Of the products sampled for this study, 26 products had been manufactured locally by Pakistani companies, 34 samples had been produced in India, 8 products in the United Arab Emirates, 12 products in Thailand, 11 products in China, 2 products in South Korea, 5 products in the United States of America, and 5 products were made by companies in France (Fig. 1).
Figure 1. Country of origin of the cosmetic products investigated in this study
From the evaluation of the solid content of the cosmetic products under study, it could be seen that out of 103 products, 27 products (26.2%) did not contain any microbeads at all, 20 products (19.4%) contained walnut shells as abrasive, 3 products (2.9%) contained hydrated silica as the only solid abrasive, and 6 products (5.9%) exhibited microcrystalline cellulose as the sole solid abrasive (Table 1, Fig. 2). 10 other products (9.7%) incorporated microcrystalline cellulose in their formulation, but then invariably in combination with polythene microbeads. It was found that 47 (45.6%) products incorporated plastic microbeads, including 44 (42.7%) products that exhibited polythene microbeads. 10 (9.7%) of the products which revealed polythene had microcrystalline cellulose as a co-constituent.
Table 1
Country of origin, color, shape and polymer compositions collected from 103 facial scrubs purchased from different markets of Punjab, Pakistan
Sample | Country | Color | Shape | Polymer (MBs) composition by FTIR |
SH1 | Pakistan | - | - | no solid particles were present |
SH2 | Pakistan | golden | irregular | walnut shells |
SH3 | United Arab Emirates | brown | irregular | walnut shells |
SH4 | India | - | - | no solid particles were present |
SH5 | USA | colorless | irregular | polyethylene |
SH6 | India | red | irregular | polyethylene |
SH7 | India | white | spherical | microcrystalline cellulose |
SH8 | Pakistan | - | - | no solid particles were present |
SH9 | Pakistan | brown | irregular | walnut shells |
SH10 | Pakistan | yellow, green | spherical, granular | polyethylene |
SH11 | India | white, red | irregular | polyethylene |
SH12 | Thailand | white | granular | polyethylene |
SH13 | India | - | - | no solid particles were present |
SH14 | India | - | - | no solid particles were present |
SH15 | India | - | - | no solid particles were present |
SH16 | Korea | blue | irregular | polyethylene, microcrystalline cellulose |
SH17 | USA | - | - | no solid particles were present |
SH18 | Pakistan | - | | no solid particles were present |
SH19 | Korea | - | | no solid particles were present |
SH20 | India | red | spherical | ethylene acrylate co-polymer |
SH21 | UAE | - | - | no solid particles were present |
SH22 | India | - | - | no solid particles were present |
SH23 | Pakistan | - | - | no solid particles were present |
SH24 | UAE | - | - | no solid particles were present |
SH25 | China | - | - | no solid particles were present |
SH26 | India | - | - | no solid particles were present |
SH27 | India | - | - | no solid particles were present |
SH28 | Pakistan | - | - | no solid particles were present |
SH29 | India | colorless | spherical | walnut shells |
SH30 | India | - | - | no solid particles were present |
SH31 | India | - | - | no solid particles were present |
SH32 | Pakistan | brown | irregular | walnut shells |
SH33 | United Arab Emirates | red, blue | granular | polyethylene |
SH34 | Pakistan | yellow | irregular | polyethylene |
SH35 | India | brown | irregular | walnut shells |
SH36 | India | blue, white | irregular | polyethylene |
SH37 | India | blue | spherical | polyethylene |
SH38 | France | colorless | irregular | polyethylene |
SH39 | India | white | spherical | hydroxylated silica gel |
SH40 | Pakistan | - | - | no solid particles were present |
SH41 | Pakistan | blue, yellow | irregular | polyethylene |
SH42 | India | red | irregular | polyethylene, microcrystalline cellulose |
SH43 | India | brown | granular | ethylene acrylate co-polymer |
SH44 | Pakistan | brown | irregular | polyethylene |
SH45 | Pakistan | - | - | no solid particles were present |
SH46 | Thailand | blue | irregular | polyethylene |
SH47 | United Arab Emirates | red | irregular | polyethylene |
SH48 | Pakistan | brown, blue | irregular | polyethylene |
