Analytical Letters

ISSN: 0003-2719 (Print) 1532-236X (Online) Journal homepage: http://www.tandfonline.com/loi/lanl20

Experimental and Theoretical Characterization of

Metal Complexation with Humic Acid

G. O. Bosire, B. V. Kgarebe & J. C. Ngila

To cite this article: G. O. Bosire, B. V. Kgarebe & J. C. Ngila (2016): Experimental and
Theoretical Characterization of Metal Complexation with Humic Acid, Analytical Letters, DOI:
10.1080/00032719.2016.1141415

To link to this article: http://dx.doi.org/10.1080/00032719.2016.1141415

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May 2016.
Published online: 06 May 2016.

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 Experimental and Theoretical Characterization of Metal

Complexation with Humic Acid

G. O. Bosire

Department of Applied Chemistry, University of Johannesburg, Johannesburg, South Africa

B. V. Kgarebe
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Analytical Services Department, National Institute for Occupational Health, Johannesburg, South

Africa

J. C. Ngila*

Department of Applied Chemistry, University of Johannesburg, Johannesburg, South Africa

Address correspondence to J. C. Ngila, Department of Applied Chemistry, University of

Johannesburg, PO Box 17011, Doornfontein, 2028 Johannesburg, South Africa. Tele:

+27115596196. Fax: +27115596425. E-mail: jcngila@uj.ac.za; jcngila2002@yahoo.com;

orinajeff@gmail.com

Supertitle: Environmental Analysis

Received 16 July 2015; revised 9 January 2016; accepted 10 January 2016.

Abstract

This study investigated the bonding of calcium and magnesium to specific sites in humic acid as

a function of pH, temperature, and trace metal concentrations. Other metals were investigated but

not in detail. Using a surface complexation model with well-defined phenolic and carboxylic

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 sites in humic acid, the fractions of calcium/magnesium and trace metals that bond with the

various sites were quantified. These sites were also classified as monodentate or bidentate. The

goal of the study was to understand the conditions that favor calcium/magnesium bonding to

bidentate humic acid. Therefore, adsorption measurements were performed followed by surface

complexation simulations. The total metal and labile metal ion formed in the ultrafiltrate were

determined by inductively coupled plasma – mass spectrometry and square wave anodic

stripping voltammetry, respectively. The results showed that the adsorption capacity of each
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metal to humic acid was influenced by pH and metal loading. For example, zinc(II) and

copper(II) were statistically different in their adsorption capacities. The Morel and Dzombak

surface complexation models showed stronger lead and copper interactions with monodentate

sites compared to bidentate sites. The phenolic sites were weakly involved in bonding, and the

bonding capacities of calcium and magnesium ions to phenolic or carboxylic were pH dependent.

For example, lead(II) employed only 5% of bidentate carboxylic-phenolic sites at 45C showing

95% favorable calcium/magnesium bonding to these sites in humic acid. These results may allow

substantial scale reduction.

Keywords: bidentate, humic acid, monodentate, surface complexation model

INTRODUCTION

The presence of Ca and Mg in surface water impacts on scale formation in water pipes

due to their high precipitation potentials. However, the formation of stable complexes of Ca/Mg

with humic acid in natural organic matter may keep these metals in aqueous form and minimize

scaling. There is considerable literature on the interaction of metal cations to natural organic

matter fractions. For example, a number of studies have discussed the coordination of metals to

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 humic acid (Lu and Allen 2002; Tipping 2002; Guthrie et al. 2005; Zhou, Yan, and Gu 2005;

Cheng and Allen 2006; Mostofa et al. 2013). While these studies have also included Ca/Mg

bonding to natural organic matter fractions, detailed studies of bonding site coordination have

not been well documented. It is possible to understand the competition between Ca/Mg and other

cations to natural organic matter fractions, such as humic and fulvic acid. Because Mg/Ca are the

main scaling metals, keeping them in solution, in stable complexes, is of prime concern. This

study addresses the fundamental question of preferred sites of Ca/Mg binding to humic acid in
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the presence of other metal cations at various pH and temperature conditions.

