Table 2.
Human biomonitoring studies of pyrethroid exposure based on urine samples from European populations.
| Country, Region, (Cohort) | Study Population | Sampling Year and Method | Analytical Method and Quality Control (QC), Correction Method for Urine Dilution | LOD/LOQ, DF, and Urinary Concentrations (μg/L Unless Other Stated) | Exposure Determinants Reported | Ref | |
|---|---|---|---|---|---|---|---|
| Northern EU | 3-PBA | Specific metabolites | |||||
| Denmark, Funen (OCC) | Pregnant women (n = 948) | 2010–2012; Spot urine (morning after overnight fasting), GW 28 |
Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards, participation in G-EQUAS for 3-PBA, trans-DCCA, and cis-DBCA; Creatinine |
LOD: 0.03 DF: 94.3 P50: 0.24 P75: 0.46 |
4F-3PBA LOD: 0.2 DF: 0.1 trans-DCCA LOD: 0.4 DF: 11.4 cis-DCCA LOD: 0.5 DF: 2.8 cis-DBCA LOD: 0.5 DF: 3.0 |
3-PBA not significantly related to any demographic characteristics, no information on diet or home use of pesticides | Dalsager et al., 2019 [39] |
| Denmark, Funen (DGCC) | Children, 10–16 y (n = 143) | 2011–2012; Spot urine |
Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards, participation in G-EQUAS for 3- PBA, trans-DCCA, and cis-DBCA; Creatinine |
LOD: 0.03 DF: 100 P50: 0.56 P95: 8.90 |
trans-DCCA LOD: 0.4 DF: 9.8 P95: 2.3 cis-DCCA LOD: 0.5 DF: 2.8 cis-DBCA LOD: 0.5 DF: 2.1 |
Higher 3-PBA in samples from autumn/winter than spring/summer, and if mother were occupationally exposed to pesticides | Andersen et al., 2021 [38] |
| Sweden, Scania | Adolescents aged 17–21 (approx. 200 per year in 2000, 2004, 2009, 2013, and 2017) | 2000–2017; Spot urine |
Enzymatic hydrolyses; LC-MS/MS; QC: spiked urine samples, participate in Erlangen inter-laboratory comparison for 3-PBA; Urine density and creatinine |
LOD: 0.009 DF: 96–100 P50: 0.11–0.21 P95: 0.56–0.92 |
4F-3PBA LOD: 0.005 DF: 42–74 P50: <LOD–0.01 P95: 0.02–0.06 CFCA LOD: 0.006 DF: 39–90 P50: <LOD–0.02 P95: 0.05–0.40 DCCA LOD: 0.017 DF: 97–99 P50: 0.16–0.22 P95: 0.53–0.89 |
Increasing temporal trend for 3-PBA (3.7% per year), no information on exposure sources | Noren et al., 2020 [23] |
| Sweden, Uppsala County (POPUP) | Women, after delivery (n = 178) | 2009–2014; Morning spot urine, 3 weeks after delivery |
Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards, participate in Erlangen inter-laboratory comparison; Urine density |
LOD: 0.03 DF: 98 P50: 0.22 Max: 2.59 |
NR | Increasing trend in 3-PBA from 2009 to 2014, no information on determinants | Gyllen-hammar et al., 2017 [32] |
| Sweden, Värmland county (SELMA) | Pregnant women (n = 718) | 2007–2010; FMV, GW 10 |
Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards; Creatinine |
LOD: 0.017 DF: 99 GM (GSD) 0.16 (2.7) |
NR | NR | Tanner et al., 2020 [53] |
| Western EU | |||||||
| Belgium, Flanders, FLEHS IV | Adolescents, 14–15 y (n = 415) | 2017–2018, spot urine |
Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards, participation in G-EQUAS for 3-PBA; Specific gravity |
LOD: 0.03 DF: 99.5 P50: 0.87 P90: 2.77 |
NR | Higher 3-PBA associated with higher household education in binary analyses | Schoeters et al., 2022 [36] |
| Belgium, Walloon region | Children, 9–12 y (n = 258) from five different locations (urban or agricultural) | 2016; FMV |
Enzymatic hydrolyses; GC-MS/MS; QC: Internal standards and materials from previous G-EQUAS programs; Creatinine |
LOQ: 0.09 DF: 99.6 P50: 0.98 P95: 5.33 |
4F-3PBA LOQ: 0.11 DF: 2.2 trans-DCCA LOQ: 0.15 DF: 93.2 P50: 0.66 P95: 4.29 cis-DCCA LOQ: 0.50 DF: 40.3 P95: 2.01 |
Higher trans-DCCA and 3-PBA associated with indoor use of pyrethroids, and negatively associated with consumption of grey bread (graubrot) | Pirard et al., 2020 [37] |
| France, NutriNet-Sante | Adults from general population, mean age 58.5 y (n = 300, divided in two matched groups based on low (<10%) or high (>50%) organic food consumption from questionnaire | 2014; Spot urine, fasted 6 h before collection |
Samples were analysed both without and with a deconjugation step included. Enzymatic hydrolyses: LC-MS-MS; QC: internal standards and control samples; Creatinine |
LOD: 0.02 Organic DF: 23 Mean: 0.12 Conventional DF: 35 Mean: 0.13 |
4F-3PBA LOD: 0.02 Organic: DF: 3 Mean: 0.012 Conventional: DF: 3 Mean: 0.014 |
3-PBA was slightly lower if high organic food consumption but only significant when urine samples were analysed without a deconjugation step (mean: 0.026 vs. 0.042 μg/L for high and low organic intake) | Baudry et al., 2019 [2] |
| France (ELFE) | Pregnant women (n = 1077), nationally representative | 2011; Spot urine, at delivery |
Enzymatic hydrolyses; GC-MS/MS; QC: Internal standards and control samples; Creatinine |
LOD: 0.004 DF: 100 P50: 0.36 P95: 1.89 |
4F-3PBA LOD: 0.005 DF: 17.8 P95: 0.02 trans-DCCA LOD: 0.006 DF: 100 P50: 0.26 P95: 2.29 cis-DCCA LOD: 0.003 DF: 100 P50: 0.16 P95: 0.91 cis-DBCA LOD: 0.005 DF: 100 P50: 0.23 P95: 1.38 |
Urinary concentrations of pyrethroid metabolites (3-PBA or sum of metabolites) were positively related to smoking during pregnancy, consuming of fish and alcohol, domestic pesticide use and living in the vicinity of crops during pregnancy. | Dereu-meaux et al., 2018, 2016 [19,46] |
| France, Brittany (PELAGIE) | Children, 6 y, (n = 245), 55 % rural residence | 2009–2012; FMV |
No information on deconjugation; LC-MS/MS for 3-PBA and 4-F-3PBA GC-MS/MS for Trans-DCCA, Cis-DCCA, and Cis-DBCA; QC: Internal standards; Creatinine |
LOD: 0.008 DF: 63 P50: 0.02 P95: 0.20 |
4F-3PBA LOD: 0.003 DF: 15.8 P95: 0.02 trans-DCCA LOD: 0.01 DF: 95 P50: 0.22 P95: 1.75 cis-DCCA LOD: 0.07 DF: 64 P50: 0.09 P95:0.49 cis-DBCA LOD: 0.07 DF: 84 P50: 0.20 P95: 1.12 |