SH49 | India | - | - | no solid particles were present |
SH50 | India | red, blue | irregular | polyethylene |
SH51 | China | white | irregular | polyethylene |
SH52 | Pakistan | red | irregular | polyethylene |
SH53 | India | - | - | no solid particles were present |
SH54 | USA | brown | irregular | polyethylene, microcrystalline cellulose |
SH55 | India | blue | irregular | ethylene acrylate co-polymer |
SH56 | Thailand | white | Irregular | polyethylene |
SH57 | India | - | - | no solid particles were present |
SH58 | United Arab Emirates | red | irregular | polyethylene |
SH59 | Pakistan | red, blue | irregular | polyethylene, microcrystalline cellulose |
SH60 | Thailand | brown | irregular | walnut shells |
SH61 | India | - | - | no solid particles were present |
SH62 | China | golden | irregular | walnut shells |
SH63 | India | colorless | irregular | polyethylene, microcrystalline cellulose |
SH64 | Thailand | blue | irregular | polyethylene |
SH65 | China | red | irregular | walnut shells |
SH66 | Thailand | brown | Irregular | walnut shells |
SH67 | United Arab Emirates | golden | irregular | polyethylene, microcrystalline cellulose |
SH68 | Pakistan | brown | irregular | walnut shells |
SH69 | India | blue | irregular | polyethylene |
SH70 | USA | brown | spherical, granular | polyethylene, microcrystalline cellulose |
SH71 | Thailand | red, blue | irregular | walnut shells |
SH72 | China | red | irregular | walnut shells |
SH73 | France | red | spherical, granular | microcrystalline cellulose, polyethylene |
SH74 | Pakistan | blue | irregular | polyethylene |
SH75 | France | white | irregular | microcrystalline cellulose, polyethylene |
SH76 | India | red, blue | spherical, granular | polyethylene |
SH77 | Pakistan | brown | irregular | hydroxylated silica gel |
SH78 | China | golden | irregular | walnut shells |
SH79 | USA | red, blue | spherical, granular | microcrystalline cellulose, polyethylene |
SH80 | Thailand | red | irregular | walnut shells |
SH81 | United Arab Emirates | white | irregular | polyethylene |
SH82 | India | - | - | no solid particles were present |
SH83 | Pakistan | brown | irregular | walnut shells |
SH84 | China | colorless | irregular | polyethylene |
SH85 | Thailand | blue, white | spherical, granular | polyethylene |
SH86 | France | red | irregular | ethylene acrylate co-polymer |
SH87 | France | red, blue | irregular | polyethylene |
SH88 | India | white | irregular | microcrystalline cellulose |
SH89 | Thailand | golden | irregular | walnut shells |
SH90 | China | white | irregular | microcrystalline cellulose |
SH91 | Pakistan | blue | spherical, granular | microcrystalline cellulose |
SH92 | China | white | irregular | polyethylene |
SH93 | India | red | irregular | walnut shells |
SH94 | Pakistan | brown | irregular | walnut shells |
SH95 | Pakistan | colorless | irregular | polyethylene |
SH96 | Pakistan | blue | spherical, granular | polyethylene |
SH97 | Pakistan | - | - | no solid particles were present |
SH98 | China | brown | irregular | walnut shells |
SH99 | Thailand | white | irregular | microcrystalline cellulose |
SH100 | India | brown | irregular | hydroxylated silica gel |
SH101 | China | red | irregular | polyethylene |
SH102 | Thailand | blue | irregular | polyethylene |
SH103 | India | colorless | irregular | microcrystalline cellulose |
Figure 2. Composition of solids of the 103 cosmetic products sampled for the study
Table 1. Country of origin, color, shape and polymer compositions collected from 103 facial scrubs purchased from different markets of Punjab, Pakistan
Figure 3 shows a typical example of an IR spectrum depicting polythene. The spectrum was obtained from the solids of product SH-12. The characteristic absorptions are 2915, 2847, 1472, 1465, 730, 717 cm− 1. A peak at around 2915 cm− 1corresponds to the asymmetric stretching of C-H bonds in CH2 groups, the peak around 2847 cm− 1corresponds to the symmetric stretching of C-H bonds in CH2 groups, the two peaks at 1472 cm− 1 and 1465 cm− 1correspond to the bending deformation of the polymer backbone, the peaks at 730 cm− 1 and 720 cm− 1correspond to the rocking deformation of the CH2 groups(Gulmine et al., 2002).
