Seasonal hypoxia enhances sediment iron-bound phosphorus release in a subtropical river reservoir.

Dams worldwide commonly accelerate the eutrophication of reservoirs. While the seasonal hypoxia in deep reservoirs is widely acknowledged, there is limited research on its impact on benthic phosphorus (P) cycling and P fraction release from the reservoir sediments. Here we show that seasonal hypoxia enhances sediment P release and P fluxes at the sediment-water interface (SWI) which might alter P dynamics in deep reservoirs. We conducted a detailed measurement of sediment P fractions through the SEDEX approach, combined with a labile P gradient analysis using the diffusive gradients in thin films (DGT) technique to understand P cycling patterns in sediments during the transition period from spring (oxic) to late summer (hypoxic) conditions. The sediment P pool was predominantly composed of iron-bound phosphorus (Fe-P, 76-80 %), primarily due to the widespread occurrence of lateritic red soil (rich in Fe2O3/MnO2) in subtropical areas. More organic-P was observed in summer compared to spring. A significant increase in labile P occurred at the depth of 0-4 cm and 0-1 cm in spring and summer, respectively, where sediment P release was primarily governed by the reduction of Fe-P and the generation of S2-. A higher apparent fluxes of phosphate across the SWI were observed in summer characterized by higher temperature and lower oxygen levels. The current results suggest that seasonal hypoxia was a crucial factor affecting P cycling and diffusion in deep reservoirs. These findings present important implications for the ecology and management of the watershed-coast ecosystem.

Root-mediated acidification, phosphatase activity and the phosphorus-cycling microbial community enhance phosphorus mobilization in the rhizosphere of wetland plants.

Rhizoremediation of wetland plants is an environmentally friendly strategy for sediment phosphorous (P) removal, the basic underlying principle of which is the complex interactions between roots and microorganisms. This study investigated the immobilization and mobilization mechanisms of P in the rhizosphere of wetland plants using high-resolution spatial visualization techniques and metagenomic sequencing. Two-dimensional visualization of the spatial distribution of P, iron (Fe) and manganese (Mn) indicated that the sequestration of Fe-oxides rather than Mn-oxides caused the depletion of labile P, resulting in an increase in the Fe-adsorbed P fraction. Plants altered the rhizospheric environments and P-cycling microbial community to mobilize low-availability P from sediments. Mineral P solubilization and organic P mineralization were enhanced by local acidification and increased phosphatase activity, respectively. Microbial P mobilization also increased with increasing relative abundances of P solubilization and mineralization genes (gcd and phnW) and decreasing P transportation genes (ugpA, ugpB, and pit) genes in the rhizosphere. These processes led to the remobilization of 10.04 % of inorganic P, and 15.23 % of organic P, in the rhizosphere during the incubation period. However, the resupply of P via the above processes did not compensate for the depletion of rhizospheric P via root uptake and mineral sequestration. Our results provide novel insights into the mechanisms of rhizospheric P cycling, which will help to inform future phytoremediation strategies.

Algal-derived dissolved organic matter accelerates mercury methylation under cyanobacterial blooms in the sediment of eutrophic lakes.

Mercury (Hg), especially in the form of methylmercury (MeHg), poses a significant threat to both organisms and the environment due to its extreme toxicity. While methylation process of Hg in sediments has been extensively studied, recognition of its associated risks and mechanisms during cyanobacterial blooms remains limited. This study investigated the distribution characteristics of Hg and MeHg in sediments of Taihu Lake, China. The concentration of Hg and MeHg varied within the range of 96.0-212.0 ng g-1 and 0.1-0.5 ng g-1, respectively. Higher ecological risks of Hg were found in algal-dominated regions compared to macrophyte areas. The significant correlations observed between Hg, MeHg, and algal-derived dissolved organic matter (ADOM) components C1 and C2 in algal-dominated regions indicate a close association between ADOM components and the Hg methylation process. These components are involved in the absorption or complexation of Hg, participate in redox reactions, and modulate microbial activity. The dsrB gene in sulfate-reducing bacteria (SRB) was found to accelerate the metabolic pathways of Hg methylation. These findings indicate that ADOM could enhance the methylation process of Hg during cyanobacterial blooms, which warrants attention.

