Accepted Manuscript

REEs geochemical characteristics of lower Cambrian phosphatic rocks in the

Gorgan-Rasht Zone, northern Iran: Implications for diagenetic effects and
depositional conditions

Ali Abedini, Ali Asghar Calagari

PII: S1464-343X(17)30349-7

DOI: 10.1016/j.jafrearsci.2017.08.018

Reference: AES 3000

To appear in: Journal of African Earth Sciences

Received Date: 25 April 2017

Revised Date: 18 August 2017

Accepted Date: 28 August 2017

Please cite this article as: Ali Abedini, Ali Asghar Calagari, REEs geochemical characteristics of
lower Cambrian phosphatic rocks in the Gorgan-Rasht Zone, northern Iran: Implications for
diagenetic effects and depositional conditions, Journal of African Earth Sciences (2017), doi:
10.1016/j.jafrearsci.2017.08.018

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 ACCEPTED MANUSCRIPT

1 REEs geochemical characteristics of lower Cambrian phosphatic

2 rocks in the Gorgan-Rasht Zone, northern Iran: Implications for

3 diagenetic effects and depositional conditions

4

5 Ali Abedini a,* and Ali Asghar Calagari b

7 a,* Department of Geology, Faculty of Sciences, Urmia University, 57153165, Urmia, Iran (Tel: +9844

8 32972134; Fax: +984432753172)

9 b Department of Earth Sciences, Faculty of Natural Sciences, University of Tabriz, 5166616471, Tabriz,

10 Iran (Tel: +984133392699; Fax: +984133392703)

11 *Corresponding author. Email address: abedini2020@yahoo.com and a.abedini@urmia.ac.ir

12
13

14 Abstract

15 The phosphatic rocks in the Gorgan-Rasht structural Zone (north of Iran) are widely developed

16 within the Soltanieh Formation of Upper Neoproterozoic-Lower Cambrian age. These rocks

17 extend in length over 60 km, vary in thickness from 2.2m to 5m, and lie along the boundary of

18 the Middle dolomite and the Upper shale members (lower Cambrian) of the Soltanieh Formation.

19 In this research, the geochemical characteristics of 16 phosphatic samples using rare earth

20 elements (REEs) within a section in the Soltanieh Formation were investigated. The entire

21 phosphatic samples show characteristically typical hat-shaped distribution patterns of REEs,

22 strong negative Ce anomalies (Ce/Ce*=0.30-0.51), and slightly positive Eu anomalies

23 (Eu/Eu*=1.34-1.73). The geochemical evidence such as hat-shaped distribution patterns, MREEs

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24 enrichment relative to LREEs and HREEs, and values of Er/Nd, Y/Ho, La/Nd, and (La/Yb)N

25 ratios together with positive correlation between pairs of Eu/Eu*-Ce/Ce* and REEs-Ce/Ce* and

26 negative correlation between pair of (Dy/Sm)N-Ce/Ce* reveal the important role of diagenetic

27 processes in the distribution and concentration of REEs in the phosphatic rocks. This study

28 demonstrated that the strong negative Ce anomalies and weak positive Eu anomalies are valuable

29 indicators for determining redox conditions of diagenetic fluids existing during the development

30 of the phosphatic rocks, and also suggest upwelling and mixing of organic-rich anoxic bottom

31 seawaters with aerobic oxic seawaters before the development and progression of

32 phosphatization processes in the depositional site. The geochemical parameters like Y/Ho ratio

33 and strong positive correlation between REEs-TOC suggest that terrigenous materials along with

34 organic matters were the principal source of REEs in the phosphatic rocks.

35

36 Key words: Phosphatic rocks, Cambrian, Rare earth elements, Soltanieh Formation, Gorgan-

37 Rasht zone, Iran.

38

39 1. Introduction

40 During recent years, geochemistry of rare earth elements (REEs) has proved to be one of the

41 best tools for determining conditions of depositional environments and understanding of

42 formation mechanism of sedimentary phosphatic rocks, and hence has received worldwide

43 attention by many researchers (e.g. Elderfield and Greaves, 1982; Wright et al., 1987; Ilyin,

44 1998; Rao et al., 2002; Chanhau and Ruizhong, 2005; Baioumy et al., 2007; Fazio et al., 2007;

45 Awadalla, 2010; Baioumy, 2011; Jiyan et al., 2013; Al-Hobaib et al., 2013; Khan et al., 2012,

46 2016; Abed et al., 2016; Xin et al., 2016; Kechiched et al., 2016; Abou El-Anwar et al., 2017;
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47 Auer et al., 2017; Zhu and Jiang, 2017). Distribution patterns of REEs and variations of anomaly

48 values of Eu and Ce in phosphatic sedimentary rocks are highly dependent upon various factors

49 including conditions of the depositional environment and the degree of interaction between

50 seawaters and land-derived detrital materials (Khan et al., 2012). Parameters like weathering,

51 diagenesis, and metamorphism can remarkably influence the concentration of REEs and their

52 distribution patterns in phosphatic rocks (McArthur and Walsh, 1984). The results of recent

53 researches revealed that geochemical investigations of REEs in sedimentary phosphatic rocks

54 can furnish valuable information on paleo-seawaters and/or diagenetic fluids (e.g. Shieds and

55 Stille, 2001; Zhu et al., 2014; Mustcente et al., 2014; Xin et al., 2016; Auer et al., 2017; Zhu and

56 Jiang, 2017).

57 The phosphatic sedimentary deposits in Iran were developed temporally in six discrete

58 periods: (1) Lower Cambrian, (2) Ordovician-Silurian, (3) Upper Devonian, (4) Upper

59 Cretaceous, (5) Paleocene, and (6) Eocene-Oligocene. Spatially, these deposits are widely spread

60 within five structural zones: (1) Central Iran, (2) Alborz-Azarbaidjan, (3) Gorgan-Rasht, (4)

61 folded Zagros, and (5) Sanandaj-Sirjan (Namadmalian et al., 1998).

