Dong-Xing Guan

Effect of aging on arsenic and lead fractionation and availability in soils: Coupling sequential extractions with diffusive gradients in thin-films technique

We coupled the diffusive gradients in thin-films (DGT) technique with two sequential extraction methods to investigate the influence of aging on As and Pb fractionation and availability in three soils spiked with As (40 or 400mgkg(-1)), Pb (150 or 1500mgkg(-1)) or As+Pb (40mgkg(-1) As and 150mgkg(-1) Pb). During aging, As moved from the more available (non-specifically and specifically sorbed) to less available (amorphous and crystallized Fe/Al) fractions while Pb moved from the first three fractions (exchangeable, carbonate and Fe/Mn hydroxide) to organic fraction. However, even after 33-week aging, much more As and Pb were in the least available residual fraction in spiked soils than native soils (11-59% vs. 1.2-12%). Relatively, As in spiked soils was much more available than Pb with 11-14% As and 46-59% Pb in the residual fraction. Correlation analysis indicated that As in the non-specifically and specifically sorbed fractions and Pb in the exchangeable fraction were likely sources of DGT-measured labile As and Pb. The fact that As and Pb distribution and availability in spiked soils were significantly different from native soils suggests caution needs to be exercised when using spiked soils for research.

Characterization of arsenic-resistant endophytic bacteria from hyperaccumulators Pteris vittata and Pteris multifida

We isolated and characterized As-resistant endophytic bacteria (AEB) from two arsenic hyperaccumulators. Their plant growth promoting traits and the relation between As tolerance and transformation were evaluated. A total of 41 and 33 AEB were isolated from Pteris vittata (PV) and Pteris multifida (PM) respectively. PV AEB represented 2genera while PM AEB comprised of 12 genera, with Bacillus sp. being the most dominant bacteria from both plants. All AEB had limited ability in solubilizing P and producing indole acetic acid (IAA) and siderophore. All isolates tolerated 10mM arsenate (As(V)), with PV isolates being more tolerant to As(V) and PM more tolerant to arsenite (As(III)). Bacterial arsenic tolerance was related to their ability in As(III) oxidation and As(V) reduction as well as their ability to retain As in the biomass to a varying extent. Though AEB showed limited plant growth promoting traits, they were important in arsenic tolerance and speciation in plants.

Activated charcoal based diffusive gradients in thin films for in situ monitoring of bisphenols in waters

Widespread use of bisphenols (BPs) in our daily life results in their elevated concentrations in waters and the need to study their environmental impact, which demands reliable and robust measurement techniques. Diffusive gradients in thin films (DGT) is an in situ passive sampling approach which provides time-integrated data. In this study we developed a new methodology, based on DGT with activated charcoal (AC) as a binding agent, for measuring three BPs (BPA, BPB, and BPF) which incorporated and tested its performance characteristics. Consistent elution efficiencies were obtained using methanol when concentrations of BPs were low and a methanol-NaOH mixture at high concentrations. The diffusion coefficients of BPA, BPB, and BPF in the diffusive gel, measured using an independent diffusion cell, were 5.03 × 10(-6), 5.64 × 10(-6), and 4.44 × 10(-6) cm(2) s(-1) at 25 °C, respectively. DGT with an AC binding gel had a high capacity for BPA, BPB, and BPF at 192, 140, and 194 μg/binding gel disk, respectively, and the binding performance did not deteriorate with time, up to 254 d after production. Time-integrated concentrations of BPs measured in natural waters using DGT devices with AC gels deployed in situ for 7 d were comparable to concentrations measured by an active sampling method. This study demonstrates that AC-based DGT is an effective tool for in situ monitoring of BPs in waters.

