Skip to main content
Environmental Sciences Europe
Download PDF

Diverging trends of plasticizers (phthalates and non-phthalates) in indoor and freshwater environments—why?

Environmental Sciences Europe volume 34, Article number: 46 (2022) Cite this article

Abstract

Background

European chemicals management aims to protect human health and the environment from legacy and emerging contaminants. The plasticizer market changed in response to the restriction of low molecular weight (LMW) phthalate plasticizers such as Di (2-ethylhexyl) phthalate (DEHP) due to their hazardous properties. We investigated patterns and trends of 19 regulated and emerging plasticizers in house dust from German homes and in suspended particulate matter (SPM) from major German rivers. The samples were used from the mid-2000s and late 2010s from two governmental long-term monitoring programs in Germany.

Results

While the sum of the respective plasticizer levels hardly changed over the study period, we observed a significant decrease of LMW phthalates in both house dust (2003/06, 80% of the ∑plasticizer concentration; 2014/17, 31%) and SPM (2005, 48%; 2017, 28%). This was accompanied by their substitution with high molecular weight (HMW) phthalates and non-phthalates. HMW phthalates increased from 19% of the ∑plasticizer concentration to 46% between the mid-2000s and the late 2010s in house dust, and from 50% to 63% in SPM samples. Diisononyl phthalate (DINP) replaced DEHP as the dominant plasticizer in both compartments. A significant tenfold increase (p < 0.05) was observed in SPM samples for Di (2-propylheptyl) phthalate (DPHP) (1–13%), compared to low levels in house dust (2014/17, 1%). Non-phthalates increased to 23% of the ∑plasticizer concentration in house dust but only to 9% in SPM (mid-2000s: house dust, < 1%; SPM, 1.5%). In recent house dust samples, Di (2-ethylhexyl) terephthalate (DEHT) had the third highest concentration of all plasticizers and contributed 18% to the total load, whereas Tris (2-ethylhexyl) trimellitate (TOTM) was one of the major non-phthalates in SPM samples.

Conclusions

Unlike in the indoor environment, the substitution of LMW phthalates in the aquatic environment was characterized by a significant shift towards plasticizers with potentially hazardous properties. DPHP and TOTM were identified by European chemical regulation as potentially endocrine disrupting compounds and persistent, bioaccumulative and toxic compounds. Our data document the need for integrated chemicals management to safeguard the transition to a non-toxic environment.

Background

European chemicals policy aims to protect human health and the environment from substances of concern. Precautionary substance and product regulations are in place to prevent the use and marketing of these substances. With the Green Deal [40], the EU is also pursuing new, ambitious goals, such as the zero-pollution action plan for a non-toxic environment. Integral part of the zero-pollution action plan is the chemical strategy for sustainability (CSS), which aims to better protect humans and the environment from hazardous chemicals [41]. High-volume industrial chemicals include plasticizers (global production in 2018: 7.45 Mt [20]), the main additives for flexible PVC. The use of some phthalate plasticizers has been successively restricted in the EU since the late 1990s due to their endocrine disrupting (ED) properties, especially in sensitive applications for humans, such as baby products, children's toys, cosmetics and food packaging [31, 33,34,35]. Di (2-ethylhexyl) phthalate (DEHP), Benzylbutyl phthalate (BBP), Diisobutyl phthalate (DIBP) and Di-n-butyl phthalate (DnBP) are included in REACH Annex XVII, restricted substances list [51], and their use is subject to authorization in the EU since 2015 (“sunset date”, [52]). The substitution of the formerly dominant plasticizer DEHP (EU market share 1996: 51%; 2015: 10% [36, 58] has led to a fundamental shift in the market since the 1990s toward HMW phthalates [45], with a simultaneous steady growth in demand for soft PVC [59, 74].

The broad use of plasticizers in large amounts in consumer and industrial products is associated with their occurrence in both the indoor and ambient environment. The ubiquitous presence of DEHP and other low molecular weight (LMW) phthalates such as BBP, DIBP, DnBP is well-documented [67, 81, 96, 98, 124]. High molecular weight (HMW) phthalates such as Diisononyl phthalate (DINP) and Diisodecyl phthalate (DIDP) have been detected in indoor air, house dust, blood plasma or in the aquatic environment, including biota [1, 10, 106, 119, 130]. Recent studies confirm the upcoming relevance of non-phthalates in indoor and ambient environment [22, 78, 84, 85, 95, 118].

This work aims to provide: (1) a comparison of patterns and trends of regulated and emerging plasticizers over more than a decade in indoor and freshwater systems and (2) an investigation of the possible reasons for different exposures in the two compartments. Finally, (3) the efficiency and coherence of current EU chemicals regulations—also in view of the new zero-pollution action plan [42].

For this purpose, representative data sets from indoor and freshwater environments were selected with the best match regarding time period, study area and the plasticizer analyte spectrum. The data on plasticizers in house dust originate from the German Environmental Surveys (GerES) IV and GerES V, which were conducted by the German Environment Agency in German households from 2003 to 2006 and from 2014 to 2017. House dust is a sink and repository for semi-volatile organic compounds and it has been used in numerous research programs as a marker of indoor exposure to plasticizers. House dust data are indicative of plasticizer abundance and composition in private households, which are directly influenced by construction materials, personal and lifestyle-products that are used in the indoor environment [13, 114]. For plasticizer exposure in large German rivers, data from measurements in suspended particulate matter (SPM) from the German Environmental Specimen Bank from 2005 to 2017 (provided by the German Environment Agency) were used. SPM is a sink and transport mechanism for solid particles and associated pollutants [77, 97]. Analysis of hydrophobic and lipophilic substances in SPM is an appropriate surrogate for sediment monitoring [37, 108]. Monitoring with SPM is applied in European long-term monitoring programs for EU priority substances [104], including the plasticizer DEHP [76].

To the best of our knowledge, trend data for Di (2-ethylhexyl) terephthalate (DEHT) in European freshwater systems are presented here for the first time.

Methods

Plasticizer selection: legacy phthalates and substitutes of DEHP

At present, about 50 substances with plasticizing properties are in commercial use [60]. Used in combination or individually, plasticizers improve flexibility, extensibility and processability of polymer plastics [23]. Some plasticizers are characterized by weatherability, low-temperature flexibility or heat resistance [68]. Plastizicers are used in a wide range of indoor and outdoor applications including roofing membranes, automotive interiors, electrical cables, cling films, sealants, flooring, wall coverings, food packaging and consumer products [60]. Plasticizers are usually grouped into phthalates and non-phthalates. Phthalates still represent the majority in the European plasticizer market, at around 60% [58]. However, since the end of the 1990s there has been a steady shift within the phthalate plasticizers from LMW phthalates toward HMW phthalates [45]. LMW phthalates are characterized by up to six carbon atoms in the main chain [70]. Furthermore, the demand for alternative plasticizers is increasing. Today, the most frequently used non-phthalates are adipates, terephthalates (main representative DEHT) and Diisononyl 1, 2-cyclohexanedicarboxylic acid (DINCH) [60].

The monitoring programs used in this study covered a total of 26 analytes. For the comparison, only those plasticizers were considered that have been detected in at least two data sets, i.e., 19 plasticizers (12 phthalates and seven non-phthalates). They are listed in Table 1 with their abbreviations, molecular weights and CAS numbers.

Table 1 Overview on the plasticizers included in this work
Full size table

Certain highly isomeric phthalates, such as DINP and DIDP, might commercially be available under different CAS numbers. Additional information on the substances such as SMILES, molecular formula and physicochemical properties are reported in the Supplementary Information (Additional file 1: Table S1). Our comparison excludes Diallyl phthalate (DAP), Di (2-methoxyethyl) phthalate (DMEP), Bis (2-butoxyethyl) phthalate (DBEP), Dipentyl phthalate (DPP), Dihexyl phthalate (DHP), Dibutyl adipate (DBA), Di (2-ethylhexyl) sebacate (DEHS), because they were observed at very low concentrations or below the limit of quantification (LOQ) in one of the studies.

Sampling programs

We compared plasticizer concentrations in Germany from two different, government-funded sampling programs. The first program, the German Environmental Survey (GerES) is a representative study of environmental exposures on the general population of Germany [111], which has been conducted since 1985. GerES investigates, among many other parameters, house dust samples from various indoor environments [110]. The second program, the German Environmental Specimen Bank (ESB), collects and investigates SPM samples from 13 riverine sites in Germany since 2005 (Additional file 1: Fig. S1). Samples are archived continuously in the German Environmental Specimen Bank [62]. The sampling sites reflect different intensities of anthropogenic impacts. Detailed characteristics of both measurement programs are given in Additional file 1: Table S2.

An important aspect of comparing exposure data from indoor and aquatic environments is similar partitioning behavior of plasticizers between SPM and water phase as well as dust and air. Adsorption of phthalate plasticizers to solids increases with their molecular weight and their octanol–water partition coefficient (KOW) [24, 25]. Likewise, the octanol–air partition coefficient (KOA) of phthalates is a strong predictor of their abundance in indoor sinks, such as settled house dust relative to their airborne concentration [125, 126] (Additional file 1: Table S1) for KOA and KOW of the plasticizers investigated). The fate of plasticizers can differ in indoor and aquatic environments, because environmental conditions are not comparable. The predominant fate of phthalates in aerobic aquatic environments is biodegradation [102], whereas losses in indoor environments caused by microbial degradation could only be demonstrated at elevated humidity [16]. However, it can be expected that these fundamental processes, e.g., sorption, degradation half-life, do not change with time. Even if a plasticizer adsorbs to a greater extent to house dust than to SPM, this will be meaningful to the plasticizer load in the respective compartment, but not for its temporal trend. Since the sampling methods for house dust and suspended particulate matter are quality assured and highly conserved [63, 121], the data of the two study programs can accurately reflect temporal trends of the plasticizers.

