BUNSEKI KAGAKU Vol. 52, No. 8, pp. 575 _ 582 2003 575 2003 The Japan Society for Analytical Chemistry 1 1 R 1 Determination of rare earth elements in river water by fully automated on-line column inductively coupled plasma mass spectrometry using iminodiacetate chelate resin as a column Seiya MITO 1, Masaki OHATA 1 and Naoki FURUTA 1 1 Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1 13 27, Kasuga, Bunkyo-ku, Tokyo 112 8551 (Received 24 March 2003, Accepted 17 June 2003) In order to determine ultra-trace levels of rare earth elements (REEs) in river water, fully automated on-line column inductively coupled plasma mass spectrometry (ICP-MS) using iminodiacetate chelate resin as a column was developed in this study. The determination of REEs in a river-water reference material (SLRS-3) was conducted by using the developed method. The obtained results were in good agreement with the recommended values. This developed method was applied to the determination of REEs in Kanda River, which flows through the center of Tokyo, and the distribution patterns of REEs were evaluated. As a result, the positive anormalies of Gd in REEs patterns were found for both river water filtered with a 0.45 µm membrane filter and that filtered and heated with nitric acid. It is considered that the positive anormaly of Gd can be attributed to the outflow of Gd compounds, which are used for MRI (magnetic resonance imaging) contrast medium. Keywords : river water ; on-line column ; ICP-MS ; iminodiacetate resin ; Gd anormaly. 1 1) 2) 7) 1 : 112 8551 1 13 27 8) 9) 7)10) 8-11) 12) Chelex-100 Muromac A-1
576 BUNSEKI KAGAKU Vol. 52 2003 Chelex-100 8- Muromac A-1 Muromac A-1 Muromac A-1 ISIS ICP-MS ICP-MS 14 139 La 140 Ce 141 Pr 146 Nd 147 Sm 151 Eu 157 Gd 159 Tb 163 Dy 165 Ho 166 Er 169 Tm 172 Yb 175 Lu Gd 2 2 1 ASX500 Cetac ISIS Yokogawa Analytical Systems ICP-MS HP4500 Yokogawa Analytical Systems 0.5 mmφ ICP-MS Fig. 1 ISIS ISIS 2 pump 1 2 2 I II I II I 0.25 ml pump 2 Fig. 1 a Fig. 1 b ICP-MS HEPA PURE SPACE PS-100 class-100 Fig. 1 Schematic diagram of ISIS (a) step 1 ; adsorption and (b) step 2 ; elution 2 2 Muromac A-1 50-100 mesh sodium form Muromac A-1 2 Muromac A-1 0.04 g 1.5 mm 50 mm 1000 µg ml 1 TAMAPURE-AA-100 68 Milli-Q Element 1.5 M HNO 3 ph 0.7 M 30 TAMAPURE-AA-100 20 TAMAPURE-AA-100 ph 3 2 3 Flow chart Fig. 2 3 0.45 µm filter A river water A 99 g 1g 200 2.5 99 g heated river water 500 ml A 0.45 µm filter particles
: ICP-MS 577 0.45 µm filter A ph 3 2 4, Table 1 1 2 1.5 M HNO 3 3 0.7 M ph 3 4 ph 3 4 5 0.7 M 7 0.25 ml 1.5 M HNO 3 ICP-MS 1 13 760 3 3 1 Table 2 Ba Table 2 lsotope Monoxide and hydroxide interferences for REEs Interferences 139 La 140 Ce 141 Pr 146 Nd 130 Ba 16 O 147 Sm 130 Ba 16 O 1 H 151 Eu 135 Ba 16 O 134 Ba 16 O 1 H 157 Gd 141 Pr 16 O 140 Ce 16 O 1 H 159 Tb 143 Nd 16 O 142 Nd 16 O 1 H 142 Ce 16 O 1 H 163 Dy 147 Sm 16 O 146 Nd 16 O 1 H 165 Ho 149 Sm 16 O 148 Sm 16 O 1 H 148 Nd 16 O 1 H 166 Er 150 Sm 16 O 150 Nd 16 O 149 Sm 16 O 1 H 169 Tm 153 Eu 16 O 152 Gd 16 O 1 H 152 Sm 16 O 1 H Fig. 2 water Flow chart for sample preparation of river 172 Yb 175 Lu 156 Gd 16 O 159 Tb 16 O 156 Dy 16 O 158 Dy 16 O 1 H 155 Gd 16 O 1 H 158 Gd 16 O 1 H Table 1 Operating sequences of ISIS for matrix separations, REEs preconcentration and elution for the detrmination of REEs in river water by automated on-1ine column ICP-MS ISIS Flow rate/ Time/ Step Solution (see Fig. 1) ml min 1 s a 1 1.5 M nitric acid 2.5 90 2 Water 2.5 60 3 Ammonium acetate buffer solution (ph 3) 2.5 60 4 Sample (ph 3) 4.0 150 5 Ammonium acetate buffer solution (ph 3) 1.0 240 6 Water 1.0 60 b 7 1.5 M nitric acid 0.35 100
