Applicability of Internal Standardization with Yttrium to ...

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Journal: Analytical Sciences

Form: Original Paper

Applicability of Internal Standardization with Yttrium to the

Solid-Phase Extraction of Trace Elements in Groundwater and

Wastewater Using an Aminocarboxylic Acid-Type Chelating

Resin

Yuki YOKOTA*, Makoto GEMMEI-IDE*, Yoshinori INOUE*, and Shigehiro KAGAYA*†

* Faculty of Engineering, University of Toyama, Toyama 930-8555, Japan

†To whom correspondence should be addressed.

E-mail: [email protected]

Analytical SciencesAdvance Publication by J-STAGEReceived October 25, 2020; Accepted January 19, 2021; Published online on January 29, 2021DOI: 10.2116/analsci.20P387

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Abstract

Internal standardization was applied to the solid-phase extraction of trace elements using some commercially

available aminocarboxylic acid-type chelating resins, InertSep ME-2, NOBIAS Chelate PA-1, and Presep

PolyChelate. The concentration of the trace elements in initial sample solution can be calculated by using the ratio of

the added amount of the internal standard element, Y, in the initial sample solution to that in the final solution after

the solid-phase extraction, which is proportional to the volume of the sample solution passed through the cartridge,

and the ratio of the volume of the initial sample solution to that of a blank solution for preparing the calibration curve.

In this solid-phase extraction, strict control of the volumes of the sample solution passed through the cartridge and

the final solution after the solid-phase extraction is not needed because these are not used in the calculation of the

trace element concentration. The solid-phase extraction with the internal standardization using Y was able to be

applied to the separation and preconcentration of some trace elements, namely Cd, Co, Cu, Fe, Ni, Pb, Ti, and Zn in

an artificial seawater spiked with the elements and some certified reference materials, EnviroMAT ES-L-1 Ground

Water and EU-L-3 Waste Water, without any interference.

Keywords Solid-phase extraction; internal standardization; aminocarboxylic acid-type chelating resin; trace

elements; inductively coupled plasma atomic emission spectrometric determination

Introduction

Solid-phase extraction using a chelating resin is a useful technique for the separation and preconcentration of trace

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elements.1–5 Various chelating resins are commercially available. Among them, a chelating resin that immobilizes

aminocarboxylic acid as a functional group is widely used for the separation and preconcentration of trace elements

in environmental water samples because it can simultaneously extract various elements.6–8 Recently, the use of

InertSep ME-2 (GL Sciences),9 NOBIAS Chelate PA-1 (Hitachi High-Tech Fielding),3,4,10–33 and Presep PolyChelate

(FUJIFILM Wako Pure Chemical),4,6,8,34–44 which are commercially available aminocarboxyilic acid-type chelating

resins, has accelerated. InertSep ME-2 has iminodiacetic acid (IDA) and tertiary amino groups,9 while NOBIAS

Chelate PA-1 immobilizes both IDA and ethylenediaminetriacetic acid groups.20,33 In Presep PolyChelate, partially

carboxylmethylated polyethyleneimine (CM-PEI) is introduced as a functional group.6,8,34,36 These resins can extract

various elements over a wide pH range; however, they scarcely collect alkali and alkaline earth elements, which are

often contained in large amounts in real environmental water samples, under acidic and neutral conditions.6,9

In general, the solid-phase extraction of trace elements is conducted using a flow method because of its

simple operation.2,45 In this method, trace elements are extracted by passing a sample solution containing the elements

through a cartridge packed with a chelating resin; then the extracted elements are eluted with a suitable eluent. After

extraction, the trace elements in the solution are mainly determined using atomic spectroscopy, such as inductively

coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-

MS). In order to determine the elements in the initial sample solution, it is necessary to know the concentration factor,

defined as the ratio of the volume of the initial sample solution to that of the eluate. Therefore, strictly control the

flow volume of the sample solution and the volume of the final solution after the solid-phase extraction is required

in order to obtain the accurate amount of trace elements in the initial sample solution using the flow method.

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The solid-phase extraction process can be automated; various flow systems have been developed.13,17,46–50

In these systems, a syringe pump and a peristaltic pump have been commonly used to deliver the sample solution. A

syringe pump can deliver a constant volume of sample solution accurately, whereas it is difficult to rapidly deliver a

large volume of sample solution in general. In contrast, a peristaltic pump can easily achieve this in a short time,

which is attractive from the viewpoint of simplicity and rapidity of the operation. However, the flow volume using a

peristaltic pump is often less accurate than that using the syringe one because the tube used with the peristaltic pump

is gradually damaged. This is a serious problem in the automated solid-phase extraction system.

