1 s2.0 S0025326X23010688 Main

Marine Pollution Bulletin 196 (2023) 115633
Contents lists available at ScienceDirect
Marine Pollution Bulletin

journal homepage: www.elsevier.com/locate/marpolbul
A recipe for plastic: Expert insights on plastic additives in the

marine environment
Thomas Maes a, *, Fiona Preston-Whyte a, Stephanie Lavelle a, Alessio Gomiero b,
Andy M. Booth c, Maria Jesus Belzunce-Segarra d, Juan Bellas e, Steven Brooks f, Adil Bakir g,
Lisa I. Devriese h, Christopher Kim Pham i, Bavo De Witte j
a
GRID-Arendal, Teaterplassen 3, 4836 Arendal, Norway
b
NORCE Climate and Environment dep, Mekjarvik 12, 4072 Randaberg, Norway
c
SINTEF Ocean, Brattørkaia 17C, 7010 Trondheim, Norway
d
AZTI, Marine Research Division, Herrera kaia z/g, Portualdea, 20110 Pasai, Spain
e
Centro Oceanográfico de Vigo, Instituto Español de Oceanografía (IEO), CSIC, Subida a Radio Faro 50, Vigo 36390, Spain
f
Norwegian Institute for Water Research (NIVA), Økernveien 94, 0579 Oslo, Norway
g
Centre for Environment, Fisheries and Aquaculture Science (Cefas), Pakefield Road, Lowestoft, Suffolk NR33 0HT, UK
h
Flanders Marine Institute (VLIZ), InnovOcean Campus, Jacobsenstraat 1, 8400 Ostend, Belgium
i
Instituto de Investigação em Ciências do Mar – OKEANOS, Universidade dos Açores, Horta, Portugal
j
Flanders Research Institute for Agriculture, Fisheries and Food (ILVO), Marine Research (ILVO-Marine), Jacobsenstraat 1, 8400 Ostend, Belgium
A R T I C L E I N F O A B S T R A C T
Keywords: The production and consumption of plastic products had been steadily increasing over the years, leading to more
Plastic pollution plastic waste entering the environment. Plastic pollution is ubiquitous and comes in many types and forms. To
Chemical additives enhance or modify their properties, chemical additives are added to plastic items during manufacturing. The
Monitoring
presence and leakage of these additives, from managed and mismanaged plastic waste, into the environment are
Pathways
Ecotoxicity
of growing concern. In this study, we gauged, via an online questionnaire, expert knowledge on the use, char
Global Plastic Treaty acteristics, monitoring and risks of plastic additives to the marine environment. We analysed the survey results
against actual data to identify and prioritise risks and gaps. Participants also highlighted key factors for future
consideration, including gaining a deeper understanding of the use and types of plastic additives, how they leach
throughout the entire lifecycle, their toxicity, and the safety of alternative options. More extensive chemical
regulation and an evaluation of the essentiality of their use should also be considered.
1. Introduction as the composition of the plastic polymer and its additives (Werner et al.,
2016). The leaching of additives is a process inherent to plastic pollu
1.1. Plastic pollution in the marine environment tion, by which plastics may exert additional harmful effects (Bridson
et al., 2021).
Since the 1950s, a significant quantity of polymers has been pro
duced, globally estimated at 9200 million metric tons in 2017 (UNEP,
2021). Inadequate waste management, and future projections show that 1.2. Additives in plastic
even in the best-case scenario, large amounts of plastic will continue to
leak into the environment (Borrelle et al., 2020; Lau et al., 2020; Nyberg Over 13,000 chemicals are associated with plastic production across
et al., 2023). Plastic pollution poses a hazard to many organisms, a wide range of applications, of which over 3200 monomers, additives,
including humans. The extent and mechanisms by which plastic pollu processing aids and non-intentionally added substances are of potential
tion affects organisms are still poorly understood. The impacts are concern due to their hazardous properties (United Nations Environment
dependent on the organism and the size and shape of the debris, as well Programme, and Secretariat of the Basel, Rotterdam and Stockholm
Conventions, 2023). On average, non-fibre plastics have been found to
* Corresponding author.
E-mail address: [email protected] (T. Maes).
https://doi.org/10.1016/j.marpolbul.2023.115633
Received 30 June 2023; Received in revised form 1 October 2023; Accepted 4 October 2023
Available online 19 October 2023
0025-326X/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
T. Maes et al. Marine Pollution Bulletin 196 (2023) 115633
contain 93 % polymer resin and 6–7 % additives by mass (Geyer et al., research focus (packaging/daily life products; inclusion of monomers).
2017), but the amount varies depending on the function of the materials; The compound groups that appeared in at least one of the three publi
for example, additives can constitute up to 80 % of the total volume in cations were compiled, and cross-referenced against reviews by Andrade
polyvinyl chloride (PVC) (Hahladakis et al., 2018). The most widely et al. (2021), Hermabessiere et al. (2017) and Hahladakis et al. (2018). If
used plastic additives being plasticisers, flame retardants, and fillers, the compound groups/chemicals were classified as high risk in at least
which together make up 75 % of global annual additive production one publication (Groh et al., 2019; Lithner et al., 2011; Rodrigues et al.,
(Geyer, 2020; Geyer et al., 2017). Though data for plastic additives 2019) and mentioned in at least two publications out of these 6 publi
production and usage is limited, based on a plastic production volume of cations, they were selected. Monomers were excluded from the final list
438 million metric tonnes, 27 million tonnes of additives are estimated to focus on additives. Solvents and initiators were also excluded as they
to have been produced in 2017 (Geyer, 2020). A key challenge in are not intended to be inherently present in the final products. With the
identifying and quantifying additives in plastic is the sheer number and aim of including emerging compounds and based on the authors’ expert
diversity of substances utilised, as well as confidentiality and commer judgement, organotins, phenylenediamines and polybrominated
cial sensitivity of obtaining information. diphenyl ethers were added to the list. The final list of additives (9)
selected for inclusion in this research is as follows: phthalates, aromatic
1.3. Additives in the environment amines, organophosphates, metal acetates, PFASs/PFOS (perfluoroalkyl
and polyfluoroalkyl substances; perfluorooctane sulfonate (PFOS) is a
Many additives, although useful for the manufacturing and func common example from the PFAS family of chemicals) metals, organo
tionality of products, have widely documented risks of contaminating tins, polybrominated diphenyl ethers and phenelynediamines. The
food, air, soil and water (Fauser et al., 2022; Rani et al., 2022; Wrona complete list of additives extracted from the publications is provided in
and Nerin, 2019). Generally, additives do not chemically bind to poly Supplementary Information (SI, Table S1).
mer chains, except reactive organic additives, e.g., some flame re An illustrative chemical from each group was provided to assist the
tardants (van Oers et al., 2012). Therefore, weakly bound additives can respondents. Offering a representative chemical for each group made it
leach out throughout the entire life cycle of plastic items; through pro easier for survey participants to frame the question but had the potential
duction, use, landfill, incineration, recycling and mismanaged waste drawback of oversimplifying the actual situation. The examples given
streams (Wiesinger et al., 2021). Plastic fragmentation allows for were as follows:
migration far from the point of origin (Geyer et al., 2017), with signif
icant proportions of plastic particles and associated additives found in • Phthalates - e.g., benzyl butyl phthalate
soils and wastewater effluents (Lithner et al., 2011; Tun et al., 2022; • Aromatic amines - e.g., 4-4-methylenedianiline
Wagner and Schlummer, 2020). These hazardous substances may persist • Organophosphates - e.g., tris(2-chloroethyl)phosphate
in the environment and/or bioaccumulate in organisms, ultimately • Metal acetates - e.g., cobalt(II)diacetate
adding to the chemical burden on our ocean and earth systems (Hansen • PFAS/PFOS - e.g., perfluorooctanoic acid
et al., 2013). Once in the environment, additives and/or contaminants • Metals - e.g., lead
can react, degrade and become even more toxic when exposed to • Organotins - e.g., fentin acetate
particular species (Hahladakis et al., 2018). Many have been classified • Polybrominated diphenyl ethers - e.g., BDE-209
as hazardous and are therefore of concern for human and environmental • Phenelynediamines - e.g., 6-PPD
health (Groh et al., 2019; Rochman, 2015; Wiesinger et al., 2021).
