenced by
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loosely-bound EPS (LB-EPS) than by tightly-bound EPS (TB-EPS).23 Storage of organic
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carbon mainly occurs in the form of polyhydroxybutyrate (PHB).24
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It has been suggested that the HiCS process reaches higher COD removal efficiencies
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compared to conventional HRAS systems.22 Previous experiments found that the energy
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recovery by the HiCS system depends on the SRT and the hydraulic retention times during
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the contact and stabilization phases, with a suggested minimum contact time of 5 min and a
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minimal stabilization time of 30 min.17, 25 Given the novelty of the HiCS process, research on
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the process is scarce, and its status as an alternative to conventional HRAS processes has
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remained hypothetical. The HiCS process has not been optimized for maximal organics
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recovery, nor is it known to what extent different biological pathways contribute to the
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overall removal of organics. In this study, the recovery of COD by means of bioflocculation
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and storage was investigated in the HiCS system at different combinations of SRT (0.24, 0.5,
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1.3 and 2.8 d), contact time (8 and 15 min) and stabilization time (15 and 40 min) to identify
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an optimal operational strategy for recovering wastewater organics. Determination of the LB-
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EPS, TB-EPS and PHB content of the biomass was performed to estimate the relative
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contribution of bioflocculation and storage toward the overall removal of organic matter.
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2. Materials and Methods
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2.1.
Reactor operation
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Eight HiCS reactors were operated as sequencing batch reactors (SBR) with a working
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volume of 3 L. Synthetic wastewater was prepared according to Aiyuk and Verstraete26 with
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a complex organic fraction composed of acetate, peptone, starch, milk powder, dried yeast
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and soy oil, at a target concentration of 800 mg COD per liter26. At this COD concentration,
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the influent can be considered representative for high-strength domestic, or for industrial
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wastewater.6 The influent was prepared in batches that were kept at 15°C and used within 2
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days. The reactors were inoculated with a 1:1 mixture of sludges from the high-rate and low-
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rate stages of the wastewater treatment plant of Nieuwveer (Breda, NL). Samples were taken
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near-daily after an acclimation period of 3 to 6 days to reach a steady-state performance over
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several cycles of SRT. An orthogonal experimental design was implemented to optimize the
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SRT, contact time (tc) and stabilization time (ts) (Table 1). Wasting of sludge was performed
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during the contact phase. The waste flow rate was adjusted manually to maintain the desired
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SRT (calculations in Supplementary Information). The SBR cycle times were controlled by a
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microcontroller (Arduino, Turin, IT). All reactors had a contact phase of differing lengths,
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with a phase for filling and reacting and a phase for wasting, a settle phase of 40 min, a
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withdraw phase of 5 min, and a stabilization phase of differing lengths. After stabilization, an
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idle phase was implemented to synchronize the cycles of parallel reactors. Table 1 lists the
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operational conditions of each reactor.
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All experiments were performed in a temperature-controlled room at 15 °C (standard
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deviation 1°C) to mimic average wastewater temperatures of Western Europe. Peristaltic
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pumps and pressurized air were used for pumping and aeration, respectively. Stirring was
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achieved with a magnetic stir bar at a 800-1000 rpm rotational speed. Measurements of the
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dissolved oxygen (DO) concentration and pH in the reactors were made near-daily. Manual 7 ACS Paragon Plus Environment
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corrections of the air flow were made to ensure that DO levels were above 1.5 mg L-1 at the
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end of the stabilization phase, in order to remain well above the oxygen half-saturation
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coefficient of 0.2 mg L-1 for heterotrophic growth27 and minimize possible effects of low DO
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concentrations on the production of EPS28 and PHB29. The pH was between 7.2 and 8.7. It
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should be noted that stabilization, contact and settling processes in SBR systems occur
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sequentially. Therefore, the SLR and the removal rates of SBR reactors are inherently lower
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compared to continuous systems, where these processes occur in parallel, and care should be
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taken when directly comparing rates between SBR and continuous systems.
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Table 1: Overview of reactor operation, sludge characteristics and COD concentrations of
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the influent and effluent. SLR: sludge-specific loading rate, VER: volume exchange ratio.
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Standard errors are shown behind values, where applicable. (*) The bCOD/COD ratio was
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0.99.
