Journal Pre-proof

Liming effects on dissolved and colloid-associated transport of cadmium

in soil under intermittent simulated rainfall

Xiang-Yu Tang (Conceptualization) (Investigation) (Writing - original

draft), Hidetaka Katou (Supervision) (Writing - review and editing),
Katsuhiro Suzuki (Methodology)

PII: S0304-3894(20)31233-4
DOI: https://doi.org/10.1016/j.jhazmat.2020.123244
Reference: HAZMAT 123244

To appear in: Journal of Hazardous Materials

Received Date: 23 February 2020

Revised Date: 4 May 2020
Accepted Date: 16 June 2020

Please cite this article as: Tang X-Yu, Katou H, Suzuki K, Liming effects on dissolved and
colloid-associated transport of cadmium in soil under intermittent simulated rainfall, Journal of
Hazardous Materials (2020), doi: https://doi.org/10.1016/j.jhazmat.2020.123244

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Liming effects on dissolved and colloid-associated transport of cadmium in soil under
intermittent simulated rainfall

Xiang-Yu Tanga,b,c,* xiangyu.tang@yahoo.com, Hidetaka Katouc, Katsuhiro Suzukid

a
State Key Laboratory of Subtropical Silviculture, Zhejiang A&F University, Hangzhou
311300, China
b
Key Laboratory of Mountain Surface Processes and Ecological regulation, Institute of
Mountain Hazards and Environment, Chinese Academy of Sciences, Chengdu 610041,
China
c
Institute for Agro-Environmental Sciences, National Agriculture and Food Research
Organization, Tsukuba, 305-8604, Japan

of
d
Central Region Agricultural Research Center, National Agriculture and Food Research
Organization, Joetsu, 943-0193, Japan

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*
Corresponding author.
E-mail address: (X.-Y. Tang).
Tel: +86 28 85235869; Fax: +86 28 85222258.
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Graphical Abstract:

Rainfall break
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Antecedent water
DW DW DW CaCl2 DW DW

Cation concentration (mmol L 1), pH

30 mg Cd kg 1, unlimed 9
Cd concentration (nmol L 1)

500 8
Peristaltic 400
7
pump Rainfall simulator Dissolved Cd
6
300 Colloidal Cd 5
Ca
4
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Mg
200 pH 3
2
Distilled water (DW) 100
1
or 5 mmol L1 CaCl2 0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Tensiometer Cumulative discharge (cm 3)

Data Moist soil

logger aggregates vs
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Rainfall break
Antecedent water
DW DW DW CaCl2 DW DW
Cation concentration (mmol L1), pH

30 mg Cd kg1, limed 9
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Cd concentration (nmol L1)

400 8
7
300 Dissolved Cd
6
Colloidal Cd 5
Ca
200 4
Mg
Effluent pH 3
100 2
collector
1
0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Cumulative discharge (cm3)

Highlights:

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 Cd transport in moist soils having realistic Cd concentrations was investigated.
 Maximum colloid-associated Cd concentration occurred in the first column effluent.
 Higher Cd enrichment on colloids occurred in limed soils relative to unlimed soils.
 Liming remarkably decreased the transport of dissolved Cd.
 28–47% of cumulative Cd transport in limed soils was in colloid-associated form.

ABSTRACT
Liming has been regarded as an effective measure to reduce the bioavailability and mobility of
cadmium (Cd) in soil. However, its effect on Cd transport in colloid-associated form remains
unclear. In this study, relative importance of dissolved and colloid-associated transport of Cd was
explored in columns packed with moist soil aggregates (diameter <2 mm) under intermittent

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simulated rainfall of distilled water or 5 mmol L−1 CaCl2 solution. The Cd2+/Ca2+ exchange
selectivity coefficient determined in column experiments displayed gradual decreases with

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decreasing ionic strength. It is proposed that the exchange selectivity coefficient determined by
repeated batch extraction can be used to predict Cd discharge in dissolved form in column effluent.

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Colloid-associated Cd was the main Cd form in the first flushing effluent sample upon resuming
infiltration of distilled water. Otherwise, Cd was transported mainly in dissolved form, accounting
for 81–93% and 54–72% of total Cd discharge for unlimed soils and limed soils, respectively.
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Liming remarkably reduced dissolved Cd concentration but only slightly enhanced colloidal Cd
transport. Cd was enriched on colloids, and the enrichment factor was enhanced by liming.
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Colloidal Cd transport through preferential pathways (e.g., macropores, shrinkage cracks, tile
drains) should be paid due attention.
Keywords: Column experiment; Liming; Colloid-facilitated transport; Exchange selectivity.
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1. Introduction
It has been generally recognized that mobile soil colloids may act as carriers of various
strongly sorbing contaminants, such as heavy metals (e.g., lead, cadmium, copper), radionuclides
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137
(e.g., Cs), nutrients (e.g., phosphorus), and pesticides in the vadose zone (e.g., de Jonge et al.,
2004; Elimelech and Ryan, 2009; Fang et al., 2011, 2016; Grolimund et al., 1996; Litaor et al.,
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1998; Villholth et al., 2000; Yin et al., 2010). The source of mobile colloids in soil is generally
considered to be the in situ release of water-dispersible colloids. Numerous field studies have
demonstrated that colloids may be detached from soil aggregates and released to drainage water at
high concentrations under both water-saturated and unsaturated conditions in response to rainfall
events (El-Farhan et al., 2000; Lenhart and Saiers, 2003; Ryan et al., 1998; Ryan and Elimelech,
1996; Schelde et al., 2002). However, in many of the previous studies, depending on the research
questions to be answered, mobile colloids prepared in advance from soil slurry or model colloids
(e.g., latex microsphere, pure clay minerals and metal oxides) have been often used in colloid and

2
colloid-associated contaminant transport studies in model systems or packed columns under
saturated or unsaturated conditions (e.g., DeNovio et al., 2004; Kretzschmar et al., 1999;
Kretzschmar and Sticher, 1997; Ryan and Elimelech, 1996; Zhuang et al., 2009). The infiltration
and draining fronts have been known to influence colloid mobilization and transport under varying
unsaturated conditions by introducing additional air-water interface (Cheng and Saiers, 2010;
Sirivithayapakorn and Keller, 2003; Wan and Tokunaga, 1997), which occurs at the rising and
receding stage of water flow upon rain event. Interruption of rainfall can lead to increase in the
size of renewable mobile colloid pools in soil, which could become larger after longer interruption
duration (Majdalani et al., 2008; Schelde et al., 2002; Zhuang et al., 2007).
Elevated cadmium (Cd) concentrations in soil were often reported, mainly as a result of
various anthropogenic activities, such as application of fertilizers containing Cd as an impurity
and industrial wastewater discharge (Alloway, 1990). According to a recent national-scale

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assessment of Cd contamination in agricultural soils across China, relatively high Cd
concentrations were found in south regions of the country (Shi et al., 2019). In Japan, paddy fields

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have suffered from serious soil Cd contamination as a result of rapid industrialization during the
1960s (Makino et al., 2007). Considering the well-known high toxicity of Cd and the potential
rapid transport of colloids relative to water, understanding the transport of Cd in both dissolved
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form and colloid-associated form is of the utmost relevance for regions having abundant
preferential pathways (e,.g. macropores, cracks) in soils (McKay et al., 1993; 2002). In the
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literature, there have been a number of laboratory column studies that have demonstrated that soil
colloids such as clay minerals (e.g., montmorillonite, kaolinite) could facilitate cadmium transport
through soils, and the increase in Cd transport by colloids was greater at higher pH and lower
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ionic strength (e.g., Chotpantarat and Kiatvarangkul, 2018; Liu et al., 2019; Wikiniyadhanee et al.,
2015). However, most of the experiments were conducted under saturated, steady-state condition
by artificially adding the mixture of cadmium ions (Cd2+) and colloids, in which the impact of air-
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water interface was not examined.

