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Identification, extraction of microplastics from edible salts and its removal

from contaminated seawater

Naveenkumar Ashok Yaranal, Senthilmurugan Subbiah,

Kaustubha Mohanty

PII: S2352-1864(20)31553-4
DOI: https://doi.org/10.1016/j.eti.2020.101253
Reference: ETI 101253

To appear in: Environmental Technology & Innovation

Received date : 2 June 2020

Revised date : 27 October 2020
Accepted date : 9 November 2020

Please cite this article as: N.A. Yaranal, S. Subbiah and K. Mohanty, Identification, extraction of
microplastics from edible salts and its removal from contaminated seawater. Environmental
Technology & Innovation (2020), doi: https://doi.org/10.1016/j.eti.2020.101253.

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1 Identification, Extraction of Microplastics from Edible Salts and its

2 removal from Contaminated Seawater
3 Naveenkumar Ashok Yaranal, Senthilmurugan Subbiah*, Kaustubha Mohanty*

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4 Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati - 781039, India.

5 Abstract

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6 Microplastics (MPs) present in edible salts may create a potential health hazard for humans.

7 The occurrence of MPs in edible salts and their extraction procedure is limited. In this work,

8 we have developed a facile and cost-effective protocol for the extraction and separation of MPs

9 from the edible salt sample. The visual assessment was performed to identify the shape, size,
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10 number, and color of microplastic particles using light and fluorescence microscopy. The

11 composition of the sample was analyzed by micro-Raman spectroscopy. A wide range of MPs

12 were found: 1400 ~ 1900 particles/kg in refined sea salt, 1900 ~ 2300/kg in unrefined sea salts,
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13 and 200 ~ 400 /kg in rock salts. A relatively high number of MPs were found in sea salts rather

14 than rock salts. Sheet type MPs with size 1 ~ 4 m were observed in rock salts. The most

15 common MPs were polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET),
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16 nylon, and polystyrene (PS). Further, MPs were effectively removed from synthetic seawater

17 with the help of a microfiltration membrane, which has the capability of arresting the transfer

18 of microplastic particles into edible salts. Therefore the use of MF/UF pretreated brine from

19 seawater desalination plant can be explored for MPs sea salt production at low cost.

20
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21 Keywords: Microplastics; sea salt; rock salt; marine pollution; microfiltration.

22

23 *Corresponding author Email address: senthilmurugan@iitg.ac.in (senthilmurugan subbiah),

24 kmohanty@iitg.ac.in (Kaustubha Mohanty)

25

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26 1. Introduction
27
28 Plastics are the most dominant solid debris in the marine environment, which contributes about

29 60 % to 80% in total. Due to improper disposal, a vast amount of plastics gets accumulated in

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30 the aquatic environment. Recent research reported that every year nearly 4.8 to 12.7 MMT of

31 plastic waste ends up in the oceans [1,2]. Another study also estimated that nearly 1.15 – 2.41

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32 MMT of plastic reaches the marine ecosystem through the river every year [3].

33

34 Microplastics (MPs) are plastic particles with less than 5 mm in size [4–6]. MPs are formed

35 due to mechanical action and the degradation of larger plastic wastes, both in aquatic and
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36 terrestrial environments [7]. Particularly MPs of size < 5 mm plastic particles or fragments are

37 accumulated in the water bodies as primary MPs [8–10]. Plastic bottles and carry bags hold a

38 significant share in plastic waste, and their degradation generates micro and nanoparticles,
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39 which further contribute as secondary MPs [11–14].

40

41 The presence of MPs in water can cause various health and environmental issues [15]. Recent

42 research focussing on MPs has brought attention to the dangers posed by MPs in the aquatic
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43 environment [16–18]. Numerous species of fish and invertebrates were found to ingest micro

44 and macro plastics [19]. Moreover, 800 species are known to be affected by marine litter [20–

45 24].

46
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47 Various reports from around the world suggested that MPs can reach humans through salts,

48 food products (fish, shellfish), and water [17,25–27]. Plastics are prepared by adding several

49 chemicals such as Bisphenol A, phthalates, and phenol, which are categorized under Endocrine

50 Disrupting Chemicals (EDCs) and were found in breast milk, human blood, tissue sample, and

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51 urine [20]. These affect the human reproductive and immune system and also increase the

52 incidence of cancer [28–30].

