Geochemical cycling of iron (Fe) mediated by sediment microbes drives the remobilization of phosphorus (P). Understanding the underlying mechanism is essential for the evaluation of P retention by wetlands. The diffusive gradients in thin film (DGT) and 16S rDNA sequencing techniques were combined to explore seasonal variations in the remobilization mechanism of sediment P in a free water surface wetland in southwest China. A significantly positive correlation between labile P and Fe concentrations was found from the sediment profiles, indicating coupled remobilization of Fe and P in the sediment. Fe-reducing bacterial genera, particularly Sphingomonas and Geothermobacter, were responsible for the reductive dissolution of Fe oxides and subsequent P release in sediment. The efflux of sediment P was higher in the rainy season (95 ± 87 ng cm⁻² d⁻¹) than in the dry season (39 ± 29 ng cm⁻² d⁻¹). Based on the significantly positive relationship between the efflux and total concentration of sediment P, we propose a promising regression equation for quantifying the release risk of sediment P. The Luoshijiang Wetland exhibited a higher release potential as indicated by a greater regression slope (0.558) compared to the other water bodies (0.055), which was mainly attributed to the lower labile Fe:P molar ratio in the sediment. Based on estimations of the diffusive flux of P at the sediment-water interface, sediment contributed more than 172 and 413 g of P per day to the water column in the dry and rainy seasons, respectively, accounting for 14.0% and 1.9% of the P mass in the surface water of the wetland.

Dissolved inorganic nitrogen (DIN) is considered the main factor that induces eutrophication in water, and is readily influenced by hydrodynamic activities. In this study, a 4-year field investigation of nitrogen dynamics in a turbulent river was conducted, and a laboratory study was performed in the approximately homogeneous turbulence simulation system to investigate potential mechanisms involved in DIN transformation under turbulence. The field investigation revealed that, contrary to NO⁻₃ dynamics, the NH⁺₄ concentrations in water were lower in flood seasons than in drought seasons. Further laboratory results demonstrated that limitation of dissolved oxygen (DO) caused inactive nitrification and active denitrification in static river sediment. In contrast, the increased DO levels in turbulent river intensified the mineralization of organic nitrogen in sediment; moreover, ammonification and nitrification were activated, while denitrification was first activated and then depressed. Turbulence therefore decreased NH⁺₄ and NO⁻₂ concentrations, but increased NO⁻₃ and total DIN concentrations in the overlying water, causing the total DIN to increase from 0.4 mg/L to maximum of 1.0 and 1.7 mg/L at low and high turbulence, respectively. The DIN was maintained at 0.7 and 1.0 mg/L after the 30-day incubation under low and high turbulence intensities (ε) of 3.4 × 10⁻⁴ and 7.4 × 10⁻² m²/s³, respectively. These results highlight the critical role of DO in DIN budgets under hydrodynamic turbulence, and provide new insights into the DIN transport and transformation mechanisms in turbulent rivers.

Antarctic melt streams are important ecosystems that increasingly face contaminant pressures from anthropogenic sources. Metal contaminants are often reported in the limno-terrestrial environment but their speciation is not well characterised, making environmental risk assessments difficult. This paper characterises labile metal concentrations in five melt streams and three shallow lakes around the Casey and Wilkes research stations in East Antarctica using chemical extracts and field deployments of diffusive gradients in thin-film (DGT) samplers. An acute toxicity test with field-collected Ceratadon purpeus and taxonomic identification of diatoms in melt streams were used to infer environmental risk. Copper and zinc were the most labile metals in the melt streams. DGT-labile copper concentrations were up to 3 μg Cu L⁻¹ in melt-stream waters but not labile below the sediment-water interface. DGT-labile zinc concentrations were consistent above and below the sediment-water interface at concentrations up to 14 μg Zn L⁻¹ in four streams, but one stream showed evidence of zinc mineralisation in the sediment with a flux to overlying and pore waters attributed to the reductive dissolution of iron and manganese oxides. Other metals, such as chromium, nickel, and lead were acid-extractable from the sediments, but not labile in pore waters or overlying waters. All streams had unique compositions of freshwater diatoms, but one had particularly reduced diversity and richness, which correlated to metal contamination and sediment physico-chemical properties such as a finer particle size. In laboratory bioassays with field-collected samples of the Antarctic moss C. purpeus, there was no change in photosynthetic efficiency following 28-d exposure to 700, 900, 1060, or 530 μg L⁻¹ of cadmium, copper, nickel, and zinc, respectively. This study shows that microorganisms such as diatoms may be at greater risk from contaminants than mosses, and highlights the importance of geochemical factors controlling metal lability.

