Cement and Concrete Research 131 (2020) 106034

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Cement and Concrete Research

journal homepage: www.elsevier.com/locate/cemconres

Long-term in situ performance of geopolymer, calcium aluminate and T

Portland cement-based materials exposed to microbially induced acid
corrosion
Cyrill Grengga, , Neven Ukrainczykb, Günther Koraimannc, Bernhard Muellerd, Martin Dietzela,
⁎

Florian Mittermayre
a
Institute of Applied Geosciences, Graz University of Technology, Rechbauerstraße 12, 8010 Graz, Austria
b
Institute of Construction and Building Materials, Technische Universität Darmstadt, Franziska-Braun-Straße 3, 64287 Darmstadt, Germany
c
Institute of Molecular Biosciences, University of Graz, Humboldstraße 50, 8010 Graz, Austria
d
Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology, Stremayrgasse 9/II, Graz, Austria
e
Institute of Technology and Testing of Building Materials, Graz University of Technology, Inffeldgasse 24, 8010 Graz, Austria

ARTICLE INFO ABSTRACT

Keywords: This contribution presents an extensive performance evaluation of metakaolin-based geopolymer and calcium
Durability aluminate mortars during a long-term field exposure to a wastewater system exhibiting intensive microbially
Alkali activated cement induced acid corrosion (MIAC) conditions. Results were compared to a high-performance OPC concrete, typi-
Calcium aluminate cement cally used for manhole fabrication. Field conditions were obtained by monitoring relative humidity, tempera-
Long-term performance
ture, H2S and CO2. Microstructural degradation and elemental distributions within each binder type over time
Corrosion
Microstructure
were recorded by electron probe microanalysis, X-ray diffraction and pH-imaging techniques, together with
Biocorrosion specimen's mass and surface-pH characterization. Microbiome and epifluorescence analyses indicated exposure-
time dependent alternating bacterial community structures within the materials. Clear differences regarding
bacterial species distribution and biodiversity were observed for the different binder types. Estimated corrosion
rates were the lowest (1.4 mm/a) and the highest (13.3 mm/a) for the tested geopolymer formulations, pointing
out that only well designed geopolymer materials may provide an improved MIAC resistance.

1. Introduction established due to chemical and microbial processes during sewage

The establishment of modern underground sewer networks as we
know them today represents a major step in the development of sani-
tary standards of modern society. Thereby, not only the rising quan-
tities of sewage produced due to growing populations and increasing
urbanisation within the last two centuries have been efficiently man-
aged, but also public health related aspects, such as water-borne dis-
eases were averted. Additionally, the hazardous impact of potential
wastewater contamination for the adjacent environments was limited
[1]. However, the World Health Organization (WHO) reported in 2005
that around 2.6 billion people are still lacking basic sanitation. This
clearly indicates the still growing demand for efficient, safe, and cost-
effective collection, transport and treatment of sewage worldwide, to-
gether with the need to maintain the long-term performance of existing
infrastructure. Frequently reported insufficient material durability
performances are mainly caused by chemically aggressive conditions
transportation [2–4]. In this matter, microbially induced acid corrosion
(MIAC) of concrete and metals is one of the central processes leading to
sewer network degradation globally, with both economic and health-
related impact. For example, MIAC accounts for 10% of all possible
damage types in overall wastewater drains and pipe infrastructure in
Germany [5]. As 38% of this infrastructure is made from concrete based
materials, it was estimated that MIAC and abrasion accounts roughly
26% (calculated as 10%/0.38) of damages in concrete wastewater in-
frastructure. The age of the average German pipe infrastructure is ap-
proaching 40 years, while about one fifth of it has reached damage that
must be rehabilitated within the next 4 years. Moreover, rapid urba-
nisation worldwide requires substantial pipe infrastructure to be newly
constructed. Therefore, an increasing necessity exists to design in-
novative and highly durable materials for wastewater infrastructure,
either newly constructed or to rehabilitate the existing damaged ones
for substantial extension of their service life. To date, no sustainable

⁎
Corresponding author.
E-mail address: cyrill.grengg@tugraz.at (C. Grengg).

https://doi.org/10.1016/j.cemconres.2020.106034
Received 25 November 2019; Received in revised form 20 February 2020; Accepted 5 March 2020
Available online 13 March 2020
0008-8846/ © 2020 Published by Elsevier Ltd.
C. Grengg, et al.
Fig. 1. Exposure conditions, together with a schematic illustration of the analytical approach conducted during each sampling point.
building material exists, which meets the long-term requirements in
such aggressive and corrosive environments [6–8]. Reasons therefore
are multifaceted and were recently summarized by Grengg et al. [6]. In
recent years, much research focused on the development of calcium
aluminate cement (CAC) based materials, demonstrating their superior
performance in MIAC environments. Up to 6 times better performance
was reported in systems using CAC compared to OPC materials [9–11].
Reasons for their superior performance are attributed to the acid buffer
capacity of aluminum hydroxide (Al(OH)3) and the formation of a pore
filling Al(OH)x gel under acid attack that exhibits better cohesion of the
degraded layer, as well as due to potential antimicrobial properties of
Al [10,12].
Ordinary Portland cement-based (OPC) materials form mainly cal-
cium silicate hydrate (C-S-H) phases and calcium hydroxide (CH) from
the hydration of the clinker phases. OPC hydration products are ther-
modynamically unstable at pH values below 10 and consequently dis-
solve or alter (decalcify) [13]. Accordingly, there is serious growing
concern about the suitability of OPC-based materials in such environ-
ments. This raises the demand for alternative types of materials with
similar physiochemical, but different microstructural and chemical
properties, ensuring chemical resistance. In this perspective, geopo-
lymer concretes (GPC) represent a promising group of materials, po-
tentially suitable for, but not exclusively, MIAC environments. Geopo-
lymer (GP) technology avoids the formation of Ca-rich acid-soluble
hydration products present in OPC and CAC binders as well as in alkali-
activated binders rich in calcium. Material properties of hardened GPC
are reached via polycondensation of alumino-silicates, thereby ex-
hibiting improved acid resistance [14–16]. GP is made from one or
several aluminosilicate materials (e.g. calcined clays, volcanic rocks or
fly ash (FA)) mixed with alkaline reagent solutions, such as soluble
sodium or potassium silicates (i.e. water glass (WG)), water and ag-
gregates to form a construction material with similar mechanical
properties compared to OPC- and CAC-based concretes [14,17]. Re-
search on alkali aggregate reaction [14,18] demonstrated that meta-
kaolin-based geopolymer mortars, although having an order of mag-
nitude higher alkali contents than PC-based mortars, exhibit negligible
swelling and loss of rigidity.
To date, data on field performances of GP in sewer environments,
affected by MIAC are scarce [19]. The present contribution presents an
2
Cement and Concrete Research 131 (2020) 106034
extensive field campaign over the duration of 18 months in which
metakaolin-based geopolymer mortars (GPM) were tested with respect
to their overall performance within a sewer system exhibiting highly
bio-chemically aggressive conditions. In this study, the performance of
geopolymer mortars was evaluated in comparison to a high-perfor-
mance OPC concrete typically used for manholes and CAC mortars ty-
pically used for repair of biodegraded concrete. This study focuses on
relevant material properties and their evolution over time documenting
progressive degradation. Monitored parameters comprise surface pH,
pH cross-section mappings, mass balancing, optical observations and
microstructural alterations, as well as a detailed characterization of
biofilm-forming bacteria.
2. Materials & methods
2.1. Environmental system characteristics
The system chosen for the field study lies in Austria close to the city
of Leoben and is part of the regional communal wastewater network.
Therein, specimens were placed in a power main outlet storage basin,
heavily affected by MIAC. The resulting severe damage to the existing
OPC based concrete structures requires integral remediation action
latest every 2–10 years. Various state-of-the-art repair materials have
been applied in the past, ranging from standard OPC-based solutions to
different lining and sealing solutions, all with little to no success. For
instance, an epoxy-based coating, applied during the last renovation in
2017 had to be completely renewed after < 1.5 years in spring 2019.
Accordingly, this system provides ideal in-situ conditions to investigate
the accelerated behavior of novel building materials under highly ag-
gressive MIAC conditions. Additionally, the storage basin contains an
elevated pedestal platform with the dimensions of roughly 3 m2, de-
signed for operational service purposes, which was used for the place-
ment of the specimen-holder boxes, avoiding any direct contact to the
wastewater (see Fig. 1 left side).
In order to evaluate the prevailing environmental system char-
acteristics, concentrations of hydrogen sulfide (H2S) and temperature
were monitored permanently, using a myDataSens1000_H2S gas
monitor. The relative humidity (r.h.) of the sewer atmosphere was re-
corded by a Voltcraft DL-121TH data logger over the period of several
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

Table 1
Chemical composition (wt%) of the binders/raw materials.
Material SiO2 Al2O3 CaO Fe2O3 TiO2 MgO Na2O K2 O SO3 H2O

