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ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 13, pp. 2867–2873.

© Pleiades Publishing, Ltd., 2015.


Original Russian Text © V.P. Zvereva, L.T. Krupskaya, 2014, published in Ekologicheskaya Khimiya, 2014, Vol. 23, No. 4, pp. 191–197.

Rare Earth Elements in Mine, Slime, and River Waters


in the Kavalerovsky and Dalnegorsky Districts
of the Russian Far East
V. P. Zverevaa–c and L. T. Krupskayac,d
a
Far East Federal University, ul. Sukhanova 8, Vladivostok, 600091 Russia
e-mail: zvereva@fegi.ru
b
Far East Geological Institute, Far East Branch, Russian Academy of Sciences,
pr. 100-letiya Vladivistoka 159, Vladivostok, 690022 Russia
c
Pacific National University, ul. Tikhookeanskaya 136, Khabarovsk, 680035 Russia
d
Far East Forestry Research Institute, Volochaevskaya ul. 71, Khabarovsk, 680020 Russia

Received September 1, 2014

Abstract—The concentrations of rare earth elements (REEs) in anthropogenic (mine and slime) and river
waters of Kavalerovsky and Dalnegorsky districts of the Far East have been estimated. The highest
concentrations of REs have been found in mine water of the Dubrovskoe deposit (Kavalerovsky district),
especially in the slime waters of the old tailing dump of the Krasnorechenskaya ore-dressing plant (KODP,
Dalnegorsky district). Contamination of the Rudnaya river water has been detected in the vicinity of the KODP
old and new tailings dumps. Taking into account that REEs are concomitant with sulfide minerals, the former
can be extracted by repeated processing of wastes from the KODP old and new tailings dumps.
Keywords: sulfides, anthropogenic waters, hypergenesis, anthropogenesis, rare earth elements
DOI: 10.1134/S1070363215130010

INTRODUCTION the sulfide ore hypergenesis zones in Primorsky Krai


have almost not been studied.
Rare earth elements (REEs) include yttrium, Deposits and wastes in the Kavalerovsky district
lanthanum, and 13 lanthanides: cerium, praseo- are classed as tin sulfide, and those in the Dalnegorsky
dymium, neodymium, samarium, europium, gadoli- district are lead–zinc (Central Ore-Dressing Plant,
nium, terbium, dysprosium, holmium, erbium, thulium, CODP) and tin–lead–zinc (Krasnorechenskaya Ore-
ytterbium, and lutetium. Extensive studies of REs have Dressing Plant, KODP).
started in 1960s due to their large-scale production.
Development of analytical methods over the past The goal of the present study was to estimate the
decades has enabled quantitative determination of REs REE content of mine, slime, and river waters in the
in host rocks, sulfide minerals, and anthropogenic and Kavalerovsky and Dalnegorsky districts of Primorsky
river waters, which favored geochemical studies of Krai. For this purpose it was necessary to analyze
REs and numerous publications in Russian and foreign distribution of REEs in anthropogenic and river waters
literature [1–9]. since 2006 until 2013 and evaluate their effect on the
hydrosphere.
Rare earth elements are present in heavy metal
sulfides. Decomposition of the latter in the course of EXPERIMENTAL
hypergene processes favors carry-over of REEs
together with heavy metals to mine, slime, and Hydrochemical samples were analyzed for REEs by
drainage waters and then to surface and ground waters. inductively coupled plasma mass spectrometry (ICP
The behavior and concentration of REEs in anthro- MS) at the Analytical Center of the Far East Geological
pogenic highly mineralized sulfate waters formed in Institute, Far East Branch, Russian Academy of

