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Phthalates in Toys Available in Indian Market

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Twenty four children’s toys and child care articles available in the local market of India were analyzed for eight phthalates as children toys are plasticized with phthalates. All toy samples showed the presence of one or more phthalates including
  Phthalates in Toys Available in Indian Market Sapna Johnson  • Nirmali Saikia  • Ramakant Sahu Received: 22 November 2010/Accepted: 22 March 2011/Published online: 20 April 2011   Springer Science+Business Media, LLC 2011 Abstract  Twenty four children’s toys and child carearticles available in the local market of India were analyzedfor eight phthalates as children toys are plasticized withphthalates. All toy samples showed the presence of one ormore phthalates including di-(2-ethylhexyl) phthalate (96%of the samples), di-iso-nonyl phthalate and di-iso-decylphthalate (42% of the samples) at a concentration rangingfrom 0.1% to 16.2%. Soft toys contain higher levels of phthalates as compared to hard toys as primary function of phthalates is softening of hard plastic materiel. Keywords  Phthalates    Plasticizers    Toys   Gas chromatograph    Mass spectraPhthalates or phthalate esters (Fig. 1) are esters of phthalicacid, mainly used as plasticizers (substances added toplastics to increase their flexibility, transparency and dura-bility). They are used primarily to soften polyvinyl chloride(PVC). PVC is a widely used material, including extensiveuse in toys and other children’s products such as chewyteethers, soft figures and inflatable toys. The most widelyused phthalates are di(2-ethylhexyl)phthalate (DEHP),dibutyl phthalate (DBP), di-iso-nonylphthalate (DINP), di-iso-decyl phthalate (DIDP), benzyl butyl phthalate (BBP)and di-n-octyl phthalate (DNOP). Phthalates can bereleased from soft PVC plastic by surface contact, espe-cially where mechanical pressure is applied (e.g. duringchewing of a PVC teether) as they are not tightly bound tothe plastic, but are present as mobile components of theplastic matrix. Phthalates, which make up 10%–40% of thetotal weight of a toy, have been under scrutiny because of their potential health effects, particularly on reproductivedevelopment (Duty et al. 2003). Children are more vul-nerable to the potential adverse effects of phthalates giventheir increased dosage per unit body surface area, immaturemetabolic system capability and developing endocrine andreproductive system. Several studies across the worldreported the presence of high levels of DINP, DEHP andeven DIOP, DIDP, DBP and other phthalates in productsintended for mouthing, or with a high potential for mouth-ing, by children of the age group 0.5–3 years and theirmigration into saliva (Stringer et al .  2000; Niinoa et al.2001; Bouma and Schakel 2002; Schreder 2007; Hitchcock  2008).There are recommendations which suggest removal of DINPandDEHPfromchildren’stoysbecauseexposuremaybe high enough to cause concern (Fiala et al. 2000). In theUnited States of America and Canada, the uncertainty inpredicting exposure levels,especiallyinveryyoungchildrenand infants, has led to the removal of all phthalates frominfant bottle nipples, pacifiers, teethers, and infant toysintended for mouthing (Kavlock et al. 2002). The EuropeanUnion (EU) has banned the use of DBP, DEHP, BBP fromchildren’s toys and childcare articles, and DINP, DIDP andDNOP from items that children are likely to put in theirmouths.Thetoysaswellasotherarticles,whichchildrenmayput in the mouth, should not contain [ 0.1% phthalate masspercent of the plasticized part of the toy according to EUregulation (1999/815/EC). Other countries including USA, S. Johnson    N. Saikia    R. SahuPollution Monitoring Laboratory, Centre for Science andEnvironment, Core 6A, Fourth Floor, India Habitat Centre,Lodhi Road, New Delhi 110003, IndiaS. Johnson ( & )Pollution Monitoring Laboratory, India Habitat Centre, Core 6A,Fourth Floor, India Habitat Centre, Lodhi Road, New Delhi110003, Indiae-mail: sapnajohnson06@yahoo.co.in  1 3 Bull Environ Contam Toxicol (2011) 86:621–626DOI 10.1007/s00128-011-0263-6  Japan, Denmark, Argentina, and Mexico, have also bannedphthalates from children’s toys. A safer alternative to PVCinclude toys made out of bio based plastics, polyethylenes,polypropylenes, thermoplastic elastomers, and ethylenevinyl acetate (EVA) that are free of phthalates. Two of themost common alternatives to phthalates are acetyl tributylcitrate (ATBC) and 1, 2-Cyclohexanedicarboxylic acid di-isononylester(DINCH),whichisderivedfromDINPandhasa similar chemical structure; however, existing data on theirchronic toxicity on