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Abstract Iron (Fe) and manganese (Mn) reactions have been regarded as the primary factors responsible for the mobilization of phosphorus (P) in lake sediments, although their individual roles are hard to distinguish. In this study, in situ mobilization of P, Fe and Mn in sediments was assessed by high resolution spatio-temporal sampling of their labile forms using diffusive gradient in thin films (DGT) and suction device (Rhizon) techniques. It was found that the monthly concentration distributions showed greater agreement and better correlation coefficients between labile P and labile Fe, than those between labile P and labile Mn, implying that Fe plays a key role in controlling P release in sediments. Furthermore, better correlations were observed between hourly changes in concentrations of soluble reactive phosphorus (SRP) and soluble Fe(II), than those between SRP and soluble Mn. Changes were observed under simulated anaerobic incubation conditions, suggesting that P release was caused by the reductive dissolution of Fe oxides. This was supported by the lack of influences on P release from reductive dissolution of Mn oxides in the sediment-water interface and top sediment layers under the anaerobic incubations. In simulated algal bloom experiments, positive correlations and consistent changes were observed between SRP and soluble Fe(II) concentrations, but not between SRP and soluble Mn concentrations. This further demonstrated the Fe-dependent and Mn-independent release of P in sediments. Therefore, Fe redox reactions have a high impact on P mobilization in sediments, while Mn redox reactions appear to have negligible influences. Graphical abstract Image 1 Highlights • Monthly distribution of labile P concentration correlated with labile Fe concentration in sediments. • Hourly change of SRP correlated with soluble Fe(II) concentrations under anoxic conditions. • Phosphorus was not released during the reductive dissolution of Mn oxides. • Consistent changes in P and Fe but not in Mn occurred in algal bloom sediments. • Fe but not Mn redox reactions should control mobilization of P in sediments. Evidence that Fe redox reactions play a key role in controlling P mobilization in sediments, while Mn redox reactions do not have a significant influence. [ABSTRACT FROM AUTHOR]

A new method for simultaneous measurement of fifteen rare earth elements (REEs) [La (Ⅲ), Ce (Ⅲ), Pr (Ⅲ), Nd (Ⅲ), Sm (Ⅲ), Eu (Ⅲ), Gd (Ⅲ), Tb (Ⅲ), Dy (Ⅲ), Ho (Ⅲ), Er (Ⅲ), Tm (Ⅲ), Yb (Ⅲ), Lu (Ⅲ), and Y (Ⅲ)] was established in this study using the diffusive gradients in thin films (DGT) technique with Chelex ® 100 binding gel. Five different types of ion exchange resins (Chelex ® 100, D418, D001-cc, 001 × 7, and HSTY ® -SS) were selected for the initial investigation of their adsorption performance for REEs. The Chelex ® 100 binding gel had the greatest uptake efficiencies of >95% for the fifteen REE ions, which was used for all subsequent experiments. The binding gel exhibited rapid binding dynamics to REEs in mixed solution of the fifteen REE ions. Elution efficiencies ranging from 86.5% to 93.8% for these REEs were obtained based on extraction using 2.0 M HCl. The Chelex ® 100 DGT uptake of the fifteen REE ions increased linearly with the deployment time and found to be independent of pH (3–9) and ionic strength (3 mM–100 mM). The capacities of Chelex ® 100 DGT for measurement of the mixed elements were determined at a range of 5.39–6.75 μg cm −2 . Application of the DGT for soil analysis showed that Chelex ® 100 DGT was a useful tool in simultaneous measurement of the fifteen REE ions, even in a soil with high concentrations of REEs. This study demonstrated the advantage of Chelex ® 100 DGT in simultaneous measurement of the fifteen REE ions due to high uptake efficiencies and a wide tolerance to environmental interference. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The release of arsenic (As) from sediments poses a risk to human health especially at high pH levels. Despite this, the distribution and kinetic response of mobile As remains unclear under varying pH conditions. In this study, a microcosm incubation experiment was performed, using sediment cores in combination with dialysis (Peeper) and thin film diffusive gradients (DGT), to investigate the distributions of mobile As (soluble As in pore water and DGT-labile As) at high vertical resolutions (2-4 mm). Results show that the concentrations of soluble As present in the water column increased 1.5-fold with an increase in pH from 5.4 to 11.2. Both soluble As in pore water and DGT-labile As exhibited stable low-level distributions in the uppermost layer beneath the sediment-water interface, followed by increasing concentration distribution with decreasing layers to middle depths. The mean concentrations of mobile As species increased with increased water pH in both sediment profiles and with upward diffusion gradients, showing a 0.2-fold increase of soluble As in the top 20-mm layer and a 0.6-fold increase in deeper 20-52-mm layers, while DGT-labile As showed a 1.0- and 1.1-fold increase in these two layers, respectively. Modeling of DGT-induced flux in sediments (DIFS) showed that the desorption rate constant increased more rapidly than the absorption rate constant, resulting in the increased availability of solid As pools, therefore resupplying the soluble As in pore water from sediments. [ABSTRACT FROM AUTHOR]

