Comparison Of Total Metal Concentrations With The EU Directive, the Canadian, the U.S., and the BIS toy safety regulation Limits
Present research only focuses on total metals concentration (TMCs). If TMCs are exceeded in high numbers, then further bioaccessibility testing is required. TMCs results are compared with the BIS, U.S., Canadian, and EU toy safety regulation limits due to the absence of national standards for toy safety regulation in Pakistan, and there are no Pakistan standards and quality control authority guidelines, especially on toys to ensure children’s safety, results of the present research were compared from other regulations available in different countries and regions are mentioned in Table 1.
The results obtained from the present research are compared with European Union (EU) Toy Safety Directive (European Council 2009). In the first stage, EU limits have been used in discussion and interpretation because the EU Toy Safety Directive delivers a more comprehensive approach to the chemical safety of toys than any other regulations. After all, it differentiates the migratable limits for various types or groups of toys, namely scraped off toy material; liquid or sticky toy material; and dry, brittle, powder-like, or pliable toy material. In order to compare the TMCs, the EU limits for scraped-off toy material have been used.
Like the United States, Consumer Product Safety Commission (U.S.CPSC) adopted the American society for testing and materials (ASTM) standard for toy safety F963-11. According to ASTM F963, 100mg/kg (total) Pb limits for substrates in children’s products and for surface coating its set 90mg/kg(soluble) for Pb, 75mg/kg(soluble) of surface coating and substrates other than clay for Cd and 60mg/kg(soluble) in surface coating and substrates for Cr (ASTM International 2017)
In Canada (Government of Canada,2016) sets limits for Pb in comsumer products or surface coating(soluble) 90mg/kg(total) and for Cd its 1000mg/kg in surface coating (soluble) and 130mg/kg(total) (Government of Canada, 2018).
In India, the Bureau of Indian Standards (BIS) is the National Standards Body of India under the Department of Consumer Affairs, Ministry of Consumer Affairs, Food & Public Distribution, Government of India. It is a statutory body established under the Bureau of Indian Standards Act, 2016. One of the main functions of BIS is to prescribe standards for covering goods and systems under the BIS regime. BIS IS:9873 regulations governing heavy metals in children’s toys and set limits for Cd is 75mg/kg, Pb 90mg/kg, and Cr 60mg/kg. BIS limits are identical to U.S. limits.
In Pakistan, to the author’s knowledge, this is the first scientific investigation design that evaluates the presence of toxic contaminations in low-priced children’s plastic toys randomly collected from the local markets of Karachi. However, several studies have been investigated to prove heavy metals present in children’s toys. Like (Kumar and Pastore 2007) found Pb and Cd in soft toys, (Godoi, Santos Jr et al. 2009) evaluated Ba, Cd, Pb, and Cr levels in the toy by using Laser-induced breakdown spectroscopy, (Greenway and Gerstenberger 2010) examined Pb level in daycares centers toys and found Pb in excess quantities, (Omolaoye, Uzairu et al. 2010) reported the levels of Pb, Cd, Ni, Cr, Cu, Zn, Co, and Mn in PVC and Non-PVC toys and high levels were obtained in PVC toys, (Sindiku and Osibanjo 2011) research indicated that Pb, Cr, Ni, and Cd found in high quantities in plastic toys, (Ahmad, Nasibullah et al. 2012) found levels of Pb, Cr, Cd, Co, Zn, Ni, and Mn in toys.(Guney and Zagury 2013) examined different toy categories for 10 elements and reported Pb, Cu, and Cd in high Concentration along with Sb, Sc, Ba, Cr, Ni, Mn, and As were within the limits in some categories, (Hillyer, Finch et al. 2014) also reported Pb, Cd and As in toys, (Kang and Zhu 2015) Investigated Pb contained in based material of plastic toys, (Turner 2018) analyzed As, Pb, Ba, Hg, Sb, Cr and Cd in Second-hand toys and found Pb and Cd exceeded in limits, (Issa and Alshatteri 2019) also investigated second-hand children’s product and high amount of Zn, Pb, Hg, and Cr detected and (Mohammed, Dial et al. 2020) also worked on children’s toys to analyzed Pb, Cr, Mn, Cu, Ni, and Cd. All former literature indicated that toxic substance in children’s items are in great concerned and investigated time to time. Past pieces of literature also indicated that Pb and Cd are highly dangerous for children health and are neurotoxin and nephrotoxin that’s why Pb and Cd are the prime focus of present research and Cr, Ni, Zn, Cu, and Mn are the secondary focus but equally important.