PC (CEM I) 18.1 3.1 51.9 4.75 0.17 1.57 0.17 0.3 2.0
CAC 5.2 51.4 36.7 2.5 1.9 0.5 0.1 0.2
Metakaolin K1 47.6 38.3 1.4 2.0 0.1 0.1
Metakaolin K2 66.2 21.3 2.5 4.1 1.0 0.5 0.1 0.5
Trass 53.4 19.4 3.4 4.9 0.6 1.2 4.5 4.0 0.2
Metakaolin + TrassK1T 49.3 32.6 1.0 2.5 1.6 0.4 1.4 1.3 0.1
Waterglass (WG) 22.0 23.0 55.0

months. Over several days, carbon dioxide (CO2) concentrations were
captured utilizing CORA, an energy-efficient NDIR-device with an
overall accuracy of ± 3% [20].
2.2. Material characteristics
In this study, three different groups of mineral-based binder systems
were tested. Two types of geopolymer, one CAC, and one OPC material.
Chemical composition of the raw materials is given in Table 1. Po-
tassium based waterglass (alkali silicate solution) had a solid content of
45 wt%, viscosity of 20 mPa s, pH of 13.5, and SiO2/K2O molar ratio of
1.5 (according to manufacturer information). Geopolymers were man-
ufactured using two types of metakaolin, a high purity white one (K1)
and a quartz-rich rust brown iron-rich one (K2), as well as Trass (nat-
ural pozzolan). Quantitative XRD using Rietveld refinement (10 wt%
spiked corundum) allocated the amorphous (~metakaolin) and quartz
mass content to be 81 wt% and 10 wt% respectively in sample K1, while
46 wt% amorphous and 40 wt% quartz in K2 ([21] data not shown).
The Trass was obtained as a commercial product according to DIN
51043, exhibiting a LOI = 5.40 wt% and a density of 2.65 g/cm3. The
compressive strength of Trass/Ca(OH)2 mortars (DIN 51043) was
7.8 MPa. The Calcium aluminate cement used contained CaAl2O4 as the
main clinker phase and the following minor phases (CaO)2(Al2O3)
(SiO2), (CaO)(TiO2) and (CaO)12(Al2O3)7 (see appendix for chemical
compositions). CEN standard sand following DIN EN 196-1 was used
(grading 0.08–2 mm, conforming to the standard size distribution),
having at least 95% quartz and following minor phases; feldspar, albite,
anorthite, microcline and muscovite as identified by XRD. The mix
design is presented in Table 2, which for the GP and CAC mortars was
chosen by fixing the workability spread at 17 ± 1 cm. In geopolymer
mixture GP-K1T, 30 wt% of metakaolin (K1) was replaced by Trass.
Mortar standard specimens (size of 160 × 40 × 40 mm) were cast
according to EN 196-1. Workability spread and compression tests were
done according to EN 1015-(3 and 11). Specimens were cured for
minimum of 28 days at 100% r.h. and 20 °C. After 28 days, CAC-based
mortars were additionally sealed and cured at 45 °C for one day to
convert the metastable phases to the stable ones.
On each hardened mortar, mercury intrusion porosimetry (MIP)
measurements were carried out using a Pascal 440 from Thermo-
Scientific. The measurements were performed up to 400 MPa with
gradual reading for each applied pressure (increase speed of about
10 MPa/min), on the previously dried sample with an evacuation
pressure of 50 μm Hg during 5 min. The pore diameter was calculated
using the Washburn equation and following mercury properties: density
13.53 g/cm3, surface tension 0.485 N/m, and contact angle 130°.
The open porosity was obtained from the water absorption mea-
surements using halves of the specimen prisms (40 × 40 × 80 mm,
cured for 28 days). Therefore, the dry mass (dried for 24 h at 105 °C),
the water saturated mass and the sample volume (Archimedes method)
were measured on at least three replicates.
Chemical compositions of the mortars were calculated based on
chemical composition of individual components, which were evaluated
by X-ray fluorescence analysis (XRF) using a wavelength dispersive X-
ray fluorescence spectrometer (PANalytical 2404).
An OPC concrete C55/67 (exposure classes: XC4/XD2/XF3/XA2L/
XA2T) according to EN 206 was used as a reference. This concrete was
fabricated with a CEM I 42.5 R SR0 (EN 197-1), a w/c ratios of 0.43,
predominantly siliceous aggregates (maximum size 16 mm) and about
4% of entrained air. Cubes of 150 mm3 were casted and cured according
to ÖNORM B4710-1. The w/b of the reference concrete is 0.43, which is
a typically used concrete in Austria for sewers according to ÖN B4710
(Table 2). The 28-days compressive strength was 84 N/mm2.
150 × 40 × 40 mm3 concrete specimens were cut out of the cube with
an angle grinder [22].
For the field exposure, all hardened mortar prisms were cut in half
resulting in dimensions of 80 × 40 × 40 mm (75 × 40 × 40 in case of
the reference OPC concrete). Prior to exposing, the specimens were
dried for 24 h at 40 °C. Subsequently, each specimen was weighted and
surface pH on four randomly distributed points was measured, using an
Extech PH100; ExStik® pH Meter. Thereafter, four (or five) replicates of
each material were placed in open plastic boxes with a voided bottom
(Fig. 1), in order to avoid the accumulation of aggressive solutions at
the bottom over time, and placed on the elevated platform in the power
main outlet basin.
2.3. Analytical methods on exposed specimens
Specimens were removed from site after 3, 6, 12 and 18 months. On
site, a photo documentation of each specimen was conducted.
Thereafter, one side of each specimen was carefully scraped and the
resulting sample was collected in a sterile tube, immediately trans-
ported to the laboratory and stored at −20 °C until further use (see

Table 2
Mixture design (g) and proportioning of the specimens (mass ratio).
Sample CEM Ia CAC MK-K1 MK-K2 TRASS WG Aggregates Sandd W (H2O) W/Bc MK(+T)b/WG

OPC 450 Silicious dmax = 16 mm 194 0.43

CAC 450 1350 225 0.45
GP-K1T 315 135 404 1350 0.32c 1.11b
GP-K2 450 356 1350 0.31c 1.27

a
CEM I 42.5 R SR0 (EN 197-1).
b
30 m.% replacement of Metakaolin by Trass.
c
Comprises the powder binder as well as the solid content of the waterglass (WG), i.e. W/B = 0.45 WG/(0.55 WG + powder).
d
CEN standard sand acc. EN 196-1.

3
C. Grengg, et al.
below section on DNA extraction). In the lab, specimens were photo-
graphed using a digital camera and dried at 40 °C for 24 h. Thereafter,
the mass of each specimen was determined and four randomly dis-
tributed surface pH measurements were conducted, using an Extech
PH100; ExStik® pH Meter.
2.3.1. Microstructural and mineralogical analyses
From one side, if present, soft deterioration layers were scraped
from the specimen's surfaces dried and subsequently powdered for
qualitative X-ray diffraction (XRD) analyses. XRD patterns were re-
corded over the range of 4–85°2Θ with a step size of 0.008°2Θ and a
count time of 40 s/step, using a PANalytical X'Pert PRO diffractometer.
The diffractometer was equipped with a Co-tube (40 kV and 40 mA), a
spinner stage, 0.5° divergence and anti-scattering slits, and a Scientific
X'Celerator detector. Mineral identification and quantification were
carried out using the PANalytical X'Pert HighScore software (version
2.2e) and pdf-2 database.
In order to guarantee stability of the remaining corrosion layers,
samples were impregnated with a low viscosity epoxy resin (Buehler;
EpoThin 2 Hardener) under vacuum conditions. Subsequently, cross-
sections with the thickness of around 5 mm were cut from the middle of
the longitudinal side of the samples using a diamond saw (see Fig. 1).
On these freshly cut cross-section surfaces, optical pH imaging
measurements were conducted using the analytical method described in
[22,23]. A sensor foil exhibiting an apparent pKa value of about 4.5 was
chosen, enabling a sensitive range of between 3.4 and 6.4. The opposite
freshly cut surface was used for Epifluorescence analyses (see below).
Thereafter the cross-sections were polished for further micro-
structural analyses. (Semi)-quantitative elemental distribution images
of aluminum, calcium, magnesium, silicon, potassium and sulfur were
recorded by electron probe microanalysis (EPMA) using a JEOL
JXA8530F Plus Hyper Probe (JEOL, Tokyo, Japan), equipped with a
field emission gun. The wavelength-dispersive analytical mode with
15 kV acceleration voltage and a beam current of 10 nA was used. A
dwell time of 15 mS and step size of 3 × 3 μm was chosen. The
quantification of the individual element mappings in wt% were per-
formed against mineral standards from SPI (Microcline for Al, K and Si;
Dolomite for Ca and Mg; Barite for S; Ilmenite for Fe). The dimensions
of the mappings were chosen in a way to image the entire deterioration
horizons, the transition zones, as well as parts of the interior intact
cementitious matrix. In order to better characterize the mineralogical
changes, element profiles from the same mapping areas, but only re-
cognizing micro-regions corresponding to the cementitious matrix of
the materials were extracted. For this, elemental cut-off concentrations
were determined to ensure disregard of pixels attributed to siliceous
aggregates.
2.3.2. DNA extraction, quality control and 16S bacterial community
analyses
To extract the DNA from the collected samples (scraped samples, see
above) the DNeasy PowerLyzer PowerSoil Kit (Qiagen) was used, fol-
lowing the manufacturer's protocol. For the bead beating option, a
PowerLyzer 24 homogenizer (Qiagen) with 45 s and 2500 rpm for
disrupting cells was used. The quality and amount of the isolated total
DNA was determined by DNA agarose gel electrophoresis and by
measuring absorbance at 280 nm in a NanoDrop microvolume spec-
trophotometer. In order to verify the presence of bacterial DNA, PCR
reactions were performed with primers specific for 16S rDNA covering
variable regions V5 and V6 as described in Grengg et al. [24]. The re-
sulting DNA amplicons were separated by DNA agarose gel electro-
phoresis. Only DNA isolated from OPC, CAC and GP that was suffi-
ciently pure and abundant, and yielded the expected PCR product, was
further analyzed by 16S profiling.
DNA samples in a volume of 15 μL (total amount of DNA was 0.3 to
2 μg) were sent to Eurofins Genomics (Ebersberg, Germany) next gen-
eration sequencing (NGS) service. Amplicons were generated targeting
4
Cement and Concrete Research 131 (2020) 106034
the V3V4 region of bacterial 16S rDNA and sequenced on Illumina
MiSeq with the 2 × 300 bp paired-end read module. Demultiplexed,
primer-clipped raw sequences in FASTQ format were further analyzed
using the Qiime 2 bioinformatics pipeline running on a MacBook Pro
computer.
Analysis of NGS 16S sequence data was done using Qiime 2, version
2019.1 [25]. FASTQ forward and reverse sequences were imported,
subsequently denoised and filtered using the DADA2 plugin. To remove
low quality bases, forward and reverse sequences were truncated to 250
and 240 bases, respectively. Alpha diversity in the samples was esti-
mated using a sampling depth of 25,000 sequences. In order to assign
taxonomy to ASVs (amplicon sequence variants) - formerly called OTUs
(operational taxonomic units) - the SILVA [26] 132 SSU database
(V3V4, 341–805) was used as a classifier.
To visualize the presence of microbial activity within the sampled
material, freshly cut cross-section surfaces were stained using fluor-
escent nucleic acid stains SYTO9 and propidium iodide (PI) using a
protocol essentially described in Grengg et al. [25]. Images with both
dyes were conducted since PI has a higher DNA/RNA binding capacity
but cannot penetrate living cells, whereas SYTO9 is able to penetrate
living cells with lower binding efficiency. From these images, multi-
channel images were prepared by overlaying the image obtained with
the fluorescence microscope prior to staining (no stain, red color)
against the image obtained after staining (SYTO9/PI, green color).
3. Results
3.1. Material characteristics
The properties of the mortars (Tables 1 and A2; Fig. A1 in Appendix)
show that by fixing the workability spread at 17 cm, the capillary
porosity was maintained around 12.5 ± 0.6% (dried at 105 °C). The
highest value was for the GP-K1T sample (13.1%) and the lowest for
GP-K2 (12.0%), which is in agreement with the lower amount of wa-
terglass used (water to reactive solid content shown in Table 2). Al-
though being more porous, the GP-K1T sample exhibited the highest
compressive strength, as it was prepared with purer metakaolin (K1),
requiring more waterglass to fix the workability (Table 2). This is also
in agreement with pore size distribution results (Fig. A1), where the
amount of gel pores (< 10 nm) decreases at the expense of capillary
pores by lowering the amount of reactive components (i.e. GP-K1T >
GP-K2, acc. to mix proportioning Table 2). The higher amount of the
reactive components, i.e. both the reactive metakaolin and waterglass
content, resulted in the highest amount of gel pores. The drying
shrinkage micro-crack formation increased in following order: GP-
K2 < GP-K1T < OPC < CAC, as detected by MIP results in the
micro-scale pore range 0.1–5 μm. In general, geopolymer mortars ex-
hibit finer pore sizes compared to the OPC and CAC based materials,
where CAC has the highest amount of coarse pores due to the conver-
sion reactions [27] (Fig. A1).
Results of compressive strength show a rapid strength development
for geopolymers. For geopolymers, the strength results do not correlate
with the open porosity (Table A2), but are in semi-quantitative agree-
ment with the amount of the gel pores (i.e. amount of geopolymer gel)
(Fig. A1).
3.2. Study site characteristics
Four (or five) replicates of each casted specimen were placed into a
sewer system, strongly affected by MIAC. Average H2S concentrations
were 65 ppm with regular maximum concentrations of up to 722 ppm,
corresponding to the pumping pulses of the system every few of hours
(Fig. 2A). Relative humidity (r.h.) ranged between 69 and 100%
(Fig. 2B). A positive correlation between temperature (T) and H2S
concentrations was observed, accompanied by a corresponding de-
crease in r.h. Results of CO2 measurements, conducted over the period
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