Methylmercury (MeHg) produced by anaerobic bacteria in lakes and reservoirs, poses a threat to ecosystem and human health due to its ability to bioaccumulate in aquatic food webs. This study used 48-hr microcosm incubations of profundal sediment and bottom water from a sulfate-rich, hypereutrophic reservoir to assess seasonal patterns of MeHg cycling under various treatments. Treatments included addition of air, Hg(II), organic carbon, and microbial inhibitors. Both aeration and sodium molybdate, a sulfate-reducing bacteria (SRB) inhibitor, generally decreased MeHg concentration in microcosm water, likely by inhibiting SRB activity. The methanogenic inhibitor bromoethanesulfonate increased MeHg concentration 2- to 4- fold, suggesting that methanogens were potent demethylators. Pyruvate increased MeHg concentration under moderately reduced conditions, likely by stimulating SRB, but decreased it under highly reduced conditions, likely by stimulating methanogens. Acetate increased MeHg concentration, likely due to the stimulation of acetotrophic SRB. Results suggest that iron-reducing bacteria (IRB) were not especially prominent methylators and MeHg production at the sediment-water interface is elevated under moderately reduced conditions corresponding with SRB activity. In contrast, it is suppressed under oxic conditions due to low SRB activity, and under highly reduced conditions (<-100 mV) due to enhanced demethylation by methanogens.

High water level fluctuations (WLFs) lead to periodic drying and re-inundation of sediments in the littoral area of eutrophic lakes. In this study, a series of littoral sediment cores were dried for different periods (5–30 d) and rewetted for 48 h. The sediment cores that dried for 30 d were then re-inundated for 90 d. The exchanges of nitrogen (N) and phosphorus (P) across the sediment–water interface (SWI) and the mechanisms were studied. The results showed that ammonium nitrogen (NH4+–N) fluxes increased after 5–25 d of drying, which was followed by an obvious decrease after 30 d of drying. The decreased NH4+–N fluxes remained at low levels during the 90 d re-inundation period. The soluble reactive P (SRP) fluxes decreased significantly after 15 d of drying. However, further re-inundation increased the SRP fluxes to their initial levels. The decreased water content and porosity, the oxidation of the sediment during drying, and the associated transformations of the N and P fractions in the sediment from drying to re-inundation influenced the exchanges of NH4+–N and SRP across the SWI. The decrease of labile NH4+–N in the sediment during drying was non-reversible, while the transformations between redox sensitive P (Fe-P) and aluminum-bound P were more likely to be reversible from drying to re-inundation. The increase of Fe-P during drying and dissolution of Fe-P during the re-inundation were responsible for the development of SRP fluxes from drying to re-inundation. Therefore, the periodic drying and re-inundation of the littoral eutrophic sediments reduced the release of NH4+–N but accelerated the release of SRP from the sediment. This should be given more consideration for the remediation and management of eutrophication in the lake and other similar lakes with high WLFs.

The diffusive oxygen uptake (DOU) of sediments inhabited by Chironomus riparius and Tubifex tubifex was investigated using a planar oxygen optode device, and complemented by measurements of bioturbation activity. Additional experiments were performed within contaminated sediments to assess the impact of uranium on these processes. After 72 h, the two invertebrate species significantly increased the DOU of sediments (13-14%), and no temporal variation occurred afterwards. Within contaminated sediments, it was already 24% higher before the introduction of the organisms, suggesting that uranium modified the sediment biogeochemistry. Although the two species firstly reacted by avoidance of contaminated sediment, they finally colonized it. Their bioturbation activity was reduced but, for T. tubifex, it remained sufficient to induce a release of uranium to the water column and an increase of the DOU (53%). These results highlight the necessity of further investigations to take into account the interactions between bioturbation, microbial metabolism and pollutants. This study highlights the ecological importance of bioturbation in metal-contaminated sediments.

