Formaldehyde, D4, MEK, and Styrene in Children’s Products Sara Sekerak, Environmental Assessment Program Overview In 2016, the Washington State Department of Ecology (Ecology) began an assessment of the data reported in the Children’s Safe Products Act (CSPA) Manufacturer Reporting Database. Under CSPA (Chapter 70.240 Revised Code of Washington (RCW)), manufacturers of children’s products offered for sale in Washington State are restricted from using certain chemicals. They are also required to report to Ecology if a product contains any Chemicals of High Concern to Children (CHCC) (Chapter 173-334 Washington Administrative Code (WAC)). Using a study performed by Smith et al. (2016) to characterize, rank, and prioritize chemicals reported in children’s products based on chemical toxicity and the potential exposure pathways, Ecology identified four priority chemicals for this study: formaldehyde, octamethylcyclotetrasiloxane (D4), methyl ethyl ketone (MEK), and styrene. These chemicals ranked high in either chemical toxicity, exposure potential, number of manufacturer reports, or a combination of these criteria. Ecology frequently performs testing on CHCCs in children’s products to verify compliance, to further understand chemical usage and presence in products, and for making policy decisions. In 2016, Ecology purchased 137 children’s products and submitted 97 component samples to the laboratory Toys/Games 34 for analysis of one or more of the four priority chemicals. Figure 1 displays the types and distribution Beauty/Personal Care/Hygiene 33 of products purchased. Manufacturer-reported data and research on the use and application of these chemicals in product-manufacturing processes helped Clothing 18 guide product selection. Household/Office 16 Data gathered from this study were used to enhance Furniture/Furnishings our understanding of chemicals used in children’s products and assess compliance with CSPA. This Baby Care 16 report describes the presence and levels of four chemicals found in a select set of children's products. This report does not attempt to assess potential Arts/Crafts/Needlework 12 exposures or impacts to human health related to the tested products. Kitchen Merchandise 8 Complete laboratory results for this study can be 0 5 10 15 20 25 30 35 requested from the author / project manager, Numbers of Products Sara Sekerak. Figure 1. Types and Distribution of Purchased Products, listed by Global Product Classification (GPC) Segment. For More Information Ecology’s CSPA website: Children's Safe Products Act CSPA Manufacturer Reporting Database: https://fortress.wa.gov/ecy/cspareporting Rational for Reporting List of CHCCs (2011 Rule): https://fortress.wa.gov/ecy/publications/documents/1704023.pdf Publication No. 17-03-020 October 2017 An Assessment of CSPA Data Methods Product Collection and Processing, and Laboratory Sample Selection This study followed a Quality Assurance Project Plan (QAPP) and QAPP addendum (Sekerak, 2016a; Sekerak, 2016b). Ecology purchased 137 children's products and one product labeled as ‘KEEP OUT OF THE REACH OF CHILDREN’. This product was available for sale amongst other children’s products, on a low shelf, in a store selling predominately children's products. Most products were purchased from 16 Puget Sound retail stores, and a small set of products were purchased from four online retailers. The standard practice of purchasing from larger chain stores was used to represent products sold and available to customers across Washington State. It is assumed that statewide each chain store mostly receives the same distribution of products. Products purchased online are also assumed to be equally accessible by most state residents. The CSPA Manufacturer Reporting Database was used to focus on categories of products to purchase. Product universal product codes (UPCs) are not entered into the database; therefore, no specific products were targeted. Supplementary literature reviews of the use of formaldehyde, D4, MEK, and styrene in manufacturing processes were used to help with the selection of products and product components to be evaluated in this study. When available, product ingredient labels were used to prioritize testing based on listings of a target chemical, synonym, or a secondary chemical known to form or decompose to release one of the four study target chemicals. All personal care products and other products sold in sealed bottles or containers were sent to the laboratories in their original sealed bottles. Containers were opened just prior to analysis preparation. Component samples from solid material matrices (e.g., fabrics, plastics, bio-based materials) were hand-reduced or cryomilled by product testing and laboratory standard operating procedures (SOPs; Wiseman