62

63 The Lower Cambrian phosphatic deposits in the Gorgan-Rasht zone contain an average of 11

64 wt% P2O5 and reserves exceeding 66 million tons (Namadmalian et al., 1998), and extend over

65 60 km with varying thicknesses between 2.2 to 5 m. Mineralogically, the principal constituent

66 minerals present in these deposits are calcite, fluor-apatite, dolomite, quartz, pyrite, muscovite,

67 and illite (Abedini et al., 2012).

68 The Soltanieh Formation (Neoproterozoic-Lower Cambrian) is widely exposed in the

69 Gorgan-Rasht Zone (northern Iran) and host to the phosphatic sedimentary deposits. Up to now,
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70 extensive stratigraphic, paleo-biologic, sedimentary, and geochemical (carbon stable isotopes)

71 investigations were carried out in the Soltanieh Formation in an attempt to determine the

72 conditions of depositional paleo-environment during the period of Neoproterozoic-Lower

73 Cambrian by different researchers (Hamdi et al., 1989; Brasier et al., 1990; Kimura et al., 1997).

74 So far, comprehensive studies concerning geochemical characteristics and behavior of

75 rare earth elements during evolution of the phosphatic rocks of the Soltanieh Formation have not

76 been done.

77 The aim of this work is to study the distribution patterns of REEs, variations of Eu and Ce

78 anomaly values, and elemental ratios as useful means for appreciating the paleo-seawater

79 conditions and diagenetic environments during phosphatization of the Lower Cambrian

80 phosphatic rocks of the Soltanieh Formation in the Vali-Aabad area of northern Iran.

81

82 2. Geological setting and studied section

83 Based upon the structural division of Iran (Nabavi, 1976), the study area is located in the

84 central part of the Gorgan-Rasht Zone (Fig 1). The stratigraphic units, from the oldest to the

85 youngest, in the study area (see Fig. 2) include Neoproterozoic Kahar Formation (slaty shale,

86 sandstone, siltstone, dolomite, and quartzite), the Neoproterozoic-Lower Cambrian Soltanieh

87 Formation (dolomite and shale), the Cambrian Barut Formation (siltstone and shale), the

88 Cambrian Ziagun Formation (shale and siltstone), the Cambrian Lalun Formation (Sandstone),

89 and the Carboniferous Mobarak Formation (limestone, dolomite, and intercalated marl). These

90 successions are overlain by the Upper Permian basic igneous lavas, pyroclastics and sandstone.

91 The Quaternary alluviums are the youngest lithologies in the area.

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92 A geologic section (~700 m thick) in the Soltanieh Formation in the Vali-Abad area shows

93 that it consists of five distinct members (see Fig. 3) which from bottom to the top are (1) Lower

94 Dolomite, (2) Lower Shale, (3) Middle Dolomite, (4) Upper Shale, and (5) Upper Dolomite.

95 Based upon sedimentary structures, lithologic facies, and fossil content, the dolomite

96 members were formed in a tidal flat shallow water environment. Dolomitization took place in a

97 Sabkha-type environment. Shale members contain intercalations of fossiliferous carbonates (<1

98 m thick) which were deposited in a sub-tidal marine environment (Kimura et al., 1997). The

99 Lower Shale Member is dark grey to black and has abundant phytoplanktonic fossils. The Upper

100 Shale Member is grey and fossiliferous (Hamdi et al., 1989; Brasier et al., 1990; Kimura et al.,

101 1997). The phosphatic horizon, with thicknesses ranging from 2.2 to 5 m, was developed along

102 the boundary of the Middle Dolomite and the Upper Shale Members (Lower Cambrian) of the

103 Soltanieh Formation. The phosphatic rocks are grey to brownish dark, and on the basis of

104 physico-morphological aspects can be divided into two groups: (1) the massive and (2) the

105 laminated. The former is less abundant and enclosed in the latter (Fig.3).

106

107 3. Sampling and laboratories methods

108 Forty (40) thin and polished sections of the phosphatic rock samples were petrographically

109 examined. In this study, for geochemical investigations, 16 representative samples collected in

110 intervals of approximately 25-40 cm across a selected profile from the phosphatic horizon within

111 the Soltanieh Formation in the Vali-Abad area (see Fig. 3). For the determination of chemical

112 composition of the phosphatic rock, all samples (#16) were dried at ~60 C and sieved to -80

113 mesh. They were then jaw-crushed to 70 % passing 10 mesh (2 mm) of which 250 g aliquots

114 were pulverized to 95 % passing 150 mesh (100 mm) in a mild steel ring and puck mill. The
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115 collected samples were chemically analyzed at the ACME Analytical Laboratories Ltd.,

116 Vancouver, Canada. Aliquots of 0.2 g sample material were weighed into a graphite crucible and

117 mixed with 1.5 g of LiBO2/Li2B4O7 flux. The flux/sample charge was heated in a muffle furnace

118 for 30 minutes at 980 C. The cooled bead was dissolved in 100 ml of 5% HNO3. An aliquot of

119 the solution was poured into a polypropylene test tube for measurement. Calibration standards,

120 verification standards and re-agent blanks were included in the sample sequence. The values of