Seasonal variations in spatial distribution, mobilization kinetic and toxicity risk of arsenic in sediments of Lake Taihu, China.

This study investigated seasonal variations in spatial distribution, mobilization kinetic and toxicity risk of arsenic (As) in sediments of three representative ecological lakes in Lake Taihu. Results suggested that the bioavailability and mobility of As in sediments depended on the lake ecological types and seasonal changes. At the algal-type zones and macrophyte-type zones, elevated As concentrations were observed in April and July, while these occurred at the transition areas in July and October. The diffusion flux of soluble As ranged from 0.03 to 3.03 ng/cm2/d, indicating sediments acted as a source of As. Reductive dissolution of As-bearing iron/manganese-oxides was the key driver of sediment As remobilization. However, labile S(-II) caused by the degradations of algae and macrophytes buffered sediment As release at the algal-type and macrophyte-type zones. Furthermore, the resupply ratio was less than 1 at three ecological lakes, indicating the resupply As capacity of sediment solid phase was partially sustained case. The risk quotient values were higher than 1 at the algal-type zones and transition areas in July, thereby, the adverse effects of As should not be ignored. This suggested that it is urgently need to be specifically monitored and managed for As contamination in sediments across multi-ecological lakes.

Application of two-dimension, high-resolution evidences to reveal the biogeochemical process patterns of trace metals in reservoir sediments.

Pollutions of trace metals (TMs) in reservoirs are blooming due to TMs were trapped efficiently in reservoir sediments by dams. Despite the mobilization of TMs in sediments have been well-documented, the patterns of biogeochemical processes occurred in sediments remain poorly understanding. Herein, a deep reservoir was selected to investigate the patterns of TMs biogeochemical processes in sediments by using high-resolution ZrO-Chelex-AgI diffusive gradient in thin films technique (HR-ZCA DGT) and the laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). 2-dimension high-resolution (2D-HR) images showed significant differential spatial enrichment of TMs (V, Mn, Fe, Co, Zn and Sb) in sediments, indicating strong heterogeneity in sediments. Correlations of TMs within microniches (diameter < 1 mm) in horizontal were usually different even contrast with that in vertical profile, suggesting distinct biogeochemical process patterns occurred in vertical vs. in horizontal. Further analyses from 2D-HR images showed the distributions of TMs in microniches reflected their mobilization that was driven by microenvironmental conditions. In contrast, distributions in sediment vertical profile recorded the diagenesis in different deposition depth. The diagenesis in sediment vertical is continuously accumulated by the discrete, microniches mobilization of TMs in horizontal. Collectively, our findings evidenced that 2D-HR data is an update complement to 1-dimension data for better interpret the biogeochemical process patterns of TMs in sediments, that have implication for water management to metals pollution in reservoir ecosystems.

Application of high-resolution techniques in the assessment of the mobility of Cr, Mo, and W at the sediment-water interface of Nansi Lake, China.

There are few studies on the simultaneous behavior of chromium (Cr), molybdenum (Mo), and tungsten (W) belonging to group VIB of the periodic table. Herein, based on high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) technology, the vertical distribution characteristics of DGT-labile and soluble Cr, Mo, and W in two lakes of Nansi Lake (Weishan Lake and Dushan Lake) were analyzed. In addition, the net diffusion fluxes and R-value (CDGT/Csol) were used to evaluate the mobility and release risk of metals at the sediment-water interface. The results showed that the DGT-labile concentrations of the three metal elements (Cr, Mo, and W) in Weishan Lake were higher than those in Dushan Lake, both in overlying water and sediment. This is mainly due to the dredging of the Dushan Lake area, which can permanently remove the polluted sediment in the lake. Meanwhile, the exogenous input is relatively high near the tourist area of Weishan Island. The net diffusion fluxes indicate that the W has a potential release risk of diffusion to the overlying water in Dushan Lake. The release of Cr, Mo, and W is thought to be related to the reductive dissolution of Fe/Mn (hydr)oxides based on Pearson correlation coefficients. The R-values of Cr and W indicate that Cr and W belong to the partial continuity case. The R-value of Mo was lower than the minimum value, meaning that Mo belongs to the single diffusion type and it is difficult for Mo sediments to supply pore water.

