Practical applications of ion exchange resins in

agricultural and environmental soil research

P. Qian and J. J. Schoenau
Department of Soil Science, University of Saskatchewan, Saskatoon, Saskatchewan, Canada S7N 5A8.
Received 22 December 2000, accepted 13 September 2001.

Qian, P. and Schoenau, J. J. 2002. Practical applications of ion exchange resins in agricultural and environmental soil
research. Can. J. Soil Sci. 82: 9–21. The use of synthetic ion-exchange resins to examine ion bioavailability in soil and sediment
Can. J. Soil. Sci. Downloaded from www.nrcresearchpress.com by 125.164.31.88 on 02/18/18

systems has attracted much attention over the years. The first report in this regard was made 7–8 yr after resins were developed in
the 1930s. So far, nearly 400 journal articles have been published related to use of resins in soil and environmental studies. The
experience gained has led to more widespread applications in research as well as practical use in soil fertility assessment and fer-
tilizer recommendations. Two commercial products developed in North America have directly resulted from years of research
efforts. Recent developments in resin technology and availability warrant an updated review of the literature to aid in better under-
standing and utilizion of this technique.
In this paper we provide an overview of historic and current developments in the use of ion exchange techniques in soil research.
We also provide specific examples of successful use of batch and diffusion-sensitive ion exchange techniques in research and com-
mercial use to assess ion availability. Finally, we address certain frequently asked questions about how the ion exchange resin tech-
nique is applied and how results are interpreted, including their advantages and limitations.

Key words: Ion exchange resin, agriculture, environment, soil research

Qian, P. et Schoenau, J. J. 2002. Application pratique des résines échangeuses d’ions dans la recherche sur les sols cultivés
For personal use only.

et naturels. Can. J. Soil Sci. 82: 9–21. L’usage de résines échangeuses d’ions pour évaluer la biodisponibilité des ions dans le sol
et les sédiments a considérablement retenu l’attention au fil des ans. Le premier rapport sur le sujet a été publié 7 ou 8 ans après
la création des résines, dans les années 30. On répertorie pour l’instant près de 400 articles sur l’utilisation de telles résines dans
les études sur le sol et sur l’environnement, dans les périodiques scientifiques. L’expérience aidant, les applications de ces
produits en recherche et pour l’évaluation de la fertilité du sol et la formulation de recommandations se sont multipliées. De
nombreuses années de recherche ont abouti à la genèse de deux produits commerciaux en Amérique du Nord. Les progrès récents
de la technologie des résines et l’existence de tels produits justifient un nouveau regard sur la littérature scientifique, si l’on veut
mieux comprendre et exploiter cette technique. Les auteurs tracent dans leurs grandes lignes l’historique des techniques d’échange
d’ions dans la recherche sur les sols et les développements récents en la matière. Ils présentent aussi des cas spécifiques où les
techniques d’échange d’ions par lot et par diffusion ont donné de bons résultats dans la recherche et le commerce pour évaluer la
disponibilité des ions. Enfin, les auteurs répondent à des questions souvent posées sur les applications de la technique des résines
échangeuses d’ions et sur l’interprétation des résultats, notamment ses avantages et ses limites.

Mots clés: Résine échangeuse d’ions, agriculture, environnement, recherche sur le sol

The earliest references to ion exchange are in relation to
soils and fertility (Thompson 1850; Way 1850). It may not
be surprising, therefore, that modern synthetic ion exchange
resins have wide potential applications in agriculture and
related areas. In fact, research using synthetic ion exchange
resins in agriculture was started as early as 1942 (Schlenker)
and 1943 (Converse et al.), which was only 7–8 yr after syn-
thetic ion exchange resin was developed (Adams and
Holmes 1935). In the early research, ion exchange resin was
used as a source of adsorbed ions for plant growth in sand
culture systems. Further studies that use ion exchangers as a
source of nutrient ions in a medium and as a means of
buffering nutrient solutions are reported (Arnon and
Grossenbacker 1947; Skogley and Dawson 1963; Skogley
1969; Checkai et al. 1987; Kerven et al. 1993). However,
the majority of ion exchange resin studies have focused on
their use in exchanging initial counterions for other ions
(e.g., nutrient ions) in the soil, thereby acting as a nutrient
9
ion sink during the extracting time, which can be used to
study bioavailability of various nutrients in soil.
The first use of ion exchange resin to measure nutrient
availability goes back to 1951 (Pratt) and 1955 (Amer
et al.). Since then, ion exchange resins have been adopted to
measure the amounts of plant-available nutrient ions in soils
and the rates at which they are released (Salomon and Smith
1957; Bowman et al. 1978; Martin and Sparks 1983;
Skogley et al. 1990). To date, based on our literature search,
there have been about 400 journal articles published. In
these papers, most of the research has been conducted using
ion exchange resins in bead forms. However, the use of ion
exchange resins in sheet or membrane form has also attract-
ed researchers’ interests, since the work of Saunders (1964),
due to its simplicity in handling and use, and the ability to
measure flux to an easily defined surface area (Saggar et al.
1990; Qian et al. 1992; Lee and Zheng 1993; McLaughlin
et al. 1993). Both resin beads and membranes have evolved
 10 CANADIAN JOURNAL OF SOIL SCIENCE
from initial usage in batch systems where beads or mem-
brane strips are shaken in soil suspension for certain time
periods (Amer et al. 1955; Arnold 1958; Turner and Gillam
1976; Martin and Sparks 1983; Qian et al. 1992; Prochnow
and Pismel 1998; Turrion et al. 1999) to diffusion-sensitive
and direct contact systems (Binkley and Matson 1983;
Skogley et al. 1990; Skogley 1992; Giblin et al. 1994; Qian
and Schoenau 1995; Kjønass 1999; Pampolino and Hatano
2000).
The resin method overcomes the disadvantage of chemi-
cal extractions that are inherently static and do not account
for the kinetics of nutrient release and transport (Curtin et al.
1987; Abrams and Jarrel 1992) and may mobilize nutrient
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forms other than those that are truly plant available (Logan
and Chaney 1983; Menon et al. 1988). It also has the advan-
tages of simplicity, cost-effectiveness, ease of use, and
applicability in soils of different regions and in multiple-
purpose agricultural and environmental studies (Skogley
1994; Skogley and Dobermann 1996). Thus, resin method-
ology has shown great potential as an innovative approach
to soil testing (Skogley 1994). The objective of this paper is
to review the different uses to which resin in bead and mem-
brane forms have been applied in the study of soil ion
dynamics and bioavailability and discuss considerations for
their successful use.
For personal use only.