53

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54 Various authors reported the presence of MPs in edible salts. According to Rist et al. (2018)

55 and Iñiguez et al. (2017), the estimated consumption of MPs through salt was 37 ~ 1000 and

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56 510 particles per year respectively, which pose a higher risk to the human health. India is the

57 third-largest producer of sea salt, and the presence of these plastic particles in salt is mainly

58 due to plastic particle contamination in seawater [7,31–33], and some MPs may have reached

59 during salt production through airborne [16,31,34]. According to the literature, Karami et al.,

60
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(2017) and Iñiguez et al., (2017) did not find any significant contribution from the packing

61 material. Till now, much consideration has been given to their sources, distributions,

62 estimation, and toxic effects. However, necessary action should also be taken to remove these

63 MPs from the polluted seawater. Globally this is a significant problem as well as a challenge
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64 to remove MPs from contaminated seawater before salt production.

65

66 In the present study, a cost-effective and straight forward protocol was adopted to identify a
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67 huge number of MPs in the edible salts. The counting of MPs was done using optical and

68 fluorescence microscope. Individual MP composition was analyzed by micro-Raman

69 spectroscopy. Although the seawater is pretreated by microfiltration process for desalination

70 application for removal of unwanted particles, and best of our knowledge it’s MPs removal
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71 efficiency is not reported yet in literature. Herein, we have reported for the first time, the

72 removal efficiency of MPs from synthetic seawater using hollow fiber microfiltration (HF-MF)

73 membranes. Such that the viability for production of MPs free sea salt by using MF/UF treated

74 brine of the desalination plant can be explored and that provide dual benefit such as effective

75 brine management and production of lowcost MPs free sea salt.

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76

77 2. Materials and Methods

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78 2.1. Materials

79 For the present study, twelve different commercial salts (rock and sea salts) sold in Indian

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80 markets were chosen. Details of the salts such as source, type, and origin are given in Table 1.

81 Hydrogen peroxide (H2O2, 30%), sodium iodide (NaI), Ion chromatography cation multi-

82 element standard VII and anion multi-element standard were purchased from Merck Life

83 Science Pvt. Ltd, Mumbai, India. Nile red dye was procured from HI-Media Laboratories Pvt.

84

85
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Ltd, Mumbai, India. Nylon filter paper (pore size 0.2 µm, dia 25 mm) was purchased from

Axiva Sichem Pvt. Ltd and polycarbonate (PCTE) filter paper (pore size 0.2 µm, dia 25 mm)

86 was purchased from Sterlitech Corporation, USA. MPs removal was carried out by

87 polypropylene (PP) based HF-MF membranes. The HF membrane contains 2200 fibers, with
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88 inner diameter 0.35 mm, outer diameter 0.5 mm and length 0.38 m. The total membrane surface

89 area was 2.64 m2. The HF membrane was procured from HI-TECH Sweet Water Technologies

90 Pvt. Ltd., Bangalore, India.

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91 2.2. Extraction of microplastics from edible salts

92 Initially, 200 g of salt was taken in a 500 mL conical flask. 100 mL of filtered H2O2 was then

93 added to the beaker for the digestion of organic compounds. For each brand of salt, three such
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94 replicates were made, and these bottles were covered and kept in an incubator shaker (Jeio

95 Tech, Model No.ISS-3075R, Korea). The samples were agitated at 100 rpm for 24 h at 65 °C

96 and followed by 48 h at 30 °C. After digestion, deionized water (800 mL) was added to each

97 sample, and the samples were stirred and left for 24 h to dissolve salts. Further, the solution

98 was filtered using vacuum filtration with PCTE/nylon filter paper. During filtration, if there is

99 no cake layer deposition on the surface of the filter paper, then MP characterization can be

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100 done directly. In case of the formation of a cake layer that hinders the analysis of MP (presence

101 of impurities such as organic materials, sand, and mineral particles in the salt), the following

102 step can be incorporated. The solution was transferred to a separating funnel and allowed the

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103 particles to settle for 24 h. It was seen that due to density difference, the low-density MPs

104 moved to the top side and high-density MPs, minerals, and undissolved impurities stay at the

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105 bottom of the separating funnel. The supernatant salt solution was then transferred and filtered

106 through filter paper, and the remaining solution left in the bottom was centrifuged at 5000 rpm.