Very few studies have previously combined experimental studies and modelling to

explain these bonding processes. Henceforth, little information is available concerning the

properties of metal-sorption sites in humic acid. However, after laboratory bonding, surface

complexation to the various sites may be described through modelling. The last decade has

witnessed considerable effort to defining the thermodynamics of humic acid-cation complexation

(Nordstrom 2007) and the development simulative models to characterize these binding

characteristics and capacities. The models include the Windermere humic acid model (V–VII)

(Kabata-Pendias 2010) and the non-ideal competitive adsorption model (Vidali, Remoundaki,

and Tsezos 2009). Successful models may be achieved by PHREEQC for pH and redox

equilibrium reactions involving the surface complexation model. In order to successfully utilize

this code, its databases were modified by the use of already defined logk values for metal-humic

acid complexes from Appelo (2005), monodentate and bidentate binding sites, and in some cases

tridentate sites (Ahmed et al. 2014).

The relatively high concentration of humic acid in the environment has led to numerous

studies on its bonding capacities to cations at different conditions. The pH changes may alter the

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 metal sorptive properties of humic acid (Gustafsson 2001; Ritchie and Perdue 2003; Tipping,

Lofts, and Sonke 2011). The charge on humic acid functional groups is also dependent on pH

(Bourg, 1988). At low pH, phenolic and carboxylic groups are protonated but as the pH

increases, the functional groups become negatively charged (Akbour et al. 2013). The pH also

controls metal transport (Bourg, 1988; Akbour et al. 2013) with organic and inorganic species in

water (Mcelmurry, Long, and Voice 2010). The mobility of metal species in aquatic

environments depends on an elaborate network of interactions occurring between transport

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processes and heterogeneous phenomena. Ideally, the concentrations of the labile metal species

are regulated by organic ligands as well as metal cations in water. At near neutral to alkaline pH,

metal bonding to humic acid is dominated by these cations (Koopal et al. 2005). This study

sought to quantify the concentrations of metal cations that bond to humic acid as a function of

pH, temperature, and Ca/Mg influence and the fractions bonded to humic acid functional groups

using the PHREEQC surface complexation model (Parkhurst and Appelo 2007).

MATERIALS AND METHODS

Reagents and Materials

All reagents used were of analytical grade unless otherwise stated. Type 1 Millipore

water (22 µM) was used in all measurements. The Ca2+, Mg2+, Zn2+, Cu2+, and Pb2+ stock

solutions were prepared from 1000 mg/L standard solutions (Sigma-Aldrich, South Africa). The

pH adjustments were performed with NaOH and HNO3 (Sigma-Aldrich, South Africa). Humic

acid standards of molecular weight less 1000 g/mole were obtained from Sigma Aldrich. All

glassware was soaked in 3 M HNO3 overnight and rinsed with deionized water prior to use. The

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 ionic strength of solutions was fixed at 0.1 M by NaCl with strirring for 12 hours to reach

equilibrium.

Binding Measurements

All cation complexation experiments were conducted in triplicate using solutions

prepared from commercially available humic acid. The pH was monitored by a meter and

calibrations performed with standards at pH 4.01 and 7.00 at 25°C. The accuracy of the pH
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measurements was ±0.05 pH units. Bonding measurements were carried out as a function of

Zn2+, Cu2+, or Pb2+ concentration (0.5 to 10 mg/L) while the concentrations of Ca2+ and Mg2+

with these cations were fixed at 5 mg/L. The pH was adjusted between 1.5 and 4.5 and the

temperature was adjusted to 25, 45 and 65C in a closed water bath system. The mass of humic

acid was held constant at 1.5 mg. At equilibrium, 25 ml were sampled and ultrafiltered by

centrifugation (Vivaspin VS15RH12, Sartorius) at 14,500 rpm for 20 minutes. The supernatant

from ultracentrifugation was collected carefully and diluted appropriately for analysis.