Plasticizers in house dust

In each of the GerES study cycles (GerES IV: 2003–2006; GerES V: 2014–2017), house dust samples were collected in a number of about 600 households spread across 150 study locations across Germany (Additional file 1: Fig. S1). The data from GerES IV (2003–2006) have been previously reported [92,93,94]. The data from GerES V (2014–2017) have been unpublished, but were generated using the same procedures.

In both cases, the sampling strategy followed a random selection procedure, which provided for population-representative house dust samples [110]. In GerES IV the mass fractions of 12 phthalates and 9 non-phthalates were determined. Briefly, the content of each vacuum cleaner bag was sieved to obtain the fraction of particles < 63 µm. This fraction was chosen to reduce the variability of the analytical results [91]. Chemical analysis of semi-volatile organic compounds (SVOC) in this fraction in GerES IV were performed by [92,93,94]. Plasticizer concentrations were determined using liquid chromatography/mass spectrometry (LC–MS) with LOQs between 0.08 and 16.5 μg/g (Additional file 1: Table S7a). For GerES V, corresponding work was performed by the Fraunhofer Institute for Process Engineering and Packaging IVV in Freising, Germany. Extracts of the GerES V data have been reported in conjunction with GerES V human biomonitoring data in Schwedler et al. [112].

Plasticizers in riverine suspended particulate matter

To compare the long-term pattern of plasticizers in indoor and freshwater systems, existing SPM data from a study on spatial and temporal trends of plasticizers in German rivers were used [95]. In the study, archived SPM samples from the ESB have been analyzed for 23 plasticizers (17 phthalates and 6 non-phthalates). The samples were collected between 2005 and 2017 at sampling sites in major German rivers, such as the Rhine, Elbe, Danube and tributaries, i.e., Saar, Saale and Mulde. A brief characterization of the sampling sites is given in Additional file 1: Table S3. Suspended particles are collected in sedimentation boxes and sampled on a monthly basis. 12 monthly samples are than pooled to one annual sample. The samples are sieved (< 2 mm), homogenized and freeze-dried (more details in the Additional file 1; [63]).

For the present work, data for the 19 plasticizers (Table 1) investigated at 11 sites in 2005 (Saar sites in 2006) and 2017 were used. The Danube sites are not included, because sampling started only in 2009.

An LC-based method has been applied for the analysis of plasticizers, which did not cover DEHT as one of the potential DEHP-substitutes. The determination of DEHT in SPM samples was performed separately by gas chromatography/mass spectrometry (GC–MS) analysis. Sampling strategy and sampling areas are identical to the study of Nagorka and Koschorreck [95]. The analytical method was based on a solvent extraction of the SPM samples. After clean-up with an alumina column the eluates were measured by gas chromatography/mass spectrometry. Details on chemicals and materials are given in the Additional file 1. In addition, parameters for extraction, clean-up, GC–MS analysis and the quality assurance can be found in the Additional file 1.

Statistics

Mean and median values of the same 19 plasticizers from the house dust and SPM studies were used for the comparative description. For harmonization, values below the LOQ were considered with 1/2 LOQ, although a different approach for values below the LOQ from GerES IV samples had been used in the original papers (replacement by 2/3 LOQ; [92,93,94]).

For house dust samples, the significance of the temporal mean differences was calculated using the Mann–Whitney U test (95% confidence interval, significance level p < 0.05). In the indoor data sets, the LOQs for the individual analytes differed both within GerES V and between GerES IV and GerES V. Prior to testing for statistical significance, a constant LOQ was established for each plasticizer. The highest LOQ (LOQmax) of the respective analyte was determined for all indoor data. All measured values below LOQmax were replaced by ½ LOQmax. For individual analytes, more than 50% of the measured values were below the LOQ in both study cycles, so that a calculation of the Mann–Whitney U statistic was not meaningful. The SPM sampling sites were identical in 2005 and 2017; therefore, a paired test was applied for SPM data. Due to the small sample size, the means were compared by a non-parametric test (Wilcoxon signed-rank test, significance level p < 0.05). No significance tests were applied for plasticizers analyzed with a detection frequency of less than 50%.

Results and discussion

House dust and freshwater environment—a comparison of plasticizer levels and pattern

LMW phthalates

We noticed a decrease of LMW phthalates (including DEHP) in samples from house dust (2003/06, 80% of the ∑plasticizer concentration; 2014/17, 31%) and SPM (2005, 48%; 2017, 28%). The significant reduction (p < 0.05) of DEHP levels was accompanied by its substitution with HMW phthalates and non-phthalates, resulting in a change in the pattern of substances in indoor and aquatic environments (Figs. 1a, b and 2). Overall, the sum of plasticizer levels hardly differed over the study period in both matrices: In house dust, the temporal change was significant, but small (mean from 1194 µg/g to 1208 µg/g, median from 981 µg/g to 855 µg/g; p < 0.05). No significant differences were found in SPM samples between 2005 and 2017 (mean from 6160 ng/g dry weight (dw) to 4400 ng/g dw; median from 3600 ng/g dw to 33220 ng/g dw; p > 0.05). Consequently, the decline of LMW phthalates does on average not noticeable reduce the total plasticizer load in both compartments. However, in detail we found diverging developments in house dust and SPM. Descriptive statistics on the plasticizers included in this comparative analysis are given in Additional file 1: Tables S7a, b. The test results for statistical significance comparing the mean difference between concentrations in the mid-2000s and in the mid-2010s are presented in Additional file 1: Table S8.

Fig. 1
figure 1

a, b Plasticizer mean concentrations in house dust and SPM samples in mid-2000s and in 2017; bars with standard error; plasticizer with marking, significance level, *p < 0.05, **p < 0.01, ***p < 0.001; without marking, p > 0.05

Full size image
Fig. 2
figure 2

Relative compositions of plasticizers in house dust and riverine SPM samples in the mid-2000s and in 2017; atoxic for reproduction; bsubstance evaluation under REACH; cpersistent, bioaccumulative, toxic; dendocrine disrupting (ED) properties with effects on the environment; esuspected ED properties with effects on human health; fED properties with effects on human health. SVHC Substance of Very High Concern, CoRAP Community Rolling Action Plan

Full size image

In samples from the mid-2000s, DEHP was the overall dominant compound in both matrices (Fig. 1a, b) and LMW phthalates accounted for 80% of the ∑plasticizer content in house dust (DEHP, 57%; C1–C7-phthalates, 23%) and 48% in SPM samples (DEHP 44%; C1–C7-phthalates 4%), respectively. In the samples from the mid-2010s, the percentage of LMW phthalates in both indoor and aquatic samples was much more similar (house dust, 31%; SPM, 28%). Furthermore, the DEHP percentages in both compartments neared a comparable level (house dust, 21%; SPM, 23%). Mean and median DEHP values have dropped by more than half compared to the mid-2000s (p < 0.05) (house dust, mean from 685 µg/g to 250 µg/g; SPM, mean from 2710 ng/g dw to 991 ng/g dw). In house dust, C1–C7-phthalates followed this trend and their levels halved since the mid-2000s (mean from 271 µg/g to 121 µg/g), due to significantly decreasing levels of DEP, DBP (∑concentration of DnBP and DIBP), BBP and DIHP. This corresponds to a decline of the median values by two thirds compared to the values from 2003/06. In contrast, in SPM, the concentration of C1–C7-phthalates remained almost unchanged (mean from 249 µg/g to 244 µg/g; median from 250 ng/g dw to 263 ng/g dw) as a decrease (p < 0.05) in BBP levels was offset by increasing DBP levels, which were, however, not statistically significant. In response to regulatory classifications as toxic, the European market shares have already decreased between 1998 and 2008 (BBP, from 3% to 1%; DBP, from 6% to 3%) [122]. BBP was widely used in the flooring industry [88], whereas primary uses of DnPB included indoor and outdoor applications, such as consumer goods, adhesives, lacquers, paints and sealants [8]. Because DIBP has similar properties as DnBP, it could be used as a substitute [29]. DBP contents up to 60% were found in foams used in grouting applications for water control in tunnels and sewer systems [88]. In addition to direct and indirect release into the environment from product uses, atmospheric deposition is suggested to be a relevant exposure pathway for DBP [128, 129].

The data indicate continuous substitution of critical phthalates such as DEHP, DBP and BBP in response to increasing regulatory action on plasticizers in Europe, which began in 1999 (Fig. 2) and concluded with the need to apply for authorization for the continued use of those plasticizers in 2015, after the so called "sunset date". This is in good agreement with human biomonitoring studies in Germany, where urine samples show a significant decrease since 1999/2000 [81, 112]. The reduction may be attributed to the displacement of DEHP and very LMW phthalates from exposure sources, such as consumer products and food contact products. A similar rapidly declining trend for LMW phthalates was observed in household dust in Taiwan between 2006 and 2014 as a result of chemical management there [75].

HMW phthalates

Over the study period, the percentage of HMW phthalates in house dust increased from 19% of the ∑plasticizer concentration to 46% and in SPM samples from 50% to 63%. DINP became the main plasticizer in both compartments. In dust samples, DINP levels increased significantly over the study period (mean from 173 µg/g to 494 µg/g). By contrast, a significant decrease was observed for DIDP (mean from 54 µg/g to 48 µg/g) and the concentrations of DPHP and DIUP remained low (DPHP, 1% of the ∑plasticizer concentration; DIUP, 1%). In samples from mid-2010s, the concentrations of DINP were 10 times higher than those of DIDP. The predominant presence of DINP in dust samples from 2014/17 may result from its increasing use in vinyl flooring, wall covering and furniture [32, 44]. Studies in indoor environments have demonstrated that PVC flooring and wallpapers are associated with higher DINP levels in dust [2, 22, 84].