BATCH PROCEDURES IN AGRICULTURAL
RESEARCH
Most of the methods developed so far are called batch
techniques, where a certain amount of soil and resin
(beads or membranes) are mixed in an excess of water and
shaken for extended periods. The results from such
techniques are strongly influenced by resin/soil/solution
ratios, extracting (shaking) time, type and ionic saturation
of the resin, temperature, method of retaining the resin,
and the method used to recover the adsorbed ions from
the resin (Dobermann et al. 1994). During extraction,
resins maintain low ion concentrations in solution,
thereby stimulating further release from soil solids
(Sparks 1987) until equilibrium is reached. Furthermore,
resin-based multi-nutrient extraction procedures perform
better than conventional multiple extraction procedures
(van Raij et al. 1986; Qian et al. 1992; Somasiri
and Edwards 1992). However, batch procedures provide
mainly an indication of amounts of specific nutrients
that can be derived from the solution phase of soil
suspensions, but not the contribution of diffusion
processes through the medium as they influence nutrient
availability. The importance of ion movement processes
in governing ion availability is well established (Barber
1984). That is why a new approach, defined as diffusion-
sensitive procedures, has emerged (Schaff and Skogley
1982; Binkley and Matson 1983), which will be described
later.
Although the current focus on use of ion exchange resin
has shifted from batch systems to diffusion-sensitive proce-
dures, batch procedures are used in many areas as research
tools. Following are some examples of applications of this
procedure.
Phosphorus Fractionation Studies – Sequential P
Extraction
When Chang and Jackson (1957) first developed the P
sequential extraction method, “labile” Pi was extracted by
NH4Cl. Ammonium chloride solution continued to be used
in many later modifications such as that of Williams et al.
(1967). It was Hedley et al. (1982), in the alternative P-frac-
tionation scheme, who used an anion exchange resin (bead
form) to extract the labile (plant-available) forms of inorgan-
ic P instead of NH4Cl. In characterizing available P, anion
exchange resin is used by shaking in a soil suspension for
16 h to measure readily available inorganic P, which includes
soluble inorganic P, “exchangeable” inorganic P and some of
the more soluble precipitated P forms. The pool measured by
resin extraction is very similar to that assessed with isotopic
dilution (Amer et al. 1955). Sibbesen (1978) and Naidu et al.
(1991) reported that resins (HCO3 and Cl forms, respective-
ly) better predicted the amount of plant-available P than the
32P isotope dilution method. Tran et al. (1992) confirmed
that resins in both HCO3 and Cl forms had better correlation
with crop P uptake than 32P isotopic exchange in all the
acidic, neutral and calcareous soils tested.
Both resin beads and membranes have shown the similar
ability to estimate available soil P (Saunders 1964), but
membrane is easier to handle when it is cut into strips and
used repeatedly (Saggar et al. 1990). A detailed description
of the resin extraction procedure as the first step in sequen-
tial P extractions is provided by Tiessen and Moir (1993). A
number of researchers have used resin membrane in P-frac-
tionation studies (O’Halloran et al. 1987; Sharpley et al.
1989; Schoenau et al. 1989; Solis and Torrent 1989; Sattel
and Morris 1992; Qian and Schoenau 2000c).
Ion Speciation in Soil Environments
Numerous chemical techniques are used for the determina-
tion of ion species, but most are tedious, time-consuming,
and not practical for routine analyses. Alternatives to these
chemical techniques are computer speciation models that
have been successful in well-defined solutions with known
total concentration of metal and ligands (e.g., McGrath et al.
1986; Hirsch and Banin 1990). However, these models are
often unable to accurately predict the species in soil solu-
tions because of the very complex, ill-defined composition
of the dissolved organic matter present. Use of ion exchange
resin gives a simple and reliable means of measuring metal
speciation in soil environments. Fotovat and Naidu (1997)
reported favorable results when using cation exchange resin
for speciation of zinc (Zn2+) and copper (Cu2+) compared to
a geochemical model named MINTEQA2. Holm et al.
(1995) concluded, in a study on speciation of cadmium and
zinc in soil solutions, that the ion exchange method deter-
mines the dissolved species experimentally with minimal
changes in the sample composition, and thus is able to work
in complex solutions with ill-defined organic ligands.
In another approach, Liang and Schoenau (1996) subdi-
vided metal contaminants (Cd, Cr, Ni and Pb) into a number
of operationally defined categories through equilibration
with ion exchange resins of different types to yield a differ-
ent system pH and/or cation affinity. Use of this form of ele-
 QIAN AND SCHOENAU — RESINS IN SOIL RESEARCH
ment “fractionation” easily predicted the relative availabili-
ty and mobility of metals under different pH environments.
It seems that the ion exchange technique is more selective
than removal by chemical reagents or digestion because it
allows distinction between labile cations and non-
adsorbable species. Use of ion exchange resin as a rapid
means of assessing metal speciation has been used in other
media such as natural water (Cox et al. 1984) and sediments
(Beveridge et al. 1989; Slavek et al. 1990) as well as solid
waste leachates (Christensen and Lun 1989).
Extracting Bioavailable Fractions of Hydrophilic
Organic Compounds in Soils
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Organic compounds with acidic functional groups will dis-
sociate at high pH, producing negatively charged moieties,
which will sorb onto anion exchange material. Anion
exchange membrane (AEM) has been used for assessing
the bioavailable fraction of herbicides and their phytotoxic-
ity in different soil types (Szmigielska et al. 1998;
Szmigielska and Schoenau 1999). The determination of her-
bicides in soils usually consists of soil sampling and sample
treatment, herbicide extraction, sample cleanup and deter-
mination by gas chromatography (GC) or high-pressure liq-
uid chromatography (HPLC). Frequent sample cleanup with
chemical extractants is time-consuming and messy, but is
necessary to reduce interference with chromatographic
For personal use only.
analysis because contaminating organic compounds are
often co-extracted. Resin membrane approaches can simpli-
fy the procedure and are performed easily and are less cost-
ly, which makes this method more efficient (Szmigielska
et al. 1998; Szmigielska and Schoenau 1999).
Low molecular weight dicarboxylic acids (such as oxalic,
malonic, succinic, fumaric, maleic and methylmalonic)
secreted by plant roots play an important role in a variety of
processes at the soil-root interface. However, their concen-
trations in root exudates are normally lower than the level
detectable by aqueous-based extractions. With ion exchange
resin, Szmigielska et al. (1995) successfully extracted and
concentrated low molecular weight dicarboxylic acids from
the rhizosphere in hydroponic growth solution. In this
method, the eluent was 0.5 M HCl that is commonly used in
nutrient ion desorption.
Use of Ion Exchange Resins In Studies of Soil
Microbiology
Anion exchange membrane used in a batch technique has
been successful in measuring soil microbial biomass P
(Kouno et al. 1995). The AEM method followed the same
procedures as the fumigation extraction (Brookes et al.