107 The centrifuged bottom solution was mixed with 4.4 M NaI solution (approximate density is

108 1.8 g/mL) to separate the high-density MPs (> 95% recovery observed) [12,35]. The

109
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supernatant was then collected and filtered. The filtered membrane was dried at 40 °C for 12 h

110 and then characterized. Flowchart for the MPs extraction from salts is shown in Fig. 1.

111 Experiments were conducted in laminar flow to avoid any airborne. Throughout the

112 experiment, no plasticware was used, and special care was taken to prevent contamination
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113 during the whole analysis as much as possible.

114 2.3. Separation of MPs by microfiltration membrane

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115 Removal of MPs was carried out using the PP-HF-MF membrane. The detailed specification

116 of PP-HF-MF membrane is reported in the author’s previous work [29,36]. The flowsheet of

117 the MF membrane set-up is shown in Fig. 2. The feed solution (synthetic seawater) was

118 prepared by dissolving edible salt (highest MPs contained salt) in 50 L deionized water (feed
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119 concentration maintained at ~ 35 g/L). The process was performed at room temperature, and

120 the feed solution was first passed to the tank. A pump was used to maintain the feed pressure

121 at 3 psig, which was connected to the HF-MF membrane through a control valve (CV1) in

122 cross-flow mode operation. The pump speed controller and control valve (CV2) was used to

123 adjust the feed flow rate and pressure, respectively. The permeate from the MF setup was

124 collected in the permeate tank, and the flow rate was measured using a flow meter (Ascorp,

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125 intelligent flow totalizer). After 50 L of permeate collection, membranes were backwashed

126 with deionized water for 2 min to prevent fouling, and the backwashed water was collected

127 from the reject side (Fig. 2) [37]. Experiments were repeated to check the membrane

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128 performance (flux and fouling) and MPs removal. The collected permeate solution was filtered

129 through PCTE filter paper using a vacuum filtration setup. The membranes and filter paper

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130 were further characterized using a microscope, FESEM and micro-Raman spectroscopy.

131
132 2.4. Light and fluorescence microscope

133 Identification and counting of MPs were done with optical (light) and fluorescence microscope

134
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(Make: Carl Zeiss Model: Axio Scope.A1, Germany). Images were obtained with 10x, 20x,

135 50x and 100x lenses. According to their physical features, visual estimation of MPs were

136 carried out to identify their shape, size, and color. Most of the MPs were white and transparent,

137 which was difficult to identify them visually [38]. Nile red (NR) dye readily adsorbs onto the
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138 MPs and makes them fluorescent when irradiated under UV/Blue/Red/Greenlight [38–40]. The

139 NR stock solution was prepared by using acetone (50 mg/L) and store at 4°C in an amber bottle.

140 The working solution (0.5 mg/L) was prepared by diluting the stock NR with n-hexane. By
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141 using 200 µL of working solution of NR, the extracted MPs were stained, and excess dye was

142 washed with 200 µL of n-hexane and observed under a fluorescent microscope after air-dried.

143 2.5. Raman spectroscopy

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144 The compositional study of MPs was done with micro-Raman spectroscopy (Make Horiba).

145 micro-Raman spectroscope was attached with a 20x and 100x objective lens (NA=0.55), and

146 Raman laser of 532 nm and 633 nm (5 mW; grating of 1800 lines/mm) with adjustable laser

147 power. Spectra were scanned for the range of 400 cm-1 – 3500 cm-1 with an acquisition and

148 accumulation time of 10 s and 2 s, respectively. The polymers were identified from the raw

149 Raman spectra and processed using Bio-Rad KnowItAll software.

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150 2.6. Field emission scanning electron microscope (FESEM)

151 The membrane morphology and composition (before the experiment and after the experiment)

152 were characterized by FESEM (Sigma 300, Zeiss) attached with an energy dispersive x-ray

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153 spectrometer (EDS). The MF membrane samples were vacuum-dried at 50 °C for 24 h and

154 sputter-coated with a thin gold layer for conduction. Images were obtained in Inlens mode at

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155 different magnification with an acceleration voltage of 3/5 kV.