Sorption of Cd to soil is weaker than other heavy metals, and the exchangeable form accounts
for a considerable proportion of total Cd (Tang et al., 2006; Voegelin et al., 2003). Measurement
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of the selectivity of soil for one cation over another, termed as cation exchange selectivity, can be
used to evaluate the effects of soil properties (e.g., soil pH, organic matter, clay minerals, iron and
aluminum oxides, and texture) and different soil treatments (e.g., liming, water management,
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ageing) on the sorption and transport of cations (Buchter et al., 1996; Curtin et al., 1998; Tang et
al., 2011; Voegelin and Kretzschmar, 2003). As one of the most widely used soil
amendments/ameliorants, liming, on one hand, decreases the mobility and bioavailablity of heavy
metals (e.g. Pb, Zn, Cd) as a result of the soil pH increase, metal hydrolysis reactions,
precipitation as hydroxides, and/or coprecipitation with carbonate (Kabata-Pendias and Pendias,
1992; Pierzynski and Schwab, 1993); on the other hand, the raised pH by liming also favors the
dispersion of clay colloids through increasing the net negative charge on soil surfaces and the ratio

3
of negative to positive charges (Haynes and Naidu, 1998; Roth and Pavan, 1991). However, at
high liming rates, the presence of high Ca2+ concentrations in soil solution, that favor flocculation
of clays and soils (Rimmer and Greenland, 1976; Roth and Pavan, 1991), is also a particular
aspect to be considered. Air-drying of soil could lead to an increase in exchangeable Cd and a
decrease in Cd2+/Ca2+ exchange selectivity coefficient (Tang et al., 2011), and thus the use of air-
dry soils in experiments may lead to the overestimation of Cd transport. Nevertheless, to the best
of our knowledge, there have been no previous studies that have investigated systematically the
effect of liming on the transport of Cd in both dissolved form and colloid-associated form in
initially moist soils upon intermittent rainfall, in which colloids were in situ mobilized like in the
field. In this study, it is hypothesized that the net impact of liming on colloidal Cd transport
depends on the difference in magnitude between the enhancement of Cd adsorption on colloids by
liming-induced pH increase and the reduction of colloid transport resulting from elevated

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coagulation by additional Ca2+ derived from dissolution of lime.
The primary aim of this study was to evaluate liming effects on the relative contribution of

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dissolved and colloid-associated form to Cd transport in a heavy clayed agricultural soil.
Mimicking field conditions, intermittent rainfall was imposed on columns packed with moist soil
aggregates with or without Ca(OH)2 addition, to reveal key chemical and physical processes
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controlling the downward transport of Cd in both forms, and to examine whether the dissolved Cd
discharge can be predicted from the exchange selectivity coefficient determined in separate batch
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experiments, and how the selectivity coefficient varies with the variation of the ionic strength.

2. Materials and methods

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2.1. Soils
A clayey topsoil (Typic Epiaquept) was collected at 0–20 cm depth in an experimental
farmland of Hokuriku Research Station of the Central Region Agricultural Research Center,
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National Agriculture and Food Research Organization, Joetsu (37°6'59" N, 138°16'28" E), Japan.
The field was converted from rice cropping to non-rice cropping (e.g., soybean, cabbage)
production in late 1980s. The soil had a pH of 5.8, a CEC of 253 mmolc kg−1, an organic carbon
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content of 20 g kg−1, and a CaCO3 content of 5.20 g kg−1. It was composed of 17% of sand (20–
2000 m), 38% of silt (2–20 m), and 45% of clay (< 2 m). Smectite was dominant in the clay
fraction. The background Cd concentration in the soil was 0.4 mg kg−1 (Tang et al., 2011).
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The collected soil was passed through a 4-mm plastic sieve after slowly lowering its water
content from field moisture to near the plastic limit. After being incorporated with 0 or 25 mmol
kg−1 of powder Ca(OH)2 and aged for a week, the soil was soaked in CdCl2 solutions (2.65 or 26.5
mg Cd L−1) at a solution/soil ratio of 1.13 L kg−1, to obtain a target total Cd of 3 or 30 mg Cd kg−1.
The Cd-added soils were kept in a muddy state for 2 months with weekly manual mixing. The soil
was then slowly dried to a gravimetric water content in the range of 0.255–0.289 kg kg−1, and
gently broken by hand to pass through a 2-mm plastic sieve so that artificial creation of easily

4
dispersible soil particles by grinding air-dried samples was avoided. Care was taken to avoid soil
drying below the soil water potential of −15 Bar, which could cause changes in the soil properties
(Katou et al., 1985; Toriyama et al., 1988). The sieved moist soils were aged further for 3 months
under moist conditions in sealed plastic bags. In view of the finding that air-drying significantly
enhances Cd release from soils, relative to the release from soils under moist conditions (Tang et
al., 2011), only the soils kept under moist condition were used for this column study of Cd
transport.
2.2. Column setup
Fig. 1 shows the schematic configuration of the soil column setup for transport experiments.
The Cd-added topsoil was packed into a stainless steel cylinder, which were 10 cm long and 11.2
cm in inner diameter and placed on a stainless steel screen (20-μm by 20-μm grid). Considering
that the colloids were in situ mobilized, the thickness of packed soil column was made to be 4 cm

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for all column experiments. Three tensiometers were installed at 0.5, 2.5, and 3.3 cm below the
soil surface and continuous reading was recorded by a data logger (21X, Campbell Scientific,

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USA). A peristaltic pump (SJ-1220, ATTO Corporation, Japan) was used to feed the simulated
rainwater at a constant flow rate to the surface of soil column through a laboratory-made rainfall
simulator with 18 needle nozzles. Excess water, i.e. the water at a pressure higher than the
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atmospheric pressure, was freely drained at the bottom of the column. Effluent sample was
manually collected from the outlet of a funnel onto which the soil column was placed.
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2.3. Intermittent simulated rainfall experiments
Intermittent simulated rainfall experiments were conducted in duplicate on packed columns
with the unlimed soil containing 3 mg Cd kg−1 (Nos. 1 and 2), the limed soil containing 3 mg Cd
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kg−1 (Nos. 3 and 4), the unlimed soil containing 30 mg Cd kg−1 (Nos. 5 and 6), and the limed soil
containing 30 mg Cd kg−1 (Nos. 7 and 8). More information about experimental soil columns can
be found in Table 1. Over 6 consecutive days, distilled water (days 1–3 and 5–6) or 5 mmol L−1
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CaCl2 (day 4) was applied for 5 h each day at an intensity of 7 mm h−1 which may be typically
found in rainy June-July in Japan. 5 mmol L−1 CaCl2 is used to mimic enhanced ionic strength
conditions after applying fertilizers. The soil column was leached with 345 mL of the influent
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(about 1.4 pore volume) each day. Effluent samples were collected every 50 mL or less (for the
last sample on each day), and a total of 41 samples were obtained in a 6-day experiment. Effluents
were analyzed for turbidity, particle size distribution, dissolved and colloid-associated Cd, the
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ionic composition, electrical conductivity (EC), and pH. Colloid-associated Cd concentration in

the effluent was determined as the difference in the Cd concentration between the filtered (through
a 0.2-μm polytetrafluoroethylene filter) and unfiltered samples, with the latter determined after
digestion with HF–HNO3–HClO4. The Cd content of discharged colloids in the effluent was
estimated by dividing cumulative colloidal Cd discharge by cumulative colloid discharge during 6-
day experiments. Enrichment factor of Cd in discharged colloids was calculated as the ratio of Cd
content of colloids to Cd content of bulk soil. After overnight draining of the column following the

