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Determination of point of zero charge of natural organic materials

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DOI: 10.1007/s11356-017-1115-7

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Environmental Science and Pollution Research
https://doi.org/10.1007/s11356-017-1115-7

RESEARCH ARTICLE

Determination of point of zero charge of natural organic materials

Elisee Nsimba Bakatula 1,2 & Dominique Richard 1,2 & Carmen Mihaela Neculita 3 & Gerald J. Zagury 1,2

Received: 20 May 2017 / Accepted: 20 December 2017

# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
This study evaluates different methods to determine points of zero charge (PZCs) on five organic materials, namely maple
sawdust, wood ash, peat moss, compost, and brown algae, used for the passive treatment of contaminated neutral drainage
effluents. The PZC provides important information about metal sorption mechanisms. Three methods were used: (1) the salt
addition method, measuring the PZC; (2) the zeta potential method, measuring the isoelectric point (IEP); (3) the ion adsorption
method, measuring the point of zero net charge (PZNC). Natural kaolinite and synthetic goethite were also tested with both the
salt addition and the ion adsorption methods in order to validate experimental protocols. Results obtained from the salt addition
method in 0.05 M NaNO3 were the following: 4.72 ± 0.06 (maple sawdust), 9.50 ± 0.07 (wood ash), 3.42 ± 0.03 (peat moss),
7.68 ± 0.01 (green compost), and 6.06 ± 0.11 (brown algae). Both the ion adsorption and the zeta potential methods failed to give
points of zero charge for these substrates. The PZC of kaolinite (3.01 ± 0.03) was similar to the PZNC (2.9–3.4) and fell within
the range of values reported in the literature (2.7–4.1). As for the goethite, the PZC (10.9 ± 0.05) was slightly higher than the
PZNC (9.0–9.4). The salt addition method has been found appropriate and convenient to determine the PZC of natural organic
substrates.

Keywords Point of zero charge . Point of zero net charge . Isoelectric point . Salt addition method . Ion adsorption method . Cation
exchange capacity . Zeta potential . Organic materials

Introduction substrates are selected based on their surface properties and

A promising approach to treat the low concentrations of ele-
ments (Sb, As, Cd, Cr, Co, Mn, Hg, Mo, Ni, Se, and Zn) found
in contaminated neutral drainage (CND) is to design a passive
reactor where metal sorption onto low-cost materials consti-
tutes the main treatment mechanism. The substrates for these
reactors can originate from industrial wastes or natural
sources, but they must be locally available to ensure cost ef-
fectiveness. To treat various types of effluents, different
Responsible editor: Philippe Garrigues
* Gerald J. Zagury
gerald.zagury@polymtl.ca
1
RIME-Research Institute on Mines and Environment,
Montréal, Canada
2
Department of Civil, Geological, and Mining Engineering-École
Polytechnique de Montréal, Montréal, QC H3C 3A7, Canada
3
RIME-Université du Québec en Abitibi-Témiscamingue,
Rouyn-Noranda, QC J9X 5E4, Canada
their sorption capacities. In the neutral pH range, depending
on their surface functional groups, some substrates might per-
form better in the presence of anions while others are more
suited for the capture of cations. Natural and organic sub-
strates possess functional groups such as carboxyl, sulfhydryl,
hydroxyl, and amino groups, responsible, by their ionization,
for the negative and positive charges on their surface. The
magnitude of the surface charge depends on the abundance
and types of functional groups present, and on the pH of the
solution (Mukherjee et al. 2011).
Points of zero charge (PZCs) are pH values at which the
surface charge components become equal to 0 under given
conditions of temperature, applied pressure, and aqueous so-
lution composition (Sposito 2008). This does not mean that
the surface has no charge at pHPZC, but rather that there are
equal amounts of positive and negative charges. PZC values
could help optimize the selection of a substrate for the treat-
ment of a CND. Substrates with low PZC values would be
best suited to treat effluents contaminated with cations, while
substrates with high PZC values would be more appropriate to
capture anions.