React or
SRT
tc:ts
Steady -state operati on
Influent flow rate
SLR (*)
Stabili zation volum e
VE R
Contactor VSS
VSS/ TSS ratio
Influent COD
Effluent COD
mg COD
mg COD
%
L-1
L-1
g bCOD g-1 VSS
min:mi d
n
d
L d-1
d-1
L
%
A
0.24 ± 0.01
15:40
21
16.0
8.1 ± 1.5
1.83
39
856 ± 97
95
919 ± 86
448 ± 40
B
0.46 ± 0.03
15:40
26
21.4
4.7 ± 0.6
1.83
39
1160 ± 106
91
660 ± 31
249 ± 15
C
1.31 ± 0.08
15:40
26
20.9
1.7 ± 0.1
1.83
39
2790 ± 130
92
668 ± 30
234 ± 22
D
2.82 ± 0.38
15:40
18
21.0
1.5 ± 0.1
1.47
51
3920 ± 189
89
843 ± 52
322 ± 10
E
0.53 ± 0.02
8:40
25
22.3
3.9 ± 0.2
1.53
49
1650 ± 95
93
834 ± 24
387 ± 27
F
0.50 ± 0.01
15:15
25
22.3
4.8 ± 0.1
1.53
49
1300 ± 35
95
834 ± 20
464 ± 18
G
0.88 ± 0.03
8:40
25
20.9
2.4 ± 0.1
1.62
46
2470 ± 100
92
844 ± 21
381 ± 16
H
0.85 ± 0.05
15:15
25
20.9
3.2 ± 0.1
1.62
46
1850 ± 74
95
835 ± 12
504 ± 15
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2.2.
mg L-1
Coagulation and settling control experiments
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Physicochemical coagulation and settling experiments of the synthetic wastewater were
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performed as controls to assess the performance of a primary settling treatment and a CEPT
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treatment under identical flow rates and reaction times as in the HiCS reactors B and C. For
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the primary settling experiment, influent was stirred in a 3 L batch reactor for 15 min, and left
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to settle for 40 min. Prior to the CEPT experiment, the coagulants Al2(SO4)3 and FeCl3 were
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tested for their optimal concentration in a series of batch tests with a dosage between 0 and
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300 mg L-1 for Al2(SO4)3 and between 0 and 700 mg L-1 for FeCl3. After 15 min of stirring
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and 40 min of settling, the transmission at 610 nm was measured spectrophotometrically. A
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dosage of 122 mg L-1 Al2(SO4)3 resulted in the clearest supernatant, and was used to perform
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the CEPT experiment. Influent was stirred in a 3 L batch reactor with addition of this optimal
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coagulant dose, stirred for 15 min and left to settle for 40 min. The physicochemical
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experiments were performed in triplicate.
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2.3.
Extraction of EPS
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A heat extraction protocol was modified from Li and Yang30 and Morgan et al.28 to extract
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the LB-EPS and TB-EPS fractions from the sludge. Sludge samples for EPS measurement
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were taken at the end of the contact phase. Sludge samples were immediately centrifuged at
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4000g for 5 min and resuspended in 10 mL of Ringer’s solution (9 g L-1 NaCl, 0.42 g L-1
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KCl, 0.48 g L-1 CaCl2 and 0.20 g L-1 NaHCO3, adjusted to pH 7.0) diluted to 25% with
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distilled water and preheated to 60°C to ensure that the suspensions reached an immediate
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temperature of 50°C. After vortexing for 1 min, the samples were centrifuged at 4000g for 10
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min to isolate the LB-EPS fraction in the supernatant. The pellets were resuspended in 10 mL
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diluted Ringer’s solution, and heated at 60°C for 30 min. After centrifugation at 4000g for 15
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min, the TB-EPS fraction was recovered from the supernatant. The EPS fractions and pellets
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were stored at -20°C until further processing.
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2.4.
comparisons
168 169 170
PHB extraction, analytical procedures, calculations and statistical
All analyses, calculations and statistical comparisons were carried out as described in the Supplementary Information.
171 172
3. Results
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3.1.