1982) with additional use of AEM strips to recover inorgan-
ic P from soil extracts. Soil microbial biomass P was esti-
mated from the amount of P trapped by AEM in
soil-suspension after corrections for P fixation by soil and P
recovery from microbial biomass released by CHCl3 fumi-
gation. This method was reported to be simpler, quicker,
more accurate, and more flexible than the conventional
CHCl3-fumigation extraction method, and is especially suit-
able in soils of high P retention capacity where the conven-
tional fumigation extraction has difficulty in overcoming P
11
fixation during the extraction and interference in the colori-
metric assay due to extracted humic substances. In a similar
study, Myers et al. (1999) suggested that the ion exchange
technique is more reliable than chemical extractants across
a range of soils with a wide range of chemical characteris-
tics. Continuous adsorption of solution P by ion exchange
membrane during the extraction keeps solution P at low lev-
els, and thus solution-P equilibrium shifts in the direction
favoring release of P from microbial cells into solution,
whereas chemical extraction leads to an continual increase
in solution P concentration and thus the equilibrium is shift-
ed in the direction which depresses further release of P from
microbial cells into solution.
Another approach in this category is the novel use of ion
exchange membrane to sample soil microorganisms
(Macdonald 1986; Hopkins et al. 1991a, b). In this
approach, fresh soil was shaken with Na chelating ion-
exchange resin in 0.1% NaCl solution to disperse the soil
and dissociate microorganisms from the soil particles.
Microorganisms were released because of conversion of
cation exchange groups in soil and on cell surfaces to the
sodium form with the Na+-salt of iminodiacetate resin
Dowex A1. The advantages of the method are that the sepa-
ration of microorganisms from soil is considerably faster
than by repeated blending, more samples can be handled,
and no aerosols are formed during separation. Proper sepa-
ration of microorganisms from soil is an important step for
a series of microbial analysis, e.g., ATP and other chemical
biomarker assays (Macdonald 1986) and bacterial DNA
extraction (Jacobsen and Rasmussen 1992).
DIFFUSION-SENSITIVE SYSTEMS IN SOIL
RESEARCH
Schaff and Skogley (1982) placed resin into cylinders that
were brought in contact with soil cores (with an intervening
porous fabric) to measure planar diffusion profiles. Binkley
and Matson (1983) used this approach directly in the field
for in situ measurements of N dynamics with a specified
quantity of loose resin beads in a porous nylon fabric bag.
As diffusion-sensitive procedures measure both the rates of
release of ions from different soil surfaces and their diffu-
sion through the bulk soil, the systems integrate both chem-
ical and biological transformations as well as diffusion to a
sink into the measure of nutrient availability. The theoreti-
cal verification of the procedures has been well-documented
(Yang et al. 1991a, b; Yang and Skogley 1992). Size,
exchange capacity, resin type, initial saturation of counteri-
ons of the resin, soil moisture content, and soil temperature
influence adsorption kinetics in this technique (Skogley and
Dobermann 1996). Current efforts in assessing ion supply
rate in soil have focused on direct burial of resin in the soil
either in the lab or in the field.
Short-term Measurement of Nutrient Supply Rate
in Soil
A short-term measurement of nutrient supply rate can be as
short as 1 h for the membrane probes and 1 d for bead cap-
sules. From our experience, a “snapshot” of nutrient ion
supply rate obtained by a short-term (1 h) burial using mem-
 12 CANADIAN JOURNAL OF SOIL SCIENCE
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Fig. 1. Relationship of K supply rate as determined by CEM bur-
ial with K extracted by three chemical methods (Qian et al. 1996b).
brane probes placed in the soil can provide an indication of
nutrient availability that is well correlated to concentration
of available nutrients obtained by conventional chemical
extractants. However, 1 h measurements are more variable
than longer-term burials.
Good correlations have been found between nutrient ions
sorbed in a 1 h cation exchange membrane (CEM) burial
and nutrients extracted by conventional chemical extracting
solutions. For K, in a study using 19 soil samples (Qian et al.
1996a), potassium extracted by 1 h CEM burial was signif-
icantly related to the K extracted by 1 M NH4OAc, ASI (Jin
and Portch 1991), and boiling 1 M HNO3 (Fig. 1). In this
study, although available K extracted by all four methods
had strong relationships with canola and wheat K uptake (r2
= 0.63 to 0.73), only the CEM burial method performed
equally well in soils representing all pH ranges, implying
that it functions well as an indicator of relative K availabil-
ity in a diverse array of soil types (Qian et al. 1996a). Good
relationships of 1 h membrane burial with commonly used
chemical extraction methods have also be found for N, P
and S in a 3 yr study using more than 400 soil samples from
across Saskatchewan (Qian and Schoenau 1996).
In a study of N and S supply for canola growth (Qian et
al. 1996b), soil N:S ratio as measured by the ratio of sorbed
nitrate to sulfate after a 1-h AEM burial, reflected the rela-
tive supply of available N and S after fertilization. The ratio
of N and S supply rates to the AEM was very similar to the
N:S ratio found in the plant at harvest. A short-term (1 h)
burial of resin membrane directly in the field may, therefore,
be used to give a quick test for proper balance of nutrient
Table 1. Coefficients of determination (r2) for relationships between
total uptake of N by canola and N extracted by different methods in a
variety of Saskatchewan soils (Qian and Schoenau 1995)
Coefficients of determination (r2)z
First Second
experiment experiment
Nutrient extraction method (ny = 23) (n = 30)
1 h AEM burial (initial) 0.69 0.42
2 wk AEM burial 0.86 0.57
(initial plus mineralization)
Initial CaCl2 extraction 0.59 0.46
CaCl2 extraction after 2 wk incubation 0.60 0.48
(initial plus mineralization)
zP < 0.001.
yn = number of soils.
supply in the soil. However, microscale variability in the
field can give rise to large variation in supply rates among
individual membranes, requiring the use of nests of mem-
branes, which can be measured individually or combined,
similar to soil cores.
Measurement of Potential Nutrient Supply Power
in Soil
A longer-term (e.g., days or weeks) burial of ion exchange
resin in soil can provide information on the dynamics
of nutrient supply, which can account for ion diffusion from
greater distances, cation exchange and slow release of
nutrients from mineralization or dissolution. Assessing
inherent soil nutrient supplying capacity/power/rate can be
used in the study of nutrient cycling and pollutants in labo-
ratory and field as well as generating or modifying fertilizer
recommendations.
Qian and Schoenau (1995) used AEM in an incubation
system for 2 wk to assess N mineralization in a range of
Western Canadian soils. They found nitrate supply rate mea-
sured by 2 wk AEM incubation to be more closely correlated
with plant N uptake than 1 h burial, indicating the longer time
provides a better measure of potential supply because it can
account for residual NO3– plus the contribution from miner-
alization (Table 1). Also, AEM sorbed nitrate over 2 wk was
more closely correlated with plant uptake than nitrate mea-
sured by a conventional incubation system (Table 1). This
could be due to cumulative inhibitory effects when nitrate is
accumulated in soil solution in a closed system (Stanford and
Smith 1972), but this is not the case in the membrane system
where AEM continuously removes the accumulated NO3–-N
from the soil solution. In a similar laboratory incubation
study, Pampolino and Hatano (2000) used ion exchange resin
capsules to measure P, K and N release from the soils for up
to 28 d. Results of this study confirmed the findings from pre-
vious studies showing that resin methods are suitable to indi-
cate the differences in nutrient transport to plant roots under
different soil moisture and texture conditions.
