[en] Diffusive gradients in thin films technique (DGT) is a dynamically passive sampling technique which has been applied increasingly to the environmental monitoring field. In the preliminary period, the DGT with zirconium hydroxide-silver iodide as the binding phase (ZrO-AgI DGT) has been developed for the determination of sulfide (S(II)). On this basis, this paper developed its determination method for inorganic arsenite (As(III)) to further realize the simultaneous and high-resolution measurements of labile inorganic As and S(II) in sediments. ZrO-AgI binding gel had a strong ability in adsorbing and fixing As(III), showing a linear increase in the initial 12.5 min. After saturation of S(II) on ZrO-AgI binding gel, the adsorption rate and adsorption capacity of As(III) reduced by 8 and 14%, respectively. A stable elution rate (89.1 ± 2.2%) was obtained by extraction of As(III) on the binding gel using a mixture solution of 1.0 M NaOH and 1.0 M H₂O₂ (1:1). The DGT capacity of As(III) determined by the ZrO-AgI DGT was 23.6 μg cm⁻². DGT uptakes of As(III) were independent of pH (4.0–9.0) and ionic strength (0.01–100 mM), and they did not interfere with each other during the uptake process. Simultaneous measurements of labile As and S(II) in four sediment cores of Taihu Lake (China) with ZrO-AgI DGT showed that they had similarly vertical distributions in the top 16-mm layer in one core and in the whole profile up to the 35 mm depth in two cores. It likely reflected a simultaneous release of As and S(II) in sediments by synchronous reduction of As-hosted oxidized iron and sulfate, respectively. The simultaneous decreases of labile As and S(II) from their co-precipitation (e.g., As₂S₃) were not obvious in deeper sediment layer through the measurement with ZrO-AgI DGT.

[en] Highlights: • High-resolution sampling showed seasonal variations in distribution of mobile P in sediments. • SRP diffusion flux at the sediment-water interface varied from − 0.01 to 6.76 mg/m²/d. • Spatial-temporal variation in mobile P was controlled by microbe-mediated Fe redox cycling. • Internal P loading accounted for 54% of increased water column TP during the prebloom-bloom period. • Internal P loading played a major role in causing seasonal nitrogen limitation for HABs. It is proposed that the internal loading of phosphorus (P) from sediments plays an important role in seasonal nitrogen (N) limitation for harmful algal blooms (HABs), although there is a lack of experimental evidence. In this study, an eutrophic bay from the large and shallow Lake Taihu was studied for investigating the contribution of internal P to N limitation over one-year field sampling (February 2016 to January 2017). A prebloom-bloom period was identified from February to August according to the increase in Chla concentration in the water column, during which the ratio of total N to total P (TN/TP) exponentially decreased with month from 43.4 to 7.4. High-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) analysis showed large variations in the vertical distribution of mobile P (SRP and DGT-labile P) in sediments, resulting in the SRP diffusion flux at the sediment-water interface ranging from − 0.01 to 6.76 mg/m²/d (minus sign denotes downward flux). Significant and linear correlations existed between SRP and soluble Fe(II) concentrations in pore water, reflecting that the spatial-temporal variation in mobile P was controlled by microbe-mediated Fe redox cycling. Mass estimation showed that the cumulative flux of SRP from sediments accounted for 54% of the increase in TP observed in the water column during the prebloom-bloom period. These findings are supported by the significantly negative correlation (p < 0.01) observed between sediment SRP flux and water column TN/TP during the same period. Overall, these results provide solid evidence for the major role of internal P loading in causing N limitation during the prebloom-bloom period.