TMCs were detected in the present research are shown in Table 2 and 3 for DCT and DPCT groups and their minimum and maximum ranges are presented in Figure 1 and evaluated in Table 4. Health hazardous metals Pb, Cd, Ni, Cr, Zn, Cu, and Mn were found in all toys samples which are illustrated in Figure 1, it should be noted that not all elements found in this research were exceeded from regulatory limits but were present in some quantities. Seven metals were investigated however, only Pb, Cd, Ni, and Cr were exceeded from EU toy safety Regulatory limits in Table 1. Pb was detected in high quantity, In total 64% of samples exceeded from EU limits at a mean concentration of 292mg/kg are summarized in Table 4 and presented in Figure 2a. 28 out of 44 samples had levels higher than EU limits and the remaining samples were also contained Pb but their concentrations were within the permissible limits. The highest level of Pb was detected in Painted car 4 (DPCT14) 1191mg/kg, Crocodile (DCT07) 1111mg/kg, Purple car2 (DPCT01) 1011mg/kg, Elephant (DCT03) 981mg/kg, which is indicated that both groups of toys contained an extremely high level of Pb contents. Low-priced samples lead to low-quality material due to which contamination risk is also very high. For Pb, Similar results were also reported in the literature (Decharat, Maneelo et al. 2013, Hillyer, Finch et al. 2014, Kang and Zhu 2015, Turner 2018, Issa and Alshatteri 2019). Pb is used as stabilizers, coloring agents, lead(II)chromate, lead(II)carbonate, lead oxides, and lead molybdates used to produce color pigments (Ismail, Mohamad et al. 2017, O'Connor, Hou et al. 2018, Njati and Maguta 2019), basic Pb salts are commonly used as thermal stabilizers to enhance material properties and to reduced material costs like fillers in plastic manufacturing and molding process (Al-Qutob, Asafra et al. 2014, Njati and Maguta 2019). Above all, Recycle plastics are also one of the great sources of toxic contaminations, especially those obtained from electronic waste.
Cd was also detected in high quantity, In total 45% of samples exceeded from EU limits at a mean concentration of 63.24mg/kg are summarized in Table 4 and presented in Figure 2a. 20 out of 44 samples had levels higher than EU limits, and the remaining samples were also contained Cd, but their concentrations were within the permissible limits. The highest level of Cd was detected in Lion (DCT11) 459mg/kg, Blue star (DCT13) 426.1mg/kg, Horse (DCT02) 397.7mg/kg, Lion (DPCT15) 111mg/kg, which is indicated that mostly DCT samples contained more Cd than DPCT, likewise Cd based pigments are also used to color plastic material and work as a stabilizer in PVC together with the salt of Pb and Ba (Turner 2019). Many pieces of literature have also been reported for Cd Contamination in Toys and baby items included; (Kumar and Pastore 2007, Omolaoye, Uzairu et al. 2010, Guney and Zagury 2012, Guney and Zagury 2013, Al-Qutob, Asafra et al. 2014).