5
6th day in the simulated rainfall experiment, the soil column was weighed and sampled every 2 cm
for the determination of soil water content and Cd remaining in soil. Cd concentration was
determined with the inductively coupled plasma mass spectrometry (ICP-MS, SPQ 8000A, Seiko,
Japan). Concentrations of cations (Ca2+, Mg2+, Na+, K+) and anions (Cl−, NO3−, and SO42−) were
measured by ion chromatography (DXi-500, Dionex Corporation, USA), and dissolved organic
carbon (DOC) analyzed using a total organic carbon analyzer (TOC-5000, Shimadzu Scientific
Instruments, Japan). The particle size distribution was determined in a 15 mL fraction cell by a
laser scattering particle size distribution analyzer (LA-920, Horiba, Ltd., Kyoto, Japan). The
colloid concentration was measured by a turbidimeter (PT-760D, DIA Instruments, Japan). A stock
colloid suspension was obtained by collecting the < 2 m fraction from the 10-cm depth with a
pipette right after a required settling time calculated for sampling at room temperature according
to Stokes’ law after dispersion of 10 g of the soil in 500 mL of distilled water, and the exact

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colloid concentration was determined by weighing the oven-dried suspension. A series of standard
colloid suspension was prepared by diluting with distilled water and used to obtain a calibration

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curve by plotting turbidity measurement against the known colloid concentration. Sodium
adsorption ratio (SAR) was calculated from measured Na+, Ca2+, and Mg2+ concentration in the
effluent (Saejiew et al., 2004).
2.4. Chemical speciation of Cd in the column effluent
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Visual MINTEQ version 2.61 (Gustafsson, 2007) was used to calculate chemical speciation of
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dissolved Cd in the effluents with solution pH, dissolved ion concentrations, and dissolved organic
matter (DOM) as inputs. The modified Gaussian DOM database values for component DOM1 by
Christensen and Christensen (1999) was used and a charge density of −7.18 molc (kg C)−1 was
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assumed, which are provided in the Visual MINTEQ.

2.5. Estimation of Cd2+/Ca2+ exchange selectivity coefficient
Cation exchange reaction was assumed to the dominating mechanism of Cd2+ release to the
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aqueous phase:
CaX2 + Cd2+ = CdX2 + Ca2+ (1)
The exchange selectivity coefficient, KCd/Ca, was calculated for the effluent samples collected
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at different times from

QCd aCa
K Cd/Ca  (2)
QCa aCd
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Here X represents an exchanger with a charge of −1 on solid phase, Q is the amount of cation
adsorbed per unit mass of soil (mol kg1), a is the activity of free metal cations in the aqueous
solution phase, and the subscripts refer to the cation species. The exchangeable Ca (QCa) and Cd
(QCd) were estimated as the initial exchangeable pools QCa0 and QCd0 for the 1st sample, or the
differences between the initial exchangeable pools and the measured cumulative amounts of
discharged Ca and Cd in the aqueous solution phase from a unit mass of soil before the effluent
sample (for the 2nd to 41th sample) was collected. The QCa0 and QCd0 values were assumed to be

6
identical to those of similarly prepared moist soils in the previous study (Tang et al., 2011) such
that QCa0 = 103 mmol kg−1, QCd0 = 12.1 and 138 mol kg−1 for the unlimed soils having a total Cd
of 3 and 30 mg kg−1, respectively, and QCd0 = 2.6 and 27.4 mol kg−1 for the limed soils having a
total Cd of 3 and 30 mg kg−1, respectively. To obtain the value of QCa0, 100 mL of 1 mol L−1
ammonium acetate (pH 7.0) was applied to 5g of soil (packed in a leaching column) for 4 h and
the eluted solution was analyzed for Ca2+. The activities of free Ca2+ and Mg2+ in column effluent
were estimated using visual MINTEQ. Data from the first column effluent samples (representing
the early flushing composed of the antecedent water replaced by the newly infiltrating water or 5
mmol L1 CaCl2), and the later samples the fourth to sixth sample representing the quasi-steady
state leaching during infiltration of water or 5 mmol L1 CaCl2) were used to analyze the
relationship between KCd/Ca and the ionic strength.
2.6. Determination of critical coagulation concentration of soil in CaCl2 solution

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The critical coagulation concentration (CCC) is the electrolyte concentration at which the
electrostatic repulsive forces become lower than Van der Waals attractive forces between two

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particles. In this study, using limed and unlimed moist control soil, subjected to the same
treatments except that Cd was not added to soil, the critical coagulation concentrations were
determined by visual observation of the behavior of the soil dispersed in a series of CaCl2
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concentrations (0–1 mmol/L) at a soil (g): solution (mL) ratio of 1:50 (Lagaly and Ziesmer, 2003).
The suspension was shaken for 2 h in glass test tubes, and then placed in a rack for 3 h before
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visual inspection. The CaCl2 concentration, at which a distinct boundary between the solution and
coagulated soil phases can be observed, was taken as the CCC value, which was used to judge
whether the ionic composition favored colloid dispersion or not.
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3. Results
3.1. Critical coagulation concentration of soil particles
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The CCC value in CaCl2 solution increased from 0.40 mmol L–1 for the unlimed soil to 0.60
mmol L–1 for the limed soil. Critical coagulation concentrations have been reported for various
clay minerals, and the dependence of CCC on pH and sodium adsorption ratio (SAR) has been
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demonstrated by a number of experimental studies (Goldberg et al., 1991; Keren et al., 1988;
Permien and Lagaly, 1994; Swartzen-Allen and Matejevic, 1976). Soil dispersion increases with
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increasing sodium adsorption ratio (SAR) and pH (Goldberg and Forster, 1990). In this study, the
liming-induced increases in pH of soil suspensions with 0.40 mmol L–1 and 0.60 mmol L–1 CaCl2
were 0.5 and 0.6 unit, respectively, which could be partially responsible for the enhanced CCC
values observed. It has been recognized that pH increase can lead to greater negative charges on
soil particles, which results in the dominance of repulsive forces between particles and increased
soil dispersion (Haynes and Naidu, 1998).
3.2. Response of colloid transport to simulated rainfall

