Perfluoroalkane acids in human milk under the global monitoring plan of the Stockholm Convention on Persistent Organic Pollutants (2008–2019)

doi:10.1007/s11783-022-1541-8

Front. Environ. Sci. Eng.

2022, Vol. 16

Issue (10) : 132 https://doi.org/10.1007/s11783-022-1541-8

RESEARCH ARTICLE

Perfluoroalkane acids in human milk under the global monitoring plan of the Stockholm Convention on Persistent Organic Pollutants (2008–2019)

Heidelore Fiedler¹(

), Mohammad Sadia¹, Thomas Krauss², Abeer Baabish¹, Leo W.Y. Yeung¹

¹. School of Science and Technology, MTM Research Centre, Örebro University, SE-701 82 Örebro, Sweden
². Fundaçao Oswaldo Cruz (FIOCRUZ), Instituto Nacional de Controle de Qualidade em Saúde (INCQS), Avenida Brasil, 4365 – Manguinhos EP 21.040-900, Rio de Janeiro – RJ, Brazil

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Abstract

● Perfluorooctanesulfonic acid and perfluorooctanoic acid highest in human milk.

● All other perfluoroalkane substances had median values of zero (101 samples).

● Branched PFOS recommended to be analyzed separately from linear isomer.

● PFOS and PFOA showed differentiated regional and income distribution.

● Human health risk assessment values not yet available at global level.

Within the global monitoring plan (GMP) established by article 16 of the Stockholm Convention on Persistent Organic Pollutants, perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) are recommended for analysis in core matrices to assess occurrence and changes geographically and with time. In 101 samples consisting of 86 national pools and 15 pools from States in Brazil obtained between 2008 and 2019, PFHxS was detected in 17% of the national pools and none in Brazil. PFOA and PFOS had a detection frequency of 100% and 92%, respectively. Other perfluoroalkane substances (PFAS) had either low detection frequencies and median values of zero (carboxylic acids C₄–C₁₁; except PFOA) or could not be quantified in any sample (sulfonic acids, C₄–C₁₀, and long-chain carboxylic acids, C₁₂–C₁₄). Correlation between PFOA and PFOS was moderately (r = 0.58). Whereas median values were almost identical (18.9 pg/g f.w. for PFOS; 18.6 pg/g f.w. for PFOA), PFOS showed larger ranges (< 6.2 pg/g f.w.–212 pg/g f.w.) than PFOA (< 6.2 pg/g f.w.–63.4 pg/g f.w.). It was shown that wealthier countries had higher PFOA concentrations than poorer countries. No difference in concentrations was found for samples collected in countries having or not having ratified the Stockholm Convention amendments to list PFOS or PFOA. The goal to achieve 50% decrease in concentrations within ten years was met by Antigua and Barbuda, Kenya, and Nigeria for PFOS and by Antigua and Barbuda for PFOA. In a few cases, increases were observed; one country for PFOS, four countries for PFOA.

Keywords Human biomonitoring Human breast milk LC-MS/MS analysis Lifestyle parameters

Corresponding Author(s): Heidelore Fiedler

Issue Date: 24 April 2022

Cite this article:

Heidelore Fiedler,Mohammad Sadia,Thomas Krauss, et al. Perfluoroalkane acids in human milk under the global monitoring plan of the Stockholm Convention on Persistent Organic Pollutants (2008–2019)[J]. Front. Environ. Sci. Eng., 2022, 16(10): 132.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-022-1541-8
https://academic.hep.com.cn/fese/EN/Y2022/V16/I10/132