Instrumental Analysis

The concentrations of the metal ions in the ultrafiltrates were determined by inductively

coupled plasma – optical emission spectrometry (ICP-OES) (Spetro Arcos, with a Cetac ASX-

520 auto sampler). The fractions of Zn2+, Cu2+, and Pb2+ bonded to humic acid, [M]ads were

calculated by

[M ]ads  [M ]total  [M ]UF (1)

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 where M is Zn, Cu, or Pb, [M] total is the total Zn, Cu, or Pb concentration of the initial

mixture before equilibration and [M] UF is the fraction of Zn, Cu, or Pb concentration in the

ultrafiltrate after equilibration.

Square wave anodic stripping voltammetric (SWASV) measurements were performed on

an Autolab/PGSTAT128N workstation (Metrohm AG, Switzerland). The resulting peak heights

were introduced into the Randles Secvik equation at 25°C (Sato, Yui, and Yoshikawa 1996) and

their concentrations were calculated.

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Geochemical Surface Complexation/Denticity Modelling

Coupling PHREEQC with other models has been reported previously (Appelo, Verweij,

and Schäfer 1998; Appelo and Postma 2005). In the Dzombak-Morel surface complexation

model, eight bonding sites in humic acid were categorized as four for weak sites containing

carboxylic groups and four for strong sites containing phenolic groups. In these simulations, the

Tipping and Hurley’s database WHAM in PHREEQC format assumes that the abundance of type

carboxylic and phenolic sites are nHA (mol/g) and nHB = 0.5*nHA (mol/g), respectively.

Throughout the simulations, the surface complexation model was employed. First, the

SOLUTION_MASTER_SPECIES definition for the complexing sites on humic acid and the

SURFACE_SPECIES for protons defination, Zn+2, Pb+2, Cu+2, Mg+2 and Ca+2 were defined in

the input files. Second, for pH and temperature simulations, the SURFACES were defined, with

number of sites for 1.5 mg humic acid. In the PHREEQC-Tipping and Hurley Windermere’s

humic acid model, the humic acid had a total charge of 7.1 meq/g (milliequivalent per gram),

distributed over four monoprotic carboxylic sites (nHA carrying a charge of 2.84 meq/g humic

acid), four monoprotic phenolic sites (nHB, charge = 1.42 meq/g humic acid), and twelve

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 diprotic sites that combined carboxylic and phenolic charges (charge = 2.84 meq/g humic acid).

Based on these definitions, the results were simulated over a range of temperature and pH values.

Catrouillet et al. (2014) identified the sources describing the intrinsic proton dissociation

constants for type A and B sites and their distribution terms pkA, pkB, ΔpkA, and ΔpkB (Catrouillet

et al. 2014). These distribution terms also show the fraction of proton sites that form bidentate

sites. Further, ion adsorption by humic acids is described by specific complexation parameters,

logkMA and logkMB for carboxylic and phenolic sites, respectively. These are related by the
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expression:

logkMB  3.39*logkMA 1.15 R2  0.80 (2)

Typically, logk values for the eight sites show that they may act as monodentate,

bidentate, or tridentate donors towards a given ion. The logk values are calculated from logkMA

and ΔLk1A for a monodentate carboxylic site and logkkB and ΔLk1B for a monodentate phenolic

site. In addition, the logk of the two monodentate sites for a weak bidentate site, logk of the two

monodentate sites and 1*ΔLk2 (9% of the sites) and 2*ΔLk2 (0.9% of the sites) for a strong

bidentate site were also calculated.

