- Email: [email protected]
Bisphenol A and its structural analogues in household waste paper
Waste Management xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Waste Management journal homepage: www.elsevier.com/locate/wasman
Bisphenol A and its structural analogues in household waste paper K. Pivnenko a,⇑, G.A. Pedersen b, E. Eriksson a, T.F. Astrup a a b
Department of Environmental Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark National Food Institute, Technical University of Denmark, DK-2860 Søborg, Denmark
a r t i c l e
i n f o
Article history: Received 12 May 2015 Revised 13 July 2015 Accepted 13 July 2015 Available online xxxx Keywords: EDCs Bisphenol F Bisphenol S MSW Hazardous substances
a b s t r a c t Bisphenol A (BPA) is an industrial chemical produced in large volumes. Its main use is associated with polycarbonate plastic, epoxy resins and thermal paper. In contrast to other applications, thermal paper contains BPA in its un-reacted form as an additive, which is subjected to migration. Receiving a significant amount of attention from the scientific community and beyond, due to its controversial endocrine-disrupting effects, the industry is attempting to substitute BPA in variety of applications. Alternative phenolic compounds have been proposed for use in thermal paper; however, information to what extent BPA alternatives have been used in paper is sparse. The aim of the present work was to quantify BPA and its alternatives (bisphenol S (BPS), bisphenol E (BPE), bisphenol B (BPB), 4-cumylphenol (HPP) and bisphenol F (BPF)) in waste paper and board from Danish households, thermal paper receipts, non-carbon copy paper and conventional printer paper. BPA was found in all waste paper samples analysed, while BPS was identified in 73% of them. Only BPB was not identified in any of the samples. BPA and BPS were found in the majority of the receipts, which contained no measurable concentrations of the remaining alternatives. Although receipts showed the highest concentrations of BPA and BPS, office paper, flyers and corrugated boxes, together with receipts, represented the major flux of the two compounds in waste paper streams. Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction Bisphenol A (BPA, 4,40 -isopropylidenediphenol) is a chemical produced in large volumes for a variety of applications in consumer and industrial products. The vast majority of BPA is used as a (building block) starting substance in the polymerisation of polycarbonate plastics and epoxy resins, while the main additional use is as an additive (Geens et al., 2011). As an additive, one of its main uses is in thermal paper, where it is used as a ‘‘developer’’ or ‘‘co-reactant’’, triggering colour formation in the paper when exposed to heat. Thermal paper is mostly used in consumer receipts (i.e. point-of-sale receipts, admission and lottery tickets, etc.) which (conventionally) contain the BPA developer in its ‘‘free’’ (un-polymerised) form in up to 3.2% of the paper’s weight (Östberg and Noaksson, 2010). It is estimated that thermal paper used within the European Union weighs in at around 168,000 tonnes/annum and contains 1890 tonnes of BPA (JRC-IHCP, 2008). Although substantial controversy surrounds BPA as an endocrine disruptor (Vandenberg et al., 2009), toxicological assessments have shown its endocrine-disrupting effects on living organisms, even in ⇑ Corresponding author.
low doses (Christiansen et al., 2014; vom Saal and Hughes, 2005). Due to its potential migration from food-contact materials, BPA has been identified as a contaminant in foodstuffs (e.g. Cao et al., 2010; EFSA, 2013; Sajiki et al., 2007; Schecter et al., 2010; Yoshida et al., 2001), and the intake of such contaminated foods has in turn been pointed out as the main human exposure route (EFSA, 2013; Schecter et al., 2010) and resulted in quantifiable levels in humans (e.g. He et al., 2009; Vandenberg and Chahoud, 2010; Yang et al., 2003). Geens et al. (2012) estimated that thermal paper was the second largest source, after canned food and beverages, of exposure to BPA for the general population in Belgium. The latest scientific risk assessment on BPA in relation to public health, conducted by the European Food Safety Authority (EFSA), identified no health concerns from the actual level of human BPA exposure. However, a 12 times lower tolerable daily intake was recently established by the EFSA (EFSA, 2015). Additionally, BPA is a widespread environmental pollutant, and its presence in a variety of environmental samples has been confirmed (Arditsoglou and Voutsa, 2010; Barceló and Petrovic, 2011; Hansen and Lassen, 2008; Liao et al., 2012a). Potential hazards related to human BPA exposure have promoted the gradual abandoning of its use in consumer products, starting with a ban by several countries (e.g. EU, USA, China, Canada, etc.) of BPA in baby and infant polycarbonate products.
E-mail address: [email protected] (K. Pivnenko). http://dx.doi.org/10.1016/j.wasman.2015.07.017 0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
2
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
The phasing out of BPA in thermal paper has also been promoted, and in several cases it has even been banned (e.g. Japan (NITE, 2003); Connecticut, USA (State of Connecticut, 2013)). The US EPA identified 19 substances that could potentially be used in thermal paper as BPA substitutes through stakeholder involvement and based on their physical and chemical properties and commercial use (US EPA, 2014). Another study identified five phenolic alternatives to BPA based on their chemical structure (Rosenmai et al., 2013). Only bisphenol S (BPS; 4,40 -sulfonyldiphenol) and bisphenol F (BPF, Bis(4-hydroxyphenyl)methane) were identified as alternatives in both studies. Several of the BPA alternatives (including BPS and BPF) have already been documented as contaminants in a variety of food products sold in the United States (Liao and Kannan, 2013). Similarly to BPA, both BPS and BPF have been used in epoxy glues and polymerisation reactions (Fromme et al., 2002; Viñas et al., 2010). Driven by increasing awareness and demand, the main suppliers of thermal paper already provide BPA- and phenol-free products to the market (Appvion, 2013). Although industry information on substitutes used in thermal paper is not readily available, BPS has been previously identified in thermal paper, and other structural analogues of BPA can also be present (Goldinger et al., 2015; Liao et al., 2012b). Lee et al. (2015) showed the highest total concentrations of bisphenols (including BPA and BPS) in waste water sludge from treatment plants receiving discharge from paper and textile industries. A study conducted by the Danish EPA identified BPS in 25% of its thermal paper samples (Miljøstyrelsen, 2011), without quantifying the levels of BPS present. Similarly, Liao et al. (2012b) showed measurable quantities of BPS in all (n = 111) samples of thermal paper analysed in their study. Being structurally similar to BPA (Fig. 1), its phenolic analogues are suspected to have similar toxicological profiles, a notion which has been confirmed by several toxicological assessments (Chen et al., 2002; Goldinger et al., 2015; Kitamura et al., 2005; Rosenmai et al., 2014). In one study, 4-cumylphenol (HPP, 4-(2-phenylpropan-2-yl)phenol) was shown to have 12 times higher estrogenic activity when compared to BPA (Terasaki et al., 2005), which means that the substitution of BPA with structurally similar compounds may not solve the issue of the presence of the endocrine-disrupting chemicals in consumer products. Being present in their ‘‘free’’ form in thermal paper as an additive, phenolic compounds are readily transferable to human skin on contact (Biedermann et al., 2010), and to foodstuff, if present, in food contact materials (Maragou et al., 2008). Liao et al. (2012b) found that exposure to BPS via the handling of paper
H3C
was almost entirely dominated by contact with thermal receipts. The highest exposure group was related to occupational exposure, e.g. cashiers, waiters, etc. High recycling rates achieved by the paper industry reduce the possibility of selecting the source of secondary raw materials, which in turn increases the potential of undesirable chemicals, including BPA and its alternatives, being reintroduced into the paper cycle. Liao and Kannan (2011a) suggested thermal paper recycling as one of the sources of high BPA concentrations found in the paper currencies from several countries. It has been estimated that around 30% of thermal paper will end up in the paper recycling loop (JRC-IHCP, 2008), and although the thermal paper used in Europe represents less than 0.5% of the weight of the total paper collected for recycling (CEPI, 2013), concentrations of phenol-based substances (i.e. BPA) can be up to three orders of magnitude higher than in other paper products (Liao and Kannan, 2011b). Hence, phenolic compounds present in thermal or other waste paper fractions can be spread into newly manufactured paper products and may potentially end up in, for example, food-contact paper materials, thus posing a higher risk of exposure to the general public. The aim of the present study was to study the presence of BPA and five selected phenol-based structural analogues (BPS, bisphenol E (BPE, 4,40 -Ethylidenebisphenol), bisphenol B (BPB, 2,2-Bi s(4-hydroxyphenyl)butane), HPP and BPF) in waste paper and board from Danish households, thermal paper receipts, non-carbon copy paper (NCR) and conventional printer paper. 2. Materials and methods 2.1. Paper samples Waste paper and board were sampled from household solid waste derived from a municipality in Southern Denmark, where the source segregation of certain waste fractions (i.e. paper, board, metals, plastics, etc.) was in place. The sampling is described in detail in (Edjabou et al., 2015). In brief, sampling was done in accordance with a Nordtest method (Nordtest, 1995) for solid waste sampling and characterisation. The method suggests including at least 100 households for a period of one week in a sampling campaign, in order to produce representative samples. Household waste paper and board samples were manually sub-sorted into more detailed fractions based on their physical characteristics (e.g. paper thickness) and their applications (magazines, shipping boxes, etc.). The sampling campaign covered (a) source-segregated waste paper