25
700 A H2S (ppm)
T(°C)

600
20

500

15
H2S (ppm)

400

T(°C)
300 10

200
5
100

0 0
0 50 100 150 200 250 300 350
time (days)
100 7000
r.h. (ppm)
T(°C) B 17
CO2 (ppm)
T(°C) C 16
95 6000
16 14
90
5000
15 12
CO2(ppm)
r.h.(%)

T(°C)
85
T(°C)

4000
14 10
80
3000
13 8
75
12 2000 6
70
11 1000 4
65
0 5 10 15 20 25 30 17 Nov 18 Nov 19 Nov 20 Nov 21 Nov
time (days) time

Fig. 2. Average concentration of H2S and temperature (T) over the period of one year (A), together with typical humidity levels (B). CO2 concentrations ranged
between 800 and 6500 ppm over the period of 4 days (C).

of several days, indicate high concentrations between 800 and
6500 ppm (Fig. 2C).
3.3. Optical, mineralogical and microstructural observations
Optical observation of the specimens extracted after 6, 12 and
18 months of exposure showed high variations (Fig. A2). The OPC
specimens exhibit strong surface alterations including swelling,
cracking and spalling, with strongly increasing intensities over time.
The GP-1KT showed strong signs of deterioration after 12 month of
exposure, such as cracking, efflorescence and leaching, accompanied by
the precipitation of potassium‑aluminum-sulfate (K-Alum: KAl
(SO4)2·12H2O) salt. After 18 months of exposure, major (outer) portions
of the GP-K1T specimen completely lost its structural integrity and high
deterioration rates were observed. In contrast to OPC and GP-K1T,
substantially less deterioration was observed on the CAC and the GP-K2
specimens. After 18 months of exposure, low degree of swelling was
observed on the CAC specimens corresponding to the precipitation of
expansive sulfate salts such as gypsum (see XRD and EPMA measure-
ments), while a low degree of surface cracking, efflorescence and the
precipitated K-alum salt was observed on the surface (layer) of GP-K2
specimen.
The evolution of the surface pH of all materials showed a strong
reduction from the initial 11.4 ± 0.6 (OPC), 10.0 ± 0.1 (CAC),
10.3 ± 0.1 (GP-K1T) and 10.4 ± 0.2 (GP-K2), to as low as 2.0 ± 1.0
(OPC), 3.1 ± 0.4 (CAC), 2.0 ± 1.0 (GP-K1T) and 3.9 ± 0.1 (GP-K2)
after 18 months of exposure (Fig. 3). Interestingly, the CAC and both GP
materials exhibit a similar pH trend showing a gradual pH reduction
between 0 and 6 months, followed by a strong drop in pH between
months 6 and 12, from 9.5 ± 0.1 (GP-K1T), 8.9 ± 0.2 (GP-K2) and
8.3 ± 0.3 (CAC) to below 4.5. Between months 12 and 18, only a slight
pH reduction was observed on the CAC (3.1 ± 0.4) and GP-K2
(3.9 ± 0.1) while the pH of GP-K1T dropped to around 2.0 ± 1.0. By
contrast, the pH of the OPC material exhibited a strong drop from initial
11.4 ± 0.6 to 8.4 ± 0.5 after only 3 months of exposure, followed by
gradual decrease in surface pH between months 3 and 9 to 6.6 ± 0.6,
before again a steep drop was observed to 2.0 ± 1.0 after 18 months.
No mass loss was observed on OPC and CAC materials, but small
mass gains after 18 months of 3.9 wt% and 1.0 wt%, respectively,
which corresponds to the secondary precipitation of sulfate salts con-
firmed by XRD and EPMA analyses (Fig. 3). Both GP materials exhibited
a small gain in mass until 12 months (GP-K1T: 4.3 wt%) and 9 months
of exposure (GP-K2: 0.34 wt%), which correlates with the precipitation
of potassium alum (see XRD analyses). Between 12 and 18 months, a
strong mass loss of 40.0 wt% was observed on the GP-K1T specimen.
Contrarily, only a relatively small decrease in mass of 5.2 wt% was
measured for the GP-K2 in the period between 9 and 18 months (Fig. 3).
Qualitative XRD bulk analyses of the corrosion layers, scraped from
one side of each specimen surface after 12 and 18 month of exposure,
confirmed the dissolution of the Ca-(Si)-hydrate rich cementitious ma-
trix of the OPC material and the precipitation of high amounts of ex-
pansive gypsum (Gp) and elemental sulfur (S0) (Table A3). Within the
deterioration layers of the CAC materials the initial main phases of the
cement matrix (namely, C3AH6, C2AS and AH3) were largely dissolved
resulting in the formation of high quantities of secondary Gp (with
increasing amounts with time) and K-Alum (Fig. A3). Additionally, a