156 2.7. Ion chromatography

157 The salt solution composition (anion and cation concentrations) was determined using ion

158 chromatography (925 Eco IC, Metrohm) with a conductivity detector attached with Metrohm

159
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A Supp 5-250/4.0 and Metrosep C 6-150/4.0 analytical columns.

160 3. Results and Discussion

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161 3.1. Identification of MPs in salt samples

162 In the present study, we have identified the MPs in twelve Indian edible salt brands. A variety

163 of MPs with varying shape, color, size and polymer types were found in all salt brands, which
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164 are shown in Fig. 3. Microplastic size ranging from ≥ 20 µm to ≤ 5 mm were found. White and

165 transparent MPs visual identification was carried out with the fluorescence microscope using

166 NR dye (Maes et al., 2017; Shim et al., 2016), as shown in Fig. 3b and 3c). Table 1 shows the

167 origin, source and number of MPs present in the salt samples. A high count of MPs were
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168 observed in IN-8 (1832 ± 40 particles/kg) and fewer counts in IN-11 (275 ± 25 particles/kg)

169 salt samples. Unrefined (coarse) sea salts (IN-8 and IN-9) contained a large number of MPs

170 with bigger particle size when compared to refined salts. IN-10, IN-11, and IN-12 are refined

171 rock salts which showed more of flat sheet MPs.

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172 3.2. Classification of microplastics

173 In terms of shapes, fragment type MPs were abundant in all brands of salts, with an average of

174 44%, followed by fibers 39%, film/sheet 13%, and pellet 4%. The distribution of microplastic

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175 particles in terms of colors was in the order of white (20%), transparent (18%), blue (11%), red

176 (9%), green (8%), brown (8%), black (7%), purple (6%), pink (5%), orange (4%), yellow (2%)

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177 and grey (2%). The percentage of the MPs in the size ranges of 10 - 100 µm, 0.1-1 mm, 1-2

178 mm, 2-3 mm, 3-4 mm, and 4-5 mm are 38%, 32%, 17%, 9%, 3%, and 1% respectively as

179 shown in Fig. 4. It was observed that in all salt samples, white and transparent color MPs were

180 abundant, and more than half of the MPs were in the range of 10 µm to 1 mm size.
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181 3.3. Raman spectroscopy analysis

182 A total of 36 samples, including replicates, were verified through µ-Raman spectroscopy. 50

183 MPs of each salt samples were taken and analyzed. The µ-Raman spectroscopy results of the
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184 MPs are shown in Fig. 5. Overall, 60% of particles were identified as synthetic polymers, 14%

185 particles were unidentified because of their unclear spectra, 19% particles matched with color

186 pigments which were used in the plastic production, and about 7% matched with silicate
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187 mineral particles. Major polymers such as PE, PP, PET, Nylon, PS and polyvinyl chloride

188 (PVC) were found. The average composition of the MPs in sea salts was PE (26%) > PP (20%)

189 > PET (20%) >PS (10%) > Nylon (15%), and > PVC (4%). Whereas, in rock salts it was PP

190 > (41%) PET > (37%) PE > ( 15%) and PVC > (3%). The other polymers were rarely found
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191 and had an average contribution of about < 10%. Additionally, the obtained spectra were also

192 compared with the earlier report [41,42]. A comparison of the average profiles of MPs in Indian

193 edible salts based on color, shape, size, and polymers are analyzed (Fig. S1).

