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"Answering the urgent call for Chlorinated Paraffin standards"

¹³C Labelled CPs
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Conference abstracts

Posters

CHLOFFIN answering the urgent call for chlorinated paraffin standards
van Mourik, L.M., Ricci, M., Valderhaug, S., Gorovoi, A., Brandsma, S. Button, J., Liu H., de Boer, J., and Johansen, J.E. - SETAC Europe 30th Annual Conference 2020, May 3-7, 2020 (virtual meeting). Poster ID: 3.07P.3.
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New Standards for Chlorinated Paraffins – Eurostars CHLOFFIN Project
Valderhaug, S., Gorovoi, A., van Mourik, L.M., Ricci, M., Brandsma, S. Button, J., de Boer, J., Liu H., and Johansen, J.E. - SETAC Europe 30th Annual Conference 2020, May 3-7, 2020 (virtual meeting). Poster ID: 3.07P.6.
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The EUROSTARS CHLOFFIN Project, new standards for the quantification of chlorinated paraffins
Huiling Liu, Solveig Valderhaug, Olga Gozhina, Alexey Gorovoy, and Jon Eigill Johansen Chiron AS, Stiklestadveien 1, N-7041 Trondheim, Norway (Presented at RAFA 2019)
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Mission SCCPossible: certifying a reference material for short-chain chlorinated paraffins
Van Mourik, L.M., Lava, R., Leonards, P.E.G., de Boer, J., Ricci, M. SETAC Europa Conference 2019, May 26-30, 2019, Helsinki, Finland
Optimizing determination methods for chlorinated paraffins (CPs) to evaluate their levels in Australia
Van Mourik, L.M., Leonards, P.E.G., Gaus, C., Mueller, J.F., de Boer, J. SETAC Europa Conference 2019, May 26-30, 2019, Helsinki, Finland
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Presentations

Reach for the Stars: An introduction to NPS REFORM and CHLOFFIN Eurostars projects
Jenny Button - Chiron AS, Stiklestadveien 1, N-7041 Trondheim, Norway (Presented at LTG, Dec 2019)
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Certification of the first matrix Reference Material for Short-Chain Chlorinated Paraffins
Core working group 2019. 25 September 2019, Wageningen, The Netherlands
Standardization of methods - lessons learnt from the QUASIMEME interlab studies
Core working group 2019. 25 September 2019, Wageningen, The Netherlands
Current capabilities in analyzing chloro alkanes, Advances in polychloro alkane (chlorinated paraffin) analysis
Van Mourik, L. M., de Boer, J., Leonards, P.E.G., Mueller J.F. , February 26, 2019, Amsterdam, The Netherlands
Virtual discussion meeting on chlorinated paraffins

PROGRAM

Welcome and opening

Louise van Mourik (Department of Environment and Health (E&H), Vrije Universiteit (VU), NL)

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SESSION 1 - CURRENT STATE OF KNOWLEDGE

CP Industry Testing (past, present, future): Overview of REACH Dossier and How to Access Data
Andrew Jaques (MCCP consortium, USA),
Chris Howick (Inovyn, UK),
Richard Mariner (Eurochlor, Belgium)
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SESSION 2 - CURRENT STATE OF ANALYSIS

Detection, identification, and quantification of chlorinated paraffins
Bo Yuan (Department of Environmental Science, Stockholm University, Sweden)
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SESSION 3 - WAY FORWARD

EFSA’s risk assessment on CPs in food and feed
Martin Rose (University of Manchester, UK),
Pim Leonards (E&H VU)
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Related publications from project partners