2867
2868 ZVEREVA, KRUPSKAYA

Table 1. Concentrations of REEs in mine waters in the Dalnegorsky and Kavalerovsky districts (μg/L)
Sampling site
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
and time
Backgrounda 0.145 0.195 0.049 0.220 0.059 0.015 0.060 0.009 0.052 0.010 0.029 0.004 0.026 0.004
b
Background 0.312 0.456 0.084 0.371 0.091 0.023 0.102 0.014 0.076 0.015 0.04 0.005 0.033 0.005
1st Sovetskii mine
October 2007 1.400 2.600 0.300 1.500 0.300 0.100 0.300 <0.100 0.200 NDc 0.100 0.100 <0.1 0.200
June 2009 2.600 3.760 0.650 2.610 0.520 0.110 0.480 0.060 0.340 0.06 0.170 0.020 0.14 0.020
June 2010 0.140 0.280 0.030 0.150 0.030 0.009 0.030 0.004 0.024 0.005 0.013 0.001 0.011 0.002
July 2011 1.710 3.440 0.420 1.700 0.340 0.070 0.340 0.050 0.250 0.05 0.120 0.020 0.09 0.010
October 2012 0.510 1.010 0.120 0.490 0.100 0.020 0.100 0.010 0.070 0.01 0.030 0.004 0.024 0.003
Khrustal’noe deposit
June 2009 5.40 11.30 1.30 4.400 0.700 0.300 0.800 0.200 0.500 0.2 0.200 <0.100 0.2 <0.100
October 2009 1.49 1.36 0.13 0.420 0.050 0.014 0.080 0.010 0.060 0.01 0.030 0.004 0.015 0.002
June 2010 1.50 1.13 0.10 0.370 0.050 0.014 0.080 0.009 0.050 0.01 0.030 0.002 0.02 0.002
October 2010 1.72 1.21 0.13 0.400 0.050 0.010 0.080 0.010 0.050 0.01 0.030 0.003 0.014 0.002
July 2011 0.95 0.90 0.09 0.300 0.040 0.010 0.060 0.008 0.050 0.01 0.030 0.003 0.014 0.002
October 2012 0.37 0.31 0.03 0.110 0.020 0.007 0.030 0.004 0.020 0.005 0.012 0.001 0.007 0.001
October 2013 1.55 1.30 0.11 0.403 0.054 0.034 0.127 0.015 0.051 0.012 0.041 0.003 0.019 0.003
Dubrovskoe deposit
July 2008 10.06 26.75 3.24 12.86 2.86 0.600 2.990 0.420 2.16 0.36 0.85 0.110 0.63 0.090
June 2009 4.28 6.43 0.64 2.22 0.37 0.080 0.380 0.050 0.24 0.04 0.10 0.010 0.05 0.010
October 2009 3.18 4.13 0.36 1.17 0.17 0.036 0.200 0.025 0.12 0.02 0.05 0.005 0.024 0.003
June 2010 13.40 20.10 1.88 6.67 1.04 0.220 1.360 0.140 0.69 0.12 0.27 0.030 0.13 0.015
October 2010 27.86 46.83 4.78 16.90 2.83 0.600 3.110 0.380 1.87 0.32 0.75 0.080 0.37 0.040
October 2012 35.70 55.60 5.47 19.10 2.93 0.600 3.690 0.430 2.10 0.37 0.86 0.080 0.42 0.050
October 2013 19.84 30.54 2.76 9.14 14.80 0.300 2.730 0.450 0.91 0.17 0.72 0.036 0.24 0.350
a
Kavalerovsky district. b Dalnegorsky district. c Not detected.