Though measuring additive composition in litter is developing (Corami
et al., 2021, 2022; Rosso et al., 2022), the composition of additives in 2.2. Survey approach
plastic products and debris is largely unknown.
A staggered survey approach was devised to measure the knowledge
1.4. Aim of this study among experts who share a common interest in additives, chemical
pollution, or the marine environment. The survey was initially released
Given the gaps in knowledge acknowledged within literature (14 February 2022–3 March 2022) to experts within the working groups
regarding additives, the authors set out to measure the knowledge of of the International Council for the Exploration of the Sea (ICES) related
additives from experts. In this study, we gauged expert knowledge to marine litter (WGML), marine chemistry (MCWG) and biological ef
through an online survey and evaluated the outcome against objective fects of contaminants (WGBEC). In the second phase, a broader range of
data. This study focuses on understanding knowledge in relation to (i) relevant experts were invited to answer the survey (4 March 2022–6
the use of additives globally, (ii) the characteristics of plastic additives May 2022). A complete list of organisations to which the survey was
(this refers to entry sources and pathways), and (iii) the risks associated distributed can be found in SI (Table S2). The results from all surveys
with plastic additives in the environment. were combined for analysis.
A survey (provided in the SI, Table S3) was compiled to collect de
2. Methods mographic information of each respondent, as well as their knowledge
on the following topics for each compound group/chemical:
This study employed an online survey to gauge how experts involved
in plastic production or plastic litter research perceive their knowledge • if they were aware of the production volumes?
of plastic additive chemicals, with the aim of evaluating potential dis • Whether other sources and routes exist, aside from plastics, through
parities between perception and actual knowledge. which these compound groups enter the marine environment?
• whether there are standardised and established techniques for ana
2.1. Selection of compound groups/chemicals lysing this compound group, and if there are, to specify the method?
Compound groups were selected following a literature review using • if these compound groups are persistent, bioaccumulative and/or
“additives”, “chemicals” and “plastic” as keywords. Three publications toxic?
that contained comprehensive lists of hazardous or high-risk additives • if these compound groups cause a risk to the lower marine trophic
and monomers (Groh et al., 2019; Lithner et al., 2011; Rodrigues et al., levels (plankton, algae etc.)?
2019) were used to define compound groups and select examples. The • if these compound groups cause a risk to the higher marine trophic
lists in each publication differed significantly, due to the difference in levels (fish, mammals, birds etc.)?
2
The respondent’s personal information was collected, processed, and posed by various additives to aquatic organisms at various positions in
managed within General Data Protection Regulation (GDPR) and other the food chain (see S.I. S7). Initially, representative chemicals were
relevant international privacy laws. selected from each of the plastic additive chemical groups used in this
study. Scientific databases such as Web of Science, Scopus, Google
Scholar and PubMed were then explored to compile the reported lethal
2.3. Data analysis
and sublethal toxicity levels of the selected plastic additives. Search
terms comprised of specific keyword combinations, including the names
2.3.1. Statistics
of selected plastic additives, were used to identify scientific papers
Descriptive statistics were applied to assess the expert responses.
focusing on aquatic toxicity. Relevant articles and reports were selected
and reviewed to establish the lethal and sublethal toxic effects of the
• To begin, demographic information of the respondents was sum
selected substances, and the available toxicity data (lowest effect con
marised using Tableau Public, an accessible online tool for data
centration, LOEC, median lethal concentration, LC50, median effective
visualisation. This step allowed us to gain insights into the attributes
concentration, EC50) was collated (SI, Table S7). Finally, aquatic or
of the survey participants, such as age, gender, and professional
ganisms were grouped into three trophic levels (namely microalgae,
background.
invertebrates, fish), and the toxicity threshold values for each chemical
• Microsoft Excel was used to organise and present the remaining
were estimated by calculating the average of the EC50/LC50/LOEC
survey data, ensuring that it was readily accessible for further
values obtained in the literature review within each trophic level.
analysis.
• For questions employing the Likert scale, median responses were
3. Results
considered (data provided in SI, Fig. S4). ‘I don’t know’ responses
were treated and reported separately. The remaining responses were
The survey was completed by 50 respondents, 17 ICES experts and 33
transformed into percentages of the total respondent count,
other specialist stakeholders. Of the 50 individuals (Fig. 1), the majority
excluding instances where ‘I do not know’ was chosen.
(82 %) were based in Europe, followed by Sub-Saharan Africa (10 %),
• To convey the intricate hierarchies within data concerning open-
Australia and Oceania (4 %), Asia (2 %) and North America (2 %). The
ended questions, tree-maps were employed. These tree-maps
majority of the respondents were employed in research and/or academia
consist of nested rectangles, with each larger rectangle subdivided
(76 %), the remaining fractions were employed in government (16 %),
into smaller ones, proportionally representing distinct responses.
NGO/IGO sector (6 %) and civil society (2 %). The invited professionals
This visualisation method helped capture the diversity of responses
from the industry chose not to participate in this survey. In terms of
to open-ended questions.
gender, 44 % were female, 52 % were male, and 4 % preferred not to say.
Most of them were in the age groups of 41–50 (32 %), 31–40 (28 %), and
2.3.2. Available lowest effect concentration (LOEC) data
51–60 (24 %). The vast majority (98 %) of the participants held a
A dedicated literature review was conducted to validate and sub
postgraduate degree.
stantiate the responses provided by the participants regarding the risk
Fig. 1. Map showing the demographics of all respondents.
3
3.1. Use of additives globally for metal acetates, aromatic amines and phenylenediamines (unknown
production volume by at least 50 % of respondents). The highest level of
The participants exhibit a deficiency in their understanding of the awareness regarding production quantities was observed for phthalates
use of additives globally (total production volumes) (Fig. 2a), especially and metals. More than 70 % of respondents indicated being able to
Fig. 2. Respondent’s knowledge of the approximate volumes of compound groups produced globally, relative to each other with a) the respondents who answered ‘I
don’t know’ (%) and b) results from respondents with ‘I don’t know’ responses removed (%).
4
estimate the relative production volumes for these compound groups, regulation and the necessity of their use are also important. When
which also revealed the highest median scores (provided in SI Fig. S4). considering other important questions (Fig. 10), questions around al
Phthalates and metals were recognised as being produced in large vol ternatives featured prominently (4 additional questions were listed).
umes by 37 and 32 % of respondents. Other concerns include information around environmental/economic
factors, gaps in knowledge on research and gaps in knowledge on
3.2. Characteristics of additives recycling.
The prevailing response among the participants regarding which
For most compound groups, experts acknowledged routes leading knowledge gaps should be tackled was the need for more research on
into the marine environment that didn’t involve plastics, with the alternative options (Fig. 11). Subsequently, in descending priority, there
exception of aromatic amines and phenylenediamines, whereby at least is a need for additional research on the impact, expanded risk assess
50 % of respondents were unsure (Fig. 3a and b). ments, further investigation into additives that leach under varying
environmental conditions, and more comprehensive life cycle analyses.
3.3. Monitoring of additives The respondents also submitted additional questions, which could be
divided into the following topics (Fig. 12): research questions, alterna
For metal acetates and phenylenediamines, a relatively high number tives and recycling, and environmental/economic.
of respondents were unaware of the availability of analytical methods
(62 % and 60 % of respondents, respectively) (Fig. 4a). For phthalates, 4. Discussion
organophosphates, PFAS/PFOS, metals, and PBDEs, >50 % of the ex
perts mentioned the existence of established methods for analysing these The leakage of additive chemicals into the environment from plastics
compounds in the marine environment. Respondents were unsure of the is of growing concern. Even though a wide range of additives is used in
other chemical groups or mainly indicate that methods are available but plastic products, there is a significant lack of information regarding their
not yet standardised (Fig. 4b). Fig. 5 summarises the methods named by use, characteristics, monitoring, and their potential risks to the marine
respondents. environment.