194 Along with polymer, pigmented particles were also identified (Fig. S2). Pigments spectra

195 interference with polymer spectra hindered the identification of MPs [43] [31]. Furthermore,

196 raw Raman spectra was hard to analyze, as polymers underwent a different type of degradation

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197 and biofilm formation [41]. Compositional characteristics of the MPs have been done with -

198 Raman spectroscopy, which can identify  20 m MPs particles compared to FTIR [44]. PE,

199 PP, and PET were the predominant MPs in the salt samples, which was reliable with reports

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200 on their widespread distribution in the marine environment [43]. Almost 20% of the isolated

201 particles were identified as color pigments (Irgalite blue, indigo, burnt umber, and mortoperm

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202 blue) [41,45]

203 3.4. Separation of microplastics using HF-MF membrane

204 A simple micro-filtration technique was used for the removal of MPs from synthetic seawater.

205 For the experimental purpose, we have selected unrefined IN8 (1.75 kg) salt, which was

206
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dissolved in 50 L distilled water to produce synthetic seawater. The prepared feed solution (5

207 L) was filtered through nylon filter paper and observed under the microscope, and the images

208 are shown in Fig. 6a, which contains approximately 403 MPs per 5 L (~ 2300 MPs/kg). The
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209 synthetic seawater was passed through the HF-MF setup maintained at 3 psig pressure.

210 Permeate collected was passed through a nylon filter and observed in the microscope. The

211 result is shown in Fig. 6b. Varying from 0-3 numbers and size less than 10 m fibers were
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212 observed, which is maybe due to airborne contamination (Fig. S3). Pure water permeability

213 after the experiment was slightly reduced from 66. 5 to 65.3 LPH at 3 psig pressure due to the

214 deposition of the foreign particles over the membrane, and the permeate flow rate was also

215 continuously decreased with respect to time [29,37]. To avoid fouling and to scale on the
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216 membrane surface, the membrane was backwashed for 2 min after every 50 L permeate

217 collection. Permeate flow rate and membrane life increases with membrane backwashing.

218 3.5. Ion Chromatography (IC)

219 When synthetic seawater was passed through the HF-MF membrane, the permeate collected

220 was analyzed using IC. Sample solutions were prefiltered through a 0.2 μm membrane filter

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221 and diluted for the analysis (200x and 500x). It is widely accepted that apart from the prevailing

222 concentration of NaCl, saltwater also contains trace amounts of calcium, potassium, and

223 magnesium salts. These salts are either chlorides or sulphates and constitute about 5%-10%.

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224 The standard solutions of both anions and cations were used for making the calibration curve,

225 and the linearity of the calibration graph was in the concentration range of 0.1 to 10 mg/L.

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226 Prepared synthetic feed solution contained Na+ and Cl- concentration of 11.22 g/L and 20.88

227 g/L, respectively. When the feed is passed through the HF-MF membrane, the feed

228 concentration at the permeate side decreased initially, however, after 15 minutes, the feed

229 concentration becomes equal to the permeate concentration (Fig. S4)

230 3.6. FESEM and EDX

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231 The surface morphology of the virgin and experimented membranes were evaluated by

232 FESEM. FESEM images clearly show that the membrane is porous at the inner and outer
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233 surface. The membrane was in excellent condition even after backwashing(Fig. S5).

234 Furthermore, the Energy-dispersive spectra show that there was no deposition of salts over the

235 membrane (Fig. S6).

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236 3.7. Discussion

237 Various studies reported different methods to extract MPs from edible salts. However, the

238 efficiency and cost were not up to the mark [43]. Mostly, the loss of MPs was observed in the

239 centrifugation step [1]. In the present study, we have extracted more than 95% of MPs from
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240 the solution by density separation with the addition of NaI followed by centrifugation. The

241 number of MPs in sea salt and rock salt was 1291 ± 35 - 1832 ± 40 particles/kg, and 275 ± 25

242 - 308 ± 24 particles/kg respectively. The number of MPs in sea salts is higher (approximately

243 five times) than the rock salts due to its extensive distribution of anthropogenic MPs in the

244 marine environment [46]. The majority of the particles were less than 1000 m in size as

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245 similarly observed by Yang et al. (2015). We also estimated that the consumption of MPs

246 through Indian sea salts is about 2700 - 4200 particles per year and the same for rock salts was

247 nearly 520 - 760 particles per year. Further, the health effects due to the ingestion of MPs on

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248 humans were reported extensively [17,20,25,47]. Health issues may arise due to the following

249 ways: i) ingest of plastic particles, ii) leaching of plastic additives to the bloodstream, and iii)

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250 desorption of the absorbed persistent organic pollutants (POPs) and biological pathogens on

251 plastic particles [19,48–50].

