NMR as a Discovery Tool: Exploration of Industrial Effluents Discharged Into the Environment.

NMR provides unprecedented molecular information, urgently needed by environmental researchers and policy makers. However, NMR is underutilized in environmental sciences due to the lack of available technologies, limited environmental-specific training opportunities, and easy-to-use workflows. NMR has considerable potential as a discovery tool for novel pollutants, and by-products, exemplified by the recent discovery of the degradation by-product of a rubber additive, 6PPD-quinone, now considered one of the most toxic compounds presently known. This work represents a proof-of-concept case study highlighting the use of NMR to profile effluents from 38 industries across Ontario, Canada. Wastewater effluents from various industrial sectors were analyzed using several 1D and 2D H/C NMR and F experiments and were screened both unconcentrated and after lyophilization. Common species could be identified using human metabolic NMR databases, but environmental-specific NMR databases desperately need further development. An example of manually identifying unusual NMR signatures is included; these resulted from phosphinic and phosphonic acids originating from the electroplating industry, for which the environmental impacts are not well understood. Basic H NMR quantification is performed using ERETIC, while an optimized approach combining relaxation agents and steady-state-free-precession F NMR, to reduce detection limits (at 500 MHz) to sub-ppb (< 1 μg/L) in under 15 min, is demonstrated. The future potential of benchtop NMR (80 MHz) is also considered. This paper represents a guide to others interested in applying NMR spectroscopy to environmental media and demonstrates the potential of NMR as a complementary tool to assist MS in environmental pollutant and by-product discovery.