Removal efficiencies and sludge production
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With an increasing SRT from 0.24 to 2.8 d (reactors A to D), the total COD removal
175
efficiency increased significantly from 52% at SRT 0.24 d to 65% at SRT 1.3 d, after which
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it decreased slightly to 60% at SRT 2.8 (not significant) (Figure 1A). At an SRT of 0.5 d,
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decreasing tc from 15 (reactor B) to 8 min (reactor E) did not result in a lower CODtot
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removal, while a decrease of ts from 40 to 15 min (reactor F) significantly lowered the
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removal efficiency to 44%. The same trend was observed at higher SRT (reactors C, G and
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H), but since the effective SRT of these reactors did not equal their designed SRT of 1 d,
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quantitative comparison is preliminary. Correlation analysis revealed that only the ts was
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significantly correlated to the removal efficiency of CODtot and CODdiss, with a positive
183
correlation coefficient (Table S1). It should be noted that correlation analysis may only
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detect linear or monotonic associations between variables, and no non-linear associations, as
185
may be the case between the SRT and the removal efficiencies for CODpart, CODcoll and
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CODdiss, which showed an optimum at an intermediate SRT.
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Removal of CODpart contributed most to the total COD removal, with removal percentages
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between 80 and 93% which did not differ significantly among the reactors. Regarding the
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influence of SRT and tc:ts ratio, the removal percentages of dissolved COD followed the same
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trends as for CODtot; the highest CODdiss removal efficiency was observed at an SRT of 1.3 d
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removal efficiency to a mere 5%. The lowest and most variable removal efficiencies were
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observed for colloidal COD, which was even negative in reactor A (Figure 1A).
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Figure 1: (A) COD removal efficiencies for the different reactors. Error bars show
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standard errors (SE). (B) Average balance of COD fractions leaving each reactor, relative to
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incoming COD. Error bars show standard errors.
199 200
The observed sludge yield showed a decreasing trend with increasing SRT (Figure S1).
201
The lowest yield was observed at an SRT of 2.8 d (reactor D), which was significantly lower
202
than in the reactors with a shorter SRT, where the observed yield approximated the
203
theoretical maximum of 1 g CODsludge g-1 CODremoved. Changes in tc and ts had no significant
204
effect on the observed sludge yield. This was confirmed by correlation analysis (Table S1),
205
where the yield was significantly correlated to the SRT (ρ = -0.88) but not to the tc or ts.
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The influent contained, on average, 0.04±0.08 mg L-1 NO2--N, 2.4±0.8 mg L-1 NO3--N, and
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4.1±2.9 mg L-1 PO43--P. Whereas no nitrite and nitrate were added to the synthetic
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wastewater, these values were consistent with the nitrite and nitrate concentrations in the tap
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water used for the synthetic wastewater. Removal efficiencies of combined nitrite and nitrate
210
ranged between 59% and 92%, presumably due to denitrification, with the highest removal in
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reactors C and G. Removal of orthophosphate ranged between 20% and 63%, with the
212
highest removal in reactor B.
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It should be noted that there were variations in mixed-liquor VSS concentrations among
214
reactors as a result of the different SRTs, and this resulted in a range of different SLRs
215
(Table 1). Therefore, care should be taken when directly comparing performances between
216
reactor A, which had a very high SLR, and reactors C and D, whose SLR was in the lower
217
range of values obtained. For the same reason, any effects of SRT on reactor performance
218
described in this study may, in part, also be due to the coupled differences in SLR.
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220
3.2.
Recovery of organic matter
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An overall COD balance was made over each reactor to monitor the fractions of COD that
223
entered and exited the reactor systems via waste sludge, effluent and losses to oxidation, as
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presented in Figure 1B.
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The best performance was observed at the three lowest SRTs (reactors A, B and C), with
227
average COD recovery percentages of 54, 53 and 55% and oxidation percentages of 10, 10
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and 14%, respectively, which did not differ significantly. Only at the longest SRT of 2.8 d
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(reactor D), a clear effect of the SRT on reactor performance could be observed, with a
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significantly lower recovery of 18% and an oxidation of 44%. While changes in tc and ts did
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not significantly change the fraction of COD oxidized, a decrease in tc from 15 to 8 min (in
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reactors E and G) resulted in a significantly higher fraction of colloidal COD in the effluent
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and a decrease in ts from 40 to 15 min (reactors F and H) resulted in a significant reduction in
234
the fraction of recovered sludge and significant increases in the fractions of colloidal and
235
dissolved COD in the effluent. Correlation analysis did not show strong associations between
236
the COD recovery percentage and operational variables (Table S1), but the fraction of
237
CODdiss leaving the reactors was negatively correlated to the ts.
