Unexpected Dioxin Formation During Digestion of Soil with Oxidizing Acids

Dioxins, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), are among the most toxic unintentionally produced persistent organic pollutants, and their emission is of great concern. Herein, we discovered abundant dioxin formation in soil and various organic carbon-containing matrices after digestion with aqua regia. Sigma 17PCDD/Fs concentrations were in the range of 66.6-142,834 pg/g dw (5.6-17,021 pg WHO2005-TEQ/g dw) in 19 soil samples after digestion with aqua regia for 6 h. Sigma 17PCDD/Fs concentration was significantly and positively correlated with soil organic carbon content (R-2 = 0.89; p < 0.01). Compared with cellulose and lignin, humic acid served as an important organic matter component that was converted to PCDD/Fs during soil digestion. Strong oxidation and production of reactive chlorine by aqua regia may be the key factors in the formation of PCDD/Fs. The yearly emission of PCDD/Fs due to digestion with strong acids by the inspection and testing industry was estimated to be 83.8 g TEQ in China in 2021 based on the highest level, which was similar to 0.9% of the total dioxin inventory in China. Great attention should be paid to unexpected dioxin formation during digestion processes considering the potential risk of release from laboratories and enterprises.

Automated summary

This study discovered abundant dioxin formation in soil and organic carbon-containing matrices after digestion, with significant correlation observed between Sigma 17PCDD/F concentration and soil organic carbon content. Humic acid was found to be an important component in the conversion of organic matter to PCDD/Fs during digestion. The strong oxidation and production of reactive chlorine by aqua regia were identified as key factors in PCDD/F formation. The annual emission of PCDD/Fs due to digestion with strong acids by the inspection and testing industry was estimated to be 83.8 g TEQ in China in 2021, highlighting the importance of addressing unexpected dioxin formation during digestion processes.