Internal standardization is generally utilized to determine trace elements in ICP-AES and ICP-MS because

it can reduce some interferences, especially physical interference, which causes a change in the solution volume

introduced into plasma. This technique can also be used to correct the volume of the sample solution. When a constant

amount of a trace element with a constant amount of an internal standard element is spiked to each solution, which

has a slightly different volume, almost the same results are obtained in the determination of the trace element using

the internal standardization. This technique seems to be applicable to solid-phase extraction. If recovery of the

internal standard element is quantitative in the solid-phase extraction, the amount of the internal standard element

will be proportional to the volume of sample solution passed through the cartridge. In this case, the amount of the

internal standard element will also be correlated to the amounts of trace elements in the solution after the extraction.

Therefore, it is expected that accurate amounts of trace elements are obtained by applying the internal standardization

to solid-phase extraction even if both the volume of the sample solution passed through the cartridge and that of the

final solution after the extraction are varied to some extent.

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In this study, a fundamental investigation regarding the applicability of internal standardization to the solid-

phase extraction of trace elements is conducted using ICP-AES. Three aminocarboxylic acid-type chelating resins,

InertSep ME-2, NOBIAS Chelate PA-1, and Presep PolyChelate, were used. The relationship between some trace

elements, which were quantitatively recovered with these chelating resins, and an internal standard element was

investigated in detail; a peristaltic pump was employed in the extraction. The separation and preconcentration of trace

elements in certified reference materials (ES-L-1 Ground Water and EU-L-3 Waste Water) was also attempted using

the solid-phase extraction with internal standardization.

Theory

Figure 1 shows a diagram of the proposed application of internal standardization to solid-phase extraction. An internal

standard element (ISE, y0 mg) is added to V0 L of an initial sample solution containing x0 mg of a trace element (TE).

The solution pH is adjusted by adding a buffer solution and/or appropriate acid/base; the volume of the sample

solution is V0 + α L. The sample solution (V1 L) is passed through a cartridge packed with a chelating resin; it is

allowed that V1 is smaller than V0 + α. If the trace element and the internal standard element are quantitatively

extracted and back-extracted with the chelating resin under the conditions for solid-phase extraction, the amount of

each element recovered (x1 mg and y1 mg) is proportional to the volume of the sample solution passed through the

cartridge (Eq. 1).

𝑉"𝑉# + 𝛼

=𝑥"𝑥#=𝑦"𝑦#

(1)

The amount of the trace element before the solid-phase extraction is given by

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𝑥# = 𝑦# ×𝑥"𝑦". (2)

In ICP-AES, an emission intensity, I, for an element and its concentration (C mg L−1) in a solution have a proportional

relationship,

𝐼 = 𝐶𝑘, (3)

where k is constant. Thus the emission intensities of the trace element and the internal standard element can be written

as follows:

𝐼56 =𝑥"𝑉7× 𝑘56 (4)

𝐼9:6 =𝑦"𝑉7× 𝑘9:6, (5)

where kTE and kISE are constants; in this theory, it is assumed that they are almost constants in all solutions.

In ICP-AES determination with internal standardization, it is convenient to determine a trace element using

software in the ICP-AES apparatus. In many cases, it is allowed that solutions, which are prepared by adding an

appropriate amount of trace element, constant amount of internal standard element, and acid and diluting the solutions

with deionized water, are available for preparing calibration curves. When y0 mg of the internal standard element is

contained in VBlank L of a blank solution for the calibration curve, the emission intensity of the internal standard

element in the blank solution (IISE-Blank) is given by

𝐼9:6<=>?@A =𝑦#

𝑉=>?@A× 𝑘9:6. (6)

The emission intensity of the trace element (ITE(Corr.)) in both solutions for the calibration curve and the solution after

the solid-phase extraction is corrected based on the ratio of the emission intensity of the internal standard element for

each solution (IISE) to IISE-Blank.

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𝐼56(CDEE.) = 𝐼56 ×𝐼9:6<=>?@A𝐼9:6

. (7)

Therefore, ITE(Corr.) is expressed by

𝐼56(CDEE.) =𝑥"𝑉7× 𝑘56 ×

𝑦#𝑉=>?@A

× 𝑘9:6𝑦"𝑉7× 𝑘9:6

=𝑥"

𝑉=>?@A×𝑦#𝑦"× 𝑘56. (8)

From Eqs. 3 and 8, the corrected concentration of the trace element (CTE(Corr.) mg L−1) in each solution, which is

obtained by the software, can be expressed as follows:

𝐶56(CDEE.) =𝑥" ⋅ 𝑦#

𝑉=>?@A ⋅ 𝑦". (9)

By using Eqs. 2 and 9, the concentration of the trace element, x0/V0 mg L−1, can be given by

𝑥#𝑉#=𝑦# ⋅ 𝑥"𝑉# ⋅ 𝑦"

=𝑥" ⋅ 𝑦#

𝑉=>?@A ⋅ 𝑦"×𝑉=>?@A𝑉#

= 𝐶56(CDEE.) ⋅𝑉=>?@A𝑉#

. (10)

In this equation, α L, V1 L, and V2 L do not appear. Therefore, the concentration of trace elements can be calculated

without strict controls of α L, V1 L, and V2 L.