121 Ba and Y were determined by inductively coupled plasma emission spectrometry (ICP-ES). Rare

122 earth elements (REEs) contents were determined by inductively coupled plasma mass

123 spectrometry (ICP-MS). The detection limits for Tb, Tm, and Lu are 0.01 ppm; for Pr, Eu, and

124 Ho 0.02 ppm; for Er 0.01 ppm; for Sm, Gd, Dy, and Yb 0.05 ppm; for La, Ce, and Y 0.1 ppm;

125 for Nd 0.3 ppm; for Ba 1 ppm. The TOC (total organic carbon) values of the phosphatic samples

126 were measured by the Vario EL III elemental analyzer. The detection limit for the TOC was ~30

127 g. The REEs contents were normalized to Post-Archean Australian Shale (PAAS) (Taylor and

128 McLennan, 1985). Additionally, the geochemical data were evaluated by correlation coefficient

129 analysis, elemental ratios, and plotting of binary diagrams. The Pearsons correlation coefficients

130 for elemental distribution were determined for all the phosphatic rock samples by using SPSS-16

131 computer software.

132

133 4. Results

134 4.1. Petrography

135 Petrographic examinations show that calcite and dolomite constitute the major fabric of the

136 phosphatic rocks. Calcite is more abundant (determined by dyeing) than dolomite and encloses

137 the fluor-apatite (Fig. 4a). Fluor-apatite is brown in color and is observed in two forms: (1)

138 peloids dispersed in the matrix (Fig. 4b) and (2) microsphorite (authigeneic phosphatic micrite)
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139 scattered within the void spaces of the matrix. Quartz occurs as fine-grained accessory mineral

140 within allochems, and also fills the void and fracture spaces (Fig.4c). Lesser amounts of

141 muscovite, as fine scattered flakes, is present within the groundmass. The most important and

142 conspicuous characteristics of the phosphatic rocks are the presence of phosphatic peloids in the

143 form of fossil casts (Fig. 4d) displaying flowage features produced by the function of diagentic

144 pore waters (Fig. 4e). Pyrite (<3 %) is present as anhedral to euhedral dispersed and solitary

145 crystals within the matrix (Fig. 4f). Based upon microscopic examinations, the diagenetic

146 processes influenced the mineralogy and texture of the phosphatic rocks at two separate stages:

147 early and late diagenesis. Phosphatization of the pre-existing materials such as fossils (Fig. 4d) is

148 reckoned to be the typical effects of the early diagenetic processes on the phosphatic rocks. The

149 formation of post-fracturing quartz veinlets (Fig. 4c) and recrystallization of dolomites are

150 conceived to be the most important effects of the late diagenetic processes of the phosphatic

151 rocks.

152

153 4.2. Geochemisrty

154 The results of chemical analyses of the phosphatic rocks are listed in Table 1. According to

155 Table 1the total concentration values of REEs in the phosphatic samples which have a variation

156 range of 96.32-226.45 ppm, are less than that of the mean universal value (457 ppm) in apatite

157 crystals of phosphorites (Altschulet, 1980). The concentration values of LREEs (La-Nd), MREEs

158 (Sm-Ho), and HREEs (Er-Lu) show variation ranges of 46.19-164.37 , 23.50-44.12 , and 2.82-

159 11.78 ppm, respectively. The variation ranges of concentration values of Ba and Y are 197-380

160 and 41.2-106.5 ppm, respectively (Table 1). Geochemical parameters such as Ba/Sm, Ba/Nd,

161 La/Nd, and Y/Ho ratios in the phosphatic rocks have values within the range of 28.75-232.17,
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162 5.71-44.87, 1.17-1.50, and 33.80-71.08, respectively (Table 2). The distribution pattern of REEs

163 normalized to Post-Archean Australian Shale (PAAS) (Taylor and McLennann, 1985) indicate

164 the enrichment of MREEs relative to LREEs and HREEs (MREEs/LREEs = 2.26-3.08 and

165 MREEs/HREEs = 1.26-2.24), and also the occurrence of strong negative Ce anomalies and

166 slightly positive Eu anomalies in the phosphatic samples (Fig.5). Ce anomaly (Ce/Ce*) values

167 were calculated by using the following equation (Eq. 1):

168 Ce/Ce* = CeN / (0.5LaN + 0.5PrN) (Bau and Dulski, 1996) (1)

169

170 Furthermore, the anomaly values of Eu (Eu/Eu*), Pr (Pr/Pr*), and Y (Y/Y*) were quantitatively

171 calculated by using the following equations (Eqs. 2, 3, and 4):

172 Eu/Eu* = EuN / (SmN GdN)0.5 (Taylor and McLennann, 1985) (2)

173 Pr/Pr* = PrN/(0.5CeN + 0.5NdN) (Bau and Dulski, 1996) (3)

174 Y/Y* = 2YN/(DyN + HoN) (Fazio et al., 2007) (4)

175

176 Where N stands for normalized values of La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, and Y relative to

177 PAAS. The Eu/Eu* and Ce/Ce* values have ranges of 1.18-1.73 and 0.30-0.51, respectively

178 (Table 2). The Pr/Pr* and Y/Y* values have ranges of 1.04-1.37 and 1.15-2, respectively. The

179 total TOC of the phosphatic samples has a range of 0.56-3.87 % (average of 2.91%) ( Table 2).