Cyanobacterial blooms increase the release of vanadium through iron reduction and dissolved organic matter complexation in the sediment of eutrophic lakes.

Vanadium (V), a hazardous environmental contaminant, can be highly toxic to aquatic or even human life. Nonetheless, knowledge of its redox geochemistry and mobility in sediments, especially those of eutrophic lakes, remains limited. In this study, we combined in situ high-resolution sampling and laboratory simulation experiments for monitoring soluble and labile V to reveal the mobilization mechanism of V in the sediment of Lake Taihu. The results showed that the concentration of soluble V (1.18-5.22 µg L-1) exceeded the long-term ecotoxicology limitation proposed by the government of the Netherlands. The highest value appeared in summer (July to September), with an average concentration of 3.87 µg L-1, which exceeded the short-term exposure limit. The remobilization of V in summer was caused by the combined effect of the reduction of Fe(hydr)oxides and dissolved organic matter (DOM) complexation, which accelerated the release of associated Fe-bound V and increased the solubility of DOM-V. Additionally, V showed high mobility in winter, owing to the species of V(Ⅲ)/V(Ⅳ) being oxidized to V(Ⅴ) with higher solubility. It is noteworthy that the elevated remobilization of V in sediments increases the risk of V release from sediments, which poses the threat of water V pollution in Lake Taihu.

Sediment arsenic remediation by submerged macrophytes via root-released O2 and microbe-mediated arsenic biotransformation.

Arsenic (As)-contaminated water restoration is extremely challenging because As remobilization from sediments can result in episodic or long-term release of As to the overlying water. In this study, by combining high-resolution imaging techniques with microbial community profiling, we examined the feasibility of utilizing the rhizoremediation of submerged macrophytes (Potamogeton crispus) to decrease As bioavailability and regulate its biotransformation in sediments. Results showed that P. crispus considerably decreased the rhizospheric labile As flux to lower than 4 pg cm-2 s-1 from larger than 7 pg cm-2 s-1, suggesting its effectiveness in promoting As retention in sediments. Iron plaques induced by radial oxygen loss from roots decreased the mobility of As by sequestering it. Additionally, Mn-oxides may act as an oxidizer for the oxidation of As(III) to As(V) in the rhizosphere, which can further increase the As adsorption owing to the strong binding affinity between As(V) and Fe-oxides. Furthermore, microbially mediated As oxidation and methylation were intensified in the microoxic rhizosphere, which decreased the mobility and toxicity of As by changing its speciation. Our study demonstrated that root-driven abiotic and biotic transformation contribute to As retention in sediments, which lays a foundation for applying macrophytes to the remediation of As-contaminated sediments.

Development and validation of the DGT technique using the novel cryogel for measuring dissolved Hg(II) in the estuary.

The complex seawater matrix has significantly influenced the determination of estuarine dissolved Hg(II), hindering its monitoring and risk assessment in maricultural areas. In this work, SiO2-SH-DGT assembled by the sulfhydryl-modified silica cryogel (SiO2-SH cryogel) as the novel binding phase was developed to tackle this problem. The uniform dispersion of the cryogel into binding gel was advantageous for achieving remarkable and comparable capacity, which endowed the estimated diffusion coefficient (D) to be 1.39-3.08 times of the existing research. The SiO2-SH-DGT performance was independent of pH (3-9), ionic strength (10-800 mM), fulvic acid at low content, and seawater matrix (Na+, K+, Ca2+, Cl-), but the high content of Mg2+ did interfere with the Hg(II) accumulation, which manifested as competitive adsorption and diffusion. Therefore, the calibrated model was established by calibrating accumulated mass (M') and diffusion coefficient (D') based on the Mg2+ concentration, its high accuracy was further verified in the lab. Finally, SiO2-SH-DGT was deployed in the three typical aquaculture areas in Beibu Gulf, field trials achieved the actual Hg(II) level to be 1.52-5.38 ng/L with consideration of the diffusion boundary layer. The finding could provide new thought and technical support for metal pollution monitoring in estuary maricultural areas.