Figure 3. FT-IR spectrum of polythene containing microbead of product SH-12
Ferret diameter size range (µm) graphs of the microbeads collected from 76 products are listed below, in Table 2 and in Figures A 1–76 (Suppl. Data) for products SH-2 to SH-103. The size distribution graphs were plotted to compare and analyze the size range of microbeads existing in the 76 products. The average size of 3 samples was used to plot the distribution graphs for each product on an excel sheet by using the pivot graph option. To facilitate a comparison of the microbead size distribution of different products, the start and end values for the presentation of the distribution were fixed at 1 and 350 µm, respectively, with a difference of 50 µm per bin for all 76 products.
The distribution pattern of 76 products revealed that 29 products (SH-2, SH-3, SH-4, SH-7, SH-10, SH-12, SH-16, SH-20, SH-32, SH-42, SH-60, SH-69, SH-70, SH-71, SH-73, SH-85, SH-86, SH-87, SH-90, SH-91, SH-93, SH-94, SH-95, SH- 96, SH-98, SH-99, SH-100, SH-101 and SH-103) have a non-uniform size distribution, 4 products (SH-11, SH-43, SH-76 and SH-92) have a left-skewed size distribution, 43 products (SH-6, SH-9, SH-29, SH-33, SH-34, SH-35, SH-36, SH-37, SH-38, SH-39, SH-41, SH-44, SH-46, SH-47, SH-48, SH-50, SH-51, SH-52, SH-54, SH-55, SH-56, SH-58, SH-59, SH-62, SH-63, SH-64, SH-65, SH-66, SH-67, SH-68, SH-72, SH-74, SH-75, SH-77, SH-78, SH-79, SH-80, SH-81, SH-83, SH-84, SH-88, SH-89 and SH-102) have a right-skewed size distribution.
In this study, the microbead size range of 46 samples was represented by the size bin 1µm-50µm. The smallest size bead, however was found to be 12.7µm. The upper size range of 2 samples was represented by the size bin ending at 300µm, and in 2 samples were there beads with a size slightly over 300µm. Overall, the majority of the analyzed cosmetic products were found to have the majority of their beads with a diameter size ranging from 12.7 µm to 200 µm.