5
C. Grengg, et al.
Fig. 3. Surface pH evolution of outsourced specimens with time (A), together with the change in mass in % (B). The yellow shaded area (in A) corresponds to the
measurements conducted on strongly deteriorated specimen surfaces after 18 months (OPC and GP_K2), where highly uneven surfaces and high water absorptivity
prevented stable pH measurements, highlighted by high pH variations of up to 2 pH units. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
strong increase of the amorphous content with time was observed.
Mineralogical characterization of the GP materials revealed that the
corrosion products were elemental sulfur (S0) and high quantities of
potassium alums (K-Alum) (Table A3, Fig. A4). Within the GP-K2 ma-
terial, low amounts of gypsum (Gp) were formed, corresponding to the
higher Ca concentrations of the metakaolin K2 (1.6 wt%) compared to
K1T (0.8 wt%).
Element distribution images (Figs. 4 and 5) and element profiles
(Appendix Figs. A5–A7) showed strong mineralogical and micro-
structural changes within the deterioration layers of the different ma-
terials after 12 and 18 months of exposure. Within the OPC material,
complete dissolution of the Ca-rich cement matrix in the micro-
structurally deteriorated cement layers, as well as an intensive new
precipitation of Ca sulfate salts progressed. After 18 months of ex-
posure, penetration of biogenic H2SO4 led to swelling of the specimen,
combined with crack formation and a complete destabilization of the
microstructure to a depth of approx. 3.9 mm after 12 months, and
9.5 mm after 18 months of exposure. The transition from intact to
strongly corroded concrete is marked by an increase in Mg, Fe and, to a
lesser extent, Al concentrations followed by a strong decrease of the
latter elements and Ca, as well as by the counter-rotating successive
incorporation of S (Figs. 4a, A5). The corrosion layers consist almost
exclusively of the newly formed calcium sulphates, recognizable by the
corresponding Ca and S accumulation areas in combination with less
dominant layered amorphous silicon horizons and relicts of undissolved
siliceous aggregates (Fig. 4a).
The BSE and elemental images conducted on the CAC specimen
revealed a similar corrosion pattern, although significantly lower cor-
rosion depths of around 0.5 mm after 12 months and 3.2 mm after
18 months (Figs. 4a, A6). Again, the transition to the intact cement
matrix is characterized by a strong depletion of Ca and Al and con-
current concordant areas of Ca and S incorporation, as well as layered
Si accumulation horizons. In contrast to the OPC material, no accu-
mulation zones of Mg or Fe were detected.
The depth of microstructural alteration within the GP materials is
characterized by a depletion of K and Al and associated (micro)crack
formation (Fig. 5). At the transition between intact and altered GP
framework, a sequence of elemental changes was observed (Fig. A7).
Beginning from the sound inner matrix (right side of Fig. A7), the in-
nermost transition area with a width of roughly 0.3 mm is characterized
by strongly decreasing K concentrations, while Al and Si keep the
concentration levels of the intact GP framework. Next, an Al accumu-
lation zone of roughly 0.5 mm thickness was observed, having higher
6
Cement and Concrete Research 131 (2020) 106034
average concentrations compared to the intact GP framework. Within
this area, K decrease flattens out, while no changes in Si concentrations
are observed. The end of this zone, close to the surface, is defined by
strong drop of K and Al concentrations and an opposing slight increase
of Si concentrations. There is no change within the Fe concentrations
between intact GP framework and the deterioration zones. In addition,
no S incorporation was detected within the GP-K2 material, while low
degree accumulation zones were observed within the thick deteriora-
tion layer of the GP-K1T material after 12 month. Interestingly, higher
Si concentrations in respect to the intact GP network were observed
within these deterioration layers. On the GP-K1T specimen high cor-
rosion rates were obtained, namely around 6.0 mm after only
12 months of exposure, leading to a complete deterioration and dis-
solution of large parts of the specimen after 18 months (as described up
to 40% mass loss), preventing the fabrication of a reliable EPMA
sample. Contrarily, the GP-K2 specimen displayed the lowest dete-
rioration depths of 0.2 mm after 12 and 2.1 mm after 18 months
(Fig. 5).
Optical pH images were taken from the same cross-section and are
displayed in Fig. 6. The core regions of the OPC, CAC and GP-K2 spe-
cimen's cross-sections obtained pH values above 6.4 (grey color; out of
calibration), whereas the measured pH throughout the strongly dete-
riorated GP-K1T specimen did not exceed this value. The near surface
regions of all specimens exhibited low pH values between 3.6 and 6.0,
although average pH values within these deterioration layers of the
OPC material were on average about one pH unit higher, compared to
the CAC and GP-K2 material. The average depth of these low pH areas is
in good agreement with the thickness of the deterioration layers ob-
tained from EPMA. A sharp transition exists between the high pH core
areas and the low pH near-surface deterioration regions, which is in
agreement with the observed mineralogical transition zone between
intact cementitious matrix and the deterioration layers. In this context,
it is important to point out that due to the development of thick, soft
deterioration layers on the OPC material featuring extremely low me-
chanical strength, two sides were entirely scraped off for microbiome
and XRD analyses. Accordingly, the pH image obtained is missing for
these two sides (left and lower side of OPC in Fig. 6). This loss of ma-
terial is quantified by lower cross-section dimensions of roughly
32 × 32 mm on average (initial specimen dimensions 40 × 40 mm). In
contrast, the CAC and GP-K2 still exhibit their initial dimensions
(40 × 40 mm) and shape due to higher structural integrity. While the
decrease in pH within the CAC material seems to proceed quite con-
sistently from all sides, the pH evolution within the GP-K2 material
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

12 month 18 month
OPC CAC OPC CAC

BSE

500 µm 500 µm 500 µm 500 µm

high high high high

low low low low

Ca

500 µm 500 µm 500 µm 500 µm

high high high high

low low low low

500 µm 500 µm 500 µm 500 µm

high high high high

low low low low

Al

500 µm 500 µm 500 µm 500 µm

high high high high

low low low low

Si

500 µm 500 µm 500 µm 500 µm

intact corrosion intact corrosion intact corrosion intact corrosion

microstructure layers microstructure layers microstructure layers microstructure layers
deterioration 9.5 mm 3.2 mm
3.9 mm 0.5 mm
depth

Fig. 4. Displays BSE images, together with the element distribution images of Al, Ca, Si and S throughout the deterioration layers, the transition zone and the intact
cement matrix of the OPC and CAC material after 12 and 18 month of exposure. Microstructural alteration depths were characterized reaching values of 3.9 mm after
12 months and 9.5 mm after 18 months for the OPC material, while low depths of 0.5 mm after 12 months and 3.2 mm after 18 months were determined for the CAC
material.

proceeds non-uniformly, where one side (lower side in Fig. 6) shows
significantly thicker, up to roughly 5 mm, lower pH ranges. The ma-
terial GP-K1T shows throughout the entire cross-section extremely low
pH values, corresponding to the intensive degree of deterioration.
3.4. Microbial community structures
Microbial community analysis of 16S rRNA Illumina MiSeq am-
plicon sequence data of CAC, GP-K1T and GP-K2 revealed microbial
colonization patterns that are overall consistent with the current sci-
entific view regarding the succession of bacteria during progression of
MIAC [28–30]. Autotroph, acidophilic sulfur oxidizing bacteria
(ASOBs) are dominant in all samples analyzed (Fig. 7, dark blue color).
However, although the indicated specimens were collected at the same
time point (12 months) and from the same location in the sewage
system, the detailed bacterial community compositions on different
materials exhibit striking variations. While the biofilm of the GP-K1T
consists almost entirely of described ASOBs (At. thiooxidans 48.9%, At.
ferrooxidans 31.4%), within the biofilm of the CAC and GP-K2 high
abundances of heterotroph, acidophilic Acetobacteraceae were found
(Fig. 7). A strongly dissenting microbial community structure was
found on the OPC material. Interestingly, the dominant autotrophs in
the OPC sample mainly belong to Halothiobacillaceae which are neu-
trophilic, together with high abundances of anaerobically growing
heterotrophs from the Firmicutes phylum (Peptostreptococcaceae and
Clostridiaceae). This is in accordance with the higher pH values
measured within the deterioration layers of the OPC specimen with
apparent values around 6, as well as with the expected anoxic to
anaerobic conditions within the thick deterioration layers observed
[28,29].
Epifluorescence images obtained of the materials after 18 months of
exposure showed that the biofilm expanded throughout the entire de-
terioration layers of all materials (Figs. 8, A8). Thereby the depth of
biofilm penetration always corresponds to the individual micro-
structural deterioration depths of each material, seen within the ele-
mental profiles (Figs. A5–A7) and images (Figs. 4 and 5) as well as
within the pH images (Fig. 6). These results are in agreement with
previous findings on OPC reported by Grengg et al. [29].
In order to be able to better evaluate the results of bacterial pro-
filing, more time intervals, namely 6 months for OPC and GP-K1T;
9 months for CAC; and 18 months for GP-K2, were investigated and
compared to the bacterial community composition after 12 months.
Fig. 9 shows a heat-map of microbial taxa that reached a relative
abundance of > 10% in at least one sample. Microbial communities
found on OPC and GP-K1T materials at 6 months are dominated by
neutrophilic SOB (NSOBs) which almost exclusively belong to the genus
Halothiobacillus. Sanger sequencing of 16S rDNA clones (variable re-
gions V5V6), simultaneously conducted on all materials after 6 month
of exposure revealed a similar dominance of Halothiobacillus sp. with 5/
10 (OPC), 3/10 (CAC), 7/10 (GP-K1T), 9/10 (GP-K2) clones, respec-
tively (data not shown). The biofilm extracted from the CAC material
after 9 months consist almost entirely of acidophilic bacteria

7
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

12 month 18 month
GP_K1T GP_K2 GP_K1T GP_K2

BSE

500 µm 500 µm 500 µm

high high high

low low low

loss of outermost deterioration layers

Al

measurement not possible

500 µm 500 µm 500 µm

high high high

low low low

Si

500 µm 500 µm 500 µm

high high high

low low low

500 µm 500 µm 500 µm

high high high

low low low

500 µm 500 µm 500 µm

high high high

low low low

Ca

500 µm 500 µm 500 µm

intact corrosion intact corrosion intact corrosion

microstructure layers microstructure layers microstructure layers
deterioration 2.1 mm
6.0 mm 0.2 mm roughly 20.0 mm
depth

Fig. 5. BSE and elemental distribution images of Al, Ca, K, Si and S showing microstructural alterations occurring within the GP-K1T and GP-K2 material after 12 and
18 months of exposure. Alteration horizons reached 0.2 mm after 12 months and 2.1 mm after 18 months within the GP-K2 material, while 6.0 mm within the GP-
K1T material. Due to the fast progressing deterioration of the GP-K1T material and associated loss of the deterioration layers after 18 months of exposure no stable
measurement was possible.