Use of Resin Measured Nutrient Supply Rates in
Agronomic Research
As longer-term burial of ion exchange resin has the advan-
tage in accounting for the dynamics of nutrient supply, agro-
 QIAN AND SCHOENAU — RESINS IN SOIL RESEARCH
nomic research has benefited from this approach. Following
are some examples summarized from the current literature.
Ziadi et al. (1999) used AEM to assess soil N availability
in situ in grass forage systems, and found that the NO3 flux-
es to the AEM were significantly related to N fertilizer rates
at all sites and that forage N uptake was better related with
NO3 fluxes to the AEM than with NO3 concentration mea-
sured by water extraction. These results confirmed a previ-
ous study conducted by Pare et al. (1995). In this study, the
authors concluded that the AEM technique has many practi-
cal advantages over conventional extraction and can be con-
sidered a promising tool for assessing soil N availability to
forage grasses. Similar experiments to study N availability
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have also been conducted in forested soils using resin beads
in nylon bags (Krause and Ramlal 1987; Hart and Firestone
1989).
Using the direct in-field burial of resin membranes, the
impact of tillage and landscape position on N availability
was tested (Jowkin and Schoenau 1998). The study showed
that the resin membrane burial technique provides a good
index to reveal differences among soils in N release poten-
tial as affected by long-term management. This method,
along with the 15N technique, revealed that landscape posi-
tion had a much greater impact on N availability and crop
yield than tillage practices. Wander et al. (1995) conducted
a similar study and suggested that the AEM method was
For personal use only.
superior to the chemical extraction (2 M KCl) in assessing
the impact of tillage and winter cover practices on spatial
and temporal NO3-N availability. Ion exchange membrane
also proved to be a good tool to determine the effect of
added swine manure on N and P availability. Addition of
swine manure effluent into soils led to a significant increase
in measured supply rates of available N and P that appeared
to be related to mineralization of organic N and P (Qian and
Schoenau 2000a, b).
Ion exchange resin has also been successfully used to
assess soil nutrient supply in lowland rice fields
(Dobermann et al. 1997). In this study, resin capsules were
selected and elements were simultaneously extracted in situ
in the rice field. Placement of resin capsules in situ allowed
monitoring of the bioavailability of soil nutrients in rice
fields. Although this method showed evidence of large
microvariations in soil nutrient supply in tropical lowland
rice fields, it provides a more accurate measurement of soil
nutrient supply and its temporal and spatial variability under
field conditions, as use of resin minimized physical and
chemical disturbance of the soil and is sensitive to on-site
conditions not discerned by most other field and laboratory
techniques.
Assessing Soil Nutrient Transformations
(Mineralization and Immobilization)
In a study to evaluate in situ soil N transformations in two
lowland rainforests (Zou et al. 1992), anion and cation
exchange resins (bead form) in nylon bags were placed at
the top and bottom of undisturbed soil cores. The top bags
were used to remove N from throughfall and the bottom
bags collected N leached from the soil cores during the incu-
bation. With this method, the authors successfully measured
13
N flux and also mineralization and immobilization in the
studied areas. A similar procedure was also conducted in
dryland agroecosystems to evaluate in situ net soil N miner-
alization (Kolberg et al. 1997; Bhogal et al. 1999). Bhogal
et al. (1999) concluded resin-core incubation technique not
only provided a measure of net N mineralization, but also
nitrate leaching. Similar studies using this technique are
reported by DiStefano and Gholz (1986), Binkley et al.
(1992), Aarnio and Martikainen (1995) and Mulder et al.
(1997).
In a different approach to measure net N mineralization,
Friedel et al. (2000) mixed resin beads with soil samples.
After incubation, NH4-N and NO3-N in soil-bead mixtures
were extracted by 2 M KCl. Because of intimate contact and
short diffusion paths, the NH4+ mineralized from organic
compound was readily adsorbed by the resin, and thus nitri-
fication, accumulation and subsequent losses of mineralized
N are prevented. The authors suggested that soil-bead mix-
tures may mimic sink functions of plant roots, and nutrient
sorption can be regarded as a functional analogy to nutrient
uptake by roots.
Anion exchange membrane has also been used to measure
S supply potential. In an incubation study to evaluate possi-
ble use of elemental sulfur as a S fertilizer after it was com-
bined with dried anaerobically digested sewage sludge
and/or hydrated lime, Sulewski and Schoenau (1998) found
a faster oxidation of element S when it was blended with
Ca(OH)2 in either S alone or the mixture of S and digested
sewage sludge, which agreed with sulfate accumulation
trends obtained by CaCl2 extraction.
Assessing Nutrient Movement in Soils
In a study to obtain accurate information on movement of
soil-applied chemicals towards water tables, Li et al. (1993)
compared resin capsule with conventional vacuum extrac-
tion in both laboratory and field using bromide as a tracer.
Results from the laboratory column study showed that resin
capsule methodology was effective for describing bromide
leaching in a uniformly packed soil column under either
continuous or intermittent unsaturated water flow, whereas
the vacuum extraction method was less favorable because
the amount of surface-applied water and time required for
bromide peak concentrations to occur at various column
depths appeared to be affected by the applied suction force
and removal of solution. Field results demonstrated the
effectiveness of resin capsules for detecting bromide trans-
port as influenced by irrigation intensity, plant water use,
and plant bromide uptake.
In a study to detect nitrate leaching, Pampolino et al.
(2000) compared resin capsules (RC) with suction cups
(SC), pan lysimeter (PL) and subsurface drainage (DR)
directly in an upland field. Results of this study showed that
RC was able to intercept continuously a representative
amount of the nitrate moving through macropores or bypass
flow, and the amount of NO3– adsorbed by the RC was pri-
marily affected by rapidly moving water rather than matrix
flow or diffusion. In this study, the authors suggested that
the RC method is accurate, simple and easy to use, which
holds promise for nitrate leaching measurements.
 14 CANADIAN JOURNAL OF SOIL SCIENCE
Kjønaas (1999) used mixed resin bags to evaluate the in
situ efficiency of resins in retaining dissolved inorganic N
(NH4-N and NO3-N) and suggested that resins generally
manage to reflect the input of dissolved inorganic N and the
seasonal variations well. Although the resins were not able
to adsorb all the incoming nitrate, use of resin gave valuable
information on small-scale input and output of N from soil
and was able to reflect and explain small-scale differences
in N transformations and NO3-N leaching. Schnabel (1983)
found in a lab study that >95% of dissolved inorganic N was
removed from the percolating solution until the resins were
one-third to one-half N saturated, which is equivalent to an
input of 750 to 1000 kg N ha–1.
