Tracing the attenuation of fipronil and its transformation products from a rice paddy field to receiving rivers using polar organic chemical integrative samplers.

Irrational use of fipronil for rice pest control often occurred, resulting in high concentrations of fipronil and its transformation products (TPs) (collectively termed fiproles) in aquatic sediment, calling for a better understanding of the migration and transformation of fipronil in surface water as well as efficient methods for source identification. Herein, the fate and transport of fiproles from a paddy field to receiving rivers were assessed in Poyang Lake basin, Jiangxi, China using polar organic chemical integrative samplers with mixed-mode adsorbents (POCIS-MMA). Average concentrations of fiproles in water were 6.16 ± 6.32 ng/L, with median, minimum, and maximum values being 2.99 ± 0.67, 0.40 ± 0.08, and 18.6 ± 3.1 ng/L, respectively. In all samples, over half of fiproles (55.9 %-90.8 %) presented in the form of TPs and fipronil desulfinyl was the dominant TP. Two approaches were applied for source identification, including the change of molar concentration ratios of fipronil to its TPs and the relative attenuation values of fiproles normalized to a reference compound (acetamiprid) that was stable in aquatic environment. While the paddy field upstream was the main source of waterborne fiproles, additional input sources in the downstream region were identified. The present study indicated that the combination of attenuation of molar concentration ratios of micro-pollutants to their respective TPs and relative attenuation values of micro-pollutants' concentrations normalized to a reference compound measured by POCIS is an effective means to study the migration and transformation of micro-pollutants in field.

Occurrence and water-sediment exchange of systemic insecticides and their transformation products in an agriculture-dominated basin.

Neonicotinoids (NEOs) and fipronil (FIP) are ubiquitous in aquatic environment, yet the transformation and water-sediment exchange are largely unknown for these systemic insecticides and their transformation products (TPs). Herein, occurrence, field-based partitioning coefficients, and fugacity fractions (ff) of NEOs, FIP, and their TPs were analyzed in the drainage and receiving rivers near a rice paddy field. NEOs and FIPs were frequently detected in the sediments with concentrations of TPs being often higher than the parent compounds. Average ff values of NEOs (0.944-1.00) were larger than those of FIPs (0.399-0.716), indicating NEOs had a greater tendency to diffuse from sediment into water. Similar as well-studied hydrophobic compounds, hydrophobicity was the main factor impacting the water-sediment exchange of moderately hydrophobic FIPs. Alternatively, electrostatic interactions governed the fate of hydrophilic NEOs in water-sediment system. The log Kd values of NEOs were positively correlated with their N/C ratios (p < 0.05), possibly because the negatively charged sediments (zeta potential were from -19.1 ± 0.6 to -5.84 ± 0.57 mV) generated electrostatic attraction with amino functional group. Our study highlighted the ubiquitousness of TPs and distinct water-sediment interaction for moderately hydrophobic and hydrophilic insecticides in an agriculture-dominated watershed.

Spatial distribution of benthic toxicity and sediment-bound metals and arsenic in Guangzhou urban waterways: Influence of land use.

The effects of land use on pollutant loads in sediments have been well documented; however, its influence on spatial variations in sediment toxicity remains largely unknown. In the present study, the toxicological effects of 17 sediments collected from Guangzhou waterways were evaluated using two benthic invertebrates (Chironomus dilutus and Hyalella azteca), along with quantification of heavy metals and arsenic in the sediments. The impacts of land-use configuration on sediment toxicity and occurrence of heavy metals and arsenic were analyzed. The sediments presented moderate lethality (<40 %) in the two test species and significantly altered their enzymatic activity, including the activities of oxidative stress biomarkers and acetylcholine esterase. Metals (Ag, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) and arsenic were detected in all the sediments, with total concentrations ranging from 238 to 1019 mg/kg of dry weight. Both the toxicity and chemical results displayed spatially dependent patterns but were related to different land use types. Toxicity was most influenced by agricultural and aquacultural activities, while metal and arsenic pollution was most influenced by urban land areas. The present findings are expected to provide essential knowledge for developing strategies that reduce the chemical pollution and ecotoxicological risk in sediments.