In SPM, DINP concentrations and patterns hardly changed over the study period (mean from 1730 ng/g dw to 1340 ng/g dw; share from 28% to 31%). Nevertheless, it became the main compound in the SPM samples as the DEHP content continuously decreased. In the mid-2000s, DIDP percentages in SPM samples were four times higher than in house dust, but did not change much since then (2005, 20%; 2017, 19%). Concentrations for DIUP were low (< 1% of the ∑plasticizer concentration) compared to other HMW phthalates, and moreover, a significant decrease was observed. However, we observed a striking tenfold increase (p < 0.05) in DPHP concentrations (mean from 57 ng/g dw to 550 ng/g dw) in SPM samples, although DPHP has been under regulatory scrutiny and included on the Community Rolling Action Plan (CoRAP) list since 2014. (Fig. 2; [46, 47]) DPHP was advertised in the early 2000s as an DEHP substitute for outdoor applications [82], and like DIDP, it is used for the manufacture of wires, cables, hoses and tarpaulins [44]. Its weather resistance and low migration rates give DPHP advantages over other DIDP specifications for the use in outdoor applications, such as cladding and roofing [101, 117]. Although DPHP is registered for both outdoor and indoor use in durable materials with low release rates [53], our house dust data suggest that it contributes only little to indoor exposure (2014/17, 1% of the ∑plasticizer concentration).

Non-phthalates

The use of non-phthalates in the European plasticizer market was almost constant between 1999 and 2005, but then increased from 7% of the ∑plasticizer concentration to 40% in 2017 [17, 59]. In the mid-2000s, the share of non-phthalates was comparatively low (house dust, < 1%; SPM, 1.5%). The indoor samples reflected the shift from phthalates to non-phthalates more pronouncedly than the SPM samples. In the mid-2010s, non-phthalates accounted for 23% in house dust, but only for 9% in SPM.

Also, the pattern of non-phthalates in the more recent samples differed significantly in the samples from the two compartments. In house dust samples from mid-2010s, the mean values of DEHT and DINCH have increased by a factor of 90 and 40, respectively, compared to samples from the mid-2000s. DEHT became the third highest fraction (mean 220 µg/g) and contributed 18% of the total load, while DINCH and ATBC stayed much less relevant with 3.5% and 1.5%, respectively. TOTM, an extremely low volatile plasticizer was only detected at low levels in house dust. Trends for ATBC could not be verified, because ATBC was not part of the analyte spectrum in GerES IV, the first house dust sampling cycle. However, indicative data from 2009 resulted in a GM of 2.4 µg/g and an arithmetic mean of 6.5 µg/g [93], which were lower values than the results presented here for 2014/17, suggesting a rise in ATBC levels. In general, non-phthalates, such as DEHT, ATBC, and DINCH, which was introduced in 2002, are preferably used as DEHP substitutes in sensitive, consumer-oriented applications, such as toys for children under the age of 3, soft plastic shoes, medical devices, and pharmaceutical coatings [4, 38, 123].

In contrast to house dust samples, the plasticizer pattern in SPM samples from mid-2010s is still very much dominated by phthalates (2017, 91% of the ∑plasticizer concentration). We identified emerging non-phthalates, TOTM, DEHT and DINCH, each with 2–3.5% of the total content. Although ATBC also showed an increasing trend in these samples [95], the levels remained comparably low in 2017 compared to the other DEHP substitutes. For TOTM, exposure pathways in the environment independent of urban waste water can be assumed, since it had limited relevance in house dust samples. TOTM is typically applied in the automotive industry and in cable insulations [61]. In samples from the river Mulde, TOTM accounted for 0.5% of the total plasticizer burden in 2005 and for 9% in 2017. The sampling site is located downstream the Bitterfeld–Wolfen Chemical Park, one of the largest areas for the chemical industry in Eastern Germany. Increasing TOTM levels can be caused by growing industrial settlement in this area after a restructuring process [9, 21]. In highly industrialized bays in Korea TOTM had a share of 36% of the overall plasticizer concentration in sediments which were characterized by automotive plants [79].

Current studies of house dust in various European indoor environments (households, kindergartens, schools, offices) show comparable results as presented here: For example, Larsson et al. also detected DINP, DEHP, DEHT, and DINCH as major plasticizers in dust from 100 Swedish schools and preschools (2017) [84]. Similarly, DINP, DEHP, DEHT, and DINCH were the dominant components in domestic indoor environments from Central/Northern Europe [22, 30]. The proportion of non-phthalates (up to 45% of ∑plasticizers) was even higher than in the GerES V dust samples. Data from other EU countries suggest, that there may be country-specific differences, e.g., in households in Belgium, DINCH exposure was 21% and in house dust from apartments in Stockholm, ATBC was the major non-phthalate besides DEHT [127]. Comparison with data from outside the EU is challenging. Chemical management varies considerably between regions and on a global scale. DEHP still dominates the plasticizer market [83]. Therefore, target analytes were often restricted to DEHP and other LMW phthalates. House dust samples in China, for example, were strongly dominated by DEHP and DBP [87]. Studies in Thailand and Quatar revealed a plasticizer pattern with DEHP as the main plasticizer, closely followed by DINP [3, 105]. In contrast, DEHT, ATBC and DEHP were the plasticizers with the highest concentrations in US homes [73, 114, 118]. Bi et al. [12] detected DEHP levels in US low-income homes, which were comparable to our results (median, 155 µg/g and mean, 271 µg/g). Similar to the EU restrictions, U.S. Consumer Product Safety Commission (CPSC) had banned the use of DEHP, DBP and BBP in toys and childcare articles in 2008 [28]. Recent investigations on plasticizer levels in sediments from non-industrial coastal areas in Korea are in good agreement with our data and confirm a low proportion of non-phthalates (3–10%) of the total plasticizer burden in aquatic environments [78, 85]. DINP and DEHP were the main phthalates. Among the non-phthalates, the highest concentrations were found for TOTM and DEHT [80]. DEHT and TOTM were detected at levels similar to our data (DEHT, mean 141 ng/g dw; TOTM, mean 150 ng/g dw). DPHP, the major substitute of DEHP in the German SPM samples, was not analyzed in these studies. Several studies have documented the dominant occurrence of DEHP in the mid-2000s in house dust and in sediments or suspended particulate matter from aquatic environments [11, 64, 100, 107, 113, 124]. However, literature data on HMW phthalates and non-phthalates in indoor and riverine samples from this period are largely missing. Sediment studies in Sweden in 2006 found levels for DEHP, DINP, and DIDP that were comparable to our 2005 SPM data (DEHP, 82–2800 ng/g dw; DINP, 130–3200 ng/g dw; DIDP, 190–3400 ng/g dw) [26]. In this study DEHA was the only non-phthalate analyzed (68–520 ng/g dw).

Regulatory discussion of the data

Regulatory assessment of plasticizers

Figure 3 presents the current regulatory status of plasticizers investigated here in the EU. From the 19 substances that were found abundant in samples from the German indoor and aquatic environment, six LMW phthalates (DEHP, DnBP, DIBP, BBP, DcHP, DIHP) have so far been identified as substances of very high concern (SVHC) [54]. Four of those (DEHP, DnBP, DIBP, BBP) have also been restricted under REACH [51]. Two further HMW phthalates, DINP and DIDP, are banned from use in toys, which can be taken into mouth [55]. However, both substances are not identified as SVHC [49, 56]. An overview of the different regulatory processes in the EU for all substances listed in Table 1 can be found in Additional file 1: Table S6a, b and Fig. S2. In the 1980s, first concerns were raised over the health effects of plasticizers and the need for chemical management [66, 120]. The example of DEHP chemical management in Europe shows that it can take almost 20 years to regulate a compound of concern, from the first report of a toxicological concern to the initial provisional EU-wide regulation for phthalates in toys. In 1999, the European Commission (EC) imposed a temporary ban on the use of DEHP together with five other plasticizers (DnBP, BBP, Di-n-octyl phthalate (DnOP), DINP, DIDP) in children's toys that can be put in the mouth [31]. Similar steps have been taken by regulatory bodies in other regions [19, 28, 90]. Only in 2014, DEHP was identified as SVHC because of its ED properties in the environment [48]. Along with DnBP, DIBP and BBP, an identification as SVHC due to ED properties to human health followed in 2017 [39]. For the first time, a substance risk assessment of plasticizers identified a concern about ED effects in both, humans and in the environment. Overall, from 1999 it took another 20 years to establish an—almost—complete ban of DEHP in the EU (Fig. 2, for a more detailed timeline Additional file 1: Fig. S2). The far greater share of the plasticizers (incl. all non-phthalates) has either not been subject to any kind of regulation (i.e., authorization or restriction) or are still in the process of being evaluated by authorities (Fig. 3).

Fig. 3
figure 3

Present regulations of the plasticizers investigated in this work under the EU chemical management; aauthorized for Food Contact Materials; SVHC Substance of Very High Concern, CoRAP Community Rolling Action Plan, RoHS Restriction of (the use of certain) Hazardous Substances in electrical and electronic Equipment

Full size image

In 2012, TOTM had been the first non-phthalate plasticizer for which a substance evaluation had been initiated due to its suspected persistent, bioaccumulating and toxic (PBT) properties (Fig. 2; [43]). Furthermore, a potential ED concern for the environment was identified in 2020 [50]. Substances that persist for long periods of time in the environment and have a high potential to accumulate in biota are of specific concern, because their long-term effects are rarely predictable [57]. Once released into the environment, exposure to these substances is very difficult to reverse, even if emissions are stopped. The prevention of irreversible exposure is a central element of the precautionary principle in the European chemicals regulation and the backbone of existing PBT/vPvB regulation [27]. Our data show increasing TOTM concentrations in both indoor and freshwater environments and warrant rapid finalization of the regulatory PBT and ED assessment, which has now been ongoing for nearly a decade. Similarly, in 2014, DPHP was included in the CoRAP [46, 47] due its suspected ED effects on human health. It was not until six years later that the substance evaluation for DPHP was initiated under REACH. During this period, both use [109] and the exposure of the aquatic environment to DPHP have increased manifold. It is important to note that the identification as an SVHC and inclusion in the SVHC Candidate List does not directly correspond to a ban or a strict regulation of the substance.