252 The present results confirmed the occurrence of MPs in edible salts and are in line with the

253 earlier reports from various parts of the world as compared in Table 2. Edible salt is obtained

254
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in 3 different ways: solar evaporation, mining of rock salts, and well brines. Almost

255 everywhere, the harvesting of salt from seawater is carried out with solar evaporation, which

256 gives 99% NaCl [51]. Processing of salt can be divided into two approaches i) coarse salt and

257 ii) fine salt. (i) saltwater pumped to the artificially created ponds and evaporated up to its
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258 saturation point in open basins. Impurities present in the brine are drained off. The concentrated

259 brine is crystalized, which is then gathered by mechanical harvesting machines [52,53]. Coarse

260 salts can be further packed for distributions; (ii) to increase the quality of salt, coarse/crude salt
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261 is washed by a highly saturated brine solution to remove suspended solids and again dissolved

262 in water to remove impurities which are trapped inside the salt crystals (Mg and Ca compounds

263 are removed by the chemical-physical process to get 99.6 % purity) [54]. The cleaned salt is

264 mixed with a known quantity of iodine, then crystallized to produce fine salt particle for end-
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265 use. MPs can be entirely removed by adopting a microfiltration method either in the first

266 approach, before pumping the saltwater to the ponds or in the second approach when salt

267 dissolves in water. This method is capable of eliminating MPs having a size greater than 10

268 m from the saltwater. The study reveals that PP-MF membranes can be used to remove MPs

269 based on its low cost, high packing density, pre-existing configuration, and manufacturers.

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270 In advanced membrane-based desalination process, the feed seawater is pretreated by MF/UF

271 membrane to remove unwanted particle that can damage the reverse osmosis (RO) membrane.

272 In the RO process, the pretreated seawater is further concentrated as brine by separating water

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273 from pretreated seawater. Presently the concentrated seawater is being discharged back into

274 deep sea for effective management of brine without affecting the marine ecosystem. Therefore

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275 the use of desalination plant brine for sea salt production may enable dual benefit (i) effective

276 brine management by minimizing capital and operating expenditure of brine disposal at deep

277 sea. (ii) MPs free salt production using pretreated brine. However, one has to evaluate the

278 detailed health impact due to fouling resistance chemical such as scale inhibitors or

279
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antiscalants, which is added in the membrane desalination process to reduce the membrane

280 fouling rate.

281 Conclusion
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282 In the current study, we have successfully developed a facile and cost-effective methodology

283 to extract the MPs from the salt samples. More than 95% of MPs were isolated from the salts

284 samples. White and transparent MPs visual identification was made easy with the NR dye. A
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285 total of 99.3% of MPs were successfully removed from the synthetic seawater by using a

286 hollow fiber membrane. The IC result showed that there is no reduction in salt concentration.

287 Hence, MF membranes can be used to remove anthropogenic contaminants present in seawater.

288 To the best of our knowledge, this is the first report where we successfully removed > 10 m
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289 MPs from sea derived salts, which can be further used in the large scale industry. In another

290 aspect, the brine generated from seawater desalination plant can be used to produce low-cost

291 MPs free sea salt, wherein health impact for scale inhibitors or antiscalants added during the

292 desalination process has to be evaluated.