3.4. The risks posed by additives 4.1. General considerations regarding gaps in knowledge
3.4.1. Persistent, bioaccumulative and/or toxic nature The respondent’s knowledge on different chemical groups is highly
The respondents knowledge of the persistent, bioaccumulative and/ variable, which partly reflects the historical research focus on specific
or toxic (PBT) nature of the compound groups is presented in Fig. 6. groups. This duality is reflected in the survey results. For example, the
Overall, the PBT nature is most known for metals, PFAS/PFOS and risk of phthalates to lower marine trophic levels was estimated as an
phthalates, while a larger group of respondents expressed being unsure extreme risk (45 %) to no risk at all (16 %), with 38 % responding that
about phenylenediamines, aromatic amines and methyl acetates. they did not know (Fig. 7). The highest degree of knowledge was found
Phthalates, PFAS/PFOS, metals, organotins and PBDEs reach the highest for compounds that are known to have a high environmental persistence
PBT scores, with most respondents indicating that these compound and/or bioaccumulation potential, such as metals, PFAS/PFOS and
groups possess each characteristic. A slight difference in response can be PBDEs. These compound groups are already classified as priority sub
noted, with PFAS/PFOS and phthalates scoring highest on persistence stances within European marine legislation, such as the Marine Strategy
(38 % and 34 % of respondents, respectively), metals, PBDE’s and Framework Directive (MSFD) and/or in monitoring programmes of
organotins scoring highest on bioaccumulation (33 %, 33 % and 33 % of regional sea conventions in European waters (Tornero and Hanke,
respondents) and phenylenediamines, aromatic amines, metal acetates 2018). Ongoing marine environmental monitoring for many of these
scoring high on toxicity (47 %, 47 % and 45 % of respondents). priority compounds has resulted in large datasets on their occurrence
and toxicity in different media, fostering a good knowledge of the re
3.4.2. Risk to lower marine trophic levels spondents. In contrast, phenylenediamines such as 6-PPD have only
The participants’ understanding of the risk of compound groups to recently caught attention of the research community and regulators
the lower levels of marine ecosystems appears to be largely lacking or (Tian et al., 2021; Wagner et al., 2022), resulting in less knowledge of
unknown for all the compound groups (Fig. 7a), especially for phenyl this compound group by respondents. A large group of respondent’s
enediamines, metal acetates and aromatic amines. More respondents are mention being unaware of the production volumes (58 %), PBT char
aware of the risks of metals (Fig. 7a). Knowledge of the risk is dominated acteristics (58 %) or risks to lower (70 %) and higher (56 %) aquatic
by average or extreme risk, whereas “no risk” was seldom selected organisms of phenylenediamines (Figs. 2a, 7a, 8a). Nevertheless, the 6-
(Fig. 7b). A conflicting response was given for phthalates with 16 % of PPD oxidation product, 6-PPD-quinone, has recently been demonstrated
respondents indicating no risk while 45 % indicating very high risk. to be ecotoxicological relevant and could be categorised as highly toxic
Organotins, organophosphates and PBDEs were highlighted as an for aquatic organisms (Tian et al., 2021, 2022) (see also Fig. S7).
extreme risk to lower marine trophic levels by over 50 % of respondents.
Respondents also recognise the risk of aromatic amines and metals, 4.2. What is known about the use of plastic additives?
where “no risk” was not selected.
The release of plastic additive chemicals and their impacts on the
3.4.3. Risk to higher marine trophic levels environment depends on the volumes produced, their use and their
The survey participants exhibit a stronger awareness of the risks to respective pathways into the marine environment. Estimating the vol
higher marine trophic levels (as shown in Fig. 8a) compared to their ume of chemicals produced and used globally for plastic production is
understanding of risks at lower trophic levels (illustrated in Fig. 7a) challenging for several reasons. First, the production of plastic involves a
across all the compound groups. complex supply chain that spans multiple countries and companies,
making it difficult to obtain accurate data on the volume of plastic ad
3.5. The way forward and knowledge gaps ditive chemicals used. Second, the vast array of plastic types requires
different chemical inputs (types and amounts), depending on the desired
The participants prioritise inquiring about the safety of alternative properties of the final product. Finally, some of the chemicals used in
options when engaging with stakeholders (Fig. 9). At the same time, plastic production are not specifically produced for that purpose and
more than half of the respondents indicate that questions on further have multiple uses in various industries, making it difficult to
5
Fig. 3. Respondent’s knowledge of existing sources and pathways, other than plastics, of these compound groups in the marine environment with a) the respondents
who answered ‘I don’t know’ (%) and b) results from respondents with ‘I don’t know’ responses removed (%).
6
Fig. 4. The respondent’s knowledge (%) of standardisation and developed methods to analyse these compound groups with a) the respondents who answered ‘I don’t
know’ (%) and b) results from respondents with ‘I don’t know’ responses removed (%).
7
Fig. 5. Tree-map visualisation of methods that respondents are aware of to analyse the compound groups, in which the hierarchal data is displayed in nested tri
angles, with each larger rectangle subdivided into smaller ones proportionally representing different methods. Interpretation involves understanding the size and
colour of the rectangles to grasp the most commonly suggested methods for each compound group. Data and abbreviations also presented in SI Table S5.
distinguish between the amount of chemicals produced for plastic pro and other functional additives (e.g., antioxidants, heat stabilisers, UV
duction and those produced for other purposes. The lack of transparency stabilisers and biocides) are used in lower volumes (0.001–3 % of mass).
and comprehensive management practices by chemical producers and Non-intentionally added substances (NIAS) are chemicals added without
plastic manufacturers, combined with fragmented policies and incom a technical reason during the production process. They are often present
plete publicly available information, are significant barriers to in food packaging from which they can easily migrate into food. NIAS
increasing our knowledge of the volumes and types of additive chem alone may account for more than half of the number of chemicals in
icals used in plastic production. plastics (Geueke et al., 2018).
4.2.1. Production and usage of plastic additives 4.2.2. Volumes of additives entering the marine environment
Packaging, automotive, consumer goods, construction and elec The current study highlighted an existing lack of knowledge among
tronics are some of the most important markets for plastic additives experts regarding the production volumes and usage of plastic additives,
(Hahladakis et al., 2018). Regulations and reporting vary by country or particularly metal acetates, aromatic amines, and phenylenediamines.
region, but many plastic applications necessitate a safety or technical This could indicate a lack of transparency on the use of specific groups of
data sheet that mandates the disclosure of additives exceeding a certain additives. Chemical inventories and databases available for 19 countries
percentage. This requirement applies to items such as building materials have revealed the registration of over 350,000 chemicals and chemical
and household applications, but not to basic consumer products e.g., compounds (Wang et al., 2020). The European Chemicals Agency
toys. A random plastic item can easily contain around 20 additives, with (ECHA), which is the administrative and technical support for the
fillers and plasticisers used in the highest volumes (van Oers et al., Registration, Evaluation, Authorisation and Restriction of Chemicals
2012). Fillers (e.g., calcium carbonate, metal powder, clay) often (REACH) regulations, maintains one of the most comprehensive in
constitute up to 50 % of the mass of plastics and represent around 28–50 ventories. As of March 2023, ECHA’s database contains over 26,000
% of the world’s additive market (Geyer et al., 2017; Hansen et al., 2013; REACH registrations. Around 80 % of these substances, however, are yet
UNEP, 2021). Primarily, they’re added to polymers to cut costs, enhance to be assessed, and data on production volumes and applications are still
aesthetics, shape, durability (UV protection), and simplify polymer lacking (Persson et al., 2022). In this study, applicants’ responses on
manufacturing (Groh et al., 2019; Wagner and Schlummer, 2020; Wie plastic additive production volumes were cross-checked against the
singer et al., 2021). Reinforcement additives, such as glass fillers, can ECHA database (SI, Table S6). Commonly used metal and phthalate
account for an additional 15–30 % of the volume of plastic materials compounds represent some of the highest production volumes, agreeing
(Hansen et al., 2013). Plasticisers are used to increase flexibility and can with expert opinions gathered in this survey. However, it is difficult to
constitute 10–80 % of the mass of plastic materials, representing around estimate what proportions (particularly of metals) are used in plastic
22–34 % of the world’s additive market (>80 % of which are phthalates) manufacturing. Phthalates are the most widely used plasticiser, with
(Geyer et al., 2017; UNEP, 2021; van Oers et al., 2012). Flame retardants PVC accounting for ~80 % of total phthalate consumption (Holland,
(12–18 % of mass) are also used in relatively high volumes and, together 2018). The global phthalate plasticiser market is estimated to be
with fillers and plasticisers, account for around 75 % of all additives approximately 6–8 million tonnes per year, with China, the USA and
(Geyer et al., 2017; Hansen et al., 2013). Colourants (0.25–5 % of mass) Europe accounting for about 70 % of the market (Holland, 2018; United
8
b)
Fig. 6. Respondent’s knowledge of the compound group’s persistent, bioaccumulative and/or toxic nature with a) the respondents who answered ‘I don’t know’ (%)
and b) results from respondents with ‘I don’t know’ responses removed (%).