578 BUNSEKI KAGAKU Vol. 52 2003 Table 3 Formation-yield of monoxide and hydroxide Interfering Formation-yield, Interfering Formation-yield, monoxide hydroxide BaO 0.036 BaOH 0.080 LaO 0.712 LaOH 0.085 CeO 0.837 CeOH 0.077 PrO 0.819 PrOH 0.056 NdO 0.700 NdOH 0.048 SmO 0.139 SmOH 0.030 EuO 0.023 EuOH 0.023 GdO 0.378 GdOH 0.048 TbO 0.383 TbOH 0.030 DyO 0.234 DyOH 0.016 HoO 0.212 HoOH 0.014 ErO 0.217 ErOH 0.014 TmO 0.104 TmOH 0.009 YbO 0.013 YbOH 0.010 LuO 0.534 LuOH 0.021 Table 4 Element Analytical results for the concentration of REEs in SLRS-3 and the detection limits obtained by automated on-1ine column ICP- MS DL/ Found/ Reference value 3) / pg g 1 pg g 1 pg g 1 La 0.03 230 1 230 2 Ce 0.08 263 5 300 8 Pr 0.09 53.0 0.6 51 2 Nd 0.07 224 3 220 4 Sm 0.04 40 1 42 6 Eu 0.03 7.1 0.6 6.0 2 Gd 0.05 32.2 0.8 32 3 Tb 0.02 4.3 0.3 4.2 0.2 Dy 0.02 20.7 0.7 19 1 Ho 0.02 4.5 0.3 4.4 1 Er 0.06 12.4 0.3 12 2 Tm 0.06 2.0 0.3 1.7 1 Yb 0.07 10.9 0.6 11.4 2 Lu 0.002 2.2 0.3 2.3 0.2 pg g 1 Table 2 Table 3 14 Ba 100 ng g 1 m/z m/z 0.013 0.837 0.009 0.085 3 2 SLRS-3 National Research Council of Canada Table 4 SLRS-3 3) Ce 5 Ce 4) Ce 249 9pgg 1 5 Na : 1500 µg g 1 Mg : 200 µg g 1 K: 100 µg g 1 Ca : 100 µg g 1 10 pg g 1 108 95 10 Fig. 3 Sampling points at Kanda river
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580 BUNSEKI KAGAKU Vol. 52 2003 Table 5 (a) Analytical results for the concentration of REEs for river water (pg g 1 ) Element Inogashira Zenpukuzi Wada Shin-edogawa Suidobashi Asakusabashi Sumida Park Park Park River La 0.37 0.072 3.1 1.0 1.1 1.2 3.8 Ce N.D. N.D. 3.3 5.8 10 4.0 12 Pr 0.22 0.092 0.81 0.30 0.36 0.40 0.78 Nd 0.30 0.070 3.5 1.1 1.5 1.6 3.5 Sm 0.42 0.18 1.1 0.48 0.66 0.54 1.0 Eu 0.29 0.15 0.41 0.22 0.27 0.25 0.35 Gd 0.40 0.14 2.5 35 25 19 11 Tb 0.32 0.15 0.43 0.26 0.29 0.28 0.38 Dy 0.61 0.22 3.6 2.1 2.5 2.2 3.1 Ho 0.40 0.14 1.3 0.91 1.0 1.0 1.1 Er 0.58 0.20 5.7 4.5 5.3 4.9 4.0 Tm 0.36 0.088 1.1 0.90 1.1 1.0 0.63 Yb 0.62 0.17 8.7 6.9 8.7 8.1 3.4 Lu 0.36 0.12 1.9 1.5 1.9 1.7 0.55 Table 5 (b) Analytical results for the concentration of REEs for heated river water (pg g 1 ) Element Inogashira Zenpukuzi Wada Shin-edogawa Suidobashi Asakusabashi Sumida Park Park Park River La 2.8 3.8 9.6 12 3.3 2.6 5.4 Ce 2.9 3.9 11 32 14 7.3 15 Pr 0.51 0.67 1.7 2.6 0.73 0.63 0.91 Nd 1.2 1.9 6.3 7.7 2.5 2.9 4.6 Sm 0.44 0.34 1.5 0.93 1.1 0.96 1.3 Eu 0.26 0.12 0.52 0.28 0.20 0.22 0.29 Gd 0.36 0.19 3.2 57 40 34 16 Tb 0.16 0.12 0.48 0.33 0.23 0.28 0.38 Dy 0.49 0.27 4.0 2.8 3.0 2.9 3.5 Ho 0.21 0.14 1.5 1.1 1.1 1.1 1.2 Er 0.50 0.22 6.4 5.4 5.8 5.9 5.3 Tm 0.14 0.083 1.3 1.2 1.2 1.2 0.86 Yb 0.47 0.22 10 9.8 11 11 6.5 Lu 0.21 0.17 2.2 2.2 2.5 2.5 1.2 Table 5 (c) Analytical results for the concentration of REEs for particles 0.45 µm (pg g 1 ) Element Inogashira Zenpukuzi Wada Shin-edogawa Suidobashi Asakusabashi Sumida Park Park Park River La 2400 660 14000 7500 5800 7000 29000 Ce 5500 1600 22000 13000 10000 13000 62000 Pr 550 110 2300 1300 1100 1400 6500 Nd 2000 450 8300 4500 4300 5700 26000 Sm 440 130 1500 900 860 1200 5300 Eu 71 N.D. 420 210 220 290 1200 Gd 290 21 1500 1100 1200 1400 4900 Tb 20 N.D. 230 120 130 170 720 Dy 320 28 1400 800 920 1100 4200 Ho 21 N.D. 260 140 160 190 770 Er 130 3.4 730 450 470 550 2200 Tm N.D. N.D. 79 32 43 56 270 Yb N.D. N.D. 480 220 270 350 1700 Lu N.D. N.D. N.D. N.D. N.D. N.D. 210
: ICP-MS 581 Fig. 4 Chondrite-normalized distribution patterns of REEs for river water, (b) heated river water and (c) particles 0.45 µm
582 BUNSEKI KAGAKU Vol. 52 2003 SLRS-3 0.45 µm A 0.45 µm A Gd Gd MRI Gd