(Acidithiobacillaceae and Acetobacteraceae), with a shift from Acid- 4. Discussion

ithiobacillus thiooxidans towards Acidithiobacillus ferrooxidans between 9
and 12 months. On the GP-K2 material a strong shift from acidophilic While the overall better performance of CAC materials in MIAC
dominated biofilm towards a similar community patterns as described environments has been reported within several studies
within the OPC (43.2% Peptostreptococcaceae) material between 12 and [7,10,11,31–33], to date, data on field performances of geopolymer (or
18 months was observed. AAM) materials within MIAC environments are sparse [19]. However,
Shannon Indices (H index), statistically calculated as a measure for numerous lab studies and empirical tests have shown their potential
the diversity of the different biofilms, revealed overall reducing diver- ability to perform well within various acidic (abiotic) environments
sities with time of exposure, except for the CAC material which shows a [16,17,34,35].
counter-rotating trend (Fig. 9). After 12 month of exposure the highest
H index of 4.14 and 4.02 was observed on the GP-K2 and OPC material,
respectively, while significantly lower values of 2.44 and 2.42 were 4.1. Corrosion mechanisms
obtained for the CAC and GP-K1T materials. Thereby, the CAC material
generally exhibits the lowest biodiversity. Due to the fundamental chemical and microstructural differences
between the OPC and CAC compared to the GP materials, two generally
different corrosion patterns were observed. Thereby the deterioration of

8
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

6.4 materials are dominated by the dissolution of the calcium rich, hydrate-
6.0 based cementitious matrix and concurrent precipitation of expansive
5.6 corrosion products (mainly gypsum) due to biogenic acid production.
On the OPC material, the strong precipitation of secondary sulfate
5.2
salts led to swelling of the specimen, accompanied by an overall gain in
OPC

4.8 mass, resulting in the formation of up to 10 mm thick corrosion layers

4.4 after 18 month of exposure. These thick corrosion layers might be the
4.0 reason for the development of anaerobic, heterogenic dominated bio-
5mm
3.6 film observed after 12 months (Fig. 7). Therein, the initially developed
autotroph biofilm dominated by a succession of NSOBs and with de-
6.4 creasing pH by ASOBs is entrapped by secondary formed gypsum and
6.0 amorphous silica precipitates. Epifluorescence images of the dete-
5.6 rioration layers confirmed biofilm development within the entire cor-
rosion layers of the material (Fig. 8), which is in concordance with
5.2
findings of field observations previously reported by Grengg et al. [29].
CAC

4.8 With increasing thickness, oxygen penetration is limited and overall

4.4 anoxic to anaerobic conditions are established, triggering the coloni-
4.0 zation of heterotrophic bacteria, growing on the autotroph biofilm.
5mm 3.6 Within these late stages of corrosion, high corrosion rates have been
reported [2,24,39]. Accordingly, with gravitationally driven loss of
6.4 material and associated decrease in deterioration layer thickness, po-
6.0 tentially cycles of alternating autotroph and heterotroph dominated
5.6 biofilms established over time. Further extensive research on this topic
is necessary to confirm this hypothesis.
GP-K1T

5.2
Within recent years, several hypotheses were proposed explaining
4.8 the superior resistance of CAC materials in MIAC environments. While
4.4 several studies argue for combined solid state specific (formation of Al
4.0 (OH)x gel lowering porosity) and bacteriostatic effects of Al3+ [10,31],
5mm
3.6 more recent findings trace the superior performance of CAC vs. OPC
mainly back to the intrinsic resistance of phases initially present or
6.4 precipitated during the acid-driven deterioration process [33,40,41]. In
6.0 contrast, the bacteriostatic effects of Al3+ on the growth of relevant
5.6 ASOB could not be verified [41,42]. These new findings are largely in
agreement with the results obtained within this study [33,40]. EPMA
GP-K2

5.2
4.8
4.4
4.0
5mm
3.6
Fig. 6. pH images of the OPC, CAC, GP-K1T and GP-K2 recorded using t-DLR
imaging technique after 18 month of exposure (right column), together with an
optical picture of the same surfaces.
the OPC and CAC materials comply with the well-described 3 step
corrosion model, first described by Islander et al., and in recent years
adopted and extended by various studies [2,6–8,29,36]. Since the scope
of this study is not to review these well-established models, the fol-
lowing discussion will focus on novel findings obtained from the pre-
sent study. In this context, the synergy of prevailing environmental
parameters represents a central aspect controlling the duration of the
initial, (predominantly) abiotic phase of corrosion. While the impact of
H2S concentrations on initial surface pH reduction has been described
as a key for MIAC [37,38], minor relevance has been attributed to CO2
and r.h. so far. To the knowledge of the authors, the first field data on
CO2 concentrations over the durations of several days within MIAC
environments are presented herein. The analyzed high CO2 concentra-
tions (regularily up to 6500 ppm), periodically low r.h. of roughly 70%
and associated higher gas diffusion rates indicate their relevance for the
strong surface pH reduction observed on the materials. The impact of
CO2 is not only on carbonation or on acidity, but should be emphasized
as important on the initial development and continuing growth and
activity of biofilms on material surfaces. Therein, CO2 is an integral
compound used by the autotroph bacteria during chemosynthesis. The
second and third stages of corrosion observed on the OPC and CAC
elemental mappings confirmed the dissolution of the CAC cementitious
microstructure within the low pH deterioration layers at low rates.
Interestingly, XRD results confirmed the presence of C3AH6 as a residue
of the initial CAC microstructure within the same areas in low con-
centrations. Furthermore, the formation of significant amounts of sec-
ondary X-ray amorphous phases within the deterioration layers with
time was observed, corresponding to the formation of Al(OH)x gel and
amorphous Si-gels. The extent of Al(OH)x gel formation within the pore
spaces could not be fully verified. However, it is likely that this newly
formed gel effectively reduces open porosity and preserves cohesion in
the CAC material, resulting in lower acid diffusion rates. These findings
correspond to field observations conducted by Khan et al. within a
sewer system with similar aggressive environmental conditions over the
period of 24 months [33]. The biofilm observed on the CAC materials
within this study was almost entirely composed of acid producing
ASOBs and expands throughout the entire deterioration horizons
(Fig. 8). At the same time, it exhibited by far the lowest biodiversity of
all tested materials (Fig. 9). Especially after 9 month of exposure, a low
H index of 1.85 was measured. This implies that Al3+ might have
certain inhibiting effects on the growth of symbiotic microorganisms,
such as heterotrophs and fungi, potentially effecting biogenic metabo-
lism mechanisms in the long term [43].
To the knowledge of the authors, the data presented in this study are
the first one on Low-Ca- geopolymer/AAM binder systems tested in
MIAC field conditions. There exists one other study describing a long
term field exposure of high Calcium FA-based AAMs [19]. However,
due to the very different chemistry and associated microstructure, as
well as due to the critical role of Calcium regarding dissolution and neo-
formation of secondary sulfate salts a direct comparability may be in-
admissible. The observed deterioration mechanisms on the metakaolin-
based GP materials can be characterized as follows: (i) Initial lowering
of the surface pH due to leaching of alkali (K+) cations (initially being

9
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

A 100 Other B 100

Pseudomonadaceae
Moraxellaceae
relative abundance (%)

relative abundance (%)

Halothiobacillaceae
Enterobacteriaceae
Burkholderiaceae
50 Shewanellaceae 50
Rhizobiaceae
Caulobacteraceae Other
Erysipelotrichaceae Acidithiobacillaceae
Peptostreptococcaceae Acetobacteraceae
Lachnospiraceae Peptostreptococcaceae
0 Clostridiaceae 1 0 Parachlamydiaceae
OPC CAC

C 100 D 100
Other
Rhodanobacteraceae
relative abundance (%)

relative abundance (%)

Pseudomonadaceae
Enterobacteriaceae
Burkholderiaceae
50 50 Acidithiobacillaceae
Other Rhizobiaceae
Acidithiobacillaceae Acetobacteraceae
Acetobacteraceae Peptostreptococcaceae
Erysipelotrichaceae Clostridiaceae 1
Peptostreptococcaceae Staphylococcaceae
Clostridiaceae 1 Corynebacteriaceae
0 0
GP_K1T GP_K2

Fig. 7. 16S bacterial communities after 12 months of in situ exposure of the indicated material samples. Bacterial communities were determined as described in
Materials and methods, the relative abundance of bacteria at the Family level is given. Families below 1% are grouped as “Other” (grey). Brown hues: Firmicutes;
pink, purple and blue hues: Proteobacteria; dark blue: autotrophs (neutrophilic SOB: Halothiobacillaceae, acidophilic SOB: Acidithiobacillaceae). (For interpretation of
the references to color in this figure legend, the reader is referred to the web version of this article.)