Decrease in macrofauna density increases the sediment phosphorus release and maintains the high phosphorus level of water column in Lake Taihu: A case study on Grandidierella taihuensis.

Internal phosphorus (P) loading can increase the P level in the water column and further sustains cyanobacterial blooms. This study focused on the role of benthic fauna bioturbation in affecting the sediment P release and the P level of water column in a eutrophic lake, Lake Taihu. The macrofauna density decreased from 4766.56 ± 10541.80 ind/m2 in 2007 to 345 ± 447.63 ind/m2 in 2020 due to the frequent bottom-water hypoxia in Lake Taihu. The reduced macrofauna density majorly resulted from Grandidierella taihuensis, Limnodrilus hoffmeisteri, and Tanypus chinensis larvae, and their total density decreased by approximately 97% in 2020 compared to 2007. G. taihuensis, one of the major benthic faunas, was further used as a representative to investigate the effects of bioturbation on sediment P release using high-resolution sampling and imaging techniques. The results show that G. taihuensis can increase the O2 penetration depth by more than 20 mm through bio-irrigation, and causes the redox conditions in burrows and surrounding sediments to change dramatically within a few minutes due to the intermittent ventilation. Subsequent oxidation of the soluble Fe(II) led to the formation of Fe-oxide bound P in the surface sediments, thereby increasing the P retention in the sediments. When the G. taihuensis density was 1563 ind/m2 at the sampling site, approximately 0.12 g m-2 yr-1 P can be retained in sediments. As previous studies have shown that L. hoffmeisteri and T. chinensis played a similar role in increasing the P retention in sediments through their bioturbation activities, the sharp decline in benthic fauna density and burrowing activities in Lake Taihu should be an important reason for maintaining the high P level in the water column by decreasing the P retention in sediments.

Stimulation of high-concentration dissolved nitrogen and reactive phosphorus in Lake Taihu sediments on the initiation and maintenance of cyanobacterial blooms.

The spatio-temporal variation of dissolved inorganic nitrogen (DIN: NH4+-N, NO2--N, and NO3--N) and dissolved reactive phosphorus (DRP) in Meiliang Bay of Lake Taihu sediments and their potential effects on the cyanobacterial blooms were studied. Monthly sampling was performed using high-resolution dialysis sampling devices (HR-Peeper) and two important results were observed in April (the initiation period of cyanobacterial bloom) and June-August (the maintenance period of cyanobacterial blooms). In April, high concentrations of dissolved NO2--N and NO3--N, probably caused by the groundwater influx, were observed in deep anoxic sediments (below 110 mm). NO2--N and NO3--N are good electron acceptors for the mineralization of organic P under anaerobic conditions and should lead to an increase in DRP concentrations in sediments, DRP released from sediments thus further stimulating the cyanobacterial growth and the outbreak of severe cyanobacterial blooms in May due to the extremely low concentrations of DRP in the water body. From June to August, high concentrations of NO2--N, NO3--N, and DRP were observed in the surface sediment, which was caused by the release of NH4+-N from the mineralization of cyanobacterial debris. This should play an important role in maintaining cyanobacterial growth, especially in stimulating the occurrence of cyanobacterial blooms during September, when N and P were co-limited. This study revealed high-concentration DIN and DRP in Lake Taihu sediments potentially stimulated the initiation and maintenance of cyanobacterial blooms.

Selective and simultaneous high resolution 2-D imaging of AsIII, CrIII and SbIII and dissolved oxygen by developing a new DGT technique comprising a hybrid sensor.

