Sub-Part-Per-Billion Level Sensing of Fentanyl Residues from Wastewater Using Portable Surface-Enhanced Raman Scattering Sensing

Abstract

Detection of illicit drug residues from wastewater provides a new route toward community-level assessment of drug abuse that is critical to public health. However, traditional chemistry analytical tools such as high-performance liquid chromatography in tandem with mass spectrometry (HPLC-MS) cannot meet the large-scale testing requirement in terms of cost, promptness, and convenience of use. In this article, we demonstrated ultra-sensitive and portable surface-enhanced Raman scattering sensing (SERS) of fentanyl, a synthetic opioid, from sewage water and achieved quantitative analysis through principal component analysis and partial least-squares regression. The SERS substrates adopted in this application were synthesized by in situ growth of silver nanoparticles on diatomaceous earth films, which show ultra-high sensitivity down to 10 parts per trillion in artificially contaminated tap water in the lab using a commercial portable Raman spectrometer. Based on training data from artificially contaminated tap water, we predicted the fentanyl concentration in the sewage water from a wastewater treatment plant to be 0.8 parts per billion (ppb). As a comparison, the HPLC-MS confirmed the fentanyl concentration was below 1 ppb but failed to provide a specific value of the concentration since the concentration was too low. In addition, we further proved the validity of our SERS sensing technique by comparing SERS results from multiple sewage water treatment plants, and the results are consistent with the public health data from our local health authority. Such SERS sensing technique with ultra-high sensitivity down to sub-ppb level proved its feasibility for point-of-care detection of illicit drugs from sewage water, which is crucial to assess public health.

A surface‐enhanced Raman sensor for trace identification and analysis of high‐priority drugs of abuse with portable and handheld Raman devices

“…[ 27–34 ] Additional studies have reported the SERS detection of a wide range of abused drugs in solution, [ 35 ] such as cocaine, [ 36 ] amphetamines, [ 37,38 ] ring substituted amphetamines, [ 39–41 ] bath salts, [ 42,43 ] opioids [ 21,35,44–48 ] including drug mixtures laced with fentanyl, [ 49–53 ] hallucinogens, [ 27,54,55 ] marijuana active ingredients, [ 35 ] and other prescription and over the counter drugs. [ 35 ] Sensitivity at low detection limits is possible even at sub‐nanogram per milliliter levels, as has been observed for fentanyl in wastewater [ 11 ] and reported in aqueous solution. [ 21 ] Most of the reported drug studies with SERS of biofluids have been performed in urine or simulated urine.…”

“…One technology that offers great promise in overcoming such limitations is surface-enhanced Raman spectroscopy (SERS). SERS is versatile in its use and application and offers the ability to detect various drugs of concern at low concentration levels directly from surfaces, [9] as trace components in tablets or powders, [10] in wastewater, [11] and in biofluids, [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] including saliva. [27][28][29][30][31][32][33][34] Additional studies have reported the SERS detection of a wide range of abused drugs in solution, [35] such as cocaine, [36] amphetamines, [37,38] ring substituted amphetamines, [39][40][41] bath salts, [42,43] opioids [21,35,[44][45][46][47][48] including drug mixtures laced with fentanyl, [49][50][51]…”

Quantitative Sensing of Domoic Acid from Shellfish Using Biological Photonic Crystal Enhanced SERS Substrates

“…Functionalization of the DE substrates was achieved using an in situ growth protocol previously optimized and published by our group [ 24 , 25 , 26 ]. Briefly, the DE coated substrates were soaked in a 1:1 solution of SnCl 2 and HCl (20 mM) for 30 min to allow effective binding of Sn 2+ ions on the silica rich diatom skeleton.…”

Forensic Identification of Fentanyl and its Analogs by Electrochemical-Surface Enhanced Raman Spectroscopy (EC-SERS) for the Screening of Seized Drugs of Abuse

“…The use of SERS for analyzing drug analytes has become quite popular. In fact, the investigation of many drugs of abuse has been explored with SERS including amphetamines, MDMA, and amphetamine-like substances (Bell et al, 2000;Sägmüller et al, 2001;Faulds et al, 2002); barbiturates (Farquharson and Lee, 2000); mephedrone (Mabbott et al, 2013); and other types of drugs including cocaine, morphine, hydrocodone, fentanyl, codeine, diazepam, and fentanyl analogs (Farquharson et al, 2011;Rana et al, 2011;Leonard et al, 2017;Haddad et al, 2018;Shende et al, 2019b;Wang et al, 2019, Smith et al, 2021Wang H. et al, 2021;Wang L. et al, 2021;Wilson et al, 2021;Zhang et al, 2021). The use of SERS has also enabled the analysis of these drug analytes in toxicological specimens such as urine, saliva, and blood (Inscore et al, 2011;Andreou et al, 2013;D'Elia et al, 2018;Shende et al, 2019a;Sivashanmugan et al, 2019;Han et al, 2021).…”