excess in pore solution), CO2 and H2S penetration inwards triggering
carbonation and acid-base reactions within the first months of exposure
(Fig. 3). These reactions are expected to cause microstructural altera-
tions, such as decalcification of the partially formed C-A-S-H type
phases through formation of different calcium carbonate polymorphs
[44]. However, the degree of microstructural alteration within the GP
materials used in this study is most likely limited to K+-leaching due to
low Ca contents of 0.8 and 1.6 wt% for the GP-K1T and GP-K2, re-
spectively (Table A1) [45]. (ii) Reaching suitable conditions for mi-
crobial colonization, biogenic sulfuric acid diffusion led to the (more
excessive than in (i)) leaching of the charge-compensating alkalis (K+,
part of GP structure) and subsequent replacement by hydronium
(H3O+) or other cations (e.g. aluminum species). Additionally, dis-
solution and transport of excess Si-monomers and dimers - not actively
participating in the GP framework - occurs, which results in the pre-
cipitation of amorphous Si-gel within the low pH ranges of the mate-
rials. Thereby, the presence and thus the entailed amount of pre-
cipitates of such non-framework Si species is controlled by the Si/Al
ratio of the GP mixture [15,46]. (iii) With increasing acid production
and associated decreasing pH to below 4.0, de-alumination of the
geopolymer framework microstructure due to the hydrolysis of the
Si–O–Al bonds proceeded within the outermost corrosion layers
(Fig. 5). This resulted in a reduction of the integrity and structural
strength of the geopolymer framework within these areas [47]. The
detailed reaction mechanisms (e.g. congruent vs. incongruent dissolu-
tion) leading to the development of these Al-depleted, Si-rich corrosion
layers are still the subject of discussion. Sturm et al. proposed that at
least a part of the silica is released into solution and subsequently
precipitates as Si-rich gel [48]. EPMA mappings conducted within this
study support these findings, since higher Si concentrations, in respect
to the intact GP framework, were measured within the deterioration
layers of the GP materials (Fig. 5). This indicates that progressing acid
penetration with time has led to stepwise/gradual congruent (com-
plete) dissolution of the GP framework and immediate re-precipitation
of Si-rich gel out of the strongly oversaturated solutions within these
boundary layers, in agreement with partial de-alumination of GP-ma-
trix. In this context, the potassium-silicate solution content of the GP
mixture, and thus excess of potassium and water (i.e. porosity, Table
A2), most likely plays a crucial role regarding the durability of the GP
material. Due to the (2.5 wt%) higher potassium content within the GP-
K1T material (Table 1), increased amount of K leaching resulted in the
formation of higher quantities of K-Alum (Fig. A1). Resulting cracking
and associated higher porosity prevented the effective formation of the
protective amorphous Si–rich (aluminosilicate) gel within the GP-K1T
material, as observed within the GP-K2 material. The development of
such amorphous, relatively low porosity Si–rich gel layers within the
GP-K2 material are in accordance with the observed shift in micro-
biological community structure towards anaerobic dominated bacterial
strains (Peptostreptococcaceae, At. ferrooxidans) between 12 and
18 months of exposure (Fig. 9). Gevaudan et al. hypothesized that the
released supplementary cations (e.g. Ca2+ and Fe3+, and other heavy
metals) may act as replacements for the initial charge-balancing cations
(here primarily K+), and may have a key share in inhibiting electro-
philic attack of GP gels by hydronium cations [47]. Therefore, the
higher iron and calcium content (Table A1) in the GP-K2 compared to
GP-K1T -originating mainly from the different clay raw material used

10
C. Grengg, et al.
white multichannel
SYTO9
OPC
1 cm
PI
OPC
1 cm
SYTO9
GP-K1T
1 cm
PI
GP-K1T
1 cm
Fig. 8. Multichannel biofilm distribution images of OPC, CAC, GP-K1T and GP-K2 specimens after 18 months of exposure obtained from dividing the fluorescence
microscope image prior to staining (no stain, white) against the image obtained after staining (multichannel). Biofilm expands throughout the entire deterioration
layers of the different materials as indicated by green to orange color codes. (For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)
(Table 1) - could also explain the improved resistance of the GP-K2.
More research is needed to answer these open questions, which are
raised by discussion of the results of the current research.
4.2. Overall performance evaluation
After 18 months of exposure within a sewer system exhibiting
highly aggressive MIAC, strong variations in durability between the
tested OPC, CAC and GP materials were observed. Average corrosion
depths of 9.5 mm (OPC), 3.2 mm (CAC), 20.0 mm (GP-K1T) and
2.1 mm (GP-K2) were verified by BSE, elemental mappings and pH
imaging (Fig. 4a, b, 5). After 12 months of exposure, all materials ex-
hibit highly acidic conditions suitable for the growth of ASOBs, which
were confirmed by microbiome analyses (Fig. 7). Thus all materials
reached the highest level of biological and chemical aggressiveness
within the first year of exposure [2,6,7]. Accordingly, deterioration
rates observed between 12 and 18 months are suitable to be used as an
indication for long-term durability predictions of the tested materials,
assuming consistent (i.e. highly aggressive) environmental conditions.
Following this concept, average annual corrosion rates of 11.2 mm/a
for OPC, 5.4 mm/a for CAC, 28 mm/a for GP-K1T and 3.8 mm/a for GP-
K2 material were estimated. The high resistance of CAC material
against MIAC was mainly attributed to physiochemical and miner-
alogical material characteristics (see Corrosion mechanisms), which is
in accordance with [41,42]. Low biodiversity observed on the CAC
specimens potentially indicates a certain bacteriostatic effect of Al on
11
Cement and Concrete Research 131 (2020) 106034
white multichannel
CAC
1 cm
CAC
1 cm
GP-K2
1 cm
GP-K2
1 cm
microbial growth of relevant symbiotic heterotrophs and fungi; how-
ever, its impact on material durability needs further systematic in-
vestigations.
The reasons for the large variation in resistance, observed between
the two metakaolin-based GP materials, are multifaceted. Firstly, due to
the high Si content within the GP-K2, the presence of non-framework
building excess Si-monomers and dimers positively contributed to the
formations of described Si-rich gels. Secondly, the high amounts of fine
(partially) unreacted (quartz) particles in the K2 clay (values given in
section on Material characteristics), are reported to act as a filler ma-
terial within the GP structure [49]. This enabled the GP-K2 synthesis
with reduced amount of waterglass for same workability as in GP-K1T,
reducing open porosity from 13.1% to 12%, respectively. Both of these
material properties effectively reduce the diffusion of corrosive sub-
stances, such as the diffusion of acids. Additionally, the variations in
waterglass contents led to 2.5 wt% higher potassium concentrations
within the GP-K1T, compared to the GP-K2 mixture, and associated
higher K-leaching and K-Alum precipitation rates. This increased K-
Alum precipitation is seen in the observed mass gain of GP-K1T of up to
4.3 wt% within the first 9 months of exposure, followed by a strong loss
in mass due to increased cracking and acid penetration rates (Fig. 3).
Accordingly, the effective formation of a protective layer of amorphous
Si-rich gels, clogging porosity, did not proceed. Additionally, higher
SiO2/Al2O3 ratios within the GP-K2 mixture (3.7 compare to 2.3 in GP-
K1T) (Table A1), resulted in associated higher framework stability
under acid attack. Due to the amphoteric behavior of Al, exhibiting high
C. Grengg, et al.
Fig. 9. Distribution of dominant bacterial species on the investigated field samples. Bacterial communities were determined as described in Materials and methods,
the relative abundance of identified bacterial species is given. Only species that were found at a relative abundance of > 10% in at least one sample, are shown in the
heatmap matrix. White: no OTU/ASV present; blue: < 1%; green: 1–5%; yellow: 5–20%; red: > 20%. As an estimation for bacterial alpha-diversity, the Shannon
index (H´) is given. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
solubility within strongly acidic conditions, its concentrations within
the GP framework is most likely one of the key aspects determining GP
durability in MIAC environments.
5. Conclusion
This study developed an interdisciplinary field approach including
optical, chemical, microstructural, mineralogical and microbiological
methodologies to comparatively assess the overall in-situ performance
of CAC, GP and OPC materials within a strongly chemically aggressive
sewer system. The main findings are summarized as follows:
• High CO concentrations of up to 6500 ppm indicate its central role
2
in MIAC environments not only in respect to initial carbonation
reactions, but also as a source for microbial metabolic reactions
within later stages of corrosion.
• Strong shifts towards anaerobic biofilms over time were observed,
wherein heterotroph bacteria within the thick deterioration layers of
the OPC material dominated the biofilms. This indicates alternating
microbial community structures within the later stages of corrosion,
regulated by impeded oxygen supply due to the formation of thick
corrosion layers. A similar trend was observed within the microbial
community structures of geopolymer GP-K2, coinciding with the
formation of low porosity due to the formation of amorphous Si-rich
gel layers, which are expected to reduce oxygen availability.
• Obtained annual corrosion rates in descending order are: 28 mm/a
for the GP-K1T, 11.2 mm/a for the OPC, 5.4 mm/a for the CAC, and
3.8 mm/a for the GP-K2 materials.
• Low corrosion rates of the CAC material were attributed to the in-
trinsic resistance of Al-rich phases initially present and precipitated
during the deterioration process and partial formation of Al(OH)x
gel. Bacteriostatic effects on ASOBs, as sometimes reported in the
literature due to the high Al concentrations, were not observed,
however, the low biodiversity measured suggest certain effects on
the growth of symbiotic microorganisms such as heterotrophs and
12
Cement and Concrete Research 131 (2020) 106034
fungi.
• Geopolymer framework deterioration under MIAC conditions leads
to an almost complete dissolution of the Al and large parts of the Si
polymer framework and outwards diffusion followed by re-pre-
cipitation of amorphous Si-rich gels at low pH degraded zones.
• The higher resistance of the Geopolymer GP-K2 material (compared
to GP-K1T) is attributed to the lower potassium silicate pro-
portioning and associated stability of the geopolymer framework
due to the higher SiO2/Al2O3 ratio, lower K+ leaching, higher iron
content, as well as lower initial porosity.
CRediT authorship contribution statement
Cyrill Grengg: Conceptualization, Methodology, Investigation,
Validation, Writing - original draft, Visualization, Project adminis-
tration, Supervision. Neven Ukrainczyk: Validation, Resources,
Writing - original draft. Günther Koraimann: Validation,
Investigation, Visualization, Writing - review & editing. Bernhard
Mueller: Methodology, Visualization. Martin Dietzel: Writing - re-
view & editing. Florian Mittermayr: Conceptualization,
Methodology, Investigation, Writing - review & editing.
Declaration of competing interest
There arises no conflict of interests by publishing this work.
Acknowledgement
The authors gratefully thank the Graz University of Technology
(Austria) scientific grant program and TU Darmstadt for financial sup-
port. Financial support was greatly appreciated by Peter Rappold and
the Department of Water Resources Management, Styria, as well as by
Heinz Lackner and the Department of Energy, Residential Constructions
and Technology, Styria. Special thanks to Walter Fussi for providing the
multiple access to the exposure site.
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

Appendix A

Table A1
Chemical composition of mortar specimens obtained by XRF analyses (in wt%).

