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For soils and sediments, which are complex and heterogeneous, root-triggered processes, bioturbation of benthic communities, and local decomposition of reactive organic materials can greatly increase their biogeochemical heterogeneity. In practice, common monitoring methods can only be used to determine the centimeter- to millimeter-scale heterogeneity from vertical or horizontal one-dimensional profiles. However, significant heterogeneity exists in both soils and sediments on the millimeter to sub-millimeter scales. Therefore, in-situ and high-resolution sampling and imaging methods are essential to capture the spatial and temporal heterogeneity of soils and sediments. This article reviews micro-scale sampling methods in soil and sediments, including diffusive equilibration in thin films (DET), diffusive gradient in thin films (DGT), planar optodes (PO), nanoparticle- and microparticle-based luminescence imaging, and soil zymography. Besides, we introduce their imaging principles and approaches in detail, and discuss some problems and solutions during imaging. Micro-scale sampling and imaging methods have given us many insights into the biogeochemical processes in soils and sediments, but the full potential of these methods has not been exhausted yet. Finally, the potential directions for the development of micro-scale sampling methods in the study of complex biogeochemical processes in heterogeneous soils and sediments are prospected. [ABSTRACT FROM AUTHOR]

A large number of ex situ sampling techniques have been used traditionally to investigate the impact and fate of pollutants in soil, sediment and waters. However, the distribution and form of chemical species present are often altered prior analysis, due to the alterations during sampling and transfer to the laboratory. Alternatively, a robust in situ passive sampling technique, diffusive gradients in thin films (DGT), has been developed for the measurement of labile concentrations, species and distribution of various solutes in soil, sediment and waters. Here we review the recent developments in DGT device configurations and components, e.g., binding agents, diffusive phases and filter membranes. We highlight new configurations for effectively reducing the measurement errors and the disturbance of environmental media. We discuss DGT applications for the analysis of soil, sediment and water, such as evaluation of bioavailability and toxicity, measurement of nutrients and organic substances, and assessment of relationships between multiple solutes. We also present the coupling of DGT with other in situ measurement techniques such as dialysis samplers (Peeper), diffusive equilibrium in thin films (DET) and planar optodes (PO). [ABSTRACT FROM AUTHOR]

Purpose: Phosphorus influence on arsenic bioavailability in soils and its toxicity to plants is widely recognized. This work compares competitive influence of P on As bioavailability in dry and flooded soils. Materials and methods: Pot experiments were carried out in dry and flooded soils, respectively. Bioavailable As in soils was measured using diffusive gradients in thin films (DGT), soil solution concentration, and three single chemical extraction methods. Results and discussion: P concentration at 50 mg/kg promoted wheat growth in dry soil. At concentrations above 50 mg/kg, P competition inhibited wheat growth and enhanced As toxicity. In flooded soil, the rice height and biomass decreased with the increase of P addition. P concentrations above 800 mg/kg were lethal to the rice. The content of As absorbed by wheat and rice roots as well as shoots increased with the increase of P concentration. The bioavailability of As in wheat- and rice-grown soils, determined by all methods, also increased with the increase of P concentration. The correlation analysis between the bioavailable As measured by the all three methods and the content of As in plants showed a significant positive correlation. The Pearson correlation coefficient for the DGT method was higher comparing to all other methods. DGT-induced fluxes in soils (DIFS) modeling further showed sharp decreases of Tc (the characteristic time to reach equilibrium between available solid As pool and soil solution As from DGT perturbation) and increases of desorption and adsorption rate constants (k1 and k−1) of As in P-amended soils, reflecting that the kinetic release of As from available solid As pools became much easy from P competition. Conclusions: P competition in both dry and flooded soils could significantly increase bioavailability of As and further increase its toxicity. Competition effect was more pronounced in flooded soil. DGT is a more accurate method for As bioavailability evaluation in both dry and flooded soils. [ABSTRACT FROM AUTHOR]

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]

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]

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]

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]