Much attention has been paid to the availability of arsenic (As) in soils, while few studies were carried out on the comparison between the dry and flooded soils using different methods. In this study, chemical sequential extraction and diffusive gradients in thin films (DGT) techniques were employed to study the availability of As in soils amended with a range of exogenous As followed by one-year incubation under dry and flooded conditions, respectively. The results showed that the proportions of available solid As pools, including non-specifically adsorbed As (F1) and specifically adsorbed As (F2), had consistent increases with the increase of As amendment. The concentration of DGT-measured As ( C ) and dissolved As in soil solution ( C ) also increased up to 2573 (dry) and 1823 (flooded) times and 4067 (dry) and 3105 (flooded) times of the control, respectively, while their ratios ( R) showing the extent of C sustained from solid resupply decreased from 0.17 to 0.10 (dry) and 0.35 to 0.21 (flooded). Modelling with DGT-induced fluxes in soils (DIFS) further showed an increase of T (the characteristic time to reach equilibrium from DGT perturbation) and decreases of desorption and adsorption rate constants ( k and k ) with the increase of As amendment, reflecting a decrease in kinetic exchange rate of As between available solid As pool and soil solution. The flooded soils had greater values of R, k and k and lower value of T in comparison with the dry soils, indicating a greater availability of As under the flooded condition. [ABSTRACT FROM AUTHOR]

In-situ characterization and assessment of arsenic (As) mobility in sediments was scarce. In this study, the distributions of labile As at a vertical resolution of 2 mm were obtained in the sediments of a large Lake Taihu through in-situ measurements using a Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique. The DGT-labile As, interpreted as DGT flux ( F DGT ), exhibited three different patterns in the lake, with all the patterns generally showing an increasing mobility followed by a decreasing mobility with sediment depth. The mobility of As could be characterized by the average F DGT (0.06–1.27 pg cm −2 s −1 ) in the top 10 mm surface sediments, the maximal F DGT ( F DGT-M , 0.14–2.44 pg cm −2 s −1 ) in the end of the initial increasing phase of F DGT , and the diffusion length ( ΔL , 28–66 mm) from the depth showing the F DGT-M to the sediment-water interface. The upward mobilization of labile As from the deep sediments to the surface sediments and overlying water became evident when F DGT-M > 1.7 pg cm −2 s −1 or ΔL < 41 mm. The results, for the first time, showed a prospect in in-situ risk assessment of the pollution of sediment As. It was suggested that the increasing mobility of As in the upper sediments was controlled by the reduction of As(V) and the reductive dissolution of Fe(III) (hydr)oxides, while the decreasing mobility in the deep sediments was attributed to immobilization of As(III) by secondary Fe(II)-bearing minerals. [ABSTRACT FROM AUTHOR]

