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.

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.

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).

Method for phosphate oxygen isotopes analysis in water based on in situ enrichment, elution, and purification.

The phosphate oxygen isotope (δ18OP) ratio has been proven to be an effective tool to trace the sources and biogeochemical cycles of phosphorus (P) in aquatic ecosystems. However, the enrichment of phosphate (PO4) and the removal of impurities are quite complex and easy to cause PO4 loss in current δ18OP analytical methods. Moreover, the δ18OP value obtained by the commonly-used instantaneous sampling method is more of the instantaneous information of P, which is accidental or uncertain for accurate identification of the P source. In this study, a new method of in situ enrichment, elution, and purification of PO4 (ISEEP) was developed for δ18OP analysis in waters. This method utilized a PO4 binding phase (Zr-Oxide gel) to selectively in situ adsorb PO4 in water and exhibited an adsorption capacity per unit area of up to 789.3 µg P/cm2. The PO4 on the gel was eluted easily with a 1 M NaOH solution. More than 99.7% of the common anions, cations, and dissolved organic matter (DOM), as well as more than 90% of the trace elements were removed synchronously after adsorption and elution of PO4. The recovery rate of PO4 in the whole procedure was as high as 92.8%. The XRD and SEM examinations showed that the ISEEP can obtain high-purity Ag3PO4 solid for the δ18OP measurement. The reliability of the ISEEP method is confirmed by the measured δ18OP value and standard deviation of parallel samples from different types of natural waters obtained by both the ISEEP and the current popular McLaughlin (2004) method. It provides a good prospect of this new method for tracing the P sources and their biogeochemical cycling in aquatic ecosystems.

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.

Application of DGT/DIFS combined with BCR to assess the mobility and release risk of heavy metals in the sediments of Nansi Lake, China.

The heavy metal contamination of the aquatic ecosystem is still prevalent even after reduction of the external anthropogenic inputs of the metals. The release of labile heavy metals from the sediments into the water is a potential risk, responsible for the contamination of the aquatic system. Herein, samples of sedimentary column cores were collected in Nansi Lake, and the distribution profiles of the labile and soluble metals (Cd, Cu, Ni, Pb, and Zn) were obtained by the diffusive gradient in thin films (DGT) and the high-resolution dialysis (HR-peeper) technique. Furthermore, the mobility, bioavailability and release risk of the heavy metals were assessed using the results of geochemical sequential extraction, DGT as well as the DGT-induced fluxes in sediments (DIFS) model. The results showed that the profile characteristics of the DGT-labile and soluble heavy metals showed irregular distribution in the sediment cores and Cd, Pb, Zn had an obvious positive correlation with Fe/Mn (p < 0.05). Ni, Cu, and Zn existed primarily in the residual fraction (accounting for 58-76%), while Cd and Pb existed in the reducible fraction (accounting for 50-67%). The Cd and Ni (0.027-0.185) had higher mobility coefficients compared with Pb, Cu, and Zn (0-0.011), and positive diffusive fluxes also proved that Cd and Ni were easy to be released from the sediments. In addition, the R values of five metals (0.18-0.85) ranged between Rdiff to 0.95, indicating that all the metals had partially sustained case from the sediments solid phase. Based on the DIFS model, the five metals had weak mobility from the sediment to pore water, but the release risks in the Nansi Lake should also be of concern, especially for the highly mobile Cd and Ni in the Dushan Lake.

Peak Chromium Pollution in Summer and Winter Caused by High Mobility of Chromium in Sediment of a Eutrophic Lake: In Situ Evidence from High Spatiotemporal Sampling.

To study the mechanisms of chromium (Cr) mobilization in sediments of eutrophic lakes, monthly sampling was performed in the Meiliang Bay of Lake Taihu, China, combined with laboratory experiments. High-resolution dialysis and diffusive gradients in thin film (DGT) sampling techniques were used. Results indicated that in July 2016 and January 2017, the concentrations of soluble Cr and DGT-labile Cr(VI) in the overlying water exceeded both drinking and fishery water quality standards, resulting from the high mobility of Cr in sediments. In July (summer), the high concentration of soluble Cr (134.04 ± 7.20 µg/L) detected in the anaerobic sediments was primarily caused by the complexation of Cr(III) with dissolved organic matter (DOM). This mechanism was supported by an observed simultaneous increase of soluble Cr and DOM under simulated anaerobic conditions. In January (winter), the high concentrations of soluble Cr (97.55 ± 9.65 µg/L) and DGT-labile Cr(VI) (25.83 ± 1.25 µg/L) in aerobic sediments were primarily caused by reoxidation of Cr(III) by Mn(III/IV) oxides as evidenced by the lowest concentrations of soluble and DGT-labile Mn(II). This study sheds light on the full-year variation and mechanisms of Cr mobilization in eutrophic lake sediments and suggests the urgent need for remediation of Cr pollution especially for winter.