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293 ACKNOWLEDGEMENTS

294 The authors are thankful to the Central Instrument Facility and Center for Nanotechnology,

295 Indian Institute of Technology, Guwahati (IITG), India, for providing all analytical facilities.

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296

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462
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463
464
465
466
467
468
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469
470
471
472
473
474
475
476
Jou

477
478
479
480
481
482
483
484
485
486
487

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488
489
490
491
492
493

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494
495
496
497

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498
499
500
501
502 Table 1. Microplastics in edible salts.
503
504
Samp
le ID
Source Type
salt
of Produced/
Procured
re- Cake forms
on
membrane
the
No
particles/kg
of

salt: Optical
No
505
particles/kg
salts:
of

506
microscope Florescence
microscope
507
IN-1 Sea salt Refined Gujarat, India No 1326 ± 30 1525±25
IN 2 Sea salt Refined Gujarat, India No 1291 ± 35 1464±30508
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IN 3 Sea salt Refined Gujarat, India Yes 1428 ± 30 1634±20
IN 4 Sea salt Refined Gujarat, India No 1549 ± 25 1755±18509
IN 5 Sea salt Refined Gujarat, India Yes 1604 ± 20 1878±40
IN 6 Sea salt Refined Gujarat, India Yes 1544 ± 40 1736±25
510
IN 7 Sea salt Refined Gujarat, India Yes 1540 ± 35 1865±22511
IN 8 Sea salt Unrefined Tamil Nadu, Yes 1832 ± 40 2248±36
India 512
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IN 9 Sea salt Unrefined Tamil Nadu, Yes 1760 ± 35 1910±15

India 513
IN 10 Rock salt Refined Mumbai, India Yes 282 ± 30 347 ± 20
IN 11 Rock salt Refined Haryana, India Yes 275 ± 25 313 ± 514
26
IN-12 Rock salt Refined Gurgaon, Yes 308 ± 24 387 ± 30
Delhi
515
516
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517
518
519
520
521
522
523
524
525
526
527

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528
529
530
531
532
533

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534
535
536
537

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538
539
540
541
542
543
544 Table 2. Comparison of the previous literature with present study.
References Number of particles/kg
Sea salt Well/Roc
k salt/
PE PET
re-
PP PVC
Composition %
Nylon PU PS Pigment Uniden
tified
Yang et al. 550-681 7-204 8.5 16.3 4.7 0.8 - - - - -
2015
Iñiguez et 50-280 115-185 3.3 83.3 6.7 - - - - - -
al. 2017
Karami et 1-10 1-10 13.8 2.8 16.6 - 1.4 - 2.8 23.6 29.1
lP
al. 2017
Kim et.al 0-1674 0-148 22.9 26.9 20 - - - - - 15.4
2018
Kosuth et 46.7 to 806 113 to - - - - - - - - -
al., 2018 367
Gündoğdu, 16-84 9-16 12.5 18.8 18.8 12.5 12.5 25 - - -
2018
(Seth and 56-103 - 22 61 - - 16 - - - -
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Shriwastav
, 2018
Renzi and 1600- - - - - - - - - - -
Blašković, 19800
2018
Lee et al., 0-10 - 34.9 2.3 39.5 - - - 14 - 6.6
2019
Lee et 98-2395 25 4 60 3 - 3 - - -
al.,2020
Jou

Present 1434-2284 287-417 15 16 16 2 8 1 5 17 15

study
545
546
547
548
549
550
551
552
553
554

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555
556
557
558
Collection of various salts

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200 g of salt + 100 mL of filtered H2O2 (30%) in 500 mL beaker

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Digestion of organic matter, in orbital shaker at 80 rpm,
65 ºC for 24 h, further 48 h at 30 ºC

Deionized water (800 mL) was added to the sample and kept for 24 h

Sample was filtered through Nylon/PCTE

re- Centrifuge at 5000 rpm, supernatant

filter membrane was collected and filtered

centrifuged bottom solution

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Deposition of cake layer over the membrane was mixed with 4.4 M NaI
Top

Separating Centrifuged at 5000 rpm, supernatant

NO Yes
funnel was collected and filtered
Bottom
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Characterization of the extracted microplastics

559
560
561 Fig. 1. The protocol for MPs extraction from sea salts.
562
563
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564
565
566
567
568
569
570

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P - Pump
Permeate
P Tank
- Pressure Gauge