3-PBA and Cis-DBCA higher in children living in proximity (<500 m) to crops. 3-PBA correlated to high fruit consumption, parental occupational pesticide exposure. cis-DBCA related to high consumption of cereal and whole grain bread. Higher trans/cis-DCCA when floor cleaning at least twice a week; cis-DCCA associated with daily consumption of pasta, rice, or semolina. Organic food intake was associated with lower 3-PBA, cis-DBCA and trans-DCCA. | Gloren-nec et al., 2017 [28] |
| France, Brittany (PELAGIE) | Pregnant women (n = 205), 55.1% rural residence | 2002–2006; FMV, GW 6–19 |
No information on deconjugation; LC-MS/MS for 3-PBA and 4-F-3PBA, GC-MS/MS for trans- and cis-DCCA, and cis-DBCA; QC: Internal standards; Creatinine |
LOD: 0.008 DF: 30.2 P90: 0.075 |
4F-3PBA LOD: 0.003 DF: 8.8 trans-DCCA LOD: 0.01 DF: 98 P50: 0.14 P90: 0.57 cis-DCCA LOD: 0.07 DF: 64.9 P50: 0.09 P90: 0.30 cis-DBCA LOD: 0.07 DF: 68.3 P50: 0.11 P90: 0.39 |
NR | Viel et al., 2017, 2015 [29,54] |
| France (Pilot-ELFE study) |
Pregnant women (n = 93) | 2007; Spot urine at delivery |
Acidic hydrolysis; GC-MS/MS: QC: Isotope-labelled internal standards; Creatinine |
LOD: 0.046 DF: 100 P50: 0.37 P95: 3.06 |
4F-3PBA LOD: 0.1 DF: 2 DCCA LOD: 0.04 DF: 100 P50: 0.34 P95: 4.13 CFCA LOD: 0.004 DF: 18 P95: 0.15 cis-DBCA LOD: 0.02 DF: 86 P50: 0.13 P95: 0.54 |
NR, method validation study | Hardy et al., 2021 [55] |
| France (ENNS) | Adults, 18–74 y (n = 396), nationally representative | 2006–2007; FMV |
Acidic hydrolysis/; GC- MS/MS; QC: Internal standards and quality control samples; Creatinine |
LOD: 0.03 DF: 98.1 P50: 0.65 P95: 4.36 |
4F-3PBA LOD: 0.03 DF: 29.8 P95: 0.82 trans-DCCA LOD: 0.03 DF: 86.1 P50: 0.31 P95: 3.85 cis-DCCA LOD: 0.03 DF: 56.1 P50: 0.13 P95: 1.42 cis-DBCA LOD: 0.03 DF: 83.1 P50: 0.36 P95:2.33 |
Associations with higher intake of solanaceous (e.g., tomatoes, aubergines) vegetables and shellfish and non-significantly with fish intake. | Fréry et al., 2017 [20] |
| France, Limousine region | Adults, 24–62 y, (n = 39) |
No information on sampling year; Spot urine | Acidic hydrolysis; LC-MS/MS; QC: Isotope-labelled internal standards; Creatinine |
LOD: 0.015 DF: 100 P50: 0.63 P95: 2.05 |
LOD: 0.015 all metabolites 4F-3PBA DF: 10 P95: NR trans-DCCA DF: 100 P50: 0.33 P95: 1.10 cis-DCCA DF: 97 P50: 0.19 P95: 0.49 cis-DBCA DF: 97 P50: 0.18 P95: 0.69 |
NR, method development study | Le Grand et al., 2012 [56] |
| Germany | Adults, 26–58 y (n = 38) | 2012; Spot urine |
Acidic hydrolysis; GC-MS/MS; QC: Isotope-labelled internal standards; Creatinine |
LOQ: 0.01 DF: 100 P50: 0.22 P95: 1.79 |
LOQ: 0.01 all metabolites 4F-3PBA DF: 5 trans-DCCA DF: 100 P50: 0.17 P95: 0.92 cis-DCCA DF: 100 P50: 0.08 P95: 0.57 cis-DBCA DF: 80 P50: 0.04 P95: 0.28 CFCA DF: 90 P50: 0.04 P95: 0.98 |
NR, method development study | Schettgen et al., 2016 [24] |
| Germany (GerES IV) |
Children, 3–14 y (n = 598), nationally representative | 2003–2006; Spot urine |
NR but references to previous GerES-studies | LOQ: 0.1 DF: 98 P50: 0.43 P95: 3.80 |