Sciences, using a Thermo Scientific ELEMENT XR 4.5 (Dy), 4 (Ho), 2.5–4.3 (Er), 4–20 (Tm), 2.7–4.2
instrument. (Yb), and 4–40 (Lu). The REE content of anthro-
pogenic mine waters of the Khrustal’noe and Dubrov-
RESULTS AND DISCUSSION skoe Deposits in the Kavalerovsky district (Table 1)
was also higher than the background values by factors
The results of analysis of mine and slime waters are of, respectively, 1.6–58 and 22–246 (La), 1.6–58 and
given in Tables 1–3. 21.2–285 (Ce), 1.8–265 and 7.3–111.6 (Pr), 1.4–20 and
The concentrations of REEs in the mine water of 5.3–86.8 (Nd), 7.7 (single sample) and 2.9–240.3
the 1st Sovetskii mine in the Dalnegorsky district (Table 1) (Sm), 2 (single sample) and 2.4–40 (Eu), 1.3–2.1 and
exceeded the background values by factors of 1.5 to 3.3–61.5 (Gd), 1.1–22.2 and 2.7–50 (Tb), not exceeded
8.3 (La), 0.6–8.2 (Ce), 1.4–7.7 (Pr), 0.4–7 (Nd), 1.1– (Khrustal’noe deposit) and 2.3–41.5 (Dy), 2 and 2–37
5.7 (Sm), 3–4.8 (Eu), 2.9–4.7 (Gd), 3.6–4.3 (Tb), 2.6– (Ho), 1.4–6.9 and 1.7–29.7 (Er), 2.5 (Tm, only

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RARE EARTH ELEMENTS IN MINE, SLIME, AND RIVER WATERS 2869

Table 2. Concentrations of REEs in slime waters of tailings dumps in the Kavalerovsky district (μg/L)

Sampling site and


La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
time
Backgrounda 0.145 0.195 0.049 0.220 0.059 0.015 0.060 0.009 0.052 0.010 0.029 0.004 0.026 0.004
2nd Tailings dump (Fabrichnyi settlement)
August 2008 8.100 9.200 0.800 2.100 0.300 0.200 0.5 <0.1 0.3 <0.1 0.2 <0.1 <0.1 <0.1
October 2009 0.400 1.010 0.110 0.430 0.120 0.030 0.12 0.016 0.08 0.015 0.034 0.004 0.025 0.003
July 2011 0.180 0.220 0.030 0.130 0.030 0.010 0.04 0.005 0.024 0.004 0.01 0.001 0.006 0.001
3rd Tailings dump (Fabrichnyi sttlement)
July 2006 5.000 14.0 2.00 7.00 1.000 <1.000 <1.000 <1.000 <1.00 <1.000 <1.000 <1.000 <1.00 <1.00
August 2008 5.400 11.3 1.30 4.40 0.700 0.300 0.800 0.20 0.50 0.20 0.200 <0.100 0.200 <0.10
June 2009 8.100 14.6 1.60 6.08 1.040 0.240 1.020 0.120 0.61 0.10 0.230 0.300 0.130 0.020
June 2010 2.490 7.87 1.09 4.59 0.880 0.200 0.880 0.100 0.47 0.080 0.180 0.020 0.110 0.003
October 2010 1.310 3.72 0.51 2.12 0.370 0.010 0.350 0.040 0.20 0.030 0.070 0.008 0.040 0.005
July 2011 2.000 6.55 0.90 4.00 0.800 0.180 0.700 0.100 0.40 0.060 0.100 0.001 0.006 0.001
October 2012 9.870 24.0 3.01 11.80 2.210 0.500 2.200 0.270 1.24 0.200 0.450 0.050 0.250 0.030
October 2013 0.650 2.31 0.34 1.61 0.353 0.082 0.472 0.087 0.20 0.036 0.151 0.008 0.074 0.009
Dubrovskoe tailings dump
June 2009 20.00 50.8 6.60 30.20 8.10 2.80 9.50 1.4 6.700 1.200 2.700 0.400 1.800 0.300
October 2009 0.810 1.69 0.18 0.70 0.13 0.03 0.12 0.02 0.080 0.010 0.030 0.004 0.020 0.003
June 2010 2.360 4.89 0.50 2.12 0.4 0.08 0.40 0.05 0.200 0.040 0.100 0.010 0.060 0.008
October 2010 0.500 0.96 0.12 0.43 0.08 0.02 0.08 0.01 0.050 0.010 0.020 0.003 0.020 0.003
July 2011 2.310 4.76 0.50 2.02 0.37 0.08 0.30 0.04 0.200 0.040 0.100 0.010 0.060 0.010
October 2012 2.020 4.37 0.50 1.88 0.34 0.07 0.30 0.38 0.200 0.030 0.070 0.010 0.050 0.005
October 2013 0.820 1.75 0.21 0.76 0.18 0.04 0.26 0.05 0.095 0.018 0.091 0.007 0.043 0.007
Vysokogorskoe tailings dump
June 2009 0.160 0.52 0.06 0.25 0.06 0.010 0.060 0.010 0.040 0.010 0.020 0.003 0.020 0.002
June 2010 0.020 0.02 0.005 0.02 0.01 0.003 0.010 0.001 0.010 0.001 0.003 <0.001 0.003 0.001
October 2010 0.020 0.01 0.005 0.02 0.01 0.002 0.010 0.001 0.005 0.001 0.004 0.001 0.003 0.001
October 2012 1.060 2.38 0.3 1.34 0.3 0.060 0.300 0.040 0.20 0.030 0.100 0.010 0.060 0.010
October 2013 0.024 0.02 0.008 0.037 0.014 0.022 0.013 0.003 0.010 0.003 0.009 0.001 0.006 0.002
a
Background water.