CH3
CH3 O HO
OH
S
OH
HO
O HO
OH
BPS 80-09-1
BPA 80-05-7 H3C
H3C
CH3
BPE 2081-08-5
CH3
HO OH
HO
BPB 77-40-7
OH
HO
HPP 599-64-4
BPF 620-92-8
Fig. 1. Molecular structure of BPA and its alternatives covered in the present study.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
intended for recycling and (b) mixed (residual) waste paper, once recyclable materials (metals, glass, paper, etc.) had been separated by the households. The sampling of both flows took place in the same period. For each of the flows, 15 fractions contributing the most to waste paper composition (flyers, newspapers, etc.), or which were expected to contain phenolic compounds (i.e. receipts), were selected for chemical analysis. Sorted waste paper and board fractions were coarsely shredded (ARP SC2000, Brovst, Denmark), in order to reduce their size, and subsequently finely shredded down to a particle size <4 mm (SM2000, Retsch, Germany). Whenever a reduced sample size was required, representative sub-sampling was performed in accordance to principles described by Petersen et al. (2005). After the samples were shredded they were lyophilised and stored in sealed glass containers at 20 °C. Samples of the thermal paper were collected from commercial establishments in the Capital Region of Denmark in October 2014. Table 1 provides information on the points where thermal paper receipts were sampled, as well as a brief description of their traits. Sampling points were selected randomly and were not chosen in order to provide information on variations induced by economic, geographical or other stratifications. At least 10 receipt items were obtained from each of the sampling points, and these were placed into separate BPA-free re-sealable plastic bags and transferred to the laboratory for sample preparation. Their weight was calculated as an average of the 10 items. Each receipt was transferred into digital format, and the printed area was estimated using freely available software for image processing and analysis (ImageJ, National Institute of Health, USA). The ratio of printed to unprinted areas was calculated, as the unprinted area contains developer in its non-reacted state which can be released into the solvent. Samples were shredded down to 2 8 mm pieces, lyophilised and then stored at 20 °C prior to analysis. Samples of unused NCR paper were purchased online. NCR 1 was made from three sheets of paper (original top sheet and two copy sheets), while NCR 2 and NCR 3 were made from two (original top sheet and a single copy sheet). Conventional printer paper was
Table 1 Sampling points and description of thermal paper receipts. #
1 2 3 4 5 6 7 8 9 10 11 12
13
Sampling point
Supermarket. Cashier receipt Supermarket. Cashier receipt Gas station. Cashier receipt Furniture retailer. Cashier receipt ATM receipt Grocery store. Cashier receipt Clothing retailer. Cahier receipt Coffee shop. Cashier receipt Parking lot. Machine receipt Supermarket. Cashier receipt Hobby retailer. Cashier receipt Sportswear retailer. Cashier receipt Restaurant. Cashier receipt
Average Weight [mg]
Printed area/total area [%]
Remarks
920
5.5
790
6.5
570
5.1
1210
8.1
Print on the back
680 280
7.4 12.6
Print on the back
780
6.6
550
4.3
470
8.0
660
5.1
640
4.0
680
6.3
460
4.2
Colour print on the back
Colour print on the back
Colour print on the back and front
Colour print on the back Colour print on the back
3
purchased from an authorised local retailer, and certificates on the 100% use of either virgin or recycled fibres were obtained from the manufacturer. Samples of NCR and printer paper were treated in the same manner as thermal paper. 2.2. Quantification Approximately 4 g and 1 g of each sample were used for waste paper and paper products extractions, respectively. Higher sample amounts used in the case of waste paper were due to the heterogeneity of the material. The shredded paper samples were placed into a glass beaker, and 100 ml ethanol (analytical grade, from Sigma–Aldrich) was added. Prior to ethanol addition, internal standard, IS (bisphenol A-d16 in ethanol, from Sigma–Aldrich), was added to each of the samples, thereby allowing some time to be absorbed by the paper matrix. The sample extracts were heated under reflux for 1 h (Extraction System B-811, Büchi). The paper and board samples were then removed from the beakers, and the ethanol extract was sub-sequentially evaporated down to approximately 2 ml and then transferred into a volumetric flask. Ethanol was added to the extract, up to 5 ml of the total volume. The ethanol extracts were analysed by liquid chromatography negative electrospray ionisation tandem mass spectrometry LC-ESI-MS/MS, using an Agilent 1200 Series HPLC (Agilent Technologies, CA, USA) equipped with a reversed-phase XTerra CSH C18 column, 2.6 lm, 2.1 100 mm (Waters, Milfold, USA) with an injection volume of 3 lL. The column was maintained at 40 °C. Mobile phases A = milli-Q water and B = methanol were employed. The gradient was applied as follows: initial 80% of solvent A reduced to 55% in 1 min, followed by 10%/min reduction until it reached 20%. Additional reduction down to 2% in 1 min was followed by holding for 6.5 min. The MS detector used was a Micromass Quattro Ultima (Waters, Milford, USA). Multiple reaction monitoring (MRM) was used for monitoring the MRM transition reactions m/z 227.1 > 212.1 and 227.1 > 133.1 for BPA, 249.0 > 108.0 and 249.0 > 155.9 for BPS, 213.1 > 198.1 and 213.1 > 197.1 for BPE, 241.1 > 211.1 and 241.1 > 147.0 for BPB, 211.1 > 196.1 and 211.1 > 133.1 for HPP, 199.1 > 93.0 and 199.1 > 105.0 for BPF and 241.1 > 223.1 for d16-BPA. Capillary voltage was kept at +3 kV, and the desolvation temperature was maintained at 400 °C. Cone voltage was kept at 40 V. Concentrations of BPA and BPA analogues in the samples were quantified by external standard calibration (r2 > 0.99) with correction for the IS recoveries. Limits of detection (LOD) were calculated in accordance with ISO 11843-2:2000 and are presented in Tables 2–4. Detection limits for paper products (Table 4) were two orders of magnitude higher when compared to waste paper, as substantially higher concentrations were expected, resulting in higher dilution factors. All samples were analysed in single and the relative standard deviation of four samples spiked with standards was <5% for all substances analysed. A triplicate of virgin fibre-based paper, previously shown not to contain measurable quantities of target substances, was spiked with known amounts of phenolic compounds, before solvent addition, in order to calculate the recovery of the method. Recoveries in spiked matrices ranged from 78 ± 5% for BPS to 144 ± 9% for BPE (see Tables 2–4 for details). The results presented were not compensated for by the calculated recovery. 3. Results and discussion 3.1. Waste paper Concentrations of target substances in waste paper from source-segregated and mixed household waste are presented in
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
4
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
Table 2 Concentrations of BPA and its structural analogues (lg/g dry matter (dm)) in source-segregated paper from household waste. Waste paper fraction Recovery (%) LOD Receipts Corrugated boxes Shipping Food Non-food Newspapers Flyers Glued Non-glued Office paper Envelopes Folding boxes Food Non-food Magazines Glued Non-glued Beverage cartons Books Total Noa Fa (%) Min Max Medianb a b
% of waste paper
0.005 15.7 9.5 4.9 1.4 22.5 43.2 16.6 26.6 3.6 0.6 3.4 2.3 1.1 9.3 2.9 6.4 0.1 1.5 100
BPA [80-05-7]
BPS [80-09-1]
BPE [2081-08-5]
BPB [77-40-7]
HPP [599-64-4]
BPF [620-92-8]
BPAi [%]
BPSi [%]
98 ± 3 0.02 8300
78 ± 5 0.07 210
144 ± 9 0.04 0.60
141 ± 6 0.03
113 ± 6 0.06
130 ± 3 0.04
1.3
3.7
130 9.6 7.9 2.0
1.3 0.92 0.55
0.12
0.14 0.17 0.24
38.2 1.5 0.3 1.4
43.9 15.7 3.0 5.6
2.9 1.7 480 8.8
1.5 1.4 53.4 0.2
4.1 9.5 3.8 0.4
5.0 2.3
0.38 0.45
0.053 0.061
0.4 0.1
3.3 1.6
0.41 0.31 1.5 7.5
0.075
0.062
0.0 0.1 0.0 0.3 100
1.0 1.6 0.0 2.7 100
15 100 0.31 8300 5.0
11 73
1 7
0 0
3 20
5 33
No: number of cases where a substance was identified, F (%): frequency of detection. In cases where values are
Table 3 Concentrations of BPA and its structural analogues (lg/g dry matter (dm)) in paper from non-sorted household waste. Waste paper fraction Recovery (%) LOD Receipts Corrugated boxes Shipping Food Non-food Newspapers Flyers Glued Non-glued Office paper Envelopes Folding boxes Food Non-food Magazines Glued Non-glued Beverage cartons Books Total Noa Fa (%) Min Max Medianb a b
% of waste paper
0.5 9.5 3.5 4.6 1.3 11.2 24.2 9.0 15.0 8.5 3.2 16.4 9.6 6.7 7.2 1.1 6.1 15.1 4.3 100
BPA [80-05-7]
BPS [80-09-1]
BPE [2081-08-5]
BPB [77-40-7]
HPP [599-64-4]
BPF [620-92-8]
BPAi [%]
BPSi [%]
98 ± 3 0.02 8100
78 ± 5 0.07 170
144 ± 9 0.04
141 ± 6 0.03
113 ± 6 0.06
130 ± 3 0.04
58.6
59.4
6.1 8.4 26 2.2
9.1 0.92 1.3
0.3 0.6 0.5 0.4
22.3 2.9 1.2 0.5
1.1 4.4 280 36
0.27 0.16 0.54 0.43
0.1 1.0 34.4 1.7
1.9 2.1 3.0 0.9
4.8 5.6
0.13 0.45
0.7 0.5
0.7 2.3
0.40 1.2 0.41 17
0.0 0.1 0.1 1.1 100
0.1 0.3 0.7 1.8 100
15 100 0.40 8100 5.6
11 73
0 0
0 0
1 7
3 20
No: number of cases where a bisphenol was identified, F (%): frequency of detection. In cases where values are
Tables 2 and 3, respectively. The highest concentrations of BPA in source-segregated and residual waste paper, in both cases, were found in receipts (8300 and 8100 lg/g dry matter, respectively), as expected based on the literature presented in the introduction. The second highest concentration was attributed to office paper
in both cases. The office paper fraction included discarded paper items commonly used in offices and administration-related activities, i.e. copy and writing paper, invoices, administration forms, etc. This fraction could potentially include NCR paper, which may contain BPA (Fukazawa et al., 2001), thereby explaining the relatively
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
5
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx Table 4 Concentration of BPA and its structural analogues (lg/g dry matter (dm)) in thermal paper and paper products samples (NCR: non-carbon copy paper).
