Retrospective nationwide occurrence of fipronil and its degradates in U.S. wastewater and sewage sludge from 2001 - 2016

Akash M. Sadaria, Cameron W. Labban, Joshua C. Steele, Megan M. Maurer, Rolf Halden

Research output: Contribution to journalArticle

Abstract

The insecticide fipronil is under regulatory scrutiny worldwide for its toxicity to pollinators and aquatic invertebrates. We conducted the first U.S. nationwide, longitudinal study of sewage sludges for fiproles, i.e., the sum of fipronil and its major degradates (fipronil sulfone, sulfide, amide, and desulfinyl). Archived sludges (n = 109) collected in three campaigns over 15 years were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing ubiquitous fiprole occurrence (0.2–385.3 μg/kg) since 2001 and a significant increase (2.4 ± 0.3 fold; p < 0.005) both from 2001 to 2006/7 and from 2001 to 2015/6, but not a significant increase from 2006/7 to 2015/6 (p = 0.275). A geospatial analysis showed fiprole levels in municipal sludges to be uncoupled from agricultural use of fipronil on cropland surrounding sampled municipalities, thus pointing to non-agricultural uses (i.e., spot-on treatment and urban pest control) as a major source of fiprole loading to wastewater. Whereas anaerobic digestion was correlated with increases in fipronil sulfide at the expense of parental fipronil (p < 0.001), total fiprole levels in sewage sludges were similar regardless of the solids treatment approach applied (p = 0.519). Treatment plant effluent available from 12 facilities in 2015/6 contained fiproles at 0.3–112.9 ng/L, exceeding the United States Environmental Protection Agency (USEPA) aquatic invertebrate life benchmark for chronic fipronil exposure (11 ng/L) in 67% of cases. Whereas the USEPA identified fipronil in sludge only recently (2015), retrospective analyses and modeling conducted here show contaminant ubiquity and nationwide increases of fiprole mass (compared to 2001 levels) in U.S. municipal sludge (1140 ± 230 kg in 2015/6), and treated effluent nationwide (1970 ± 390 kg in 2015/6) over the past 15 years.

Original languageEnglish (US)
Pages (from-to)465-473
Number of pages9
JournalWater Research
DOIs
StatePublished - May 15 2019

Fingerprint

Environmental Protection Agency
Sewage sludge
Effluents
Wastewater
Pest control
wastewater
Insecticides
Anaerobic digestion
Liquid chromatography
Amides
Dilution
Isotopes
Mass spectrometry
Toxicity
sludge
Impurities
invertebrate
sulfide
effluent
Invertebrates

Keywords

  • Fipronil
  • Sewage sludge
  • Treated effluent
  • United States

ASJC Scopus subject areas

  • Ecological Modeling
  • Water Science and Technology
  • Waste Management and Disposal
  • Pollution

Cite this

Retrospective nationwide occurrence of fipronil and its degradates in U.S. wastewater and sewage sludge from 2001 - 2016. / Sadaria, Akash M.; Labban, Cameron W.; Steele, Joshua C.; Maurer, Megan M.; Halden, Rolf.

In: Water Research, 15.05.2019, p. 465-473.

Research output: Contribution to journalArticle

Sadaria, Akash M. ; Labban, Cameron W. ; Steele, Joshua C. ; Maurer, Megan M. ; Halden, Rolf. / Retrospective nationwide occurrence of fipronil and its degradates in U.S. wastewater and sewage sludge from 2001 - 2016. In: Water Research. 2019 ; pp. 465-473.
@article{b9cc146ad5804ee781e3eb76a9212e66,
title = "Retrospective nationwide occurrence of fipronil and its degradates in U.S. wastewater and sewage sludge from 2001 - 2016",
abstract = "The insecticide fipronil is under regulatory scrutiny worldwide for its toxicity to pollinators and aquatic invertebrates. We conducted the first U.S. nationwide, longitudinal study of sewage sludges for fiproles, i.e., the sum of fipronil and its major degradates (fipronil sulfone, sulfide, amide, and desulfinyl). Archived sludges (n = 109) collected in three campaigns over 15 years were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing ubiquitous fiprole occurrence (0.2–385.3 μg/kg) since 2001 and a significant increase (2.4 ± 0.3 fold; p < 0.005) both from 2001 to 2006/7 and from 2001 to 2015/6, but not a significant increase from 2006/7 to 2015/6 (p = 0.275). A geospatial analysis showed fiprole levels in municipal sludges to be uncoupled from agricultural use of fipronil on cropland surrounding sampled municipalities, thus pointing to non-agricultural uses (i.e., spot-on treatment and urban pest control) as a major source of fiprole loading to wastewater. Whereas anaerobic digestion was correlated with increases in fipronil sulfide at the expense of parental fipronil (p < 0.001), total fiprole levels in sewage sludges were similar regardless of the solids treatment approach applied (p = 0.519). Treatment plant effluent available from 12 facilities in 2015/6 contained fiproles at 0.3–112.9 ng/L, exceeding the United States Environmental Protection Agency (USEPA) aquatic invertebrate life benchmark for chronic fipronil exposure (11 ng/L) in 67{\%} of cases. Whereas the USEPA identified fipronil in sludge only recently (2015), retrospective analyses and modeling conducted here show contaminant ubiquity and nationwide increases of fiprole mass (compared to 2001 levels) in U.S. municipal sludge (1140 ± 230 kg in 2015/6), and treated effluent nationwide (1970 ± 390 kg in 2015/6) over the past 15 years.",
keywords = "Fipronil, Sewage sludge, Treated effluent, United States",
author = "Sadaria, {Akash M.} and Labban, {Cameron W.} and Steele, {Joshua C.} and Maurer, {Megan M.} and Rolf Halden",
year = "2019",
month = "5",
day = "15",
doi = "10.1016/j.watres.2019.02.045",
language = "English (US)",
pages = "465--473",
journal = "Water Research",
issn = "0043-1354",
publisher = "Elsevier Limited",