[en] Highlights: • The dissolved Cr level was higher in Meiliang Bay than in East Taihu. • The DGT-labile Cr(VI) level was higher in East Taihu than in Meiliang Bay. • The high Cr mobility in summer was caused by DOC complexation with Cr(III). • The Cr(III) oxidization by Mn(III/IV) caused the high Cr mobility in winter. -- Abstract: To study the mechanisms of chromium (Cr) mobilization in sediments of lakes with different ecotypes, seasonal sampling was performed in the macrophyte-dominated East Taihu (MDET) and cyanobacteria-dominated Meiliang Bay (CDMB) in Lake Taihu. Concentrations of labile Cr(VI) and dissolved Cr were assessed using diffusive gradients in thin films (DGT) and high-resolution dialysis passive sampling devices, respectively. Results indicated that in pore water the dissolved Cr concentrations and in sediments total Cr and Cr fractions concentrations (dissolved, exchangeable and carbonate fraction (F1), Fe-Mn oxide fraction (F2), organic/sulfide fraction (F3)) were lower in MDET than in CDMB. However, the highly toxic DGT-labile Cr(VI) concentrations were higher in MDET sediments than in CDMB sediments. In the two lake zones, the seasonal variations in concentrations of dissolved Cr and DGT-labile Cr(VI) were significant, while total Cr and Cr fractions showed negligible changes (except F1 fraction). In summer, the high mobility of dissolved Cr (MDET: 103.42 ± 10.82 μg/L; CDMB: 108.99 ± 4.24 μg/L) were mainly caused by dissolved organic matter complexing with Cr(III). In winter the high mobility of dissolved Cr (MDET: 100.27 ± 22.04 μg/L; CDMB: 102.01 ± 8.81 μg/L) and DGT-labile Cr(VI) (MDET: 28.26 ± 3.73 μg/L; CDLZ: 25.82 ± 2.26 μg/L) were primarily caused by the oxidization of Cr (III) by Mn(III/IV) oxides. This study establishes the mechanisms for seasonal variation of Cr mobilization in different lake ecological zones, highlighting the urgent need for remediation of Cr pollution, especially in macrophyte-dominated lake zones.

[en] Highlights: • Pb mobility differed in sediments in the algae- and macrophyte-dominated areas. • Fe/Mn redox reduction, DOM complexation increased Pb mobility in algae-dominated area in spring, summer. • Sulfide, Fe/Mn oxide absorption decreased Pb mobility in algae-dominated area in fall, winter. • Root, plaque accumulation decreased Pb mobility in macrophyte-dominated area in spring, summer. • DOM complexation increased Pb mobility in fall and winter in macrophyte-dominated area. -- Abstract: This study examined lead (Pb) pollution in algae- and macrophytes-dominated sediments, using diffusive gradient in thin films (DGT) and dialysis (HR-Peeper) techniques. Lead pollution varied by season in the two different ecotype sediments. In the algae-dominated zone, the highest concentrations of DGT-labile Pb and dissolved Pb occurred in April and July, respectively. The reductive dissolution of Fe/Mn oxides was identified as an important driver for Pb releases in April and July. This was supported by the decrease of the reducible fraction of Pb in sediments during those sampling periods. Furthermore, dissolved organic matter (DOM) complexation with Pb in sediments also significantly increased the dissolved Pb concentrations in July. The Pb-DOM complexes accounted for 95% of the total chemical species of Pb in pore water, calculated by Visual MINTEQ 3.1 model. Low concentrations of labile and dissolved Pb were observed in October and January; these resulted from the formation of Pb-sulfide precipitates and adsorption by Fe/Mn oxides. It was supported by the high rate of Pb(HS)₂ precipitation (saturation index > 0), at 36%, in October samples and the high reducible fraction of Pb in sediments in January samples. In the macrophytes-dominated region, there was a decrease of labile and dissolved Pb concentrations in April and July. It is likely because of the uptake of Pb by submerged macrophyte roots and the Fe/Mn plaques in the root surface. High concentrations of labile and dissolved Pb were observed in October and January, likely resulting from the DOM complexation with Pb in sediments. This was supported by the fact that the Pb-DOM complexes accounted for 90% and 87% of the total chemical species of Pb in October and January, respectively.