At least three different points of zero charge are described
in the literature: (1) the PZC, (2) the point of zero net charge
(PZNC), and (3) the point of zero net proton charge (PZNPC).
The PZC is the pH value for which the net surface charge is
null and the diffuse ion swarm vanishes. It is also called the
isoelectric point (IEP) because, at this pH value, particles do
not move when exposed to an electric field (Stumm and
Morgan 1996). The PZNC is the pH value for which the net
charge due to sorbed ions, other than H+ and OH−, is equal to
0. It corresponds to the pH where the anion exchange capacity
(AEC) and the cation exchange capacity (CEC) of the sub-
strate are equivalent (Sposito 2008; Zelazny et al. 1996). The
PZNPC is the pH value for which the net charge due to H+ and
OH− ions, complexed by surface functional groups, is null.
According to Sposito (2008) and Zelazny et al. (1996),
PZNPC must be distinguished from the point of zero salt
effect (PZSE) or common intersection point (CIP) defined as
the crossing point between three or more potentiometric titra-
tion curves obtained at different ionic strengths. According to
Appel et al. (2003), PZNPC and PZSE are equivalent and
other researchers (Kosmulski 2009; Malik et al. 2002;
Mahmood et al. 2011) only mention PZC and IEP.
In this study, three methods were compared to measure
PZC, IEP, and PZNC. The first method tested, the salt addition
method, is often used to measure the PZC of organic sub-
strates (Ofomaja and Ho 2008; Kyziol-Komosinska et al.
2010; Sepulveda and Santana 2013). In the literature, the salt
addition method is referred to by different names such as the
powder addition method (Jirekar et al. 2014; Bhagavathi et al.
2015), the solid addition method (Ofomaja and Ho 2007;
Ngah and Hanafiah 2008; Belviso et al. 2014), or the batch
equilibration method (Smičiklas et al. 2000). Its advantages
are its rapid and easy execution. However, it is argued that this
method is not applicable to substrates that do not possess a
CIP, such as humic and fulvic acids, and many other materials
for which the surface charging is not exclusively due to pro-
tonation or deprotonation of surface sites (Kosmulski 2012;
Kosmulski 2009). The second method tested, the zeta poten-
tial method, is based on the measurement of the electrical
potential (zeta potential) reflecting the potential difference be-
tween the shear plane in Stern’s double layer model and the
bulk phase (Stumm and Morgan 1996). IEP measurements
based on this method have been carried out with success on
pure mineral substances but their interpretation remains am-
biguous in the case of heterogeneous materials such as soils
(Zelazny et al. 1996; Appel et al. 2003; Kosmulski 2012). A
disadvantage of the zeta potential method is that its measure-
ments can only be carried on colloids and truly dissolved
solids (ex., 30 nm–25 μm), implying that the solid fraction
of the substrates cannot be tested. The third method tested, the
ion adsorption method, is based on the measurements of the
AEC and CEC of the substrates. The advantages of this meth-
od are that it combines the results of CEC and AEC obtained
Environ Sci Pollut Res
at several pH values, as well as the result of the PZNC. It is,
however, a time-consuming method.
Values of PZC, IEP, and PZNC reported in the literature for
various substrates are summarized in Table 1, along with their
determination method. Although the list in Table 1 is not ex-
haustive, it appears that the salt addition method was often
used to obtain the PZC of natural organic substrates or vege-
table wastes, and that few studies used the potentiometric
method or other types of titration methods. There is no clear
agreement between PZC obtained by different authors, as
PZC depends greatly on the origin of the substrate. Other
methods, such as the ion adsorption and the zeta potential
methods, have little or not been used to measure the PZNC
and IEP of these types of materials. For studies reporting IEP
results with the zeta potential method, substrates mostly show
negative zeta potentials over the pH range tested. When IEP
values are reported, the positive zeta potentials are either as-
sumed beyond the data range or very low, and the pHIEP is
close to 1. Finally, only one study tested the ion adsorption
method in an unsuccessful attempt to measure the PZNC of
wood ash.
As limited measurements were reported in the literature
with the zeta potential and ion adsorption methods for organic
substrates, and as PZC results obtained by the salt addition and
other titration methods are quite variable, it seems difficult to
select any of these methods. Therefore, the objectives of the
present study were (1) to determine the PZC, IEP, and PZNC
of selected organic substrates available near mining sites in
Quebec (Canada), including brown algae, green compost, ma-
ple sawdust, sphagnum peat moss, and wood ash, using three
different techniques: salt addition, ion adsorption as well as
the zeta potential methods; and (2) to compare the results
obtained using these methods. Furthermore, in an attempt to
validate the experimental protocols used in this study, natural
kaolinite and synthetic goethite were used as reference mate-
rials, because their PZCs are documented in the literature.
Materials and methods
Materials and reagents
The wood ash was a by-product from a co-generation plant
located at Kirkland Lake, Canada; the maple sawdust came
from P.W.I. Industries, Canada; the green compost originated
from the city of Montréal (produced from green wastes and
leaves); the sphagnum peat moss was purchased from a local
retailer (Home Dépôt, Montréal); and the brown algae
(ASCO-PURE kelp), made from cold-water brown seaweed
Ascophyllum nodosum, was provided by Organic Ocean Inc.
(Rimouski, Quebec, Canada). All substrates were air-dried
and kept at room temperature. Compost and peat moss were
sieved to less than 5 mm and placed in plastic ziplock bags,
Environ Sci Pollut Res