}

TY - JOUR

T1 - Retrospective nationwide occurrence of fipronil and its degradates in U.S. wastewater and sewage sludge from 2001 - 2016

AU - Sadaria, Akash M.

AU - Labban, Cameron W.

AU - Steele, Joshua C.

AU - Maurer, Megan M.

AU - Halden, Rolf

PY - 2019/5/15

Y1 - 2019/5/15

N2 - The insecticide fipronil is under regulatory scrutiny worldwide for its toxicity to pollinators and aquatic invertebrates. We conducted the first U.S. nationwide, longitudinal study of sewage sludges for fiproles, i.e., the sum of fipronil and its major degradates (fipronil sulfone, sulfide, amide, and desulfinyl). Archived sludges (n = 109) collected in three campaigns over 15 years were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing ubiquitous fiprole occurrence (0.2–385.3 μg/kg) since 2001 and a significant increase (2.4 ± 0.3 fold; p < 0.005) both from 2001 to 2006/7 and from 2001 to 2015/6, but not a significant increase from 2006/7 to 2015/6 (p = 0.275). A geospatial analysis showed fiprole levels in municipal sludges to be uncoupled from agricultural use of fipronil on cropland surrounding sampled municipalities, thus pointing to non-agricultural uses (i.e., spot-on treatment and urban pest control) as a major source of fiprole loading to wastewater. Whereas anaerobic digestion was correlated with increases in fipronil sulfide at the expense of parental fipronil (p < 0.001), total fiprole levels in sewage sludges were similar regardless of the solids treatment approach applied (p = 0.519). Treatment plant effluent available from 12 facilities in 2015/6 contained fiproles at 0.3–112.9 ng/L, exceeding the United States Environmental Protection Agency (USEPA) aquatic invertebrate life benchmark for chronic fipronil exposure (11 ng/L) in 67% of cases. Whereas the USEPA identified fipronil in sludge only recently (2015), retrospective analyses and modeling conducted here show contaminant ubiquity and nationwide increases of fiprole mass (compared to 2001 levels) in U.S. municipal sludge (1140 ± 230 kg in 2015/6), and treated effluent nationwide (1970 ± 390 kg in 2015/6) over the past 15 years.

AB - The insecticide fipronil is under regulatory scrutiny worldwide for its toxicity to pollinators and aquatic invertebrates. We conducted the first U.S. nationwide, longitudinal study of sewage sludges for fiproles, i.e., the sum of fipronil and its major degradates (fipronil sulfone, sulfide, amide, and desulfinyl). Archived sludges (n = 109) collected in three campaigns over 15 years were analyzed by isotope dilution liquid chromatography tandem mass spectrometry, revealing ubiquitous fiprole occurrence (0.2–385.3 μg/kg) since 2001 and a significant increase (2.4 ± 0.3 fold; p < 0.005) both from 2001 to 2006/7 and from 2001 to 2015/6, but not a significant increase from 2006/7 to 2015/6 (p = 0.275). A geospatial analysis showed fiprole levels in municipal sludges to be uncoupled from agricultural use of fipronil on cropland surrounding sampled municipalities, thus pointing to non-agricultural uses (i.e., spot-on treatment and urban pest control) as a major source of fiprole loading to wastewater. Whereas anaerobic digestion was correlated with increases in fipronil sulfide at the expense of parental fipronil (p < 0.001), total fiprole levels in sewage sludges were similar regardless of the solids treatment approach applied (p = 0.519). Treatment plant effluent available from 12 facilities in 2015/6 contained fiproles at 0.3–112.9 ng/L, exceeding the United States Environmental Protection Agency (USEPA) aquatic invertebrate life benchmark for chronic fipronil exposure (11 ng/L) in 67% of cases. Whereas the USEPA identified fipronil in sludge only recently (2015), retrospective analyses and modeling conducted here show contaminant ubiquity and nationwide increases of fiprole mass (compared to 2001 levels) in U.S. municipal sludge (1140 ± 230 kg in 2015/6), and treated effluent nationwide (1970 ± 390 kg in 2015/6) over the past 15 years.

KW - Fipronil

KW - Sewage sludge

KW - Treated effluent

KW - United States

UR - http://www.scopus.com/inward/record.url?scp=85062680385&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85062680385&partnerID=8YFLogxK

U2 - 10.1016/j.watres.2019.02.045

DO - 10.1016/j.watres.2019.02.045

M3 - Article

SP - 465

EP - 473

JO - Water Research

JF - Water Research

SN - 0043-1354

ER -