Experimental

Apparatus

The solution pH was adjusted using a Horiba F-22 pH meter. The determination of elements was conducted

using a PerkinElmer Optima 7300 DV inductively coupled plasma atomic emission spectrometer; the measurement

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conditions were the same as previously reported,8 except for the analytical wavelength of Y (371.029 nm).51,52

PerkinElmer Syngistix for ICP software was employed to calculate the concentration of the element based on the

internal standardization.

Reagents

Three commercially available aminocarboxylic acid-type chelating resins, Presep PolyChelate (250 mg

packed into a 3 mL solid-phase extraction cartridge, FUJIFILM Wako Pure Chemical), NOBIAS Chelate PA-1 (250

mg packed into a 6 mL cartridge, Hitachi High-Tech Fielding), and InertSep ME-2 (250 mg packed into a 6 mL

cartridge, GL Sciences), were used. The deionized water used for all investigations was prepared using a Merck Milli-

Q Gradient. An ICP multi-element standard XVI (As, Be, Ca, Cd, Co, Cr, Cu, Fe, Li, Mg, Mn, Mo, Ni, Pb, Sb, Se,

Sr, Ti, Tl, V, Zn; 100 mg L−1 each; Merck) and a Y standard stock solution (1000 mg L−1, Kanto Chemical) were

employed as standard solutions; these solutions were diluted appropriately before use. Certified reference materials,

EnviroMAT Ground Water (ES-L-1) and EnviroMAT Waste Water (EU-L-3), which were purchased from SCP

Science, were used to validate the solid-phase extraction with internal standardization. The other reagents used were

of guaranteed or analytical reagent grade.

Procedure

A deionized water-based sample solution was prepared by adding appropriate amounts of each element and

Y as an internal standard element to 100 mL or 1000 mL (V0) of deionized water. Artificial seawater, which was

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prepared in accordance with the literature,53,54 was also used instead of deionized water. After the addition of 0.5 mL

or 5 mL of 1 mol L−1 ammonium acetate solution to 100 mL or 1000 mL of the sample solution, respectively, the pH

was adjusted using nitric acid and aqueous ammonia; the volume of the sample solution is V0 + α.

The solid-phase extraction was performed using two solid-phase extraction apparatuses, A and B, as shown

in Figs. S1 and S2, respectively, in the Supporting Information. The resins were conditioned with 5 mL of methanol,

10 mL of 3 mol L−1 nitric acid, 20 mL of deionized water, and 10 mL of 0.1 mol L−1 ammonium acetate solution, in

that order, at a flow rate of approximately 3 mL min−1. Most of the sample solution (V1) was passed through the

cartridge at a flow rate of approximately 10 mL min−1; it is allowed that V1 is smaller than V0 + α. The resin was

washed with 20 mL of deionized water; the extracted elements were eluted with 3 mL of 3 mol L−1 nitric acid and

then approximately 3 mL of deionized water using a vacuum manifold (GL Sciences). The eluate was diluted to 10

mL or around that (V2) with deionized water; each element contained in the final solution was determined using ICP-

AES with the internal standardization, using Y as an internal standard element.

For analysis of the certified reference material, ES-L-1 Ground Water or EU-L-3 Waste Water, 2.5 mL or

1.25 mL of the ammonium acetate solution was added to 500 mL (ES-L-1) or 250 mL (EU-L-3) of the sample solution

(V0) after the addition of 10 µg of Y. The solution pH was adjusted to 5.5, and then the solid-phase extraction was

conducted.

For the preparation of calibration curves, solutions were prepared by adding appropriate amounts of each

trace element, constant amount of Y, and 3 mL of 3 mol L−1 nitric acid and diluting to around 10 mL with deionized

water; only the blank solution was adjusted exactly to 10 mL (VBlank) using a volumetric flask.

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Results and Discussion

Selection of internal standard element

In the proposed technique described above, the following requirements have to be satisfied: (i) an internal

standard element is not contained in the initial sample solution, or its content is negligible; (ii) the internal standard

element can be easily determined, and it does not interfere with the determination of trace elements; (iii) the trace

element and the internal standard element must be quantitatively extracted with and eluted from the chelating resin;

and (iv) the volume of the sample solution passed through a cartridge packed with chelating resin should be

proportional to the extracted amounts of both the trace elements and the internal standard element. These points were

investigated using deionized water-based sample solutions containing 21 elements. In the investigations, apparatus

A was used; the volume of the final solution after the solid-phase extraction was adjusted to 10 mL with deionized

water.