Table 1 PZC/IEP of natural organic substrates

Substrate PZC/IEP Method (electrolyte) References

Algae 3.1–3.3 Salt addition (NaCl 0.1 N) Malik et al. (2002)

6.0 Powder addition (NaCl 0.1 N) Knappe et al. (2004)
7.12 Salt addition (NaNO3 0.1–0.001 M) Lim et al. (2013)
9.05 Salt addition (KNO3 0.1 M) Maurya et al. (2014)
1.6 Zeta potential (NaCl 0.1 N) Malik et al. (2002)
Compost 7.5 Salt addition (KCl 0.05 M) Durán et al. (2006)
7.72 Salt addition (NaCl 0.05 N) Kyziol-Komosinska et al. (2010)
6.4 Salt addition (NaCl 0.05 N) Bhagavathi et al. (2015)
<2 Zeta potential (not specified) Al-Mashaqbeh and McLaughlan (2015)
Saw dust 4.4 Salt addition (KNO3 0.1 M) Nordin et al. (2001)
6.91 Salt addition (KNO3 0.01 M) Ofomaja and Ho (2007)
7.29 Salt addition (NaCl 0.01 M) Sing et al. (2011)
5.4 Salt addition (KNO3 0.01 M) Bajpai et al. (2012)
3.32 Salt addition (NaCl 0.01 M) Zou et al. (2013)
4.7 Salt addition (NaNO3 0.01 M) Šillerova et al. (2013)
4.32 Salt addition (KNO3 0.01 M) Witek-Krowiak (2013)
Peat 3.3 Salt addition (KCl 0.1–1 M) Sepulveda et al. (2008)
6.56 Salt addition (NaCl 0.01 M) Balasubramanian et al. (2009)
4 Salt addition (NaCl 0.01 M) León-Torres et al. (2012)
3.68 Salt addition (NaCl 0.1 M) Sepulveda and Santana (2013)
3.9 Salt addition (NaNO3 0.01 M) Šillerova et al. (2013)
2 Salt addition (KNO30.1 M) Zehra et al. (2015)
Wood ash 1.5 Zeta potential (D-H2O) Mukherjee et al. (2011)