Table 2
Size, quantity and ash contents of the MBs collected from the 76 personal care products (facial scrubs) that contained solid content, purchased from different markets and shopping malls of Punjab, Pakistan
Sample | Size range of the microbeads (µm) | Average size of microbeads (µm) | Microbeads weight in g per 10 g of product | No. of micro-beads per 10 g of product | Weight percentage (%) of ash obtained from the particles |
SH2 | 53.6-201.3 | 78.7 ± 19.6 | 0.3011 ± 0.0191 | 7011 ± 198 | 3.1 |
SH3 | 76.2-256.4 | 89.3 ± 15.9 | 0.2103 ± 0.0312 | 7463 ± 322 | 4.9 |
SH5 | 65.7-234.5 | 76.4 ± 17.1 | 0.3102 ± 0.0323 | 6537 ± 232 | 0.9 |
SH6 | 101.6-298.7 | 115.3 ± 20.4 | 0.1923 ± 0.0453 | 5754 ± 313 | 4.3 |
SH7 | 98.9-167.8 | 101.3 ± 29.7 | 0.2612 ± 0.0324 | 4575 ± 133 | 6.9 |
SH9 | 132.3-224.9 | 160.6 ± 13.9 | 0.2652 ± 0.0346 | 5670 ± 134 | 8.4 |
SH10 | 87.1-206.4 | 95.8 ± 11.6 | 0.1236 ± 0.0436 | 4575 ± 432 | 32.6 |
SH11 | 57.0-110.9 | 78.3 ± 23.9 | 0.2172 ± 0.0437 | 3575 ± 134 | 4.9 |
SH12 | 25.2-196.8 | 95.3 ± 19.3 | 0.2532 ± 0.0432 | 8638 ± 342 | 34.1 |
SH16 | 145.7-263.9 | 168.3 ± 25.3 | 0.2635 ± 0.0234 | 4783 ± 353 | 0.39 |
SH20 | 98.6-153.9 | 115.4 ± 17.4 | 0.1226 ± 0.0243 | 3785 ± 453 | < 5.0 |
SH29 | 54.4-198.5 | 69.3 ± 12.4 | 0.2721 ± 0.0274 | 3468 ± 324 | 2.9 |
SH32 | 98.2-156.9 | 115.9 ± 18.4 | 0.2127 ± 0.0257 | 4785 ± 235 | 3.7 |
SH33 | 165.1-203.4 | 187.3 ± 36.4 | 0.2651 ± 0.0357 | 3765 ± 435 | 0.95 |
SH34 | 69.9-208.2 | 89.4 ± 23.0 | 0.2126 ± 0.0343 | 3568 ± 356 | 6.9 |
SH35 | 72.8-300.6 | 98.9 ± 15.3 | 0.2510 ± 0.0136 | 8664 ± 364 | 4.6 |
SH36 | 89.9-156.7 | 110.8 ± 17.4 | 0.1271 ± 0.0657 | 7864 ± 321 | 9.1 |
SH37 | 35.8-199.2 | 74.7 ± 16.4 | 0.1119 ± 0.0264 | 8786 ± 231 | 3.0 |
SH38 | 143.7-205.9 | 178.4 36.5 | 0.2123 ± 0.0264 | 8584 ± 364 | 13.9 |
SH39 | 46.0-109.6 | 93.4 ± 23.3 | 0.3213 ± 0.0864 | 8386 ± 432 | 3.9 |
SH41 | 98.5-165.9 | 142 ± 27.0 | 0.2193 ± 0.0583 | 8754 ± 254 | 5.2 |
SH42 | 96.2-176.8 | 110.0 ± 15.8 | 0.1932 ± 0.0174 | 8463 ± 432 | 0.58 |
SH43 | 53.8-145.9 | 74.9 ± 16.3 | 0.2012 ± 0.0532 | 3754 ± 235 | 6.2 |
SH44 | 24.6–90.7 | 78.4 ± 12.4 | 0.1942 ± 0.0742 | 8543 ± 542 | 3.9 |
SH46 | 25.8-154.8 | 78.3 ± 14.3 | 0.2128 ± 0.0345 | 8467 ± 243 | < 6.0 |
SH47 | 21.9–97.4 | 85.8 ± 12.3 | 0.1921 ± 0.0836 | 9536 ± 432 | 9.3 |
SH48 | 16.8-183.6 | 98.3 ± 14.3 | 0.1823 ± 0.0263 | 9885 ± 243 | 6.5 |