In the determination of trace elements using ICP-AES, Y and Yb are widely used as internal standard

elements55–57 because they are easily ionized and barely interfere with their determination.58–60 In real environmental

water, such as groundwater, river water, and seawater, the amounts of Y and Yb in such water samples are generally

extremely small;61 that is, these elements satisfy requirement (i) described above when trace elements in such water

samples are separated and preconcentrated using the solid-phase extraction. In this study, Y was selected as an internal

standard element because it is inexpensive compared with Yb; Y also absolutely satisfies requirement (ii).

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An internal standard element usable in the proposed theory has to be quantitatively extracted and eluted

with chelating resin as described in requirement (iii). Table 1 shows the results of the solid-phase extraction of Y as

well as the 21 elements using 100 mL of a sample solution with three aminocarboxylic acid-type chelating resins at

pH 5.56,9 at a flow rate of approximately 10 mL min−1. Y could be quantitatively recovered using Presep PolyChelate,

NOBIAS Chelate PA-1, and InertSep ME-2. Eleven elements, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, and Zn, were

also quantitatively extracted with Presep PolyChelate and NOBIAS Chelate PA-1; however, InertSep ME-2 could

extract 10 elements, excluding Mn. Figure 2 shows the effect of pH on the solid-phase extraction of Y. The extraction

behavior was similar to those for the elements recovered quantitatively, except for Mo and V.6,9

Then 20 mL–100 mL of each sample solution was passed through the cartridge packed with each

aminocarboxylic acid-type chelating resin, and Y and the elements were extracted. The relationship between the

volume of the sample solution passed through the cartridge and the relative emission intensity of Y, defined as the

ratio of the emission intensity using each volume of the sample solution to that using 100 mL, is shown in Fig. 3. The

relative emission intensity was proportional to the volume of the sample solution. On the other hand, Fig. 4 shows

the relationship between the relative emission intensity of Y and that of each element, which was quantitatively

recovered, as shown in Table 1. Good correlations were obtained with 9 elements excluding Mo and V among the

quantitatively recovered 11 elements. These results indicate that there is a proportional relationship between the

volume of the sample solution passed through the cartridge and the extracted amounts of Y and the 9 elements; thus

requirement (iv) was satisfied. From these results, it can be seen that Y is applicable to the proposed theory as an

internal standard element for the solid-phase extraction of the 9 elements. For Mo and V, however, the slight

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difference was observed; this would be due to the difference in the extraction behavior of between Mo or V6,9 and Y

as shown in Fig. 2. The difference is possibly magnified with increasing matrices in sample solutions. Therefore, it

should be necessary for the application to these elements to pay attention to matrices in sample solutions.

Verification of the proposed theory

In the proposed theory, when the volume of initial sample solution (V0) is known, it is allowed that a certain

amount of solution (α), such as buffer solution and acid/base for pH adjustment, is added. Strict control of the volume

of the sample solution (V1) passed through a cartridge packed with chelating resin is also not needed. To verify these

points, the following investigations were conducted.

The pH of deionized water-based sample solution (100 mL, V0) containing 10 µg of each element and 10

µg of Y was adjusted to 5.5 by adding the ammonium acetate solution, nitric acid, and aqueous ammonia. And then

10 mL of deionized water was added to the solution; the solution volume was approximately 110 mL. The solid-

phase extraction was conducted by passing approximately 110 mL of the solution through the cartridge packed with

Presep PolyChelate. The recoveries of the 9 elements, which were quantitatively recovered with Presep PolyChelate

as shown in Table 1, are shown in Table S1 in the Supporting Information. The recoveries were in the range of 90 ±

2.3 % (for Co, mean ± standard deviation, n = 5)–101 ± 1.6 % (for Cu).

The recoveries of some elements using each aminocarboxylic acid-type chelating resin were also

investigated using 90 mL–110 mL (V1) of 1000 mL (V0) of deionized water-based sample solution. The obtained

results are shown in Fig. 5. The recoveries of the 9 elements were almost constant regardless of the change in volume

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of the sample solution passed through the cartridge. Figure 6 shows recoveries of the elements using 480 mL–520

mL (V1) of 1000 mL (V0) of the sample solution with Presep PolyChelate. The quantitative recoveries were obtained

with extremely small variations.