In 2016, the outcome of an assessment of the non-phthalates DEHT, ATBC and DINCH was published by the evaluating member state authority concluding that no further regulatory action was deemed necessary at the moment [5,6,7]. The initial reason of concern for the assessment was that those non-phthalates are known, or suspected, to be used as an alternative to phthalates that were previously identified as SVHC and included in the Candidate List (e.g., DEHP). Independent of the outcome of the REACH assessment, our data show the ubiquitous presence of these compounds especially in indoor environments and, to a lesser extent—in freshwater environments.

Molecular weight shift

In samples from both compartments, we observed a shift towards plasticizers with higher molecular weight during the study period (Fig. 4a–d). In house dust samples, the place of LMW phthalates has been taken in particular by DINP as well as DEHT and DINCH, which have at least the same molecular weight as DEHP (DEHT) or a slightly higher one (DINP, DINCH). In samples from 2014/17, these three substances account for 62% of the total load. Their use is not subject to any restrictions with a few exceptions (DINP; Additional file 1: Table S6a, b). We did not observe a replacement of LMW phthalates by other short-chain non-phthalates, e.g., DBA (see “Methods” chapter ‘Plasticizer selection: legacy phthalates and substitutes of DEHP’), which were also considered as potential substitutes for regulated phthalates [14]. Other European studies support this finding [22, 65]. In SPM samples, the growth rate of higher molecular weight phthalates and non-phthalates is less prominent than in house dust samples. However, HMW phthalates already constituted a comparatively strong proportion in the mid-2000s. In general, plasticizers with low volatility and migration rate are more suitable for stressed outdoor applications with respect to hydrolysis, leaching and microbial degradation [72, 116]. However, the increase of DPHP and TOTM during the study period was partially compensated by slightly decreasing DINP and DIDP contents. In contrast to the indoor environment, the substitution of DEHP in freshwater environments is accompanied by a noticeable shift towards potentially critical plasticizers. The percentage of plasticizers classified as a potential concern in the investigated riverine systems is now 16%, compared to only 2% in house dust. The proportion of plasticizers in SPM samples, which are not classified as hazardous, accounted for 56% compared to 68% in house dust samples.

Fig. 4
figure 4

a–d Scatterplots of molecular weight and hydrophobicity (log KOW) showing the relative differences and trends between house dust and SPM samples (DMP, DINA and DEHAz are not pictured due to their constantly low concentrations); circular areas are normalized to 100%; log KOW values were determined with the quantitative structure–activity relationship (QSAR) model JANUS (Additional file 1: Table S1; [103])

Full size image

We suspect that this trend will be further continued in freshwater environments, since DPHP in particular is increasing rapidly in the SPM samples. HMW phthalates are usually marketed as moderate or highly branched isomer mixtures. As reported, the water solubility of phthalates with branched chains is higher than of those with linear chains [71, 86]. Therefore, leaching can be expected even for very low volatile plasticizers which is supported by our data. In a long-term study of geomembranes installed on Italian dams, plasticizer losses of up to 22% were observed [18]. Substitutes such as DEHT, DINCH, and ATBC are less recommended for outdoor building and construction applications due to their poor weathering properties and high migration rate (ATBC) [88, 99, 115]. In addition, terephthalate esters (e.g., DEHT) in PVC are less compatible and more difficult to process than conventional phthalates with the same carbon atom number [69].

Conclusions

The data show that over the past 20 years, the chemical industry has modified their production and marketing strategies by substituting the former “blockbuster” plasticizer DEHP in indoor and outdoor applications. Our findings suggest that non-toxic chemicals, such as DEHT, are becoming more abundant in indoor materials and products, while low volatile, potentially hazardous plasticizers such as DPHP and TOTM with suspected PBT and ED properties seem to have become the new additives for PVC in outdoor applications. We hypothesize that EU chemical management for plasticizers has put a focus on human health related concerns. Indeed, product-specific regulations between 1999 and 2007 were exclusively related to consumer goods and food packaging materials. In 2007, REACH entered into force and up to now, REACH has initiated 27 regulatory processes for the plasticizers investigated in this work (group entries were counted as one process). Only six of these activities address environmental impacts and two EU regulations focusing on environmental concerns have been introduced up to date (Water Framework Directive (WFD), Waste Framework Directive). Furthermore, some REACH regulations include exemptions for certain uses of plasticizers, where no consumer exposure is expected but environmental exposure is likely to occur (e.g., the wide-scope restriction of DEHP, DnBP, DIBP and BBP exempts articles exclusively for industrial or agricultural use or use in open air) [51].

Domestic product use as a source for plasticizer contamination in surface waters cannot be excluded. However, other studies support the assumption that continuous discharge of urban wastewater from residential areas is not the main contributing factor [15]. Malnes et al. reported comparable levels of ATBC in wastewater-impacted Swedish rivers and in a lake with no wastewater discharge (2022) [89]. The highest plasticizer concentrations, and likewise, the highest TOTM levels in sediments from Korean bays were found at sampling sites, which were surrounded by automobile, construction and petrochemical industry [79].

Due to its ubiquity in the environment, plasticizers have raised concerns pertaining to continuous exposure of the human population. Our data/observations document the need for an integrated exposure assessment in the sense of the precautionary principle in chemicals management, as well as toxicity assessment/identification of hazard arising from the new introduced substances. In the long term, a stronger focus on regulation, which is largely based on human health concerns will turn out to be detrimental for both protection goals due to the fact that humans also can be exposed to hazardous substances via the environment. However, up to now this overlap remains largely unrecognized in the different chemical regulations and environmental risks are not sufficiently addressed in risk assessment.

Availability of data and materials

All data generated or analyzed during this study are included in this published article and its additional information file.

Abbreviations

ATBC:

Acetyl tributyl citrate

BBP:

Benzylbutyl phthalate

CAS:

Chemical Abstracts Service

CSS:

Chemicals Strategy for Sustainability

CoRAP:

Community Rolling Action Plan

DAP:

Diallyl phthalate

DBA:

Dibutyl adipate

DBEP:

Bis (2-butoxyethyl) phthalate

DEHA:

Di (2-ethylhexyl) adipate

DEHAz:

Di (2-ethylhexyl) azelate

DEHP:

Di (2-ethylhexyl) phthalate

DEHS:

Di (2-ethylhexyl) sebacate

DEHT:

Di (2-ethylhexyl) terephthalate

DEP:

Diethyl phthalate

DBP:

Dibutyl phthalate

DcHP:

Dicyclohexyl phthalate

DIBP:

Diisobutyl phthalate

DIDP:

Diisodecyl phthalate

DHP:

Dihexyl phthalate

DIHP:

Diisoheptyl phthalate

DINA:

Diisononyl adipate

DINCH:

Diisononyl 1, 2-cyclohexanedicarboxylic acid

DINP:

Diisononyl phthalate

DIUP:

Diisoundecyl phthalate

DMEP:

Di (2-methoxyethyl) phthalate

DMP:

Dimethyl phthalate

DnBP:

Di-n-butyl phthalate

DPHP:

Di (2-propylheptyl) phthalate

DPP:

Dipentyl phthalate

dw:

dry weight

ED:

Endocrine disruptor

ESB:

German Environmental Specimen Bank

EU:

European Union

GerES:

German Environmental Survey

GC–MS:

Gas chromatography/mass spectrometry

HMW:

High molecular weight

LC–MS:

Liquid chromatography/mass spectrometry

LOQ:

Limit of quantification

K OA :

Octanol–air partition coefficient

K OW :

Octanol–water partition coefficient

LMW:

Low molecular weight

PBT:

Persistent, bioaccumulative, toxic

PVC:

Polyvinyl chloride

QSAR:

Quantitative structure–activity relationship

REACH:

Registration Evaluation Authorisation and Restriction of Chemicals

RoHS:

Restriction of (the use of certain) Hazardous Substances in electrical and electronical Equipment

SMILES:

Simplified Molecular Input Line Entry Specification

SPM:

Suspended particulate matter

SVHC:

Substance of Very High Concern

SVOC:

Semi-volatile organic compound

TOTM:

Tris(2-ethylhexyl) trimellitate

WFD:

Water Framework Directive

References

  1. Abb M, Heinrich T, Sorkau E, Lorenz W (2009) Phthalates in house dust. Environ Int 35(6):965–970. https://doi.org/10.1016/j.envint.2009.04.007

    Article  CAS  Google Scholar 

  2. Ait Bamai Y, Araki A, Kawai T, Tsuboi T, Saito I, Yoshioka E, Kanazawa A, Tajima S, Shi C, Tamakoshi A, Kishi R (2014) Associations of phthalate concentrations in floor dust and multi-surface dust with the interior materials in Japanese dwellings. Sci Total Environ 468:147–157. https://doi.org/10.1016/j.scitotenv.2013.07.107

    Article  CAS  Google Scholar 

  3. Al Qasmi NN, Al-Thaiban H, Helaleh MIH (2019) Indoor phthalates from household dust in Qatar: implications for non-dietary human exposure. Environ Sci Pollut Res 26:421–430. https://doi.org/10.1007/s11356-018-3604-8

    Article  CAS  Google Scholar 

  4. ANSES (French agency for food, environmental and occupational health & safety) (2016a) opinion of the french agency for food, environmental and occupational health & safety on "plastic toys and children's equipment intended for children under three years of age". Request No 2013-SA-0176. https://www.anses.fr/en/system/files/CONSO2013SA0176RaEN.pdf

  5. ANSES (French agency for food, environmental and occupational health & safety) (2016b) regulatory management option analysis for DEHT - conclusion document. https://echa.europa.eu/de/rmoa/-/dislist/details/0b0236e1809b6287