PFAA	Africa(N = 27)	Asia(N = 18)	CEE(N = 12)	GRULAC(N = 21)	WEOG(N = 8)	Overall(N = 86)
ΣPFOS
Mean (SD)	15.8 (10.7)	27.7 (46.7)	36.4 (22.1)	24.3 (18.3)	27.9 (13.5)	24.4 (26.0)
Median　[Min, Max]	13.6[0, 44.6]	16.2[0, 212]	32.6[12.2, 83.3]	18.4[0, 65.3]	24.3[13.5, 51.4]	18.9[0, 212]
PFOA
Mean (SD)	17.1 (10.4)	18.1 (7.17)	30.6 (9.16)	23.4 (12.6)	31.7 (13.4)	22.1 (11.7)
Median　[Min, Max]	15.7[6.20, 63.4]	17.4[9.98, 35.0]	30.7[12.6, 48.8]	19.7[7.81, 61.5]	33.4[17.7, 57.8]	18.6[6.20, 63.4]
PFHxS
Mean (SD)	0.489 (1.78)	6.90 (26.1)	2.37 (4.54)	2.61 (7.75)	4.28 (6.53)	2.96 (12.8)
Median　[ Min, Max]	0[0, 7.56]	0[0, 111]	0[0, 12.9]	0[0, 34.8]	0[0, 17.4]	0[0, 111]
L_PFOS
Mean (SD)	12.4 (8.58)	21.9 (33.7)	28.4 (18.5)	17.4 (12.3)	20.4 (8.70)	18.6 (19.1)
Median　[Min, Max]	11.5[0, 37.5]	14.3[0, 154]	24.0[9.92, 70.5]	15.3[0, 42.7]	18.1[10.5, 36.3]	15.2[0, 154]
br_PFOS
Mean (SD)	3.43 (2.48)	5.72 (13.2)	7.97 (4.78)	6.88 (6.18)	7.56 (4.99)	5.77 (7.34)
Median　[Min, Max]	3.16[0, 8.06]	2.51[0, 57.8]	6.39[2.29, 18.3]	5.64[0, 22.6]	5.46[2.60, 15.1]	4.19[0, 57.8]
PFBA
Mean (SD)	54.7 (221)	60.6 (161)	32.3 (26.0)	22.6 (37.5)	4.23 (4.61)	40.3 (145)
Median　[Min, Max]	0[0, 1160]	7.78[0, 688]	33.8[0, 78.5]	0[0, 113]	3.57[0, 10.1]	0[0, 1160]
PFPeA
Mean (SD)	1.49 (3.70)		0.791 (2.74)	1.89 (8.67)		1.04 (4.84)
Median　[Min, Max]	0[0, 12.6]		0[0, 9.49]	0[0, 39.7]		0[0, 39.7]
PFHxA
Mean (SD)	6.76 (13.0)	3.98 (9.96)	8.07 (11.5)	11.5 (36.5)		6.89 (20.3)
Median　[Min, Max]	0[0, 45.8]	0[0, 34.9]	2.64[0, 31.7]	0[0, 163]		0[0, 163]
PFHpA
Mean (SD)	1.06 (2.64)	1.08 (3.15)		1.04 (4.75)		0.811 (3.10)
Median　[Min, Max]	0[0, 9.24]	0[0, 10.5]		0[0, 21.8]		0[0, 21.8]
PFNA
Mean (SD)	0.654 (3.40)	2.52 (4.30)	5.57 (4.76)	1.26 (4.23)	3.18 (6.43)	2.11 (4.52)
Median　[Min, Max]	0[0, 17.7]	0[0, 11.2]	6.42[0, 14.8]	0[0, 17.7]	0[0, 17.5]	0[0, 17.7]
PFDA
Mean (SD)		0.930 (2.71)				0.195 (1.27)
Median　[Min, Max]		0[0, 8.68]				0[0, 8.68]
PFUnDA
Mean (SD)	0.243 (1.26)		0.599 (2.08)	0.340 (1.56)	0.775 (2.19)	0.315 (1.44)
Median　[Min, Max]	0[0, 6.57]		0[0, 7.19]	0[0, 7.13]	0[0, 6.20]	0[0, 7.19]

Tab.1 Descriptive statistics for all quantified PFAA in national pools according to compound and UN region (pg/g f.w.) (N = 86; SD = standard deviation; values at lower-bound)

Fig.1 Box plots for concentrations of all quantified PFAA according to the five regions (y-axis zoomed to 120 pg/g f.w); if not otherwise indicated ‘PFOS’ refers to the sum of L- and br-PFOS (N = 86).The whiskers represent the minimum and maximum concentrations without the outliers. The lower border of the box represents the first quartile (25%), the line inside the box the median and the upper border is the third quartile (75%). The asterisk represents the mean value. The dots outside the whiskers are outliers, which were defined as all concentrations greater or smaller the interquartile range multiplied by 1.5.