Nations Environment Programme, and Secretariat of the Basel, Rotter enter the environment. Identifying the routes of their release is essential
dam and Stockholm Conventions, 2023). for effective management, regardless of whether it’s due to poor plastic
waste handling or other factors. To reliably assess the risk to wildlife, we
must determine the chemical identity, quantity, and exposure to these
4.3. Characteristics of additives additives (Adlard, 2019). A current understanding of the pathways of
each plastic additive chemical group into the marine environment, from
Plastic additives enter the environment via various sources and both plastic and other sources, is presented below.
routes. To assess the risk of released additives in the environment, it’s
crucial to know global production volumes and understand how they
9
Fig. 7. The respondent’s knowledge of the risk of the compound groups/chemicals to the lower marine trophic levels with a) the respondents who answered ‘I don’t
4.3.1. Phenylenediamines other phenylenediamines and phenylenediamine mixtures are used as

Most respondents (64 %) were unsure about the pathways, other antioxidant additive chemicals in vehicle tyres, as well as other rubber
than plastics, of phenylenediamines into the marine environment and latex products including shoe soles, conveyor belts, and floor cov
(Fig. 3a), most likely reflecting that this group of chemicals is not very erings. TWPs and tyre crumb rubber have been identified as important
high profile from an environmental risk perspective. Large knowledge land-based sources of microplastics in the environment (Kole et al.,
gaps still remain on their environmental occurrence and fate (Huang 2017; Magnusson et al., 2016; Parker-Jurd et al., 2020). A complex
et al., 2021). The chemical p-phenylenediamine is primarily used as a mixture of chemicals has been demonstrated to leach from TWPs and
dye intermediate and as a dye (National Center for Biotechnology In crumb rubber once they are released to the marine environment
formation, 2022a). Both N-(1,3-dimethylbutyl)-N′-phenyl-p-phenyl (Capolupo et al., 2020, 2021; Halsband et al., 2020). Zeng et al. (2023)
enediamine (6-PPD) and N-(1,3-dimethylbutyl)-N′-phenyl-p- reported the widespread occurrence and distribution of PPDs and their
phenylenediamine-quinone (6-PPDQ) are chemicals associated with derived PPD-Qs in sediments on a large geographical scale, among
vehicle tyres, and therefore with tyre wear particles (TWPs) and end of which 6PPD and 6PPD-Q were the most prevalent in the aquatic envi
life tyres repurposed as crumb rubber that is commonly used in road ronment. Total sedimentary concentrations of PPDs and PPD-Qs pre
asphalt and infill material for artificial turf sports fields. A number of sented a clear spatial trend with decreasing levels from urban rivers
10
Fig. 8. The respondent’s knowledge of the risk of the compound groups/chemicals to the higher marine trophic levels with a) the respondents who answered ‘I don’t
(medians: 39.7 and 15.2 ng/g) to estuaries (14.0 and 5.85 ng/g) and known natural sources of PBDEs have been identified except for a few
then toward coasts (9.47 and 2.97 ng/g) and deep-sea regions (5.24 and marine organisms that produce forms of PBDEs that contain higher ox
3.96 ng/g) (Zeng et al., 2023). Data highlighted the importance of rivers ygen levels (US EPA, 2017), meaning these derive entirely from
as pathways for the entry of those compounds to the marine anthropogenic sources. PBDEs have been used widely since the 1970s as
environment. flame retardants in polyurethane foams in upholstery, polymer resins,
and plastics used as components in electrical equipment (Environment
4.3.2. PBDEs Agency, 2019). PBDEs are not chemically bound to the plastic or foam in
The majority of respondents (72 %) were aware of the pathways, in which they are incorporated, resulting in high potential for their
addition to plastics, of PBDEs into the marine environment (Fig. 3b). No leaching into the environment (Kwan and Takada, 2016; Tanaka et al.,
11
Fig. 9. Respondent’s suggestions as to important questions to ask stakeholders (e.g., a policy maker or the plastic industry) concerning the use of plastic additives.
Fig. 10. Tree-map visualisation of the ‘other’ questions the respondents think are important to ask stakeholders (e.g. policy maker or plastic industry) concerning
plastic additives. The hierarchal data is displayed in nested triangles, with each larger rectangle subdivided into smaller ones proportionally representing different
methods. Interpretation involves understanding the size and colour of the rectangles to grasp the most commonly suggested questions for each factor considered.
2015). Although PBDEs are not considered to be very mobile due to their and in biota at all trophic levels (Barber et al., 2021; de Wit et al., 2010;
high sorptive properties and high hydrophobicity (Environment Agency, Law et al., 2014; Yogui and Sericano, 2009). PBDEs can enter the
2019), they have been detected in marine sediments across the globe environment from various sources. Wastewater treatment plants have
12
Fig. 11. Respondent’s suggestions as to important knowledge gaps that need to be addressed urgently to support policies on standards and legislation for plas
tic additives.
Fig. 12. Tree-map visualisation of the “other” inquiries raised by the respondents, which they believe are crucial knowledge gaps requiring immediate attention to
bolster policies on standards and regulations for plastic additives. The hierarchal data is displayed in nested triangles, with each larger rectangle subdivided into
smaller ones proportionally representing different methods. Interpretation involves understanding the size and colour of the rectangles to grasp the most commonly
suggested questions for each factor considered.
been shown to be a substantial source of PBDEs in the environment. (WWTPs) along the U.S. and Mexico Border with concentrations ranging
Peng et al. (2009) detected PBDEs in sewage treatment plants in the from 30.2 to 342 ng L− 1 in wastewater influents, from not detected to
Pearl River Delta (South China) in concentrations ranging from 13.3 to 209 ng L− 1 in effluents, and from not detected to 1303 ng g− 1 in sludge.
2496.4 ng L− 1 in the raw wastewater with 0.9 to 4.4 ng L− 1 in the treated Both studies also suggested the incomplete removal of PBDEs from the
effluent (Peng et al., 2009). Rocha-Gutierrez and Lee (2013) also WWTPs (in some cases) leading to continuous release of PBDEs to rivers
investigated the occurrence of PBDEs in Wastewater Treatment Plants and irrigation canals or via sewage sludge (Rocha-Gutierrez and Lee,
13
2013; Peng et al., 2009). PFAS to the natural environment include landfill sites, industrial dis
charges and local historical contamination – especially around sites such
4.3.3. Organotins as military bases and airports where there may have been significant use
The majority of respondents (72 %) were aware of the pathways, in of aqueous film-forming foams during firefighting training. PFAS can be
addition to plastics, of organotins in the marine environment (Fig. 3b). present in soil from such historical sources or from spreading sewage
Organotins are mainly used as biocides, polyvinyl chloride stabilisers sludge to land. Because PFAS is moderately soluble in water, it can enter
and industrial catalysts to manufacture silicone and polyurethane foams surface waters from contaminated soil and leach to groundwater. PFAS
(Sousa et al., 2014). In the marine environment, organotins were pre has a moderate potential to sorb to soil and a lower sorption potential in
viously used extensively in antifouling solutions and paints, although sediments. The degree of sorption can vary depending on the level of
several of the most toxic, such as tributyltin (TBT), have since been salinity, pH and total organic carbon (Environment Agency, 2004,
banned. They do, however, remain as a legacy pollutant in places where 2021). PFAS is mainly transported in the dissolved phase in rivers rather
such paints are still used or where such paints remain on older ships. The than being adsorbed to suspended solids and has the potential for long-
environmental behaviour of organotin antifouling compounds in the range transport in the water column. PFAS has been detected in UK
marine environment is complex, as seawater pH strongly affects their freshwater, estuarine and coastal biota (Environment Agency, 2021) and
speciation (Beyer et al., 2022). TBT is, however, expected to behave sediments (Barber et al., 2021). PFAS were detected above quantitation
relatively similarly to other hydrophobic organic contaminants under limits in 85 of the 103 sediment samples analysed, at concentrations up
∑
typical seawater pH. TBT-contaminated sediments are likely to play a to 4.93 μg/kg d.w. for PFAS (or 4.54 μg/kg d.w. normalised to 1 %
role as a major reservoir of potential pollution unless active sediment TOC) (Barber et al., 2021).