180

181 5. Discussion

182 5.1. PAAS- normalized REEs patterns

183 Distribution pattern of REEs in sedimentary phosphatic rocks can be used as important

184 indicator for the determination of depositional conditions and physico-chemical characteristics of
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185 diagenetic environments (Zhu et al., 2014; Xin et al., 2016; Khan et al., 2016). Research on old

186 and modern phosphatic deposits demonstrated that distribution patterns of REEs normalized to

187 PAAS in phosphatic rocks can be categorized into two distinct groups: (1) seawater-like and (2)

188 hat-shaped (e.g. Jiang et al., 2007; Pi et al., 2013; Zhu et al., 2014; Xin et al., 2016). The hat-

189 shaped REEs pattern which is sometimes called bell-shaped REEs distribution is characterized

190 by enrichment of MREEs and depletion of HREEs whereas the seawater-like REEs pattern is

191 distinguished by enrichment of HREEs and negative Ce anomalies (Bau and Dulski, 1996; Zhu

192 et al., 2014).

193

194 In this study, the phosphatic samples display the hat-shaped REEs pattern (Fig. 5). The bivariate

195 diagram of (Sm/Yb)N-(Sm/Pr)N (Garnit et al., 2012) (Fig. 6a) indicates enrichment of MREEs

196 relative to LREES and HREEs during phosphatization processes in the Gorgan-Rasht Zone.

197 Similar patterns of sedimentary phosphatic deposits for the same period of time (Neoproterozoic-

198 Lower Cambrian) from different parts of the world reported also show the same pattern (Felitsyn

199 and Morad, 2002; Jiang et al., 2007; Zhu et al., 2014; Xin et al., 2016). The hat-shaped REEs

200 distribution pattern is peculiar to severely altered phosphorite (Lecuyer et al., 1998; Picard et al.,

201 2002). There is strong evidence for the occurrence of diagenetic alteration effects in the studied

202 phosphatic samples (e.g. Zhao et al., 2013; Muscente et al., 2014). Diagenetic alteration can

203 produce relatively high concentration of REEs in general, and accounts for the preferential

204 enrichment of MREEs within phosphatic rocks in particular (Shields and Stille, 2001). By using

205 the above premise, it is conceivable that the diagenetic effects occurred in the course of

206 phosphogenesis of rocks in the studied section. Furthermore, the hat-shaped REEs pattern

207 together with a strong negative Ce anomaly of the phosphatic samples indicate preferential
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208 incorporation of MREEs during prolonged exposure to seawaters (Koeppenkastrop and De

209 Carlo, 1992; Reynard et al., 1999; Auer et al., 2017).

210

211 5.2. Ce anomaly

212 Cerium anomaly can be used as an effective tracer in determining redox conditions of

213 depositional environment for sediments and sedimentary rocks (Xin et al., 2016; Khan et al.,

214 2016). Cerium anomalies (Ce/Ce*) in the phosphatic samples (Table 2) ranges from 0.30 to 0.51

215 (mean of 0.42) indicating negative anomalies. Since the values of Ce anomalies may become

216 overestimated due to the high concentration of La (Bau and Dulski, 1996) and/or to the artificial

217 calculations (Morad and Felitsyn, 2001), thus it is necessary before interpretation, that the

218 authenticity of this anomaly be examined by applying various geochemical techniques. In this

219 study, the bivariate plot of Pr/Pr*-Ce/Ce* (Bau and Dulski, 1996) was used to assess the degree

220 of La effect on Ce anomaly values (Fig. 5b). In this plot, five domains were defined as follows:

221 I: no La and Ce anomaly;

222 IIa: positive La anomaly and no Ce anomaly;

223 IIb: negative La anomaly and no Ce anomaly;

224 IIIa: positive Ce anomaly;

225 IIIb: negative Ce anomaly.

226

227 According to Figure 6b, most of the data points lie within the IIIb field (Ce/Ce*<0.95) thus

228 verifying the genuineness of the negative Ce anomaly values. Moreover, to determine the effects

229 of artificial calculations on Ce anomaly values, bivariate plot of (La/Sm)N-Ce/Ce* was used.

230 According to Morad and Felitsyn (2001), when there is a lack of correlation between the pairs
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231 (La/Sm)N-Ce/Ce* and the ratio of (La/Sm)N is less than 0.35, the obtained Ce anomalies were not

232 affected by artificial calculations. The (La/Sm)N values in the phosphatic samples have a range

233 of 0.77-1.11 which are greater than 0.35. The bivariate plot of (La/Sm)N-Ce/Ce* (Fig. 7a)

234 illustrates that there exist no significant positive correlation (r = 0.11) between the two

235 parameters. Therefore, a combination of the results obtained from the above two geochemical

236 techniques indicates that the Ce negative anomalies of the phosphatic samples delineates the real

237 redox conditions of the depositional environment of the phosphatic rocks. The negative Ce

238 anomalies indicate oxic condition for depositional environment of the phosphatic rocks.

239

240 In addition to analytic effects, diagenetic processes can also affect Ce anomaly values. The

241 effects of diagenetic processes on Ce anomalies can be evaluated by using a series of diagnostic

242 geochemical parameters. The negative correlation between pairs (Dy/Sm)N-Ce/Ce* and positive

243 correlation between pairs REEs-Ce/Ce* are two geochemical criteria for determining the effects

244 of diagenetic processes on Ce anomalies (Shields and Stille, 2001). The bivariate plot of

245 (Dy/Sm)N-Ce/Ce* illustrated a moderate negative correlation between Ce/Ce* and (Dy/Sm)N (r

246 = -0.69) (Fig. 7b), and also a strong positive correlation between REEs and Ce/Ce* (r = 0.95;

247 statistically significance level of 0.01) (Fig. 7c) among the phosphatic samples. These

248 correlations suggest that the diagenetic processes have played an important and effective

249 controlling role on variation of Ce anomaly values in these phosphatic rocks.