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Microsite Assessment of Soil Nutrient Supply
Rates in Forest Ecosystems
Huang and Schoenau (1996) used resin membranes encap-
sulated in plastic frames (probes) to assess nutrient supply
rates at a given location in the forest floor horizon with lit-
tle site disturbance. In this procedure, the membrane probes
were inserted directly into the soil where they were allowed
to remain for 2 h. After the membrane probes were removed
from the soil and washed free of soil with deionized water,
a hole punch was used to cut out a small piece of membrane
corresponding to a specific depth, matching the depth of the
L, F and H horizons. Each of the punched membrane circles
For personal use only.
(6-mm diameter) was transferred to a clean autoanalyzer
sample cup with 3 mL of 0.5 M HCl added for a 1-h elution,
and then directly determined for inorganic N, P (auto-ana-
lyzer) and K (flame-emission).
Results showed that available nutrient levels measured by
this method, as well as water extraction, exhibited consider-
able variability among sampling points within the
microplot. The benefit in using the AEM method is that this
technique accounts for other factors affecting nutrient sup-
ply to roots and micro-organisms, apart from the total con-
centration of soluble nutrient. Furthermore, this method
does not require soil collection, making the technique well
suited to multiple measurements of soil nutrient supply
(Huang and Schoenau 1996).
Mapping Nutrient Patterns in the Root Zone Using
Large Sheets of Membrane
Fan et al. (1992a, b) divided an undisturbed soil profile into
20 microzones with an area of 22.5 cm2 each and then
pressed membrane onto each microzone of the undisturbed
soil profile with a pressure of 10 g cm–2 for 12 and 24 h to
assess patterns of available P and K in the profile. In the P
study, results showed a significant correlation between
membrane extractable P and 0.5 M NaHCO3 extractable P.
The r2 in six different testing conditions ranged from 0.63 to
0.97 (n = 20). In the K study, results also showed significant
correlations between membrane-extractable K and conven-
tional 1 M NH4OAc extractable K. In the 14 different mea-
surements, the r2 ranged from 0.79 to 0.95 (n = 20). With a
similar approach, Fan et al. (1998) studied the relationship
between the P release rate and P capacity of an undisturbed
soil. Phosphorus release rate was obtained by continuously
resin-extracting P 21 times over a 24-h period each time.
Phosphorus fractionation was also performed to obtain infor-
mation on soil P capacity. The authors found that Fe-P and
Al-P were the major sources for phosphorus released during
the 21 d of incubation when moisture was at field capacity.
Measuring Micronutrients and Metal Toxicity in
Soils
Theoretically, cation exchange resin should be able to
extract heavy metal ions (e.g., Cd, Ni, Cu, and Zn) from a
medium. However, most heavy metal ions are present in
very low concentrations in solution in uncontaminated soils
due to their strong affinity for the solid phase or their asso-
ciation with organic compounds and other ligands in soils.
When bound, heavy metal cations are less competitive than
other cations, such as Ca, Mg, K and Na, for the exchange
sites on the resin. Chelating ion exchange membrane has a
relative affinity of approximately 5000 to 1 for divalent over
monovalent cations and a very strong attraction for transi-
tion metals, even in highly concentrated salt media.
However, our experiments showed that commercial chelat-
ing membrane was difficult to handle due to its flexibility
and degradation after use. An “in house” chelating mem-
brane was produced by saturating anion exchange mem-
brane with a chelating agent such as EDTA or DTPA. When
AEM is placed in a dilute solution of chelating agent, the
chelating agent binds to the anion exchange membrane pro-
ducing a membrane with the ability of adsorbing anions and
cations (Liang and Schoenau 1995). With this method,
Liang and Schoenau (1995) removed Cd, Cr, Pb and Ni
from soils that had been spiked with those metals and found
that the supply rates of metals to the membrane were close-
ly correlated with plant metal uptake and toxicity. The mem-
branes can be recycled by saturating again in the chelating
agent solution after elution.
USE OF RESINS IN SOIL TESTING
Although the use of resin technology to measure nutrient
availability in research applications has a 50-yr history, its
practical use in soil testing for fertilizer recommendations is
relative new, and has been conducted only in a few institu-
tions worldwide since the 1980s. van Raij (1996) reported
that a procedure was developed and introduced into routine
soil testing in Brazil. Starting in 1983, this method has
increased confidence in soil testing and has become widely
accepted there. In Brazil, about 70 laboratories in 8 states
are performing P extraction with ion-exchange resin. van
Raij (1996) indicated that the number of soil samples ana-
lyzed yearly increased from 65 000 in 1982 to about 300 000
in 1996. The major advantages of using resin in soil testing
is to provide a better index of relative nutrient availability
and consistency over a wide range of soil types. As well, all
the major nutrient elements can be extracted simultaneously
with one extraction, which makes the procedure easy and
cost-effective.
For the diffusion-sensitive system approach, two com-
mercial products are available in North America. One is the
PRS™ probe, which is made by encapsulating the resin
membrane in a plastic frame to create a probe (Fig. 2). The
other is the resin capsule, which is made by sealing the resin
 QIAN AND SCHOENAU — RESINS IN SOIL RESEARCH
Can. J. Soil. Sci. Downloaded from www.nrcresearchpress.com by 125.164.31.88 on 02/18/18
Fig. 2. Diagrams of PRSTM membrane probes (a) and UNIBEST
resin capsules (b).
beads inside a porous shell to form a compact rigid sphere
capsule (Fig. 2). Companies based on the two patented prod-
For personal use only.
ucts have been established in Saskatchewan for the PRS™
probe (Western Ag Innovations, Saskatoon, SK, Canada)
and in Montana (UNIBEST, Bozeman, MT, USA) for the
resin capsule, respectively. These two companies not only
sell the resin products, but also provide various advisory ser-
vices for proper use of their products. Both companies claim
that use of resin extraction in soil testing reduces laboratory
cost by 50 to 70% and improves testing accuracy
(http://www/westernag.ca and http://www.unibestinc.com).
Supply rates of nutrients to resins may be used as a basis
for fertilizer recommendations (Havlin et al. 1999). A com-
puter model, the PRS Nutrient Forecaster™ developed by
Western Ag Innovations (Saskatoon, SK, Canada), has been
used in Western Canada for 3 yr to provide fertilizer recom-
mendations to producers. In this approach, a prediction of
soil nutrient supply is made based on measured nutrient sup-
ply to the PRS™ resin membrane probe and input of para-
meters such as soil water content, temperature and texture.
The program models soil nutrient supply and crop demand
as a function of soil, crop and environmental conditions
entered into the program, and thus predicts the requirement
for additional fertilizer nutrient. UNIBEST usually provides
two types of resin capsules. One is called PST-1 capsule that
adsorbs chemical elements (as ions) from the soil matrix.
The other is named the ENV capsule that adsorbs organics
that are in the soil from both liquid and vapor phases. With
proper installation tools (Wecsa, Fort Collins, CO USA),
both types of capsules can be installed at depth in the soil.