  6. ANSES (French agency for food, environmental and occupational health & safety) (2016c) regulatory management option analysis for ATBC - conclusion document.https://echa.europa.eu/de/rmoa/-/dislist/details/0b0236e180785866

  7. ANSES (French agency for food, environmental and occupational health & safety) (2016d) regulatory management option analysis for DINCH - conclusion document. https://echa.europa.eu/de/rmoa/-/dislist/details/0b0236e1809b630b

  8. ATSDR (Agency for Agency for Toxic Substances and Disease Registry) (2001) Toxicological profile for Di‐n‐butyl phthalate. US department of health and human services.https://www.atsdr.cdc.gov/toxprofiles/tp135.pdf

  9. Bathelt H (2009) Re-bundling and the development of hollow clusters in the east german chemical industry. Eur Urban Reg Stud 16:363

    Article  Google Scholar 

  10. Blair JD, Ikonomou MG, Kelly BC, Surridge B, Gobas FAPC (2009) Ultra-trace determination of phthalate ester metabolites in seawater, sediments, and biota from an urbanized marine inlet by LC/ESI-MS/MS. Environ Sci Technol 43:6262–6268. https://doi.org/10.1021/es9013135

    Article  CAS  Google Scholar 

  11. Bergé A, Cladière M, Gasperi J, Coursimault A, Tassin B, Moilleron R (2013) Meta-analysis of environmental contamination of phthalates. Environ Sci Pollut Res Int 20:8057–8076. https://doi.org/10.1007/s11356-013-1982-5

    Article  CAS  Google Scholar 

  12. Bi C, Maestre JP, Li H, Zhang G, Givehchi R, Mahdavi A, Kinney KA, Siegel J, Horner SD, Xua Y (2018) Phthalates and organophosphates in settled dust and HVAC filter dust of U.S. low-income homes: association with season, building characteristics, and childhood asthma. Environ Int 212:916–930. https://doi.org/10.1016/j.envint.2018.09.013

    Article  CAS  Google Scholar 

  13. Bi C, Wang X, Li H, Li X, Xu Y (2020) Direct transfer of phthalate and alternative plasticizers from indoor source products to dust: laboratory measurements and predictive modeling. Sci Total Environ 55(1):341–351. https://doi.org/10.1021/acs.est.0c05131

    Article  CAS  Google Scholar 

  14. Biron, M (2009) Phthalate ousting: not so easy but some alternatives are viable. SpecialChem.https://polymer-additives.specialchem.com/tech-library/article/phthalate-ousting-not-so-easy-but-some-alternatives-are-viable

  15. Björklund K, Cousins AP, Strömwall A-M, Malmqvist P-A (2009) Phthalates and nonylphenols in urban runoff: occurrence, distribution and area emission factors. Sci Total Environ 407(16):4665–4672. https://doi.org/10.1016/j.scitotenv.2009.04.040

    Article  CAS  Google Scholar 

  16. Bope A, Haines SR, Hegarty B, Weschler CA, Peccia J, Dannemiller KC (2019) Degradation of phthalate esters in floor dust at elevated relative humidity. Environ Sci Process Impacts. https://doi.org/10.1039/c9em00050j

    Article  Google Scholar 

  17. Cadogan, D (2007) The current plasticizer situation in Europe. Phthalates and new plasticisers for PVC Conference. Copenhagen, Denmark. https://slideplayer.com/slide/6418484/

  18. Cazzuffi D, Gioffré D (2020) Lifetime assessment of exposed PVC-P geomembranes installed on Italian dams. Geotext Geomembr 48(2):130–136. https://doi.org/10.1016/j.geotexmem.2019.11.015

    Article  Google Scholar 

  19. CCPSA (Canada Consumer Product Safety Act) (2016) Phthalates regulations. https://laws-lois.justice.gc.ca/eng/regulations/SOR-2016-188/page-1.html.

  20. Ceresana (2019) Market study: plasticizers (5th Edition). https://www.ceresana.com/en/market-studies/chemicals/plasticizers/

  21. Chemie Park Bitterfeld-Wolfen (2022) Website. https://www.chemiepark.de/en/the-chemical-park/history/

  22. Christia C, Poma G, Harrad S, de Wit CA, Sjostrom Y, Leonards P, Lamoree M, Covaci A (2019) Occurrence of legacy and alternative plasticizers in indoor dust from various EU countries and implications for human exposure via dust ingestion and dermal absorption. Environ Res 171:204–212. https://doi.org/10.1016/j.envres.2018.11.034

    Article  CAS  Google Scholar 

  23. Coaker, W (2005) Flexible PVC. In: Wilkes, CE, Daniels, CA, Summers, JW (eds) PVC Handbook. Carl Hanser, ISBN 978–3446227149.

  24. Cousins I, Mackay D (2000) Correlating the physical-chemical properties of phthalate esters using the ‘three solubility’ approach. Chemosphere 41:1389–1399. https://doi.org/10.1016/S0045-6535(00)00005-9

    Article  CAS  Google Scholar 

  25. Cousins IT, Mackay D, Parkerton TF (2003) Physical-chemical properties and evaluative fate modelling of Phthalate esters. In: Staples CA (ed) Series anthropogenic compounds. Springer, Berlin, pp 57–84

    Chapter  Google Scholar 

  26. Cousins, A P, Remberger, M, Kaj, L, Ekheden, Y, Dusan, B, Brorström-Lundén, E (2007) Results from the swedish national screening programme 2006 - subreport 1: Phthalates. IVL (Swedish Environmental Research Institute), B1750. https://www.ivl.se/download/18.343dc99d14e8bb0f58b7517/1445515659841/B1750.pdf

  27. Cousins IT, Vestergen R, Wang Z, Scheringer M, McLachlan MS (2016) The precautionary principle and chemicals management: the example of perfluoroalkyl acids in groundwater. Environ Int 94:331–340. https://doi.org/10.1016/j.envint.2016.04.044

    Article  CAS  Google Scholar 

  28. CPSC (United States Consumer Product Safety Commission) (2008) Consumer Product Safety improvement act, section 108: phthalate limitation in toys and certain child care articles. https://www.cpsc.gov/Regulations-Laws--Standards/Statutes/The-Consumer-Product-Safety-Improvement-Act

  29. CPSC (United States Consumer Product Safety Commission) (2011) Toxicity review for diisobutyl phthalate (DiBP, CASRN 84-69-5). https://www.cpsc.gov/s3fs-public/ToxicityReviewOfDiBP.pdf

  30. Demirtepe H, Melymuk L, Codling G, Murínová LP, Richterová D, Rašplová V, Trnovec T, Klánová J (2021) Targeted and suspect screening of plasticizers in house dust to assess cumulative human exposure risk. Sci Total Environ 781:146667. https://doi.org/10.1016/j.scitotenv.2021.146667

    Article  CAS  Google Scholar 

  31. EC (European Commission) (1999) 1999/815/EC: Commission decision of 7 December 1999 adopting measures prohibiting the placing on the market of toys and childcare articles intended to be placed in the mouth by children under three years of age made of soft PVC containing one or more of the substances di-iso-nonyl phthalate (DINP), di(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), di-iso-decyl phthalate (DIDP), di-n-octyl phthalate (DNOP), and butylbenzyl phthalate (BBP). OJ L 315/46. https://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:1999:097:0014:0032:EN:PDF

  32. EC (European Commission) (2003) European Union risk assessment report 1,2-benzenedicarboxylic acid, di-C8–10-branched alkyl esters, C9-rich and di-“isononyl” phthalate (DINP). EUR 20784 EN. https://echa.europa.eu/documents/10162/83a55967-64a9-43cd-a0fa-d3f2d3c4938d

  33. EC (European Commission) (2004) Commission Directive 2004/93/EC of 21 September 2004 amending Council Directive 76/768/EEC for the purpose of adapting its Annexes II and III to technical progress. OJ L300/13. https://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:32004L0093&from=DE

  34. EC (European Commission) (2005) Directive 2005/84/EC of the European Parliament and of the Council of 14 December 2005 amending for the 22nd time Council Directive 76/769/EEC on the approximation of the laws, regulations and administrative provisions of the Member States relating to restrictions on the marketing and use of certain dangerous substances and preparations (phthalates in toys and childcare articles). OJ L344/40. https://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:32005L0084&from=DE

  35. EC (European Commission) (2007) Commission Directive 2007/19/EC of 30 March 2007 amending Directive 2002/72/EC relating to plastic materials and articles intended to come into contact with food and Council Directive 85/572/EEC laying down the list of simulants to be used for testing migration of constituents of plastic materials and articles intended to come into contact with foodstuffs. OJ L 91/17. https://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:32007L0019&from=DE

  36. EC (European Commission) (2008) European union risk assessment report—bis (2-ethylhexyl)phthalate (DEHP). https://echa.europa.eu/documents/10162/e614617d-58e7-42d9-b7fb-d7bab8f26feb

  37. EC (European Commission) (2009) Common implementation strategy for the water framework directive (2000/60/EC) - guidance Document no. 19 guidance on surface water chemical monitoring under the water framework directive.https://circabc.europa.eu/sd/a/e54e8583-faf5-478f-9b11-41fda9e9c564/Guidance

  38. EC (European Commission) (2011) Request for international review of commission Decision C(2016) 3549 - Phthalates and their alternatives: health and environmental concerns. https://ec.europa.eu/environment/aarhus/pdf/35/Annex_11_report_from_Lowell_Center.pdf

  39. EC (European Commission) (2017) Commission implementing decision on the identification of bis (2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), benzyl butyl phthalate (BBP) and diisobutyl phthalate (DIBP) as substances of very high concern according to Article 57(f) of Regulation (EC) No 1907/2006 of the European Parliament and of the Council. https://echa.europa.eu/documents/10162/88c20879-606b-03a6-11e4-9edb90e7e615