238 239
Physicochemical coagulation and settling experiments were performed to assess the COD
240
removal efficiency and organic matter recovery of a primary settling treatment and a CEPT
241
treatment under identical conditions of influent composition, flow rates and reaction times as
242
in the HiCS reactors B and C. The results are presented in Table 2 and compared to the HiCS
243
reactors B and C, which had the best performance of all reactors in terms of COD removal
244
efficiency and organic matter recovery. Primary settling of the influent resulted in a poor
245
removal efficiency and organic matter recovery, whereas coagulation with Al2(SO4)3
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followed by settling resulted in an organic matter recovery equal to that in the optimal HiCS
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reactors. However, the HiCS reactors performed significantly better in terms of COD
248
removal efficiency since, besides recovery, an additional part of the incoming COD was
249
oxidized.
250 251 252 253
Table 2: Comparison of COD removal efficiency and organic matter recovery of the primary settling and CEPT experiments, and the best-performing HiCS reactors (B and C).
254 Reactor SRT tc:ts
COD removal efficiency Particulate
Colloidal
Dissolved
Organic Total
matter recovery
d
%
%
%
%
%
Settling
81.6 ± 1.2
20.7 ± 5.5
-1.0 ± 0.8
30.1 ± 1.0
30.6 ± 1.0
Coagulation + settling
79.2 ± 2.8
60.0 ± 2.0
22.4 ± 0.6
49.8 ± 1.4
50.5 ± 1.3
HiCS B
0.46
15:40 90.6 ± 1.6
19.8 ± 14.2
29.7 ± 5.4
61.8 ± 2.1
53.2 ± 6.9
HiCS C
1.31
15:40 87.6 ± 4.8
14.9 ± 15.3
34.1 ± 6.6
64.6 ± 3.0
55.1 ± 3.4
255 256
257
3.3.
Extracellular polymeric substances and poly-β-hydroxybutyrate
258 259
The concentrations of proteins and carbohydrates in the tightly bound EPS fractions were
260
always between two to eight times higher than in the loosely bound EPS fractions (Figure 2).
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Figure 2: Specific protein and carbohydrate concentrations of the loosely (top) and tightly bound (bottom) EPS fractions. Error bars show standard errors (SE).
264 265
In the LB-EPS fraction, carbohydrate concentrations showed a gradual decline with
266
increasing SRT, to a minimum of 2.3 g g-1 VSS at an SRT of 2.8 d (reactor D). In the TB-
267
EPS fraction, the carbohydrate concentrations remained stable around a level of 18 g g-1 VSS,
268
and none of the reactors showed significant differences. Protein concentrations were more
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variable, and were the main factor determining changes in the protein-to-carbohydrate (P/C)
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ratio. The P/C ratio significantly increased with increasing SRT to a maximum of 6 mg mg-1
271
at an SRT of 1.3 d (reactor C) in both the LB-EPS and TB-EPS fractions, after which the
272
ratio declined again at an SRT of 2.8 d (reactor D). At an SRT of 0.5 d, a decrease of the tc to
273
8 min (reactor E) and ts to 15 min (reactor F) had no significant influence on the protein-to-
274
carbohydrate ratio in the LB-EPS fraction, but caused a strong decrease in the TB-EPS
275
fraction, compared with a tc:ts ratio of 15:40 min (reactor B). Correlation analysis showed
276
that the EPS composition did not monotonously correlate to operational variables (Table S1).
277
Correlations with COD removal efficiency were generally negative for the carbohydrate
278
fractions and positive for the protein fractions of the EPS. The strongest correlations were
279
between the protein content in the TB-EPS fraction and the CODtot (ρ = 0.90) and CODdiss
280
removal efficiency (ρ = 0.74), between the protein content in the LB-EPS fraction and the
281
CODcoll removal efficiency (ρ = 0.79), and between the carbohydrate fraction in the LB-EPS
282
fraction and the CODpart removal efficiency (ρ = -0.83).