Nuclear magnetic resonance as a tool to determine chlorine percentage of chlorinated paraffin mixtures.
Valderhaug, S., Liu, H., Gorovoy, A., Johansen, J.E., van Mourik, L., de Boer, J., Gautuna, O.R. - Chemosphere Volume 308, Part 3, December 2022, 136312.
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Assessment of four rounds of interlaboratory tests within the UNEP coordinated POPs project.
Fiedler, H., van der Veen, I., de Boer, J. - Chemosphere Volume 288, September 2022, 132441.
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Semiquantitative Characterization of Bromo-chloro Paraffins and Olefins in the Australian Environment.
He, C., van Mourik, L., Brandsma, S., Thai, P., Wang, X., Chen, S., Thomas, K.V., Mueller, J.F. - Environ. Sci. Technol. 2022, 56, 17, 12452–12459.
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Determination of chlorinated paraffins (CPs): Analytical conundrums and the pressing need for reliable and relevant standards.
Fernandes, A.R., Vetter, W., Dirks, C., van Mourik, L.M., Cariou, R., Sprengel, J. Heeb, N., Lentjes, A., Kratschmer, K. - Chemosphere Volume 286, January 2022, 131878.
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Chlorinated paraffins and tris (1-chloro-2-propyl) phosphate in spray polyurethane foam - a source for indoor exposure?
Brandsma, S.H., Brits, M., de Boer, J., Leonards, P.E.G. - J. Haz. Mat. Volume 416, 15 August 2021, 125758.
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Combining High-Resolution Gas Chromatographic Continuous Fraction Collection with Nuclear Magnetic Resonance Spectroscopy: Possibilities of Analyzing a Whole GC Chromatogram.
van Mourik, L.M., Janssen, E., Breeuwer, R., Jonker, W., Koekkoek, J., Arrahman, A., Kool, J., Leonards, P.E.G. - Anal. Chem. 2021, 93, 6158−6168 .
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Combining High-Resolution Gas Chromatographic Continuous Fraction Collection with Nuclear Magnetic Resonance Spectroscopy: Possibilities of Analyzing a Whole GC Chromatogram
Van Mourik, L.M., Janssen, E., Breeuwer, R., Jonker, W., Koekkoek, J., Arrahman, A., Kool, J., Leonard, P.E.G. - Anal. Chem. 2021, 93, 15, 6158–6168
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The underlying challenges that arise when analysing short-chain chlorinated paraffins in environmental matrices.
van Mourik, L.M., Lava, R., O’Brien, J., Leonards, P.E.G, de Boer, J., Ricci, M. - Journal of Chromatography A 1610 (2020) 460550.
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Short-, medium-, and long-chain chlorinated paraffins in South African indoor dust and cat hair.
Brits M., Rohwer, E.R., De Vos, J., Weiss, J.M., Brandsma, S.H., de Boer, J. - Chemosphere Volume 238, 2020, 124643.
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Chlorinated Paraffins – State of Science, Insights, Challenges and the Way Forward
van Mourik, L.M., Brandsma, S., Yuan, B. and Castro, M. - SETAC Europe 30th Annual Conference: SciCon Session Summaries, August 2020 Issue
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For the first time at SETAC, a session solely focusing on Chlorinated Paraffins (CPs) was held. CPs have become a topic of emerging concern, especially after a category of CPs (Short Chain Chlorinated Paraffins, [SCCPs], C10-13) was added to the Persistent Organic Pollutants of the UN Stockholm Convention. Lately, CPs have been a prominent topic at different conferences, such as Dioxin 2019 and with more than 60 scientific publications in 2019.

Though SCCPs were restricted in 2017, there are still many challenges present today due to the high degree of complexity associated with these substances of unknown or variable composition, complex reaction products or biological materials (UVCBs); in particular, on the risk assessment and accurate quantification of their in-use categories medium- and long-chain chlorinated paraffins (MCCPs C14-17, and LCCPs C>17, respectively). The aims of this session were to address:
- What do we currently know about the environmental hazard of CPs (i.e., PBT properties);
- What are currently the key challenges obtaining such information; and
- >What are the knowledge gaps that need to be urgently addressed?>
Roughly 40 representatives from academia, government and industry joined the live session discussion at SETAC SciCon. Louise van Mourik (session chair) briefly introduced the session by giving an overview of the state-of-the-art and the presentations included in this session. The session opened with few technical questions directed at some of the participants with oral presentations.

The key points of the live session discussion included:

The PBT assessment of CPs and their partitioning properties. Significant progress has been achieved on the quantification of the PBT and partitioning properties of CPs. Mafalda Castro (Stockholm University) presented two methods adapted to address the laboratory bioaccumulation and toxicity testing of different CPs in aquatic biota; while Jort Hammer (National Institute for Environmental Studies, Japan) predicted congener-specific partition properties of different individual CPs via COSMOtherm (in silico) and GC retention indices. Louise van Mourik (Vrije Universiteit Amsterdam) focused on MCCPs and presented a summary of updated substance properties such as PBT, log Kow and water solubility.

Indoor and outdoor exposure to CPs in Europe. Aline Arriola (Akvaplan-niva AS) presented a comparison of SC and MCCPs levels in aquatic biota and the possibility that these chemicals undergo trophic dilution in ectotherms from Norwegian lakes was addressed in the live session. Sicco Brandsma (VU University Amsterdam) presented high levels of both MC and LCCPs in PUR foams (even in products where CPs are not listed in the components list), which could contribute to major indoor exposure. In respect to this presentation, during the live session several issues were raised such as the increasing prevalence of LCCPs in these products and the usability of CPs in PUR foam products. Bo Yuan (Stockholm University) presented his work on the assessment of human exposure to CPs in a Norwegian cohort through dermal contact, in which high levels of total CPs covering a range of C7 to C48 were found in hand wipes (up to 18,000 ng).