CONSIDERATIONS IN OPTIMIZING RESIN
TECHNIQUES
Physical and chemical properties of both resin and medium
(soil) are important factors influencing performance of the
15
technique. Certain considerations regarding inherent proper-
ties of the resin and how these properties affect ion
exchange in the media are required for successful use of
resin in soil studies. These considerations include (1) type of
resin used, (2) chemical stability in the process of extraction
and desorption, (3) counterion on/in the resin for ion
exchange, (4) how long the resin should and can be kept in
the soil, (5) moisture and temperature effects, (6) competi-
tive ion effects, (7) what eluents should be used for desorp-
tion, (8) re-use, (9) how to interpret the values obtained, and
(10) accuracy and limitations to this technology. Certain
questions (e.g., the type of resin to choose) have been
addressed in detail in a previous review paper (Skogley and
Dobermann 1996) and certain questions (e.g., how long the
resin should be kept in the soil) are determined by
researchers’ own needs and goals, and can be determined
using related scientific literature already discussed.
However, there are still questions that need to be addressed.
Consideration of the following will mostly be based on our
practical experiences integrated with those from other
researchers and information on basic resin properties.
Chemical Stability
Resins, either in bead form or in membrane form, are rela-
tively stable in acid, alkali, organic solvents and strong
reducing and some oxidizing agents. Such stability ensures
that the resin matrix remains chemically unchanged by ionic
interactions, which take place at the functional groups, and
the resins can be readily regenerated. However, if placed in
an oxidant, the resin membrane will undergo some degrada-
tion in most cases (such as decreasing crosslinkage of cation
exchanger) and explosion may occur if a strong oxidant is
heated. If an oxidant must be used, the process must be car-
ried out under controlled conditions in order to avoid irre-
versible damage. For example, the concentration of nitric
acid used should never be more than 1%.
We have experienced a phenomenon in which the resin
membrane may become darker when it is left in soil for
extended periods. This is because organic matter (such as
fulvic and humic acids) have accumulated in its lattice. In
this case, we do not suggest removing the organic matter
using any oxidants. Because soil organic matter is mostly
trapped in the resin lattice, the ion exchange sites are large-
ly unaffected. However, periodic measurement of exchange
capacity is a good laboratory practice to detect any possible
problems. Of note is the fact that in some tropical soils,
destruction of the membrane by termites has been observed,
which may limit the burial time that can be used.
Selection of Resin Counterion for Ion Exchange
Ion exchange reactions are reversible, and all reversible
reactions proceed towards an equilibrium state in which all
reactants and products are present. When ion exchangers are
equilibrated with a solution containing a mixture of ions,
proportions adsorbed by the resin will not be the same as
ionic proportions in the bulk solution. Knowing resin rela-
tive selectivity (affinity) is a prerequisite for choosing a
proper counterion for the resin in use. Ion exchange selec-
tivity (affinity) is attributable to several factors and its order
 16 CANADIAN JOURNAL OF SOIL SCIENCE
for selected ions is different from one group to another
group of resin products. However, the same or a similar type
of resin product generally provides a similar order for
selected ions with the exception of some specific products
for special use. Resin manufacturing and distribution com-
panies will provide a list of selectivities of specific resins for
various cations and anions.
Generally speaking, cations and anions with the lowest
affinity to the resin are best for use as the counterions. The
H form for cation resin and OH form for anion resin have
been shown to work well (Tran et al. 1992). This concept is
used in mixed-bed resin capsules (Skogley et al. 1990).
However, in some cases, the H form is not suitable in cal-
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careous soils due to the formation of CO2 and HCO3– when
resin-H reacts with CaCO3. A larger quantity of Ca accu-
mulated by the resin will affect K and NH4+ adsorption
when resin is in the soil for a longer period of time. This is
particularly true when resin membrane is used, as the mem-
brane has a lower capacity than resin beads. A resin mem-
brane with Na as counterion can be considered because its
relative affinity is the next lowest in the order. The NH4-
form of cation exchange resin may also be desirable in K
supply rate assessment as the potassium ion present in the
clay mineral interlayers can be more easily exchanged by
the ammonium ion than the sodium ion. For example, our
data showed 1.5 times more K extracted by NH4+ saturated
For personal use only.
resin than by Na saturated resin (Qian et al. 1996a). For
anion exchange resin, we use HCO3– as a counterion
because the HCO3– displaced by nutrient ions in soil mim-
ics to a certain extent the HCO3– produced in the rhizos-
phere due to the excretion of CO2 by plant roots and
microorganisms. However, Kjønaas (1999) suggested
HCO3– may not be a suitable counterion in acid soils with a
pH below 4.5.
Length of Resin Residence in Soils
A longer term of resin burial or residence in the soil usually
gives a measure that includes ion diffusion from greater dis-
tances and nutrient release from mineralization or dissolu-
tion. In a study conducted by Ziadi et al. (1999), resin
membrane was kept in soil for 240 d. As researchers, we can
decide how long the resin should be kept in soils, but cannot
guarantee its performance as a sink in media during the
extraction period, which is arbitrarily decided. How long
resin can be kept in media as a sink depends on various fac-
tors, such as exchange capacity of resin, nutrient availabili-
ty and conversion (chemical and biological) as well as the
conditions (e.g., moisture and temperature) of the media
during the burial.
The ion exchange capacity is an inherent factor of the
resin to be considered if it performs as a sink or a dynamic
exchanger during the period of in situ extraction. When
resin capacity is large enough to easily sorb all the ions
released throughout the exposure period, the resin functions
as a sink. Otherwise, the resin-soil system will change its
function from sink to a dynamic exchanger (Cooperband
and Logan 1994). One should always bear in mind that ion
adsorption by resin never acts as a sink indefinitely.
However, if a batch system is considered, the word “sink”
may be more appropriate when the cation or anion supply
from a small amount of soil is much less than the quantity of
resin used.
The exchange capacity of resin in membrane form is gen-
erally lower than that of the same type of resin in bead form.
A major reason is that resin membrane is made by enmesh-
ing resin permanently in the polytetrafluorethylene (PTFE)
backbone. Skogley (1992) reported that the resin capsules
can be left in soil for months. We do not feel that mem-
branes can be kept in soils for so long. In an agricultural soil
with an “average” level of nutrients and “ideal” conditions
of moisture and temperature, a rule of thumb we use is that
the resin membrane is kept in soil no longer than 2 wk (Qian
and Schoenau 1995). If a longer measurement time is nec-
essary, the existing membrane can be replaced by a new one
and the amount supplied over the subsequent 2 wk added to
the previous to obtain the cumulative supply for the entire
burial period (Qian and Schoenau 2000a, b). With careful
manipulation, the disturbance of soil while replacing resin
can be minimized.
Ion exchange capacity of each type of resin can be
obtained from manufacturing and distribution companies.
One must keep in mind that capacity reported by the manu-
facturer is a maximum because the smallest size of ion is
used in the measurement. Also, ion exchangers may vary
between batches of material, so an important aspect of qual-
ity control is a check of resin capacity. This may be done by
the commercial supplier. The standard method to measure
resin exchange capacity is titration, using standard alkali
titration for cation exchanger and standard acid titration for
basic anion exchanger. However, a convenient means to
assess resin capacity is to saturate the resin with an ion and
measure the amount of ion sorbed by the resin after elution.