RESULTS AND DISCUSSION

Speciation

This section presents results of the amounts of the metal cations for different fractions

(species) as a function of temperature and pH. These fractions include the [Cu] and [Pb]

adsorbed on the humic acid surface, [Cu]ads and [Pb]ads; the total [Pb] and [Cu] in the ultrafiltrate,

and the labile and complexed Cu2+ and Pb2+ in the ultrafiltrate. The concentrations of the

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 complexed metal ions were calculated as the difference between the total and the labile metal

ions in the ultrafiltrate. In natural water, humic acid exists in dissolved and suspended (solid)

forms. Its solubility in water increases with pH and ionic strength (Kipton, Powell, and Town

1992)

Effect of Metal Loading on Metal-Humic Acid Binding

Figures 1 and 2 show the variations of [Zn]ads and [Cu]ads, respectively, as a function of
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pH from 1.5 to 4.5 at various concentrations of the metal ions. The results showed that [Zn]ads

and [Cu]ads increased with the initial concentrations of Cu2+ and Zn2+. The adsorption of

increasing concentrations of Zn2+ and Cu2+ on humic acid was measured and compared. At metal

concentrations of 2.5 and 5 mg/L, the results suggested that Cu was more adsorbed by humic

acid than Zn. In addition, the trends in individual metal adsorptions were evaluated statistically

by analysis of variance (ANOVA) and the root mean square error (RMSE). The latter was used

to measure the absolute errors between the values (Bonten et al. 2008). The values obtained

using 2.5, 5, and 10 mg/L of Zn2+ binding to humic acid differed significantly from each other

(p < 0.05, ANOVA; root mean square error = 0.9308), just as those obtained using 2.5, 5 and

10 mg/L of Cu2+ (p < .05, ANOVA; root mean square error = 1.0171). This observation suggests

comparable Cu and Zn binding characteristics to humic acid, as reported in the literature by De

La Rosa, Santos, and Araújo (2011) and Kang, Zhang, and Wang (2011). Contrary to

suggestions by Kang, Zhang, and Wang (2011) indicating stronger adsorption of Cu2+ to humic

acid than Zn2+, this study reveals that at 10 mg/L of each cation, Zn2+ was relatively more

adsorbed to humic acid than Cu2+ (Figure 1). Generally, [Zn]ads and [Cu]ads increased with the

pH. Within the pH range in this study, the [Zn]ads values and [Cu]ads values did not differ

significantly (p > 0.05, ANOVA).

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 The other observation was the synergistic or antagonistic influence of Mg2+ on Ca2+ and

Ca2+ on Mg2+ as each was adsorbed by humic acid (Figure 3). Notably, Mg2+ bonding to humic

acid increased in the presence of Ca2+, whereas Ca2+ bonding to humic acid decreased in the

presence of Mg2+. These effects were observed as the pH increased from pH 3 and above. Below

pH 3, the presence of the second metal had a synergistic effect on the bonding to humic acid.

The Influence of Temperature

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The labile metal ion concentrations after humic acid equilibration were calculated by

using stripping peaks generated at distinct metal potentials. Figure 4 shows the peak heights

measured as current for Pb2+ and Cu2+ at 25, 45, and 65C. Analyzing the aforementioned

fractions helped elucidate an important aspect of adsorptive speciation: that the characteristics

and reactivity of a metal species depend on the form in which they exist in water and as a

function of temperature. The labile Cu2+ and Pb+2 ions were highest at 45C and lowest at 65C.

A possible explanation for this phenomenon may be that the molecules were energized and hence

in solution at 45C. However, at even at 65C, the ion complexed in solution with the soluble

fraction of humic acid.

Table 1 shows calculated differences in the adsorbed and complexed [Pb]. The adsorbed

and complexed species [Pb] were not significantly different (p > 0.05, ANOVA;

RMSEPb = 0.4621), while the Cu concentrations for the adsorbed and complexed species were

significantly different (p < 0.05, ANOVA; RMSECu = 0.5534). A temperature increase from 25

to 65C led to increased concentrations of adsorbed copper. On the other hand, the [Pb]ads values

reduced at 45C. The complexed metal ions in this study differed depending on the cation and

temperature. These results agree with the literature on adsorption isotherms of various metals

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 (Li, Qinyan, and Baoyu 2010). Each metal, therefore, exhibits unique adsorption properties with

humic acid. However, this temperature dependent adsorption and complexation only displayed a

consistent trend for [Pb]ads.