SH50 | 43.1–97.9 | 83.5 ± 21.1 | 0.1132 ± 0.0243 | 9985 ± 103 | 7.0 |
SH51 | 12.9-165.7 | 99.4 ± 23.4 | 0.1150 ± 0.0753 | 9978 ± 212 | 3.9 |
SH52 | 24.6–97.4 | 79.0 ± 17.3 | 0.1321 ± 0.0396 | 9965 ± 251 | 5.2 |
SH54 | 32.1–94.6 | 76.9 ± 14.9 | 0.1342 ± 0.0163 | 9994 ± 231 | 9.1 |
SH55 | 53.0-197.5 | 110.3 ± 23.9 | 0.1231 ± 0.0537 | 8754 ± 532 | 1.9 |
SH56 | 34.6–87.9 | 58.3 ± 11.2 | 0.3245 ± 0.0281 | 9956 ± 231 | 3.5 |
SH58 | 25.7–79.5 | 69.4 ± 17.3 | 0.3712 ± 0.0642 | 9947 ± 253 | 7.8 |
SH59 | 25.6–96.7 | 75.9 ± 21.4 | 0.2831 ± 0.0542 | 9685 ± 432 | 2.8 |
SH60 | 23.7-106.5 | 69.4 ± 12.1 | 0.2941 ± 0.0861 | 9675 ± 241 | 5.1 |
SH62 | 25.1–98.7 | 76.3 ± 11.5 | 0.2198 ± 0.0127 | 9466 ± 232 | 7.0 |
SH63 | 32.7-143.9 | 83.5 ± 31.7 | 0.1938 ± 0.0372 | 9674 ± 242 | 4.3 |
SH64 | 12.7-163.9 | 73.9 ± 12.6 | 0.1953 ± 0.0537 | 9678 ± 342 | 6.0 |
SH65 | 23.4-153.7 | 87.4 ± 17.3 | 0.3721 ± 0.0736 | 9686 ± 102 | 3.2 |
SH66 | 38.9–90.1 | 73.9 ± 18.3 | 0.2812 ± 0.0652 | 9467 ± 321 | 4.9 |
SH67 | 21.7-142.5 | 80.4 ± 11.2 | 0.1974 ± 0.0692 | 8754 ± 401 | 3.6 |
SH68 | 21.4–96.6 | 76.4 ± 11.0 | 0.3283 ± 0.0362 | 9578 ± 201 | 5.1 |
SH69 | 43.6-151.5 | 73.9 ± 12.3 | 0.2932 ± 0.0635 | 9567 ± 439 | 9.1 |
SH70 | 32.5-206.7 | 74.9 ± 12.9 | 0.2954 ± 0.0762 | 8646 ± 253 | 1.9 |
SH71 | 43.8-143.8 | 98.3 ± 17.2 | 0.1923 ± 0.0128 | 8545 ± 368 | 3.5 |
SH72 | 22.3-108.9 | 68.9 ± 10.2 | 0.3202 ± 0.0382 | 7535 ± 425 | 7.8 |
SH73 | 43.7-176.7 | 98.3 ± 17.3 | 0.3021 ± 0.0537 | 8675 ± 195 | 2.8 |
SH74 | 32.4–98.9 | 63.7 ± 17.9 | 0.2943 ± 0.0283 | 9545 ± 309 | 5.1 |
SH75 | 23.5-124.7 | 76.5 ± 18.3 | 0.2943 ± 0.0382 | 8543 ± 372 | 7.0 |
SH76 | 43.1–97.7 | 78.9 ± 11.2 | 0.2321 ± 0.0832 | 9653 ± 382 | 4.3 |
SH77 | 23.6-142.7 | 87.7 ± 21.2 | 0.2912 ± 0.0638 | 9575 ± 321 | 6.0 |
SH78 | 19.4-156.3 | 69.4 ± 11.0 | 0.3020 ± 0.0284 | 8575 ± 382 | 3.2 |
SH79 | 26.4-197.1 | 65.5 ± 10.9 | 0.2738 ± 0.0970 | 9574 ± 482 | 4.9 |
SH80 | 24.9-203.4 | 95.5 ± 10.2 | 0.3294 ± 0.0093 | 8463 ± 372 | 3.6 |
SH81 | 29.5-175.3 | 98.3 ± 21.6 | 0.3098 ± 0.0564 | 9654 ± 372 | 9.1 |
SH83 | 46.8-206.9 | 114.5 ± 23.9 | 0.2392 ± 0.0621 | 8643 ± 463 | 1.9 |
SH84 | 17.8-153.5 | 85.4 ± 19.5 | 0.1932 ± 0.0238 | 9574 ± 392 | 3.5 |
SH85 | 27.3-145.3 | 87.9 ± 11.4 | 0.1723 ± 0.0382 | 8448 ± 301 | 7.8 |
SH86 | 34.6-106.8 | 79.4 ± 17.3 | 0.1932 ± 0.0621 | 8743 ± 372 | 2.8 |
SH87 | 43.2-242.8 | 118.3 ± 23.1 | 0.2076 ± 0.0752 | 7457 ± 289 | 5.1 |