283 284
The intracellular PHB concentration at the end of the contact phase showed a strong
285
influence of the SRT, with a significant increase from a concentration of 2.6 to 21 mg g-1
286
VSS with increasing SRT up to 1.3 d (reactor C), followed by a strong decline by 41% at an
287
SRT of 2.8 d (Figure S2). A change in the tc did not result in differences in PHB
288
concentration, but a decrease in ts from 40 min (reactor B) to 15 min (reactor F) caused a
289
significant PHB decrease by 60% at an SRT of 0.5 d. Correlation analysis showed no
290
monotonous correlation between the PHB content and operational variables (Table S1). The
291
PHB content was, however, positively correlated to the removal efficiencies of total (ρ =
292
0.95), particular (ρ = 0.71) and dissolved (ρ = 0.74) COD. Furthermore, the PHB content was
293
negatively correlated to the carbohydrate fraction of LB-EPS (ρ = -0.83) and positively to the
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protein fraction of the TB-EPS (ρ = 0.86). Measurements with a ten-minute interval within
295
each reactor cycle showed that PHB concentrations never changed considerably from feast to
296
famine phase.
297 298 299
4. Discussion
300
4.1.
Reaching sufficient effluent quality
301
The HiCS system is designed to be the primary stage of a two-stage activated sludge
302
system, because the operational strategy to achieve maximal redirection of organic carbon in
303
HRAS systems (i.e., lowering the SRT and raising the SLR) typically result in a deterioration
304
of overall COD and nutrient removal efficiencies.12, 16, 31 In this study, the COD removal
305
efficiency increased with SRT, but declined again at the longest SRT of 2.8 d, primarily
306
because of lower removal of colloidal and dissolved COD. This may be due to the combined
307
effects of improved biosorption with increasing SRT, and a higher incidence of hydrolysis or
308
release of soluble microbial products (SMP). Indeed, experiments with high-rate membrane
309
bioreactors (MBR) at short SRT showed an increase in SMP with increasing SRT between
310
0.5 and 2 d.32 Within the range of short SRTs tested here, an optimum was found between 0.5
311
and 1.3 d.
312
To allow organic matter removal in activated sludge by the relatively rapid processes of
313
sorption and bioflocculation, studies have shown that a minimal contact time of 5 or 10
314
minutes was required.33,
315
significantly when the tc was lowered from 15 to 8 min, but a higher fraction of colloidal
316
COD left the system through the effluent. Possibly, the bioflocculation process was not
317
complete after 8 min. A longer contact time of 15 min is therefore recommendable to obtain a
318
more stable operation of the HiCS system and effluent quality.
34
In this study, the fraction of recovered COD did not differ
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A strong decrease in COD removal was observed when the ts was lowered from 40 to 15
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min. This indicates that a stabilization period of 15 min is not sufficient for the sludge to
321
deplete its adsorbed or stored COD and regenerate, and is in accordance with Huang and Li25
322
who found that stabilization times should be at least 30 min. Tsang et al.35 found that the
323
relative ratio of feast-to-famine retention times determines the strength of the selection
324
pressure toward bioflocculation. According to the kinetic selection theory,20 both
325
bioflocculation and storage should therefore be favored when stabilization times are longer.
326
An optimal ts for the HiCS system is therefore more likely to be found above 35 min17 or 40
327
min, as observed in this study.
328
Comparison between physicochemical coagulation and settling tests demonstrated that the
329
HiCS system at these optimal SRTs achieves a higher overall COD removal efficiency
330
compared to CEPT, especially in the particulate and dissolved COD fractions. The CEPT
331
control experiment removed 22% CODdiss, and is in concurrence with previous studies who
332
found that alum-based CEPT can remove some CODdiss by adsorption onto the formed
333
Al(OH)3 gel.36 However, the CEPT experiment was not optimized for factors such as shear
334
force and reaction times, and a fully optimized CEPT system may achieve a better COD
335
recovery than what was obtained in this study.