Simultaneous measurements of arsenic and sulfide using diffusive gradients in thin films technique (DGT).

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.

Simultaneous Measurements of Eight Oxyanions Using High-Capacity Diffusive Gradients in Thin Films (Zr-Oxide DGT) with a High-Efficiency Elution Procedure.

A zirconium oxide binding gel-based diffusive gradients in thin films (Zr-oxide DGT) was developed for simultaneous measurements of P(V), As(V), Cr(VI), Mo(VI), Sb(V), Se(VI), V(V), and W(VI). All of the oxyanions were rapidly bound to Zr-oxide gel with differences in binding affinity. The eight bound oxyanions were successfully recovered by one-step elution using a mild reagent of 0.2 M NaOH-0.5 M H2O2 by overcoming the problems in analyses of the oxyanions. The optimized elution time was reduced to 3-5 h from 24-48 h required by other DGTs. DGT uptakes of all the oxyanions were independent of pH (4.42-8.45) and ionic strength (0.1-500 mM). The DGT capacities for six oxyanions detected in multioxyanion solution were only 0.19 to 0.35 times of those detected in single-oxyanion solution, reflecting a strong competition among the oxyanions during DGT uptake. Except for Se(VI) in seawater, Zr-oxide DGT accurately measured all of the oxyanions in synthetic freshwater and seawater, with the capacities ∼29 to >2397 times and ∼7.5 to 232 times those of two commonly used DGTs (Metsorb and precipitated ferrihydrite (PF) DGTs) in freshwater and seawater, respectively. Measurements by Zr-oxide DGT in contaminated sediments were in agreement with only two oxyanions with the two commonly used DGTs; the two DGTs accumulated less or no mass of other oxyanions. This study demonstrates significant advantage of Zr-oxide DGT over the other DGTs in simultaneous measurements of the eight oxyanions due to the former's high capacity and a wide tolerance to environmental interferences, together with a high efficiency in elution.

Variation of arsenic concentration on surfaces of in-service CCA-treated wood planks in a park and its influencing field factors.

Wood preservatives can protect wood from dry rot, fungi, mould and insect damage, and chromated copper arsenate (CCA) has been used as an inorganic preservative for many years. However, wood treated with CCA has been restricted from residential uses in the EU from June 30, 2004, due to its potential toxicity. Such a regulation is not in place in China yet, and CCA-treated wood is widely used in public parks. A portable XRF analyser was used to investigate arsenic (As) concentration on surfaces of in-service CCA-treated wood planks in a popular park as well as the influencing field factors of age in-service, immersion and human footfall. With a total of 1207 readings, the observed As concentrations varied from below the detection limit (<10 mg/kg) to 15,746 mg/kg with a median of 1160 mg/kg. Strong variation of As concentrations were observed in different wood planks of the same age, on the surface of the same piece of wood, inside the same piece of wood, and different surfaces of walkway planks, hand rails and poles in the field. The oldest planks exhibited high As concentrations, which was related to its original treatment with high retention of CCA preservative. The effect of immersion in the field for about 4 months was insignificant for As concentration on the surfaces. However, a significant reduction of As was observed for immersion combined with human footfall (wiping by shoes). Human traffic in general caused slightly reduced and more evenly distributed As concentrations on the wood surfaces. The strong variation, slow aging and relatively weak immersion effects found in this study demonstrate that the in-service CCA-treated wood poses potential health risks to the park users, due to easy dermal contact especially when the wood is wet after rainfall. It is suggested that further comprehensive investigations and risk assessments of CCA-treated wood in residential areas in China are needed, and precautionary measures should be considered to reduce the potential risks to residents and visitors, especially children.

Improved diffusive gradients in thin films (DGT) measurement of total dissolved inorganic arsenic in waters and soils using a hydrous zirconium oxide binding layer.