For example, we determine anion exchange membrane
exchange capacity by saturation with KH2PO4 or KCl solu-
tion for 24 h and measure the concentration of H2PO4– or
Cl– in the eluent after desorption. This allows us a means of
quality control by ensuring that exchange capacity among
our lab stock of membranes is uniform and is not changing
over time.
Influence of Soil Moisture and Temperature on
Ion Adsorption
Soil moisture and temperature are important factors affect-
ing ion supply to and adsorption on/in the resin. A study
conducted by Qian and Schoenau (1996) showed the
amount of nitrate-N, phosphate-P, potassium and sulfate-S
removed from two Chernozemic soils by buried resin mem-
brane decreased significantly with decreasing moisture con-
tent in the soil (Table 2). The decrease in ion supply rate
with decreasing soil moisture content reflects the relation-
ship between soil moisture content and diffusive flux of
nutrient ions. As the soil becomes drier, the diffusion path
becomes longer and more tortuous, as the large pores are no
longer filled with soil solution. This is the same limitation
on diffusive flux that plant roots encounter in the field as the
soil dries out. Similar results were obtained by Schaff and
Skogley (1982) in a study of the moisture effects on diffu-
sion of K, Ca and Mg to the resin in bead form. Moisture

Table 2. Nutrient ion supply rate as determined by 1 h burial of AEM and CEM in two soils at five soil moisture contents (Qian and Schoenau 1996)
Soil 1
Moisture N P K S
Saturated 88a 2.1a 240a
100% FC 55b 1.7b 196b
70% FC 37c 1.0c 141c
45% FC 21d 0.7c 101d
15% FC 4e 0.2d 50e
Values are means triplicated analyses.
a–e Values followed by the same letter in a column are not significantly different (P < 0.05).
Can. J. Soil. Sci. Downloaded from www.nrcresearchpress.com by 125.164.31.88 on 02/18/18
contents in the field are highly variable and most nutrient
uptake occurs when the plant is actively growing under
moist soil conditions. Moisture variations in the field can be
a significant source of variation in ion supply rates mea-
sured with resins in the field.
Although temperature effects on ion diffusion to resins is
relatively less than moisture effects (Schaff and Skogley
1982; Qian and Schoenau 1996), increase in temperature
does lead to a significantly increased rate of nutrient accu-
mulation, subsequently increasing the quantity of adsorbed
nutrient accumulated during the prescribed time, which
results from microbial conversions as well as through
altered dynamics of nutrient movement towards resin (Yang
For personal use only.
et al. 1991b). Temperature effects were specific to nutrients,
having either positive or negative influences depending on
whether microbial conversion was involved (e.g., N and S)
or whether the influence was due to the rate of nutrient dif-
fusion to the resin (e.g., K and P).
Thus, what can we recommend for a length of resin bur-
ial in soils? Generally, we suggest a shorter residence time
for resins in the laboratory than in the field. In the laborato-
ry, we can easily set up an “ideal” condition for ion adsorp-
tion. We generally use soil at about 80% field capacity in
longer-term (2 wk or more) incubation. In the field, mois-
ture contents and temperature are highly variable. Thus, if
one desires to monitor the nutrient supply rate differences
under conditions of moisture and temperature as they exist
in the field, there is no need to adjust moisture level around
the site of resin placement. If one desires to eliminate any
moisture effects from the measurement in a comparison
study, we recommend to add water after burial in dry soils
to ensure that the soil in the vicinity of the resin probes or
resin capsules is at or near field capacity to provide a con-
sistent water level initially.
Competition for Ion Adsorption
Ion adsorption by the resin is also affected by competition,
both biologically and chemically when resin is placed in
soils. Competition from nutrient conversion by microorgan-
isms will affect supply available to the resin for adsorption
(Giblin et al. 1994; Subler et al. 1995). Subler et al. (1995)
reported significantly less NO3-N accumulated by AEM in
soils under strongly N-immobilizing conditions. In a wheat-
straw-amended soil, membrane-bound NO3-N declined
between 3 and 14 d in this study. Obviously, soil nutrient
QIAN AND SCHOENAU — RESINS IN SOIL RESEARCH 17
Soil 2
N P K S
(µg 10 cm–2)
348a 141a 2.3a 109a 25a
254b 100b 1.4b 91b 20b
154c 98b 0.7c 78c 19b
84d 57c 0.5d 47d 13c
10e 12d 0.2d 24e 6d
status and possible conversion should also be kept in mind
for a decision on how long the resin can be placed in soils.
However, we should also acknowledge that a decrease in ion
adsorption due to competition from microbial immobiliza-
tion of nutrients represents conditions in the soil because
plant roots will meet the same competition.
Competition from plant roots is obvious when ion
exchange resins are placed in soils where plants are grow-
ing. Binkley (1984) found that resin bags were poor com-
petitors for N in pots containing grass. Competition from
plant uptake of nutrients should be particularly taken into
account in field resin burial during the growing season. To
eliminate the effect of root competition in the field, a cylin-
der can be used to isolate the resins from plant roots (Huang
and Schoenau 1996).
Termination of Extraction, Desorption and
Regeneration
When a resin, either in bead or membrane form, is removed
from soil, soil particles adhering to its surface should be
immediately washed off as ion adsorption from these parti-
cles may continue beyond the sample period, which may
cause errors in resin analysis. During the washing process,
the water used and the area in which they are handled must
be free of ion contamination, especially when working in the
field. Once cleansed, the ion desorption process may be
postponed for up to a month if resin is kept clean at low tem-
perature, e.g.. 4°C, even when the resin membrane is dried
(unpublished data). Skogley et al. (1997) compared freezing
conditions (–20°C) with low temperature (2°C) and room
temperature (20°C) and found that storage of resin capsules
under cool condition (2°C) before desorption is the most
suitable condition and storage time can be as long as 56 d
without changes in amounts of ions recovered. Also, humid-
ity did not affect ion recovery.
Desorption, also called elution, is a counterion exchange.
In an elution, the nutrient ions held on the ion exchange
resin must be displaced by ions in the eluting solution. The
desorption solution or the eluent must be selected based on
ion strength and dissociation constant. Dilute strong acid
(e.g., 1 M HCl or H2SO4) or its salt (e.g., NaCl or KCl) is
usually recommended. If a desired ion has lower selectivity,
a higher concentration and/or larger volume of solution
must be considered. Theoretically, a single elution cannot
accomplish complete (100%) removal of the ions held by
 18 CANADIAN JOURNAL OF SOIL SCIENCE
the resin in a batch elution. However, as the rate of ion dis-
placement is proportional in the elution, a single elution is
sufficient to establish a value.