the other substrates (with particle size varying from 2 to
10 mm) were not sieved prior to testing.
The characterization of the five organic materials included
pH, water content, specific surface area, extractable metals,
elemental analysis (total C, total Kjeldahl nitrogen (TKN),
and total P), total organic carbon (TOC), dissolved organic
carbon (DOC), and analysis by Fourier transform infrared
spectroscopy (FTIR).
The natural kaolinite (Al2O3 · 2SiO2 · 2H2O) and the syn-
thetic goethite (FeO(OH)), containing 30–60% Fe, were pur-
chased from Sigma-Aldrich, Canada.
Solutions of 0.1 and 0.05 M of NaNO3 were used to
maintain ionic strength (I) and compare the effects of
these different strengths during PZC experiments.
Standardized solutions of 0.1 M HNO3 and NaOH were
prepared for pH adjustment.
All reagents (Thermo Scientific™, Canada) were analytical
grade. The pH measurements were carried out with a pH meter
(Thermo Scientific™, Orion™ Star A211 pH Benchtop meter,
Canada) using a combined glass Ag/AgCl (3.3 mol/L KCl)
electrode. The combined electrode was calibrated with a set of
three buffers (pH 4, 7, and 10), and the measurements were
precise to 0.01 pH.
Point of zero charge determination
Salt addition method (PZC)
The salt addition technique was performed by adding identical
amounts of substrate to a set of solutions of the same ionic
strength at different pH values (Anderson and Rubin 1981;
Tan et al. 2008; Mahmood et al. 2011). In a series of 50-mL
centrifuge tubes, 0.2 g of sample was added to 40.0 mL of
0.1 M NaNO3 solution. The pH was adjusted with 0.1 M
HNO3 and 0.1 M NaOH as needed, to obtain the appropriate
pH range of 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11 (± 0.1 pH units).
The pH values of the supernatant in each tube were denoted as
pHi. The samples were shaken for 24 h using a rotary agitator
(Wrist-Action Shaker, Cole Parmer 51704 Series) at 200 rpm.
After settling, the pH values of the supernatant in each tube
were measured and denoted as pHf. The PZC was obtained
from the plot of ΔpH (=pHf – pHi) against pHi. Experiments
were repeated with a 0.05 M NaNO3 solution. Each set of
experiments was performed in triplicate and the mean value
was recorded. Samples of natural kaolinite and synthetic goe-
thite were also analyzed by the above procedure for compar-
ison with previously published values.

Zeta potential measurements method (IEP)
The method consists of four steps: (1) 1 g of sample was added
to a beaker containing 100 mL of deionized water, the mixture
was homogenized, and then passed through a 25-μm sieve. (2)
The sifted sample was added in a centrifuge tube containing
50 mL of 0.1 M NaNO3 solution, and then the mixture was
stirred gently for few minutes. Eight samples were prepared in
the same manner. (3) pH in each tube was adjusted using
0.1 M HNO3 and 0.1 M NaOH solutions to obtain the follow-
ing range (pH 2 to 11), i.e., pH 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11
(± 0.1). (4) The adjustment was done by stirring the centrifuge
tube until a stable pH value was reached. Then, the pH and the
zeta potential of the individual suspension were recorded.
Zeta potential measurements were performed with a
ZetaCOMPACT analyzer (version 7.06) supplied by CAD
Instruments (Les Essarts-le-Roi, France). The experiment
was repeated a second time, using a 0.05 M NaNO3 solution.
The PZC or IEP is defined as the pH at which the zeta poten-
tial is 0. It was obtained by plotting the curve of zeta potentials
against pH values measured in each tube.
Ion adsorption method (PZNC)
Determination of CEC and AEC for charged surfaces as a
function of pH and I can be accomplished via the ion adsorp-
tion method (Appel et al. 2003; Marcano-Martinez and
McBride 1989). One gram of sample was placed in pre-
weighed 50-mL polyethylene centrifuge tubes to which
20 mL of 1 M NaCl was added. The samples were shaken
for 1 h, centrifuged for 10 min at 10,000g (Beckman A-20),
and the supernatant was discarded. Amounts of 20 mL of
0.5 M NaCl were then added to the centrifuge tubes and the
pH was adjusted with 0.1 M HCl or NaOH solutions to values
ranging from 4 to 9 to span the expected points of zero net
charge. The tubes were then shaken for 12 h using a wrist
action rotary agitator (Cole Parmer 51704 Series), centrifuged,
and the supernatant was discarded. Washing cycles with 0.5 M
NaCl and pH adjustments were performed two more times,
with shaking times of 1 h. The rigorous washing procedure
was carried out to ensure exchange sites were saturated with
Na+ and Cl−. Five washes were then performed with 20 mL of
0.1 and 0.05 M NaCl, with pH readjustment and shaking times
of 1 h.
After the final NaCl wash, the supernatant’s pH was mea-
sured. The supernatants were discarded and samples were
weighed to compensate for any entrained NaCl solution.
Adsorbed Na+ and Cl− were then displaced by five successive
washes with 20 mL solutions of 0.5 M NH4NO3. Extracts
were combined and filtered through a 0.45-μm Whatman filter
paper and stored at 4 °C prior to analysis. Concentrations of
Na+ and Cl− were determined by atomic absorption spectros-
copy (AAS, Perkin Elmer, AAnalyst 200) and colorimetric
Environ Sci Pollut Res
method (Smart Spectrophotometer, LaMotte), respectively.
Cation exchange capacity and anion exchange capacity were
calculated following Eqs. (1) and (2):
a 1
CEC ¼ 
10 23
 