250

251 5.3. Eu anomaly

252 Having two different valencies (Eu2+ and Eu3+), Eu compared with other REEs tends to

253 generate Eu anomaly in natural environments (De Baar et al., 1985). Positive Eu anomalies
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254 reported from different phosphatic deposits indicate reducing and anoxic depositional

255 environment (Jiang et al., 2007; Xin et al., 2016). Some researchers believe that the occurrence

256 of positive Eu anomalies is connected to organic matters (Kidder et al., 2003). Besides

257 environmental conditions, the occurrence of positive Eu anomalies may occur due to an

258 analytical artifact. This takes place as a result of interference of high Ba concentration during

259 chemical analysis particularly when ICP-MS method is used (Jiang et al., 2007). Considering

260 the positive Eu anomaly (Eu/Eu*) values (1.34-1.73; mean of 1.40) for the phosphatic rocks

261 (Table 2) and using ICP-MS analytic method for REEs in this research, it is essential to verify

262 the genuineness of the positive Eu anomalies, and to make sure these anomalies are not

263 associated with analytical artifacts.

264 Recent investigations have shown that positive correlation between Eu/Eu* and ratios like

265 Ba/Sm and Ba/Nd are applicable geochemical parameters for evaluation of Ba analytical effect

266 on Eu anomaly values (Jiang et al., 2007; Ling et al., 2013). By noting to the negative

267 correlation between pairs Eu/Eu*-Ba/Sm (r = -0.25) (Fig. 7d) and Eu/Eu*-Ba/Nd (r = -0.30)

268 (Fig. 7e), the analytical effects on the positive Eu anomalies can be ruled out. Thus, these

269 anomalies strongly suggest reducing and anoxic depositional conditions for the phosphatic rocks.

270 The presence of organic matter and pyrite in the phosphatic samples also strongly advocates for

271 this conception. Comparison of Eu anomaly values in the studied samples with those of well-

272 known phosphatic deposits in the world shows that the phosphatic horizon of the Soltanieh

273 Formation in the Gorgan-Rasht Zone (north of Iran) are very similar to those in Abu Tarbur,

274 Egypt (Ismael, 2002), Gezhongwu, China (Chunhua and Ruzihong, 2005), Masrana and Kimoi,

275 India (Khan et al., 2016), Gafsa, Tunisia (Ounis et al., 2008), Yangtze Gorges, China (Xin et al.,

276 2016), and Sonrai, India (Khan et al., 2012). Moreover, Shields and stille (2001) show that later
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277 diagenetic processes can generate strong positive correlation between Eu and Ce anomalies. The

278 positive Eu anomalies and strong positive correlation between Eu/Eu* and Ce/Ce* (r = 0.88;

279 statistically significance level of 0.01) (Fig.7f), allow us to infer that Eu anomalies in the studied

280 phosphatic samples are a very suitable indicator for determining the reducing and anoxic nature

281 of the diagenetic fluids.

282 It seems that the occurrence of negative Ce anomaly and positive Eu anomaly are the result of

283 upwelling and mixing of organic-rich anoxic bottom seawaters with aerobic (oxic) shallow

284 seawaters before development of the phosphatic rocks in depositional basin.

285

286 5.4. Source of REEs and ratios of Y/Ho and Er/Nd

287 In sedimentary phosphatic rocks, REEs can be derived from different sources including

288 seawaters, terrigenous materials, and organic matters (Trappe, 1998; Zhu et al., 2014). The

289 typical hat-shaped REEs pattern indicates a detrital origin for these elements in the studied

290 phosphatic rocks. This interpretation can be further evaluated by Y/Ho ratio. Yttrium has an

291 ionic radius and charge analogous to Ho and Dy. Therefore, Y can be inserted between Ho and

292 Dy in distribution pattern of REEs (Bau, 1996). Although Ho has similar geochemical behavior

293 with Y, it can be removed from seawaters much (2 times) faster. This is connected with

294 difference in degree of stability of surficial complexes, and brings about notable superchondritic

295 marine ratio of Y/Ho (Bau, 1996; Nozaki et al., 1997). The Y/Ho values of ~28 and 60 are

296 characteristic of terrigenous and seawater origins for REEs, respectively (Bau, 1996; Bau and

297 Dulski, 1996; Nozaki et al., 1997; Webb and Kamber, 2000; Zhao et al., 2013). In this study,

298 the phosphatic rocks have Y/Ho values within the range of 24.45-33.38 (mean of 28.92)

299 indicating a terrigenous source for REEs. Moreover, the strong positive correlation between
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300 TOC and REEs (r = 0.87; statistically significance level of 0.01) (Fig. 8) indicates that besides

301 terrigenous source, organic matters also played a crucial role in providing REEs in the

302 phosphatic rocks.

303 The Value of Er/Nd ratio of the normal seawaters is ~0.27 (De Baar et al., 1988). The detrital

304 materials together with diagenetic processes can bring about preferential concentration of Nd

305 relative to Er, and hence reduce the Er/Nd value to less than 0.1 (German and Elderfield, 1990;

306 Bellanca et al., 1997). The values of Er/Nd ratio in the studied phosphatic rocks varies from 0.11

307 to 0.19 (mean of 0.14). These ratio values confirm the detrital origin of the REEs, and reveal the

308 effective role of diagentic processes in the distribution of Er and Nd in the studied phosphatic

309 rocks.