Surface Complexation Modelling

Temperature Dependent Pb2+ and Cu2+ Surface Complexation Model Simulations

Surface complexation calculations were performed by Tipping and Hurley’s database

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with the Windermere’s humic acid model in PHREEQC. This model was used to calculate the

proportions of Pb2+ and Cu2+ bonded on the monodentate and bidentate sites in humic acid. As

defined by the model, these binding sites were further divided into carboxylic and phenolic

monodentate sites, while the bidentate ones were divided into carboxylic-carboxylic and

carboxylic-phenolic binding sites. The denticity-based results are reported at 25, 45 and 65°C.

Figures 5 and 6 show that the percentage of Pb2+ and Cu2+ adsorbed to HA are distinct

and depend on the denticity. The adsorbed Pb2+ ([Pb]ads) are more distributed into monodentate

sites at 25C than adsorbed Cu2+ ([Cu]ads). Figure 6 shows the ratio of [Pb]ads adsorbed on

monodentate carboxylic acid sites to the bidentate carboxylic-carboxylic sites was approximately

1:1 at 25C. However, increasing the temperature to 45C decreased Cu2+ bonding to carboxylic-

carboxylic bidentate sites in humic acid, while Pb2+ bonding to carboxylic-carboxylic bidentate

sites in humic acid increased with temperature. In model solutions, however, increasing the

temperature did not affect the amount of Pb2+ and Cu2+ bonded to monodentate carboxylic sites

in humic acid. The observation on copper bonding may be explained by the decrease in Cu

bonding constants as the Cu:humic acid ratio increased (Craven, Aiken, and Ryan 2012), the low

carboxylic-carboxylic site complexation capacity (7%) compared to the complexation capacity of

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 Cu to all humic acid sites (Fuentes et al. 2013), and the decrease in conditional equilibrium

constants Ka for Cu bonding to humic acid with increasing temperature (Ghabbour et al. 2006).

The phenolic functional groups were less involved in bonding. The results show an

insignificant number of total phenolic sites (<1%) involved in bonding to humic acid for Pb and

Cu. However, Pb2+ showed higher bonding to monodentate phenolic sites at 35C than Cu2+. The

bidentate carboxylic-phenolic sites were less than 5% of the total phenolic sites for Cu and Pb
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from 25 to 65C. The pH was of prime importance because of its influence upon the preferred

binding sites. The results obtained in this study agreed with earlier models based on the

suggestion that metals bond more to carboxylic sites at acidic pH than to hybrid (with carboxylic

and phenolic ends) or phenolic sites (Catrouillet et al. 2014).

The total Cu and Pb bonding to humic acid on monodentate and bidentate sites are shown

in Figures 5 and 6, respectively. Based on these denticity classifications, the values of [Cu]ads

and [Pb]ads on humic acid were higher on monodentate sites than on bidentate sites. In addition,

increasing the temperature enhanced Pb-humic acid bonding on monodentate sites but reduced

bidentate bonding. Monodentate bonding on Cu-humic acid remained constant with increasing

temperature. However, its bidentate binding increased with temperature. These observations

report the denticity preferences of these metals as a function of temperature. The literature

suggested that the conditional equilibrium constants Ka for Cu to humic acid varied with

temperature (Ghabbour et al. 2006).

Simulations of pH Dependent Ca2+ Surface Complexation

Table 2 shows simulations of adsorbed Ca as a function of pH. Accordingly, the ratio of

Ca bonding to phenolic to carboxylic monodentate sites (phenolic/carboxylic-ratio) increased

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 with pH as the phenolic/carboxylic-ratios were 1.1 × 104 at pH 2, 2.4 × 103 at pH 5, 5.8 × 102

at pH 7, and 6.5 × 102 at pH 9. Model estimations show high bonding to monodentate HA sites

with an increase at pH 9 (Figure 7). This trend was not followed at pH values between 6 and 7

for monodentates, showing less Ca2+ bonding compared to bidentates.

