Seasonal variation of chloro-s-triazines in the Hartbeespoort Dam catchment, South Africa

Highlights: • Summer contributed the highest triazine herbicide loads into the Hartbeespoort Dam. • The Crocodile River is the major source of herbicides in the Hartbeespoort Dam. • Atrazine groundwater concentrations in the Hartbeespoort Dam proximity are > 130 ng L⁻¹. • DET is the most abundant triazine metabolite in the Hartbeespoort Dam catchment. • Atrazine metabolites were detected in fish muscle. Seasonal variation of eight chloro-s-triazine herbicides and seven major atrazine and terbuthylazine degradation products was monitored in the Hartbeespoort Dam catchment using gas chromatography–mass spectrometry (GC–MS) and liquid chromatography-mass spectrometry (LC-MS/MS). Lake, river and groundwater were sampled from the Hartbeespoort Dam catchment over four seasons and the downstream Jukskei River was monitored during the winter season. Triazine herbicide concentrations in the Hartbeespoort Dam were in the order atrazine > simazine > propazine > ametryn > prometryn throughout the four seasons sampled. Triazine herbicide concentrations in the Hartbeespoort Dam surface water were highest in summer and gradually decreased in successive seasons of autumn, winter and spring. Terbuthylazine was the only triazine herbicide detected at all sampling sites in the Jukskei River, though atrazine recorded much higher concentrations for the N14 and Kyalami sites, with concentrations of 923 and 210 ng L⁻¹ respectively, compared to 134 and 74 ng L⁻¹ for terbuthylazine. Analytical results in conjunction with river flow data indicate that the Jukskei and Crocodile Rivers contribute the greatest triazine herbicide loads into the Hartbeespoort Dam. No triazine herbicides were detected in the fish muscle tested, showing that bioaccumulation of triazine herbicides is negligible. Atrazine and terbuthylazine metabolites were detected in the fish muscle with deethylatrazine (DEA) being detected in both catfish and carp muscle at low concentrations of 0.2 and 0.3 ng g⁻¹, respectively. Desethylterbuthylazine (DET) was detected only in catfish at a concentration of 0.3 ng g⁻¹. With atrazine herbicide groundwater concentrations being > 130 ng L⁻¹ for all seasons and groundwater ∑ triazine herbicide concentrations ranging between 527 and 367 ng L⁻¹, triazine compounds in the Hartbeespoort Dam catchment may pose a risk to humans and wildlife in light findings of endocrine and immune disrupting atrazine effects by various researchers.