Cr and Ni were also found in exceeded levels, but as compared to Pb and Cd their quantities were less in numbers and only 5% Cr and 2% Ni exceeded from EU Limits at a mean concentration of 244mg/kg and 362mg/kg are summarized in Table 4 and presented in Figure 2a. out of 44 only 2 samples for Cr and only 1 sample for Ni exceeded from EU Limits. Cr exceeded in samples included Elephant (DCT03) 561mg/kg and Crocodile (DCT07) 479mg/kg, both of these samples were also contaminated from the high amount of Pb and Cd and also contains low levels of Zn, Ni, Cu, and Mn as Cr are also used in pigments Cr(VI) as the brightly colored yellow pigment of PbCrO4 (Turner 2018). Ni only exceeded in 1 sample in the highest quantity that is Study boy (DCT08) 3000.1mg/kg however in that sample Pb and Cd were not detected although other elements Zn, Cr, Mn, and Cu were detected in lesser quantities. Series of experiments in past literature indicated low levels of contaminations also detected in toys that are (Leal, Catarino et al. 2016, Sobhanardakani and Babaei 2016, Karaś and Frankowski 2018, Al Kindi and Ali 2020, Mohammed, Dial et al. 2020) on the other hand in most literature levels of Zn, Cr, Ni, Cu, Mn were reported in high quantities (Al-Qutob, Asafra et al. 2014, Ismail, Mohamad et al. 2017).
TMCs results were also compared with the U.S., Canadian, and BIS Regulations are shown in Table 1. BIS and U.S. limits are identical and are shown in similar results in Table 4 and combine represented in Figure 2b. In this case, Cr was higher in numbers, as In total 45% of samples were exceeded U.S. limits as well as BIS limits. 20 out of 44 samples showed a higher Cr level concerning U.S. and BIS. For Pb, 30% of samples exceeded and for Cd only 16% exceeded from respected limits. 13 toys for Pb and 7 toys for Cd were exceeded out of 44 samples in total, and for Canadian limits; 30% of samples contained Pb levels were above the total or soluble limit, 13 toys samples out of 44 exceeded. For Cd soluble limits, not a single sample exceeded Canadian limits.
In Figure 2a-2b, If we compared toy safety regulations limits with TMCs, it shows that more samples contain Pb and Cd from EU Limits as compared to BIS, U.S., and Canadian limits. However, concerning BIS and U.S. limits more samples contain Cr as Cr has in higher percentage shows in Figure 2b and a lower percentage in Figure 2a. In another word, the number of toys samples comparing with EU limit Pb > Cd > Cr > Ni pattern observed Alternatively, by comparing with U.S. and BIS limits Cr > Pb > Cd pattern observed for the number of samples.
Figure 3 concludes a total number of toys samples Exceeded from toxic levels concerning EU limits of toy safety regulations which are the most comprehensive regulation in all. Total samples (n= 44) had analyzed for toxic contamination, purchased from different sites of Karachi indicated that’s 28 samples for Pb, 20 samples for Cd, 2 samples for Cr, and only 1 sample for Ni exceeded from EU limits of scraped-off toy materials, but it should be noted that all 44 samples contain some amounts of Zn, Cu, Mn, Pb, Cr, Cd, and Ni. However, their levels had not crossed the permissible limits.
Total Metal Concentrations in low-priced plastics toys (DCT)
DCT group contains 23 toys samples are presented in Table 2 and summarized in Table 5a. samples were coded as DCT01-DCT23, digestion was performed by using the dry ashing method as reported in (Kumar and Pastore 2007, Omolaoye, Uzairu et al. 2010, Mohammed, Dial et al. 2020) and analyzed by atomic absorption spectrophotometer at Global Environmental Lab in Karachi, Pakistan.
The majority of the toys samples in the DCT group contain high levels of contamination. Overall, results were compared with different toy safety regulation limits are summarized in Table 1. 83 % of toys samples, 19 out of 23 were exceeded from EU limits of scraped-off toy material for Pb, 65% samples 15 out of 23 toys for Cd, 9% samples 2 out of 23 toys for Cr and 4% of toy 1 out of 23 toy samples for nickel were also exceeded from EU limits are summarized in Table 5a and represented in Figure 4a. The TMCs of Zn, Mn, and Cu were also detected but levels were within the EU limits. For Pb, the results of DCT03, DCT05, DCT07, and DCT18 were extremely higher in numbers. for Cd, DCT02, DCT11, and DCT13 were extremely high. For Cr, DCT03, and DCT07 and for Ni, only DCT08 was extremely higher than allowable scrap-off materials limits set by EU-Derivative. In DCT average values for Pb 205.33mg/kg, Cd 85.64mg/kg, Ni 225.92mg/kg, Cr 153.17mg/kg, Zn 220.93mg/kg, Mn 894.78mg/kg and Cu 135.66mg/kg clearly indicated metals existence in toys samples are shown in Table 5a. contamination levels in the DCT group were summarized in pattern as Pb>Cd>Cr>Ni.