Abstract Differences in trophic status can lead to different water quality and sediment geochemistry characteristics, influencing antimony (Sb) mobility in sediments and its release into the water column. In this study, seasonal sampling was conducted in algal- and macrophyte-dominated zones of Lake Taihu, China. High-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were used to measure soluble Sb and DGT-labile Sb in the sediment-water profiles at a 4 mm vertical resolution. Results showed that total Sb in sediments from the two zones were on average 3.50 mg/kg and 3.21 mg/kg in the algal- and macrophyte-dominated zones, respectively, with the residual fraction being 96.3% and 95.4% of the total Sb contents in the two zones. In winter, soluble Sb concentrations in both zones increased. This was probably due to the oxidation of Sb(III) to Sb(V) by Mn and Fe oxides. In summer and autumn, soluble Sb concentrations in the algal-dominated region remained low. This is attributed to the dominance of insoluble Sb(III) in sediments under anoxic conditions under eutrophic environments. In contrast, soluble Sb concentrations in the macrophyte-dominated zone were significantly high in summer and were 4.15-times higher than limits set by the World Health Organization (WHO). This likely resulted from the photochemical and rhizospheric oxidation of insoluble Sb(III) compounds. It is suggested that Sb contamination in the sediment-water system of the macrophyte-dominated zone deserves additional attention. Highlights • Antimony (Sb) mobility differed in algae- and macrophyte-dominated (MD) regions. • Photochemical and rhizospheric oxidation increased Sb mobility in the MD region in summer. • Mn and Fe oxide oxidation increased Sb mobility in two regions during winter. • Sb mobilization manifested mainly in the transition between Sb(III) and Sb(V). [ABSTRACT FROM AUTHOR]

Sediments have a heterogeneous distribution of labile redox-sensitive elements due to a drastic downward transition from oxic to anoxic condition as a result of organic matter degradation. Characterization of the heterogeneous nature of sediments is vital for understanding of small-scale biogeochemical processes. However, there are limited reports on the related specialized methodology. In this study, the monthly distributions of labile phosphorus (P), a redox-sensitive limiting nutrient, were measured in the eutrophic Lake Taihu by Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) on a two-dimensional (2D) submillimeter level. Geographical information system (GIS) techniques were used to visualize the labile P distribution at such a micro-scale, showing that the DGT-labile P was low in winter and high in summer. Spatial analysis methods, including semivariogram and Moran’s I, were used to quantify the spatial variation of DGT-labile P. The distribution of DGT-labile P had clear submillimeter-scale spatial patterns with significant spatial autocorrelation during the whole year and displayed seasonal changes. High values of labile P with strong spatial variation were observed in summer, while low values of labile P with relatively uniform spatial patterns were detected in winter, demonstrating the strong influences of temperature on the mobility and spatial distribution of P in sediment profiles. [ABSTRACT FROM AUTHOR]

The efficiencies of capping agents in immobilizing sediment phosphorus (P) are widely assessed using a short-term batch adsorption method. This is done based upon the assumption that the immobilization process can be simplified to an adsorption process. In this study, the immobilization efficiency of calcium-rich attapulgite (NCAP) for sediment P was assessed using both the batch adsorption and sediment core incubation methods. The techniques of high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) were employed to measure the soluble reactive P (SRP) and labile P in sediment cores, respectively. The results showed a high immobilization efficiency (on average, 95%) of the NCSP for SRP in the sediment during the 10-day batch adsorption, whereas 26% of Fe bound P and 48% of Al bound P were transformed into Ca bound P. In contrast, the capping of NCSP in sediment core caused a maximum of 145% increase in SRP concentration in the overlying water during the 110-day incubation. The concentrations of SRP and DGT-labile P exhibited increases of 176% and 193% in the top 30 mm and 20 mm sediment layers, respectively. No considerable transformation occurred from active Fe and Al bound P to stable Ca bound P. The contrasting results from NCSP amendment highlighted the difference in interactions between the NCSP and the sediments under the two assessment methods. As the incubation using sediment cores approached the field conditions, a long-term test based upon this method is strongly recommended before the costly field trial. [ABSTRACT FROM AUTHOR]