  40. EC (European Commission) (2019) Communication from the commission to the European parliament, the European council, the council, the European economic and social committee and the committee of the regions—The European green deal. COM (2019) 640 final.https://ec.europa.eu/info/sites/default/files/european-green-deal-communication_en.pdf

  41. EC (European Commission) (2020) Communication from the commission to the European parliament, the council, the European economic and social committee and the committee of the regions - chemicals strategy for sustainability towards a toxic-free environment. https://ec.europa.eu/environment/pdf/chemicals/2020/10/Strategy.pdf

  42. EC (European Commission) (2021) Communication from the commission to the European parliament, the council, the European economic and social committee and the committee of the regions - pathway to a healthy planet for all eu action plan: 'towards zero pollution for air, water and soil'. https://ec.europa.eu/environment/pdf/zero-pollution-action-plan/communication_en.pdf

  43. ECHA (European Chemicals Agency) (2012) Community Rolling Action Plan (CoRAP). https://echa.europa.eu/documents/10162/13628/corap_2012_en.pdf/0f6967f5-b6b3-484b-896f-32bfb3598ba9

  44. ECHA (European Chemicals Agency) (2013) Evaluation of new scientific evidence concerning DINP and DIDP. https://echa.europa.eu/documents/10162/31b4067e-de40-4044-93e8-9c9ff1960715

  45. ECHA (European Chemicals Agency) (2014a) Submission of information on DIDP CAS#68515-49-1, EC#271-091-4 as an alternative to DEHP applications for authorisation - submitter: exxonmobil petroleum and chemical B.V.B.A.https://echa.europa.eu/documents/10162/18074545/a4a_comment_49_1_attachment_en.pdf

  46. ECHA (European Chemicals Agency) (2014b) Justification for the selection of a substance for CoRAP inclusion - bis (2-propylheptyl) phthalate. https://echa.europa.eu/documents/10162/ccac47ac-5202-02b2-02d1-5197d6f87af6

  47. ECHA (European Chemicals Agency) (2014c) Community Rolling Aciton Plan (CoRAP) update covering years 2014, 2015 and 2016. https://echa.europa.eu/information-on-chemicals/evaluation/community-rolling-action-plan/corap-list-of-substances

  48. ECHA (European Chemicals Agency) (2014d) Inclusion of substances of very high concern in the candidate list for eventual inclusion in annex XIV. ED/108/2014. https://echa.europa.eu/documents/10162/30b654ce-1de3-487a-8696-e05617c3173b

  49. ECHA (European Chemicals Agency) (2018) Opinion of the committee for risk assessment (RAC) proposing harmonised classification and labelling at EU level of 1,2-Benzenedicarboxylic acid, di-C8-10-branched alkylesters, C9-rich; [1] di-“isononyl” phthalate; [2] [DINP]. CLH-O-0000001412-86-201/F.https://echa.europa.eu/documents/10162/56980740-fcb6-6755-d7bb-bfe797c36ee7

  50. ECHA (European Chemicals Agency) (2020) Tris(2-ethylhexyl) benzene-1,2,4-tricarboxylate, decision on substance evaluation.https://echa.europa.eu/documents/10162/f7881694-9737-9bb2-48d2-64affb546f83

  51. ECHA (European Chemicals Agency) (2022a) Substances restricted under reach—Annex XVII Entry 51. https://www.echa.europa.eu/substances-restricted-under-reach

  52. ECHA (European Chemicals Agency) (2022b) authorisation list entry 04-07. https://echa.europa.eu/authorisation-list?p_p_id=disslists_WAR_disslistsportlet&p_p_lifecycle=1&p_p_state=normal&p_p_mode=view&p_p_col_id=column-1&p_p_col_pos=1&p_p_col_count=2&_disslists_WAR_disslistsportlet_javax.portlet.action=searchDissLists

  53. ECHA (European Chemicals Agency) (2022c) Bis(2-propylheptyl) phthalate—substance infocard. https://echa.europa.eu/de/substance-information/-/substanceinfo/100.053.137

  54. ECHA (European Chemicals Agency) (2022d) Candidate list of substances of very high concern for authorisation. https://echa.europa.eu/candidate-list-table

  55. ECHA (European Chemicals Agency) (2022e) Substances restricted under REACH - Annex XVII Entry 52. https://www.echa.europa.eu/substances-restricted-under-reach

  56. ECHA (European Chemicals Agency) (2022f) Di-''isodecyl'' phthalate - Substance infocard. https://echa.europa.eu/de/substance-information/-/substanceinfo/100.043.601

  57. ECHA (European Chemicals Agency) (2022g) PBT assessment. https://echa.europa.eu/understanding-pbt-assessment

  58. ECPI (European Council for Plasticisers and Intermediates) (2018) Focus on plasticisers & flexible PVC. https://www.plasticisers.org/wp-content/uploads/2018/10/ECPI_proposal_V19b_15022016.pdf

  59. ECPI (European Council for Plasticisers and Intermediates) (2019) Focus on plasticisers. https://www.plasticisers.org/wp-content/uploads/2019/01/PLASTICISERS_LEAFLET_UPDATE_15012019_for_REPRINT_2019.pdf

  60. ECPI (European Council for Plasticizers and Intermediates) (2022a) Plasticizers information center. https://www.plasticisers.org/plasticisers/

  61. ECPI (European Council for Plasticizers and Intermediates) (2022b) Trimellitates. https://www.plasticisers.org/plasticiser/trimellitates/

  62. ESB (2022a) German environmental specimen bank - concept.https://www.umweltprobenbank.de/en/documents/11426

  63. ESB (2022b) German environmental specimen bank—suspended particulate matter.https://www.umweltprobenbank.de/en/documents/profiles/specimen_types/14940

  64. Fromme H, Lahrz T, Piloty M, Gebhart H, Oddoy A, Rüden H (2004) Occurrence of phthalates and musk fragrances in indoor air and dust from apartments and kindergartens in Berlin (Germany). Indoor Air 14:188–195. https://doi.org/10.1111/j.1600-0668.2004.00223.x

    Article  CAS  Google Scholar 

  65. Fromme H, Schütze A, Lahrz T, Kraft M, Fembacher L, Siewering S, Burkardt R, Dietrich S, Koch HM, Völkel W (2016) Non-phthalate plasticizers in German daycare centers and human biomonitoring of DINCH metabolites in children attending the centers (LUPE 3). Int J Hyg Environ Health 219:33–39. https://doi.org/10.1016/j.ijheh.2015.08.002

    Article  CAS  Google Scholar 

  66. Gangolli SD (1982) Testicular effects of phthalate esters. Environ Health Perspect 45:77–84. https://doi.org/10.1289/ehp.824577

    Article  CAS  Google Scholar 

  67. Gao DW, Wen ZD (2016) Phthalate esters in the environment: a critical review of their occurrence, biodegradation, and removal during wastewater treatment processes. Sci Total Environ 541:986–1001. https://doi.org/10.1016/j.scitotenv.2015.09.148

    Article  CAS  Google Scholar 

  68. Godwin AD, Krauskopf LG (2008) Monomeric plasticizers. In: Grossmann RF (ed) Handbook of Vinyl formulation, 2nd edn. Wiley, New Jersey, pp 173–221

    Chapter  Google Scholar 

  69. Godwin, A (2011) Terephthalate esters. In: Applied plastics engineering handbook, Chapter 28.7. https://www.sciencedirect.com/topics/materials-science/plasticizer

  70. Giuliani A, Zuccarini M, Cichelli A, Khan H, Reale M (2020) Critical review on the presence of phthalates in food and evidence of their biological impact. Int J Environ Res Public Health 17:5655. https://doi.org/10.3390/ijerph17165655

    Article  Google Scholar 

  71. Gustafsson E, Bowden TM, Rennie AR (2020) Interactions of amphiphiles with plasticisers used in polymers: understanding the basis of health and environmental challenges. Adv Interface Colloid Sci 277:102109. https://doi.org/10.1016/j.cis.2020.102109

    Article  CAS  Google Scholar 

  72. Hakkarainen M (2008) Migration of monomeric and polymeric PVC plasticizers. In: Albertsson AC, Hakkarainen M (eds) Chromatography of sustainable polymeric materials. Springer, Berlin, pp 159–185

    Chapter  Google Scholar 

  73. Hammel SC, Levasseur JL, Hoffman K, Phillips AL, Lorenzo AM, Calafat AM, Webster TF, Stapleton HM (2019) Children’s exposure to phthalates and non-phthalate plasticizers in the home: the TESIE study. Environ Int 132:105061. https://doi.org/10.1016/j.envint.2019.105061

    Article  CAS  Google Scholar 

  74. IHS Markit (2018) Plasticizer—chemical economics handbook. https://ihsmarkit.com/products/plasticizers-chemical-economics-handbook.html

  75. Huang CN, Chiu YH, Cho HB, Lee CW (2019) Children’s exposure to phthalates in dust and soil in Southern Taiwan: a study following the phthalate incident in 2011. Sci Total Environ 696:133685. https://doi.org/10.1016/j.scitotenv.2019.133685

    Article  CAS  Google Scholar 

  76. JDS3 (Joint Danube Survey 3) (2015) Final scientific report. http://www.danubesurvey.org/jds3/jds3-files/nodes/documents/jds3_final_scientific_report_1.pdf

  77. Kellner E, Hubbard JA (2018) Spatiotemporal variability of suspended sediment particle size in a mixed-land-use watershed. Sci Total Environ 615:1164–1175. https://doi.org/10.1016/j.scitotenv.2017.10.040

    Article  CAS  Google Scholar 

  78. Kim S, Lee YS, Moon HB (2020) Occurrence, distribution, and sources of phthalates and non-phthalate plasticizers in sediment from semi-enclosed bays of Korea. Mar Pollut Bull 151:110824. https://doi.org/10.1016/j.marpolbul.2019.110824