LOQ: 0.01 for all metabolites trans-DCCA DF: 86 P50: 0.25 P95: 2.46 cis-DCCA DF: 60 P50: 0.12 P95: 1.00 |
Girls had higher concentrations than boys, no information on determinants | Schulz et al., 2009 [21] |
| Germany (GerES IV), pilot study |
Children, 2–17 y (n = 396), Berlin and two rural areas | 2001–2002; Morning spot urine |
No information on deconjugation; GC-MS; Internal standards and participation in G-EQUAS |
LOQ: 0.1 DF: 90 P50: 0.29 P95: 2.35 |
LOQ: 0.01 for all metabolites 4F-3PBA DF: <1 trans-DCCA DF: 74 P50: 0.19 P95: 1.73 cis-DCCA DF: 56 P50: 0.11 P95: 0.74 cis-DBCA DF: 22 P95: 0.52 |
3-PBA, cis- and trans-DCCA negatively associated with child age and positively with permethrin in house dust, use of biocides indoor, consumption of boiled vegetables, and Berlin sampling area | Becker et al., 2006 [43] |
| Germany | Occupational exposure: male workers exposed to pesticides in agriculture (n = 19), pest control (n = 15) or greenhouses (n = 2) | Sampling year is unclear; 24 h urine collected after pyrethroid application, repeated sampling for some workers |
Acidic hydrolysis; GC-MS; Internal standards; Creatinine |
LOD: 0.5 DF: 67–100 P50: 0.6–2.9 μg/g crea |
4F-3PBA LOD: 0.5 DF: 0–3 DCCA LOD: 0.5 DF: 46–100 P50: <LOD–2.9 μg/g crea cis-DBCA LOD: 0.3 DF: 0–71 P50: <LOD–0.50 μg/g crea |
Highest concentration of 3-PBA and DCCA in pest control workers. | Hardt and Angerer 2003 [47] |
| Germany, Frankfurt am Main | General population, 0–65 y (n = 1177), urban residence | 1998; Spot urine |
Acidic hydrolysis; GS-MS; QC: internal standards and participation in G-EQUAS; Creatinine |
NR | LOD: 0.1–0.2 for all metabolites 4F-3PBA DF: 16.4 P95: 0.27 trans-DCCA DF: 65.3 P50: 0.24 P95:1.43 cis-DCCA DF: 29.4 P95: 0.51 cis-DBCA DF: 19.3 P95: 0.30 |
No significant correlation with age, smoking habits, sampling season or permethrin in dust | Heudorf and Angerer 2001 [57], Schettgen et al., 2002 [58] |
| Germany, Frankfurt am Main | Children 0–17.9 y, (n = 673), urban residence | 1998; Spot urine |
Acidic hydrolysis; GC-MS; QC: internal standards and participation in G-EQUAS; Creatinine |
NR | LOD 0.1–0.2 for all metabolites, DFs not provided 4F-3PBA P95: 0.30 trans-DCCA P50: 0.25 P95: 1.22 cis-DCCA P95: 0.44 cis-DBCA P95: 0.30 |
No correlation with age of the children or permethrin in dust | Heudorf et al., 2004 [59] |
| Germany | Residents after pyrethroid used indoors, (n = 56) |
1996–1998; collected before and day 1 and 3, and 4–6 months and 10–12 months after application, Spot and 24 h urine |
Acidic hydrolysis; GC-MS; QC: internal standards; Creatinine |
LOD: 0.2 DF: 5–28 P95: 0.2–1.8 |
4F-3PBA DF: 0–5 P95: <LOD–LOD trans-DCCA DF: 4–32 P95: <LOD–1.5 cis-DCCA DF: 3–21 P95: >LOD–0.6 cis-DBCA DF: 0–6 P95: <LOD–0.3 |
Highest concentrations seen 1 and 3 days after application but most samples were below LOD | Leng et al., 2003 [51] |
| Germany, Hannover |