In the investigations described so far, the volume of the final solution (V2) after the solid-phase extraction

was adjusted to 10 mL with deionized water. However, strict control of the volume of the final solution is also not

needed in the proposed theory. The effect of the volume of the final solution was investigated using 100 mL of the

sample solution. When the volume of the final solution was adjusted to approximately 8 mL (V2) in a 15 mL centrifuge

tube after the solid-phase extraction using Presep PolyChelate, the 9 elements were quantitatively recovered; 90 ±

3.0 % (for Zn)–105 ± 5.5 % (for Cu) of the recoveries were obtained (Table S2 in the Supporting Information). These

results indicate that a certain degree of variation in the volume of the final solution is allowed when internal

standardization is applied to the solid-phase extraction using aminocarboxylic acid-type chelating resins. The

recovery test was also conducted when approximately 90 mL of the sample solution was passed through the cartridge

and the final solution was adjusted to roughly 12 mL (V2). The recoveries for the 9 elements were in the range of 84

± 7.7 % (for Mn)–110 ± 4.2 % (for Cu) (Table S3 in the Supporting Information).

Furthermore, the recovery test was conducted under the conditions as follows: V0 = 100 mL, V0 + α = ca.

110 mL, V1 = 50 mL, and V2 = ca. 8 mL. As shown in Table S4 in the Supporting Information, the recoveries in the

range of 95 ± 2.5 % (for Fe)–101 ± 1.6 % (for Mn) were obtained.

In Tables S1–S4, the results for Mo and V are also appended as supplements; they were comparable to

those for the other 9 elements.

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Additionally, in the preparation of calibration curves, the volume of solutions used for the preparation is

also not so important if the volume of the blank solution (VBlank) is exactly known. Good straight lines were obtained

even when the volumes of the solutions varied (Table S5 and Fig. S3 in the Supporting Information).

From these results, it can be concluded that the proposed theory is applicable to the solid-phase extraction

of the 9 elements using aminocarboxylic acid-type chelating resins and Y as the internal standard element. Under the

appropriate conditions, it is also available for Mo and V.

Application to analyses of certified reference materials

In order to evaluate the applicability of solid-phase extraction with internal standardization, separation and

preconcentration of the 9 elements in certified reference materials were conducted. The results for Mo and V are also

appended.

Before the investigation, calibration curves were prepared. Good linear relationships were obtained in a

concentration range of 0 mg L−1–1.0 mg L−1 for all of the elements; the R2 values of the elements were 0.9997–

1.0000. Then the effect of coexisting ions was investigated using an artificial seawater-based sample solution. The

obtained results using the three aminocarboxylic acid-type chelating resins are shown in Table 2. The recoveries of 9

elements were 90 %–105 % when Presep PolyChelate was applied. For NOBIAS Chelate PA-1, the recovery of Mn

from the deionized water-based sample solution was insufficient, although 92 %–110 % of the recoveries were

obtained for the other 8 elements. InertSep ME-2 recovered the 8 elements at 85 %–105 %. The standard deviations

(n = 3) for the elements recovered quantitatively were small in all of the chelating resins. These results indicate that

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the requirements (i)–(iv) described above were satisfied for the solid-phase extraction of the elements in such a

solution; the assumption for kIS and kTE in the theory also seems to be allowed.

Based on these results, the solid-phase extraction using Presep PolyChelate, which gave excellent results

as shown in Table 2, with internal standardization was applied to analyses of the certified reference materials; in these

cases, approximately 50-fold and 25-fold enrichments were achieved, respectively. Tables 3 and 4 show the results

obtained by solid-phase extraction with apparatuses A and B as shown in the Supporting Information, respectively;

Ti was not determined because its consensus value is not given. There was no significant difference between the

determined value and the consensus value in either apparatus. It seems that the solid-phase extraction with internal

standardization is applicable to the separation and preconcentration of these elements in such environment water and

wastewater as well as industrial effluent. Additionally, similar results were obtained for both apparatus A and

apparatus B, which supply sample solutions in batch and flow systems, respectively; it also seems that this concept

is applicable to the automation of the operation for the solid-phase extraction.

Conclusions

The internal standardization using Y as the internal standard element was applicable to the solid-phase extraction of

the 9 trace elements using some commercially available aminocarboxylic acid-type chelating resins prior to their

ICP-AES determination. In the solid-phase extraction with internal standardization, it is not necessary to strictly

control the volumes of both the sample solution passed through the cartridge packed with chelating resin and the final

solution after the solid-phase extraction when an appropriate amount of internal standard element is added to the

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initial sample solution. Y is an excellent internal standard element: its content in various samples is negligible, it can

be easily determined using ICP-AES without any interference with regard to trace elements, and it can be

quantitatively recovered using the chelating resins used for this study. The calculation based on the internal

standardization was conducted using software in the ICP-AES apparatus. Solid-phase extraction with internal

standardization could be applied to the separation and preconcentration of the elements in the certified reference

materials (groundwater and wastewater). Solid-phase extraction with internal standardization can be applied even

when the volume of the sample solution passed through the cartridge packed with chelating resin is not accurate or

precise; it is expected to be useful in various fields, such as the development of an automated flow system. The

proposed theory would be applicable to solid-phase extraction using other aminocarboxylic acid-type chelating resins

as well as other types of chelating resins if an appropriate internal standard element is selected.

