Chromatography Research International

Review Article

New Developments in Liquid Chromatography Mass Spectrometry for the Determination of Micropollutants

Table 1

Determination of pharmaceutical compounds in environmental samples by LC coupled to mass spectrometry.


Compounds	Samples	Extraction	Determination	Analytical parameters	Reference

SMMX, SDMX, SMXZ, STZL, SCPD, SMRZ, SMTZ, OXTC, MCLN, DOXN, MECN, CTCL, DEMN, and TCLN	River water, sewage and agricultural wastewater	Online SPE	LC-MS ESI (PI)	Recoveries: 74.3–116.5% LOQs: 0.09–0.11 g·L⁻¹	[40]

ENR, LOM, LVFX, FLX, SPFX, AMX, OTC, and SQX	Lake water, river water and sewage effluent	MIP	LC-Qq-IT ESI (PI) MRM	Recoveries: 76.3–94.2% RSD < 9.1% LODs: 3.2–6.2 ng·L⁻¹	[41]

4-Acetamidophenol, carbamazepine, (+)-cis-diltiazem hydrochloride, norfluoxetine hydrochloride, ranitidine hydrochloride, sulfamethoxazole, caffeine, trimethoprim, atorvastatin, lovastatin, levofloxacin, and sertraline	River water	SPE	UHPLC-QqQ ESI (PI) MRM	Mean recovery: 77.9% Mean RSD: 7.3% LODs < 4.1 ng·L⁻¹	[47]

28 basic/neutral pharmaceuticals	River water	SPE	UHPLC-QqQ ESI (PI) MRM	LOQs: 0.3–50 ng·L⁻¹	[48]

18 androgens and progestogens	River water and wastewater	SPE	UHPLC-QqQ ESI (PI) MRM	Recoveries: 77–100% RSD: 1.7–12% LODs: 0.01–50 ng·L⁻¹	[51]

49 pharmaceuticals and 6 metabolites	Wastewater	SPE	UHPLC-QqLIT ESI (PI and NI) MRM and IDA	Recoveries: 55–111% RDS < 5% LODs: 0.02–50 ng·L⁻¹	[52]

Ketoprofen, naproxen, diclofenac, and ibuprofen	Sewage sludge	HF-LPME	LC-MS ESI (NI) SIM	Recoveries: 52–63% RSDs: 0.5–7% LODs < 10 g·L^-1	[58]

Levofloxacin, norfloxacin, ciprofloxacin, and enrofloxacin	Marine sediments and sewage sludge	MAME	LC-QqQ ESI (PI) MRM	Recoveries > 73% RSD < 8% LODs: 0.15–0.55 g·kg⁻¹	[60]

Ibuprofen, diclofenac, and salicylic acid	Wastewater	HF-LPME	LC-MS/MS	Recoveries: 52–100% RSDs: 1.1–1.6%. LODs: 20–300 ng·L⁻¹	[114]

Ibuprofen, naproxen, clofibric acid, piroxicam, ketorolac, bezafibrate, fenoprofen, diclofenac, and indomethacin	Wastewater	HF-LPME	LC-MS/MS	Recoveries: 80–111% RSDs: 3.4–32% LOQs: 0.5–42 ng·L⁻¹	[115]

Estrone, 17-estradiol, estriol, ethynyl estradiol, and diethylstilbestrol	Surface water and wastewater	In-tube SPME	LC/MS/MS	Recoveries: 86.1–106.8 LODs: 2.7–11.7 ng·L⁻¹	[116]

36 endocrine-disrupting chemicals, including estrogens and progestogens	Potable and river water	SPE	UHPLC-QqTOF	Recoveries: 46%–134% LODs < 0.72 ng·L⁻¹	[117]

17β-estradiol, estriol, and 17α-ethinylestradiol	Sewage sludge	MAE	LC-QqQ ESI (PI) MRM	Recoveries: 71.7–103.1% RSD < 12% LODs: 0.6–3.5 g·kg⁻¹	[63]

28 estrogenic compounds	Sewage sludge	UAE	LC-QqQ ESI (PI and NI) MRM	Recoveries: 44–200% RSD: 0.6–11.6% LODs: 0.08–2.06 g·kg⁻¹	[64]

Oestrone, testosterone, androstenedione, norethindrone, levonorgestrel, and progesterone	Soil	PLE	LC-QqQ ESI (PI) MRM	Recoveries: 45–100% RSD: 2.2–10.3% LODs: 0.08–2.84 g·kg⁻¹	[65]

Estrone, 17α-estradiol, 17-estradiol, estriol, 17α-ethinylestradiol and diethylstilbestrol, and five conjugates	Sewage sludge	PLE	LC-QqQ ESI (PI) MRM	Recoveries > 81% RSD < 6% LODs < 26 g·kg⁻¹	[66]

α-estradiol, -estradiol, estriol, estrone, ethynylestradiol and their sulfate, glucuronide, and acetate conjugates	River sediments	MAE	LC-Qq-IT ESI (NI) MRM	Recoveries: 83–107% RSD: 4.9–9.6% LODs < 1 g·kg⁻¹	[67]

Abbreviations: LC: liquid chromatography; UHPLC: ultrahigh pressure liquid chromatography; MS: mass spectrometry; QqQ: triple quadrupole; IT: ion trap; LIT: lineal ion trap; ESI: electrospray ionization; APCI: atmospheric pressure chemical ionization; APPI: atmospheric pressure photoionization; NI: negative ion mode of ionisation; PI: positive ion mode of ionisation; SIM: selected ion monitoring; MRM: multiple reaction monitoring; SRM: selected reaction monitoring.
SPE: solid phase extraction; HF-LPME: hollow-fiber liquid-phase microextraction; MIP: molecularly imprinted polymer; UAE: ultrasound assisted extraction; PLE: pressurised liquid extraction; MAE: microwave-assisted extraction; MAME: microwave-assisted micellar extraction.
RSD: relative standard deviation; LOQ: limit of quantification; LOD: limit of detection.
SMMX: sulfamonomethoxine; SDMX: sulfadimethoxine; SMXZ: sulfamethoxazole; STZL: sulfathiazole; SCPD: sulfachloropyridazine; SMRZ: sulfamerazine; SMTZ: sulfamethazine; OXTC: oxytetracycline HCl; MCLN: minocycline HCl; DOXN: doxycycline hyclate; MECN: meclocycline sulfosalicylate; CTCL: chlortetracycline HCl; DEMN: democlocycline HCl; TCLN: tetracycline.
ENR: enrofloxacin; LOM: lomefloxacin; LVFX: levofloxacin; FLX: fleroxacin; SPFX: sparfloxacin; AMX: amoxicillin; OTC: oxytetracycline; SQX: sulfaquinoxaline.