Residents after pyrethroid (permethrin) used indoors in homes with carpets of wool, 9 months–78 y (n = 145), | 1996–1998, 24 h urine from adults, spot urine from young children |
Method not described but reference to Leng et al., 1997 (se study above) | LOD: 0.2 DF: 28 P95: 0.90 |
DCCA LOD: 0.2 DF: 19 P95: 1.50 |
Most samples below LOD, children tended to have higher detection frequency than adults although not statistically significant (few children included) | Berger-Preiss et al., 2002 [52] |
| UK | Adults, 63.8 ± 10.4 y (n = 111, representing 65 twin pairs from the TwinsUK-cohort) | No information | Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards |
LOD: 0.015 DF: 80 P50: 0.12 P75: 1.8 |
4F-3PBA LOD: 0.015 DF: 10 trans-DCCA LOD: 0.02 DF: 96.9 P50: 0.18 P75: 1.2 cis-DCCA LOD: 0.01 DF: 98.4 P50: 0.07 P75: 0.38 cis-DBCA LOD: 0.015 DF: 95.4 P50: 0.08 P75: 0.42 |
No difference between urban or rural residence, not possible to investigate impact of organic food as planned because of few participants with high intake of organic food | Mesnage et al., 2022 [60] |
| UK, Lothian, Kent and Norfolk | Farmers and residents in agricultural areas, <100 m from sprayed fields, Adults >18 y (n = 238) and children 4–12 y (n = 58); 140 with repeated samples | 2011–2012; FMV within 2 days after spraying events and outwith the spraying season (140 with repeated samples) |
Enzymatic hydrolyses; LC-MS/MS; QC: Participate in G-EQUAS; Creatinine |
cis/trans-DCCA LOD: 1.0 DF: 7 Max conc (μg/g crea): Outwith spraying season: 15.4 Within spraying season, 10.8 After spray event: 7.0 |
No difference related to spraying activity or spraying season but low detection frequency (high LOD) | Galea et al., 2015 [48] | |
| UK, | Randomly sought adult volunteers, >18 y (n = 405), nationwide |
NI on sampling year (after 2005); Spot urine |
No description but all analyses were carried out by an ISO9001: 2008 accredited laboratory with internal quality control, participation in G-EQUAS; Creatinine |
LOD: 0.5 nM DF: 87 P95: 6.1 |
LOD: 0.5 nM for all metabolites trans-DCCA DF: 66 P95: 1.6 cis-DCCA DF: 54 P95: 0.8 cis-DBCA DF: 50 P95: 1.6 CFCA DF: 41 P95: 3.2 |
NR | Bevan et al., 2013 [22] |
| Eastern EU | |||||||
| Poland, Łódź | Women, 25–45 y (n = 450) attending a fertility clinic, | 2017–2019; 1–2 spot urine per IVF cycle (total 739 urine samples) |
No information on deconjugation; GC–MS; QC: No information; Specific gravity |
LOD: 0.1 DF: 68 GM: 0.35 GSD: 2.66 |
LOD: 0.1 for all metabolites trans-DCCA DF: 45 GM: 0.43 GSD: 2.48 cis-DCCA DF: 34 GM: 0.29 GSD: 2.18 cis-DBCA DF: 22 GM: 0.28 GSD: 2.51 |
NR | Radwan et al., 2022 [61] |
| Poland Łódź | Young men, 19–33 y (n = 306), urban area residence | 2015–2018; morning spot urine |
Acidic hydrolysis; GC-MS; QC: Internal standards (spiked urine samples); participation in G-EQUAS; Specific gravity |
LOD: 0.1 DF: 69 P50: 0.20 P95: 1.67 |