et al., 2016; MEL, 2016). Laboratory Procedures ^ Table 1. Laboratory Methods . Ecology’s Manchester Environmental Laboratory (MEL) analyzed component samples of formaldehyde, MEK, and Analyte Preparation Analysis Analysis (CAS Number) Method Method Instrument styrene. A contract laboratory performed the analysis of D4. Table 1 outlines the preparation and analysis methods Formaldehyde EPA 8315AP EPA 8270DSIM GC/MS and instrumentation for all analyses. (50-00-0) For this study MEL developed a method for the extraction D4 ALS SOP ALS SOP and analysis of formaldehyde in consumer products based GC/MS (556-67-2) SVM-D4SO SVM-D4SO on EPA 8315A. The performance-based modifications to MEK the preparation technique included a reduction in sample EPA 5030B EPA 8260C GC/MS size and extraction fluids, as well as the addition of (78-93-3) surrogates to monitor extraction efficiency. Analysis was Styrene EPA 5030B EPA 8260C GC/MS performed by gas chromatography/mass spectrometry (100-42-5) (GC/MS; EPA 8270DSIM) as an alternative to high- ^Method names are specific to the lab that performed the analysis. performance liquid chromatography—ultraviolet/visible GC/MS: gas chromatography/mass spectrometry spectroscopy (HPLC-UV/Vis). The D4 analysis was performed following a sediments and Biosolids GC/MS method modified for testing consumer products. MEK and styrene were analyzed using established product testing methods, based on EPA Method 8260C. All MEL data were reviewed and verified as prescribed in MEL’s Lab Users Manual– Tenth Edition (Ecology, 2016). The MEL Quality Assurance coordinator validated the D4 contract lab data following EPA’s National Functional Guidelines for Superfund Organics Methods Data Review (EPA, 2014). Discussions of the data quality for all datasets were summarized in written case narratives prepared by MEL. These case narratives are available upon request. 2 An Assessment of CSPA Data Data Quality and Usability Quality control (QC) tests and measurement quality objectives (MQOs) are outlined in the study plan (Sekerak, 2015). With few exceptions, the results met acceptance criteria for all analyses. There are no limitations on the use of the data as reported. Qualifiers were assigned to some data within this study: “J” indicating that the associated result is an estimate. “U” indicating that the analyte was not detected at the quantitation limit. “UJ” signifying that the quantitation limit is an estimate. “NJ” where the analyte was tentatively identified in the sample but the result value reported is an estimate. Method blanks (MBs), laboratory control samples (LCSs), LCS duplicates, duplicates (DUPs), matrix spikes (MSs), and MS duplicates were analyzed with each batch of samples. No analytes were detected above the method reporting limits (RLs) in the MBs associated with each sample batch. Due to the persistent presence of low background levels of formaldehyde, the reporting limit was raised to 10 parts per million (ppm) for the first batch of samples analyzed. In subsequent batches, procedure modifications were successful in reducing contamination and a reporting limit of 5 ppm was obtained. For D4, a reporting limit of 0.026 ppm was achieved by the contract laboratory. The contract laboratory originally reported data below the RL and flagged these results as estimates. “J” flagged data below the reporting limit were changed by the project manager to 0.026 ppm “U”, indicating that the analyte was not detected at or above the quantitation limit. This change does not affect the quality of the data reported. A range of actual reporting limits are displayed in Table 2. All LCS and LCS duplicates were extracted and analyzed as appropriate and met acceptance criteria. Matrix spikes for one sample exhibited poor recovery of the concentration of added formaldehyde; the source sample was qualified as an estimate. All other precision and bias criteria were met. Table 2. Summary Statistics of Priority Chemicals in For D4, one duplicate sample was reported slightly Children’s Products. above the range of the calibration curve and was qualified as an estimate. The source sample was analyzed within the calibration curve and not Analyte Formaldehyde D4 MEK Styrene qualified as a result of the qualification assigned to the duplicate. Number 84 43 60 60 (n) As the method requires, all surrogates and internal standards were performed as specified. Four formal- RL* 4.19 - 20.1 0.026 0.77 - 43.1 0.77 - 43.1 dehyde samples were reported as estimates due to (ppm) low surrogate recoveries (<50%). This was due to severe matrix interferences. Two additional formal- (ppm)* 31 22 0 9 dehyde QC samples (MB and DUP) also had low surrogate recoveries. All results associated with this % > RL 37% 51% 0% 15% MB and the source sample