remediation measures, such as dredging and capping, are performed
(Beyer et al., 2022; Langston and Pope, 1995). 4.3.6. Metal acetates
Over half of respondents (54 %) were aware of the pathways, in
4.3.4. Metals addition to plastics, of metal acetates into the marine environment
Most respondents (92 %) were aware of the pathways, in addition to (Fig. 3b). For example, zinc acetate is used as the catalyst for the in
plastics, of metals into the marine environment (Fig. 3b). Heavy metals dustrial production of vinyl acetate, a precursor to PVA and EVA. Other
are natural constituents of the Earth’s crust, generally being found in uses for zinc acetate include its use as a wood preservative, mordant in
very low concentrations (Ansari et al., 2004). However, industrial and dyeing, antiseptic, feed additive, a cross-linking agent for polymers,
anthropogenic activities such as industrial waste discharges, agricultural catalyst, waterproofing agent, therapeutic styptic and astringent, and
practices, coastal construction and dredging have increased their con topical fungicide (National Center for Biotechnology Information,
centrations in the marine environment (Ansari et al., 2004; Fu and 2022b). Sodium acetate is used in the textile industry and synthetic
Wang, 2011; Shah, 2021). While plastics do not represent an important rubber production. Sodium acetate is also used in the food industry as a
source of metals into the marine environment, metals can be found in so- preservative (E262) and buffer in the cosmetics industry in various
called ‘oxo-biodegradable’ plastics in which a prooxidative additive is personal care products. Metal acetates enter the marine environment
added to initiate degradation. The most common additives on the mainly from land-based sources via sewage and riverine discharge
market are d2w and TDPA (Totally Degradable Plastic Additives), usu (National Center for Biotechnology Information, 2022c).
ally produced from cobalt, manganese, and iron compounds (Markowicz
and Szymańska-Pulikowska, 2019; Ojeda et al., 2009). Furthermore, a 4.3.7. Organophosphates
number of plastic additive chemicals and catalysts were based on The majority of respondents (72 %) were aware of the pathways, in
compounds of toxic metals (and metalloids), like arsenic, cadmium, addition to plastics, of organophosphates into the marine environment
chromium (VI), and lead. Despite subsequent restrictions, hazardous (Fig. 3b). These chemicals are the main components of herbicides,
metal additives remain in plastics in societal circulation, where they pesticides and insecticides. Organophosphate esters have also been
continue to leach into the natural environment (Turner and Filella, widely used as flame retardants and plasticisers (Castro-Jiménez et al.,
2021). 2016). Organophosphate flame retardants are not chemically bound to
the polymer with potential for leaching into the surrounding environ
4.3.5. PFAS/PFOS ment (Liao et al., 2020). Organophosphates are thought to enter the
The majority of the respondents (78 %) were aware of the pathways, marine environment mainly from land-based sources via atmospheric
in addition to plastics, of PFAS/PFOS into the marine environment transport and riverine discharge (Xie et al., 2022). These chemicals have
(Fig. 3b). PFAS have unique physicochemical properties due to their also been detected in coastal waters and sediments, with the highest
combination of hydrophilic and lipophilic characteristics. Certain PFAS concentrations being found mainly near to populated and industrial
family chemicals (e.g., PFOS) and PFAS-related substances have been areas (Liao et al., 2020; Xie et al., 2022).
used historically to provide soil, oil and water resistance to textiles,
clothes, home furnishings and upholstery, carpets and leather, paper and 4.3.8. Aromatic amines
packaging, and coatings and coating additives. Some major industry Half of the respondents (50 %) were unsure about the pathways, in
sectors using PFAS chemicals include aerospace and defence, automo addition to plastics, of aromatic amines into the marine environment
tive, aviation, food contact materials, textiles, leather and apparel, (Fig. 3a). These chemicals are mainly used in the creation of artificial
construction and household products, electronics, firefighting, food dyes, as well as oil refining, synthetic polymers, adhesives, rubbers,
processing, and medical articles (ECHA, 2022). Despite the recent re perfume, pharmaceuticals, pesticides and explosives. Aromatic amines
strictions on use, older consumer products such as carpets, textiles and can also be generated from diesel fuel combustion, as well as the com
upholstery treated with PFOS or PFAS-related substances will continue bustion of wood chips, rubber and tobacco. Some types of aromatic
to act as a source of these chemicals. Emissions can occur during the use, amines are also generated during cooking (Pereira et al., 2015). Aro
washing and disposal of such items, entering the environment through matic amines are used as precursors of azo dyes, which represent about
wastewater treatment works or waste management facilities. The two-thirds of all synthetic dyes produced, making them the market’s
available scientific evidence suggests only a limited removal of PFAS/ most widely used class of organic dyes (Freeman, 2013). Aromatic
PFOS is likely to occur through adsorption to sludge. Academic studies amines enter the marine environment mainly from land-based sources
indicate that PFOA and PFOS may also be formed during wastewater via the atmosphere, sewage and riverine discharge (Pereira et al., 2015).
treatment from precursor compounds (Environment Agency, 2004,
2021; Xiao, 2022). Additional and potentially significant sources of
14
4.3.9. Phthalates additive migration into relevant environmental media should be eval
A majority of respondents (78 %) were aware of the pathways, in uated through the whole plastic life cycle to identify where such emis
addition to plastics, of phthalates into the marine environment (Fig. 3b). sions are most likely to occur (Askham et al., 2023). There is also an
As phthalates are mainly used as plasticisers, they are found in a wide urgent need for representative additive chemical-containing plastic
range of polymer- and plastic-based consumer products, such as adhe reference materials to evaluate leaching more accurately and repro
sives, sealants, paints, rubber materials, wires and cables, flooring, ducibly, as well as for use in ecotoxicity testing for establishing clear
packaging, food contact materials, medical devices, sports equipment regulatory guidelines. As the methods used to prepare homogenous
and personal care products (ECHA, 2022). The primary sources of plastic additive chemical exposure solutions can strongly impact
phthalate esters in the marine environment include leaching from bioavailability and toxicity, harmonised testing approaches need to be
plasticised plastic materials, industrial water, wastewater discharges developed, which consider marine and freshwater media, also incor
and riverine discharge. As some phthalate esters have a low water sol porating solid matrices with variable contents of organic matter.
ubility and a high octanol-water partition coefficient, they can become
concentrated in suspended matter and sediment (Arfaeinia et al., 2019). 4.5. Risks posed by additives
Phthalates can be considered ubiquitous in the environment, with
several studies reporting the occurrence and abundance of the 4.5.1. The risks posed by additives in the environment
commonly used di(2- ethylhexyl) phthalate (DEHP) in environmental The physicochemical properties of the plastic polymers (e.g., poly
samples, including marine waters, sediment and biota (Hidalgo-Serrano mer type, crystallinity, porosity, degree of degradation), the physico
et al., 2022). Phthalates are also semi-volatile organic compounds. Their chemical properties of the different additives (e.g., molecular weight,
atmospheric transport has also been shown to be an important route of hydrophobicity) and the properties of the surrounding media (pH,
entry in the environment with DEHP and DBP being the main com temperature, salinity, UV levels) may significantly influence the degree
pounds in both indoor and outdoor air phthalates (Jia et al., 2019; Tran and rate of the diffusion-controlled process of plastic additive migration
et al., 2022). Phthalates can also accumulate in settled dust (Bi et al., from plastic items and particles to the environment. When present in
2018; Hua et al., 2022). Urban road dust has also been suggested as an aquatic compartments, aqueous leaching of plastic additives into natural
additional transport pathway of phthalates into surface waters (Tran waters can result in conventional chemical exposure to organisms.