A millimeter-scale investigation is key to the understanding of the competitive effects of phosphate(P) on arsenic(As) mobility in sediments by taking the great biogeochemical heterogeneity of the sediments into consideration. In this study, a microcosm experiment was performed in this aspect using high-resolution dialysis and diffusive gradients in thin films (DGT) to simultaneously measure dissolved and labile P, As, and iron (Fe) in sediments, respectively. With the increase of P content in water from 0.02 mg L −1 to 0.20 and 2.4 mg L −1 , consistent release of As from sediments was observed. The concentrations of DGT-labile As increased significantly especially in the upper sediment layer (up to 12 times of the 0.02 mg P L −1 treatment) due to the competition of phosphate, which corresponded well to the increase in DGT-labile P. There was limited increase in dissolved P and As contents due to the buffering provided by sediment solids, while the concentrations of both dissolved and DGT-labile Fe in sediments decreased. A stoichiometric calculation showed that 47% and 8% of the added P were removed through Fe(II) precipitation for the 0.20 and 2.4 mg P L −1 treatments, respectively, which greatly suppressed the release of As induced by P competition for the 0.20 mg P L −1 treatment. The DGT-induced fluxes in sediments (DIFS) modeling showed an increase in solid resupply to pore water As from elevation of water P through the increases of the desorption rate constant from 5.4 to 31( × 10 −7 ) s −1 and the sorption rate constant from 1.8 to 22( × 10 −4 ) s −1 . [ABSTRACT FROM AUTHOR]

A new method for the simultaneous measurements of eight cations [Fe(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II)] and eight oxyanions [P(V), V(V), Cr(VI), As(III)/As(V), Se(VI), Mo(VI), Sb(V), and W(VI)] was established in this study using the diffusive gradients in thin films (DGT) technique with an improved ZrO-Chelex binding gel. The binding kinetics of each analyte in a mixed solution indicated a rapid uptake on the ZrO-Chelex gel. The anions exhibited slower absorption rates compared to the cations, which did not affect the DGT uptake. Stable elution efficiencies for these cations and anions were obtained based on a two-step extraction procedure using 1.0 M HNO 3 for elution of the cations followed by a mixed solution containing 0.2 M NaOH and 0.5 M H 2 O 2 for elution of the anions. Simultaneous measurements of the cations and anions with the ZrO-Chelex DGT were validated in mixed solutions and found to be independent of solution pH (5–9) and ionic strength (2–3 mM to 750 mM). The capacities of the ZrO-Chelex DGT for single measurements of Fe(II), P(V), Cd(II), As(III), and As(V) were determined at 99.5, 127.6, 301.2, 33.3, and 87.4 μg cm −2 . Except for Se(VI) in seawater, accurate measurements of all of these cations and anions in natural freshwater and seawater were obtained using the ZrO-Chelex DGT. The performance of this technique for simultaneous measurements of 16 elements was also tested in sediments. [ABSTRACT FROM AUTHOR]

Excessive phosphorus (P) input plays an important role on the release of heavy metals in sediments under the eutrophic environment. In this study, a microcosm experiment with 40-day incubation using homogenized sediments was performed to investigate this aspect at a millimeter resolution. Diffusive gradient in thin films (DGT) and dialysis (Peeper) techniques were employed to simultaneously measure labile and dissolved P, Pb, Cd, Zn, Co and Ni in sediments at a millimeter scale, respectively. The results showed that an increase of water P from 0.02 mg L − 1 to 0.20 and 2.4 mg L − 1 generally led to intensified decrease of DGT-labile metals from the 10th to 20th days after the onset of incubation. The decrease in dissolved metals in pore water also appeared on the 20th day. The degree of decrease in the five metals was in the order of Pb > Cd > Zn > Co > Ni, which has a negative correlation with the solubility constants ( K sp ) of each metal-P precipitate. This indicated that the negative effect was caused by the precipitation of metal P. On the 40th day during incubation, the concentrations of DGT-labile metals had different increasing pattern compared to those on the 20th day. The extent of metal recovery was positively correlated with the change of desorption rate constant ( k − 1 ) and negatively correlated with the change in the characteristic time ( T c ) to reach equilibrium from DGT perturbation derived from DGT-induced fluxes in sediments (DIFS) modeling. This suggested that the recovery of metal lability from elevated water P was a result of the increased releases of metals from sediment solids. [ABSTRACT FROM AUTHOR]