7
 Colloid concentration in the column effluents showed quick responses to the concentrations of
coexisting ions and little differences were observed between the two Cd contamination levels
(Figs. 2–3). On the 1st day, upon displacement of the antecedent soil solution by the infiltrating
distilled water (abbreviated as DW), there was a continuous, sharp increase in the colloid
concentration for the first three effluent samples, which was associated with rapid decrease of Ca2+
concentration from 6.09–9.96 mmol L–1 in the first effluent to 2.28–3.50 mmol L–1 in the third
effluent; while in the later effluents colloid concentration either slightly increased or decreased
with accompanying decrease of Ca2+ concentration to 0.51–0.86 mmol L–1. Exceptions were
observed in the column experiments 5 and 6 with the limed soil containing 3 mg Cd kg−1, where
continuous sharp increases in the colloid concentration were observed throughout the 1st day with
a relatively high Ca2+ concentration in the last effluent being 1.65 and 2.35 mmol L–1 for
experiments 5 and 6, respectively. On the 2nd, 3rd, and 6th day with DW infiltration, all the soil

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columns showed similar trends: the highest concentration appeared in the first effluent sample and
decreased sharply in the first two to three samples. This was followed by further decrease with

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diminishing rate in the later effluents of the day. It should be noted that the Ca2+ concentrations in
the first sample of the 2nd day exceeded the corresponding CCC values, i.e., 0.40 mmol L–1 for the
unlimed soil and 0.60 mmol L–1 for the limed soil. This suggests that hydrodynamic forces, rather
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than electrostatic dispersion, played a major role in generating and transporting colloid during
early flushing. Given the relatively high porosity (0.635  0.003 cm3 cm–3) and hand-prepared < 2
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mm moist soil aggregates in the present study, it is likely that capillary forces exerted by moving
air–water interfaces associated with wetting fronts may scavenge colloids from soil particle
surfaces and facilitate their transport, as proposed previously by other researchers (Gomez-Suarez
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et al., 1999, 2001; Saiers et al., 2003; Shang et al., 2009).

Infiltration of 5 mmol L1 CaCl2 on the 4th day nearly completely suppressed the colloidal
discharge from the columns. This can be explained by coagulating effects of Ca2+ at
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concentrations exceeding the CCC. Resumed infiltration of DW on the 5th and 6th days did not
recover colloid concentration to the level on the 1st day, although the Ca2+ concentration in the
effluent on the 4th day was lower than that of the first effluent on the 1st day derived mainly from
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the antecedent water in soil. Much shorter duration, i.e., 18 h, of rainless period before resuming
the DW infiltration on the 6th day, as compared with 3 months of storage under moist condition
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before the first day, could lead to a remarkably smaller renewable pool of dispersible colloids in
soil available for mobilization and transport. A high peak colloid concentration observed in the
first effluent sample on the 4th day was due to the resident water exhibiting a low concentration of
Ca2+ below the CCC, which had infiltrated on the previous day.
Irrespective of soil Cd concentration, the 6-day cumulative discharge of colloids was found to
be slightly lower in the limed soils (108.2133.7 mg per kg of soil) than in the unlimed soils
(142.1148.6 mg per kg of soil) (Table 1). In particular, the colloid discharge on the 1st day was
markedly lower in the limed soils, indicating a suppressing effect of additional Ca2+ introduced by

8
liming as Ca(OH)2 on colloid mobilization and transport. This is in line with the finding that Ca-
illite particles can form flocs in saturated Ca(OH)2 solutions (Greene et al., 1978). Such
suppressing effect was marginal on the 2nd to 6th days.
Surface ponding did not occur during the eight intermittent simulated rainfall experiments. The
soils were nearly saturated with the water potential being 1 to 3 cm at the quasi-steady state.
These indicate air-water interface played a role in colloid mobilization and transport throughout
the experiments.
3.3. Particle size distribution of discharged colloids
Fig. 4 presents particle size distribution (PSD) of colloids discharged from the soil columns.
The PSD of the colloids in the effluent always showed bi-modal patterns, which is in agreement
with a previous observation that in situ mobilized soil colloidal particles were highly polydisperse
(Grolimund et al., 1998). No significant differences in PSD were observed neither between the

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unlimed and limed soils nor between the two different Cd contamination levels. During the DW
infiltration, the percentage of the fine (< 2 m) fraction of colloids decreased over time in

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exchange for the increase in the coarse(> 2 m) fraction. On both the 3rd day (DW infiltration) and
the 4th day (5 mmol L1 CaCl2 infiltration), marked differences in PSD between the first effluent

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samples and later (the fourth or the sixth) effluent samples were observed. The first effluent
samples represented the antecedent water in soil displaced by invading water while the fourth or
sixth samples represented the pore water approaching quasi-steady state, physicochemically or
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hydrodynamically, upon infiltration of DW or 5 mmol L1 CaCl2 on the same days. Interestingly,
low Ca2+ concentrations (below the CCC values) at the later stage of DW infiltration did not lead
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to enhanced mobilization and transport of colloids in the fine fraction. It is likely that the
renewable pool of fine colloids, which could be replenished during the rainless (no water flow)
period, seemed more limited in size, as compared with the coarse fraction, so that the discharge of
the fine fraction was concentrated in the early flushing stage.
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3.4. Selectivity of Cd2+-Ca2+ exchange

The exchange selectivity KCd/Ca during simulated rainfall was critically dependent on the ionic
strength I as the dissolved ion concentrations were gradually lowered by leaching (Fig. 5).
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Relatively high KCd/Ca of 22.2–26.3 were found for early effluents with the ionic strength I > 15
mmol L1 during DW infiltration on the 1st day. When the ionic strength was lowered to I  3
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mmol L1, slightly smaller KCd/Ca of 8.4–19.2 were obtained. Further decrease of the ionic strength
to I < 1 mmol L1 led to KCd/Ca of 2.3–10.2 irrespective of liming and Cd concentration level.
Upon infiltration of 5 mmol L1 CaCl2 on the 4th day, the ionic strength of the effluents increased
to I  15 mmol L1 with a concomitant increase of the exchange selectivity to KCd/Ca of 18.2–31.4,
which is comparable to those (18.231.7) obtained for similarly prepared moist soils by repeated
batch extraction with 5 mmol L1 CaCl2 (Tang et al., 2011). The KCd/Ca values again decreased to
the previous levels after DW infiltration on the 5th and 6th days. There were significant (P < 0.01)
relationships between KCd/Ca and ionic strength (Fig. 5). The decrease of Cd2+/Ca2+ exchange

9
selectivity during leaching was associated with a slower decrease of dissolved Cd2+ relative to
dissolved Ca2+. In view of the decrease in the cation exchange capacity of soils having variable-
charge sites with decrease in the ionic strength (Katou, 2002), a plausible explanation for the
above results is that Cd2+ was preferentially adsorbed onto variable-charge sites with a high
Cd2+/Ca2+ exchange selectivity, which release the adsorbed cations as the ionic strength was
lowered by leaching. However, given relatively low dissolved Cd concentrations at the later quasi-
steady stage of DW infiltration, this decrease in KCd/Ca did not significantly affect total Cd release
from the soil in dissolved form. In contrast, during infiltration of 5 mmol L−1 CaCl2, Cd2+-Ca2+
exchange reaction was very likely the dominant process controlling Cd release not only in the
unlimed soils but also in the limed soils. The above results suggest that the KCd/Ca value measured
in repeated batch experiments as proposed by Tang et al. (2011) can be used to predict Cd release
in dissolved form in column experiments upon irrigation with high salinity water or rainfall when