Recovery (%) LOD #1 #2 #3 #4 #5 #6 #7 #8 #9 #10 #11 #12 #13 Min Max Median Nob Fb (%) Printer paper (recycled) Printer paper (virgin) NCR 1 NCR 2 NCR 3 a b
BPA [80-05-7]
BPS [80-09-1]
BPE [2081-08-5]
BPB [77-40-7]
HPP [599-64-4]
BPF [620-92-8]
98 ± 3 2
78 ± 5 7 5700 8.48 8100
144 ± 9 4
141 ± 6 3
113 ± 6 6
130 ± 3 4
Lowest concentrations (<20 lg/g) were excluded from median value calculations. No: number of cases where a bisphenol was identified, F (%): frequency of detection.
high concentration of BPA in the office waste paper fraction. On the other hand, three samples of printing paper, the main constituent of the office paper fraction, contained insignificant amounts of BPA (0.02 lg/g), according to Liao and Kannan (2011b). Corrugated boxes used for the shipment of goods showed concentrations of BPA higher than 100 lg/g, albeit only in the case of source-segregated waste paper, which could be the direct result of paper recycling, as casing materials have the highest recycling rates in the EU (CEPI, 2013). An additional source of BPA in board material could be the hydrolysis of epoxy resins potentially used in ink and adhesive formulations containing BPA (ANSES, 2011). In both cases, i.e. source-segregated and residual waste paper, BPA was quantified in all fractions with a variety of concentrations. This could indicate ongoing spreading of BPA through paper recycling, as the use of BPA in paper is limited to specific applications such as thermal paper. The study conducted by Vinggaard et al. (2000) showed that none of the 11 paper samples made from virgin fibres contained BPA. Additionally, analysis of unprinted board sourced from four paper mills in Germany revealed measurable contents of BPA, but only in those products which contained recycled paper (BMELV, 2012). On the other hand, 80% of almost 100 paper samples analysed by Liao and Kannan (2011b) contained measurable amounts of BPA. The authors also suggested paper recycling as the main source of BPA presence, as most of the paper items analysed were made from recycled paper (Liao and Kannan, 2011b). BPS was present in the majority of samples and was quantified in 11 (73%) samples in both waste flows, thereby indicating its spreading in use or through waste paper recycling. The highest concentrations (up to 210 lg/g) were once again related to receipts. Concentrations of BPS in receipts were considerably lower than those of BPA, thus indicating that the latter is still the predominant developer used in thermal paper sold on the Danish market. An earlier study by the Danish EPA found BPS in 25% of the thermal paper receipts analysed, while 70% of the samples contained measurable amounts of BPA (Miljøstyrelsen, 2011). The authors suggested that BPS was used in more wear-resistant
receipts that are expected to be exposed to more extreme conditions (e.g. gas stations) or have a prolonged life span (e.g. furniture and appliance retail outlets). The waste paper fraction containing receipts was followed by corrugated shipping boxes, which nevertheless showed at least one order of magnitude lower concentrations. This could suggest the spreading of BPS through paper recycling or the use of epoxy glues, in which BPS can be employed as a curing agent (Viñas et al., 2010). Fig. 2 presents a comparison between BPA and BPS levels in source-segregated and residual waste paper. The data presented do not include outliers, i.e. samples with significantly higher levels, outside the 1.5 of the interquartile range (i.e. receipts, office paper, etc.). Although BPA variations in the residual waste seemed to be higher than in source-segregated waste paper, the means of the two flows showed no significant difference when compared with a t-test (p-value > 0.05). Similarly, in the case of BPS, no significant difference was detected (p-value > 0.05). The results indicate that the amounts of BPA and BPS are at the same level in total source-segregated and residual waste paper flows. Additionally, this conclusion suggests that any contamination as a result of the co-mingled collection of waste does not contribute to the presence of BPA and BPS. Of the remaining substances, BPF was identified as having the highest frequency of detection, respectively in 33% and 20% of the cases in the two flows, as shown in Tables 2 and 3. The level of BPF was at a significantly lower concentration in the given samples compared to the level of BPA. Moreover, in both flows, measurable quantities of BPF were found only in board packaging (both corrugated and non-corrugated), which could be related to the use of adhesives based on epoxy resins which may include BPF as a raw material (Goodson et al., 2002). Pérez-Palacios et al. (2012) did not identify BPF in any of the eight recycled paper products they analysed. HPP was found in low levels in 20% and 7% of the samples from source-segregated and residual waste paper, respectively, and it was identified in corrugated boxes, glued magazines and in books, with the latter containing one order of magnitude higher concentrations. Shipping corrugated boxes
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
0.8
µg/g
0.0
0
5
0.2
10
0.4
0.6
20 15
µg/g
25
1.0
30
1.2
35
6
Source-segregated
Residual
Source-segregated
BPA
Residual
BPS
Fig. 2. Boxplot of source-segregated versus residual waste paper for BPA and BPS. Outliers (e.g. receipts) are excluded from the representation.
(source-segregated) contained the highest number of phenolic compounds, as four out of the six substances analysed were detected in this fraction (Table 2). The contribution of each of the fractions to the total amounts of BPA and BPS in the waste paper was calculated in accordance with Eq. (1), where F is the percentage contribution of a given fraction to waste paper composition, and C is the concentration (lg/g dry matter (dm)) of either BPA or BPS in the respective fraction. The results are presented in the last two columns in Tables 2 and 3. The data show that receipts might not make a large contribution to the presence of BPA and BPS, as is the case in source-segregated waste paper, due to the low contribution of receipt paper in this flow. In source-segregated waste paper, office paper contributes over 53% to the total content of BPA, while for the residual flow this figure is just below 35%. Similarly, for BPS, corrugated boxes and flyers represent the majority of the substance flow in source-segregated waste paper. Most of the receipts end up in the residual fraction of waste paper, which explains their much greater contribution to the BPA and BPS amounts in the flow (Table 3).
Fi Ci BPAi or BPSi ð%Þ ¼ P15 100% j¼1 ðF j C j Þ
ð1Þ
Lu et al. (2013) compared concentrations of BPA in different media. When comparing our results to this study, the median concentrations of BPA we found in waste paper (5.0 and 5.6 lg/g dry matter, respectively) were comparable to the concentrations found in canned foods. Other media, including selected plastic products, indoor dust, paper currency, supermarket receipts and thermal paper, contained from one to six orders of magnitude higher BPA concentrations (Lu et al., 2013). As evidenced in Table 4, most of the thermal paper receipts sampled (93%) contained measurable quantities of BPA. Concentrations measured ranged from
collected from Japan, Korea and Vietnam showed somewhat lower maximum concentrations between 0.05) between BPA or BPS concentrations and the printed area of the respective receipt samples. This indicates that the extent of unprinted area on a thermal paper receipt does not influence significantly the extractable amount of BPA and BPS. Such information is useful when assessing human exposure to phenolic compounds from handling thermal paper receipts. None of the two printer paper samples analysed showed the presence of any of the substances of interest in this study, which suggests that none of the phenol-based substances is used in virgin printer paper production, as well as the fact that the grades selected for producing recycled printer paper may have excluded contamination by articles containing e.g. BPA. NCR 1 and 2 contained relatively low concentrations of BPA, while NCR 3 did not contain any of the substances analysed. Concentrations of BPA in NCR 1 and 2 failed to explain the relatively high concentrations
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
7
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx Table 5 Physical and chemicals properties of bisphenols of interest. Phase distribution: water/solid/air.
BPA [80-05-7] BPS [80-09-1] BPE [2081-08-5] BPB [77-40-7] HPP [599-64-4] BPF [620-92-8] a
Mol. WT (g/mol)
Boiling point (°C)
Water solubility (mg/L)
LogKow
Kh (atm m3/mol)
Koc (L/kg)
Phase distribution (w/s/a)
Biodegradability
228.29 250.27 214.27 242.32 212.29 200.24
361 423 357 375 328 352
300 1100 265 29 18 543
3.4 1.2 3.2 4.1 4.1 2.9
9.16E12 2.70E15 6.90E12 1.22E11 8.80E08 1.44E12
3.77E+04 1.83E+03 2.53E+04 7.38E+04 2.93E+04 1.51E+04
–/x/– x/x/– –/x/– –/x/– –/x/– –/x/–
Readily Inherently Inherently Inherently Inherentlya Readily
Not readily biodegradable under aerobic conditions. Limited data available for full assessment.
of the compound in the office waste paper samples analysed (Tables 2 and 3). Since neither virgin nor recycled printer paper samples contained any BPA, other paper items, such as fax paper and thermal paper, could be present in office paper waste fraction and could be potential sources of BPA in the samples analysed. 3.2. Implications on paper recycling Table 5 summarises the physical and chemical properties of the substances in focus. Distribution between the water, solid and air phases is based on the methodology described by Baun et al. (2006). All of the phenolic compounds covered showed high affinity for the solid phase, indicating that they may be retained in paper fibres when waste paper is recycled. In the recycling process, short fibres are removed as sludge while the rest are incorporated into newly manufactured paper. If phenol-based substances follow the path of the longer fibres, the presence of substances in paper products not intended to contain them is expected. A study commissioned by German authorities has shown the presence of BPA only in board produced from recycled waste paper (BMELV, 2012). BPS was the only substance that showed high affinity to both water (also indicated by its higher solubility, Table 5) and solid phases, meaning that predicting its behaviour in a recycling process may be challenging. None of the substances is expected to volatilise during recycling (Table 5). Nevertheless, the specific physical and chemical conditions governing a paper recycling process may influence significantly the partitioning of substances between different phases. As an example, alkalinity may increase the solubility of BPA by a factor of 100 (Kosky et al., 1991), which should not lead to the considerably higher release of BPA into the water phase at a paper mill, as pH conditions are expected to be close to neutral (Rigol et al., 2002). Additionally, paper production methods are designed to optimise water use, primarily through recirculation. In such conditions, BPA will be put in contact with paper fibres constantly, and only a small fraction of it will finally be discarded along with the effluent (Fukazawa et al., 2002). Nonetheless, relatively low concentrations in the effluent waste water still make paper production one of the most important sources of BPA release into the aquatic environment (Fürhacker et al., 2000). Being chemically related substances, BPA alternatives are expected to behave similarly to BPA in the paper recycling process. If phenolic substances are actually removed from the paper matrix, they may be emitted from a paper mill and end up in the environment, thereby making their persistence and biodegradation critical. As an example, BPA and BPF were characterised as readily biodegradable, with BPF showing higher biodegradation rates under both aerobic and anaerobic conditions (Ike et al., 2006; Nicolucci et al., 2011). Similarly, Danzl et al. (2009) showed biodegradation sequence of BPF > BPA BPS in their experiment, with BPF being the most biodegradable in seawater environment, which is supported by the results of quantitative structure–activity relationship (QSAR) modelling in the Danish (Q)SAR Database
(Miljøstyrelsen, 2013). Nevertheless, BPA has been characterised as a pseudo-persistent chemical, as limited restrictions on its production and uses result in continual environmental release (Flint et al., 2012). The other BPA alternatives focused on in this study show lower degradation rates and cannot be characterised as readily biodegradable. The degradation sequence for the remaining bisphenols was found to be BPS > BPE > BPB (Ike et al., 2006).