336
The best effluent quality was obtained by reactor C, with an average COD concentration
337
of 234 ± 22 mg L-1. Whereas absolute effluent COD concentrations will differ according to
338
the specific influent strength and composition, this value is far above the effluent standards of
339
many urbanized regions, such as the standard of 125 mg L-1 COD set forth by the European
340
Union.37 Moreover, the potential for biological nitrogen and phosphorus removal is limited in
341
high-rate systems, due to the short SRT.38, 39 Therefore, high-rate systems typically require
342
further polishing of organics and nutrients from the effluent during secondary treatment.40 To
343
attain energy-neutral wastewater treatment, optimization efforts should combine the
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optimization of organics recovery in HRAS systems with the development and
345
implementation of energy-efficient technologies for downstream nutrient removal. For
346
example, anammox-based deammonification requires 60% less energy for nitrogen removal
347
compared to conventional nitrification/denitrification,41 and much work is being performed to
348
improve the feasibility of anammox-based nitrogen removal under mainstream conditions.42
349
For efficient deammonification, a low bCOD/N ratio is desirable,43 presumably below 1.4 g
350
bCOD g-1 N44, 45. Since raw domestic wastewater typically has a ratio above 9 g bCOD g-1 N
351
6
, optimization of the HiCS system should primarily focus on redirecting organic carbon.
4.2.
352
Improving the bioflocculation and storage response
353
The removal of CODtot peaked to more than 60% in the reactors with an SRT of 0.5 d and
354
1.3 d. Because the extent of oxidation only varied around 10%, these reactors effectively
355
removed organic matter by means of conservational mechanisms, such as bioflocculation and
356
storage. The COD removal efficiencies were correlated with higher concentrations of
357
proteins and lower concentrations of carbohydrates in the EPS. The positive correlation
358
between the EPS protein concentrations and COD removal supports the hypothesis that the
359
hydrophobic moieties of EPS proteins are responsible for the bioflocculation process,46 and
360
concurs with the experimental results of Xie et al.47 who suggested that EPS proteins play a
361
more important role in bioflocculation than carbohydrates. The protein-to-carbohydrate ratio
362
peaked at an intermediate SRT of 1.3 d. This is similar to what was observed by Faust et al.14
363
and may explain why both positive and negative correlations with SRT have been reported.14,
364
48
365
the results of Yang and Li49 who found that the TB-EPS content of activated sludge reactors
366
remained relatively constant under changing conditions of carbon source in the synthetic
367
wastewater, SRT and loading rate. The TB-EPS proteins varied among reactors and showed
368
strong positive correlations with the CODtot and CODdiss removal efficiencies (Table S2).
The nearly constant level of TB-EPS carbohydrates in all reactors may be consistent with
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This suggests that the formation of TB-EPS proteins may be associated with the metabolic
370
conversion of soluble substrates. Conversely, the LB-EPS protein content showed a strong
371
positive correlation with the CODcoll removal efficiency. This corresponds to the observation
372
that the bioflocculation performance of sludge is mainly associated with the LB-EPS fraction,
373
as has been shown in literature.23, 49 Further work should be performed to determine the
374
contribution of different EPS fractions towards the removal of CODpart, CODcoll and CODdiss.
375
Whereas the complex synthetic wastewater in current study was selected to reflect realistic
376
amounts of CODpart and CODdiss, organic and ammonia-nitrogen, as found in raw domestic
377
sewage,26 differences in influent composition and strength may result in changes in LB- and
378
TB-EPS production when the HiCS system is operated with real wastewater of medium to
379
low strength. It should also be noted that EPS measurement is sensitive to the specific
380
extraction method50, and the existence of several often-used methods may prevent direct
381
comparison among reported measurements in literature.
382
The settling characteristics of the sludge were addressed indirectly through monitoring the
383
effluent quality and organics recovery performance of the reactors. In all reactors, the
384
constant settling time of 40 min and maximum travel distance of 7.5 cm subjected the sludge
385
to an equivalent upflow velocity of 0.11 m h-1, which is far below the range of 1.3-3 m h-1
386
typically employed in primary treatment stages with sludge return,6 and was deemed
387
sufficiently low to minimize effects of differences in sludge settleability on reactor
388
performance in this study. However, additional optimization of the settleability and
389
bioflocculation properties could further improve the solids/liquid separation and organics
390
recovery in the HiCS system, as evidenced by the presence of particulate and colloidal COD
391
in the effluent of all reactors.