310

311 5.5. Y anomaly and other ratios of REEs

312 The Yttrium anomaly and La/Nd ratio are valuable indicators for estimating post-depositional

313 changes related to variations of compositions of circulating fluids (Fazio et al., 2007). Both

314 parameters are commonly influenced by redox variation of seawater environment (Zhang et al.,

315 1994; Bau et al., 1996), and their values decrease in sediments with increase in intensity of

316 diagenesis (Shields and Stille, 2001). In modern seawaters, the Y anomaly and La/Nd ratio have

317 ranges of 1.5-2.3 and 0.8-1.3, respectively (Shields and Stille, 2001). According to our results,

318 the values of Y/Y* and La/Nd ratios in the phosphatic samples have ranges of 1.17-1.59 and

319 0.75-1.20, respectively. The bivariate plot of La/Nd-Y/Y* (Fazio et al., 2007) (Fig. 9a) shows

320 that the values of both parameters in the phosphatic rocks are less than those of seawaters, and

321 also testifying to the progressive diagenetic processes during evolution of the phosphatic rocks

322 and influence on the distribution and concentration of REEs.

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323 The Yttrium anomaly and (La/Sm)N ratio are important geochemical indicators for

324 determining the role of weathering processes in development and evolution of sedimentary

325 phosphatic rocks (Chunhua and Ruizhong, 2005). Weathering can give rise to strong positive

326 correlation between Y/Y* and (La/Sm)N (Shields and Stille, 2001). Furthermore, laboratory

327 investigations showed that weathering processes are the effective agents in preferentially

328 leaching of MREEs relative to the rest of REEs in Phosphatic shales (Hannigan and Sholkovitz,

329 2001). In other words, LREEs and HREEs relative to MREEs become enriched in sedimentary

330 phosphatic rocks during weathering processes. The bivariate plot Y/Y*-(La/Sm)N (Fig. 9b)

331 indicates a weak positive correlation (r = 0.43) between Y and (La/Sm)N. In addition, the

332 distribution pattern of REEs normalized to PAAS indicates enrichment of MREEs relative to

333 LREEs and HREEs during phosphatogenesis in the samples in this section (see Fig. 5). In fact,

334 the weakly positive correlation along with the MREEs enrichment attests to the fact that

335 weathering processes did not play an important role in the distribution of REEs in these

336 phosphatic rocks.

337

338 5.6. La/Yb and La/Sm Characteristics

339 By comparing the REEs partition coefficients in apatite and water, various mechanisms

340 including adsorption and substitution can be suggested. Reynard et al. (1999) presented a

341 bivariate diagram (La/Yb)N-(La/Sm)N for the discrimination of different mechanisms leading to

342 incorporation of REEs into apatite crystal lattice (Fig. 10). Based upon this diagram, the

343 (La/Yb)N ratio is not affected during substitution processes but in case the adsorption mechanism

344 is dominant it shows an incremental trend. On the other hand, the value of (La/Sm)N normally

345 remains constant during adsorption but in the case of substitution this value decreases. The
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346 values of (La/Sm)N in the phosphatic samples have a range of 0.77-1.11 (Table 2) which is

347 comparable with the corresponding values of modern seawaters (0.79-1.66; Reynard et al.,

348 1999). The values of (La/Yb)N in the studied samples have a range of 0.83-2.02 (see Table 2)

349 which are greater than the corresponding values of the modern seawaters (0.20-0.50; Reynard et

350 al., 1999 ) (Fig.10). The values of (La/Yb)N ratio in the studied phosphatic samples relative to the

351 corresponding values of the modern seawaters may indicate the absorption of REEs by fluor-

352 apatite during diagenesis (Reynard et al., 1999). Moreover, the decrease of (La/Sm)N values

353 from 1.11 to 0.77 suggest that substitution of REEs in apatite did play a role during evolution of

354 the phosphatic rocks and it seems that both adsorption and substitution mechanisms had

355 significant role in concentration of REEs by fluor-apatite during diagenetic processes of the

356 phosphatic rocks.

357

358 6. Conclusions

359 The most important results obtained from the geochemical considerations of REEs in the

360 Lower Cambrian phosphatic deposit in the Gorgan-Rasht Zone (north of Iran) are as follows:

361 1- Geochemical parameters such as hat-shaped distribution pattern of REEs, ratios of Y/Ho and

362 Er/Nd, positive correlation between pairs of Ce/Ce*-Eu/Eu* and Ce/Ce*-REEs, and negative

363 correlation between Ce/Ce* and (Dy/Sm)N along with Y anomaly, ratios of La/Nd, (La/Sm)N,

364 and (La/Yb)N and enrichment of MREEs relative to LREEs and HREEs suggest the controlling

365 effective and role of diagenetic processes in the distribution and concentration of REEs in the

366 phosphatic rocks.

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367 2- The presence of pyrite along with organic materials indicates that development and evolution

368 of the phosphatic rocks took place by the activity of reducing diagentic fluids under anoxic

369 conditions.

370 3- Besides terrigenous origin for REEs, the organic matter also played an important role in

371 distribution and concentration of REEs.

372 4- The positive Eu and negative Ce anomalies record redox features of the diagenetic fluids, and

373 suggest upwelling and mixing of the organic-rich anoxic bottom waters with the aerobic (oxic)

374 shallow seawaters during phosphatogenesis processes in the depositional site.

375 5- The hat-shaped REEs pattern as well as strong negative Ce anomalies in the phosphatic rocks

376 suggests preferential absorption of MREEs during prolonged exposure to seawaters.