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the soil contains appreciable amounts of dissolved Ca.
3.5. Response of dissolved and colloidal Cd transport to simulated rainfall

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Irrespective of liming and Cd contamination level, dissolved Cd concentration in the effluent
showed similar temporal variations to those of Ca2+ (Figs. 23), suggesting the presence of
exchange reactions between adsorbed Cd with Ca2+ in the aqueous phase. In particular, a much
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more drastic and quicker drop in dissolved Cd concentration in the effluent occurred with time on
the 1st day in the unlimed soils, as compared with the limed soils. The high cation concentrations
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in the first effluent samples (Figs. 2–3) reflect chemical equilibria between the “old” pre-rainfall
water in soil pores and solid phase during the 3-month ageing period. In terms of dissolved Cd
concentrations in effluent samples upon DW infiltration on the 1st to 3rd day, liming was found to
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markedly reduce dissolved Cd discharge by 38  19% and 47  16% for the soils containing 3 and
30 mg Cd kg−1, respectively.
According to the data of the quasi-steady state samples, Infiltration of 5 mmol L−1 CaCl2
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greatly enhanced dissolved Cd transport in the soil columns. This was typically observed in the
sixth samples of the days, where dissolved Cd concentrations in effluents from the unlimed and
limed soils containing 3 mg Cd kg−1 on the 4th day were 9.2  1.9 and 2.8  0.8 times those on the
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other days with DW application. Enhanced Cd discharges were also observed in the soils
containing 30 mg Cd kg−1 of larger magnitudes, by 14.7  0.1 times in the unlimed soil and 4.8 
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0.3 times in the limed soil. Liming-induced pH increases by 0.7  0.2 unit should be responsible
for the marked reductions of dissolved Cd discharge by 79  2% upon infiltration of 5 mmol L−1
CaCl2. No significant differences in liming-induced percentage reduction of dissolved Cd
discharge were found between the two soil Cd contamination levels.
Liming substantially decreased the 6-day cumulative dissolved Cd discharge, by 65% and 73%
on average for the soils containing 3 and 30 mg Cd mg−1, respectively (Table 1).
There were marginal or small differences in the colloid-associated transport of Cd between
unlimed and limed soils at both contamination levels of Cd (Figs. 2–3). Irrespective of liming

10
treatment, colloidal Cd concentration exhibited peak values of 0.78–1.35 g L−1 and 7.14–8.85 g
L−1 for the soils containing 3 and 30 mg Cd kg−1, respectively, in the first effluent samples of the
days. The maximum contribution of colloidal Cd to total Cd discharge were also observed in the
1st flushing effluent sample, with 61–69% for the unlimed soils and 77–84% for the limed soils.
Infiltration of 5 mmol L−1 CaCl2 on the 4th day completely suppressed the colloid-associated
transport of Cd for all column experiments.
The 6-day cumulative colloidal Cd discharge in the limed soils was slightly larger than that in
the unlimed soils (Table 1). This enhanced discharge of colloidal Cd is attributable to liming-
induced increases (by 0.6  0.1 unit) of effluent pH, which could lead to enhanced adsorption of
Cd onto colloids (Table 1 and Figs. 2–3). This was corroborated by the markedly higher Cd
contents of discharged colloids observed for the limed soils than those for the unlimed soils.
Enrichment of Cd in colloidal particles, relative to bulk soil, was also observed for the unlimed

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soils at both Cd contamination levels, but of smaller magnitudes as compared with the limed soils.
In addition, colloids exhibited higher enrichment factors of Cd for the soils having lower total Cd

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concentration, irrespective of whether the soil was unlimed or unlimed. Enrichment of Cd in the <
1 m particle fraction by a factor of 1.5 and 2.2 has been reported for two agricultural soils
polluted by wastewater and smelter dust respectively (Zhang et al., 2013).
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Colloidal Cd discharge accounted for 7–19% and 28–46% of total Cd discharge during 6-day
experiments for unlimed and limed soils, respectively, indicating that the relative importance of
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colloidal Cd discharge was much higher for the limed soils. This was a result of marked decreases
in the dissolved Cd transport in the limed soils.
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4. Discussion
4.1. Mechanism of colloid mobilization and transport
In this study, colloids discharged to the effluent were generated in situ within the column of
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cultivated soil, which can better mimic colloid generation and transport in the field, as compared
with the experiments in which colloidal particles of external origin were introduced into the
columns. This is a field-like experimental condition used also in a number of other studies (e.g.,
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Jacobsen et al., 1997; Kaplan et al., 1993; Mohanty et al., 2015). The observed suppressing effect
of 5 mmol L−1 CaCl2 on colloid transport is not surprising, in view of the established knowledge
that increased ionic strength coupled with divalent cation Ca2+ hampers in situ mobilization of
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colloid (Han et al., 2014; Kretzschmar et al., 1999; Roy and Dzombak, 1996).
The replenishment of renewable colloid pool available for mobilization upon rainfall event has
been attributed to wetting-drying cycles (Kaplan et al., 1993) or freeze-thaw cycles (Worrall et al.,
1999) during the period preceding the rainfall. Most of studies on colloid mobilization and
transport (Bradford and Torkzaban, 2008; Molnar et al., 2015), however, have been conducted
under steady infiltration conditions, focusing on a single infiltration event itself, rather than
intermittent rainfall which commonly occurs in the field. In the present study, the percentage of

11
the fine (< 2 m) colloid size fraction in the first effluent on DW infiltration days was higher than
that in the quasi-steady state effluent samples later on the same days (Fig. 4). This suggests that,
compared with the coarse (> 2 m) fraction, the generation of the fine fraction depended to a
greater extent on the dispersion process on the wetted surface of soil aggregates and in the water-
filled inter-aggregate voids during the rainless period (Majdalani et al., 2008) as well as the
mobilization of colloids by adsorption on the moving air-water interface (Wan and Tokunaga,
1997). In contrast, it was likely that the generation of the coarse fraction depended on the shearing
force exerted by flowing water at water-solid interface. This was indicated by the much slower
decrease in the coarse colloid concentration, obtained by the colloid concentration (Figs. 23)
multiplied by the percentage of the > 2 m colloid size fraction in the measured PSD (Fig. 4). For
example, in column experiment No. 1, the coarse colloid concentration decreased from 24.0 mg
L−1 in the first sample to 8.9 mg L−1 in the sixth sample on 3rd day, while the fine colloid

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concentration depleted more quickly from 64.8 mg L−1 to 9.8 mg L−1 in the same effluent samples.
The average effluent pH was higher for the limed soils, relative to the unlimed soils, by 0.45–

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0.75 pH unit (Figs. 2–3). However, this did not result in greater colloid discharge in the former,
given that the effluent pH was higher than 6 for both the limed and unlimed soils. The SAR values

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in the column effluent were slightly higher for the unlimed soils (0.24–0.47) than for the limed
soils (0.19–0.37), and this could have led to higher dispersibility and larger colloid discharges in
the unlimed soils. These results were consistent with the higher CCC value for the limed soils, and
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indicative of apparent stabilizing effects of liming on soil aggregates.
4.2. Liming effects on Cd release in the dissolved and colloidal form: comparison between
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column leaching and batch extraction experiments