humans is insufficient (Schmidt 2008).ToyssoldintheIndianmarkethavebeenshowntocontainshockingly high levels of lead and cadmium (Kumar andPastore 2007) but there is no report on phthalates in toys.With regard to safety guideline for toys, Bureau of IndianStandards (BIS) has published three standards, but none of them gives limit for phthalates in children’s toys and child-care articles. Therefore it was considered imperative toundertake a study on phthalates in children’s toys and otherchildcare articles available in the Indian market. Materials and Methods Twenty four toy samples of major brands from organizedand unorganized sectors (manufactured in India, Taiwan,China and Thailand) were purchased randomly from vari-ous markets in Delhi in the month of October 2008 andanalyzed for the following phthalates. Phthalate referencestandards -dimethyl phthalate (99.9%), diethyl phthalate(99.5%), di-n-butyl phthalate (99.9%), benzyl butylphthalate (99.2%), di-2-ethylhexyl phthalate (99.9%),di- n -octyl phthalate (99.2%), di-iso-nonyl phthalate(99.0%), di-iso-decyl phthalate (99.0%) were obtainedfrom Sigma Chemicals, USA.All solvents used were purchased from E-Merck. Eachlot of reagents was checked for phthalate contamination.Phthalate reference standards were obtained from SigmaChemicals, USA. Other chemicals were purchased froms. d. Fine Chem Ltd.Samples were extracted according to the method of Rastogi (1998). Five grams of each sample was extracted inSoxhlet Apparatus using 100 mL of dichloromethane for16 h at 40  C. The extract was concentrated under vacuumto 10 mL using a rotary evaporator at 30  C.The samples were analyzed for Phthalates by using a GasChromatograph (Thermoquest-Trace GC) equipped with 63 Ni selective electron-capture detector (ECD). A DB- 5(5%-phenyl-methylpolysiloxane) capillary column (30 m 9  0.25 mm  9  0.25  l m) was used for the analysis andnitrogenwas used as carrier and makeup gas with a flow rateof 0.5 and 30 mL/min, respectively. Employing split lessmode, 2.0  l L of the final extract was injected at a tempera-ture of 250  C. The detector was maintained at 300  C. Cali-bration curves for all the phthalates were prepared at theconcentrations range from 0.1 to 5  l g/mL. The curves werelinear (R2  C  0.999) over the range of 1.0–5.0  l g/mL forDINP and DIDP and for other phthalates it was 0.1–1.0 l g/mL. Identification of phthalates was performed by com-paring the retention time (Rt) of the samples’ peaks with theRt of the phthalate standards. The detection limit was 5 ng/g(w/w) for DINP and DIDP and 1 ng/g for other phthalates.No phthalates were detected in reagent blanks. The phtha-lates present in high concentrations were analyzed afterappropriate dilution of the sample extracts with hexane. Thedeterminations were performed in triplicate samples usingexternalstandardtechniquewithacalibrationstandardcloseto the estimated concentrations of phthalates in the sampleextract. The recovery of all of the investigated phthalatesunder the experimental conditions was 85%–105%. Therelative standard deviation (RSD) for the determination of most of the phthalates was within 10%.GC chromatograms of DINP and DIDP overlap partly.Therefore, when aproductcontained DINPas well asDIDP,the content of both of these phthalates in the product wasdetermined together as DINP (DINP is currently the mostcommon plasticizer used in children toys). When a productcontains both DNOP and DINP, DNOP in such a productcould not be determined by the present method because of interference by isomeric GC peak(s) of DINP. The GCseparation of the phthalates under study as well as chro-matographic pattern of DINP and DIDP is shown in Fig. 2aand chromatogram of toy sample no. 22 is shown in Fig. 2b.The identity of phthalates detected in the samples byGC–ECD was confirmed by GC–MS, Model FinniganPolaris Q Ion trap GC/MS n with EI ionization (70 eV), inFull Scan mode. The samples were injected using a pro-grammable temperature injector (PTV). The carrier gaswas helium with a 0.5 mL/min flow rate employing thesplit less mode. 1.0  l L of the final extract was injected at atemperature of 250  C keeping the ion source at 230  C,Mass Range: 50–650 m/z. The limit of detection rangedfrom 0.1 to 3.0 ng/g. OROR'OO Fig. 1  Generalchemicalstructureofphthalates. RandR 0 =  C n H 2n ? 1 ;n  =  4–15622 Bull Environ Contam Toxicol (2011) 86:621–626  1 3  Fig. 2 a  Chromatogram of the standard mixture of phthalates. Peak identity: 1. DMP; 2. DEP; 3. DBP; 4. BBP; 5. DEHP; 6. DNOP;7. DINP  ?  DIDP.  b  Chromatogram of sample extract from Toy No. 22. Peak identity: 5. DEHP; 7. DINP  ?  