A new diffusive gradients in thin films technique (HR-MPTS DGT) with mercapto-functionalized attapulgite in a binding gel was developed for simultaneous two-dimensional (2-D) chemical imaging of AsIII, CrIII and SbIII selectively at the submillimeter scale, combined with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. The HR-MPTS DGT exhibited selective accumulation of AsIII, SbIII and CrIII (> 97%), yet negligible accumulation of AsV, SbV and CrVI (< 2%). Accumulation of AsIII, CrIII and SbIII on the binding gel had a linear relationship (R2 > 0.99) with the corresponding standardized laser ablation signals, proving the feasibility of LA-ICP-MS analysis. Analysis for AsIII, CrIII and SbIII was provided with favorable analytical precision (relative standard deviation <10%). With the purpose of evaluating the dynamics of AsIII, CrIII, SbIII and O2 in the rooting zone, a hybrid sensor, which comprises the HR-MPTS gel overlying an O2 planar optode, was deployed in rhizosphere sediments. Results showed that the consumption of both AsIII and SbIII due to the oxidation extended ~4.48 mm into the sediments, which was consistent with the extension length of the oxidized sediment layers around the roots created by O2 leakage.

Mechanistic insights into trace metal mobilization at the micro-scale in the rhizosphere of Vallisneria spiralis.

Mobilization of trace metals in the rhizosphere of macrophytes is controlled by root-driven chemical changes, especially the steep gradients of O2 and pH from the rhizosphere to bulk sediments. Here, the O2 and pH dynamics, and the distribution of trace metal, in the rhizosphere of Vallisneria spiralis were obtained using planar optodes and diffusive gradients in thin films, respectively. Radial O2 loss (ROL) and acidification occurred on all visible roots of V. spiralis and exhibited highly spatiotemporal dynamics depending on the root growth and various environmental conditions. Trace metals showed different mobilization mechanisms in the rhizosphere. ROL and produced Fe(III) (oxyhydr)oxides decreased the mobility of Fe, As, Co, V and W in the rhizosphere. However, Mn, Ni and Cu exhibited greater mobility in the rhizosphere than bulk sediments as a result of the oxidation of metal sulfide and proton-induced dissolution of minerals. In particular, Co and Ni presented increased activity at the interface between rhizosphere and bulk sediment, which was attributed to the redox dissolution processes of Fe and Mn as a result of ROL and rhizosphere acidification. These results provide new insights into the roles of macrophyte root-induced O2 and pH changes in controlling trace metal mobility in sediments.

Evaluation of the Potential Release Tendency of Metals and Metalloids from the Estuarine Sediments: Case Study of Rasa Bay.

Assessing the environmental quality of coastal systems is important not only for the management and protection of such areas, but also for improving the quality of water resources. Since sediment itself can often be a source of certain toxic elements, in addition to information on the distribution of metals in the water column and in the sediment itself, it is useful to determine the bioavailable forms of individual elements, particularly toxic ones. In this study, water and sediment geochemical data were supplemented with oxyanion mobility in sediments estimated by diffusion gradients in thin film (DGTs). The data obtained indicate that the chemical composition of the water in the Rasa River estuary primarily reflects the high input of suspended sediment from the catchment, the mixing of freshwater and seawater, and to a lesser extent the effects of anthropogenic activities. Although sediment composition is primarily determined by geological and hydrodynamic conditions in the catchment, it also indicates moderate enrichment in Co, Cr, Mo and Ni. In contrast, the distribution of oxyanions in sediment pore water indicates the influence of sediment as a source of some elements in the bottom water; e.g., sediment contributes to 40% of the arsenic bottom water budget. The obtained depth profiles of the oxyanion distribution in the sediment pore water indicate an early onset of suboxic to anoxic conditions in Rasa Bay, which is prone to rapid sedimentation. All this demonstrates the need to consider the bioavailable forms of elements when assessing environmental quality, as the lack of such information can lead to an incomplete assessment, especially in dynamic coastal systems such as estuaries.

Phosphorus acquisition strategy of Vallisneria natans in sediment based on in situ imaging techniques.