A high-capacity diffusive gradients in thin films (DGT) technique has been developed for measurement of total dissolved inorganic arsenic (As) using a long shelf life binding gel layer containing hydrous zirconium oxide (Zr-oxide). Both As(III) and As(V) were rapidly accumulated in the Zr-oxide gel and could be quantitatively recovered by elution using 1.0 M NaOH for freshwater or a mixture of 1.0 M NaOH and 1.0 M H2O2 for seawater. DGT uptake of As(III) and As(V) increased linearly with deployment time and was independent of pH (2.0-9.1), ionic strength (0.01-750 mM), the coexistence of phosphate (0.25-10 mg P L(-1)), and the aging of the Zr-oxide gel up to 24 months after production. The capacities of the Zr-oxide DGT were 159 µg As(III) and 434 µg As(V) per device for freshwater and 94 µg As(III) and 152 µg As(V) per device for seawater. These values were 5-29 times and 3-19 times more than those reported for the commonly used ferrihydrite and Metsorb DGTs, respectively. Deployments of the Zr-oxide DGT in As-spiked synthetic seawater provided accurate measurements of total dissolved inorganic As over the 96 h deployment, whereas ferrihydrite and Metsorb DGTs only measured the concentrations accurately up to 24 and 48 h, respectively. Deployments in soils showed that the Zr-oxide DGT was a reliable and robust tool, even for soil samples heavily polluted with As. In contrast, As in these soils was underestimated by ferrihydrite and Metsorb DGTs due to insufficient effective capacities, which were likely suppressed by the competing effects of phosphate.

Comparison of diffusive gradients in thin film technique with traditional methods for evaluation of zinc bioavailability in soils.

The technique of diffusive gradients in thin film (DGT) has been shown to be a promising tool to assess zinc (Zn) bioavailability in soils, but there exists considerable debate on its suitability. In this study, Zn bioavailability was systematically investigated in wheat- and maize-grown soils using this technique and seven traditional methods, including soil solution concentration and six widely used single-step extraction methods (HAc, EDTA, NaAc, NH4Ac, CaCl2, and MgCl2). The concentrations of Zn in the shoots and roots of these two plant species increased continuously with increasing additions of Zn to the soils, accompanied by significant decreases in shoot biomass and root biomass at Zn concentrations greater than 400 mg kg(-1) for maize and 800 mg kg(-1) for wheat. Zinc uptake and accumulation was higher in maize roots than in wheat roots. Both the concentrations of bioavailable Zn measured by DGT (CDGT) and soil solutions (Csol) increased linearly with increasing additions of Zn to the soils, while no strong linear relationships were observed for the extraction methods. Higher concentrations of extractable Zn, lower values of Csol, and larger values of R (i.e., the ratio of CDGT to Csol) were observed in maize-grown soils compared with those of wheat-grown soils, while the values of C DGT between the two plants were similar. These findings demonstrate that there likely exists a stronger resupply of Zn from the soil solid phases in maize-grown soils to satisfy a higher Zn uptake and accumulation in this plant. Linear correlation analyses showed that CDGT had the highest correlation coefficients with plant Zn concentrations compared with other traditional methods, implying that the DGT technique is more sensitive and robust in reflecting Zn bioavailability in soils to plants.

Bioavailability assessment of phosphorus and metals in soils and sediments: a review of diffusive gradients in thin films (DGT).

This paper provides an overview of the principle and latest development of the diffusive gradients in thin films (DGT) technology and its applications in environmental studies with a focus on bioavailability assessment of phosphorus and metals in sediments and soils. Compared with conventional methods, DGT, as a passive sampling method, has significant advantages: in situ measurement, time averaged concentrations and high spatial resolution. The in situ measurement avoids artificial influences including contamination of samples and sample treatment which may change the forms of chemicals. The time averaged concentration reflects representative measurement over a period of time. The high-resolution information captures the biogeochemical heterogeneity of elements of interest distributed in microenvironments, such as in the rhizosphere and the vicinity of the sediment-water interface. Moreover, DGT is a dynamic technique which simultaneously considers the diffusion of solutes and their kinetic resupply from the solid phases. All the advantages of DGT significantly promote the collection of "true" information of the bioavailable or labile forms of chemicals in the environment. DGT provides potential for applications in agriculture, environmental monitoring and the mining industry. However, the applications are still at the early testing stage. Further studies are needed to properly interpret the DGT-measured results under complex environmental conditions, and standard procedures and guideline values based on DGT are required to pave the way for its routine applications in environmental monitoring.

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.

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.

Gel-based coloration technique for the submillimeter-scale imaging of labile phosphorus in sediments and soils with diffusive gradients in thin films.

