Sorption, mobility, and bioavailability of PBDEs in the agricultural soils: Roles of co-existing metals, dissolved organic matter, and fertilizers.

Polybrominated diphenyl ethers (PBDEs) are common pollutants released from electronic waste (e-waste) dismantling and recycling activities. Our city-wide survey of agricultural soils in Qingyuan (40 sampling sites), where e-waste recycling has been active, observed exceedance of PBDEs above background levels (average of 251.9ngg, 87 times the regional baseline concentration) together with elevated levels of metals/metalloids at the contamination hotspots, such as As (180.4mgkg), Cu (100.7mgkg), Zn (93.4mgkg), Pb (37.8mgkg), Cr (15.1mgkg), and Cd (0.3mgkg). Hence, a twenty-cycle batch sorption test on composite soil samples from the e-waste site was conducted to study the fate of BDE-28 (2,4,4'-tribromodiphenyl ether) and BDE-99 (2,2',4,4',5-pentabromodiphenyl ether) under the influence of co-existing trace elements (TEs) (Cu, Pb, Zn, and Cd, which exceeded Chinese Environmental Quality Standard for Soils), dissolved organic matter (extracted from local peat), and locally available commercial fertilizer. The results showed that the presence of TEs barely affected the sorption of BDEs, probably because the low concentration of BDEs in the environment resulted in nearly complete sorption onto the soil. In contrast, metals sorption onto soil was promoted by the presence of BDEs. The mobility of BDE-28 was higher than BDE-99 in water leaching tests, while the leaching concentration of BDE-99 was further reduced in simulated acid rain possibly due to protonation of π-accepting sites in soil organic matter. In the freshly spiked soil, BDEs of greater hydrophobicity and larger molecular size exhibited higher bioavailability (due to greater affinity to Tenax extraction), which was contrary to the field contaminated soil. Similarly, the co-occurrence of metals and fertilizer increased the bioavailability of newly sorbed BDE-99 more than BDE-28 in the soil. These results illustrate the need to holistically assess the fate and interactions of co-existing organic and inorganic pollutants in the agricultural soils.