Acknowledgement

This work was partly supported by a grant from the Salt Science Research Foundation (No. 2004).

Supporting Information

Additional information and supplementary data associated with this article are given as Supporting Information. This

is available free of charge on the Web at http://www.jsac.or.jp/analsci/.

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22

Table 1 Recoveries of Y and 21 elements using each aminocarboxylic acid-type chelating resin

Element Recovery a, %

Presep PolyChelate NOBIAS Chelate PA-1 InertSep ME-2

Y 99 ± 1.5 107 ± 3.2 101 ± 1.3

As 96 ± 1.1 57 ± 3.7 79 ± 0.6

Be 20 ± 6.8 0 ± 0.0 2 ± 0.4

Ca 1 ± 0.5 5 ± 4.8 4 ± 4.6

Cd 91 ± 1.1 82 ± 1.3 89 ± 0.8

Co 98 ± 1.2 92 ± 2.0 100 ± 0.9

Cr 89 ± 1.1 63 ± 3.1 76 ± 1.1

Cu 105 ± 2.1 102 ± 1.5 104 ± 1.0

Fe 93 ± 0.6 79 ± 5.3 88 ± 1.3

Li 0 ± 0.0 0 ± 0.0 0 ± 0.0

Mg 0 ± 0.1 0 ± 0.1 0 ± 0.0

Mn 100 ± 1.6 85 ± 2.5 13 ± 2.0

Mo 100 ± 7.2 106 ± 6.8 109 ± 9.0

Ni 88 ± 6.6 96 ± 2.1 98 ± 0.7

Pb 94 ± 0.9 74 ± 4.4 88 ± 0.9

Sb 8 ± 0.2 3 ± 0.3 5 ± 0.5

Se 43 ± 0.7 15 ± 1.7 25 ± 1.0

Sr 1 ± 0.1 0 ± 0.0 0 ± 0.1

Ti 96 ± 1.1 80 ± 6.3 91 ± 2.2

Tl 2 ± 0.7 3 ± 0.5 4 ± 0.7

V 90 ± 3.6 87 ± 5.5 95 ± 1.9

Zn 90 ± 1.5 80 ± 1.8 90 ± 1.0

Extraction (apparatus A): Initial sample volume (V0), 1000 mL; sample volume after pH adjustment (V0 + α), ca. 1000 mL; Y, 100 μg; each element, 100 μg; pH, 5.5; flow volume (V1), 100 mL; flow

rate, ca. 10 mL min−1. Elution: 3 mol L−1 HNO3, 3 mL; final volume (V2), 10 mL.

a: Mean ± standard deviation (n = 5).

23

Table 2 Recoveries of 11 elements in artificial seawater-based sample solution using each resin

Element Recovery a, %

Presep PolyChelate NOBIAS Chelate PA-1 InertSep ME-2

Cd 90 ± 1.1 92 ± 0.8 85 ± 1.8

Co 93 ± 2.4 95 ± 0.9 90 ± 3.9

Cu 105 ± 1.7 110 ± 1.1 105 ± 2.4

Fe 97 ± 3.4 96 ± 1.1 93 ± 2.6

Mn 96 ± 1.8 56 ± 1.0 3 ± 0.9

Ni 93 ± 4.7 99 ± 2.6 98 ± 1.6

Pb 97 ± 3.0 96 ± 0.7 95 ± 2.6

Ti 100 ± 4.5 96 ± 5.6 97 ± 1.0

Zn 93 ± 0.5 93 ± 1.4 85 ± 3.3

Mo 16 ± 1.7 22 ± 0.6 58 ± 20

V 89 ± 5.8 103 ± 2.4 98 ± 5.9

Extraction (apparatus A): Initial sample volume (V0), 100 mL; sample volume after pH adjustment

(V0 + α), ca. 100 mL; Y, 10 μg; each element, 10 μg; pH, 5.5; flow volume (V1), 100 mL; flow rate,

ca. 10 mL min−1. Elution: 3 mol L−1 HNO3, 3 mL; final volume (V2), ca. 10 mL.

a: Mean ± standard deviation (n = 3).