et al., 2022). Their environmental fate, transport and transformation/ Under certain conditions, plastic additives may also leach directly into
degradation under natural conditions are, however, highly dependent organisms following the ingestion of plastic particles (Kühn and van
on their physical and chemical properties (Prasad, 2021). Franeker, 2020). Therefore, risk assessment of plastic additives must
also consider their persistence in the natural environment and their
4.4. Monitoring additives in the environment potential for accumulation in specific matrices (e.g., sediments) and
bioaccumulation across different trophic levels. Exposure to released
The analysis of extractable and leachable organic chemicals from plastic additives could potentially lead to multiple adverse effects in a
plastic debris is typically performed using gas chromatography mass range of organisms. In humans, exposure to additives have been linked
spectrometry (GC–MS) or liquid chromatography mass spectrometry with impacting childhood development, the nervous and endocrine
(LC-MS) techniques. Owing to their sensitivity, specificity, reproduc system (Lithner et al., 2011), impairing reproductive functions and
ibility, and versatility, both analytical techniques have been widely causing carcinogenic effects, even at very low doses (Aurisano et al.,
utilised for the quantification and semi-quantitative screening of 2021; Meeker et al., 2009). However, only a limited number of additives
leaching compounds, including plastic additives (Adlard, 2019). Anal have been widely studied, with even less considering low dose, long-
ysis of inorganics usually involves spectrometric or spectroscopic term or mixed substance effects. Still, they may include harmful com
detection using inductively coupled plasma mass spectrometry (ICP- pounds such as bisphenol A (BPA) or metals, including cadmium, lead or
MS), ICP atomic/optical emission spectroscopy (ICP-AES/ICP-OES) or arsenic (van Oers et al., 2012).
atomic absorption spectrometry (AAS) (Dehouck et al., 2016). Most Knowing and dissociating the mechanisms of plastic toxicity that are
respondents appeared to be relatively knowledgeable about the avail driven by (i) the physical polymer material and (ii) plastic-associated
able instrumentation and the most commonly used analytical techniques chemicals (additives and NIAS) is of high importance for conducting
for detecting and quantifying the different plastic additives (Fig. 5). This robust risk assessment and for the development of effective mitigation
included GC–MS for more non-polar and semi-volatile organic sub strategies. The risks associated with any chemicals emitted into the
stances such as phthalates, PBDEs and organotins, LC-MS for thermally environment can be divided into two assessment categories. First is the
unstable, polar or non-volatile compounds such as PFAS/PFOS and ar type of risk that a chemical presents; Is the chemical persistent, bio
omatic amines, and ICP-based approaches for metals. accumulative or toxic to organisms, or a combination of all three. Sec
A majority (at least 50 %) of respondents indicated that standardised ond is the trophic level at which the chemical represents a hazard; Is the
methods are available for phthalates, organophosphates, PFAS/PFOS, chemical a threat to lower or higher marine trophic levels, or both? In
metals, metal acetates, organotins and PBDE’s (Fig. 4). Respondents this study, we assessed experts’ understanding regarding the risks linked
frequently refer to available ISO standard methods specific to soil or to plastic additives, identified which trophic levels are most susceptible
freshwater samples for plastic additive analysis. However, it should be to these risks, and then compared this with existing threshold values for
stressed that specific analytical needs might be required for marine specific chemicals.
samples due to the higher salt concentration in the respective matrices
or due to lower contaminant concentrations in the marine environment. 4.5.2. PBT assessment
For aromatic amines and phenylenediamines in particular, the re The survey results show that the respondents are confident of their
spondents were typically unable to suggest standardised methods, knowledge regarding the PBT properties of Figure 6metal, PFAS/PFOS
highlighting the need for efforts on method standardisation to correctly and phthalate plastic additives (Fig. 6b). This might indicate there is a
estimate the risks of these groups of plastic additives in the marine comprehensive level of research and widespread dissemination of in
environment. formation available within the scientific community and beyond,
Additional focus needs to be given to providing information on the particularly for these specific sets of plastic additives. Furthermore,
relative abundance of different additive chemical groups in plastics, as some of the general PBT data available for these chemicals and metals
well as improved data regarding the relevant physicochemical proper derives from a wealth of research conducted over many decades that has
ties (e.g., vapour pressure, boiling point, solubility and KOW) for pre not been directly focused on their use as plastic additives. In contrast,
dicting their migration into surrounding media. Furthermore, plastic many respondents expressed a low level of knowledge regarding the PBT
15
properties of phenylenediamines, methyl acetates, organophosphates 4.5.3.1. Risks to lower trophic levels. The majority of respondents
and aromatic amines (Fig. 6a). This result indicates a low level of perceived the risk of organotins (66 %) and, to a slightly lesser extent,
knowledge regarding the risks associated with these plastic additives, organophosphates (53 %) as being high for low marine trophic levels
including from individuals working directly in the field of plastics and (Fig. 7b). This result is supported in part by the reasonable quantity of
additives. While some PBT data is available for these groups of chem available toxicity data for these two plastic additive chemical groups.
icals, they are less studied and there has been inadequate knowledge For example, fentin acetate (organotin group chemical) was the most
transfer of the existing data to the broader scientific community and the toxic to microalgae (Walsh et al., 1985; Fargašová, 1996) and to in
public. This lack of knowledge and knowledge transfer has the potential vertebrates (Roessink et al., 2005; Novelli et al., 2002) among the
to result in delayed scientific advice and preventive actions. It is also selected compound groups (SI, Fig. S7). Despite a perceived high risk by
important to note that regulatory toxicity assessment of most chemicals respondents, the tris(2-chloroethyl) phosphate (organophosphate group
is conducted in single compounds, generally using methods that employ chemical) has been reported to cause only moderate toxicity to aquatic
high-dose, short-term responses of a specific indicator organism (often a invertebrates (Yoshioka, 1986) (SI, Fig. S7). In the case of aromatic
freshwater organism). This approach limits our understanding of long- amines, metal acetates and phenylenediamines, respondents typically
term, low-dose impacts and mixed chemical exposures throughout the perceived these compound groups to be a lower risk. In this case, the
food web (Leslie et al., 2022), typically only defining a quantitative perceived low risk of phenylenediamines contrasts with the reported
boundary for safe exposure levels regarding a specific chemical or toxicity of these substances to marine invertebrates (SI, Fig. S7). Spe
compound. Only a few chemical pollutants have been defined by cifically, the phenylenediamine 6-PPD has been shown to affect immo
quantitative boundaries with regards to causing ecosystem-level impacts bility, population growth and mortality of aquatic invertebrates (Isanta-
(e.g., CO2, CFCs). Navarro et al., 2022; Hiki and Yamamoto, 2022). The results suggest
that the respondents had more accurate risk perceptions for the more
4.5.3. Risks at different trophic levels common and widely discussed plastic additive chemical groups, espe
Understanding the PBT of additives within the marine environment cially those representing chemicals and chemical classes that have been
is an important part in understanding the risks additives pose, across studied for many years. In contrast, lesser known or emerging plastic
different tropic levels. The ecotoxicological consequences of plastic additive chemical groups saw more discrepancies between perceived
additives are gaining interest within the research community, however, and experimentally determined toxicity and risks. However, it is
there often remains a disconnect between persistent, bioaccumulative, important to highlight that >35 % of respondents provided a ‘do not
and/or toxic data generated for individual chemicals within in each know’ response to all plastic additive chemical groups, with the
plastic additive chemical group included in the current study and the exception of metals (24 %). In the case of metal acetates, aromatic
link to (micro)plastic toxicity interpretation. amines and phenylenediamines, >50 % of respondents gave an answer
In this study, respondents were asked to consider the perceived risk of ‘do not know’ (Fig. 7a).
associated with the different plastic additives to higher and lower tro
phic level marine organisms in function of the persistent, bio 4.5.3.2. Risks to higher trophic levels. The majority of respondents
accumulative and/or toxic nature of each chemical group. For most (60–75 %) perceived the risk of phthalates, organophosphates, PFAS/
additives, the respondents felt they had a greater knowledge of the risks PFOS, metals and organotins as being high for high marine trophic levels
to higher trophic marine level organisms than for those from lower (Fig. 8b). The perceived high risk for organotins and phthalates is sup
trophic levels (Figs. 7 and 8). This difference in perceived knowledge ported by the available toxicity data for these compounds (SI, Fig. S7).