4. Conclusions BPA was measured in all analysed waste paper samples. As BPA is only used for a limited range of paper products (i.e. thermal paper), this suggests potential spreading of BPA through recycling of secondary waste paper. BPS is an important substitute for BPA, as it was identified in more than 70% of the waste paper samples. Although both BPA and BPS showed the highest concentrations in thermal paper receipts, other fractions (i.e. office paper, board boxes) may constitute important flows of the chemicals found in household waste paper. No significant differences in BPA and BPS concentrations were observed between source-segregated and residual waste paper. From the remaining analogues, only BPB was not identified in any of the samples. Most of the analysed thermal paper receipts contained BPA in concentrations reaching 17,600 lg/g. Similarly to waste paper, the results suggest BPS as the main BPA alternative in thermal paper, as it was measured (in concentrations reaching 7300 lg/g) in most of the samples not containing BPA in significant quantities. None of the remaining phenolic compounds (BPE; BPB, HPP and BPF) was measured in the thermal receipts samples. Two samples of thermal paper (4 and 5) suggested the use of alternative phenol-based or non-phenolic developers. Neither common printer paper nor NCR paper could explain the relatively high concentrations of BPA in the office waste paper fraction. Chemical and physical properties of the substances suggested their affinity with paper fibres and the potential contamination of newly manufactured paper products which utilise recycled waste paper as a secondary material. Acknowledgements The authors would like to express their sincere gratitude to Lisbeth Krüger Jensen (National Food Institute, Technical University of Denmark) for her assistance in the analytical part of the work. The Danish Research Council is acknowledged for its financial support through the 3R Research School and the IRMAR project. References ANSES, 2011. Effets sanitaires du bisphénol A. Connaissances relatives aux usages du bisphénol A. ANSES, French Agency for Food, Environmental and Occupational Health & Safety, Paris. Appvion, 2013. Free Statement. (accessed 03.03.15).
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
8
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
Arditsoglou, A., Voutsa, D., 2010. Partitioning of endocrine disrupting compounds in inland waters and wastewaters discharged into the coastal area of Thessaloniki, Northern Greece. Environ. Sci. Pollut. Res. Int. 17, 529–538. http://dx.doi.org/ 10.1007/s11356-009-0172-y. Barceló, D., Petrovic, M. (Eds.), 2011. The Ebro River Basin. The Handbook of Environmental Chemistry. Springer, Berlin, Heidelberg. http://dx.doi.org/ 10.1007/978-3-642-18032-3. Baun, A., Eriksson, E., Ledin, A., Mikkelsen, P.S., 2006. A methodology for ranking and hazard identification of xenobiotic organic compounds in urban stormwater. Sci. Total Environ. 370, 29–38. http://dx.doi.org/10.1016/ j.scitotenv.2006.05.017. Biedermann, S., Tschudin, P., Grob, K., 2010. Transfer of bisphenol A from thermal printer paper to the skin. Anal. Bioanal. Chem. 398, 571–576. BMELV, 2012. Ausmaß der Migration unerwünschter Stoffe aus Verpackungsmaterialien aus Altpapier in Lebensmitteln, BMELV, German Federal Ministry of Food, Agriculture and Consumer Protection. (accessed 27.01.14). Cao, X.-L., Corriveau, J., Popovic, S., 2010. Bisphenol A in canned food products from Canadian markets. J. Food Prot. 73, 1085–1089. CEPI, 2013. Key Statistics. European Pulp and Paper Industry 2012. Confederation of European Paper Industries, Brussels. Chen, M.-Y., Ike, M., Fujita, M., 2002. Acute toxicity, mutagenicity, and estrogenicity of bisphenol-A and other bisphenols. Environ. Toxicol. 17, 80–86. Christiansen, S., Axelstad, M., Boberg, J., Vinggaard, A.M., Pedersen, G.A., Hass, U., 2014. Low-dose effects of bisphenol A on early sexual development in male and female rats. Reproduction 147, 477–487. http://dx.doi.org/10.1530/REP-130377. Danzl, E., Sei, K., Soda, S., Ike, M., Fujita, M., 2009. Biodegradation of bisphenol A, bisphenol F and bisphenol S in seawater. Int. J. Environ. Res. Public Health 6, 1472–1484. http://dx.doi.org/10.3390/ijerph6041472. Edjabou, M.E., Jensen, M.B., Götze, R., Pivnenko, K., Petersen, C., Scheutz, C., Astrup, T.F., 2015. Municipal solid waste composition: sampling methodology, statistical analyses, and case study evaluation. Waste Manage. 36, 12–23. http://dx.doi.org/10.1016/j.wasman.2014.11.009. EFSA, 2013. DRAFT Scientific Opinion on the risks to public health related to the presence of bisphenol A (BPA) in foodstuffs – Part: exposure assessment. EFSA Panel Food Contact Mater. Enzym. Flavourings Process. Aids. EFSA, 2015. Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF). Scientific Opinion on the risks to public health related to the presence of bisphenol A (BPA) in foodstuffs. EFSA J. 2015 13. Flint, S., Markle, T., Thompson, S., Wallace, E., 2012. Bisphenol A exposure, effects, and policy: a wildlife perspective. J. Environ. Manage. 104, 19–34. http:// dx.doi.org/10.1016/j.jenvman.2012.03.021. Fromme, H., Küchler, T., Otto, T., Pilz, K., Müller, J., Wenzel, A., 2002. Occurrence of phthalates and bisphenol A and F in the environment. Water Res. 36, 1429– 1438. Fukazawa, H., Hoshino, K., Shiozawa, T., Matsushita, H., Terao, Y., 2001. Identification and quantification of chlorinated bisphenol A in wastewater from wastepaper recycling plants. Chemosphere 44, 973–979. http://dx.doi.org/ 10.1016/S0045-6535(00)00507-5. Fukazawa, H., Watanabe, M., Shiraishi, F., Shiraishi, H., Shiozawa, T., Matsushita, H., Terao, Y., 2002. Formation of chlorinated derivatives of bisphenol A in waste paper recycling plants and their estrogenic activities. J. Health. Sci. 48, 242–249. Fürhacker, M., Scharf, S., Weber, H., 2000. Bisphenol A: emissions from point sources. Chemosphere 41, 751–756. http://dx.doi.org/10.1016/S00456535(99)00466-X. Geens, T., Goeyens, L., Covaci, A., 2011. Are potential sources for human exposure to bisphenol-A overlooked? Int. J. Hyg. Environ. Health 214, 339–347. http:// dx.doi.org/10.1016/j.ijheh.2011.04.005. Geens, T., Goeyens, L., Kannan, K., Neels, H., Covaci, A., 2012. Levels of bisphenol-A in thermal paper receipts from Belgium and estimation of human exposure. Sci. Total Environ. 435–436, 30–33. http://dx.doi.org/10.1016/ j.scitotenv.2012.07.001. Goldinger, D.M., Demierre, A.-L., Zoller, O., Rupp, H., Reinhard, H., Magnin, R., Becker, T.W., Bourqui-Pittet, M., 2015. Endocrine activity of alternatives to BPA found in thermal paper in Switzerland. Regul. Toxicol. Pharmacol. http:// dx.doi.org/10.1016/j.yrtph.2015.01.002. Goodson, A., Summerfield, W., Cooper, I., 2002. Survey of bisphenol A and bisphenol F in canned foods. Food Addit. Contam. 19, 796–802. http://dx.doi.org/10.1080/ 02652030210146837. Hansen, A., Lassen, P., 2008. Screening of Phenolic Substances in the Nordic Environments. Nordic Council of Ministers, Copenhagen. He, Y., Miao, M., Herrinton, L.J., Wu, C., Yuan, W., Zhou, Z., Li, D.-K., 2009. Bisphenol A levels in blood and urine in a Chinese population and the personal factors affecting the levels. Environ. Res. 109, 629–633. http://dx.doi.org/10.1016/ j.envres.2009.04.003. Ike, M., Chen, M.Y., Danzl, E., Sei, K., Fujita, M., 2006. Biodegradation of a variety of bisphenols under aerobic and anaerobic conditions. Water Sci. Technol. 53, 153–159. JRC-IHCP, 2008. European Union Risk Assessment Report: 4, 40 isopropylidenediphenol (Bisphenol-A). Eur. Union 2008, pp. 201–245. http:// dx.doi.org/10.2788/40195. Kitamura, S., Suzuki, T., Sanoh, S., Kohta, R., Jinno, N., Sugihara, K., Yoshihara, S., Fujimoto, N., Watanabe, H., Ohta, S., 2005. Comparative study of the endocrinedisrupting activity of bisphenol A and 19 related compounds. Toxicol. Sci. 84, 249–259. http://dx.doi.org/10.1093/toxsci/kfi074.