Dubrovskoe deposit), 2.6 (single sample) and 1.9–24.3 (Sm), 0.007–0.6 (Eu), 0.03–3.39 (Gd), 0.004–0.45
(Yb), and not exceeded (Khrustal’noe deposit) and 2.5– (Tb), 0.02–2.16 (Dy), 0.005–0.37 (Ho), 0.012–0.86
87.5 (Lu). (Er), 0.001–0.08 (Tm), 0.011–0.63 (Yb ), and 0.001–
0.35 (Lu). The total concentration of all REEs in
The concentrations of REEs in mine waters varied anthropogenic waters of the 1st Sovetskii mine
in the following ranges (μg/L): 0.14–3.57 (La), 0.28– changed from 0.73 (June 2010) to 11.54 μg/L (June
55.6 (Ce), 0.03–5.47 (Pr), 0.11–19.1 (Nd), 0.2–14.8 2009), of the Khrustal’noe deposit, from 1.71 (October

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2870 ZVEREVA, KRUPSKAYA

Table 3. Concentrations of REEs in slime waters of tailings dumps in the Dalnegorsky district (μg/L)

Sampling site and


La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
time
Backgrounda 0.312 0.456 0.084 0.371 0.091 0.023 0.102 0.014 0.076 0.015 0.04 0.005 0.033 0.005