LOD: 0.1 for all metabolites trans-DCCA DF: 76 P50: 0.26 P95: 2.07 cis-DCCA DF: 36 P95: 0.94 cis-DBCA DF: 32 P95: 0.93 |
trans-DCCA and 3-PBA associated with dog ownership, pesticide use indoor and household pets. Seeds and nuts consumption was also associated with higher 3-PBA and vegetable juice intake with higher trans-DCCA. | Rodzaj et al., 2021 [45] |
| Poland | Women, 25–39 y, (n = 511), attending a fertility clinic | No information on sampling year (likely after funding grant in 2017); Spot urine |
Acidic hydrolysis; GC–MS; QC: Isotope-labelled internal standards and participation in G-EQUAS; Specific gravity |
LOD: 0.1 DF: 66.5 P50: 0.25 P95: 2.28 |
LOD: 0.1 for all metabolites trans-DCCA DF: 34.9 P95: 3.47 cis-DCCA DF: 32.8 P95: 1.54 cis-DBCA DF: 19.4 P95: 2.17 |
NR | Jurewicz et al., 2020 [62] |
| Poland, Gdansk, | General population, 5–77 y (n = 132), Urban residence |
2010–2011; FMV |
Acidic hydrolysis; GC-MS; QC: Internal standards; Creatinine |
LOD: 0.1 DF: 80 P50: 0.26 P95: 1.15 |
LOD: 0.1 for all metabolites trans-DCCA DF: 7 P95: 0.12 cis-DCCA DF: 8 P95: 0.15 cis-DBCA DF: 11 P95: 0.31 |
No age or sex related differences in 3-PBA | Wielgo-mas et al., 2013 [63] |
| Poland, North | Children <18 y (n = 184) and parents (n = 190); Urban or rural residence |
2012; FMV |
Acidic hydrolysis; GC-MS; QC: Internal standards, participation in G-EQUAS; Creatinine |
LOD: 0.1 DF: 82.4 P50: 0.25 (all); 0.29 (children); 0.23 (adults) P95: 1.24 (all) |
LOD: 0.1 for all metabolites trans-DCCA DF: 46.8 P95: 1.00 cis-DCCA DF: 46 P95: 0.89 cis-DBCA DF: 17.1 P95: 0.50 |
Higher concentrations of all metabolites in rural areas, higher 3-PBA in participants using pesticide containing pet care products in the last 6 months for both rural and urban locations. Higher 3-PBA in children than adults | Wielgo-mas and Piskuno-wicz 2013 [40] |
| Poland, Łódź | Adult men, 23–45 y (n = 195) recruited from fertility clinic | 2008–2011; Spot urine |
Acidic hydrolysis; GC-MS; QC: participation in G-EQUAS; Creatinine |
LOD: 0.1 DF: 71.6 P50: 0.16 P95: 0.50 |
LOD: 0.1 for all metabolites Trans-DCCA DF: 65.5 P50: 0.16 P95: 0.62 cis-DCCA DF: 58 P50: 0.12 P95: 0.46 cis-DBCA DF: 16.8 P95: 0.27 |
NR | Radwan et al., 2015, Jurewicz et al., 2016 [64,65] |
| Slovenia, Ljubljana (PHIME) | Children 7–8 y (n = 168) and their mothers (n = 168) | 2016; Spot urine |
Enzymatic hydrolyses; UPLC-MS/MS; QC: Isotope-labelled internal standards and participation in G-EQUAS; Specific gravity and creatinine |
LOD: 0.018 Children DF: 80 P50: 0.40 Max: 12.0 Mothers DF: 76 P50: 0.24 Max: 12.0 |
4F-3PBA LOD: 0.019 Children DF: 30 Max: 0.53 Mothers DF: 16 Max: 0.73 |
Children had higher concentrations than mothers, no significant associations with demographic variables (education, smoking, BMI etc.) | Bravo et al., 2020 [41] |
| Southern EU | |||||||
| Cyprus, Limassol (ORGANIKO) | Children, 10–11 y (n = 177), urban area | 2017; FMV |