DIDPBull Environ Contam Toxicol (2011) 86:621–626 623  1 3  Results and Discussion All 24 toy samples showed the presence of at-least one ormore phthalates (Table 1). DEHP was detected in 96% of the samples at low concentrations, ranging from \ 0.1%–2.6%. DINP and DIDP were detected in 42% of the sam-ples ranging from \ 0.1%–16.2%. DBP and BBP weredetected in 5 and 3 toys out of 24 toys analysed, respec-tively and concentrations were \ 0.1%–0.2%; too low tohave plasticizing function and could be present as a con-taminant of another phthalate; constituent of ink or paintused in toys.DEHP, DBP, BBP and DINP  ?  DIDP havebeen found to reduce testosterone production by the fetuswhich can result in off target reproductive developmentand abnormal genitals. DINP may be a risk for youngchildren who routinely mouth DINP plasticized toys for75 min per day or more (Bogen et al. 2001). The totalamount of phthalates exceeded the EU limit (0.1% of theplasticized part of the toy) in more than 50%t of thesamples analyzed. Total phthalate concentration in 24samples ranged \ 0.1%–16.22%. Maximum value is 162times higher than the EU limit of 0.1% of the plasticized Table 1  Phthalates detected in baby toy samples (percent mass basis)Toy No. Type Country Soft/hard DBP BBP DEHP DINP  ?  DIDP Totalphthalates (%)No. of times of the EUlimit (0.1% by mass)1 Teether-1 India Soft  \ 0.1 ND  \ 0.1 ND  \ 0.1 Within limit2 Gum Soother-1 India Soft  \ 0.1 ND  \ 0.1 ND  \ 0.1 Within limit3 Gum Soother-2 India Soft ND ND  \ 0.1 ND  \ 0.1 Within limit4 Animal Figurine India Soft ND ND 0.1 ND 0.1 15 Pip Squeaks Toy India Soft ND ND  \ 0.1 16.2 16.2 1626 Squeeze Toy-1 China Soft ND ND  \ 0.1 6.0 6.0 607 Teether-2 Taiwan Soft  \ 0.1 ND 0.3 ND 0.3 38 Soft & Hard Biter Taiwan Hard 0.2 ND  \ 0.1  \ 0.1 0.2 29 Toy-ball China Soft ND ND  \ 0.1 ND  \ 0.1 Within limit10 Baby Rattle-1 Thailand Hard ND  \ 0.1  \ 0.1 ND  \ 0.1 Within limit11 Softy-Soft Keys China Hard ND ND  \ 0.1 ND  \ 0.1 Within limit12 Bath Fish China Soft ND ND 0.1 ND 0.1 113 Baby Rattle-2 India Hard ND ND  \ 0.1 ND  \ 0.1 Within limit14 Baby Rattle-3 China Hard ND ND  \ 0.1 ND  \ 0.1 Within limit15 Rattle & Teether China Hard ND ND  \ 0.1 ND  \ 0.1 Within limit16 Squeeze Toy-2 China Soft ND ND  \ 0.1 7.1 7.1 7117 Inflatable-1 China Soft ND ND  \ 0.1 4.4 4.4 4418 Doll China Hard  \ 0.1 ND ND 4.5 4.5 4519 Barbie Doll India Hard ND  \ 0.1  \ 0.1 0.2 0.2 220 Toy -My Little Pony China Hard ND  \ 0.1  \ 0.1 0.2 0.2 221 Squeeze Toy-3 China Soft ND ND  \ 0.1 6.2 6.2 6222 Squeeze Toy-4 China Soft ND ND  \ 0.1 8.0 8.0 8023 Inflatable-2 China Soft ND ND 2.6 ND 2.6 2624 Bath Duck China Soft ND ND 0.2 ND 0.2 2DMP, DEP and DNOP were not detected in any of the samplesValues are average of triplicateND  =  Not detected Table 2  Characteristic ions for major phthalates detected in toy samplesS. No. Phthalate CAS Retention time (min) Molecular weight Primary ion Secondary ions1 di-n-butyl phthalate 84-74-2 13.99 278.34 149 205, 2232 Benzyl butyl phthalate 85-68-7 22.19 312.35 149 91, 2063 di(2-ethylhexyl) phthalate 117-81-7 26.37 390.54 149 167, 2794 di-iso-nonyl phthalate 68515-48-0 31.97 418.60 149 167, 293624 Bull Environ Contam Toxicol (2011) 86:621–626  1 3  part of the toy. Squeeze toys (Toy No. 6, 16, 17, 18, 21, 22,23), manufactured in China, contained 2%–8% of totalphthalates and pip squeak toy (Toy No. 5) from Indiacontained more than 16% of total phthalates. Majority of the toys which contained high levels of phthalates weremanufactured in China.DINP was found in very high concentration in manysamples, especially in Chinese toys; which reflects amarked shift away from DEHP towards the use of thepoorly characterized isomeric phthalates. The samplescontaining higher quantities of DINP  ?  DIDP containedsmaller quantities of DEHP, perhaps as a contaminant inthe manufacturing process. Phthalates were also detected inbaby teethers and soothers made from non-toxic food gradesilicone rubber in very low concentrations ( \ 0.1%).The phthalates-BBP, DBP, DEHP and DINP detected intoy samples were confirmed by GC–MS. The dominantfragment of all phthalates measured in electron impactionization MS is at m/z149 this is a result of the loss of thealkyl ester groups and the formation of protonated phthalicanhydride moiety. Characteristic ions – primary and sec-ondary ions and the retention time for major phthalatesdetected in toy samples are given in Table 2. Mass Spectrafor sample no. 22 are given in Fig. 3a, b.The soft toys contained higher levels of phthalatesas compared to hard toys like rattles. Young children Fig. 3 a  Mass spectra of sample extract from Toy No. 22(DINP).  b  Mass spectra of sample extract from Toy No. 22(DEHP)Bull Environ Contam Toxicol (2011) 86:621–626 625  1 3
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