The present study demonstrated that liming greatly suppressed Cd discharge from the soil
columns particularly when the ionic strength of the effluent was high, i.e., in the early effluents on
the 1st day with DW infiltration and in the later effluents during 5 mmol L−1 CaCl2 infiltration
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(Figs. 2 and 3). Naidu et al. (1994) reported that CdOH+ species formed above pH 8 had a greater
affinity for sorption sites than Cd2+. It has been well established that an increase in pH increases
the net negative charge through the dissociation of H+ from weakly acidic functional groups of soil
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organic matter and some clay minerals (Curtin et al., 1996; Thomas and Hargrove, 1984),
resulting in the increase in total cation adsorption (Naidu et al. 1994). While precipitation of Cd as
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Cd(OH)2 is likely to result in a greater Cd retention at pH above 10 (Naidu et al., 1994), the
highest pH of the column effluents obtained for limed soils in the present study was about 7.3.
Calculation with Visual MINTEQ showed that the main species of Cd in the aqueous phase were
free Cd2+, Cd-DOM, and CdCl+ for both the first and quasi-steady state effluent samples of all the
days irrespective of liming treatment. The activity of free Cd2+ was always the highest, accounting
for 3671% of dissolved Cd, and the CdCl+ ranked the second place (3134%) only when
relatively high concentrations of CaCl2 present in the effluents. Otherwise, Cd-DOM took the
second place (752%) in the quasi-steady effluents of DW infiltration days showing low Cl−

12
concentrations. Employing a newly developed, repeated batch extraction method assuming a
constant KCd/Ca, Tang et al. (2011) estimated the exchangeable Cd pools, QCd0, in unlimed and
limed soils prepared in the same way as in the present study. They obtained the estimates of QCd0
= 1.36 and 0.29 mg kg−1 for the unlimed and limed soils having a total Cd of 3 mg kg−1,
respectively, and QCd0 = 15.5 mg kg−1 and 3.08 mg kg−1 for the unlimed and limed soils having a
total Cd of 30 mg kg−1, respectively. The 6-day cumulative dissolved Cd discharge (Table 1) was
5.48 g kg−1, 1.89 g kg−1, 64.5 g kg−1, and 17.5 g kg−1 for the unlimed and limed soils
containing 3 mg Cd kg−1, unlimed and limed soils containing 30 mg Cd kg−1, respectively, which
only accounted for 0.40%, 0.65%, 0.42%, and 0.57% of initial exchangeable Cd, respectively. The
similar percentages of dissolved Cd discharges from the unlimed and limed soils at both Cd
contamination levels corroborated the assumption of a constant Cd2+/Ca2+ exchange selectivity by
Tang et al. (2011). The suppressed dissolved Cd discharge observed for the limed soils can be

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attributed to liming-induced reduction in the exchangeable Cd pool in soil. Therefore, we judge
that the exchangeable Cd pools in the experimental soils were correctly estimated by the repeated

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batch extraction method, and suggest that the dissolved Cd discharge may be predicted with a
reliable estimate of exchangeable Cd pool in soil.
Table 2 compares the dissolved Cd release observed in the column leaching with DW and 5
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mmol L−1 CaCl2 in the present study with the Cd release in the single batch extraction with DW
and 5 mmol L−1 CaCl2, respectively (Tang et al., 2011). For the unlimed soils, Cd release in the
re
column leaching with water was close to that in the batch extraction with water irrespective of the
large difference in the soil/water ratio, which was 8 times as large in the column leaching. For the
limed soils, however, Cd release was somewhat lower in the column leaching. It was reported that
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liming could lead to better aggregation and larger microporosity (Hati et al., 2008). A plausible
explanation is that the release of dissolved Cd through intra-aggregate micropores in the limed
soils was slow during the DW infiltration, resulting in ineffective Cd release. The situation was
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very different in 5 mmol L1 CaCl2 where Ca2+-Cd2+ exchange reaction was the dominant
mechanism for the release of dissolved Cd. It was found that Cd release from the exchangeable Cd
pool was not exhaustive, and that the highest dissolved Cd concentrations in column effluent, 3.21
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g L−1 and 0.71 g L−1, respectively, for the unlimed and limed soils with 3 mg Cd kg−1, and 39.9
g L−1 and 8.11 g L−1, respectively, for the unlimed and limed soils with 30 mg Cd kg−1 (Figs. 2–
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3), were almost identical to those (3.03 g L−1, 0.43 g L−1, 46.2 g L−1, and 6.28 g L−1,
respectively) found in the batch extraction with 5 mmol CaCl2 (Tang et al., 2011). The predicted
Cd release in 5 mmol L1 CaCl2 by dividing the measured Cd release in single batch extraction by
26, the ratio of soil/solution ratio for the column leaching to that for the batch extraction, was
similar to the measured Cd release from column leaching (Table 2). This corroborates the
explanation that the release of dissolved Cd was through cation exchange with Ca2+ as formulated
in Eq. (2).

13
 On the other hand, liming did not promote particle dispersion in DW but instead led to a slight
decrease in 6-day cumulative colloid transport, with the most marked reduction taking place on the
1st day of DW infiltration (Table 1). Despite this, slightly larger 6-day cumulative colloidal Cd
transport was observed in the limed soils than the unlimed soils. This was due to greater
enrichment of Cd on the discharged colloidal particles in the limed soils, with Cd enrichment
factors of 1.35–2.48 and 2.22–3.58 in the unlimed and limed soils, respectively. It can be inferred
that liming-induced pH increases enhanced Cd adsorption on suspended colloids in the pore water.
Particle size distribution of the discharged colloids did not show obvious differences between the
unlimed and limed soils (Fig. 4). The results imply the concentration of Cd in easily-dispersible
colloids in the limed soil, although precise mechanisms are unknown. In the long term, continuous
discharge of colloids containing Cd at elevated concentrations, through tile drain system or to
groundwater through macropores, may lead to Cd accumulation in sediment or aquifer.

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Subsequent desorption of Cd could pose potential threat to water safety and aquatic ecosystems.

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5. Conclusions
A heavy-clayey soil collected from a farmland was spiked with Cd, with or without prior
liming, to obtain target concentration of 3 or 30 mg-Cd kg−1. After ageing, moist soil aggregates
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with diameter < 2 mm was carefully prepared and packed into columns. Intermittent simulated
rainfall experiments were conducted for 6 days, with DW or 5 mmol L−1 CaCl2 solution, to
re
explore the relative importance of dissolved and colloid-associated transport of Cd. In both the
unlimed and limed soils, colloid-associated Cd constituted the main form of discharged Cd in the
first effluent sample after resuming rainfall with DW. Otherwise, Cd was transported mainly in the
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dissolved form, accounting for 81–93% and 54–72% of total Cd discharge for unlimed soils and
limed soils, respectively. Liming remarkably decreased dissolved Cd discharge while only slightly
enhanced colloidal Cd discharge. Enrichment of Cd on discharged colloidal particles was observed
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in both the limed and umlimed soils, with the Cd enrichment factor greater in the limed soils.
Irrespective of total Cd content and whether the soils had been limed or unlimed, 0.40–0.57% of
the initial exchangeable Cd pools, estimated by repeated batch extraction in separate experiments,
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was discharged in the dissolved form. At ionic strengths I > 15 mmol L1, the Cd2+/Ca2+ exchange
selectivity coefficient of KCd/Ca  22.2–26.3, calculated from the estimates of initial exchangeable
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Cd pools and cumulative amount of discharged Cd and Ca, was almost identical to that obtained in
the repeated batch experiments with 1–5 mmol L1 CaCl2. While KCd/Ca showed gradual decreases
with decreasing ionic strength, possibly due to preferential Cd desorption from variable-charge
sites, dissolved Cd discharge was of minor importance at low ionic strengths. Consequently,
cumulative dissolved Cd discharge during whole periods of DW and 5 mmol L−1 CaCl2 infiltration
was predictable using KCd/Ca obtained by the repeated batch experiments. Due attention should be
paid to the effects of liming on colloid-associated Cd, which may be transported through such