Phosphorus (P) availability is closely related to the distributions of pH, O2 and phosphatase activities in the rhizosphere of plants growing in soils and sediments. In this study, the P uptake processes and mechanisms of Vallisneria natans (V. natans) during two vegetation periods (i.e., week three and six) were revealed using three noninvasive 2D imaging techniques: planar optode (PO), diffusive gradients in thin films (DGT) and zymography. The results showed that increased phosphatase activity, O2 concentration and root-induced acidification were observed together in the rhizosphere of root segments and tips. In week three, when V. natans was young, the flux of DGT-labile P accumulated more in the rhizosphere in comparison with the bulk sediment. This was because increased phosphatase activity (of up to 35%) and root-induced acidification (with pH decreasing by up to 0.25) enhanced P acquisition of V. natans by the third week. However, the flux of DGT-labile P turned to depletion during weeks three to six of V. natans growth, after Fe plaque formed at the matured stage. The constant hydrolysis of phosphatase and acidification could not compensate for the P demand of the roots by the sixth week. At this stage, Fe plaque become the P pool, due to P fixation with solid Fe(III) hydroxides. Subsequently, V. natans roots acquired P from Fe plaque via organic acid complexation of Fe(III).

Terrain-modulated deposition of atmospheric lead in the soils of alpine forest, central China.

Alpine ecosystem has a potential to intercept the transport of atmospheric metals, while the regulation mechanisms with variations in altitude and slope direction remain unclear. In this study, the soil and moss samples on the northern and southern slopes of Shennongjia Mountain were collected with altitude to quantitatively identify the sources of lead (Pb) and to decipher the regulation mechanisms of altitude and slope on the Pb distribution. The results showed that the concentrations of Pb decreased evidently with soil depth, and in the O (organic soils) and A (surface mineral soils) horizons they increased with altitude. The Pb isotopes and moss biomonitoring revealed that Pb was mainly from atmospheric deposition, and the sources included fossil fuel combustion, ore mining and smelting. Based on a binary mixing model of Pb isotopes, the percentage of atmospheric Pb in the O and A horizons and mosses averaged 58.8%, 43.7% and 71.0%, respectively. Atmospheric wet deposition strikingly controlled the distribution of soil Pb along the altitude. Canopy filtering and leaching also impacted the accumulation of Pb in the forest floor. The significant difference in the atmospheric Pb accumulation in the soils between the two slopes was not observed as expected, since atmospheric dry deposition from northwestern China contributed to the Pb accumulation on the northern slope according to the Pb isotopic ratios and air mass trajectories. The results of this study indicate that altitude determines the distribution pattern of atmospheric Pb, while slope direction screens the source region of Pb in alpine ecosystems.

Enhancing the retention of phosphorus through bacterial oxidation of iron or sulfide in the eutrophic sediments of Lake Taihu.

Microbial activity can enhance the sequestration of phosphorus (P) in sediments, but little is known about the mechanisms behind it. In this study, sediment cores were sampled from the most eutrophic Meiliang Bay of Lake Taihu, and three treatments were set up in a laboratory incubation experiment, involving (a) the non-treated sediment cores, (b) inoculation, and (c) sterilization. The dissolved and labile iron (Fe) and P were obtained by high-resolution dialysis and the diffusive gradients in thin films (DGT) technique, respectively. AgI-based DGT was used for measuring the 2D distribution of labile sulfide. The bacterial community was investigated using a scanning electron microscope and 16S rRNA high throughput sequencing technique. The results showed that sterilization reduced the capacity of sediment to immobilize P, and that the critical sediment depth layer for microbial P sequestration was 0-10 mm. In addition, sterilization or inoculation significantly changes the structure of bacterial communities. Fe or S oxidation under micro-aerobic or anaerobic conditions played an important role in bacterial retention of P in the sediments. Nitrate-reducing coupling Fe(II)-oxidizing bacteria (Acidovorax) in the inoculated sediment and electrogenic sulfur-oxidizing bacteria (Candidatus Electronema) in the non-treated sediment were identified as the key bacterial genera responsible for the retention of P in sediments. This implies that bacterial communities could quickly establish the ability for negative feedback regulation by inoculation once the function and structure of indigenous sediment bacteria are seriously impaired, although this needs further validation in the field.