presents a somewhat unusual situation given that bioaccumulation and Fentin acetate caused cytological alterations (Strmac and Braunbeck,
toxicity data is typically much more widely available for lower trophic 1999), and benzyl butyl phthalate caused effects on the feeding and
organisms, given the low cost and relative ease of producing it. It is shoaling behaviour of fish (Wibe et al., 2002; Kaplan et al., 2013).
important to note that the respondents may have a scientific background However, the available data for metals (Pb) indicate only moderate
more strongly anchored in PBT and risk knowledge related to higher toxicity to fish (Reynolds et al., 2018; Karthikeyan et al., 2021), while
trophic-level organisms. organophosphates and PFAS/PFOS substances presented the lowest
The literature review revealed plastic additives toxicity threshold toxicity among the selected substances (Giesy et al., 2010) (SI, Fig. S7).
levels for a range of aquatic organisms from different trophic levels, at Although the risk of PBDEs and phenylenediamines for high trophic
both sublethal and lethal exposures (Table & Fig. S7, Supplementary levels was mostly perceived as moderate to high by the respondents
Information). Fig. S7 shows the log toxicity threshold values for three (Fig. 8), the available toxicity data indicate that BDE-209 and 6-PPD are
different trophic levels that have been calculated for a selection of highly toxic to fish (SI, Fig. S7). BDE-209 has been shown to cause
plastic additive chemicals representing the chemical groups included in oxidative damage and genotoxicity in fish, affecting their swimming
the current study. The LOEC for each substance was: 0.1 μg/L for BDE- activity (Pérez-Iglesias et al., 2022), whereas 6-PPD affected the
209, 0.5 μg/L for fentin acetate, 15 μg/L for lead, 18.2 μg/L for 4-4- hatching and swimming behaviour and inhibited acetylcholinesterase
methylenedianiline, 25 μg/L for 6-PPD, 100 μg/L for benzyl butyl activity (Hiki and Yamamoto, 2022; Ji et al., 2022; Varshney et al.,
phthalate, 2.2 mg/L for tris(2-chloroethyl) phosphate and 6.25 mg/L for 2022). Again, the results suggest that the respondents had more accurate
perfluorooctanoic acid. This information was used to discuss the re risk perceptions for the more common and widely discussed plastic
spondents answers in Section 3.4. additive chemical groups (e.g., organotins, phthalates), especially those
Data for different trophic levels is often missing, therefore, deter representing chemicals and chemical classes that have been studied for
mining the risk of plastic additives to organisms at different trophic many years. Similar to the low trophic level risks, lesser known or
levels is thus important to address in the future, as this may vary emerging plastic additive chemical groups (e.g., phenylenediamines)
significantly between individual chemicals. The literature review (see saw more discrepancies between perceived and experimentally deter
SI, Table and Fig. S7) suggests that benzyl butyl phthalate and BDE-209 mined toxicity and risks for higher trophic levels. It is again worth
pose a hazard to fish only, 6-PPD pose a hazard to invertebrates and fish noting that >30 % of respondents provided a ‘do not know’ response for
(no microalgae data were available), while fentin acetate may impact all the organophosphate, organotin, aromatic amine, metal acetate and
three trophic levels and could threaten aquatic ecosystems. The use of phenylenediamines plastic additive chemical groups, with this rising to
these four specific plastic additives, as well as others in the respective >50 % of respondents for the last three groups (Fig. 8a). Overall, the
chemical groups, should be considered for urgent regulation. results from the low and high trophic levels questions indicate a specific
lack of knowledge regarding the risk of the aromatic amine, metal
16
acetate and phenylenediamines plastic additive chemical groups. This reduced knowledge transfer between the plastic production industry and
finding is not necessarily unexpected for metal acetates, for which there other stakeholder experts.
is scarce aquatic toxicity data, and for phenylenediamines, for which
there is fragmentary information. However, there is more information 5. Conclusions
available on the toxicity of aromatic amines in aquatic organisms,
indicating that the flow and dissemination of information for this spe To fully understand and assess the impact of plastic additives on the
cific group of plastic additive chemicals may not be sufficient. (marine) environment, detailed information on production volumes,
usage, pathways and risks is indispensable. This study represents the
4.5.4. Limitations in studying the risks of additives perspectives and current knowledge of highly educated, mainly research
The toxicity studies with plastic additives conducted to date and academic, experts, predominantly in Europe, concerning chemical
demonstrate that the choice of organism, assay and biological response use for additives in plastics and other applications globally.
is an important consideration (Karami, 2017). For example, standard
acute toxicity assays may lack realism and alternative long-term expo
sure experiments are needed (Barrick et al., 2021). Similarly, certain
sublethal biological responses may be more relevant for some additive
groups than others, depending on the mechanism of toxicity of each type 5.1.1. Use of additives
of substance (Capolupo et al., 2021). The integration of sublethal stress This survey demonstrated a lack of knowledge on production vol
indices covering a variety of toxicity mechanisms (e.g., neurotoxicity, umes and use of plastic-related additives, particularly metal acetates,
endocrine disruption, genotoxicity, oxidative stress, immunotoxicity) aromatic amines and phenylenediamines. Survey participants expressed
into plastic additive toxicity assessment can assist in documenting a greater awareness regarding the production quantities of phthalates,
broader range of potential adverse outcome pathways (Jeong and Choi, metals, and PFAS, and they noted that these additives are manufactured
2022). Moreover, it may help in the development of toxicodynamic as in substantial amounts.
sessments for plastic additives, where integrating a high throughput
assay that tests an extended selection of different biological endpoints 5.1.2. Characteristics of additives
over short timescales may assist in differentiating the toxic effect of In this study, most of the responses emphasized that there are
plastic particles from that of additives, as well as between one group of broader sources and routes, beyond plastics, for most additives. There
additives and another (Gao et al., 2022). Differentiation of the toxico are substantial gaps in knowledge regarding comparative ecotoxicity
logical effects of plastic particles from their associated chemical addi studies of diverse polymer types and the effects of the related weathering
tives and NIAS can be achieved through the use of combined testing phenomena. These can increase and decrease (micro)plastics’ sorption
approaches using exposures comprising samples representing (i) plastic capacity for environmental contaminants and alter their mobility
particles plus leachates, and (ii) leachates only. There is also potential to through environmental compartments. Although the results of many
conduct long term leaching of chemicals from plastic particles followed studies investigating the effects of plastic leachates have been presented,
by isolation and testing of the pre-leached particles in toxicity studies to there is a lack of comparative studies that differentiate between the
identify the effects derived only from the physical particles. Measuring impact of plastic degradation and the co-occurring release of additives.
endpoints at lower levels of the biological organisation may become Other issues of concern among experts revolve around what occurs to
more relevant in the future, while assays that selectively follow up the these plastic additives as plastics break down or how they affect recy
different toxicity pathways may be necessary to characterise individual cling procedures, which underscore the necessity for comprehensive Life
and ecosystem effects fully (Lemos, 2021). Cycle Assessment (LCA) studies.
