Detection of Pharmaceuticals, Personal Care Products, and Pesticides in Water Resources by APCI-LC-MS/MS

Significance of the topic

The occurrence of pharmaceuticals, personal care products, pesticides and endocrine disruptors in water resources is an emerging environmental concern. These compounds enter surface and drinking waters via human and animal waste, agricultural runoff and improper disposal. Even at ultra-trace levels (ng/L), they can affect aquatic ecosystems and pose potential risks to human health. Comprehensive analytical methods are required to monitor a wide range of organic contaminants and guide water treatment decisions.

Objectives and study overview

This work aimed to develop a streamlined method combining solid phase extraction (SPE) with atmospheric pressure chemical ionization liquid chromatography-tandem mass spectrometry (APCI-LC-MS/MS) for simultaneous quantification of diverse organic wastewater contaminants at low ng/L concentrations. Fourteen representative compounds spanning pharmaceuticals, personal care products, hormones and pesticides were targeted. The method was applied to samples collected from the Mille Iles, des Prairies and St. Lawrence rivers in the Montreal region to assess contaminant occurrence and concentration variations.

Methodology

The analytical workflow included:

• Collection of triplicate 1 L samples from each river, acidified with sulfuric acid and stored at 4 °C.
• Filtration through 0.7 µm and 0.45 µm membranes prior to extraction within 24 hours.
• SPE using 200 mg C18 cartridges: conditioning with methanol and water, sample loading, washing and nitrogen drying.
• Elution with methyl tert-butyl ether/methanol mixtures, evaporation under nitrogen and reconstitution in aqueous formic acid/methanol containing isotopically labeled standards.

Instrumentation

Chromatographic separation was performed on a Thermo Scientific Surveyor HPLC system with a Hypersil GOLD C18 column (50×2.1 mm, 3 µm) at 30 °C. A TSQ Quantum Ultra triple quadrupole mass spectrometer equipped with an APCI source operated in positive and negative modes. Key parameters included a vaporizer temperature of 500 °C, capillary temperature of 250 °C, and selective reaction monitoring transitions for each analyte.

Key results and discussion

The method demonstrated excellent performance:

• Limits of detection ranged from 0.03 to 2 ng/L in surface water.
• Recoveries between 72 % and 94 % with RSD values of 3–11 % across compounds.
• Minimal matrix effects (< 13 % suppression or enhancement) in real samples.
• Good linearity (R2 > 0.99) up to 100 ng/L.

All targeted analytes were detected in the river samples. Caffeine (16–24 ng/L), atrazine (1.5–39 ng/L), salicylic acid (10–33 ng/L) and gemfibrozil (4–14 ng/L) showed the highest concentrations. Carbamazepine, clofibric acid and certain hormones were found at lower levels (≤ 5 ng/L), while some compounds appeared only at trace levels near the detection limit.

Benefits and practical applications of the method

This approach offers several advantages:

• A single SPE-LC-MS/MS workflow for multiple compound classes reduces time and resource requirements.
• APCI ionization enhances sensitivity for low-polarity analytes like steroids and reduces matrix interferences.
• Detection capabilities at sub-ng/L levels support compliance monitoring and risk assessment.
• Method adaptability allows integration into routine environmental monitoring programs.

Future trends and potential applications

Ongoing and future developments may include:

• Integration of high-resolution mass spectrometry for non-target screening of unknown emerging contaminants.
• Automation of sample preparation and data processing to increase throughput.
• Expansion of analyte scope to include transformation products and novel personal care ingredients.
• Real-time monitoring tools and remote sensing to support rapid water quality assessments.
• Data integration with modelling platforms to predict contaminant fate and guide treatment strategies.

Conclusion

The developed APCI-LC-MS/MS method provides a robust, sensitive and efficient solution for simultaneous trace analysis of diverse organic pollutants in surface waters. Its successful application to Montreal watershed samples underscores widespread occurrence of pharmaceuticals, personal care products, pesticides and hormones, informing water management decisions and treatment upgrades.

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