377

378 Acknowledgments

379 This work was fully supported financially by the Bureau of Deputy of Research and

380 Complementary Education of Urmia University. We would like to state our thanks and

381 appreciation to the authorities of this bureau. Our gratitude is further expressed to Dr. Damien

382 Delvaux, Prof. Abdulkader M. Abed, and an anonymous reviewer for reviewing our manuscript

383 and making critical comments and valuable suggestions.

384

385 References

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532 https://doi.org/10.1017/S001675681700022X.

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537

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539

540 Fig.1: Geologic map showing the divisions of structural zones of Iran (Nabavi, 1976) in which

541 the study area lies in the Gorgan-Rasht zone in the north of country.

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549

550

551 Fig.2: Geologic map of the study area in the Gorgan-Rasht zone in which the position of the

552 studied selective section is marked by asterisk.

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557

558

559

560 Fig.3: Stratigraphic column of the Soltanieh Formation in the studied section in the Gorgan-

561 Rasht zone. Shown in this column are also the positions of analyzed samples (filled circles)

562 collected from the phosphatic rocks.

563
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564

565 Fig.4: Photomicrographs of the studied phosphatic rocks. (a) Dyed (red color) calcite crystals as
566 dominant mineral phase in the phosphatic rocks (XPL). (b) Presence of fluor-apatite as ploid
567 (XPL). (c) Presence of quartz veinlet within the phosphatic rocks (XPL). (d) Phosphatic peloids
568 in the form of fossil casts (XPL). (e) Peloids showing fluidal feature generated by the influence
569 of pore waters during diagenesis (PPL). (f) Three forms of pyrite crystals within the phosphatic
570 rocks: anhedral (Py1), subhedral (Py2), and euhedral (Py3) (reflective light).
571
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572
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576 Fig.5: Distribution pattern of REEs normalized to PAAS (Taylor and McLennan, 1985) in the

577 phosphatic rocks of the studied section.

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590 Fig.6: (a) Bivariate plot of (Sm/Yb)N - (Sm/Pr)N (Garnit et al., 2012). According to this diagram

591 the majority of the data points lie within the MREEs-enriched domain. (b) Position of the data

592 points in bivariate plot of Pr/Pr*-Ce/Ce* (Bau and Dulski, 1996). In this diagram, the

593 occurrence of Ce anomaly is assessed by enrichment of La in five domains which are as follows:

594 I: no La and Ce anomaly; IIa: positive La anomaly and no Ce anomaly; IIb: negative La anomaly

595 and no Ce anomaly; IIIa: positive Ce anomaly; and IIIb: negative Ce anomaly.

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604
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606 Fig.7: Bivariate plots of (a) Ce/Ce*-(La/Sm)N, (b) Ce/Ce*-(Dy/Sm)N , (c) Ce/Ce*-REEs, (d)

607 Eu/Eu*-Ba/Sm, (e) Eu/Eu*-Ba/Nd, and (f) Eu/Eu*-Ce/Ce* in the phosphatic rocks of the studied

608 section.

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617 Fig.8: Bivariate plot of REEs-TOC for the phosphatic rocks of the studied section.

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632 Fig.9: Bivariate plots of (a) Y/Y*-(La/Sm)N, (b) Y/Y*-La/Nd for the phosphatic rocks of the

633 studied section within the Gorgan-Rasht zone. The seawater field in Fig.8b is from Fazio et al.

634 (2007).

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647

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650 Fig.10: Bivariate plot of (La/Yb)N-(La/Sm)N (Reynard et al., 1999) in which the positions of data

651 points of the studied phosphatic samples are shown.

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661 Table 1 Concentration values of rare earth and certain trace elements in the phosphatic samples

662 analyzed by using ICP-ES and ICP-MS methods in the studied section.

663
Detection
R-1 R-2 R-3 R-4 R-5 R-6 R-7 R-8 R-9 R-10 R-11 R-12 R-13 R-14 R-15 R-16
limit

La (ppm) 0.1 26.8 46.2 37.2 54.2 59.9 59.4 37.7 19.4 53.8 47.7 39.7 35.2 26.6 59.2 35.9 47.6

Ce 0.1 16.4 35.3 29.1 51.6 55.2 60.8 30.2 10.8 46.4 42.7 34.1 22.6 17.3 52.3 26.5 39.2

Pr 0.02 4.74 7.38 5.68 9.88 8.88 10.84 6.52 3.12 9.15 8.39 7.07 5.72 4.79 9.37 6.22 8.36

Nd 0.3 22.9 36.8 27.2 45.7 42.3 39.6 26.7 12.87 42.9 40.3 33.3 26.9 19.4 43.5 28.2 40.3

Sm 0.05 5.07 7.12 5.42 7.75 9.01 7.78 5.16 3.41 8.24 7.79 6.68 5.51 4.23 8.51 5.87 7.76

Eu 0.02 1.11 2.04 1.65 2.62 3.05 3.25 1.51 0.85 2.51 2.42 2.09 1.34 1.15 3.02 1.51 2.32

Gd 0.05 3.47 6.85 6.15 7.88 8.97 9.71 5.71 3.01 8.71 8.14 6.51 5.21 3.99 8.45 5.49 8.51

Tb 0.01 5.12 8.22 8.03 9.49 8.43 11.52 8.88 3.42 8.41 8.31 9.03 9.33 6.64 9.35 6.92 8.29

Dy 0.05 7.74 9.78 8.77 10.47 11.33 9.55 7.38 5.84 10.56 9.78 7.78 7.95 5.79 9.79 7.56 9.74

Ho 0.02 0.99 2.12 1.85 2.37 2.39 2.31 1.37 0.65 2.21 2.04 1.43 1.41 1.13 1.97 1.35 2.05