No information on deconjugation; LC-MS/ MS; QC: Analysed in HBM4EU-accredited lab; Creatinine |
LOQ: 0.1 DF: 100 P50: 1.93 P95: 6.59 |
LOQ: 0.2 for DBCA, 0.1 for all other metabolites 4F-3PBA DF: 6 trans-DCCA DF: 100 P50: 0.93 P95: 4.28 cis-DCCA DF: 99 P50: 0.61 P95: 2.22 cis-DBCA DF: 97 P50: 0.60 P95: 3.85 CFCA DF: 30 P95: 0.27 |
Cis- and trans-DCCA were negatively associated with maternal education level and paternal education positively associated with DBCA (binary analyses) | Makris et al., 2022 [33] |
| Greece, Athens | Adults, (n = 40), part of multi-country study | 2012–2014; Spot urine |
Enzymatic hydrolyses; HPLC-MS-MS; QC: Isotope-labelled internal standards; Creatinine |
LOQ: 0.003 DF: 100 P50: 0.50 Max: 6.6 |
4F-3PBA LOQ: 0.002 DF: 80 P50: 0.01 Max: 0.2 trans-DCCA LOQ: 0.002 DF: 100 P50: 0.6 Max: 4.0 cis-DCCA LOQ: 0.003 DF: 97.5 P50: 0.8 Max: 17.0 cis-DBCA LOQ: 0.019 DF: 50 P50: 0.02 Max: 6.0 |
NR | Li and Kannan 2018 [66] |
| Italy, NACII (PHIME) | Children 7 y (n = 199) | 2014–2015; Spot urine |
Enzymatic hydrolyses; UPLC-MS-MS; QC: Isotope-labelled internal standards and participation in G-EQUAS; Specific gravity |
LOD: 0.018 DF: 81 P50: 0.56 Max: 36.0 |
4F-3PBA LOD: 0.019 DF: 24 Max: 1.3 |
No significant associations with population characteristics (education, age etc) or fish intake in binary analyses | Bravo et al., 2019 [67] |
| Italy, Rome | Adults (n = 55) patients referred to hospital for skin diseases |
No information on sampling year; Spot urine |
Acidic hydrolyses; GC-MS/SIM, QC: Internal standards; Creatinine |
LOQ: 0.5 Males: DF: 34.5 Mean (SD): 0.52 (0.32) μg/g crea Females: DF: 65.5 Mean (SD): 0.74 (0.61) μg/g crea |
Small sample size hamper significant results but tendencies to higher 3-PBA in samples collected in spring than winter, in females and among smokers, and if insecticides had been used inside or outdoor (binary analyses). Significantly associated with high intake of cooked vegetables | Fortes et al., 2013 [44] | |
| Italy, Ragusa | Occupational, male greenhouse male workers (n = 30) exposed to alpha-cypermethrin and office workers as controls (n = 30) |
No information on sampling year; Spot urine collected 3 months after occupational use of alpha-cypermethrin (Fastac) | Acidic hydrolysis; GS-MS; QC: no information; Creatinine |
LOD: 0.04 Mean (SD): 7.8 (2.1) μg/g crea for workers <LOD for controls |
Higher 3-PBA among workers occupationally exposed to alpha-cypermethrin | Costa et al., 2013 [50] | |
| Italy, EPIC (substudy) | Adults (n = 69, 51 from Florence and 18 from Ragusa) | 1993–1998; 24 h urine |
Acidic hydrolysis; GC-MS; QC: Internal spiked standards; Creatinine |
LOD: 2.5 nmol/L DF: 53.6 P50: 5.6 nmol/day Max: 52.8 nmol/day |
Higher concentrations in Florence than Ragusa, tended to be higher in overweight/obese individuals | Saieva et al., 2004 [68] | |
| Portugal, Oporto | Occupational, non-organic (n = 85) and organic (n = 36) farmers, controls from same area (n = 61) |