PCTE/Nylon
- Control Valve

of
P
- TDS Measurement

MF Membrane

pro
Setup

Feed Vacuum Filtration

Setup

Tank

P
CV1
Filtered
P
re- Nylon/PCTE
CV2

MICROSCOPE

CV3

Reject Tank
571
572
lP
573
574 Fig. 2. Flow diagram for removal of microplastic from synthetic seawater.
575
576
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577
578
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579
580 a)
581
582
583

of
584
585
586
587

pro
588
589
590
591
592
593
594
595
596
597
598
re-
599
600
601 b) c)
602
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603
604
605
606
607
608
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609
610
611
612
613
614
615
616
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617
618
619
620
621
622
623
624
625 Fig. 3. Microscopic images of some of the extracted MPs from various salt brands : a) and b)
626 optical microscopic images and c) florescence microscopic images.
627

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628
629
630 2% 2% White 4%
631 a) Transparent b)
632 11% 20% Black 13%
Red
633

of
Fragments
4% Pink
634 Purple 44% Fiber
8%
635 18%
Green
Sheets
Brown
636 8%
Orange Pellet
637 Blue 39%

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638 6% 5%
9%
Grey
7% Yellow
639
640 3%
641 d) PE
c) 5% 17% 15% PP
642 PET
11% 210-100 µm PS
643 PVC
38% 0.1-1 mm
644 15%
16% Teflon
1-2 mm Nylon
645 15% re- EVA
2-3 mm
646 3-4 mm 4% PAN
PU
647 4-5 mm
0% 16%
Minerals
1% 7%
648 28%
5% Unidentified
649 1% 1% 2% Pigment

650
1%
651 e) 1%
1%
3%
2% 2%

652
PE
f) PE
lP
PP 15%
15% PP
653 26% PET
PET
654 2%
PS
PS
655 4% PVC PVC
656 Teflon 37% Teflon
10% Nylon Nylon
657 EVA
EVA
658 20% 41%
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PAN PAN
659 20% PU PU
660
661
662
663
664 Fig. 4. Comparison of average profiles of MPs in Indian edible salts: a) colour, b) shape, c)
665 size, and d) polymer, e) synthetic polymer in sea salts, f) synthetic polymer in rock salts.
666
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667
668
669
670
671
672
673
674
675
676

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677

of
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re-
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678
679
680 Fig. 5. Raman spectra of the extracted polymer particles and corresponding images. a) PE, b)
681 Poly(ethylene-co-vinyl acetate, c) PET, d) Nylon, e) PP, f) poly 4-vinylpyradine, g) PVDF,
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682 h) PU, i) PS, j) PVC.

683
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684
685

of
pro
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686
687 Fig. 6. Microscopic images of some extracted MPs in a) synthetic feed solution and b)
688 permeate side MPs.
689
690

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Highlights

 Microplastics were identified in Indian edible (sea and rock) salts

 A facile and cost-effective protocol was developed to isolate the MPs from salt sample

 1832 ± 40 particles/kg MPs were observed in sea salts

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 99.3% of MPs were removed from synthetic seawater by membrane technique

 The membrane backwashing technique was used to improve the membrane efficiency

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Graphical abstract

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Identification of microplastics in table salts

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Tablesalt Filtration Microscopy Microscopic image

re-
Microplastics removal from seawater

Salt
processing

MF Membrane
lP
Setup

Synthetic
seawater Microplastics FreeSalts

Reject Tank
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 Indian Institute of Technology Guwahati
Journal Pre-proof
Guwahati – 781 039, Assam, INDIA

Ph.: +91-361 258 3527 (O)

Dr. Senthilmurugan S. +91-994 521 3864 (M)
Associate Professor Fax: +91-361-258-2291
Department of Chemical Engineering Email: senthilmurugan@iitg.ac.in

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Thursday, 12 November 2020

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Author statement
Naveenkumar Ashok Yaranal: Conceptualization, Methodology, Validation, Formal analysis, Investigation;
Resources; Writing - Original Draft, Visualization

Senthilmurugan Subbiah: Conceptualization, Methodology, Resources, Writing - Review & Editing, Supervision,
re-
Project administration, Funding acquisition

Kaustubha Mohanty: Conceptualization, Methodology, Resources, Writing - Review & Editing, Supervision,
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Thanks for your great support in advance.

Yours sincerely,
Thanks
Best Regards,
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Dr. Senthilmurugan S
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 Journal Pre-proof

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

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☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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