Mortar SiO2 Al2O3 CaO Fe2O3 TiO2 MgO Na2O K2O SO3

OPC 63.0 1.5 18.7 1.8 0.1 * 0.4 0.9 0.5

CAC 5.5 52.6 35.7 2.5 2.3 0.4 0.1 0.2 *
GP_K1T 53.5 23.4 0.8 1.8 0.8 0.4 0.8 11.8 *
GP_K2 60.7 16.3 1.6 3.0 0.7 0.3 0.2 9.2 *
⁎
Values below the detection limit.

Table A2
Compressive strength after 7 and 28 days, together with the open porosity of mortars after 28 days.

Material Compressive strength [MPa] Open porosity [%]

1 day 7 days 28 days 28 days

CAC 47.9 50.2 56.3 13.0

GP-KT1 50.1 63.8 68.4 13.1
GP-K2 48.7 61.5 60.4 12.0

Table A3
Shows the mineralogy of the deterioration layers (Qtz - quartz, Fsp – feldspar, Gp – gypsum, Katoite – C3AH6). Relative concentrations are indicated from x (trace
concentrations) to xxxx (main constituent).

Sample ID Qtz Fsp Gp Katoite Sulfur K-Alum

OPC_12m xxx x xxxx x

OPC_18m xxx x xxxx
CAC_12m xxxx x xx x
CAC_18m xxx x xxx x xx
GP-K1T_12m xxx x xxxx
GP-K1T_18m xxx x xxx
GP-K2_12m xxx x xxxx
GP_K2_18m xxx x xxxx

Fig. A1. Pore size distributions of the OPC, CAC, GP-K1T and GP-K2 materials analyzed by MIP.

13
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

Fig. A2. Optical observation of exposed specimen after 6, 12 and 18 months of exposure.

Fig. A3. Change in mineralogical composition of the intact CAC paste in comparison with the deterioration layers after 12 and 18 months of exposure. Please note
that for demonstration purposes peaks are cut at an intensity level of 2500 a.u.

14
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

Fig. A4. Change in mineralogical composition of the intact GP paste of GP-K1T and GP-K2 in comparison with the deterioration layers after 12 and 18 months of
exposure. Please note that for demonstration purposes peaks are cut at an intensity level of 2500 a.u.

15
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

Fig. A5. Quantitative element concentration profiles of Al, Ca, Mg, Fe and S, calculated from the elemental distribution mappings of the OPC material after
18 months of exposure. The transition from strongly deteriorated areas (left hand side) to intact microstructure (right hand side) is at a depth of roughly 9 mm,
marked by strongly decreasing S and increasing Ca concentrations, as well as by accumulation zones of Al, Mg and Fe.

Fig. A6. Quantitative element concentration profiles of Al, Ca, Mg, Fe and S, calculated from the elemental distribution mappings of the CAC material after
18 months of exposure. Decreasing Al and Ca concentrations and contemporaneous increasing S concentrations at a depth of roughly 3 mm mark the transition
between intact microstructure (right hand side) and the deterioration layers (left hand side).

16
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

Fig. A7. Quantitative element concentration profiles of Al, Ca, Fe, K and Si, calculated from the elemental distribution mappings of the GP-K2 material after
18 months of exposure. From the surface of the material (left hand side) until a depth of roughly 2.5 mm strongly decreasing concentrations of Al, K and Ca are
observed, together with a slight increase in Si concentrations. No change in Fe concentrations was observed.