    Article  CAS  Google Scholar 

  79. Kim S, Kim Y, Moon HB (2021) Contamination and historical trends of legacy and emerging plasticizers in sediment from highly industrialized bays of Korea. Sci Total Environ 765:142751. https://doi.org/10.1016/j.scitotenv.2020.142751

    Article  CAS  Google Scholar 

  80. Kim Y, Kim S, Liao C, Moon HB (2021) Severe contamination and time trend of legacy and alternative plasticizers in a highly industrialized lake associated with regulations and coastal development. Mar Pollut Bull 171:112787. https://doi.org/10.1016/j.marpolbul.2021.112787

    Article  CAS  Google Scholar 

  81. Koch HM, Rüther M, Schütze A, Conrad A, Pälmke C, Apel P, Brüning T, Kolossa-Gehring M (2017) Phthalate metabolites in 24-h urine samples of the German Environmental Specimen Bank (ESB) from 1988 to 2015 and a comparison with US NHANES data from 1999 to 2012. Int J Hyg Environ Health 220(2):130–141. https://doi.org/10.1016/j.ijheh.2016.11.003

    Article  CAS  Google Scholar 

  82. Kozlowski RR, Storzum U (2005) Di(2-propylheptyl) phthalate: a new plasticizer choice for PVC compounders. J Vinyl Addit Technol 11:155–159. https://doi.org/10.1002/vnl.20055

    Article  CAS  Google Scholar 

  83. Kunststoffe international (2021) Global demand for plasticizers continues to increase. Issue 2021/3. https://en.kunststoffe.de/a/news/global-demand-for-plasticizers-continues-266468

  84. Larsson K, Lindh CH, Jönsson BAG, Gionvanoulis G, Bibi M, Bottai M, Bergström A, Berglund M (2017) Phthalates, non-phthalate plasticizers and bisphenol in Swedish preschool dust in relation to children’s exposure. Environ Int 102:114–124. https://doi.org/10.1016/j.envint.2017.02.006

    Article  CAS  Google Scholar 

  85. Lee YS, Lim JE, Lee S, Moon HB (2020) Phthalates and non-phthalate plasticizers in sediment from Korean coastal waters: occurrence, spatial distribution, and ecological risks. Mar Pollut Bull 154:111119. https://doi.org/10.1016/j.marpolbul.2020.111119

    Article  CAS  Google Scholar 

  86. Letinski DJ, Connelly MJ Jr, Peterson DR, Parkerton TF (2002) Slow-stir water solubility measurements of selected alcohols and diesters. Chemosphere 48:257–265. https://doi.org/10.1016/S0045-6535(02)00086-3

    Article  CAS  Google Scholar 

  87. Li X, Zhang W, Lv J, Liu W, Sun S, Guo C (2021) Distribution, source apportionment, and health risk assessment of phthalate esters in indoor dust samples across China. Environ Sci Eur 33:19. https://doi.org/10.1186/s12302-021-00457-3

    Article  CAS  Google Scholar 

  88. Maag, J, Lassen, C, Brandt, UK, Kjølholt, J, Molander, L, Mikkelsen, SH (2010) Identification and assessment of alternatives to selected phthalates. COWI Environmental Project No. 1341 2010. https://www2.mst.dk/udgiv/publications/2010/978-87-92708-00-7/pdf/978-87-92708-01-4.pdf

  89. Malnes D, Ahrens L, Köhler S, Forsberg M, Golovko O (2022) Occurrence and mass flows of contaminants of emerging concern (CECs) in Sweden’s three largest lakes and associated rivers. Chemosphere 294:133825. https://doi.org/10.1016/j.chemosphere.2022.133825

    Article  CAS  Google Scholar 

  90. MHLW (Ministry of Health, Labour and Welfare in Japan) (2010) Bureau veritas: revision of phthalate requirements in toys under japan food sanitation law.https://www.toy-icti.org/PDFs/Jap-PhthReqRev.pdf

  91. Nagorka R, Scheller C, Ullrich D (2005) Plasticizer in house dust. Gefahrst Reinhalt Luft 65(3):95–105 (in German)

    Google Scholar 

  92. Nagorka R, Conrad A, Scheller C, Süßenbach B, Moriske HJ (2010) Plasticizers and flame retardants in household dust—Part 1: Phthalates (in German). Gefahrst Reinhalt Luft 70(3):70–76 (in German)

    CAS  Google Scholar 

  93. Nagorka R, Conrad A, Scheller C, Süßenbach B, Moriske HJ (2011a) Plasticizers and flame retardants in household dust—Part 2: non-phthalates and flame retardants. Gefahrst Reinhalt Luft 71(6):286–292 (in German)

    CAS  Google Scholar 

  94. Nagorka R, Conrad A, Scheller C, Süßenbach B, Moriske HJ (2011b) Diisononyl 1,2-cyclohexanedicarboxylic acid (DINCH) and Di(2-ethylhexyl) terephthalate (DEHT) in indoor dust samples: concentration and analytical problems Int. J Hyg Environ Health 214(1):26–35. https://doi.org/10.1016/j.ijheh.2010.08.005

    Article  CAS  Google Scholar 

  95. Nagorka R, Koschorreck J (2020) Trends for plasticizers in German freshwater environments—Evidence for the substitution of DEHP with emerging phthalate and non-phthalate alternatives. Environ Pollut 262:114237. https://doi.org/10.1016/j.envpol.2020.114237

    Article  CAS  Google Scholar 

  96. Net S, Sempéré R, Delmont A, Paluselli A, Ouddane B (2015) Occurrence, fate, behavior and ecotoxicological state of phthalates in different environmental matrices. Environ Sci Technol 49:4019–4035. https://doi.org/10.1021/es505233b

    Article  CAS  Google Scholar 

  97. Niu L, Ahlheim J, Glaser C, Gunold R, Henneberger L, König M, Krauss M, Schwientek M, Zarfl C, Escher B (2021) Suspended particulatte matter—A source or sink for chemical mixtures of organic micropollutants in a small river under baseflow conditions? Environm Sci Technolog 55:5106–5116. https://doi.org/10.1021/acs.est.0c07772

    Article  CAS  Google Scholar 

  98. OPC (California Ocean Protection Council) (2009) Toxicological profile for Di (2-Ethylhexyl) Phthalate (DEHP). http://www.opc.ca.gov/webmaster/ftp/project_pages/MarineDebris_OEHHA_ToxProfiles/DEHP%20Final.pdf

  99. Oxea (2014) Oxsoft - Oxblue. Informational leaflet. https://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=&ved=2ahUKEwim-YSczZvwAhXFxqQKHeKYBTsQFjAAegQIBRAD&url=https%3A%2F%2Fchemicals.oq.com%2Ffileadmin%2FPage%2FUnternehmen%2FMedien%2FDownloads%2FOXSOFT_OXBLUE-Bruchure_02.pdf&usg=AOvVaw1Jf9qr06LdT-IklJWZTDq3

  100. Peijnenburg WJGM, Struijs J (2006) Occurrence of phthalate esters in the environment of the Netherlands. Ecotoxicol Environ Saf 63(2):204–215. https://doi.org/10.1016/j.ecoenv.2005.07.023

    Article  CAS  Google Scholar 

  101. Perstorp (2022) Seven performance reasons to change to a C10 plastizicer. Online information. https://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=&ved=2ahUKEwilkZup9NTvAhUSOuwKHWEpCY8QFjABegQIBhAD&url=https%3A%2F%2Fwww.perstorp.com%2F-%2Fmedia%2Ffiles%2Fperstorp%2Fbrochures%2Fseven_performance_reasons_to_change_to_a_c10_plasticizer.pdf&usg=AOvVaw0zMoN-txOR7ZcaQYxNXtWZ

  102. Peterson DR, Staples CA (2003) Degradation of phthalate esters in the environment. In: Staples C (ed) Series anthropogenic compound. Springer, Berlin, pp 85–124

    Chapter  Google Scholar 

  103. Pizzo F, Lombardo A, Manganaro A, Cappelli CI, Petoumenou MI, Albanese F, Roncaglioni A, Brandt M, Benfenati E (2016) Integrated in silico strategy for PBT assessment and prioritization under REACH. Environ Res 151:478. https://doi.org/10.1016/j.envres.2016.08.014

    Article  CAS  Google Scholar 

  104. Pohlert T, Hillebrand G, Breitung V (2011) Trends of persistent organic pollutants in the suspended matter of the River Rhine. Hydrol Process 25(24):3803–3817. https://doi.org/10.1002/hyp.8110

    Article  CAS  Google Scholar 

  105. Promtes K, Kaewbooncho O, Kawai T, Miyashita K, Panyapinyopol B, Kwonpongsagoon S (2019) Human exposure to phthalates from house dust in Bangkok Thailand. J Environ Sci Health A 54(13):1269–1276. https://doi.org/10.1080/10934529.2019.1637207

    Article  CAS  Google Scholar 

  106. Remberger, M, Kaj, L, Hansson, K, Andersson, H, Brorström-Lundén, E, Lunder, H, Schlabach, M (2013) Selected Plasticizers and Additional Sweeteners in the Nordic Environment. Norden - Nordic Council of Ministers, TemaNord TN2013-505. http://www.diva-portal.org/smash/get/diva2:702020/FULLTEXT01.pdf

  107. Rudel RA, Camann DE, Spengler JD, Korn LR, Brody JG (2003) Phthalates, Alkylphenols, pesticides, polybrominated diphenyl ethers, and other endocrine-disrupting compounds in indoor air and dust. Environ Sci Technolog 37(20):4543–4553. https://doi.org/10.1021/es0264596

    Article  CAS  Google Scholar 

  108. Schubert B, Heininger P, Keller M, Claus E, Ricking M (2012) Monitoring of contaminants in suspended particulate matter as an alternative to sediments. TrAC 36:58–70. https://doi.org/10.1016/j.trac.2012.04.003