The agarose hydrogel has been increasingly used as a diffusive layer in diffusive gradients in thin films (DGT) measurements. However its diffusive characteristics have not been examined in detail. In this study, the performance of agarose gel was tested in DGT measurements of eight cations (Fe(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), and Cd(II)) and eight anions (P(V), As(V), Cr(VI), Mo(VI), Sb(V), Se(VI), V(V), and W(VI)). It was found that the thickness of agarose, a key parameter in the calculation of DGT measured concentration, remained unchanged after hydration followed by storage under the following conditions: pH 2–11, ionic strength 0–1.0 M, temperature 4–40 °C, and with the storage time extending to 300 d. Enrichment of cations and repelling of anions were observed in the gel under the ionic strengths of < 2–3 mM and <1 mM (NaNO 3 ), respectively, which was attributed to the electrostatic interactions of these ions with the fixed negatively charged groups (mainly pyruvate) in the gel. The diffusion coefficients of cations and anions through the agarose gel (plus a PVDF filter membrane) were on average 1.10 ± 0.04 times of the reported diffusion coefficients through the agarose cross-linked polyacrylamide (APA) hydrogel, typically used in DGT technique. The working pH ranges for the agarose gel-assembled DGTs were 4–10 and 5–9 for anions and cations, respectively. The use of agarose gel, either individually or along with different filter membranes, affected the overall diffusion rates of cations and anions. The measured DGT concentrations of cations and anions in filtered natural freshwater and seawater were mostly in line with those measured directly. The results showed that the agarose gel can be used as one of the standard diffusive layers in DGT measurements for a wide range of inorganic and organic analytes. [ABSTRACT FROM AUTHOR]

Understanding the labile status of phosphorus (P) in sediments is crucial for managing a eutrophic lake, but it is hindered by lacking in situ data particularly on a catchment scale. In this study, we for the first time characterized in situ labile P in sediments with the Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique at a two-dimensional (2D), submillimeter resolution in a large eutrophic lake (Lake Taihu, China, with an area of 2338 km 2 ). The concentration of DGT-labile P in the sediment profiles showed strong variation mostly ranging from 0.01 to 0.35 mg L −1 with a considerable number of hotspots. The horizontal heterogeneity index of labile P varied from 0.04 to 4.5. High values appeared at the depths of 0–30 mm, likely reflecting an active layer of labile P under the sediment–water interface (SWI). Concentration gradients of labile P were observed from the high-resolution 1D DGT profiles in both the sediment and overlying water layers close to the SWI. The apparent diffusion flux of P across the SWI was calculated between −21 and 65 ng cm −2 d −1 , which showed that the sediments tended to be a source and sink of overlying water P in the algal- and macrophyte-dominated regions, respectively. The DGT-labile P in the 0–30 mm active layer showed a better correlation with overlying water P than the labile P measured by ex situ chemical extraction methods. It implies that in situ , high-resolution profiling of labile P with DGT is a more reliable approach and will significantly extend our ability in in situ monitoring of the labile status of P in sediments in the field. [ABSTRACT FROM AUTHOR]

A two-dimensional (2D) imaging technique, planar optode (PO) technique, is developed to investigate biogeochemical processes at a high resolution in heterogeneous sediments and soils, especially at the sediment-water interface. Compositional changes with depth in sediments are usually considered to be relatively steady. However, the activities of benthic organisms can generate significant heterogeneity and complex 3D transport-reaction patterns over millimeter to meter scales in the surficial sediments. Spatial and temporal quantification of the variables such as O 2 in the bioturbated sediments promoted the development of the planar optode. Different planar optode techniques including composite planar optode for multi-analytes and the combination of planar optode with diffusive gradients in thin films (DGT) have been developed and used to study the 2D solutes distributions and/or dynamics of O 2 , pH, partial pressure of CO 2 (p CO 2), temperature, exoenzymes, and metal/metalloid ions in sediments and soils. New findings observed in laboratory-based microcosm experiments and field-based in situ studies using planar optode techniques, have significantly improved our understanding of heterogeneous biogeochemical reactions and processes. In this article we provide a critical review on the: 1) research progress using planar optode techniques; 2) principles, configurations, and devices used for planar optode systems; 3) characteristics and interferences associated with planar optode measurements; and 4) applications of planar optode in the environment. We have suggested the barriers, advantages, and research needs for the use of planar optodes. Unlabelled Image • The research progresses of 2D imaging PO technique were reviewed. • The principles, configurations and devices used for PO system were introduced. • The characteristics and interferences seen with PO measurements were evaluated. • PO applications in combination with several research cases were discussed. [ABSTRACT FROM AUTHOR]