17
C. Grengg, et al. Cement and Concrete Research 131 (2020) 106034

18
C. Grengg, et al.
Fig. A8. Epifluorescence images obtained of the materials after 18 months of exposure using either SYTO9 or PI as nucleic acid staining fluorescent dyes. False color
images for each sample reflecting the indicated fluorescence intensities are shown (no stain vs. SYTO9 or PI). The multichannel image represents an image created by
overlaying the fluorescence image prior to staining (no stain, red color) against the image obtained after staining (SYTO9/PI). Bright green areas indicate the
presence of bacterial biofilms within deterioration zones. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)
References
[1] T. Hvitved-Jacobsen, J. Vollertsen, C. Yongsiri, A.H. Nielsen, Sewer microbial
processes, emissions and impacts, Sewer Process, Networks, Paris, 2002, p. 13.
[2] B.R.L. Islander, J.S. Devinny, A. Member, F. Mansfeld, A. Postyn, H. Shih, Microbial
ecology of crown corrosion in sewers, J. Environ. Eng. 117 (1991) 751–770.
[3] T. Hvitved-Jacobsen, J. Vollertsen, A.H. Nielsen, Sewer Processes - Microbial and
Chemical Process Engineering of Sewer Networks, 2nd ed., CRC Press, London,
2013.
[4] H.S. Jensen, PhD Thesis; Hydrogen Sulfide Induced Concrete Corrosion of Sewer
Networks, Aalborg University, 2009.
[5] C. Berger, C. Falk, F. Hetzel, J. Innekamp, S. Roder, J. Ruppelt, Zustand der
Kanalisation in Deutschland: Ergebnisse der DWA-Umfrage 2015, Sonderdruck
Korrespondenz Abwasser, Abfall, 2016, https://doi.org/10.3242/kae2011/01.001.
[6] C. Grengg, F. Mittermayr, N. Ukrainzcyk, G. Koraimann, S. Kienesberger,
M. Dietzel, Advances in mineral based construction materials for sewer systems
affected by microbiological induced concrete corrosion: a review, Water Res. 134
(2018) 341–352, https://doi.org/10.1016/j.watres.2018.01.043.
[7] M. Peyre-Lavigne, A. Bertron, C. Botanch, L. Auer, G. Hernandez-Raquet, A. Cockx,
J.-N. Foussard, G. Escadeillas, E. Paul, Innovative approach to simulating the bio-
deterioration of industrial cementitious products in sewer environment. Part II:
validation on CAC and BFSC linings, Cem. Concr. Res. (2015), https://doi.org/10.
1016/j.cemconres.2015.10.002.
[8] M. Peyre Lavigne, A. Bertron, L. Auer, G. Hernandez-Raquet, J.-N. Foussard,
G. Escadeillas, A. Cockx, E. Paul, An innovative approach to reproduce the biode-
terioration of industrial cementitious products in a sewer environment. Part I: test
design, Cem. Concr. Res. 73 (2015) 246–256, https://doi.org/10.1016/j.cemconres.
2014.10.025.
[9] A.M. Goyns, M. Alexander, Performance of Various Concretes in the Virginia
Experimental Sewer over 20 Years, Balkema, 2014.
[10] J. Herisson, M. Guéguen-Minerbe, E.D. van Hullebusch, T. Chaussadent, Influence
of the binder on the behaviour of mortars exposed to H2S in sewer networks: a long-
term durability study, Mater. Struct. 50 (2017) 8, https://doi.org/10.1617/s11527-
016-0919-0.
[11] J. Herisson, M. Guéguen-Minerbe, E.D. van Hullebusch, T. Chaussadent, Behaviour
of different cementitious material formulations in sewer networks, Water Sci.
Technol. 69 (2014) 1502–1508, https://doi.org/10.2166/wst.2014.009.
[12] M. Valix, A.W.H. Cheung, J. Sunarho, H. Bustamante, The impact of calcium alu-
minate cement and aggregates on conversion and on filed performance in sewers,
Calcium Aluminates, IHS, 2014, p. 663.
[13] J. Stark, B. Wicht, Dauerhaf tigkeit von Beton, 2nd ed., Springer, 2013, https://doi.
org/10.1007/978-3-642-35278-2.
[14] F. Pacheco-Torgal, J. Labrincha, C. Leonelli, A. Palomo, P. Chindaprasit, Handbook
of Alkali-activated Cements, Mortars and Concretes, 1st Editio, Woodhead
Publishing, 2014.
[15] J. Davidovits, Geopolymer Chemistry and Applications, 4th ed., Springer, 2013.
[16] B. Singh, G. Ishwarya, M. Gupta, S.K. Bhattacharyya, Geopolymer concrete: a re-
view of some recent developments, Constr. Build. Mater. 85 (2015) 78–90, https://
doi.org/10.1016/j.conbuildmat.2015.03.036.
[17] J.L. Provis, J.S.J. van Deventer, Geopolymers. Structures, Processing, Properties
and Industrial Applications, (2009), https://doi.org/10.1533/9781845696382.
[18] R. Pouhet, M. Cyr, Alkali–silica reaction in metakaolin-based geopolymer mortar,
Mater. Struct. Constr. 48 (2014) 571–583, https://doi.org/10.1617/s11527-014-
0445-x.
[19] H.A. Khan, M.S.H. Khan, A. Castel, J. Sunarho, Deterioration of alkali-activated
mortars exposed to natural aggressive sewer environment, Constr. Build. Mater. 186
(2018) 577–597, https://doi.org/10.1016/j.conbuildmat.2018.07.137.
[20] M. Luetscher, F. Ziegler, CORA – a dedicated device for carbon dioxide monitoring
in cave environments, Int. J. Speleol. 41 (2011) 275–283.
[21] O. Vogt, N. Ukrainczyk, E.N. Koenders, Geopolymere als Spezialbaustoff,
Nachrichten Aus Der Chemie 65 (2017) 1198–1202 doi:12.
[22] C. Grengg, B. Mueller, C. Staudinger, F. Mittermayr, J. Breininger, B. Ungerböck,
S. Borisov, T. Mayr, M. Dietzel, Optical pH imaging of concrete exposed to che-
mically corrosive environments, Cem. Concr. Res. 116 (2019) 231–237, https://doi.
org/10.1051/matecconf/201819902007.
[23] B. Müller, C. Grengg, V. Schallert, M. Sakoparnig, C. Staudinger, J. Breininger,
F. Mittermayr, B. Ungerböck, S. Borisov, M. Dietzel, T. Mayr, Wide - range optical
pH imaging of cementitious materials exposed to chemically corrosive environ-
ments, RILEM Tech. Lett. 3 (2018) 39–45, https://doi.org/10.21809/rilemtechlett.
2018.72.
[24] C. Grengg, F. Mittermayr, a. Baldermann, M.E. Böttcher, A. Leis, G. Koraimann,
P. Grunert, M. Dietzel, Microbiologically induced concrete corrosion: a case study
from a combined sewer network, Cem. Concr. Res. 77 (2015) 16–25, https://doi.
org/10.1016/j.cemconres.2015.06.011.
[25] J.R. Rideout, M.R. Dillon, N.A. Bokulich, C. Abnet, G.A. Al Ghalith, H. Alexander,
E.J. Alm, M. Arumugam, Y. Bai, J.E. Bisanz, K. Bittinger, A. Brejnrod, J. Colin,
19
Cement and Concrete Research 131 (2020) 106034
C.T. Brown, B.J. Callahan, A. Mauricio, C. Rodríguez, J. Chase, E. Cope, R. Da Silva,
P.C. Dorrestein, G.M. Douglas, C. Duvallet, C.F. Edwardson, M. Ernst, J. Fouquier,
J.M. Gauglitz, D.L. Gibson, A. Gonzalez, G.A. Huttley, S. Janssen, A.K. Jarmusch,
B.D. Kaehler, K. Bin Kang, C.R. Keefe, P. Keim, S.T. Kelley, R. Ley, E. Loftfield,
C. Marotz, B. Martin, D. Mcdonald, L.J. Mciver, V. Alexey, J.L. Metcalf,
S.C. Morgan, J.T. Morton, A.T. Naimey, QIIME 2 : Reproducible, Interactive,
Scalable, and Extensible Microbiome Data Science, (2018), https://doi.org/10.
7287/peerj.preprints.27295.
[26] C. Quast, E. Pruesse, P. Yilmaz, J. Gerken, T. Schweer, P. Yarza, J. Peplies,
F.O. Glöckner, The SILVA ribosomal RNA gene database project: improved data
processing and web-based tools, Nucleic Acids Res. 41 (2013) 590–596, https://doi.
org/10.1093/nar/gks1219.
[27] D.A. Strauss Rambo, N. Ukrainczyk, F. de Andrade Silva, E. Koenders, R.D. Toledo
Filho, O. da Fonseca Martins Gomes, Calcium-aluminate mortars at high tempera-
tures: overcoming adverse conversion effects using clinker aggregates, Cem. Concr.
Compos. 96 (2019) 212–224, https://doi.org/10.1016/j.cemconcomp.2018.12.
002.
[28] S. Okabe, M. Odagiri, T. Ito, H. Satoh, Succession of sulfur-oxidizing bacteria in the
microbial community on corroding concrete in sewer systems, Appl. Environ.
Microbiol. 73 (2007) 971–980, https://doi.org/10.1128/AEM.02054-06.
[29] C. Grengg, F. Mittermayr, G. Koraimann, F. Konrad, M. Szabó, A. Demeny,
M. Dietzel, The decisive role of acidophilic bacteria in concrete sewer networks: a
new model for fast progressing microbial concrete corrosion, Cem. Concr. Res.
(2017), https://doi.org/10.1016/j.cemconres.2017.08.020.
[30] X. Li, G. Jiang, U. Kappler, P. Bond, The ecology of acidophilic microorganisms in
the corroding concrete sewer environment, Front. Microbiol. 8 (2017) 683, https://
doi.org/10.3389/FMICB.2017.00683.
[31] J. Herisson, E.D. van Hullebusch, M. Moletta-Denat, P. Taquet, T. Chaussadent,
Toward an accelerated biodeterioration test to understand the behavior of Portland
and calcium aluminate cementitious materials in sewer networks, Int. Biodeterior.
Biodegradation 84 (2013) 236–243, https://doi.org/10.1016/j.ibiod.2012.03.007.
[32] M. Alexander, A. Goyns, C. Fourie, Experiences with a full-scale experimental sewer
made with CAC and other cementitious binders in Virginia, South Africa, Proc.
Centen. Conf. Calcium Aluminate Cem, IHS, Avignon, 2008, pp. 279–292.
[33] H.A. Khan, A. Castel, M.S.H. Khan, A.H. Mahmood, Durability of calcium aluminate
and sulphate resistant Portland cement based mortars in aggressive sewer en-
vironment and sulphuric acid, Cem. Concr. Res. 124 (2019) 105852, , https://doi.
org/10.1016/j.cemconres.2019.105852.
[34] B. Drugă, N. Ukrainczyk, K. Weise, E. Koenders, S. Lackner, Interaction between
wastewater microorganisms and geopolymer or cementitious materials: biofilm
characterization and deterioration characteristics of mortars, Int. Biodeterior.
Biodegrad. 134 (2018) 58–67, https://doi.org/10.1016/j.ibiod.2018.08.005.
[35] P. Duxson, J.L. Provis, G.C. Lukey, S.W. Mallicoat, W.M. Kriven, J.S.J. Van
Deventer, Understanding the relationship between geopolymer composition, mi-
crostructure and mechanical properties, Colloids Surfaces A Physicochem. Eng. Asp.
269 (2005) 47–58, https://doi.org/10.1016/j.colsurfa.2005.06.060.
[36] G. Jiang, X. Sun, J. Keller, P.L. Bond, Identification of controlling factors for the
initiation of corrosion of fresh concrete sewers, Water Res. (2015), https://doi.org/
10.1016/j.watres.2015.04.015.
[37] X. Li, L. O’Moore, Y. Song, P.L. Bond, Z. Yuan, S. Wilkie, L. Hanzic, G. Jiang, The
rapid chemically induced corrosion of concrete sewers at high H2S concentration,
Water Res. 162 (2019) 95–104, https://doi.org/10.1016/j.watres.2019.06.062.
[38] A.P. Joseph, J. Keller, H. Bustamante, P.L. Bond, Surface neutralization and H2S
oxidation at early stages of sewer corrosion: influence of temperature, relative
humidity and H2S concentration, Water Res. 46 (2012) 4235–4245, https://doi.
org/10.1016/j.watres.2012.05.011.
[39] M. Kiliswa, Composition and Microstructure of Concrete Mixtures Subjected to
Biogenic Acid Corrosion and Their Role in Corrosion Prediction of Concrete Outfall
Sewers, University of Cape Town, 2016.
[40] M.W. Kiliswa, K.L. Scrivener, M.G. Alexander, The corrosion rate and micro-
structure of Portland cement and calcium aluminate cement-based concrete mix-
tures in outfall sewers: a comparative study, Cem. Concr. Res. 124 (2019), https://
doi.org/10.1016/j.cemconres.2019.105818.
[41] A. Buvignier, C. Patapy, M.P. Lavigne, E. Paul, A. Bertron, Resistance to biodeter-
ioration of aluminium-rich binders in sewer network environment: study of the
possible bacteriostatic effect and role of phase reactivity, Cem. Concr. Res. 123
(2019) 105785, , https://doi.org/10.1016/j.cemconres.2019.105785.
[42] A. Buvignier, M. Peyre-Lavigne, O. Robin, M. Bounouba, C. Patapy, A. Bertron,
E. Paul, Influence of dissolved-aluminum concentration on sulfur-oxidizing bac-
terial activity in the biodeterioration of concrete, Appl. Environ. Microbiol. 85
(2019) 1–12, https://doi.org/10.1128/aem.00302-19.
[43] T. Mori, T. Nonaka, K. Tazaki, M. Koga, Y. Hikosaka, S. Noda, Interactions of nu-
trients, moisture and pH on microbial corrosion of concrete sewer pipes, Water Res.
26 (1992) 29–37 (doi:0043-1354’92 $5,00 + 0.00).
[44] S.A. Bernal, X. Ke, M. Criado, S. Mundra, J.L. Provis, Factors controlling carbona-
tion resistance of alkali-activated materials, Proc. 10th ACI/RILEM Int. Conf. Cem.
Mater. Altern. Bind. Sustain. Concr, 2017.
C. Grengg, et al.
[45] S.A. Bernal, J.L. Provis, B. Walkley, R. San Nicolas, J.D. Gehman, D.G. Brice,
A.R. Kilcullen, P. Duxson, J.S.J. Van Deventer, Gel nanostructure in alkali-activated
binders based on slag and fly ash, and effects of accelerated carbonation, Cem.
Concr. Res. 53 (2013) 127–144, https://doi.org/10.1016/j.cemconres.2013.06.
007.
[46] P.J. Gevaudan, K.M. Campbell, T.J. Kane, R.K. Shoemaker, W.V. Srubar, Cement
and concrete research mineralization dynamics of metakaolin-based alkali-acti-
vated cements, Cem. Concr. Res. 94 (2017) 1–12.
[47] J.P. Gevaudan, A. Caicedo-Ramirez, M.T. Hernandez, W.V. Srubar, Copper and
20
Cement and Concrete Research 131 (2020) 106034
cobalt improve the acid resistance of alkali-activated cements, Cem. Concr. Res. 115
(2019) 327–338, https://doi.org/10.1016/j.cemconres.2018.08.002.
[48] P. Sturm, G.J.G. Gluth, C. Jäger, H.J.H. Brouwers, H.C. Kühne, Sulfuric acid re-
sistance of one-part alkali-activated mortars, Cem. Concr. Res. 109 (2018) 54–63,
https://doi.org/10.1016/j.cemconres.2018.04.009.
[49] O. Vogt, N. Ukrainczyk, C. Ballschmiede, E. Koenders, Reactivity and micro-
structure of metakaolin based geopolymers: effect of fly ash and liquid/solid con-
tents, Materials (Basel) 12 (2019) 1–21, https://doi.org/10.3390/ma12213485.