Kosky, P.G., Silva, J.M., Guggenheim, E.A., 1991. The aqueous phase in the interfacial synthesis of polycarbonates. Part 1. Ionic equilibria and experimental solubilities in the BPA-sodium hydroxide-water system. Ind. Eng. Chem. Res. 30, 462–467. http://dx.doi.org/10.1021/ie00051a005. Lee, S., Liao, C., Song, G.-J., Ra, K., Kannan, K., Moon, H.-B., 2015. Emission of bisphenol analogues including bisphenol A and bisphenol F from wastewater treatment plants in Korea. Chemosphere 119, 1000–1006. http://dx.doi.org/ 10.1016/j.chemosphere.2014.09.011. Liao, C., Kannan, K., 2011a. High levels of bisphenol A in paper currencies from several countries, and implications for dermal exposure. Environ. Sci. Technol. 45, 6761–6768. http://dx.doi.org/10.1021/es200977t. Liao, C., Kannan, K., 2011b. Widespread occurrence of bisphenol A in paper and paper products: implications for human exposure. Environ. Sci. Technol. 45, 9372–9379. http://dx.doi.org/10.1021/es202507f. Liao, C., Kannan, K., 2013. Concentrations and profiles of bisphenol A and other bisphenol analogues in foodstuffs from the United States and their implications for human exposure. J. Agric. Food Chem. 61, 4655–4662. http://dx.doi.org/ 10.1021/jf400445n. Liao, C., Liu, F., Guo, Y., Moon, H.-B., Nakata, H., Wu, Q., Kannan, K., 2012a. Occurrence of eight bisphenol analogues in indoor dust from the United States and several Asian countries: implications for human exposure. Environ. Sci. Technol. 46, 9138–9145. http://dx.doi.org/10.1021/es302004w. Liao, C., Liu, F., Kannan, K., 2012b. Bisphenol S, a new bisphenol analogue, in paper products and currency bills and its association with bisphenol A residues. Environ. Sci. Technol. 46, 6515–6522. http://dx.doi.org/10.1021/es300876n. Lu, S.-Y., Chang, W.-J., Sojinu, S.O., Ni, H.-G., 2013. Bisphenol A in supermarket receipts and its exposure to human in Shenzhen, China. Chemosphere 92, 1190– 1194. http://dx.doi.org/10.1016/j.chemosphere.2013.01.096. Maragou, N.C., Makri, A., Lampi, E.N., Thomaidis, N.S., Koupparis, M.a., 2008. Migration of bisphenol A from polycarbonate baby bottles under real use conditions. Food Addit. Contam. Part A 25, 373–383. http://dx.doi.org/10.1080/ 02652030701509998. Mendum, T., Stoler, E., VanBenschoten, H., Warner, J.C., 2011. Concentration of bisphenol A in thermal paper. Green Chem. Lett. Rev. 4, 81–86. http:// dx.doi.org/10.1080/17518253.2010.502908. Miljøstyrelsen, 2011. Migration of Bisphenol A from Cash Register Receipts and Baby Dummies. Survey of Chemical Substances in Consumer Products No. 110, Miljøstyrelsen. Danish EPA, København. Miljøstyrelsen, 2013. Danish (Q)SAR Database, Miljøstyrelsen. Danish EPA, København.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx Vandenberg, L.N., Maffini, M.V., Sonnenschein, C., Rubin, B.S., Soto, A.M., 2009. Bisphenol-A and the great divide: a review of controversies in the field of endocrine disruption. Endocr. Rev. 30, 75–95. http://dx.doi.org/10.1210/ er.2008-0021. Viñas, P., Campillo, N., Martínez-Castillo, N., Hernández-Córdoba, M., 2010. Comparison of two derivatization-based methods for solid-phase microextraction-gas chromatography–mass spectrometric determination of bisphenol A, bisphenol S and biphenol migrated from food cans. Anal. Bioanal. Chem. 397, 115–125. http://dx.doi.org/10.1007/s00216-010-3464-7. Vinggaard, A.M., Körner, W., Lund, K.H., Bolz, U., Petersen, J.H., 2000. Identification and quantification of estrogenic compounds in recycled and virgin paper for
9
household use as determined by an in vitro yeast estrogen screen and chemical analysis. Chem. Res. Toxicol. 13, 1214–1222. Vom Saal, F.S., Hughes, C., 2005. An extensive new literature concerning low-dose effects of bisphenol A shows the need for a new risk assessment. Environ. Health Perspect. 113, 926–933. http://dx.doi.org/10.1289/ehp.7713. Yang, M., Kim, S.-Y., Lee, S.-M., Chang, S.-S., Kawamoto, T., Jang, J.-Y., Ahn, Y.-O., 2003. Biological monitoring of bisphenol A in a Korean population. Arch. Environ. Contam. Toxicol. 44, 546–551. http://dx.doi.org/10.1007/s00244-002-2124-0. Yoshida, T., Horie, M., Hoshino, Y., Nakazawa, H., 2001. Determination of bisphenol A in canned vegetables and fruit by high performance liquid chromatography. Food Addit. Contam. 18, 69–75. http://dx.doi.org/10.1080/026520301446412.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
Contents lists available at ScienceDirect
Waste Management journal homepage: www.elsevier.com/locate/wasman
Bisphenol A and its structural analogues in household waste paper K. Pivnenko a,⇑, G.A. Pedersen b, E. Eriksson a, T.F. Astrup a a b
Department of Environmental Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark National Food Institute, Technical University of Denmark, DK-2860 Søborg, Denmark
a r t i c l e
i n f o
Article history: Received 12 May 2015 Revised 13 July 2015 Accepted 13 July 2015 Available online xxxx Keywords: EDCs Bisphenol F Bisphenol S MSW Hazardous substances
a b s t r a c t Bisphenol A (BPA) is an industrial chemical produced in large volumes. Its main use is associated with polycarbonate plastic, epoxy resins and thermal paper. In contrast to other applications, thermal paper contains BPA in its un-reacted form as an additive, which is subjected to migration. Receiving a significant amount of attention from the scientific community and beyond, due to its controversial endocrine-disrupting effects, the industry is attempting to substitute BPA in variety of applications. Alternative phenolic compounds have been proposed for use in thermal paper; however, information to what extent BPA alternatives have been used in paper is sparse. The aim of the present work was to quantify BPA and its alternatives (bisphenol S (BPS), bisphenol E (BPE), bisphenol B (BPB), 4-cumylphenol (HPP) and bisphenol F (BPF)) in waste paper and board from Danish households, thermal paper receipts, non-carbon copy paper and conventional printer paper. BPA was found in all waste paper samples analysed, while BPS was identified in 73% of them. Only BPB was not identified in any of the samples. BPA and BPS were found in the majority of the receipts, which contained no measurable concentrations of the remaining alternatives. Although receipts showed the highest concentrations of BPA and BPS, office paper, flyers and corrugated boxes, together with receipts, represented the major flux of the two compounds in waste paper streams. Ó 2015 Elsevier Ltd. All rights reserved.
1. Introduction Bisphenol A (BPA, 4,40 -isopropylidenediphenol) is a chemical produced in large volumes for a variety of applications in consumer and industrial products. The vast majority of BPA is used as a (building block) starting substance in the polymerisation of polycarbonate plastics and epoxy resins, while the main additional use is as an additive (Geens et al., 2011). As an additive, one of its main uses is in thermal paper, where it is used as a ‘‘developer’’ or ‘‘co-reactant’’, triggering colour formation in the paper when exposed to heat. Thermal paper is mostly used in consumer receipts (i.e. point-of-sale receipts, admission and lottery tickets, etc.) which (conventionally) contain the BPA developer in its ‘‘free’’ (un-polymerised) form in up to 3.2% of the paper’s weight (Östberg and Noaksson, 2010). It is estimated that thermal paper used within the European Union weighs in at around 168,000 tonnes/annum and contains 1890 tonnes of BPA (JRC-IHCP, 2008). Although substantial controversy surrounds BPA as an endocrine disruptor (Vandenberg et al., 2009), toxicological assessments have shown its endocrine-disrupting effects on living organisms, even in ⇑ Corresponding author.
low doses (Christiansen et al., 2014; vom Saal and Hughes, 2005). Due to its potential migration from food-contact materials, BPA has been identified as a contaminant in foodstuffs (e.g. Cao et al., 2010; EFSA, 2013; Sajiki et al., 2007; Schecter et al., 2010; Yoshida et al., 2001), and the intake of such contaminated foods has in turn been pointed out as the main human exposure route (EFSA, 2013; Schecter et al., 2010) and resulted in quantifiable levels in humans (e.g. He et al., 2009; Vandenberg and Chahoud, 2010; Yang et al., 2003). Geens et al. (2012) estimated that thermal paper was the second largest source, after canned food and beverages, of exposure to BPA for the general population in Belgium. The latest scientific risk assessment on BPA in relation to public health, conducted by the European Food Safety Authority (EFSA), identified no health concerns from the actual level of human BPA exposure. However, a 12 times lower tolerable daily intake was recently established by the EFSA (EFSA, 2015). Additionally, BPA is a widespread environmental pollutant, and its presence in a variety of environmental samples has been confirmed (Arditsoglou and Voutsa, 2010; Barceló and Petrovic, 2011; Hansen and Lassen, 2008; Liao et al., 2012a). Potential hazards related to human BPA exposure have promoted the gradual abandoning of its use in consumer products, starting with a ban by several countries (e.g. EU, USA, China, Canada, etc.) of BPA in baby and infant polycarbonate products.