392
The COD removal efficiency strongly correlated with intracellular PHB concentrations.
393
The PHB production did change with variations in the SRT and stabilization time, but no
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temporal changes were observed within the feast-famine cycles of each reactor (data not
395
shown). Feast-famine cycling is known to select for sludge with a strong storage response,
396
even at very short SRTs below 1 d.21 The highest level of PHB observed in this study was 21
397
mg g-1 VSS (reactor C), which was considerably lower than the 40 mg g-1 VSS that may be
398
achieved in low-rate wastewater treatment systems optimized for PHA production.51
399
Considering the COD/weight ratio of 1.67 g COD g-1 PHB and COD/VSS ratio of 1.58 g
400
COD g-1 VSS in reactor C, the production of PHB only accounted for 2.3% of the recovered
401
COD. This suggests that production of storage polymers was not the predominant route of
402
COD removal in these experiments, and that bioflocculation, biomass growth and settling
403
were responsible for most of the COD removal. Beun et al.52 reviewed a number of studies
404
that subjected activated sludge to feast-famine conditions with acetate as carbon source, and
405
demonstrated that the fraction of consumed acetate going to PHB production remains
406
constant at a range of SRTs >2 d, but that PHB production is less predictable at lower SRT.
407
In a pilot HRAS study with real wastewater at an SRT of 0.5 d, Haider53 demonstrated that
408
PHB only accounted for 2% of the influent organics. Possibly, the SRTs in this study were
409
too low to selectively favor micro-organisms with a storage-dependent growth cycle.
410
4.3.
Reaching energy neutrality
411
The overall redirection of COD is determined by the product of COD removal and
412
observed sludge yield. Up to an SRT of 1.3 d, the yield approached 1 g COD g-1 COD, which
413
is well above the maximum yield of 0.4-0.7 g COD g-1 COD for heterotrophic growth.6
414
Yields higher than the heterotrophic growth yield may indicate that COD is removed by
415
processes other than cell growth, such as storage54, and it is not uncommon that growth yields
416
reported for HRAS processes approach the upper limit of 1 g COD g-1 COD.12 In this work,
417
the sludge yield was dependent on the SRT, which is a well-described phenomenon,6 but not
418
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sludge mass in an activated sludge reactor. Given these findings, the optimal operational
420
conditions of the HiCS system in terms of carbon redirection and recovery are a tc of 15 min,
421
a ts of 40 min and an SRT between 0.5 and 1.3 d. The carbon recovery percentages of 53% to
422
55% are higher than for conventional HRAS systems with an SRT between 0.5 to 1 d, which
423
achieve a recovery between 27% and 41% of incoming COD to sludge,12 although direct
424
comparison of these values is difficult because of differences in influent composition and
425
operational conditions.
426
An estimation of the potential energy recovery by means of AD can be made, considering
427
that the methane yield during AD of HiCS sludge with an SRT of 1 d was reported to be 0.73
428
g CODmethane g-1 CODsludge-fed.17 Thus, digestion of recovered sludge from the HiCS reactors
429
in this study would result in an energy recovery of 39±5% at an SRT of 0.5 d and 40±3% at
430
an SRT of 1.3 d, expressed as percentage of influent COD that is finally recovered as
431
CODmethane. With a conversion factor of 203 g COD kWh-1 - a conservative estimation,55 - a
432
methane energy content of 3.86 ×10-3 kWh g-1 COD, and an electricity conversion efficiency
433
of 0.35 kWhel hWhmethane-1 in a combined heat and power (CHP) installation,56 this would
434
allow an annual recovery of 27.1 and 27.9 kWh of electricity per population equivalent
435
(PECOD110), respectively. Müller and Kobel57 determined that typical large CAS plants in
436
Germany equipped with a CHP unit can produce 16.4 kWh PEBOD60-1 y-1 from combustion of
437
biogas. This is equivalent to about 13.3 kWh PECOD110-1 y-1 for sewage with standard
438
characteristics.6 Thus, a full-scale HiCS system could potentially achieve an energy recovery
439
of more than twice as high as that of a CAS system. It should be noted that the methane yield
440
from HRAS sludges may differ depending on the type of sludge, wastewater and anaerobic
441
digestion conditions, and values between 44% and 73% CODmethane CODsludge-fed-1 have been
442
reported.17, 58-60 Digestibility experiments of HiCS sludge should therefore be performed to
443
estimate of the energy recovery potential of the HiCS system under various conditions.