Model Applicability to Scale Formation

Scale formation is decreased by a reduction in the concentration of free calcium ions in

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aqueous solution (Bosire, Ngila, and Mbugua 2015) which is the concern of Eskom Power

Company in South Africa. Ca2+ and Mg2+ bond with dissolved organic matter to form discrete

chemical complexes, a process that reduced the concentration of free ions in solution and the

scaling potential. Other metal ions compete with calcium for dissolved organic matter, a process

that may increase the scaling potential. Tables 3 and 4 compare the measured bonding of Zn2+

and Cu2+ to humic acid in the presence of Mg2+ and Ca2+.

The modelling of the results of this study present challenges in the type and quantity of

data available for simulation. The inputs required for surface complexation modelling are limited

to equilibrium phases and their site definitions. The Dzombak and Morel surface models have

two explicit surfaces that may generate surface complexation data: the Donnan layer and the

Borkovec diffuse layers. In the current study, the surface complexation models did not use an

explicit layer.

The modified Tipping and Hurley database and Windermere’s humic acid model were

used in PHREEQC to generate monodentate and bidentate bonding. The modelling data obtained

in this study showed that metal ions strongly bonded to monodentate sites and subordinately to

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 bidentate sites. With knowledge of the impact of physicochemical parameters to selective

bonding to phenolic or carboxylic groups, specific site metal bonding was manipulated.

The progress in the development of the surface complexation modelling with explicit

surfaces and denticity based definitions allowed reasonable simulation of the data reported in this

study. However, the description may include tridentate-humic acid binding if the definitions

were included in the current databases. The adsorption on hydrated ferrous oxide and humic acid

has been described by Catrouillet et al. (2014). The current study does not consider tridentate
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systems, but gives the best predictions through monodentate and bidentate models of Ca2+, Mg2+,

Zn2+, Cu2+, and Pb2+ with humic acid.

CONCLUSIONS

The bonding of Zn2+, Cu2+, and Pb2+ with humic acid was shown to depend on

temperature, pH, metal-humic acid loading, and the presence of Ca/Mg ions. Zn2+ and Cu2+

adsorption increased with pH. As the pH increased, Mg2+ bonding to humic acid decreased in the

presence of Ca2+, whereas Ca2+ bonding to humic acid decreased in the presence of Mg2+. A

temperature increase affected uncomplexed/labile ions differently. The highest concentrations of

labile Cu2+ and Pb2+ ions were at 45C and lowest at 65C. These results formed the basis of

surface complexation modelling to identify the specific sites. The optimized parameters to

reduce scaling in industrial water pipes were pH values between 6 and 7 at 45C. The

simulations showed that more Ca bonded to phenolic sites at high pH while the carboxylic

monodentate sites were more populated at low pH. Accordingly, the ratio of Ca binding to

phenolic sites to that of Ca binding to carboxylic monodentate sites increased with pH.

Generally, model estimations showed higher bonding on monodentate humic acid sites

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 particularly at higher pH. Across temperature values, the phenolic functional groups were least

involved in bonding compared to sites with carboxylic character. However, the ratio of [Pb]ads

adsorbed on monodentate carboxylic acid sites to the bidentate carboxylic-carboxylic sites was

approximately 1:1 at 25C. Lead(II) only occupied 5% of bidentate carboxylic-phenolic sites at

45C, implying favorability for Ca/Mg bonding to humic acid. A similar trend was observed for

Cu2+, although deviations were observed at 65C.

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Acknowledgments

The authors are grateful to the University of Johannesburg and Eskom, South Africa, for

funding the work. The Centre for Nanomaterials Science Research (CNSR) in the Department of

Applied Chemistry at the University of Johannesburg is acknowledged for funding support. The

useful comments from Evans Changamu (Kenyatta University, Kenya) are highly appreciated.

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 Table 1. Concentrations of Cu and Pb adsorbed on humic acid and complexed fractions to humic
acid (mass = 0.0015 g) at 25, 45, and 65C

Temperatur Fraction of Cu and Pb (mg/L)

e (C) Adsorbed Cu in the Complexe Adsorbed Pb in the Complexe

Cu ultrafiltrate d Cu Pb ultrafiltrate d Pb

25 1.161 ± 0 3.839 ± 0.221 3.146 ± 0. 2.454 ± 0 2.546 ± 0.233 0.005 ± 0.