E-mail address: [email protected] (K. Pivnenko). http://dx.doi.org/10.1016/j.wasman.2015.07.017 0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
2
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
The phasing out of BPA in thermal paper has also been promoted, and in several cases it has even been banned (e.g. Japan (NITE, 2003); Connecticut, USA (State of Connecticut, 2013)). The US EPA identified 19 substances that could potentially be used in thermal paper as BPA substitutes through stakeholder involvement and based on their physical and chemical properties and commercial use (US EPA, 2014). Another study identified five phenolic alternatives to BPA based on their chemical structure (Rosenmai et al., 2013). Only bisphenol S (BPS; 4,40 -sulfonyldiphenol) and bisphenol F (BPF, Bis(4-hydroxyphenyl)methane) were identified as alternatives in both studies. Several of the BPA alternatives (including BPS and BPF) have already been documented as contaminants in a variety of food products sold in the United States (Liao and Kannan, 2013). Similarly to BPA, both BPS and BPF have been used in epoxy glues and polymerisation reactions (Fromme et al., 2002; Viñas et al., 2010). Driven by increasing awareness and demand, the main suppliers of thermal paper already provide BPA- and phenol-free products to the market (Appvion, 2013). Although industry information on substitutes used in thermal paper is not readily available, BPS has been previously identified in thermal paper, and other structural analogues of BPA can also be present (Goldinger et al., 2015; Liao et al., 2012b). Lee et al. (2015) showed the highest total concentrations of bisphenols (including BPA and BPS) in waste water sludge from treatment plants receiving discharge from paper and textile industries. A study conducted by the Danish EPA identified BPS in 25% of its thermal paper samples (Miljøstyrelsen, 2011), without quantifying the levels of BPS present. Similarly, Liao et al. (2012b) showed measurable quantities of BPS in all (n = 111) samples of thermal paper analysed in their study. Being structurally similar to BPA (Fig. 1), its phenolic analogues are suspected to have similar toxicological profiles, a notion which has been confirmed by several toxicological assessments (Chen et al., 2002; Goldinger et al., 2015; Kitamura et al., 2005; Rosenmai et al., 2014). In one study, 4-cumylphenol (HPP, 4-(2-phenylpropan-2-yl)phenol) was shown to have 12 times higher estrogenic activity when compared to BPA (Terasaki et al., 2005), which means that the substitution of BPA with structurally similar compounds may not solve the issue of the presence of the endocrine-disrupting chemicals in consumer products. Being present in their ‘‘free’’ form in thermal paper as an additive, phenolic compounds are readily transferable to human skin on contact (Biedermann et al., 2010), and to foodstuff, if present, in food contact materials (Maragou et al., 2008). Liao et al. (2012b) found that exposure to BPS via the handling of paper
H3C
was almost entirely dominated by contact with thermal receipts. The highest exposure group was related to occupational exposure, e.g. cashiers, waiters, etc. High recycling rates achieved by the paper industry reduce the possibility of selecting the source of secondary raw materials, which in turn increases the potential of undesirable chemicals, including BPA and its alternatives, being reintroduced into the paper cycle. Liao and Kannan (2011a) suggested thermal paper recycling as one of the sources of high BPA concentrations found in the paper currencies from several countries. It has been estimated that around 30% of thermal paper will end up in the paper recycling loop (JRC-IHCP, 2008), and although the thermal paper used in Europe represents less than 0.5% of the weight of the total paper collected for recycling (CEPI, 2013), concentrations of phenol-based substances (i.e. BPA) can be up to three orders of magnitude higher than in other paper products (Liao and Kannan, 2011b). Hence, phenolic compounds present in thermal or other waste paper fractions can be spread into newly manufactured paper products and may potentially end up in, for example, food-contact paper materials, thus posing a higher risk of exposure to the general public. The aim of the present study was to study the presence of BPA and five selected phenol-based structural analogues (BPS, bisphenol E (BPE, 4,40 -Ethylidenebisphenol), bisphenol B (BPB, 2,2-Bi s(4-hydroxyphenyl)butane), HPP and BPF) in waste paper and board from Danish households, thermal paper receipts, non-carbon copy paper (NCR) and conventional printer paper. 2. Materials and methods 2.1. Paper samples Waste paper and board were sampled from household solid waste derived from a municipality in Southern Denmark, where the source segregation of certain waste fractions (i.e. paper, board, metals, plastics, etc.) was in place. The sampling is described in detail in (Edjabou et al., 2015). In brief, sampling was done in accordance with a Nordtest method (Nordtest, 1995) for solid waste sampling and characterisation. The method suggests including at least 100 households for a period of one week in a sampling campaign, in order to produce representative samples. Household waste paper and board samples were manually sub-sorted into more detailed fractions based on their physical characteristics (e.g. paper thickness) and their applications (magazines, shipping boxes, etc.). The sampling campaign covered (a) source-segregated waste paper
CH3
CH3 O HO
OH
S
OH
HO
O HO
OH
BPS 80-09-1
BPA 80-05-7 H3C
H3C
CH3
BPE 2081-08-5
CH3
HO OH
HO
BPB 77-40-7
OH
HO
HPP 599-64-4
BPF 620-92-8
Fig. 1. Molecular structure of BPA and its alternatives covered in the present study.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
intended for recycling and (b) mixed (residual) waste paper, once recyclable materials (metals, glass, paper, etc.) had been separated by the households. The sampling of both flows took place in the same period. For each of the flows, 15 fractions contributing the most to waste paper composition (flyers, newspapers, etc.), or which were expected to contain phenolic compounds (i.e. receipts), were selected for chemical analysis. Sorted waste paper and board fractions were coarsely shredded (ARP SC2000, Brovst, Denmark), in order to reduce their size, and subsequently finely shredded down to a particle size <4 mm (SM2000, Retsch, Germany). Whenever a reduced sample size was required, representative sub-sampling was performed in accordance to principles described by Petersen et al. (2005). After the samples were shredded they were lyophilised and stored in sealed glass containers at 20 °C. Samples of the thermal paper were collected from commercial establishments in the Capital Region of Denmark in October 2014. Table 1 provides information on the points where thermal paper receipts were sampled, as well as a brief description of their traits. Sampling points were selected randomly and were not chosen in order to provide information on variations induced by economic, geographical or other stratifications. At least 10 receipt items were obtained from each of the sampling points, and these were placed into separate BPA-free re-sealable plastic bags and transferred to the laboratory for sample preparation. Their weight was calculated as an average of the 10 items. Each receipt was transferred into digital format, and the printed area was estimated using freely available software for image processing and analysis (ImageJ, National Institute of Health, USA). The ratio of printed to unprinted areas was calculated, as the unprinted area contains developer in its non-reacted state which can be released into the solvent. Samples were shredded down to 2 8 mm pieces, lyophilised and then stored at 20 °C prior to analysis. Samples of unused NCR paper were purchased online. NCR 1 was made from three sheets of paper (original top sheet and two copy sheets), while NCR 2 and NCR 3 were made from two (original top sheet and a single copy sheet). Conventional printer paper was
Table 1 Sampling points and description of thermal paper receipts. #
1 2 3 4 5 6 7 8 9 10 11 12
13
Sampling point
Supermarket. Cashier receipt Supermarket. Cashier receipt Gas station. Cashier receipt Furniture retailer. Cashier receipt ATM receipt Grocery store. Cashier receipt Clothing retailer. Cahier receipt Coffee shop. Cashier receipt Parking lot. Machine receipt Supermarket. Cashier receipt Hobby retailer. Cashier receipt Sportswear retailer. Cashier receipt Restaurant. Cashier receipt
Average Weight [mg]
Printed area/total area [%]
Remarks
920
5.5
790
6.5
570
5.1
1210
8.1
Print on the back
680 280
7.4 12.6
Print on the back
780
6.6
550
4.3
470
8.0
660
5.1
640
4.0
680
6.3
460
4.2
Colour print on the back
Colour print on the back
Colour print on the back and front
Colour print on the back Colour print on the back
3
purchased from an authorised local retailer, and certificates on the 100% use of either virgin or recycled fibres were obtained from the manufacturer. Samples of NCR and printer paper were treated in the same manner as thermal paper. 2.2. Quantification Approximately 4 g and 1 g of each sample were used for waste paper and paper products extractions, respectively. Higher sample amounts used in the case of waste paper were due to the heterogeneity of the material. The shredded paper samples were placed into a glass beaker, and 100 ml ethanol (analytical grade, from Sigma–Aldrich) was added. Prior to ethanol addition, internal standard, IS (bisphenol A-d16 in ethanol, from Sigma–Aldrich), was added to each of the samples, thereby allowing some time to be absorbed by the paper matrix. The sample extracts were heated under reflux for 1 h (Extraction System B-811, Büchi). The paper and board samples were then removed from the beakers, and the ethanol extract was sub-sequentially evaporated down to approximately 2 ml and then transferred into a volumetric flask. Ethanol was added to the extract, up to 5 ml of the total volume. The ethanol extracts were analysed by liquid chromatography negative electrospray ionisation tandem mass spectrometry LC-ESI-MS/MS, using an Agilent 1200 Series HPLC (Agilent Technologies, CA, USA) equipped with a reversed-phase XTerra CSH C18 column, 2.6 lm, 2.1 100 mm (Waters, Milfold, USA) with an injection volume of 3 lL. The column was maintained at 40 °C. Mobile phases A = milli-Q water and B = methanol were employed. The gradient was applied as follows: initial 80% of solvent A reduced to 55% in 1 min, followed by 10%/min reduction until it reached 20%. Additional reduction down to 2% in 1 min was followed by holding for 6.5 min. The MS detector used was a Micromass Quattro Ultima (Waters, Milford, USA). Multiple reaction monitoring (MRM) was used for monitoring the MRM transition reactions m/z 227.1 > 212.1 and 227.1 > 133.1 for BPA, 249.0 > 108.0 and 249.0 > 155.9 for BPS, 213.1 > 198.1 and 213.1 > 197.1 for BPE, 241.1 > 211.1 and 241.1 > 147.0 for BPB, 211.1 > 196.1 and 211.1 > 133.1 for HPP, 199.1 > 93.0 and 199.1 > 105.0 for BPF and 241.1 > 223.1 for d16-BPA. Capillary voltage was kept at +3 kV, and the desolvation temperature was maintained at 400 °C. Cone voltage was kept at 40 V. Concentrations of BPA and BPA analogues in the samples were quantified by external standard calibration (r2 > 0.99) with correction for the IS recoveries. Limits of detection (LOD) were calculated in accordance with ISO 11843-2:2000 and are presented in Tables 2–4. Detection limits for paper products (Table 4) were two orders of magnitude higher when compared to waste paper, as substantially higher concentrations were expected, resulting in higher dilution factors. All samples were analysed in single and the relative standard deviation of four samples spiked with standards was <5% for all substances analysed. A triplicate of virgin fibre-based paper, previously shown not to contain measurable quantities of target substances, was spiked with known amounts of phenolic compounds, before solvent addition, in order to calculate the recovery of the method. Recoveries in spiked matrices ranged from 78 ± 5% for BPS to 144 ± 9% for BPE (see Tables 2–4 for details). The results presented were not compensated for by the calculated recovery. 3. Results and discussion 3.1. Waste paper Concentrations of target substances in waste paper from source-segregated and mixed household waste are presented in
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
4
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
Table 2 Concentrations of BPA and its structural analogues (lg/g dry matter (dm)) in source-segregated paper from household waste. Waste paper fraction Recovery (%) LOD Receipts Corrugated boxes Shipping Food Non-food Newspapers Flyers Glued Non-glued Office paper Envelopes Folding boxes Food Non-food Magazines Glued Non-glued Beverage cartons Books Total Noa Fa (%) Min Max Medianb a b
% of waste paper
0.005 15.7 9.5 4.9 1.4 22.5 43.2 16.6 26.6 3.6 0.6 3.4 2.3 1.1 9.3 2.9 6.4 0.1 1.5 100
BPA [80-05-7]
BPS [80-09-1]
BPE [2081-08-5]
BPB [77-40-7]
HPP [599-64-4]
BPF [620-92-8]
BPAi [%]
BPSi [%]
98 ± 3 0.02 8300
78 ± 5 0.07 210
144 ± 9 0.04 0.60
141 ± 6 0.03
113 ± 6 0.06
130 ± 3 0.04
1.3
3.7
130 9.6 7.9 2.0
1.3 0.92 0.55
0.12
0.14 0.17 0.24
38.2 1.5 0.3 1.4
43.9 15.7 3.0 5.6
2.9 1.7 480 8.8
1.5 1.4 53.4 0.2
4.1 9.5 3.8 0.4
5.0 2.3
0.38 0.45
0.053 0.061
0.4 0.1
3.3 1.6
0.41 0.31 1.5 7.5
0.075
0.062
0.0 0.1 0.0 0.3 100
1.0 1.6 0.0 2.7 100
15 100 0.31 8300 5.0
11 73
1 7
0 0
3 20
5 33
No: number of cases where a substance was identified, F (%): frequency of detection. In cases where values are
Table 3 Concentrations of BPA and its structural analogues (lg/g dry matter (dm)) in paper from non-sorted household waste. Waste paper fraction Recovery (%) LOD Receipts Corrugated boxes Shipping Food Non-food Newspapers Flyers Glued Non-glued Office paper Envelopes Folding boxes Food Non-food Magazines Glued Non-glued Beverage cartons Books Total Noa Fa (%) Min Max Medianb a b
% of waste paper
0.5 9.5 3.5 4.6 1.3 11.2 24.2 9.0 15.0 8.5 3.2 16.4 9.6 6.7 7.2 1.1 6.1 15.1 4.3 100
BPA [80-05-7]
BPS [80-09-1]
BPE [2081-08-5]
BPB [77-40-7]
HPP [599-64-4]
BPF [620-92-8]
BPAi [%]
BPSi [%]
98 ± 3 0.02 8100
78 ± 5 0.07 170
144 ± 9 0.04
141 ± 6 0.03
113 ± 6 0.06
130 ± 3 0.04
58.6
59.4
6.1 8.4 26 2.2
9.1 0.92 1.3
0.3 0.6 0.5 0.4
22.3 2.9 1.2 0.5
1.1 4.4 280 36
0.27 0.16 0.54 0.43
0.1 1.0 34.4 1.7
1.9 2.1 3.0 0.9
4.8 5.6
0.13 0.45
0.7 0.5
0.7 2.3
0.40 1.2 0.41 17
0.0 0.1 0.1 1.1 100
0.1 0.3 0.7 1.8 100
15 100 0.40 8100 5.6
11 73
0 0
0 0
1 7
3 20
No: number of cases where a bisphenol was identified, F (%): frequency of detection. In cases where values are
Tables 2 and 3, respectively. The highest concentrations of BPA in source-segregated and residual waste paper, in both cases, were found in receipts (8300 and 8100 lg/g dry matter, respectively), as expected based on the literature presented in the introduction. The second highest concentration was attributed to office paper
in both cases. The office paper fraction included discarded paper items commonly used in offices and administration-related activities, i.e. copy and writing paper, invoices, administration forms, etc. This fraction could potentially include NCR paper, which may contain BPA (Fukazawa et al., 2001), thereby explaining the relatively
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
5
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx Table 4 Concentration of BPA and its structural analogues (lg/g dry matter (dm)) in thermal paper and paper products samples (NCR: non-carbon copy paper).