No information on sampling year; Spot urine | No information on deconjugation; ELISA Immunoassay, QC: internal standards; Creatinine |
Mean Total pyrethroid, μg/mmol crea, Organic: 0.06 Non-organic: 0.08 Controls: 0.13 |
No significant differences | Costa et al., 2014 [31] | |
| Spain, INMA-Granada-Cohort | Male adolescents, 15–17 y (n = 134), 71.6% from urban area | 2017–2019; FMV |
No information on deconjugation; LC-MS/MS; QC: no information; Creatinine |
LOD: 0.12 DF: 19.4 P95: 0.25 |
NR | Freire et al., 2021 [30] | |
| Spain, Valencia Region, BIOVAL | Children, 5–12 y (n = 568), 78% from urban area | 2016; FMV |
Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards and participation in G-EQUAS; Creatinine |
LOQ: 0.50 DF: 79 P50: 1.63 P95: 11.57 |
4F-3PBA LOQ: 0.13 DF: 4 DCCA LOQ: 5.00 DF: 20 P95: 46.7 cis-DBCA LOQ: 1.25 DF: 14 P95: 5.6 |
Intake of fresh vegetables within 72 h | Fernán-dez et al., 2020 [34] |
| Spain, Valencia | Women (n = 116), lactating mothers, 2–8 weeks after birth, 80% from urban areas | 2015; FMV |
Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards and participation in G-EQUAS; Creatinine |
LOQ: 0.50 DF: 65 P50: 1.7 P95: 18.8 |
No significant associations with population characteristics or dietary variables | Fernán-dez et al., 2020 [35] | |
| Spain, Catalonia and Galicia | Occupational, adults (n = 125), 36% farmworkers | No information on sampling year; Spot urine | Enzymatic hydrolyses; UPLC-MS-MS; QC: Isotope-labelled internal standards and participation in G-EQUAS; Specific gravity and creatinine |
LOD: 0.018 DF: 82 P50: 1.5 Max: 20.5 |
4F-3PBA LOD: 0.019 DF: 54 P50: 0.08 Max: 0.34 |
Higher 3-PBA concentrations in farmworkers | Gari et al., 2018 [49] |
| Spain, Valencia | Children 6–11 y (n = 125) | 2010; FMV |
Enzymatic hydrolyses; LC-MS/MS; QC: Isotope-labelled internal standards; Creatinine |
LOQ: 0.8 DF: 23 P95: 12.3 μg/g crea |
4F-3PBA LOQ: 0.2 DF: 0 trans-DCCA LOQ: 0.4 DF: 26 P95: 4.44 μg/g crea cis-DCCA LOQ: 0.4 DF: 10 P95: 1.26 μg/g crea cis-DBCA LOQ: 0.8 DF: 23 P95: 3.77 μg/g crea |
No significant associations with population characteristics or dietary variables | Roca et al., 2014 [69] |
DF: detection frequency (%>LOD/LOQ); FMV: first morning void; German External Quality Assessment Scheme (G-EQUAS); NR: not reported; P50: 50th percentile (median); P25, P75, P90, P95: the respective percentile; GM: geometric mean; GSD: geometric standard derivation; SD: standard derivation; GW: gestational week; 3-PBA: 3-phenoxybenzoic acid; 4-F-3-PBA: 4-fluoro-3-phenoxybenzoic acid; cis-DCCA: cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid; trans-DCCA: trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid; cis-DBCA: cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid; CFCA (3-(-2-Chloro-3,3,3-trifluoroprop-1-enyl)-2,2- dimethyl-cyclopropane-carboxylic acid; crea: creatinine.