100
 ½meq=100g dry biomass ð1Þ
b
a  1 
AEC ¼ 
10 35:5
 
100
 ½meq=100g dry biomass ð2Þ
b
Where
a Concentration of sodium (mg/L) or chloride (mg/L)
b Mass of dry biomass (g)
Graphs of CEC and AEC vs pH were then plotted and the
pH where cation adsorption was equal to anion adsorption is
the PZNC, corresponding to the point of intersection of two
curves. Samples of natural kaolinite and synthetic goethite
were also analyzed by the above procedure for comparison
with previously published values. Finally, the Chapman
method (1965) was also used for the determination of CEC
of the organic materials. Samples (4 to 5 g) were treated with
33 mL of 1 N CH3COONa followed by rinsing (three times)
with isopropyl alcohol (99%). The samples were further treat-
ed with 33 mL of 1 N CH3COONH4 in order to liberate the
Na+ which were then analyzed by atomic absorption spectro-
photometry (AAS).
Results and discussion
The physical and chemical characteristics of the tested organic
materials are presented in Table 2. The results show that total
carbon content for maple sawdust and peat moss is around
50%, which is within the typical range (C 40–60%) expected
for these types of materials (Zagury et al. 2006). Except for
wood ash, the low specific surface areas of organic materials
are comparable to those found in previous studies
(Balasubramanian et al. 2009; Izquierdo et al. 2012). For in-
stance, Izquierdo et al. (2012) reported a specific surface area
of 1.3 m2/g for peat and values between 0.66 and 1.07 m2/g for
compost. Moreover, the high specific surface area of wood ash
(45.9 m2/g) was consistent with the value (43.8 m2/g) reported
by Calugaru et al. (2017).
Salt addition method (PZC)
The experimental curves (plots of ΔpH vs pHi) obtained fol-
lowing the salt addition technique are presented in Fig. 1.
Environ Sci Pollut Res

Table 2 Physical and chemical characteristics of organic materials (mean ± standard deviation)

pH P (mg/g) N(TKN) (mg/g) C total (%) TOC (%) DOC (mg/L) SSA (m2/g)

Wood ash 8.94 ± 0.09 2.40 ± 0.05 1.29 ± 0.36 19.9 ± 2.19 18.6 ± 2.33 6.36 ± 0.81 45.9
n=3 n=3 n=3 n=2 n=2 n=6
Maple sawdust 5.12 ± 0.10 0.13 ± 0.03 n.a 50.1 ± 0.42 49.3 ± 1.63 669 ± 6.08 0.91
n=3 n=2 n=2 n=2 n=6
Green compost 6.59 ± 0.08 16.5 ± 0.38 8.15 ± 0.14 17.3 ± 4.31 15.2 ± 0.64 79.5 ± 1.86 3.24
n=3 n=2 n=3 n=2 n=2 n=6
Peat moss 5.65 ± 0.19 0.20 ± 0.02 10.7 ± 0.72 53.4 ± 0.00 53.3 ± 0.99 132 ± 6.98 1.43
n=3 n= 2 n=3 n=2 n=2 n=6
Brown algae 5.37 ± 0.00 1.08 ± 0.01 10.8 ± 0.07 34.9 ± 0.07 26.1 ± 0.35 5680 ± 1.60 0.17
n=3 n=2 n=2 n=2 n=2 n=8

n.a not analyzed, TOC total organic carbon, DOC dissolved organic carbon, SSA specific surface area