Lake sediments are widely used as environmental archives to reconstruct past changes in contaminants deposition, provided that they remain immobile after deposition. Arsenic (As) is a redox-sensitive element that may be redistributed in the sediments during early diagenesis, for instance along with iron and manganese, and thus depth profiles of As might not provide a reliable, unaltered record of past deposition. Here, we use inverse diagenetic modelling to calculate fluxes of As across the sediment-water interface and interpret As sedimentary records in eight lakes along a 80 km transect from the Giant and Con mines, Northwest Territories, Canada. The sediment cores were dated using ²¹⁰Pb methods and analyzed for solid-phase and porewater As, Fe, Mn and organic C concentrations. We reconstructed the history of As deposition by correcting for the varying mobility patterns and calculated contemporary As deposition fluxes. Correction for diagenesis was substantial for three of the eight lakes, suggesting that lakes with lower sedimentation rates, which allows longer residence of As within the reactive zones defined by the model, enhance the influence of diagenesis. Results show that solid phase As peaks coincides with the period of high emissions from past gold ore roasting activities. Results also show that sediments sustained present-day As fluxes to the water column of study lakes within 50 km of the mines, while sediment in study lakes further than 50 km acted as As sinks instead.

We investigated the effect of hypoxic-anoxic range of dissolved oxygen (DO) on metal release/bioavailability at sediment-water interface (SWI) in the Ganga River. Here, we consider eight sites in the main river stem along 518 km; sixty sites downstream two point sources and two tributary confluences covering 630 km; and an incubation experiment to verify these results. We found higher concentrations of metals and bioavailable fractions at SWI at two locations of main stem and up to 700 m, 1000 m, 400 m and 500 m downstream Assi drain, Wazidpur drain, Ramganga confluence and Varuna confluence respectively where DO at SWI (DOₛw) was <2.0 mgL⁻¹. The incubation experiment did show higher levels of metal- and P-release and bioavailability under anoxic-hypoxic range of DO. The risk assessment code and eutrophication index indicated high to very high risks of contaminated river sediment and water to aquatic environment at sites with hypoxic-anoxic range of DOₛw. Further, the principal component analyses separated metals and bioavailable fractions opposite to FDAase indicating greater risk at these locations. The study, which forms the first report on benthic hypoxia/anoxia-driven metal release, potential bioavailability and risk to the Ganga River ecosystem will help understanding how human-driven perturbations influence geochemical cycling of metals and ecosystem responses in large rivers.

It is well known that sediment internal loading can worsen lake water quality for many years even if effective measures have been taken to control external loading. In this study, a 12-month field study was carried out to reveal the relationship between sediment phosphorus (P) and nitrogen (N) forms as well as their fluxes across sediment-water interface from the most polluted area of Lake Chaohu, a large shallow eutrophication lake in China. The possible contribution of mobile fraction of P and N to lake eutrophication is also analyzed. The results indicate that the content of total P and N and their forms in water and sediment were rather dynamic during the year-long field investigation. Low concentrations of P and N from sediment and overlying water were observed in the winter but increased sharply in summer. The phosphate and ammonium fluxes showed evident seasonal variation, and higher fluxes can be observed in warmer seasons especially during the period of algal bloom with high sedimentation. The reduction of ferric iron and degradation of organic matter could be responsible for the increased P flux from sediment in algal bloom seasons, which is consistent with the seasonal variation of P forms in sediment. A comparison of the mole ratio of P flux:N flux to both the P:N mole ratio in sediments and the Redfield ratio was used to further distinguish the dominant sediment P forms’ release during seasonal variation. Moreover, the anoxic condition and enhanced microbial activity in warmer seasons contribute a lot to the ammonium release from sediment. Consequently, the nutrient fluxes seasonally influence their corresponding nutrient concentrations in the overlying water. The results of this study indicate that sediment internal loading plays an important role in the eutrophication of Lake Chaohu.

A thorough understanding of the labile status and dynamics of phosphorus (P) and iron (Fe) across the sediment-water interface (SWI) is essential for managing internal P release in eutrophic lakes. Fe-coupled inactivation of P in sediments is an important factor which affects internal P release in freshwater lakes. In this study, two in-situ high-resolution diffusive gradients in thin films (DGT) techniques, Zr-Oxide DGT and ZrO-Chelex DGT, were used to investigate the release characteristics of P from sediments in a large freshwater lake (Dongting Lake, China; area of 2691 km2) experiencing a regional summer algal bloom. Two-dimensional distributions of labile P in sediments were imaged with the Zr-Oxide DGT without destruction of the original structure of the sediment layer at four sites of the lake. The concentration of DGT-labile P in the sediments, ranging from 0.007 to 0.206 mg L−1, was highly heterogeneous across the profiles. The values of apparent diffusion flux (Fd) and release flux (Fr) of P varied between −0.027–0.197 mg m−2 d−1 and 0.037–0.332 mg m−2 d−1, respectively. Labile P showed a high and positive correlation (p < 0.01) with labile Fe(II) in the profiles, providing high-resolution evidence for the key role of Fe-redox cycling in labile P variation in sediments.