Er 0.03 2.51 5.71 5.23 6.75 6.47 7.01 3.82 1.78 5.87 5.52 3.93 3.89 3.02 5.31 3.75 5.59

Tm 0.01 0.31 0.76 0.73 0.85 0.86 0.81 0.55 0.24 0.78 0.72 0.51 0.52 0.39 0.67 0.48 0.74

Yb 0.05 1.05 3.52 3.33 3.92 4.17 3.58 2.01 0.71 3.61 3.27 1.98 2.15 1.72 3.01 2.01 3.25

Lu 0.01 0.11 0.25 0.24 0.26 0.28 0.29 0.19 0.09 0.27 0.24 0.15 0.16 0.17 0.21 0.16 0.24

Ba 1 197 380 315 261 259 568 1198 432 226 338 246 262 243 296 239 338

Y 0.1 26.8 56.3 50.9 75.3 70.2 65.4 33.5 21.7 72.3 59.8 45.2 40.1 28.9 55.4 39.6 59.8

TOC - 2.28 2.36 2.91 4.11 3.16 4.81 3.12 0.56 4.47 3.87 2.11 3.25 1.18 3.11 2.14 3.16

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675 Table 2 Concentration values of some geochemical parameters calculated for the phosphatic

676 samples of the studied section.

677

R-1 R-2 R-3 R-4 R-5 R-6 R-7 R-8 R-9 R-10 R-11 R-12 R-13 R-14 R-15 R-16

REELa-Lu 98.32 172.05 140.58 213.74 221.24 226.45 137.70 66.19 203.42 187.32 154.26 127.89 96.32 214.66 131.92 183.95

LREELa-Nd 70.84 125.68 99.18 161.38 166.28 170.64 101.12 46.19 152.25 139.09 114.17 90.42 68.09 164.37 96.82 135.46

MREESm-Ho 23.50 36.13 31.87 40.58 43.18 44.12 30.01 17.18 40.64 38.48 33.52 30.75 22.93 41.09 28.7 38.67

HREEEr-Lu 3.98 10.24 9.53 11.78 11.78 11.69 6.57 2.82 10.53 9.75 6.57 6.72 5.30 9.20 6.40 9.82

(MREEs/LREEs)N 3.00 2.60 2.91 2.28 2.35 2.34 2.69 3.37 2.42 2.50 2.66 3.08 3.05 2.26 2.68 2.58

(MREEs/HREEs)N 2.17 1.29 1.23 1.26 1.35 1.38 1.68 2.24 1.42 1.45 1.87 1.68 1.59 1.64 1.65 1.45

Eu/Eu* 1.24 1.37 1.33 1.57 1.59 1.73 1.30 1.25 1.39 1.42 1.49 1.18 1.32 1.67 1.25 1.33

Ce/Ce* 0.32 0.41 0.43 0.50 0.51 0.53 0.42 0.30 0.46 0.47 0.45 0.35 0.34 0.48 0.39 0.43

Pr/Pr* 1.22 1.09 1.10 1.12 1.04 1.27 1.27 1.37 1.12 1.10 1.14 1.20 1.37 1.09 1.21 1.13

Y/Y* 0.75 0.99 1.01 1.20 1.08 1.11 0.84 0.84 1.19 1.07 1.08 0.95 0.90 1.01 0.98 1.07

(La/Sm)N 0.77 0.94 1.00 1.02 0.97 1.11 1.06 0.83 0.95 0.89 0.86 0.93 0.91 1.01 0.89 0.89

(La/Yb)N 1.89 0.97 0.83 1.02 1.06 1.23 1.39 2.02 1.10 1.08 1.48 1.21 1.14 1.45 1.32 1.08

(Dy/Sm)N 1.82 1.64 1.93 1.61 1.50 1.46 1.70 2.04 1.53 1.49 1.39 1.72 1.63 1.37 1.53 1.49

(Sm/Pr)N 1.73 1.56 1.54 1.27 1.64 1.16 1.28 1.76 1.45 1.50 1.52 1.55 1.42 1.46 1.52 1.50

(Sm/Yb)N 2.46 1.03 0.83 1.01 1.10 1.11 1.31 2.45 1.16 1.22 1.72 1.31 1.25 1.44 1.49 1.22

Ba/Sm 38.86 53.37 58.12 33.68 28.75 73.01 232.17 126.69 27.43 43.39 36.83 47.55 57.45 34.78 40.72 43.56

Ba/Nd 8.60 10.33 11.58 5.71 6.12 14.34 44.87 33.57 5.27 8.39 7.39 9.74 12.53 6.80 8.48 8.39

La/Nd 1.17 1.26 1.37 1.19 1.42 1.50 1.41 1.51 1.25 1.18 1.19 1.31 1.37 1.36 1.27 1.18

Y/Ho 27.07 26.56 27.51 31.77 29.37 28.31 24.45 33.38 32.71 29.31 31.61 28.44 25.58 28.12 29.33 29.17

Er/Nd 0.11 0.16 0.19 0.15 0.15 0.18 0.14 0.14 0.14 0.14 0.12 0.14 0.16 0.12 0.13 0.14

678

679

680

681

682
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1. The phosphatic rocks in northern Iran were widely developed within the Soltanieh Formation.

2. Diagenesis has played the important role in distribution of REEs in the phosphatic.

3. Ce and Eu anomalies are valuable indicators for determining redox conditions of diagenetic

fluids.

4. Terrigenous materials and organic matters were the principal source of REEs in the phosphatic

rocks.