New CODP tailings dump


October 2007 1.500 3.400 0.400 1.600 0.400 0.100 0.400 0.100 0.400 0.100 0.2 <0.100 0.100 NDb
June 2009 0.200 0.200 <0.100 0.200 <0.100 <0.100 <0.100 <0.10 <0.100 <0.100 <0.1 <0.100 <0.10 <0.100
June 2010 0.010 0.010 0.003 0.008 0.005 0.007 0.003 0.001 0.002 0.001 0.001 <0.001 0.002 <0.001
July 2011 0.040 0.010 0.001 0.010 0.020 0.080 0.015 0.002 0.013 0.002 0.01 0.002 0.010 0.002
October 2012 0.060 0.130 0.013 0.050 0.012 0.006 0.014 0.002 0.010 0.002 0.006 0.001 0.005 <0.001
October 2013 0.415 1.069 0.095 0.441 0.102 0.048 0.105 0.021 0.164 0.015 0.054 0.006 0.056 0.005
New KODP tailings dump
July 2006 31.00 77.00 9.000 42.00 11.000 0.100 4.000 2.000 10.000 2.000 4.0 <0.100 <0.10 <0.100
June 2009 0.300 0.500 0.200 0.300 <0.100 <0.100 0.200 <0.10 <0.100 <0.100 <0.1 <0.100 <0.10 <0.100
July 2011 0.209 0.256 0.024 0.100 0.020 0.010 0.036 0.005 0.030 0.006 0.014 0.002 0.009 0.001
October 2012 0.066 0.123 0.014 0.050 0.013 0.010 0.018 0.002 0.013 0.002 0.006 0.001 0.004 <0.001
October 2013 0.290 0.339 0.030 0.130 0.031 0.086 0.038 0.008 0.068 0.008 0.023 0.002 0.014 0.002
Old KODP tailings dump
July 2006 41.00 104.0 13.00 59.00 16.000 5.000 17.000 2.000 12.000 2.00 5.0 <1.000 3.00 <1.000
October 2007 66.70 558.0 18.50 91.90 23.200 7.600 29.000 3.500 19.800 3.20 0.8 4.900 0.60 23.60
June 2010 63.00 152.0 18.40 84.80 22.900 8.620 31.300 4.450 23.400 4.09 9.72 1.140 6.470 0.870
June 2009 8.56 19.54 2.480 10.52 2.930 1.040 3.650 0.530 2.790 0.47 1.12 0.130 0.720 0.100
July 2011 183.0 418.0 56.20 254.0 69.600 25.900 87.500 12.90 67.700 11.80 28.8 3.350 18.90 2.560
October 2012 44.90 112.0 14.60 66.00 17.200 5.840 18.900 2.510 12.200 1.96 4.56 0.500 2.780 0.370
October 2013 47.76 131.4 14.26 70.82 18.888 5.054 14.322 3.098 13.195 2.28 6.827 0.582 3.634 0.473
a b
Background water. Not detected.

2012) to 25.3 μg/L (June 2009), and of the Dubrovskoe tailings dump was sampled only in 2008–2011; since
deposit, from 9.94 (October 2009) to 127.4 μg/L that time the slime pond has dried up. The
(October 2012). The occurrence of REEs in the concentration of REEs in the samples exceeded the
examined samples may be represented by the series background values up to 56 and 47 times for La and
Ce > Nd > Sm > Pr > Gd > La > Dy > Er > Yb > Eu > Ce, while the exceedance for the other elements ranged
Tb > Ho > Lu > Tm. from 1.5 to 16 times.
It follows from the above data that mine waters of
The concentrations of all REEs in the slime water
the Dubrovskoe deposit are most enriched in REEs and
of the Vysokogorskoe deposit exceeded the back-
that mine waters of the 1st Sovetskii mine contain
ground values only in October 2012 (Table 2) by
REEs at lowest concentrations.
factors of 7.3 (La), 12 (Ce), 6.1 (Pr, Nd), 5.1 (Sm), 4
Next, consider the REE concentrations in slime (Eu), 5 (Gd), 4.4 (Tb), 3.8 (Dy), 3 (Ho), 3.4 (Er), 2.5
waters of abandoned tailings dumps in the Kavale- (Tm, Lu), and 2.3 (Yb). Higher REE concentrations
rovskii district (Table 2). Slime water from the 2nd were found in the slime water from the 3rd tailings