14
preferential pathways as macropores, shrinkage cracks, and tile drains, and contribute to
accumulation of Cd in river sediment or aquifer in the long term.

CRediT author statement

Xiang-Yu Tang: Conceptualization, Investigation, Writing - original draft. Hidetaka

Katou: Supervision, Writing - reviewing and editing. Katsuhiro Suzuki:
Methodology.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

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Acknowledgements

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This work was financially supported by the Major Science and Technology Program of
Sichuan Province (Grant No. 2018SZDZX0029), the Japan Society for the Promotion of Science
(Grant Nos. P04575 and BR141301) and the 135 Strategic Program of the CAS Institute of
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Mountain Hazards and Environment (Grant No. SDS-135-1702). The authors wish to thank Dr. K.
Adachi of Hokuriku Research Center for providing soil samples. The authors also acknowledge
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help and assistance by Drs. T. Ohtani, S. Eguchi, K. Nakano, A. Kawasaki, and Ms F. Kuramochi.

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Peristaltic pump
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Rainfall simulator
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Distilled water or
5 mmol L1 CaCl2
Tensiometer 10 cm
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Data logger Soil 4 cm

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Effluent collector
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Fig. 1. Schematic configuration of the soil column setup for simulated rainfall
experiments.

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 120 10 120 10
DW DW DW CaCl2 DW DW DW DW DW CaCl2 DW DW
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 9 Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 9
100 100
8 8

Colloid, DOC (mg L-1)

Colloid, DOC (mg L-1)
7 7
80 80
6 6

pH
pH
60 5 Colloid 60 5

4 DOC 4
40 pH 40
3 3

2 2
20 20
1 1

0 0 0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Discharge (cm3) Discharge (cm3)
10 2 10 2

9 1.8 9 1.8

8 1.6 8 1.6
Ca 2+, Mg2+ (mmol L-1)

Ca 2+, Mg2+ (mmol L-1)

7 1.4 7 1.4

Na+, K+ (mmol L-1)

Na+, K+ (mmol L-1)

6 1.2 6 1.2
Ca
5 1 5 1
Mg
4 0.8 Na 4 0.8

3 0.6 K 3 0.6

2 0.4 2 0.4

1 0.2 1 0.2

0 0 0 0

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0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Discharge (cm3) Discharge (cm3)
1.2 4.5 1.2 4.5

4 4
1.0 1.0
3.5 3.5

Dissolved Cd (g L-1)

Dissolved Cd (g L-1)

Colloidal Cd (g L-1)

Colloidal Cd (g L-1)

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0.8 3 0.8 3

2.5 2.5
0.6 0.6
2 Colloidal Cd 2
Dissolved Cd
0.4 1.5 0.4 1.5

0.2

0.0
0 200 400 600 800 1000 1200
Discharge (cm3)
1400 1600 1800 2000
1

0.5

0
-p
0.2

0.0
0 200 400 600 800 1000 1200
Discharge (cm3)
1400 1600 1800
1

0.5

2000
0

(a) (b)
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Fig. 2. Temporal variations in the concentrations of colloid, colloidal and dissolved Cd, cations
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(Ca2+, Mg2+, Na+, and K+), dissolved organic carbon (DOC) and pH in response to intermittent
simulated rainfall in column experiments 1 (a) and 3 (b). Unlimed (a) and limed (b) soil containing
3 mg Cd kg−1 wereas used, repectively. Distilled water was supplied at a rain intensity of 7 mm h−1
for 5 h on days 1, 2, 3, 5, and 6, whereas 5 mmol L−1 CaCl2 was supplied for 5 h on day 4 at the
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same rain intensity. Dotted lines separate different days.

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 120 10 120 10
DW DW DW CaCl2 DW DW DW DW DW CaCl2 DW DW
Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 9 Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 9
100 100
8 8
Colloid, DOC (mg L-1)

Colloid, DOC (mg L-1)

7 7
80 80
6 6

pH

pH
60 5 Colloid 60 5

4 DOC
4
40 pH 40
3 3

2 2
20 20
1 1

0 0 0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Discharge (cm3) Discharge (cm3)
10 2 10 2

9 1.8 9 1.8

8 1.6 8 1.6
Ca 2+, Mg2+ (mmol L-1)

Ca 2+, Mg2+ (mmol L-1)

Na+, K+ (mmol L-1)
7 1.4 7 1.4

Na+, K+ (mmol L-1)

6 1.2 6 1.2
Ca
5 1 5 1
Mg
4 0.8 Na 4 0.8

3 0.6 K 3 0.6

2 0.4 2 0.4

1 0.2 1 0.2

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0 0 0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Discharge (cm3) Discharge (cm3)
12 60 12 60

10 50 10 50

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Dissolved Cd (g L-1)

Dissolved Cd (g L-1)

Colloidal Cd (g L-1)

Colloidal Cd (g L-1)

8 40 8 40

6 30 6 30
Colloidal Cd
Dissolved Cd
4 20 4 20

0
0 200 400 600 800 1000 1200
Discharge (cm3)
1400 1600 1800 2000
10

0
2

0
-p
0 200 400 600 800 1000 1200
Discharge (cm3)
1400 1600 1800 2000
10

0
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(a) (b)

Fig. 3. Temporal variations in the concentrations of colloid, colloidal and dissolved Cd, cations
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(Ca2+, Mg2+, Na+, and K+), dissolved organic carbon (DOC) and pH in response to intermittent
simulated rainfall in column experiments 35 (a) and 7 (b). Unlimed (a) and limed (b) soil
containing 30 mg Cd kg−1 wereas used, respectively. Distilled water was supplied at a rain
intensity of 7 mm h−1 for 5 h on days 1, 2, 3, 5, and 6, whereas 5 mmol L−1 CaCl2 was supplied for
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5 h on day 4 at the same rain intensity. Dotted lines separate different days.
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 20 3 mg Cd kg1 20 30 mg Cd kg1
Distilled 3-1 day 3, 1st sample
Water Daywater,
18 Unlimed soil 18 Unlimed soil
Distilled 3-6 day 3, 6th sample
Water Daywater,
16 16
5 mM
mmol L1 CaCl
CaCl2 st
2, day 4, 1 sample
Day 4-1
14 14
L1 CaCl
Percentage (%)