[en] Highlights: • Dredging efficacy varied by season after six years of completion. • Dredging was effective in controlling heavy metals pollution in April and July. • Efficacy results from increased inert with slower kinetic response in sediments. • Dredging negligibly affected metal mobility in October and January. • Algal degradation affected dredging efficacy by releasing additional amounts of metals. -- Abstract: Dredging is used worldwide to remove polluted sediments from water bodies. However, the dredging efficacy remains hard to identify. Here, we studied the efficacy of dredging engineering as a means to remove Cu, Cd, and Pb from polluted lake sediments, after six years of completion. Dissolved metals and DGT-labile metals were quantified in the non-dredged and post-dredged sediments by high-resolution dialysis (HR-Peeper) and diffusive gradients (DGT) in thin films techniques. April and July measurements showed that dredging was effectively remediate the polluted sediments. The dissolved Pb, Cd, and Cu contents decreased up to 30%, 44%, and 26%, and the DGT-labile contents decreased up to 51%, 27%, and 33% compared with the contents in the non-dredged zone. Dredging was thus proven efficient in decreasing the labile metal fractions, increasing the capacity of available solids to bind metals, and slowing the leaching of metals from available solids in the post-dredged sediments. In October and January, the dredging efficacy was counteracted by the decomposition of algae, which increased the dissolved and DGT-labile metal concentrations in the post-dredged zone.

[en] This study investigated the effects of tubificid worm bioturbation on the lability of phosphorus (P) in microcosm sediments. High-resolution dialysis (HR-Peeper) and two types of diffusive gradients in thin films (DGT) (Zr-oxide DGT and ZrO-Chelex DGT) were used to measure soluble P and Fe, and labile P and Fe at a millimeter spatial scale. The worm bioturbation promoted P release (up to 511% of the control) to the overlying water on the 6th day, but it was reduced compared to the control (up to 171% of the control) from the 22nd day to the 102nd day because of the adsorption by Fe(III) oxyhydroxides. The worm bioturbation reduced the pore water soluble P concentration up to 48% and the DGT-labile P concentration up to 29% of the control from a sediment depth of −10 mm to approximately −130 mm before the 22nd day of incubation due to worm ingestion of sediment particles. Two-dimensional measurements of DGT-labile P also showed a much lower concentration of labile P around the worm burrow. This effect disappeared on the 53rd and 102nd day. However, the soluble P and DGT-labile P decreased again up to 41% and 38%, compared to the control from the sediment depth of −20 mm and −10 mm to approximately −130 mm, respectively, on the 152nd day of incubation due to the adsorption by Fe(III) oxyhydroxides. Soluble Fe(II) and DGT-labile Fe did not show significant changes from the worm bioturbation on the 6th day, but decreased up to 31% and 47% of the control after the 6th day. The results that worm ingestion of sediment particles is a significant driver of soluble and labile P reduction in the sediments before the 22nd day. After that, soluble and labile P reduction was attributed to P adsorption by Fe(III) oxyhydroxides. - Highlights: • High resolution techniques were employed to investigate P release from bioturbation sediments. • Worm bioturbation decreased the concentration of soluble/labile P in sediments before the 22nd day. • Bioturbation effects disappeared on the 53rd and 102nd day and emerged again on the 152nd day. • The P decreased because of ingestion by worm and adsorption by Fe(III) oxyhydroxides. - Tubificid worm bioturbation decreased the lability of P in sediments.