Fig.2 Scaled box plots for concentrations of L-PFOS and br-PFOS according to regions (N = 86). Concentrations in pg/g f.w. The whiskers represent the minimum and maximum concentrations without the outliers. The lower border of the box represents the first quartile (25%), the line inside the box the median and the upper border is the third quartile (75%). The dots outside the whiskers are outliers, which were defined as all concentrations greater or smaller the interquartile range multiplied by 1.5.

Fig.3 Box plots for concentrations of three PFAA according to 5-year period (a); with differentiation into the UN regions (b) (N = 86); unscaled with y-axis zoomed to 80 pg/g f.w. The whiskers represent the minimum and maximum concentrations without the outliers. The lower border of the box represents the first quartile (25%), the line inside the box the median and the upper border is the third quartile (75%). The asterisk represents the mean value. The dots outside the whiskers are outliers, which were defined as all concentrations greater or smaller the interquartile range multiplied by 1.5.

Fig.4 Boxplots for ΣPFOS and PFOA concentrations in countries that ratified the PFOS and PFOA amendments to the Stockholm Convention (“Yes”) and that did not ratify (“No”) (unscaled with y-axis zoomed to 80 pg/g f.w., N = 86): (a) summary, (b) grouping according to UN regions. The whiskers represent the minimum and maximum concentrations without the outliers. The lower border of the box represents the first quartile (25%), the line inside the box the median and the upper border is the third quartile (75%). The asterisk represents the mean value. The dots outside the whiskers are outliers, which were defined as all concentrations greater or smaller the interquartile range multiplied by 1.5.

Fig.5 Box plots for concentrations of ΣPFOS and PFOA (a) according to income (as WBC, unscaled with y-axis zoomed to 80 pg/g f.w) and (b) according to compound and WBC (unscaled boxplots) (N = 86). The whiskers represent the minimum and maximum concentrations without the outliers. The lower border of the box represents the first quartile (25%), the line inside the box the median and the upper border is the third quartile (75%). The asterisk represents the mean value. The dots outside the whiskers are outliers, which were defined as all concentrations greater or smaller the interquartile range multiplied by 1.5.

Fig.6 Box plots for concentrations of ΣPFOS and PFOA (a) according to population density (as PD_Code, unscaled with y-axis zoomed to 80 pg/g f.w.) and (b) according to compound and PD_Code (unscaled boxplots) (N = 86). The whiskers represent the minimum and maximum concentrations without the outliers. The lower border of the box represents the first quartile (25%), the line inside the box the median and the upper border is the third quartile (75%). The asterisk represents the mean value. The dots outside the whiskers are outliers, which were defined as all concentrations greater or smaller the interquartile range multiplied by 1.5.

Fig.7 Changes of concentrations in ΣPFOS (a) and PFOA (b) between samples; all percentages calculated to a period of 10 years (N = 23). In each figure, countries 1–6 refer to 10-year between samplings, countries 18–23 had ≤ 5 years between samplings.

Fig.8 Box plot for PFOS isomers, ΣPFOS, and PFOA according to great region (GR1, GR2, and GR3). Concentrations in pg/g f.w. The whiskers represent the minimum and maximum concentrations without the outliers. The lower border of the box represents the first quartile (25%), the line inside the box the median and the upper border is the third quartile (75%). The asterisk represents the mean value. The dots outside the whiskers are outliers, which were defined as all concentrations greater or smaller the interquartile range multiplied by 1.5.

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