Percentage (%)
5 mM
mmol th
CaCl2 2, day 4, 4 sample
Day 4-4
12 12
10 10
8 8
6 6
4 4
2 2
0 0
0.1 1 10 100 0.1 1 10 100
Particle diameter (m) Particle diameter (m)
20 3 mg Cd kg1 20 30 mg Cd kg1
18 Limed soil 18 Limed soil
16 16

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14 Percentage (%) 14
Percentage (%)

12 12
10 10

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8 8
6 6
4 4
2
0
0.1 1 10
Particle diameter (m)
100
2
0
0.1
-p 1 10
Particle diameter (m)
100
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Fig. 4. Particle size distribution of colloids discharged from the columns with (a) unlimed soil
containing 3 mg Cd kg−1, (b) unlimed soil containing 30 mg Cd kg−1 (c) limed soil containing 3
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mg Cd kg−1, and (d) limed soil containing 30 mg Cd kg−1. Data from the first and sixth samples on
water-infiltrating day 3 as well as the first and fourth samples on 5 mmol L1 CaCl2-infiltrating
day 4 are shown for experiments 1, 3, 5, and 7. The first samples of the days represent the first
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flushing whereas the fourth and sixth samples represent steady flow.
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 35 3 mg Cd kg1 35 30 mg Cd kg1
Unlimed soil Unlimed soil
30 30
25 25
20 20
KCd/Ca

KCd/Ca
15 15
10 10
y = 4.8602ln(x) + 10.094 y = 4.2777ln(x) + 10.726
5 R² = 0.9413 5 R² = 0.9568
0 0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
Ionic strength (mmol L-1) Ionic strength (mmol L-1)

35 3 mg Cd kg1 35 30 mg Cd kg1
Limed soil Limed soil
30 30

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25 25
20 20
KCd/Ca

15 KCd/Ca
15

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10 10
y = 1.5668x + 2.7442 y = 5.4351ln(x) + 6.6631
5 R² = 0.879 5 R² = 0.9284
0
0 5 10 15 20 25
Ionic strength (mmol L-1)
30 35
-p
0
0 5 10 15 20 25
Ionic strength (mmol L-1)
30 35
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Fig. 5. Relationship between Cd2+/Ca2+ exchange selectivity coefficient, KCd/Ca, and the ionic
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strength of column effluents. Data from the first effluent samples on day 1–6, the fifth samples on
day 1, and the sixth samples on days 2–6 were used. The first samples of the day represent the first
flushing after resuming infiltration whereas the fifth and sixth samples represent quasi-steady state
leaching during infiltration of water or 5 mmol L1 CaCl2 solution.
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 f
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Table 1
Summary of cadmium discharge from packed soil columns during intermittent simulated rainfall experimentsa.

pr
No. Total Soil Mass of Soil water Colloid dischargec Dissolved Colloidal Cd content Cd
Cd in pHb soil in the content Cd Cd of enrichment
soil column discharged discharged colloidse
factor

e-
Initial Final Days 1–6 Day 1 Day 2
mg kg −1
g –– cm cm–3 ––
3
–– mg colloid (kg soil)–1 –– –– g Cd (kg soil)–1 –– mg kg−1

Pr
1 Unlimed 3 5.9 382.6 0.247 0.478 148.1 43.7 38.3 4.79 1.10 7.43 2.48
2 Unlimed 3 5.9 384.6 0.242 0.413 148.6 33.3 43.4 6.17 0.82 5.49 1.83
3 Limed 3 6.8 382.5 0.247 0.448 133.7 25.6 43.8 1.45 1.26 9.4 3.14
4 Limed 3 6.8 378.9 0.256 0.426 122.2 12.6 37.1 2.34 1.31 10.7 3.58

5 Unlimed 30 5.9 382.4l 0.271 0.458 148.0 33.1 36.6 56.5 7.53 50.9 1.70
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6 Unlimed 30 5.9 376.2 0.264 0.431 142.1 30.4 41.3 72.5 5.77 40.6 1.35
7 Limed 30 6.8 381.8 0.272 0.478 119.5 22.6 37.5 16.4 7.95 66.5 2.22
8 Limed 30 6.8 379.4 0.278 0.435 108.2 21.5 30.8 18.6 7.23 66.8 2.23
a
The experiments were conducted with the columns having a soil bulk density of 0.971  0.007 g cm and pore volume of 250  1 cm . The pH of distilled
−3 3
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water and 5 mmol L1 CaCl2 applied in column experiments was 5.7 and 5.5, respectively.
b
Measured in distilled water at a soil (g):solution (mL) ratio of 1:5.
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c
Total amounts of discharged colloids per unit mass of soil on the 1st and 2nd day and during the whole period of 6 days in each column experiment.
d
Total amounts of dissolved or colloidal Cd per unit mass of soil discharged during 6-day experiment.
e
Cumulative colloidal Cd discharge divided by cumulative colloid discharge during 6-day experiment.
Table 2

25
 f
Comparison of Cd release per unit mass of unlimed and limed soil obtained by the column leaching experiments and batch extraction experiments.

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Soil In distilled water In 5 mmol L−1 CaCl2
Soil/solution ratioa Cd release b
Soil/solution ratioc Cd released Predicted Cd releasee
g mL−1 g kg−1 g kg−1 g kg−1
Column 3 mg Cd/kg 8/20 2.25  0.50 26/20 2.15  0.27 2.33

pr
leaching Unlimed
3 mg Cd/kg 8/20 0.99  0.35 26/20 0.46  0.11 0.33
Limed
30 mg Cd/kg 8/20 26.1  5.3 26/20 27.5  4.9 35.5

e-
Unlimed
30 mg Cd/kg 8/20 8.47  0.81 26/20 5.40  0.49 4.83
Limed
1.90  0.14 60.7  1.2

Pr
Batch 3 mg Cd/kg 1/20 1/20
extractiond Unlimed
3 mg Cd/kg 1/20 1.40  0.00 1/20 8.60  0.14
Limed
30 mg Cd/kg 1/20 24.6  1.1 1/20 924.0  5.7
Unlimed
30 mg Cd/kg 1/20 l 15.3  0.4 1/20 125.5  2.1
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Limed
a
Soil/solution ratio for column leaching in the distilled water infiltration stage was taken as the mass of soil (g) in the column divided by the cumulative
effluent discharge (mL) on days 1–3.
b
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Cd release from column leaching in the distilled water infiltration stage was taken as the sum of cumulative dissolved Cd discharge on days 1–3 divided by
the mass of soil in the column.
c
Soil/solution ratio for column leaching in the 5 mmol L1 CaCl2 infiltration stage was taken as the mass of soil (g) in the column divided by the cumulative
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effluent discharge (mL) of the fourth to seventh effluent samples on day 4 and the first and second effluent samples on day 5, for which the infiltrated CaCl2
solution was the main water source.
d
Data calculated from the reported results by Tang et al. (2011).

26
 f
e
Cd release from column leaching in the 5 mmol L1 CaCl2 infiltration stage was taken as the sum of the cumulative dissolved Cd discharge of the fourth to

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seventh effluent samples on day 4 and the first and second effluent samples on day 5.
f
Cd release predicted by dividing the measured Cd release by single batch extraction by 26, the ratio of soil/solution ratio for the column leaching to that for
the single batch extraction.

pr
e-
l Pr
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27