VF CORPORATION CHEM-IQSM Chemical Screening Method CHEM-IQSM Chemical Screening Method PAGE 1 © 2019 VF Corporation. All Rights Reserved Table of Contents Introduction ................................................................................................................................................................... 3 1 Scope ................................................................................................................................................................ 4 2 Normative References ...................................................................................................................................... 5 3 Terms and Definitions ...................................................................................................................................... 5 4 Principle ............................................................................................................................................................ 7 5 Safety Precautions ............................................................................................................................................ 7 6 Reagents ........................................................................................................................................................... 8 7 Apparatus and Materials .................................................................................................................................. 8 8 Sampling ........................................................................................................................................................... 8 9 Standard Preparation ....................................................................................................................................... 9 10 Sample Preparation .......................................................................................................................................... 9 11 GC-MS Analysis ................................................................................................................................................. 9 12 Data Processing and Library Searching ........................................................................................................... 13 13 Calculation and Expression of Results ............................................................................................................ 13 14 Assignment of Chemical Rating ...................................................................................................................... 16 15 Indicator Methodology ................................................................................................................................... 17 16 Test Report ..................................................................................................................................................... 18 17 Bibliography .................................................................................................................................................... 20 Annex A - CHEM-IQSM General Guidelines for Chemical Classification ........................................................................ 21 Annex B - CHEM-IQSM Table of Substances to Avoid, Direct Detection by GC-MS ...................................................... 24 Annex C - CHEM-IQSM Table of Substances to Avoid, Indirect Detection by GC-MS Using Indicator Chemicals ......... 44 Table of Tables Table 1 - Headspace sampler parameters ................................................................................................................... 10 Table 2 - GC parameters for headspace analysis ......................................................................................................... 10 Table 3 - GC parameters for acetone extract analysis ................................................................................................. 11 Table 4 - MS parameters ............................................................................................................................................. 12 Table 5 - Blank injection parameters ........................................................................................................................... 12 Table 6 - MS library search constraints ....................................................................................................................... 13 Table 7 – Indicators of DHTDMAC ............................................................................................................................... 18 Table 8 – List of STA’s with preferential concentration determination from headspace analysis .............................. 19 CHEM-IQSM Chemical Screening Method PAGE 2 © 2019 VF Corporation. All Rights Reserved Introduction The CHEM-IQSM program is a proactive method for identifying and eliminating potentially harmful and banned chemicals before they enter VF’s supply chain during the manufacturing process. Textile formulations and processing chemicals are currently screened for over 400 substances to avoid, many of which appear on VF’s Restricted Substances List (RSL). The RSL defines limit values for restricted usage substances and identifies usage banned chemicals for all final products manufactured and sold under VF brands. The RSL is updated on a regular basis to reflect changes in international laws, including those set forth under CPSA (USA), California Proposition 65, and REACH (ECHA). Whereas the RSL sets limit values for final products, CHEM-IQSM program sets limit values for substances to avoid in all textile formulations and processing chemicals during each stage of production. CHEM-IQSM program outlines a five-step process that provides actionable information on chemical selection for VF and its suppliers. 1. Each factory submits a chemical inventory. 2. VF’s CHEM-IQSM program manager determines which chemicals from the factory require screening and informs the factory. 3. The factory submits a small sample of each formulation or chemical to an approved chemical laboratory. 4. The laboratory analyzes each submitted sample for over 400 hazardous substances, giving the chemical a rating of preferred (green), allowed (yellow), due diligence required (orange), or prohibited (red). 5. The factory receives a report on all chemicals submitted and is required to follow the VF CHEM-IQSM Program guide. The goal of the CHEM-IQSM Program is to achieve responsible chemical management throughout the supply chain in a cost-effective manner and thereby improve workplace safety, environmental protection, and VF product quality. CHEM-IQSM Chemical Screening Method PAGE 3 © 2019 VF Corporation. All Rights Reserved 1 Scope This is a screening method for the semi-quantitative determination of substances to avoid (STA) in textile auxiliary samples using gas chromatography-mass spectrometry (GC-MS). Most of the chemicals used in textile formulations are organic substances with low to high volatility, allowing for efficient screening using GC-MS. For non-volatile organic substances, additional screening techniques, such as high performance liquid chromatography-mass spectrometry (HPLC-MS; LC-MS), are required. Additionally, non-volatile substances can be detected by GC-MS through the use of indicator substance, along with information provided by the factory on the composition of the textile auxiliaries (such as SDS and TDS). Indicator substances are volatile substances that are formed through degradation of a STA by heat and/or by chemical reaction and that can be used to semi-quantitatively calculate the initial concentration of the STA in the textile formulation or sample. When textile auxiliaries are produced, byproducts, impurities, residual starting materials, and/or intermediates are present and may also be used as indicator substances. The purpose of this method is to determine whether detected STA’s are within or exceed the permissible concentration ranges set forth by the CHEM-IQSM chemical screening program (see Annexes A and B). As GC-MS is capable of screening for thousands of substances, the VF Substances to Avoid list is regularly updated to incorporate new information gleaned from the screening process. This method is applicable for the screening of: • Auxiliaries and finishing agents for fibers and yarns • Pre-treatment agents • Textile auxiliaries for dyeing and printing • Colorants: dyes • Colorants: printing • Finishing assistants • Technical auxiliaries for multipurpose use in the textile industry • Dry cleaning auxiliaries • Processing chemicals in leather manufacturing • Other chemical auxiliaries in textile, leather, footwear and equipment production This method is not designed for the analysis of all STA’s, including • Metals • Inorganic salts including chlorides, sulfates, sulfites, chlorites, hypochlorites, hydroxides, etc. • Inorganic acids • Permanganates • Hydrogen peroxide • Hydroxylamines The screening of these compounds requires further due diligence, including the use of additional detection methods and instrumentation. CHEM-IQSM Chemical Screening Method PAGE 4 © 2019 VF Corporation. All Rights Reserved 2 Normative References The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. • VF CHEM-IQSM Program Manual • VF CHEM-IQSM Appendix: Substances to Avoid List (STA List) • VF CHEM-IQSM Sample Submission Guidelines • VF Restricted Substance List (RSL) 3 Terms and Definitions