Lake eutrophication and algal blooms may result in the mortality of macrozoobenthos. However, it is still not clear how macrozoobenthos decomposition affect phosphorus (P) mobility in sediments. High-resolution dialysis (HR-Peeper) and the diffusive gradients in thin films (DGT) technique were used in this study to assess the dissolved organic matter (DOM), dissolved/DGT-labile iron (Fe), P, and sulfur (S(–II)) profiles at a millimeter resolution. The decomposition of Bellamya aeruginosa significantly increased the internal loading of sediments P. The Fe(III) and sulfate were reduced under anaerobic conditions and promoted P desorption from sediments. This was supported by the significant increase in DGT-labile S(–II) and dissolved/DGT-labile P, Fe(II) and the significant positive correlation between Fe and P on day 8. The simultaneous increase in DOM and soluble reactive phosphorus (SRP) and the significant positive relationship between these factors were observed during the decomposition of B. aeruginosa. This suggested that complexation of DOM with metals may promotes the release of P from sediments. [Display omitted] • Decomposition of benthic organisms significantly increased sediment P levels. • Reduction of Fe(III) and sulfate promoted P release from sediments. • DOM complexes with metals reduced sediment P immobilization. During macrozoobenthos decomposition, the reduction and dissolution of Fe(III) oxides and the complexation of DOM with metal ions caused the massive release of P from sediments and increased the risk of lake eutrophication. [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]

There is a great heterogeneity in the distribution of mobile phosphorus (P) in natural sediments, while the assessment of P immobilization by amendment agents has mostly neglected this feature. In this study, the effects of aluminum sulfate (ALS) on P immobilization were investigated via a 60-day microcosm experiment using sampled sediment cores. The high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were first employed to establish the profiles of soluble reactive P (SRP) and DGT-labile P in aluminum-amended sediments at 2 and 1 mm resolutions, respectively. Both concentrations of two mobile P forms decreased with increasing ALS dosages. The static layers with extremely low P concentrations (≤0.060 mg L −1 for SRP and ≤0.024 mg L −1 for DGT-labile P) were observed in the upper 6–16 mm sediment layers at 6–15 ALS/P mobile treatments (mobile P is the sum of NH 4 Cl-P, BD-P, and NaOH-nrP; mol mol −1 ). The static layer was followed by an active layer in which the upward release potential ( R AL ) decreased from 33.4 to 21.9 for SRP and from 92.2 to 51.0 for DGT-labile P, respectively. As the formation of the static layer is a key to sustaining P immobilization in sediments, the minimal dosage of 9 ALS/P mobile is required for ALS capping. Modeling with DGT Induced Fluxes in Sediments (DIFS) showed a greater increase in adsorption rate constant ( k 1 , maximum 7.2-fold) compared to adsorption rate constant ( k 1 , maximum 2.2-fold), demonstrating that the release of P from sediment solids became increasingly difficult after ALS amendment. [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]

Phosphorus (P) availability is closely related to the distributions of pH, O 2 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, O 2 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). [Display omitted] • Combination of pH/O2 PO, zymography and DGT imaging techniques applied. • Increased phosphatase activity and acidification appeared when V. natans was young. • DGT-labile P accumulated in the rhizosphere when V. natans was young. • DGT-labile P depletion co-occurred with increased ACP when roots matured. • Roots could acquire P via organic acid complexation of Fe(Ⅲ) from Fe plaque. [ABSTRACT FROM AUTHOR]

Cobalt (Co) cycling is often dominated by its role as a micronutrient in marine, while little is known on its cycling in a shallow eutrophic lake. Monthly sampling was performed in eutrophic Meiliang Bay of Lake Taihu, combining two laboratory control experiments and in situ Co limitation bioassay experiments. The high-resolution dialysis and the diffusive gradients in thin films technique were used to detect dissolved and labile Co, respectively. The positive correlations between dissolved/labile Co and Mn in the sediments for 6 or 7 months demonstrated that the mobility of Co in the sediments was primarily controlled by Mn redox cycling in the field. However, it is unexpected that the dissolved and labile Co only showed a small change over one year irrespective of the significant fluctuation in dissolved/labile Mn, with the concentrations being as low as 1.08 ± 0.22 μg/L and 0.246 ± 0.091 μg/L for dissolved and labile Co in the surface 20 mm sediment, respectively. Cyanobacterial bloom simulation and aerobic-anaerobic-cyanobacterial addition experiments indicated that the level of Co in the sediment-overlying water system was strongly regulated by cyanobacterial uptake, followed by the degradation of Co-enriched cyanobacterial biomass, which offset the influence of Mn redox cycling on Co mobility in the sediment. The significant enhancement of Microcystis spp. biomass by Co addition further indicated that Co was the potential limiting nutrient for cyanobacterial blooms. This work provides new ideas for better management strategies of eutrophication in shallow lakes. [Display omitted] • The dissolved and labile Co showed little change over one year. • Co mobility was mainly controlled by cyanobacterial bloom and Mn redox. • Co was the potential limiting nutrient for cyanobacterial blooms. [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]