24

Table 3 Results for the determination of some elements in the certified reference materials (Presep

PolyChelate, apparatus A)

Ground Water (ES-L-1) Waste Water (EU-L-3)

Element Found a

/ mg L−1

Consensus value

(Tolerance interval)

/ mg L−1

Found a

/ mg L−1

Consensus value


/ mg L−1

Cd 0.010 ± 0.0006 0.010

(0.007–0.013)

0.023 ± 0.0007 0.0228

(0.0186–0.0270)

Co 0.053 ± 0.0035 0.051

(0.043–0.059)

0.083 ± 0.0021 0.0825

(0.0762–0.0888)

Cu 0.023 ± 0.0015 0.020

(0.009–0.031)

0.123 ± 0.0012 0.1060

(0.0871–0.1250)

Fe 0.014 ± 0.0004 0.021

(0.007–0.035)

0.055 ± 0.0014 0.0580

(0.0504–0.0657)

Mn 0.096 ± 0.0052 0.098

(0.073–0.119)

0.112 ± 0.0042 0.1220

(0.1070–0.1380)

Ni 0.009 ± 0.0012 0.010

(0.007–0.013)

0.081 ± 0.0079 0.0834

(0.0731–0.0938)

Pb 0.002 ± 0.0001 0.002 b 0.044 ± 0.0006 0.0418

(0.0361–0.0475)

Zn 0.020 ± 0.0015 0.021

(0.013–0.029)

0.028 ± 0.0024 0.0305

(0.0125–0.0484)

Mo 0.011 ± 0.0013 0.011

(0.008–0.014)

0.043 ± 0.0033 0.0397

(0.0327–0.0467)

V 0.010 ± 0.0010 0.010

(0.007–0.013)

0.049 ± 0.0050 0.0495

(0.0434–0.0557)

Extraction (apparatus A): Initial sample volume (V0), 500 mL (Ground Water) or 250 mL (Waste Water);

sample volume after pH adjustment (V0 + α), ca. 500 mL (Ground Water) or ca. 250 mL (Waste Water);

Y, 10 μg; pH, 5.5; flow volume (V1), 500 mL (Ground Water) or 250 mL (Waste Water); flow rate, ca. 10

mL min−1. Elution: 3 mol L−1 HNO3, 3 mL; final volume (V2), ca. 10 mL.

a: Mean ± standard deviation (n = 5). b: This value is not certified; it is listed for information only.

25

Table 4 Results for the determination of some elements in the certified reference materials (Presep

PolyChelate, apparatus B)

Ground Water (ES-L-1) Waste Water (EU-L-3)

Element Found a

/ mg L−1

Consensus value


/ mg L−1

Found a

/ mg L−1

Consensus value


/ mg L−1

Cd 0.009 ± 0.0001 0.010

(0.007–0.013)

0.022 ± 0.0007 0.0228

(0.0186–0.0270)

Co 0.051 ± 0.0007 0.051

(0.043–0.059)

0.082 ± 0.0046 0.0825

(0.0762–0.0888)

Cu 0.022 ± 0.0003 0.020

(0.009–0.031)

0.123 ± 0.0017 0.1060

(0.0871–0.1250)

Fe 0.015 ± 0.0005 0.021

(0.007–0.035)

0.055 ± 0.0018 0.0580

(0.0504–0.0657)

Mn 0.100 ± 0.0028 0.098

(0.073–0.119)

0.108 ± 0.0035 0.1220

(0.1070–0.1380)

Ni 0.010 ± 0.0004 0.010

(0.007–0.013)

0.081 ± 0.0034 0.0834

(0.0731–0.0938)

Pb 0.002 ± 0.0000 0.002 b 0.043 ± 0.0009 0.0418

(0.0361–0.0475)

Zn 0.020 ± 0.0010 0.021

(0.013–0.029)

0.027 ± 0.0016 0.0305

(0.0125–0.0484)

Mo 0.012 ± 0.0004 0.011

(0.008–0.014)

0.044 ± 0.0022 0.0397

(0.0327–0.0467)

V 0.011 ± 0.0005 0.010

(0.007–0.013)

0.050 ± 0.0020 0.0495

(0.0434–0.0557)

Extraction (apparatus B): Initial sample volume (V0), 500 mL (Ground Water) or 250 mL (Waste Water);

sample volume after pH adjustment (V0 + α), ca. 500 mL (Ground Water) or ca. 250 mL (Waste Water);

Y, 10 μg; pH, 5.5; flow volume (V1), 500 mL (Ground Water) or 250 mL (Waste Water); flow rate, ca. 10

mL min−1. Elution: 3 mol L−1 HNO3, 3 mL; final volume (V2), ca. 10 mL.

a: Mean ± standard deviation (n = 5). b: This value is not certified; it is listed for information only.