We report a highly promising technique for the high-resolution imaging of labile phosphorus (P) in sediments and soils in combination with the diffusive gradients in thin films (DGT). This technique was based on the surface coloration of the Zr-oxide binding gel using the conventional molybdenum blue method following the DGT uptake of P to this gel. The accumulated mass of the P in the gel was then measured according to the grayscale intensity on the gel surface using computer-imaging densitometry. A pretreatment of the gel in hot water (85 °C) for 5 d was required to immobilize the phosphate and the formed blue complex in the gel during the color development. The optimal time required for a complete color development was determined to be 45 min. The appropriate volume of the coloring reagent added was 200 times of that of the gel. A calibration equation was established under the optimized conditions, based on which a quantitative measurement of P was obtained when the concentration of P in solutions ranged from 0.04 mg L(-1) to 4.1 mg L(-1) for a 24 h deployment of typical DGT devices at 25 °C. The suitability of the coloration technique was well demonstrated by the observation of small, discrete spots with elevated P concentrations in a sediment profile.

Diffusive gradients in thin films technique equipped with a mixed binding gel for simultaneous measurements of dissolved reactive phosphorus and dissolved iron.

Developing a technique to track the release of phosphorus (P) and iron (Fe) simultaneously in sediments would be very useful in deepening our understanding of the internal loading process of P coupled with Fe cycling in aquatic systems. In this study, a new technique was established to measure simultaneously the dissolved reactive P (DRP) and dissolved Fe primarily released from sediment solids based on the diffusive gradients in thin films (DGT) theory. A mixed binding gel (ZrO-Chelex gel) used for assembling DGT was developed for simultaneous uptake of DRP and dissolved Fe(II) using amorphous zirconium hydroxide (Zr-oxide) and Chelex-100 resin as binding agents. Simultaneous measurements of DRP and dissolved Fe(II) with the ZrO-Chelex DGT were validated in solution and were independent of solution pH and ionic strength in normal environments. The capacities of the ZrO-Chelex DGT for measurements of DRP and dissolved Fe(II) were 90 µg P cm(-2) and 75 µg Fe cm(-2), with the latter being greater than that (45 µg Fe cm(-2)) observed with the Chelex-100 resin DGT commonly used in DGT measurements of metals. Microcosm experiments further confirmed the feasibility of the ZrO-Chelex DGT for simultaneous measurement of P and Fe in sediments, with a higher concentration of Fe being measured due to this method's higher capacity compared with the Chelex-100 resin DGT.

Speciation of organic phosphorus in a sediment profile of Lake Taihu. II. Molecular species and their depth attenuation.

The understanding of organic phosphorus (P) dynamics in sediments requires information on their species at the molecular level, but such information in sediment profiles is scarce. A sediment profile was selected from a large eutrophic lake, Lake Taihu (China), and organic P species in the sediments were detected using solution phosphorus-31 nuclear magnetic resonance spectroscopy (31P NMR) following extraction of the sediments with a mixture of 0.25 mol/L NaOH and 50 mmol/L EDTA (NaOH-EDTA) solution. The results showed that P in the NaOH-EDTA extracts was mainly composed of orthophosphate, orthophosphate monoesters, phospholipids, DNA, and pyrophosphate. Concentrations of the major organic P compound groups and pyrophosphate showed a decreasing trend with the increase of depth. Their half-life times varied from 3 to 27 years, following the order of orthophosphate monoesters > phospholipids > or = DNA > pyrophosphate. Principal component analysis revealed that the detected organic P species had binding phases similar to those of humic acid-associated organic P (NaOH-NRP(HA)), a labile organic P pool that tends to transform to recalcitrant organic P pools as the early diagenetic processes proceed. This demonstrated that the depth attenuation of the organic P species could be partly attributed to their increasing immobilization by the sediment solids, while their degradation rates should be significantly lower than what were suggested in previous studies.

Speciation of organic phosphorus in a sediment profile of Lake Taihu. I: Chemical forms and their transformation.

Organic phosphorus (nonreactive P, NRP) is a major component of P in sediments, but information about its chemical forms and dynamic transformation is limited. The chemical forms and dynamic behaviors of NRP in a sediment profile from Lake Taihu, a freshwater and eutrophic lake in China, were investigated. Five forms of NRP in the sediments were extracted based on a chemical fractionation technique, including easily labile NRP (NaHCO3-NRP), reactive metal oxide-bound NRP (HCl-NRP), humic acid-associated NRP (NaOH-NRP(HA)), fulvic acid-associated NRP (NaOH-NRP(FA)) and residual NRP (Res-TP). There were notable transformations with increasing sediment depth from the labile NaHCO3-NRP and NaOH-NRP pools to the recalcitrant HCl-NRP and Res-TP pools, which caused the NRP to become increasingly recalcitrant as the early diagenetic processes proceeded. Further analyses showed that the relative changes in contents of organic matter and reactive Fe oxides in the sediment profile triggered a competition for binding NRP fractions and led to the transformation of NRP. The results highlighted the importance of abiotic processes in regulating the diagenesis of organic P and its stability in sediments.