    Article  CAS  Google Scholar 

  109. Schütze A, Gries W, Kolossa-Gehring M, Apel P, Schröter-Kermani C, Fiddicke U, Leng G, Brüning T, Koch HM (2015) Bis-(2-propylheptyl)phthalate (DPHP) metabolites emerging in 24 h urine samples from the German Environmental Specimen Bank (1999–2012). Int J Hyg Environ Health 218(6):559–563. https://doi.org/10.1016/j.ijheh.2015.05.007

    Article  CAS  Google Scholar 

  110. Schulz C, Seiwert M, Babisch W, Becker K, Conrad A, Szewzyk R, Kolossa-Gehring M (2012) Overview of the study design, participation and field work of the German Environmental Survey on Children 2003–2006 (GerES IV). Int J Hyg Env Health 215(4):435–448. https://doi.org/10.1016/j.ijheh.2012.02.002

    Article  Google Scholar 

  111. Schulz C, Conrad A, Rucic E, Schwedler G, Reiber L, Peisker J, Kolossa-Gehring M (2021) The German Environmental Survey for Children and Adolescents 2014–2017 (GerES V)—Study population, response rates and representativeness. Int J Hyg Env Health 237:113821. https://doi.org/10.1016/j.ijheh.2021.113821

    Article  Google Scholar 

  112. Schwedler G, Conrad A, Rucic E, Koch HM, Leng G, Schulz C, Schmied-Tobies MIH, Kolossa-Gehring M (2020) Hexamoll® DINCH and DPHP metabolites in urine of children and adolescents in Germany. Human biomonitoring results of the German Environmental Survey GerES V, 2014–2017. Int J Hyg Environ Health 229:113397. https://doi.org/10.1016/j.ijheh.2019.09.004

    Article  CAS  Google Scholar 

  113. Sha Y, Xia X, Yang Z, Huang GH (2007) Distribution of PAEs in the middle and lower reaches of the Yellow River, China. Environ Monit Assess 124:277–287. https://doi.org/10.1007/s10661-006-9225-6

    Article  CAS  Google Scholar 

  114. Shin HM, Moschet M, Young TM, Bennett DH (2020) Measured concentrations of consumer product chemicals in California house dust: implications for sources, exposure, and toxicity potential. Indoor Air 30(1):60–75. https://doi.org/10.1111/ina.12607

    Article  CAS  Google Scholar 

  115. SpecialChem (2022) High molecular weight phthalate plasticizer - Key benefits. https://polymer-additives.specialchem.com/centers/high-molecular-weight-phthalates-plasticizers/key-benefits

  116. Stark TD, Choi H, Diebel PW (2005) Influence of plasticizer molecular weight on plasticizer retention in PVC geomembranes. Geosynth Int 12(1):99–110. https://doi.org/10.1680/gein.2005.12.2.99

    Article  Google Scholar 

  117. Storzum, U (2010) BASF plasticizer presentation - conference paper. https://www.researchgate.net/publication/280051725_BASF_Plasticizer_Presentation

  118. Subedi B, Sullivan KD, Dhungana B (2017) Phthalate and non-phthalate plasticizers in indoor dust from childcare facilities, salons, and homes across the USA. Environ Pollut 230:701–708. https://doi.org/10.1016/j.envpol.2017.07.028

    Article  CAS  Google Scholar 

  119. Takeuchi S, Kojima H, Saito I, Jin K, Kobayashi S, Tanaka-Kagawa T, Jinno H (2014) Detection of 34 plasticizers and 25 flame retardants in indoor air from houses in Sapporo Japan. Sci Tot Environ 491–492:28–33. https://doi.org/10.1016/j.scitotenv.2014.04.011

    Article  CAS  Google Scholar 

  120. Tomita I, Nakamura Y, Aoki N, Inui N (1982) Mutagenic/carcinogenic potential of DEHP and MEHP. Environ Health Perspect 45:119–125. https://doi.org/10.1289/ehp.8245119

    Article  CAS  Google Scholar 

  121. UBA (Umweltbundesamt/German Environment Agency) (2005) German Environmental Survey for Children (GerES IV) - Brief description of the project. BriefDescription_January2005_2.pdf (umweltbundesamt.de)

  122. Umweltbundesamt German Environment Agency (2011) Substance monograph Phthalates—New and updated reference values for monoesters and oxidised metabolites in urine of adults and children. Bundesgesundheitsbl Gesundheitsforsch Gesundheitsschutz. 54(6):770–785 (in German)

    Article  Google Scholar 

  123. Van Vliet EDS, Reitano EM, Chhabra JS, Bergen GP, Whyatt RM (2011) A review of alternatives to di(2-ethylhexyl) phthalate-containing medical devices in the neonatal intensive care unit. J Perinatol 31(8):551–560. https://doi.org/10.1038/jp.2010.208

    Article  CAS  Google Scholar 

  124. Wensing M, Uhde E, Salthammer T (2005) Plastic additives in the indoor environment—flame retardants and plasticizers. Sci Tot Environ 339(1–3):19–40. https://doi.org/10.1016/j.scitotenv.2004.10.028

    Article  CAS  Google Scholar 

  125. Weschler CJ, Salthammer T, Fromme H (2008) Partitioning of phthalates among the gas phase, airborne particles and settled dust in the indoor environment. Atmos Environ 42(7):1449–1460. https://doi.org/10.1016/j.atmosenv.2007.11.014

    Article  CAS  Google Scholar 

  126. Weschler CJ, Nazaroff WW (2010) SVOC partitioning between the gas phase and settled dust indoors. Atmos Environ 44(30):3609–3620. https://doi.org/10.1016/j.atmosenv.2010.06.029

    Article  CAS  Google Scholar 

  127. WSP Environmental Sverige (2018) Indoor pollutants in dust from NONHAZCITY pilot families in Stockholm. test report on dust Campaign, Report from work in GOA 5.4 “Test your environment”. https://thinkbefore.eu/wp-content/uploads/2020/07/5.4.Indoor-pollutants-in-dust-from-NHC-pilot-families-in-Stockholm.pdf

  128. Xie Z, Ebinghaus R, Temme C, Caba A, Ruck W (2005) Atmospheric concentrations and air–sea exchanges of phthalates in the North Sea (German Bight). Atmos Environ 39(18):3209–3219. https://doi.org/10.1016/j.atmosenv.2005.02.021

    Article  CAS  Google Scholar 

  129. Zeng F, Lin Y, Cui K, Wen J, Maa Y, Chen H (2010) Atmospheric deposition of phthalate esters in a subtropical city. Atmos Environ 44:834–840. https://doi.org/10.1016/j.atmosenv.2009.11.029

    Article  CAS  Google Scholar 

  130. Zota AR, Calafat AM, Woodruff TJ (2014) Temporal trends in phthalate exposures: findings from the national health and nutrition examination survey, 2001–2010. Environ Health Perspect 122:235–241. https://doi.org/10.1289/ehp.1306681

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Sample generation and analysis during the German Environmental Survey (GerES), cycles GerES IV and GerES V was coordinated by a comprehensive study team at German Environment Agency (UBA). We thank Anja Daniels (UBA) for coordinating the study yielding the GerES V house dust concentrations within the Federal Ministry of the Environment, Nature Conservation and Nuclear Safety (BMU) grant FKZ 3715 61 2040. We express our gratitude to Ludwig Gruber and Maria Hoppe from the Fraunhofer Institute for Process Engineering and Packaging (IVV) in Freising, Germany, who performed the analysis of the GerES V house dust samples. SPM sampling managed by the Federal Institute for Hydrology (BfG) and the operation of the ESB archive by Fraunhofer Institute for Molecular Biology and Applied Ecology is gratefully acknowledged. We thank Jürgen Arning (UBA) for providing in depth knowledge about the regulation of endocrine disruptors and performing a QSAR assessment with the JANUS tool. Finally, we would like to thank Erik Müller, who developed the analysis of DEHT in SPM samples and Stefan Clausius, Lara Bräuer and Lydia Windmüller for technical support.

Funding

Open Access funding enabled and organized by Projekt DEAL.

Author information

Authors and Affiliations

  1. German Environment Agency, Berlin, Germany

    Regine Nagorka, Wolfram Birmili, Jona Schulze & Jan Koschorreck

Authors
  1. Regine Nagorka
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wolfram Birmili
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jona Schulze
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jan Koschorreck
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

RN, JK and JS have closely collaborated to write the first draft manuscript. WB provided detailed feedback/material on specific chapters. All authors have made comments. All authors read and approved the final manuscript.

Corresponding author

Correspondence to Regine Nagorka.

Ethics declarations

Ethics approval and consent to participate

Not applicable.

Consent for publication

Not applicable.

Competing interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence this work reported in this paper.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Additional file 1: Table S1.

General information on the plasticizers investigated. Table S2. Overview of the sampling programs used for this work. Figure S1. Study locations for the German Environmental Survey (GerES) and SPM sampling points for the German Environmental Specimen Bank (ESB). Table S3. Sites of the ESB for SPM sampling. Table S4. Information on GC/MS system and parameters. Table S5. Recoveries for DEHT at different concentration levels. Table S6a. Specific product regulations. Table S6b. REACH regulation. Figure S2. Relevant regulations for the plasticizers investigated since 1999. Table S7a. Characteristic values of the plasticizer investigated in house dust samples. Table S7b. Characteristic values of the plasticizer investigated in SPM samples. Table S8. Summary of test data and significance of the differences.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nagorka, R., Birmili, W., Schulze, J. et al. Diverging trends of plasticizers (phthalates and non-phthalates) in indoor and freshwater environments—why?. Environ Sci Eur 34, 46 (2022). https://doi.org/10.1186/s12302-022-00620-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1186/s12302-022-00620-4

Keywords