SH88 | 36.0-94.5 | 67.3 ± 12.9 | 0.1872 ± 0.0563 | 9574 ± 294 | 7.0 |
SH89 | 15.8-103.6 | 58.9 ± 9.4 | 0.2314 ± 0.0543 | 8533 ± 483 | 4.3 |
SH90 | 37.2-231.2 | 132.5 ± 23.1 | 0.2532 ± 0.0729 | 6753 ± 392 | 6.0 |
SH91 | 32.4-102.8 | 75.3 ± 12.2 | 0.3654 ± 0.0281 | 8754 ± 273 | 3.2 |
SH92 | 36.0-94.5 | 65.8 ± 11.0 | 0.3765 ± 0.0635 | 9460 ± 329 | 4.9 |
SH93 | 15.8-103.6 | 58.3 ± 8.3 | 0.2987 ± 0.0542 | 9841 ± 382 | 3.6 |
SH94 | 37.2-231.2 | 101.7 ± 19.2 | 0.3421 ± 0.0529 | 9361 ± 219 | 5.1 |
SH95 | 32.4-102.8 | 76.3 ± 12.9 | 0.2543 ± 0.0372 | 9643 ± 301 | 9.1 |
SH96 | 35.3–147.0 | 83.6 ± 10.2 | 0.3057 ± 0.0537 | 8217 ± 271 | 1.9 |
SH98 | 48.2-156.9 | 130.2 ± 23.8 | 0.3765 ± 0.0537 | 8470 ± 310 | 3.5 |
SH99 | 48.1-203.4 | 136.2 ± 17.3 | 0.2908 ± 0.0453 | 7375 ± 291 | 7.8 |
SH100 | 39.9-208.2 | 116.9 ± 21.2 | 0.2973 ± 0.0273 | 7481 ± 325 | 2.8 |
SH101 | 72.8-300.6 | 143.5 ± 32.8 | 0.3276 ± 0.0672 | 5483 ± 271 | 5.1 |
SH102 | 49.9-156.7 | 110.6 ± 12.9 | 0.3032 ± 0.0437 | 7574 ± 381 | 7.0 |
SH103 | 45.8-199.2 | 79.4 ± 19.3 | 0.2947 ± 0.0836 | 9892 ± 362 | 4.3 |
Table 2. Size, quantity and ash contents of the MBs collected from the 76 personal care products (facial scrubs) that contained solid content, purchased from different markets and shopping malls of Punjab, Pakistan
The most common colors used in the studied products of the plastic microbeads were blue (35%), red (29%) and white/colorless (25%). The rest of the products had yellow (5%), brown (2%), green (2%) and golden (2%) plastic microbeads (Suppl. Figure B1). Over all products with beads (Suppl. Figure B2), the color scheme was composed of red, blue, and colorless, equally contributing 21%, golden (6%), yellow (3%) and green (1%). The much larger share of brown is due to the use of walnut shell in the products as solid abrasive material. Interestingly, walnut shell has also been found to be dyed golden and red in some cosmetic products (Habib et al., 2022). The predominance of the colors blue and colorless/white can be found in cosmetics from a number of other markets around the world. Often, blue microplastics make up by color the dominant share of microplastics found in the oceans (Coyle et al., 2020; Martin et al., 2017; Courtene-Jones et al., 2017; Lusher et al., 2014). The large share of the color red is something that may be specific to the Pakistani market.