Sustainable ex-situ remediation of contaminated sediment: A review.

Routine waterway dredging activities generate huge volumes of dredged sediment. The remediation of dredged contaminated sediment is a worldwide challenge. Novel and sustainable ex-situ remediation technologies for contaminated sediment have been developed and adopted in recent years. In this review paper, the state-of-art ex-situ treatment technologies and resource utilisation methods for contaminated sediment were critically reviewed. By applying different techniques, sediment could been successfully transformed into sustainable construction materials, such as ceramsite, supplementary cementitious materials, fill materials, paving blocks, partition blocks, ready-mixed concrete, and foamed concrete. We highlighted that proper remediation technologies should be cleverly selected and designed according to the physical and chemical characteristics of sediment, without neglecting important aspects, such as cost, safety, environmental impacts, readiness level of the technology and social acceptability. The combination of different assessment methods (e.g., environmental impact assessment, cost-benefit analysis, multi-criteria decision analysis and life cycle assessment) should be employed to comprehensively evaluate the feasibility of different sustainable remediation technologies. We call on the scientific community in a multidisciplinary fashion to evaluate the sustainability of various remediation technologies for contaminated sediment.

O2 distribution and dynamics in the rhizosphere of Phragmites australis, and implications for nutrient removal in sediments.

Root-triggered microscale variations in O2 distribution in the rhizosphere of young Phragmites australis are important for nutrient removal in sediments. In this study, the micro-scale O2 dynamics and the small-scale changes of soluble reactive phosphorus (SRP) and ammonium (NH4+) in the rhizosphere of P. australis were investigated using planar optodes and high-resolution dialysis (HR-Peeper), respectively. Results suggested that root O2 leakage has a highly variable distribution depending on the stage of root growth, the site of O2 leakage gradually shift from the entire emerging main roots to the main root tip and subsequently shifted the emerging lateral roots. The O2 concentration increased in the rhizosphere with increasing light intensity and O2 levels in the overlying water. Continuous O2 release from the lateral roots causes the formation of iron plaque on the surface of lateral roots, which reduce the mobility of P by adsorption of iron plaque in the rhizosphere. The oscillation of oxic-anoxic root zones improves nitrogen removal through the processes of anammox, heterotrophic denitrification and nitrification. This work from the micro-scale demonstrates that the O2 concentration is the spatio-temporal variations in the rhizosphere, and it presents an important role for nutrient removal in sediments.

Investigation of the combined use of capping and oxidizing agents in the immobilization of arsenic in sediments.

The combined use of capping (lanthanum modified bentonite; LMB) and oxidizing (calcium nitrate; CN) agents was investigated to immobilize arsenic (As) in sediments. The vertical changes in labile As and dissolved As were measured using diffusive gradients in thin films (DGT) and Rhizon devices. The results showed that the combined application of LMB and CN had the optimal effect on the immobilization of both DGT-labile As and dissolved As, compared to single treatments using LMB or CN. After 60 days of incubation, the maximum reduction efficiencies of DGT-labile As at sediment depths were 76.4%, 70.8%, and 44.9% of those treated with LMB + CN, CN, and LMB, respectively. After 32 days of incubation, the average concentrations of dissolved total As throughout the depths decreased from 7.71 µg/L after the control treatment without any amendments to 5.25, 4.03, and 3.15 µg/L after the addition of LMB, CN, and LMB + CN, respectively. The larger part of exchangeable As at sediment depths was converted into the reducible As mainly bound Fe/Mn oxide-hydroxides after combining LMB and CN. Due to the As(III) existing mainly in the form of electrically neutral H3AsO3 in sediments, it is hard to adsorb As(III) for the LMB and iron/manganese oxide-hydroxides formed by the oxidation effect of calcium nitrate. Thus, the single or combined LMB and CN use had much weaker effect on the immobilization of As(III) compared with As(V). The results of current study indicated that the combined use of LMB and CN could be a promising method to control the potential release of As from the sediment to the overlying water. However, this method needs further improvement to achieve a better immobilization effect on As(III) in sediments.