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RARE EARTH ELEMENTS IN MINE, SLIME, AND RIVER WATERS 2871

Table 4. Concentrations of REEs in river waters in the Dalnegorsky and Kavalerovsky districts (μg/L)
Sampling site and
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
time
Backgrounda 0.145 0.195 0.049 0.220 0.059 0.015 0.060 0.009 0.052 0.010 0.029 0.004 0.026 0.004
b
Background 0.312 0.456 0.084 0.371 0.091 0.023 0.102 0.014 0.076 0.015 0.04 0.005 0.033 0.005
Rudnaya River, 26 km
October 2007 0.2 0.2 <0.1 0.2 <0.1 <0.1 0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
June 2009 0.6 1.4 0.3 0.6 0.2 <0.1 0.2 0.1 0.2 0.1 0.2 0.1 0.1 0.1
June 2010 0.059 0.05 0.022 0.079 0.017 0.006 0.02 0.003 0.015 0.004 0.009 0.001 0.011 0.001
July 2011 0.101 0.098 0.022 0.093 0.021 0.005 0.023 0.003 0.020 0.004 0.011 0.002 0.010 0.002
October 2012 0.177 0.203 0.040 0.167 0.037 0.009 0.042 0.006 0.032 0.006 0.018 0.002 0.015 0.003
October 2013 0.079 0.076 1.426 0.099 0.024 0.029 0.025 0.005 0.018 0.002 0.016 0.002 0.011 0.002
Rudnaya River, 14.5 km downstream from the CODP tailings dump
October 2013 0.023 0.038 0.007 0.036 0.008 0.027 0.008 0.002 0.013 0.001 0.008 0.001 0.005 0.001
Rudnaya River, upstream from the KODP tailings dumps
October 2013 0.010 0.008 0.003 0.013 0.008 0.077 0.003 0.001 0.004 0.001 0.004 0.001 0.003 0.001
Rudnaya River, downstream from the KODP tailings dumps
October 2013 6.318 10.549 1.455 15.639 2.000 0.535 1.581 0.351 1.740 0.317 0.938 0.084 0.554 0.073
Partizanka River, downstream from the Dubrovskoe deposit
July 2011 0.256 0.322 0.043 0.164 0.029 0.007 0.032 0.004 0.020 0.004 0.012 0.002 0.011 0.002
Kavalerovka River (Fabrichnyi settlement)
July 2011 0.135 0.148 0.029 0.122 0.025 0.007 0.028 0.003 0.018 0.004 0.010 0.001 0.008 0.001
Vysokogorka River, downstream from Vysokogorskoe deposit
October 2009 0.08 0.07 0.026 0.119 0.032 0.005 0.03 0.004 0.023 0.005 0.012 0.002 0.011 0.002
October 2010 0.071 0.025 0.023 0.107 0.024 0.005 0.027 0.004 0.02 0.004 0.013 0.002 0.012 0.002
Vetvistyi Creek, downstream from the Vysokogorskoe tailings dump
June 2009 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
October 2010 0.746 1.303 0.136 0.481 0.090 0.020 0.111 0.014 0.070 0.013 0.032 0.004 0.022 0.003
a b
Kavalerovsky district. Dalnegorsky district.

dump (Fabrichnyi settlement); the corresponding ex- The REE concentration ranges in the slime waters
ceedance values were 4.5–68 (La), 12–123 (Ce), 9–61 are as follows (μg/L): 0.02–20 (La), 0.01–50.8 (Ce),
(Pr), 7–54 (Nd), 6–38 (Sm), 5–20 (Eu), 4–37 (Gd), 4– 0.005–6.6 (Pr), 0.02–11.8 (Nd), 0.01–8.1 (Sm), 0.002–
30 (Tb), 4–24 (Dy), 3–36 (Ho), 2–16 (Er), 2–75 (Tm), 2.8 (Eu), 0.01–9.5 (Gd), 0.001–1.4 (Tb), 0.005–6.7
and 3–10 (Yb). The slime water of the Dubrovskoe (Dy), 0.001–1.2 (Ho), 0.003–2.7 (Er), 0.001–0.4 (Tm),
deposit was characterized by the highest REE concen- 0.003–1.8 (Yb), and 0.001–0.3 (Lu). The total mineral
trations which were 3.4–138 (La), 5–260 (Ce), 2–135 content of the slime waters changed from 69 (July
(Pr), 2–137 (Nd), 2–137 (Sm), 2–180 (Eu), 2–158 2011) to 4.6 μg/L in the 2-nd tailings dump, from 5.82
(Gd), 2–156 (Tb), 4–129 (Dy), 3–120 (Ho), 3–93 (Er), (October 2013) to 55.87 μg/L (October 2012) in the
2–100 (Tm), and 2–69 times (Yb) higher than the 3rd tailings dump, from 2.21 (October 2010) to
background values. 142.3 μg/L (June 2009) in the Dubrovskoe tailings