Results are expressed at both ionic strengths (0.05 and 0.1 M)
and pHPZC was clearly identified. The pHPZC of the substrates
can be divided in three groups: (1) acidic PZC (peat moss and
maple sawdust), (2) neutral PZC (algae and compost), and (3)
alkaline PZC (wood ash). In 0.05 M NaNO3, the PZC values
of peat moss, maple sawdust, algae, compost, and wood ash
were 3.42, 4.72, 6.06, 7.68, and 9.50, respectively. When the
ionic strength was increased to 0.1 M, PZC of peat moss and
maple sawdust shifted to higher values of 4.26 and 5.89,
respectively.
A different trend was obtained for brown algae, with a
slight decrease of PZC (0.5 pH unit) when the solution ionic
strength increased; PZCs of compost and wood ash were not
significantly affected by the ionic strength of the solution.
Comparing the results of the present study to those reported
in the literature (Table 1), some PZC values were similar,
especially when the same salt (NaNO3) was used to adjust
the ionic strength (for instance, PZC of sawdust and peat in
Šillerova et al. 2013). This being said, the sawdust samples
used by previous studies were of several origins (beech saw-
dust, rubber tree sawdust) with unspecified origin sometimes.
The variability of PZC results for the same natural organic
substrate (Table 1) stresses the need to specify the species
and the experimental conditions used (salt, ionic strength).
In the present study, the different PZC values of the studied
substrates put into evidence that, even though the structural
composition is globally similar (cellulose, hemicellulose, tan-
nins, and other extractable compounds), these organic mate-
rials have different surface functional groups. In fact, FT-IR
spectra (data not shown in this paper) of these materials
depicted different functional groups such as hydroxyl, carbox-
ylic acid, methylene, ether, and alcohol for algae. The spectra
of peat moss and sawdust had the same structure with hydrox-
yl, carboxy-acid, and alcohol as the main functional groups. In
compost, siloxane, hydroxyl, and carbonate functional groups
were observed. Similarly, in wood ash, siloxane and imine
functional groups were depicted.
Natural kaolinite and synthetic goethite, used as mineral
standards, had PZC values close to those found in the
literature. Natural kaolinite had a PZC of 3.01 ± 0.03 and
3.25 ± 0.12 in 0.1 and 0.05 M NaNO3, respectively. These
values are in close agreement to those obtained by Appel
et al. (2003) and Gallez et al. (1976) in 0.1–0.001 M NaCl
(PZC of 2.8 in both cases) using the potentiometric titration
method. Peacock and Sherman (2005) as well as Unuabonah
et al. (2008) reported PZC of 4.7 and 4.4, respectively, using
the potentiometric method in 0.1 M NaNO3.
As for the synthetic goethite, PZCs were 10.9 ± 0.05 and
9.8 ± 0.02 in 0.1 M NaNO3 and 0.05 M for the salt addition
method. Research conducted by Cristiano et al. (2011) yielded
PZC of 7.20 ± 0.08 for the same method but using 0.01–
0.001 M NaClO4. For the same electrolyte, 0.01–0.5 M
NaNO 3, but using the potentiometric titration method,
Gaboriaud and Ehrhardt (2003) measured PZC of 9.1–9.2.
Kosmulski (2011) reported PZC/IEP values varying between
6.2 and 9.6, thus our value seems to be in the high end of this
range.
Zeta potential measurements method (IEP)
The plots of zeta potential vs pH for four of the five substrates
are presented in Fig. 2. The wood ash could not be analyzed
for practical reasons (the Zetameter needed to be serviced for
few weeks).
The graphs in Fig. 2 show that the studied substrates were
negatively charged throughout the entire pH range (from 2 to
11). The substrates displayed only slight differences in zeta
potentials with the two background electrolyte concentrations.
The zeta potential values varied between − 5 and − 30 mV,
thus the IEP could not be determined. Similar results were