Recovery (%) LOD #1 #2 #3 #4 #5 #6 #7 #8 #9 #10 #11 #12 #13 Min Max Median Nob Fb (%) Printer paper (recycled) Printer paper (virgin) NCR 1 NCR 2 NCR 3 a b
BPA [80-05-7]
BPS [80-09-1]
BPE [2081-08-5]
BPB [77-40-7]
HPP [599-64-4]
BPF [620-92-8]
98 ± 3 2
78 ± 5 7 5700 8.48 8100
144 ± 9 4
141 ± 6 3
113 ± 6 6
130 ± 3 4
Lowest concentrations (<20 lg/g) were excluded from median value calculations. No: number of cases where a bisphenol was identified, F (%): frequency of detection.
high concentration of BPA in the office waste paper fraction. On the other hand, three samples of printing paper, the main constituent of the office paper fraction, contained insignificant amounts of BPA (0.02 lg/g), according to Liao and Kannan (2011b). Corrugated boxes used for the shipment of goods showed concentrations of BPA higher than 100 lg/g, albeit only in the case of source-segregated waste paper, which could be the direct result of paper recycling, as casing materials have the highest recycling rates in the EU (CEPI, 2013). An additional source of BPA in board material could be the hydrolysis of epoxy resins potentially used in ink and adhesive formulations containing BPA (ANSES, 2011). In both cases, i.e. source-segregated and residual waste paper, BPA was quantified in all fractions with a variety of concentrations. This could indicate ongoing spreading of BPA through paper recycling, as the use of BPA in paper is limited to specific applications such as thermal paper. The study conducted by Vinggaard et al. (2000) showed that none of the 11 paper samples made from virgin fibres contained BPA. Additionally, analysis of unprinted board sourced from four paper mills in Germany revealed measurable contents of BPA, but only in those products which contained recycled paper (BMELV, 2012). On the other hand, 80% of almost 100 paper samples analysed by Liao and Kannan (2011b) contained measurable amounts of BPA. The authors also suggested paper recycling as the main source of BPA presence, as most of the paper items analysed were made from recycled paper (Liao and Kannan, 2011b). BPS was present in the majority of samples and was quantified in 11 (73%) samples in both waste flows, thereby indicating its spreading in use or through waste paper recycling. The highest concentrations (up to 210 lg/g) were once again related to receipts. Concentrations of BPS in receipts were considerably lower than those of BPA, thus indicating that the latter is still the predominant developer used in thermal paper sold on the Danish market. An earlier study by the Danish EPA found BPS in 25% of the thermal paper receipts analysed, while 70% of the samples contained measurable amounts of BPA (Miljøstyrelsen, 2011). The authors suggested that BPS was used in more wear-resistant
receipts that are expected to be exposed to more extreme conditions (e.g. gas stations) or have a prolonged life span (e.g. furniture and appliance retail outlets). The waste paper fraction containing receipts was followed by corrugated shipping boxes, which nevertheless showed at least one order of magnitude lower concentrations. This could suggest the spreading of BPS through paper recycling or the use of epoxy glues, in which BPS can be employed as a curing agent (Viñas et al., 2010). Fig. 2 presents a comparison between BPA and BPS levels in source-segregated and residual waste paper. The data presented do not include outliers, i.e. samples with significantly higher levels, outside the 1.5 of the interquartile range (i.e. receipts, office paper, etc.). Although BPA variations in the residual waste seemed to be higher than in source-segregated waste paper, the means of the two flows showed no significant difference when compared with a t-test (p-value > 0.05). Similarly, in the case of BPS, no significant difference was detected (p-value > 0.05). The results indicate that the amounts of BPA and BPS are at the same level in total source-segregated and residual waste paper flows. Additionally, this conclusion suggests that any contamination as a result of the co-mingled collection of waste does not contribute to the presence of BPA and BPS. Of the remaining substances, BPF was identified as having the highest frequency of detection, respectively in 33% and 20% of the cases in the two flows, as shown in Tables 2 and 3. The level of BPF was at a significantly lower concentration in the given samples compared to the level of BPA. Moreover, in both flows, measurable quantities of BPF were found only in board packaging (both corrugated and non-corrugated), which could be related to the use of adhesives based on epoxy resins which may include BPF as a raw material (Goodson et al., 2002). Pérez-Palacios et al. (2012) did not identify BPF in any of the eight recycled paper products they analysed. HPP was found in low levels in 20% and 7% of the samples from source-segregated and residual waste paper, respectively, and it was identified in corrugated boxes, glued magazines and in books, with the latter containing one order of magnitude higher concentrations. Shipping corrugated boxes
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
0.8
µg/g
0.0
0
5
0.2
10
0.4
0.6
20 15
µg/g
25
1.0
30
1.2
35
6
Source-segregated
Residual
Source-segregated
BPA
Residual
BPS
Fig. 2. Boxplot of source-segregated versus residual waste paper for BPA and BPS. Outliers (e.g. receipts) are excluded from the representation.
(source-segregated) contained the highest number of phenolic compounds, as four out of the six substances analysed were detected in this fraction (Table 2). The contribution of each of the fractions to the total amounts of BPA and BPS in the waste paper was calculated in accordance with Eq. (1), where F is the percentage contribution of a given fraction to waste paper composition, and C is the concentration (lg/g dry matter (dm)) of either BPA or BPS in the respective fraction. The results are presented in the last two columns in Tables 2 and 3. The data show that receipts might not make a large contribution to the presence of BPA and BPS, as is the case in source-segregated waste paper, due to the low contribution of receipt paper in this flow. In source-segregated waste paper, office paper contributes over 53% to the total content of BPA, while for the residual flow this figure is just below 35%. Similarly, for BPS, corrugated boxes and flyers represent the majority of the substance flow in source-segregated waste paper. Most of the receipts end up in the residual fraction of waste paper, which explains their much greater contribution to the BPA and BPS amounts in the flow (Table 3).
Fi Ci BPAi or BPSi ð%Þ ¼ P15 100% j¼1 ðF j C j Þ
ð1Þ
Lu et al. (2013) compared concentrations of BPA in different media. When comparing our results to this study, the median concentrations of BPA we found in waste paper (5.0 and 5.6 lg/g dry matter, respectively) were comparable to the concentrations found in canned foods. Other media, including selected plastic products, indoor dust, paper currency, supermarket receipts and thermal paper, contained from one to six orders of magnitude higher BPA concentrations (Lu et al., 2013). As evidenced in Table 4, most of the thermal paper receipts sampled (93%) contained measurable quantities of BPA. Concentrations measured ranged from
collected from Japan, Korea and Vietnam showed somewhat lower maximum concentrations between
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
7
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx Table 5 Physical and chemicals properties of bisphenols of interest. Phase distribution: water/solid/air.
BPA [80-05-7] BPS [80-09-1] BPE [2081-08-5] BPB [77-40-7] HPP [599-64-4] BPF [620-92-8] a
Mol. WT (g/mol)
Boiling point (°C)
Water solubility (mg/L)
LogKow
Kh (atm m3/mol)
Koc (L/kg)
Phase distribution (w/s/a)
Biodegradability
228.29 250.27 214.27 242.32 212.29 200.24
361 423 357 375 328 352
300 1100 265 29 18 543
3.4 1.2 3.2 4.1 4.1 2.9
9.16E12 2.70E15 6.90E12 1.22E11 8.80E08 1.44E12
3.77E+04 1.83E+03 2.53E+04 7.38E+04 2.93E+04 1.51E+04
–/x/– x/x/– –/x/– –/x/– –/x/– –/x/–
Readily Inherently Inherently Inherently Inherentlya Readily
Not readily biodegradable under aerobic conditions. Limited data available for full assessment.