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2872 ZVEREVA, KRUPSKAYA

dump, and from 0.1 (June 2010) to 2.75 μg/L (October (Yb), and 20–4720 (Lu), and the total mineral content
2012) in the Vysokogorskoe tailings dump. The con- of the slime water ranged from 54.28 (June 2009) to
centrations of the examined rare earth elements in the 1240.2 μg/L (July 2011). The abundance of REEs
slime waters decrease in the series Ce > La > Nd > decreased in the series Ce > Nd > La > Gd > Sm >
Gd > Sm > Dy > Pr > Er > Eu > Yb > Tb > Ho > Pr > Er > Eu > Lu > Dy > Yb > Tb > Ho.
Tm > Lu.
Apart from mine and slime waters, samples of river
Different REE concentration patterns were ob- waters were withdrawn and analyzed (Table 4). High
served in the slime waters of the old and new (both REE concentrations were found in Rudnaya River
abandoned) KODP tailings dumps and new (operating) within Krasnorechensk settlement (old and new KODP
CODP tailings dump (Table 3). The REE content of the tailings dumps), μg/L: 6.3 (La, 20 times higher than
slime water of the new CODP tailings dump varied the background concentration), 10.5 (Ce, 23), 15.6
from (μg/L) 0.01 to 1.5 for La, 0.01–3.4 (Ce), 0.001– (Nd, 42), 1.45 (Pr, 17), 2 (Sm, 22), 0.535 (Eu, 23),
0.4 (Pr), 0.008–1.6 (Nd), 0.005–0.4 (Sm), 0.006– 1.58 (Gd, 16), 0.351 (Tb, 25), 1.74 (Dy, 23), 0.317
0.048 (Eu), 0.003–0.4 (Gd), 0.001–0.1 (Tb), 0.002– (Ho, 21), 0.938 (Er, 23), 0.084 (Tm, 17), 0.554 (Yb,
0.4 (Dy), 0.001–0.1 (Ho), and 0.001–0.2 (Er). These 17), 0.073 (Lu, 15); total mineral content 42.13 μg/L.
concentrations exceeded the corresponding background
values mainly in October 2007 by factors of 4.8 (La), Samples of Rudnaya River water at 26 km, i.e.,
7.5 (Ce), 4.8 (Pr), 4.3 (Nd), 4.4 (Sm), 4.3 (Eu), 4 (Gd), considerably downstream from the KODP tailings
7.1 (Tb), 5.3 (Dy), not exceeded (Ho), 5 (Er), and 3 dumps, old CODP tailings dump, and Dalnegorsk
(Yb). The total mineral content of the slime water town, contained REEs at concentrations not exceeding
ranged from 0.05 (July 2010) to 8.7 μg/L (October the background values; an exception was Pr whose
2008). The abundance of REEs conformed to the series concentration was 17 times higher than the background
Ce > Nd > La > Sm ≥ Pr ≥ Gd ≥ Dy > Er > Eu > Ho > value. These findings indicated strong dilution of the
Tb. river water. Rudnaya River is one of the most polluted
river over the world with respect to a large number of
The concentrations of REEs in the slime water of
sulfide ore elements [10]. Increased REE concentra-
the new KODP tailings dump change in the following
tions in Vetvistyi Creek (Kavalerovsky district) were
ranges (μg/L): 0.07–31 (La), 0.12–77 (Ce), 0.014–9
observed only in 2011; they exceeded the background
(Pr), 0.05–42 (Nd), 0.013–11 (Sm), 0.01–0.086 (Eu),
values by factors of 5 (La), 6.7 (Ce), 21.9 (Nd), 2.7
0.81–4 (Gd), 0.002–2 (Tb), 0.013–10 (Dy), 0.012–2
(Pr), 1.5 (Sm), 1.3 (Eu, Ho, Er), 1.9 (Gd), 1.6 (Tb, Dy),
(Ho), 0.006–4 (Er). The background concentrations
and 1.1 (Tm). The REE concentrations in water
were exceeded mostly in July 2006 by factors of 99.4
samples withdrawn from Partizanka, Kavalerovka, and
for La, 161.8 for Ce, 107 for Pr, 113.2 for Nd, 121 for
Vysokogorka rivers were lower than the corresponding
Sm, 4.3 for Eu, 39.2 for Gd, 1429 for Tb, 131.6 for Dy,
background values.
133.3 for Ho, and 100 for Er, while no exceedance was
observed for Tm, Yb, and Lu. The total mineral CONCLUSIONS
content of the slime water ranged from 0.72 (July
2011) to 192.2 μg/L (June 2006). The REEs ranked as In summary, we have found that the mine waters in
follows with respect to their concentration: Ce > Nd > the Dubrovskoe deposit (Kavalerovsky district) are the
La > Sm > Pr > Gd ≥ Dy > Er > Tb ≥ Ho > Eu. richest in rare earth elements and that those in the 1st
The highest concentrations of all REEs were found Sovetskii mine (Dalnegorsky district) contain the lowest
in the slime water in the old KODP tailings dump, μg/L: concentrations of REEs. In the Dalnegorsky district,
8.56–183 (La), 19.54–558 (Ce), 2.48–56.2 (Pr), 10.52– the highest REE concentrations were detected in the
254 (Nd), 2.93–69.6 (Sm), 1.04–25.9 (Eu), 3.65–87.7 slime water of the old KODP tailings dump. In the
(Gd), 0.53–12.9 (Tb), 2.79–23.4 (Dy), 0.47–11.8 (Ho), Kavalerovsky district, slime waters in the Dubrovskoe
0.8–28.8 (Er), 0.13–4.9 (Tm), 0.6–18.9 (Yb), 0.10– deposit and 3rd tailings dump in the Fabrichnyi
23.6 (Lu). These concentrations were higher than the settlement were characterized by increased REE.
background values by factors of 27–586 (La), 43–1223 Pollution with REEs of Rudnaya River (Dalnegorsky
(Ce), 30–669 (Pr), 28–248 (Nd), 32–764 (Sm), 45– district) in the vicinity of the old and new KODP
1126 (Eu), 36–856 (Gd), 38–921 (Tb), 37–890 (Dy), tailings dumps and of Vetvistyi Creek (Kavalerovsky
31–786 (Ho), 20–720 (Er), 26–980 (Tm), 18–572 district) downstream from the Vysokogorskoe tailings