23 ACS Paragon Plus Environment
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444
However promising, the results of this work should be validated at various conditions to
445
reflect full-scale wastewater treatment, where there may be variations in wastewater flow
446
rate, strength, composition, temperature and other characteristics. In case of sewage treatment
447
from a combined sewer system, additional resilience is required of the activated sludge
448
system to deal with periodic dilution of sewage and increases in flow rates due to rainfall.
449
Fluctuations in wastewater flow rate create changes in the reactor HRT, which may
450
negatively impact the COD recovery performance, for example by limiting the extent of
451
substrate adsorption in the reactor and causing particle washout from the settler when the
452
HRT becomes too short, or by increasing the extent of COD oxidation in the reactor and
453
causing substrate hydrolysis in the settler when the HRT becomes too long. A continuous
454
HiCS system may provide better protection against load variations and shocks than a
455
conventional HRAS system, because at any time, a major fraction of the sludge resides in the
456
stabilization reactor and is not in contact with the influent.61 Compared to the stability of
457
controlled laboratory experiments, the fluctuating conditions of full-scale systems may result
458
in a higher diversity of the activated sludge community,62 which may in turn favor functional
459
redundancy and resilience of the system.63 However, the presence of fluctuating conditions
460
may warrant the use of safety margins when designing a full-scale HiCS system, and the
461
choice of SRT, tc, ts and other operational parameters should be made both in function of
462
maximizing organics recovery as well as maintaining a sludge community dense and resilient
463
enough to withstand perturbation.
464
To move toward a mature technology that economically competes with CEPT, primary
465
settling, and conventional HRAS processes, the HiCS process should be further optimized for
466
COD recovery. Different primary treatment technologies should be compared in terms of
467
COD recovery performance, energy balance, and operational and investment costs when
468
coupled to secondary treatment, to determine the advantages and disadvantages of each
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469
technology. For example, CEPT may have a lower investment cost compared to a HiCS
470
system, but higher operational costs due to chemical dosage, and a lower sludge digestibility
471
due to the presence of coagulants in the sludge.8
472 473
In conclusion, this study showed that high-rate contact stabilization as a primary
474
wastewater treatment technology was able to recover up to 55% of incoming organic matter
475
as sludge, which could be used for electrical energy recovery. The major share of organic
476
matter removal was attributed to conservational mechanisms such as bioflocculation, biomass
477
growth and settling, as opposed to oxidation. To reach maximal energy recovery, optimal
478
operational conditions for the HiCS process were identified as a sludge age between 0.5 and
479
1.3 d, a contact time of 15 min and a stabilization time of 40 min. Future research should
480
focus on further improving colloidal and dissolved COD recovery efficiencies, and validating
481
the performance of the HiCS system under various full-scale wastewater treatment
482
conditions, in comparison with other primary treatment technologies.
483 484
Acknowledgements
485
F.A.M and S.E.V were supported, respectively, as doctoral candidate (Aspirant) and
486
postdoctoral fellow by the Research Foundation Flanders (FWO-Vlaanderen). N.B. was
487
supported by the Inter-University Attraction Pole (IUAP) ‘µ-manager’ funded by the Belgian
488
Science Policy Office (BELSPO, P7/25). We thank Bert Bundervoet for the provision of
489
sludge inocula, Dries Seuntjens and Samnang Nop for their aid in developing the Arduino
490
controller, Veerle De Smedt, Bavo Vanneste and Greet Van De Velde for practical work and
491
Jo De Vrieze for feedback on the manuscript.
492 493
Supporting Information Available 25 ACS Paragon Plus Environment
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494
PHB extraction; Analytical procedures; Calculations and statistical comparisons;
495
Observed yield for the HiCS reactors; Intracellular PHB concentrations; Correlation
496
coefficients for operational variables and performance indicators. This material is available
497
free of charge via the Internet at http://pubs.acs.org.
498 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529 530 531 532 533
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Environmental Science & Technology
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