[en] Highlights: • Decreased SRP and DGT-labile P concentrations evidenced the efficacy of dredging. • Dredging effectiveness in winter and spring is higher than in summer and autumn. • Fe redox cycling is key to regulating dredging effectiveness. • Algal decomposition suppresses dredging effectiveness during summer and autumn. The effectiveness of sediment dredging for the control of internal phosphorus (P) loading, was investigated seasonally in the eutrophic Lake Taihu. The high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were used to measure the concentrations of soluble Fe(II) and soluble reactive P (SRP) as well as DGT-labile Fe/P in the non-dredging and post-dredging sediments. The P resupply kinetics from sediment solids were interpreted using DGT Induced Fluxes in Sediments (DIFS) modeling. The results showed no obvious improvement in water and sediment quality after dredging for 6 years, due to their geographical proximity (a line distance of approximately 9 km). However, dredging significantly decreased the concentrations of soluble Fe(II)/SRP and DGT-labile Fe/P in sediments, with effects varying at different depths below the sediment-water interface; More pronounced effects appeared in January and April. The diffusive flux of pore water SRP from sediments decreased from 0.746, 4.08 and 0.353 mg/m²/d to 0.174, 1.58 and 0.048 mg/m²/d in April, July and January, respectively. DIFS modeling indicated that the P retention capability of sediment solids was improved in April in post-dredging site. Positive correlations between pore water soluble Fe(II) and SRP as well as between DGT-labile Fe and P, reflect the key role of Fe redox cycling in regulating dredging effectiveness. This effect is especially important in winter and spring, while in summer and autumn, the decomposition of algae promoted the release of P from sediments and suppressed dredging effectiveness. Overall, the high-resolution HR-Peeper and DGT measurements indicated a successful control of internal P loading by dredging, and the post-dredging effectiveness was suppressed by algal bloom.

[en] Highlights: • Dredging effects varied by season, reflected by metalloid concentrations. • Dredging was most effective in April, July and/or January. • Efficacy due to higher fraction of inert metalloids with slower kinetic response. • Dredging had negligible and negative effects in October. • Algal decomposition and metalloid release suppressed dredging efficacy. -- Abstract: This study assessed the effectiveness of dredging in controlling arsenic (As), selenium (Se), and antimony (Sb) contamination in sediments, by examining contaminant concentrations in sediments six years after dredging was completed. High-resolution diffusive gradients in thin films (DGT) and dialysis (HR-Peeper) techniques were used to monitor the concentrations of DGT-labile metalloids and soluble metalloids in sediments, respectively. Results revealed that dredging effectively remediated metalloid contamination in sediments only in April, July and/or January. Compared to non-dredged sediments, the concentrations of soluble and DGT-labile As, Se, and Sb in dredged sediments decreased on average by 42%, 52%, and 43% (soluble), and 54%, 50%, and 53% (DGT), respectively. The effectiveness of the dredging was primarily due to the transformation of metalloids from labile to inert fractions, which increased the ability of the sediments to retain the metalloids, and the slowed rate of resupplied metalloids from available solid pools. In contrast, negligible/negative effects of dredging were seen in October, and the concentrations of soluble and DGT-labile metalloids even increased in some profiles of dredged sediments. This was mainly caused by a release of the metalloids from algal degradation, which may offset the dredging effectiveness.

[en] Highlights: • High-resolution sampling showed seasonal variations in dissolved and labile Zn. • Algal blooms reduced concentration of dissolved Zn by algal assimilation in summer. • Concentration of dissolved Zn decreased via Mn oxides adsorption of Zn in winter. • Mn oxides reduction and DOM complexation increased Zn mobilization in other seasons. -- Abstract: To assess zinc (Zn) pollution risk from sediments, this study investigated the monthly changes of dissolved Zn and labile Zn in sediment-overlying water profiles in a eutrophic bay (Meiliang Bay) of Lake Taihu (China) using high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) at a 4 mm vertical resolution. In February and March, Mn oxides reduction caused high concentrations of DGT-labile Zn (14 ∼ 235 μg L⁻¹), as evidenced by the significant correlation between DGT-labile Zn and DGT-labile Mn in sediments. In June and July, algal blooms reduced concentrations of dissolved Zn via algal assimilation. From August through October, concentrations of dissolved Zn in overlying water (338 ∼ 1023 μg L⁻¹) exceeded the water quality limit for fisheries in China (100 μg L^-1). This was attributed to reductive dissolution of Mn oxides in sediments caused by algal degradation followed by complexation of dissolved organic matter (DOM), which was identified in a simulated algal bloom experiment. In the winter, decreased Zn mobility was mainly attributed to adsorption by Mn oxides. It was concluded that enhanced Zn pollution risk from sediments is worthy of concern especially during algal degradation in eutrophic lakes.