On the other hand, when comparing DCT results from U.S. and BIS toy safety regulation Limits Table 1. it is notable that 26% of toys, 6 out of 23 were higher from U.S. and BIS limits for Pb, 22% of toys 3 out of 23 for Cd and 48% of toys 11 out of 23 were higher for Cr are summarized in Table 5a and represent in Figure 4b. compared to EU limits with U.S. and BIS limits results Figure 4a-4b indicates that level of Pb and Cd level was much higher in no of toys as compared to U.S. and BIS, however, Cr levels were high in no of toys with respect to U.S. and BIS and low in no of toys with respect to EU limits as shown in Figure 4a-4b. In brief, for EU limits Pb>Cd>Cr>Ni>othermetals and for U.S. and BIS Cr>Pb>Cd>othermetals patterns were observed. Meanwhile, by comparing the results from the Canadian Limits similar pattern was also observed for Pb but Cd levels were not exceeded from Canadian limits.
Total Metal Concentrations in low-priced plastics toys with paint or coating (DPCT)
DPCT group contains 21 toys samples are presented in Table 3 and summarized in Table 5b. samples were coded as DPCT01-DPCT21. Digestion was performed as reported in (Hillyer, Finch et al. 2014, Finch, Hillyer et al. 2015). 43% of painted toys sample 9 out of 21 for Pb and 24% samples 5 out of 21 for Cd were exceeded from EU limits for Scraped off toy materials limit are shown in Figure 5a. Ni, Cr, Zn, Cu, and Mn were also detected but levels were within the EU limits. As compared to DCT fewer levels of contamination were observed in DPCT only Pb and Cd were exceeded in number but not a single sample was exceeded for Cr and Ni. In the same way, no Zn, Cu, and Mn were detected above the EU limits in DPCT. One of the reasons is that as Pb, Cd, Cr, Ni, and many metals are used as pigments and stabilizers in paints production (O'Connor, Hou et al. 2018, Al Kindi and Ali 2020). but toys without coatings like DCT group where more contaminations are possible due to the presence of inner matrices like filler and catalyst (Turner 2019, Al Kindi and Ali 2020, Aurisano, Huang et al. 2020) Higher results were shown for Pb in samples included DPCT01, DPCT07, DPCT11, DPCT12, DPCT14, and DPCT15, And for Cd in DPCT03, DPCT04, DPCT11, DPCT15, and DPCT16 showed the highest levels. Average values of TMCs in DPCT group for Pb 263.39mg/kg, Cd 17.86mg/kg, Ni 98.33mg/kg, Cr 65.61mg/kg, Zn 259.75mg/kg, Mn 541.90mg/kg and Cu 118.56mg/kg indicated the existence of metals in painted toys. As a pattern for toxic contamination in DPCT with respect to EU limits drawn only Pb and Cd were observed Pb>Cd>other metals.
The results compared with U.S. and BIS toy safety regulation Limits are shown in Table 1 it is indicated that 33% of paint-coated toys (7 out of 21) for Pb, 43% (9 out of 21) for Cr, and 9% (2 out of 21) painted toys samples were Exceeded are represented in Figure 5b. A similar pattern of results was observed for Pb where 33% of Pb, in DPCT were exceeded Canadian limits, and 7 out of 21 toys samples exceeding from Canadian limits. By comparing no of samples from EU, BIS, U.S. and Canadian limits are shown in Figure 5a-5b summarized that with respect to EU, Pb was dominant in no of samples but with respect to U.S. and BIS limits Cr was dominant in no of samples. In brief, for EU limits Pb >Cd>othermetals whereas for U.S. and BIS limit Cr>Pb>Cd>othermetals patterns were observed.