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RARE EARTH ELEMENTS IN MINE, SLIME, AND RIVER WATERS 2873

dump should be noted. Taking into account that REEs Poligraf. Tsentr “Kievskii Universitet,” 2010.
are concomitant with sulfide minerals, sulfide ores in 2. Rimskaya-Korsakova, M.N., Cand. Sci. (Chem.)
Krasnorechensk deposits and wastes from the Dissertation, Moscow, 2005.
Krasnorechensk ore-dressing plant (14.3 million tons 3. Rogulina, L.I., Voropaeva, E.N., and Ponomarchuk, V.A.,
have been accumulated at the old and new KODP Usp. Sovrem. Estestvozn., 2013, no. 11, p. 117.
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5. Vakh, E.A., Kharitonova, N.A., and Vakh, A.S., Vestn.
ACKNOWLEDGMENTS Dal’nevost. Otd. Ross. Akad. Nauk, 2013, no. 2, p. 90.
6. Chudaeva, V.A.and Chudaev, O.V., Vestn. Dal’nevost.
The study was performed by a grant from the Otd. Ross. Akad. Nauk, 2005, no. 3, p. 66.
Russian Science Foundation (project no. 15-17-10016), 7. Caixia, F., Xianwu, B., Shen, L., and Ruizhong, H.,
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