reported in previous studies on compost (Al-Mashaqbeh and
McLaughlan 2015) and on organic agricultural adsorbents (Qi
and Aldrich 2008).
According to Cristiano et al. (2011), in organic substrates
with heterogeneous functional groups on their surface, the
dissociation constant (pK) values from different functional
groups may overlap, making it difficult to determine IEP, as
Environ Sci Pollut Res
 Environ Sci Pollut Res
ƒFig. 1Plots of ΔpH vs pHi for salt addition method for 0.05 and 0.1 M
NaNO3 (mean ± standard deviation, n = 3)
isoelectric point (PI, IEP) = ½(pK1 + pK2); pK1 and pK2 being
the dissociation constants of different functional groups.
Ion adsorption method (PZNC)
The point (or pH) where non-specific surface adsorption of
anions and cations is equivalent is defined as the PZNC.
Positive and negative charges were estimated by the measure-
ment of Na+ and Cl− retention as a function of pH and I. The
intersection points of CEC and AEC were not attained for any
of the substrates, as CEC values were far greater than those of
AEC (Fig. 3). The AECs varied between 5 and 15 meq/100 g,
noteworthy, the change of pH (from 4 to 9) as well as the ionic
strength (from 0.05 M to 0.1 M NaCl) did not significantly
affect the AECs.
The CECs of compost, wood ash, maple sawdust, and peat
moss increased with ionic strength. A contrary trend was ob-
tained for algae for which the CEC decreased with the ionic
strength, except for one value (at pH 4). In respect to the pH,
the CECs of all organic substrates (except for maple sawdust)
increased when the pH rose.
At the lower ionic strength tested (0.05 M NaCl), the CEC
values (meq/100 g) were as follows at pH 4 and 9, respective-
ly: brown algae (130.6–242.2), green compost (28.78–79.57),
wood ash (33.09–89.13), maple sawdust (75.65–94.78), and
peat moss (107.8–160). When increasing the ionic strength to
0.1 M, the CEC values (meq/100 g) were as follows: brown
algae (185.6–217.6), green compost (45.22–104.8), wood ash
Fig. 2 Variation of zeta potential
of the substrates suspension with
the pH of the solution under
various NaNO3 concentrations
(M), (mean, n = 2)
(55.65–99.13), maple sawdust (88.70–111.3), and peat moss
(143.0–187.8). Therefore, brown algae and peat moss had the
highest CECs.
Finally, the CECs obtained following the ion adsorption
method (at pH 8, 0.1 M NaCl) were compared to the CECs
measured using the Chapman method (1965) (Table 3).
As seen in Table 3, CECs from the Chapman method were
higher for brown algae and peat moss. The difference of CEC
between the two methods was about 28.9 and 10.2%, respec-
tively. Furthermore, CECs calculated from the Chapman
method were generally lower than the ones obtained using
the ion adsorption method. The difference was about 16.7,
39.5, and 24.7% for compost, maple sawdust, and wood ash,
respectively. The results stress the operationally defined as-
pect of the various CEC determination methods.
Nevertheless, these methods are useful when comparing var-
ious substrates using the same laboratory protocol.
Naturally, the most abundant anions present in organic mat-
ter are the organic anions, hydroxyl, bicarbonate, nitrate, sili-
cate, sulfate, and phosphate (Mott 1981). Thus, the AEC
values depend greatly on the anion species used in the method.
In general, the AEC values increase in the following order:
NO3 < Cl < CH3COO << SO4. There are very few published
studies about anion exchange capacity of organic matter.
Nevertheless, Duquette and Hendershot (1987) measured the
AEC of 12 soil samples from various parts of Quebec,
Canada, and found that AEC values of these soils were all
lower than 1 meq/100 g at pH between 3 and 8. Fernandez
et al. (1990) demonstrated that multicomponent natural soil
systems did not have a point of zero net charge (PZNC), but a
trajectory of zero charge depending on pH and electrolyte
 Environ Sci Pollut Res