A correct interpretation of additives toxicity is further advocated
when considering chemical-physical processes such as microplastics 5.1.3. Monitoring of additives
weathering and ageing. This makes ecotoxicity assessment challenging Standardised analytical methods are available for phthalates, or
as the number of hypothetically leachable additives can result in a ganophosphates, PFAS/PFOS, metals, and PBDE’s. For the other chem
cocktail of chemical toxicants and stressors (Hahladakis et al., 2018). ical groups, methods are available but not yet standardised, hampering
Different plastic polymers display diverse degradation patterns within further assessment and our understanding of their presence and envi
similar environmental conditions, which further confuses the hazard ronmental impact. The survey highlighted that the availability of
classification identification of both the plastic polymers as well as the standardised analytical chemical methods is limited but critical for
related additives (Andrady and Rajapakse, 2016). Ecotoxicological conducting robust environmental concentration determination and for
assessment entails the capability to differentiate between the effects of supporting the toxicity testing necessary for assessing the potential risks
microplastics from those related to the degradation phenomena. different types of plastic additive chemicals present to the marine
environment. In addition to improving and standardising methods to
4.6. Limitations of this study measure the presence of plastic additives, there is also a need to improve
the current methods for characterising the leaching of additives from
The authors acknowledge that the number of respondents (50) and, plastics into different environmental media, i.e., water, sediment and
specifically, their geographical and employment range is a limitation of biota.
this study. The number of experts within the field of additives and
toxicology is relatively small. As such, the number of respondents itself 5.1.4. Risks of additives
is not a problem and reflects the limited number of experts in the field. This survey highlights a low knowledge by survey participants of any
However, the geographical range is dominated by Europe (82 %) fol PBT nature of additives. The PBT nature is only known for metals, PFAS/
lowed by Sub Saharan Africa (10 %), with limited or no responses from PFOS and phthalates, while a larger group of respondents expressed to
other regions (Fig. 1). Thus, the present assessment does not represent be unsure about the PBT aspects of phenylenediamines, aromatic amines
the full range of experts at the global level. The respondents were and methyl acetates. Overall, the respondents show a greater knowledge
dominated by academia (78 %, Fig. 1), but did include a small number of of the risk to higher marine trophic levels than lower trophic levels for
respondents in the categories of government, NGO/IGOs and civil so most additives. The knowledge gaps on specific chemical additive
ciety representatives. However, no industry representatives completed groups indicate that risk assessments, which rely on an understanding of
the survey. Insight information from industry would have been highly the presence and toxicity of those chemicals, are lacking crucial data to
beneficial to this study – as this could have potentially highlighted any complete. With more evidence indicating that plastic-associated
17
chemicals (additives and NIAS) may be one of the primary drivers for Despite such legislation, some of these illegal additives are still in cir
observed toxicological responses to plastic exposure, there is a need for culation due to a lack of consistent enforcement (Turner and Filella,
holistic risk assessments that consider and separate plastics, additives 2021), improper waste or recycling management (Wagner and
and their associated contaminants. Schlummer, 2020), or exemptions (UNEP, 2021). In light of these
In addition, there are many questions about the potential implica fragmented efforts, the recent UNEA resolution 5/14 in Match 2022
tions of using plastic additives, both environmental and public health- requesting the convening of an intergovernmental negotiating com
focused, highlighting the need for in-depth environmental and risk mittee (INC) to develop an international legally binding agreement on
assessment studies by experts. plastic pollution, including in the marine environment, provides an
opportunity for alignment and development of a comprehensive set of
5.1.5. Way forward standards and methods that considers plastics and their additives.
In-depth environmental and risk assessment studies are also inex Global leaders and policy mechanisms such as this are needed to support
tricably linked to strengthening transparency on the use of specific the development of National Action Plans (NAPs) on marine litter and
plastic additives in products and materials toward users. Survey par plastic pollution, promoting universal bans of harmful substances,
ticipants highlight the importance of using and researching safer alter aligning chemicals of concern lists, agreeing to threshold limits for
natives and closing knowledge gaps as the way forward. However, such substances of concern in use, as well as aligning testing methods to
transitions to other options must be dealt with caution, 99 % of plastic evaluate the safety of substances and products.
feedstocks are fossil fuel-based (Nielsen et al., 2020). Although more
alternative, bio-based and biodegradable plastic materials are emerging CRediT authorship contribution statement
to market, many still rely on the same additives to provide aesthetics and
functionality (Gómez and Michel, 2013). Restrictions on some chemical Thomas Maes: Conceptualization, Methodology, Validation, Re
use have led to similar chemicals being used, which may have other sources, Writing – original draft, Writing – review & editing, Supervi
undesired consequences if not thoroughly evaluated, such as the shift in sion, Project administration, Funding acquisition. Fiona Preston-
BPA to BPS (Qiu et al., 2021; Rochester and Bolden, 2015). Overall, Whyte: Methodology, Validation, Investigation, Writing – original
collaboration is needed between environmental scientists, chemists, draft, Writing – review & editing, Project administration. Stephanie
design engineers, manufacturers and other relevant stakeholders to Lavelle: Methodology, Validation, Formal analysis, Data curation,
transition to safe and sustainable chemical use. Writing – original draft, Writing – review & editing, Visualization.
Alessio Gomiero: Validation, Writing – review & editing. Andy M.
5.1.6. A chemical group of concern - phenylenediamines e.g., 6-PPD Booth: Validation, Writing – review & editing. Maria Jesus Belzunce-
A chemical group of concern highlighted from this survey are phe Segarra: Validation, Writing – review & editing. Juan Bellas: Valida
nylenediamines – e.g., 6-PPD. Phenylenediamines, particularly 6-PPD, tion, Writing – review & editing. Steven Brooks: Validation, Writing –
come up repeatedly in this study with knowledge gaps across path review & editing. Adil Bakir: Validation, Writing – review & editing.
ways into the environment, available analytical methods, nature (i.e., Lisa I. Devriese: Validation, Writing – review & editing. Christopher
persistent, bioaccumulative, and toxic nature) and risk across tropic Kim Pham: Validation, Writing – review & editing. Bavo De Witte:
levels. It is noted that other additives (aromatic amines, metal acetates Validation, Writing – review & editing, Supervision.
and methyl acetates) all show data gaps within these areas. However,
only phenylenediamines are identified to have gaps in knowledge across Declaration of competing interest
all areas. Combined with what is known, these gaps indicate that 6-PPD
is an emerging pollutant, making 6-PPD a growing concern. The additive The authors declare that they have no known competing financial
6-PPD has been used in tires since the mid-1960s as a tire rubber anti interests or personal relationships that could have appeared to influence
oxidant additive. However, it was only in 2020 that its degradation was the work reported in this paper.
identified (Tian et al., 2021). This degradation turns 6-PPD into 6-PPD-
quinone, which is toxic and has been determined to cause acute mor Data availability
tality in salmon populations in urbanised rivers (Tian et al., 2021). What
happens to the additives and their degradation in the environment is a The data that has been used is confidential.
knowledge gap that highlights the need for more focused risk assess
ments, as additives can react with each other or contaminants or Acknowledgements
degrade to form (as with 6-PPD) and attract other toxic molecules
(Hahladakis et al., 2018). The authors would like to thank all the respondents for giving their
valuable time and technical expertise to complete the survey. The au
5.2. Implications for policy thors would like to thank the International Council for the Exploration of
the Sea (ICES) facilitating cooperation between different ICES expert
Plastics may impact human and environmental health due to the groups (working group on marine litter (WGML); marine chemistry
physical effects caused as particles as well as the (toxicological) effects working group (MCWG), working group on the biological effect of
caused by plastic additive chemicals. A holistic definition of plastic contamination (WGBEC)). Thomas Maes, Andy Booth and Lisa Devriese
encompassing chemical additives is needed to address the impact of received funding from the European Union’s Horizon Europe pro
plastic in legislation. Strategies such as the EU Green deal and the Zero gramme under grant agreement N0. 101060213 (SOS Zeropol2030
Pollution Action Plan 2030 or environmental goals such as the SDG14 project). Alessio Gomiero and Andy Booth received funding from the
targets or MSFD criteria do not specifically address the evaluation of North Atlantic Microplastics Centre –NAMC.
plastic additives in marine environments. In the lead-up to the UN
Plastic Treaty, experts and scientists are pushing for the broader defi Appendix A. Supplementary data
nition of plastic as a material made of chemicals, giving the use and
disposal of plastic additives a legally binding framework. Supplementary data to this article can be found online at https://doi.
The experts from this survey recognise the importance of regulation org/10.1016/j.marpolbul.2023.115633.
and legislation in mitigation. Policies and decision making have already
been used to mitigate additives, with some additives banned by inter
national and national regulations (Wagner and Schlummer, 2020).
18
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Marine Pollution Bulletin 196 (2023) 115633

Contents lists available at ScienceDirect

Marine Pollution Bulletin

A recipe for plastic: Expert insights on plastic additives in the

Fig. 1. Map showing the demographics of all respondents.

4.3.1. Phenylenediamines other phenylenediamines and phenylenediamine mixtures are used as

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