26

Figure captions

Fig. 1 Schematic diagram of the application of internal standardization to solid-phase extraction.

Fig. 2 Effect of pH on the solid-phase extraction of Y using each chelating resin.

Extraction (apparatus A): Initial sample volume (V0), 1000 mL; sample volume after pH adjustment (V0 + α), ca.

1000 mL; Y, 100 µg; flow volume (V1), 100 mL; flow rate, ca. 10 mL min−1. Elution: 3 mol L−1 HNO3, 3 mL; final

volume (V2), 10 mL. 〇) Presep PolyChelate. △) NOBIAS Chelate PA-1. □) InertSep ME-2.

Fig. 3 Relationship between the volume of the sample solution passed through the cartridge and the relative emission

intensity of Y.


1000 mL; Y, 100 μg; pH, 5.5; flow volume (V1), 20 mL–100 mL; flow rate, ca. 10 mL min−1. Elution: 3 mol L−1

HNO3, 3 mL; final volume (V2), 10 mL. The relative emission intensity means the ratio of the emission intensity for

each volume of the sample solution to that for 100 mL. 〇) Presep PolyChelate. △) NOBIAS Chelate PA-1. □)

InertSep ME-2.

Fig. 4 Relationship between the relative emission intensity of Y and that of each element.


27

1000 mL; Y, 100 µg; each element, 100 μg; pH, 5.5; flow volume (V1), 20 mL–100 mL; flow rate, ca. 10 mL min−1.

Elution: 3 mol L−1 HNO3, 3 mL; final volume (V2), 10 mL. 〇) Presep PolyChelate. △) NOBIAS Chelate PA-1. □)

InertSep ME-2.

Fig. 5 Effect of the solution volume passed through the cartridge on the recoveries of some elements.

Extraction (apparatus A): Initial sample volume, 1000 mL (V0); sample volume after pH adjustment (V0 + α), ca. 1000

mL; Y, 100 µg; each element, 100 μg; pH, 5.5; flow volume (V1), 90 mL–110 mL; flow rate, ca. 10 mL min−1. Elution:

3 mol L−1 HNO3, 3 mL; final volume (V2), 10 mL. 〇) Presep PolyChelate. △) NOBIAS Chelate PA-1. □) InertSep

ME-2.

Fig. 6 Effect of the solution volume passed through the cartridge on the recoveries of some elements with Presep

PolyChelate.



3 mol L−1 HNO3, 3 mL; final volume (V2), 10 mL.

Error bar shows the standard deviation (n = 3).

28

Fig. 1 Schematic diagram of the application of internal standardization to solid-phase extraction.

29

Fig. 2 Effect of pH on the solid-phase extraction of Y using each chelating resin.


1000 mL; Y, 100 µg; flow volume (V1), 100 mL; flow rate, ca. 10 mL min−1. Elution: 3 mol L−1 HNO3, 3 mL; final

volume (V2), 10 mL. 〇) Presep PolyChelate. △) NOBIAS Chelate PA-1. □) InertSep ME-2.

30

Fig. 3 Relationship between the volume of the sample solution passed through the cartridge and the relative emission

intensity of Y.


1000 mL; Y, 100 μg; pH, 5.5; flow volume (V1), 20 mL–100 mL; flow rate, ca. 10 mL min−1. Elution: 3 mol L−1

HNO3, 3 mL; final volume (V2), 10 mL. The relative emission intensity means the ratio of the emission intensity for

each volume of the sample solution to that for 100 mL. 〇) Presep PolyChelate. △) NOBIAS Chelate PA-1. □)

InertSep ME-2.

31

Fig. 4 Relationship between the relative emission intensity of Y and that of each element.


1000 mL; Y, 100 µg; each element, 100 μg; pH, 5.5; flow volume (V1), 20 mL–100 mL; flow rate, ca. 10 mL min−1.

Elution: 3 mol L−1 HNO3, 3 mL; final volume (V2), 10 mL. 〇) Presep PolyChelate. △) NOBIAS Chelate PA-1. □)

InertSep ME-2.

32

Fig. 5 Effect of the solution volume passed through the cartridge on the recoveries of some elements.



3 mol L−1 HNO3, 3 mL; final volume (V2), 10 mL. 〇) Presep PolyChelate. △) NOBIAS Chelate PA-1. □) InertSep

ME-2.

33

Fig. 6 Effect of the solution volume passed through the cartridge on the recoveries of some elements with Presep

PolyChelate.



3 mol L−1 HNO3, 3 mL; final volume (V2), 10 mL.

Error bar shows the standard deviation (n = 3).

34

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