The current nomenclature used for CPs worldwide. Chris Howick’s (INOVYN) presentation addressed the differences in chloro alkane nomenclature around the globe. A major topic of discussion during this session was the global industrial production of CPs and the adopted nomenclature of CPs (and more broadly UVCBs). This discussion benefited highly from the tripartite sector participation, especially by Howick and Andrew Jaques (RegNet Environmental Services). While CPs are commonly categorized based on their carbon chain length, in China (world’s largest producer of CPs), the categorization is based on chlorination degree. In addition, well-established data show that different CPs below certain level of chlorination are readily biodegradable. Whether regulation could benefit from categorizing in chlorination degree or having chlorination degree as a sub-group is still open, but all engaged participants agreed that the field could benefit from a harmonized nomenclature.

The discussion subsequently addressed the major global production of CPs and the major production in Asia versus Europe. There are six producers in total between Europe and North America, with a total estimated production between 10–100 tonnes a year. In China and India, the situation is diametrically different, with hundreds of manufacturers in each country and an estimated annual production volume of 2 million tonnes in total, although most production is used domestically.

Urgent needs for new standards and quantification improvement. Marina Ricci (EC-JRC) presented the Eurostars CHLOFFIN project, where the aim is to expand the library of certified matrix reference materials for CPs and synthesize different single congener standards (native and labelled). The progress so far on the certification of the first matrix reference material for SCCPs was also presented. Roberto Lava (ARPA Veneto) directly asked the panel how to find validated methods and reliable laboratories that can accurately quantify CPs for the interlaboratory characterization and certification of the matrix reference material. Ricci made a call for interest in participation of an interlaboratory characterization on the matrix reference material candidate for SCCPs during this live session. Solveig Valderhaug (Chiron AS) presented within the same project the first synthesized native single congener standards with a chlorine substitution close to that of CPs found in technical mixtures. Many other crucial stages for this project are expected to be completed by the end of 2020, which will greatly advance the field. The live session was finalized with an overall agreement on the need to develop and adopt appropriate methods, standards and reference materials for a more reliable CP quantification.

Discussions such as this one are necessary to continue to highlight the challenges in this field and as a continuation of the discussion held at SETAC SciCon, another meeting is now planned for 27 August 2020 with the same panel and additional participants. The main purpose of this meeting will be to continue the discussion and follow up on the development and adoption of new methods to reliably quantify the risk of CPs.
Toward fire safety without chemical risk.
De Boer, J., Stapleton, H.M. - Science Volume 364, 2019, pages 231-232, 6437.
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Chlorinated Paraffins in Car Tires Recycled to Rubber Granulates and Playground Tiles
Brandsma, S. H., Brits, M., Groenewoud, Q. R., van Velzen, M. J. M., Leonards, P. E. G. & de Boer, J. - Environ. Sci. Technol. 53, 7595−7603, 2019
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Developments and interlaboratory study of the analysis of short-chain chlorinated paraffins
van Mourik, L. M., van der Veen, I., Crum, S. & de Boer, J. - Trends in Analytical Chemistry. 102, May, p. 32-40, 2018
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Chlorinated paraffins in the environment: A review on their production, fate, levels and trends between 2010 and 2015
van Mourik, L. M., Gaus, P., Leonards, P. E. G. & de Boer, J. - Chemosphere. 155, p. 415-428, July 2016
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Recent developments in capabilities for analysing chlorinated paraffins in environmental matrices: A review
van Mourik, L. M., Leonards, P. E. G., Gaus, C. & de Boer, J. - Chemosphere. 136, p. 259-272. October 2015
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Laboratory intercomparison study on the analysis of short-chain chlorinated paraffins in an extract of industrial soil
Pellizzato, F., Ricci, M., Held, A., Emons, H., Bohmer, W., Geiss, S., Iozza, S., Mais, S., Petersen, M., Lepom, P. - Trends in Analytical Chemistry, Vol. 28, No. 8, 2009
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Validation of a method for the determination of short-chain chlorinated paraffins in soil and sediments
Pellizzato, F., Ricci, M., Held, A., Emons, H. - Accred Qual Assur., 14:529–540, 2009
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Analysis of short-chain chlorinated paraffins: a discussion paper
Pellizzato, F., Ricci, M., Held, A., Emons, H. - J. Environ. Monit., 9, 924–930, 2007
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The EUROSTARS CHLOFFIN Project,
new standards for the analysis of chlorinated paraffins

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Chiron - Chloffin project

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