Fe/Mn (oxyhydr)oxides reductive dissolution promoted by cyanobacterial algal bloom-derived dissolved organic matter caused sediment W release during an algal bloom in Taihu Lake.

ABSTRACT

Tungsten (W) can be toxic to aquatic organisms. However, the spatiotemporal characteristics and controlling factors of W mobility during harmful algal blooms (HABs) have rarely been investigated. In this study, simultaneous changes in soluble W, iron (Fe), manganese (Mn), and ultraviolet absorbance (UV254) in the sediment-water interface (SWI) were measured monthly using high-resolution peeper (HR-Peeper) devices. Laboratory experiments were conducted to verify the effects of environmental factors on W release. From May 2021 to October 2021, the concentration and flux of soluble W were higher than in other months. In addition, from May to October, DMAX (the depth at which the maximum concentration occurs on each profile) was 30-50 mm below the SWI, rather than the maximum depth. Principal component analysis (PCA) also divided the year into two periods, designated W-stable (December 2020, January, March, April and November 2021 with low soluble W concentration) and W-active periods (from May 2021 to October 2021 with high soluble W concentration). Laboratory experiments showed that both warming and anoxic conditions caused simultaneous release of soluble W, Fe(II), Mn, and dissolved organic matter (DOM), with strong correlations among soluble W, Fe(II), Mn. Partial least squares path modeling (PLS-PM) and random forest model showed that DOM directly affected W release or indirectly affected W release through promoting ferromanganese (oxyhydr)oxides reduction under warming and anaerobic conditions. The results of the field investigation showed that, in the W-stable period with low T, high DO, and an oxic SWI, the concentrations of soluble W, Fe, Mn, and DOM were low. The redundancy analysis (RDA) showed that these months were mainly affected by water DO. The significant and strong positive correlation among soluble W, Fe and Mn indicated that soluble W was probably scavenged by Fe/Mn (oxyhydr)oxides in the oxic water during the W-stable period. The W-active period corresponded to the cyanobacterial HABs (cyanoHABs) outbreak, with higher T, lower DO, and a more anoxic SWI. During this period, the concentrations of soluble W, Fe, Mn, and DOM were high and their correlations were stronger. RDA showed that these months were mainly affected by T, UV254, soluble Fe and Mn. These results indicated that reductive dissolution of Fe/Mn (oxyhydr)oxides driven by DOM generated in W-active period, especially cyanoHAB-derived DOM, mainly caused soluble W release. These results reveal the coupling relationship between cyanoHABs and W release and emphasize the need for prevention and control of heavy metal release in eutrophic lakes.