Resins, either in bead form or in membrane form, can be
reused frequently. However, when both cation and anion
exchange resin beads are encapsulated, it is suggested that
the mixed-bed capsules are not reused, as it is difficult to re-
generate their initial condition (H+ as counterion for cation
and OH– as counterion for anion) without first separating
the cation and anion portions of resin (Skogley et al. 1996).
Although stripping of adsorbed ions is not 100% efficient,
especially when batch elution is selected, it is not a critical
factor that affects results when the resin membrane is
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reused, provided that successive washings are used (Qian
and Schoenau 1996). The principle of regeneration of resin
membrane is the same as elution. A sufficient quantity of an
ion with lower selectivity is usually recommended. In some
cases, it is more economical and more efficient to go
through an intermediate counterion when converting to a
counterion of much lower selectivity. For example, in order
to convert a resin saturated with Cl (its selectivity is 22) to
OH form (1) , HCO3– (6) may be used as an intermediate
counterion. In this case, the resin with Cl as counterion can
be washed first with NaHCO3 and then NaOH. Because
NaHCO3 is much cheaper than NaOH, the use of household
grade NaHCO3 can represent a large savings in the long-run.
For personal use only.
We call such elution using an intermediate counterion a
two-step washing. Use of HCl (the selectivity of Cl– is 22)
as eluent (washing off nutrient ions such as NO3– with the
selectivity of 65) and sodium bicarbonate (6) for regenera-
tion (displacing Cl) is analogous to a two-step washing.
Ionic conversion can also be carried out using batch tech-
nique or column conversion. If batch techniques are used,
washing three to four times with NaHCO3 or another regen-
erating agent is necessary.
Expression of Values
In batch systems, nutrient availability measured by resins is
expressed as mg nutrient per kg of soil, the same as conven-
tional method. In diffusion-sensitive systems, nutrient sup-
ply rate is usually chosen for resin membrane ion adsorption
and is expressed as µmol or µg per cm2 of membrane surface
per unit burial time (e.g., 1 h or 2 wk), and resin adsorption
quantity (RAQ) is usually considered for resin capsule ion
adsorption and expressed as µmoles per cm2 of capsule sur-
face over time of burial (Yang et al. 1991b). Expression of
values on a per-unit of contact surface area of resin basis is
sometimes considered an impediment to widespread use of
resins as there is no simple means to translate the value to
the commonly used and familiar expression as quantity of
the nutrient per soil volume or mass. This is the greatest lim-
itation when dealing with nutrient ions, such as nitrate,
which can be quantitatively measured using a chemical
extractant, but is less of a limitation with elements like P and
K, for which the extraction is only an index of availability.
The measurement of supply rate is a dynamic assessment of
nutrient supply, different from determining the concentra-
tion (e.g., mg nutrient per kg of soil) in a soil sample. If we
consider resin’s function in adsorbing nutrient ions from soil
as they are released, we recognize that the accumulation of
ion during the adsorption period is analogous to the situation
where we analyze a plant to determine nutrient quantities
accumulated. The quantity of soil contributing to plant
uptake of elements is also difficult to assess or is unknown.
Therefore, results from resin burial techniques can be con-
sidered to be quantitative in the same sense that plant analy-
sis results are used to quantify nutrient availability from
soils in which they are grown. Thus, use of a value
expressed per unit of contact surface area of resin really rep-
resents a flux of nutrient ions towards to the resin.
Accuracy of Resin-testing Results
When diffusion-sensitive systems are used, especially in
situ in the field, accuracy may be questioned due to inher-
ently larger coefficients of variations, which is usually not
the case in batch systems. In batch systems, soil samples are
dried, mixed and ground, such that the CV among three
replicates from the same ground sample is small. Hence,
when resins are installed directly in unprocessed soils, a
larger CV should be expected as soil is not homogeneous,
especially in the field. Microscale variations in environmen-
tal conditions such as moisture and texture, biological con-
ditions such as competing plant roots and microorganisms,
and physical-chemical conditions such as residual fertilizer
from banding all create larger variability in in-situ measure-
ments in the field. The influence of such factors should be
taken into consideration and with proper sampling design
can be converted from random to systematic variability.
It is evident that variations observed in resin methodolo-
gy are mostly from inherent macro- and micro-scale vari-
ability in soil-plant systems, which is also a limitation for
other methodologies. Sound sampling strategies employed
for conventional chemical extractions (Sabbe and Marx
1987; James and Wells 1990) can be adopted for the instal-
lation of resin in the field or soil samples for laboratory
studies. If direct burial of ion exchange resin in the field is
used, our experience is that the same stratified random sam-
pling as would be used to take soil cores is also recom-
mended for selecting the burial sites. Benchmark sites can
also be identified, and repeated measurements made over a
number of years using nests of resins. It is important to
achieve good contact with soil and unified soil moisture.
Specific recommendations for ensuring consistent perfor-
mance of the PRS™ probes are available from Western Ag
Innovations, Saskatoon, SK, Canada and for the resin cap-
sules from UNIBEST, Bozeman, MT, USA.
CONCLUSIONS AND RECOMMENDATIONS
Ion exchange resins are a sensitive, biologically meaningful
tool to study the behavior of inorganic and organic ions in
the soil environment. The ability to use ion exchange resins
as dynamic exchangers or sinks under relatively undisturbed
conditions in the laboratory or field opens up a number of
possibilities for future research. Use of resins to study nutri-
ent fluxes and availability of different fertilizer forms and
placements directly in the field is an example of a future
agricultural application. A future environmental application
may be the use of resins to follow the fate of charged organ-
 QIAN AND SCHOENAU — RESINS IN SOIL RESEARCH
ic pollutant compounds from the air to the soil and ulti-
mately to groundwater. Unfamiliarity of units used to
express ion bioavailability and a higher degree of variabili-
ty inherent in the in situ diffusion sensitive applications of
resins are potential impediments to rapid adoption.
However, the unique ability of this approach to simulate
biological ion “sinks” in relatively undisturbed conditions
should encourage its future use in a variety of applications
in agricultural and environmental soil science.
ACKNOWLEDGMENT
The authors acknowledge the base financial support of the
Saskachewan Agriculture Development Fund for research
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conducted at the University of Saskatchewan described in
the paper.
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N and nitrification in scots pine forest soil treated with nitrogen
fertilizers containing different proportions of urea and its slow-
releasing derivative, ureaformaldehyde. Soil Biol. Biochem. 27:
1325–1331.
Abrams, M. M. and Jarrel, W. M. 1992. Bioavailability index
for phosphorus using ion exchange resin impregnated membranes.
Soil Sci. Soc. Am. J. 56: 1532–1537.
Adams, B. A. and Holmes, E. L. 1935. Adsorptive properties of
synthetic resins. J. Soc. Chem. Ind. Lond. 54: 1T.
Amer, F., Bouldin, D. R., Black, C. A. and Duke, F. R. 1955.
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adsorption and 32P equilibration. Plant Soil 6: 391–408.
Arnold, P. W. 1958. Potassium uptake by cation-exchange resins
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