.030 071 .135 082

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45 1.369 ± 0 3.631 ± 0.210 2.843 ± 0. 2.378 ± 0 2.622 ± 0.280 0.731 ±

.038 054 .188 0.06

65 2.238 ± 0 2.762 ± 0.126 2.106 ± 0. 2.736 ± 0 2.264 ± 0.03 0.514 ± 0.

.167 030 .200 012

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 Table 2. Model concentrations of adsorbed Ca into sites in humic acid as a function of pH

Ca2+ preferred site in [Ca] adsorbed to humic acid (moles)

humic acid pH 2 pH 5 pH 7 pH 9

Phenolic 5.224 × 108 1.464 × 105 5.459 × 104 1.764 × 102

Carboxylic 4.768 × 104 5.998 × 103 9.42 × 103 2.709 × 101

Carboxylic-carboxylic 3.061 × 107 1.0 × 105 2.22 × 105 1.740 × 103

Carboxylic-phenolic 7.0 × 109 2.794 × 105 2.363 × 104 8.218 × 103

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 Table 3. Influence of Mg/Ca to Cu2+ bonding with humic acid

pH Species adsorbed on humic acid (mg/L)

Adsorbed Cu Adsorbed Mg Adsorbed Cu Adsorbed Ca Adsorbed Cu

from Cu from a solution from a solution from a solution from a solution

solution of Cu and Mg of Cu and Mg of Cu and Ca of Cu and Ca

1.5 0.820 ± 0.023 0.5804 ± 0.011 0.9416 ± 0.009 0.041 ± 0.001 0.7818 ± 0.009

3 1.9244 ± 0.110 0.5459 ± 0.031 1.229 ± 0.089 0.6582 ± 0.04 1.6052 ± 0.071
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 Table 4. Influence of Mg/Ca to Pb2+ bonding with humic acid

p Adsorbed species (in mg/L)

H Adsorbed Adsorbed Mg Adsorbed Pb Adsorbed Ca Adsorbed Pb

Pb from Pb from a solution of from a solution of from a solution from a solution

solution Pb and Mg Pb and Mg of Pb and Ca of Pb and Ca

1 0.470 ± 0.02 0.936 ± 0.010 0.621 ± 0.003 0.147 ± 0.001 0.557 ± 0.038

. 2
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3 0.922 ± 0.03 0.824 ± 0.019 0.366 ± 0.005 1.281 ± 0.016 0.565 ± 0.008

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 Figure 1. Concentration of adsorbed zinc in mg/L from pH 1.5 to 4.5 at initial zinc
concentrations of (a) 2.5 ppm, (b) 5 ppm, and (c) 10 ppm.
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 Figure 2. Concentration of adsorbed copper to humic acid in mg/L from pH 1.5 to 4.5 at initial
copper concentrations of (a) 2.5 ppm, (b) 5 ppm, and (c) 10 ppm.
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 Figure 3. Synergistic/antagonistic effects of Mg/Ca bonding to humic acid: (a) Ca to humic acid,
(b) Mg to humic acid, (c) Ca to humic acid in Ca and Mg solution, and (d) Mg to humic acid in
Ca and Mg solution.
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 Figure 4. Stripping voltammograms of Pb at 0.475 V and Cu at 0.32 V showing the peak
heights of labile metals in ultrafiltered solutions after adsorption on humic acid at (a) 45°C, (b)
65°C, and (c) 25°C.
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 Figure 5. Proportion of Cu bonded to humic acid in various sites based on denticity as a function
of temperature.
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 Figure 6. Proportion of Pb bonded to humic acid in various sites based on denticity as a function
of temperature.
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 Figure 7. Model fits of Ca2+ bonding to humic acid based for (a) monodentate sites and (b)
bidentate sites.
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