of the compound in the office waste paper samples analysed (Tables 2 and 3). Since neither virgin nor recycled printer paper samples contained any BPA, other paper items, such as fax paper and thermal paper, could be present in office paper waste fraction and could be potential sources of BPA in the samples analysed. 3.2. Implications on paper recycling Table 5 summarises the physical and chemical properties of the substances in focus. Distribution between the water, solid and air phases is based on the methodology described by Baun et al. (2006). All of the phenolic compounds covered showed high affinity for the solid phase, indicating that they may be retained in paper fibres when waste paper is recycled. In the recycling process, short fibres are removed as sludge while the rest are incorporated into newly manufactured paper. If phenol-based substances follow the path of the longer fibres, the presence of substances in paper products not intended to contain them is expected. A study commissioned by German authorities has shown the presence of BPA only in board produced from recycled waste paper (BMELV, 2012). BPS was the only substance that showed high affinity to both water (also indicated by its higher solubility, Table 5) and solid phases, meaning that predicting its behaviour in a recycling process may be challenging. None of the substances is expected to volatilise during recycling (Table 5). Nevertheless, the specific physical and chemical conditions governing a paper recycling process may influence significantly the partitioning of substances between different phases. As an example, alkalinity may increase the solubility of BPA by a factor of 100 (Kosky et al., 1991), which should not lead to the considerably higher release of BPA into the water phase at a paper mill, as pH conditions are expected to be close to neutral (Rigol et al., 2002). Additionally, paper production methods are designed to optimise water use, primarily through recirculation. In such conditions, BPA will be put in contact with paper fibres constantly, and only a small fraction of it will finally be discarded along with the effluent (Fukazawa et al., 2002). Nonetheless, relatively low concentrations in the effluent waste water still make paper production one of the most important sources of BPA release into the aquatic environment (Fürhacker et al., 2000). Being chemically related substances, BPA alternatives are expected to behave similarly to BPA in the paper recycling process. If phenolic substances are actually removed from the paper matrix, they may be emitted from a paper mill and end up in the environment, thereby making their persistence and biodegradation critical. As an example, BPA and BPF were characterised as readily biodegradable, with BPF showing higher biodegradation rates under both aerobic and anaerobic conditions (Ike et al., 2006; Nicolucci et al., 2011). Similarly, Danzl et al. (2009) showed biodegradation sequence of BPF > BPA BPS in their experiment, with BPF being the most biodegradable in seawater environment, which is supported by the results of quantitative structure–activity relationship (QSAR) modelling in the Danish (Q)SAR Database
(Miljøstyrelsen, 2013). Nevertheless, BPA has been characterised as a pseudo-persistent chemical, as limited restrictions on its production and uses result in continual environmental release (Flint et al., 2012). The other BPA alternatives focused on in this study show lower degradation rates and cannot be characterised as readily biodegradable. The degradation sequence for the remaining bisphenols was found to be BPS > BPE > BPB (Ike et al., 2006).
4. Conclusions BPA was measured in all analysed waste paper samples. As BPA is only used for a limited range of paper products (i.e. thermal paper), this suggests potential spreading of BPA through recycling of secondary waste paper. BPS is an important substitute for BPA, as it was identified in more than 70% of the waste paper samples. Although both BPA and BPS showed the highest concentrations in thermal paper receipts, other fractions (i.e. office paper, board boxes) may constitute important flows of the chemicals found in household waste paper. No significant differences in BPA and BPS concentrations were observed between source-segregated and residual waste paper. From the remaining analogues, only BPB was not identified in any of the samples. Most of the analysed thermal paper receipts contained BPA in concentrations reaching 17,600 lg/g. Similarly to waste paper, the results suggest BPS as the main BPA alternative in thermal paper, as it was measured (in concentrations reaching 7300 lg/g) in most of the samples not containing BPA in significant quantities. None of the remaining phenolic compounds (BPE; BPB, HPP and BPF) was measured in the thermal receipts samples. Two samples of thermal paper (4 and 5) suggested the use of alternative phenol-based or non-phenolic developers. Neither common printer paper nor NCR paper could explain the relatively high concentrations of BPA in the office waste paper fraction. Chemical and physical properties of the substances suggested their affinity with paper fibres and the potential contamination of newly manufactured paper products which utilise recycled waste paper as a secondary material. Acknowledgements The authors would like to express their sincere gratitude to Lisbeth Krüger Jensen (National Food Institute, Technical University of Denmark) for her assistance in the analytical part of the work. The Danish Research Council is acknowledged for its financial support through the 3R Research School and the IRMAR project. References ANSES, 2011. Effets sanitaires du bisphénol A. Connaissances relatives aux usages du bisphénol A. ANSES, French Agency for Food, Environmental and Occupational Health & Safety, Paris. Appvion, 2013. Free Statement.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
8
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx
Arditsoglou, A., Voutsa, D., 2010. Partitioning of endocrine disrupting compounds in inland waters and wastewaters discharged into the coastal area of Thessaloniki, Northern Greece. Environ. Sci. Pollut. Res. Int. 17, 529–538. http://dx.doi.org/ 10.1007/s11356-009-0172-y. Barceló, D., Petrovic, M. (Eds.), 2011. The Ebro River Basin. The Handbook of Environmental Chemistry. Springer, Berlin, Heidelberg. http://dx.doi.org/ 10.1007/978-3-642-18032-3. Baun, A., Eriksson, E., Ledin, A., Mikkelsen, P.S., 2006. A methodology for ranking and hazard identification of xenobiotic organic compounds in urban stormwater. Sci. Total Environ. 370, 29–38. http://dx.doi.org/10.1016/ j.scitotenv.2006.05.017. Biedermann, S., Tschudin, P., Grob, K., 2010. Transfer of bisphenol A from thermal printer paper to the skin. Anal. Bioanal. Chem. 398, 571–576. BMELV, 2012. Ausmaß der Migration unerwünschter Stoffe aus Verpackungsmaterialien aus Altpapier in Lebensmitteln, BMELV, German Federal Ministry of Food, Agriculture and Consumer Protection.
Kosky, P.G., Silva, J.M., Guggenheim, E.A., 1991. The aqueous phase in the interfacial synthesis of polycarbonates. Part 1. Ionic equilibria and experimental solubilities in the BPA-sodium hydroxide-water system. Ind. Eng. Chem. Res. 30, 462–467. http://dx.doi.org/10.1021/ie00051a005. Lee, S., Liao, C., Song, G.-J., Ra, K., Kannan, K., Moon, H.-B., 2015. Emission of bisphenol analogues including bisphenol A and bisphenol F from wastewater treatment plants in Korea. Chemosphere 119, 1000–1006. http://dx.doi.org/ 10.1016/j.chemosphere.2014.09.011. Liao, C., Kannan, K., 2011a. High levels of bisphenol A in paper currencies from several countries, and implications for dermal exposure. Environ. Sci. Technol. 45, 6761–6768. http://dx.doi.org/10.1021/es200977t. Liao, C., Kannan, K., 2011b. Widespread occurrence of bisphenol A in paper and paper products: implications for human exposure. Environ. Sci. Technol. 45, 9372–9379. http://dx.doi.org/10.1021/es202507f. Liao, C., Kannan, K., 2013. Concentrations and profiles of bisphenol A and other bisphenol analogues in foodstuffs from the United States and their implications for human exposure. J. Agric. Food Chem. 61, 4655–4662. http://dx.doi.org/ 10.1021/jf400445n. Liao, C., Liu, F., Guo, Y., Moon, H.-B., Nakata, H., Wu, Q., Kannan, K., 2012a. Occurrence of eight bisphenol analogues in indoor dust from the United States and several Asian countries: implications for human exposure. Environ. Sci. Technol. 46, 9138–9145. http://dx.doi.org/10.1021/es302004w. Liao, C., Liu, F., Kannan, K., 2012b. Bisphenol S, a new bisphenol analogue, in paper products and currency bills and its association with bisphenol A residues. Environ. Sci. Technol. 46, 6515–6522. http://dx.doi.org/10.1021/es300876n. Lu, S.-Y., Chang, W.-J., Sojinu, S.O., Ni, H.-G., 2013. Bisphenol A in supermarket receipts and its exposure to human in Shenzhen, China. Chemosphere 92, 1190– 1194. http://dx.doi.org/10.1016/j.chemosphere.2013.01.096. Maragou, N.C., Makri, A., Lampi, E.N., Thomaidis, N.S., Koupparis, M.a., 2008. Migration of bisphenol A from polycarbonate baby bottles under real use conditions. Food Addit. Contam. Part A 25, 373–383. http://dx.doi.org/10.1080/ 02652030701509998. Mendum, T., Stoler, E., VanBenschoten, H., Warner, J.C., 2011. Concentration of bisphenol A in thermal paper. Green Chem. Lett. Rev. 4, 81–86. http:// dx.doi.org/10.1080/17518253.2010.502908. Miljøstyrelsen, 2011. Migration of Bisphenol A from Cash Register Receipts and Baby Dummies. Survey of Chemical Substances in Consumer Products No. 110, Miljøstyrelsen. Danish EPA, København. Miljøstyrelsen, 2013. Danish (Q)SAR Database, Miljøstyrelsen. Danish EPA, København.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017
K. Pivnenko et al. / Waste Management xxx (2015) xxx–xxx Vandenberg, L.N., Maffini, M.V., Sonnenschein, C., Rubin, B.S., Soto, A.M., 2009. Bisphenol-A and the great divide: a review of controversies in the field of endocrine disruption. Endocr. Rev. 30, 75–95. http://dx.doi.org/10.1210/ er.2008-0021. Viñas, P., Campillo, N., Martínez-Castillo, N., Hernández-Córdoba, M., 2010. Comparison of two derivatization-based methods for solid-phase microextraction-gas chromatography–mass spectrometric determination of bisphenol A, bisphenol S and biphenol migrated from food cans. Anal. Bioanal. Chem. 397, 115–125. http://dx.doi.org/10.1007/s00216-010-3464-7. Vinggaard, A.M., Körner, W., Lund, K.H., Bolz, U., Petersen, J.H., 2000. Identification and quantification of estrogenic compounds in recycled and virgin paper for
9
household use as determined by an in vitro yeast estrogen screen and chemical analysis. Chem. Res. Toxicol. 13, 1214–1222. Vom Saal, F.S., Hughes, C., 2005. An extensive new literature concerning low-dose effects of bisphenol A shows the need for a new risk assessment. Environ. Health Perspect. 113, 926–933. http://dx.doi.org/10.1289/ehp.7713. Yang, M., Kim, S.-Y., Lee, S.-M., Chang, S.-S., Kawamoto, T., Jang, J.-Y., Ahn, Y.-O., 2003. Biological monitoring of bisphenol A in a Korean population. Arch. Environ. Contam. Toxicol. 44, 546–551. http://dx.doi.org/10.1007/s00244-002-2124-0. Yoshida, T., Horie, M., Hoshino, Y., Nakazawa, H., 2001. Determination of bisphenol A in canned vegetables and fruit by high performance liquid chromatography. Food Addit. Contam. 18, 69–75. http://dx.doi.org/10.1080/026520301446412.
Please cite this article in press as: Pivnenko, K., et al. Bisphenol A and its structural analogues in household waste paper. Waste Management (2015), http:// dx.doi.org/10.1016/j.wasman.2015.07.017