Fig. 3 Cation and anion exchange capacities of substrates at various pH and ionic strengths

concentration. Some researchers (Fernandez et al. 1998; As for the mineral reference materials used in this re-
Meijer and Buurman 1987) concluded that PZNC should not search (kaolinite and goethite), the intersection points be-
exist in multicomponent systems that contain organic matter. tween CEC and AEC were obtained and the graphs are
In fact, we did not find any references in the literature where presented in Fig. 4. Kaolinite had a PZNC range of 2.9–
the ion adsorption method was successfully used to determine 3.4 at 0.1 and 0.05 M NaCl, respectively. These values are
the PZNC of organic materials. in agreement with the ones reported by Appel et al.
(2003), 2.7–3.2 at electrolyte concentrations of 0.01 and
Table 3 Cation exchange capacity of substrates using the Chapman 0.001 M. Overall, the PZNC of kaolinite for most studies
(1965) method and the ion adsorption method (mean ± standard devia- found in the literature ranges from 2.7 to 4.1 (Zhou and
tion, n = 3)
Gunter 1992; Schroth and Sposito 1997; Jiao and Hou
Organic materials CEC—Chapman method CEC—ion adsorption 2007). The PZNCs of synthetic goethite (the second min-
1 M NaOAc—pH 8.2 0.1 M NaCl—pH 8 eral reference material) were of 9.0 and 9.4 at 0.1 and
(meq/100 g) (meq/100 g) 0.05 M NaCl, respectively. These values are close to the
Brown algae 274.7 ± 9.7 195.4 ± 2.5 value of 9.1 reported by Gaboriaud and Ehrhardt (2003),
Compost 78.59 ± 1.69 91.74 ± 1.2 but slightly higher than those obtained by Appel et al.
Maple sawdust 67.39 ± 0.31 111.3 ± 4.3
(2003) (7.4–8.2). However, the electrolyte concentrations
Peat moss 191.3 ± 1.84 171.7 ± 3.4
used in this last study were ten times lower. Other studies
Wood ash 64.1 ± 8.95 85.2 ± 5.7
have reported the PZNC of synthetic goethite between 7.0
and 8.0 (Sposito 1981; Zhou and Gunter 1992).
Environ Sci Pollut Res
Fig. 4 Cation and anion exchange capacities of natural kaolinite and synthetic goethite at various pH and ionic strengths
Conclusions
Different methods to determine the PZC of five organic ma-
terials, namely maple sawdust, wood ash, peat moss, compost,
and brown algae, all potentially used for the passive treatment
of mine drainage effluents, were compared. The methods were
as follows: (1) the salt addition method, measuring the PZC;
(2) the zeta potential method, measuring the IEP; (3) the ion
adsorption method, measuring the PZNC.
The salt addition method successfully allowed the PZC
determination of natural organic substrates. Results obtained
from the salt addition method in 0.05 M NaNO3 were as
follows: 4.72 ± 0.06 (maple sawdust), 9.50 ± 0.07 (wood
ash), 3.42 ± 0.03 (peat moss), 7.68 ± 0.01 (green compost),
and 6.06 ± 0.11 (brown algae). The zeta potential method
did not allow determination of the IEP as the zeta potential
was negative throughout the pH range tested. The ion adsorp-
tion method also failed to determine the PZNC of organic
substrates. The CEC values were by far higher than those of
AEC; thus, the intersection point was not reached.
The salt addition and the ion adsorption methods
succeeded to measure the PZC as well as the PZNC of the
mineral reference materials, kaolinite and synthetic goethite,
used for the validation of the methods. The yielded PZC fell
within the ranges of the reported values. The PZNC of goe-
thite was in the high end of the values reported by other
researchers.
The study indicates that the salt addition method was suit-
able to determine the PZC of natural organic substrates. The
maple sawdust and peat moss, with acidic pHPZC, could act as
potential adsorbents for cations, whereas, wood ash, with al-
kaline pHPZC, could theoretically remove anions from mine
drainage. Compost and algae with neutral pHPZC could be
used to remove both cation and anion species from effluents.
All these organic materials will be further tested in batch and
column experiments to assess their efficiency as natural
adsorbents.
Funding information This study was funded by the NSERC (Natural
Sciences and Engineering Research Council of Canada), grant no.
469489-14, and the industrial partners of the RIME UQAT-
Polytechnique Montreal, including Agnico Eagle, Mine Canadian
Malartic, Iamgold, Raglan Mine Glencore, and Rio Tinto.
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict of
interest.
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