High-resolution measurement and mapping of tungstate in waters, soils and sediments using the low-disturbance DGT sampling technique

Increasing tungsten (W) use for industrial and military applications has resulted in greater W discharge into natural waters, soils and sediments. Risk modeling of W transport and fate in the environment relies on measurement of the release/mobilization flux of W in the bulk media and the interfaces between matrix compartments. Diffusive gradients in thin-films (DGT) is a promising passive sampling technique to acquire such information. DGT devices equipped with the newly developed high-resolution binding gels (precipitated zirconia, PZ, or ferrihydrite, PF, gels) or classic/conventional ferrihydrite slurry gel were comprehensively assessed for measuring W in waters. (Ferrihydrite)DGT can measure W at various ionic strengths (0.001-0.5molL(-1) NaNO3) and pH (4-8), while (PZ)DGT can operate across slightly wider environmental conditions. The three DGT configurations gave comparable results for soil W measurement, showing that typically W resupply is relatively poorly sustained. 1D and 2D high-resolution W profiling across sediment-water and hotspot-bulk media interfaces from Lake Taihu were obtained using (PZ)DGT coupled with laser ablation ICP-MS measurement, and the apparent diffusion fluxes across the interfaces were calculated using a numerical model.

Novel Speciation Method Based on Diffusive Gradients in Thin-Films for in Situ Measurement of CrVI in Aquatic Systems

Hexavalent chromium (Cr(VI)) is much more toxic and mobile than the trivalent species (Cr(III)) and consequently, in situ monitoring of Cr(VI) can improve the understanding of Cr biogeochemistry and toxicity in ecosystems. The passive diffusive gradients in thin-films (DGT) technique is a powerful tool for determining metal(loid) speciation, but a binding phase that absorbs only one specific species of Cr is needed. N-Methyl-d-glucamine (NMDG) functional resin was incorporated into the DGT binding phase for selective measurement of Cr(VI). This NMDG-DGT sampler exhibited a theoretically linear accumulation of Cr(VI), with negligible accumulation (<5%) of Cr(III), even after 72 h deployment. The good prediction of Cr(VI) concentration in synthetic freshwater with NMDG-DGT, even in the presence of 10-time more Cr(III), further indicated the samplers reliability in selective detection of Cr(VI). Moreover, its high capacity for Cr(VI), which exceeded 230 μg cm(-2), facilitates measurement of Cr(VI) in both uncontaminated natural waters and in slightly and heavily contaminated (ppm level) waters. Field deployment of the NMDG-DGT sampler in such waters allowed accurate measurement of time-averaged Cr(VI) concentration, indicating its robustness for in situ measurements of Cr speciation and its potential for further application in the risk assessment of Cr.

Arsenic Induced Phytate Exudation, and Promoted FeAsO4 Dissolution and Plant Growth in As-Hyperaccumulator Pteris vittata

Arsenic hyperaccumulator Pteris vittata (PV) is efficient in taking up As and nutrients from As-contaminated soils. We evaluated the mechanisms used by PV to mobilize As and Fe by examining the impacts of As and root exudates on FeAsO4 solubilization, and As and Fe uptake in four plants: As-hyperaccumulators PV and Pteris multifida (PM), nonhyperaccumulator Pteris ensiformis (PE), and angiosperm plant tomato (Solanum lycopersicum). Phytate and oxalate were dominant in fern plants (>93%), which were 50-83, 15-42, and 0-32 mg kg(-1) phytate and 10-15, 7-26, and 4-12 mg kg(-1) oxalate for PV, PM, and PE respectively, with higher As inducing greater phytate exudation and no phytate being detected in tomato exudates. PV treated with phytate+FeAsO4 had higher As and Fe contents and larger biomass than phytate or FeAsO4 treatment, which were 340 vs 20 and 130 mg kg(-1) As in the fronds and 7900 vs 1600 and 4100 mg kg(-1) Fe in the roots. We hypothesized that As-induced phytate exudation helped PV to take up Fe and As from insoluble FeAsO4 and promoted PV growth. Our study suggests that phytate exudation may be special to fern plants, which may play an important role in enhancing As and nutrient uptake by plants, thereby increasing their efficiency in phytoremediation of As-contaminated soils.

Exploring the interactions and binding sites between Cd and functional groups in soil using two-dimensional correlation spectroscopy and synchrotron radiation based spectromicroscopies

Understanding how heavy metals bind and interact in soils is essential for predicting their distributions, reactions and fates in the environment. Here we propose a novel strategy, i.e., combining two-dimensional correlation spectroscopy (2D COS) and synchrotron radiation based spectromicroscopies, for identifying heavy metal binding to functional groups in soils. The results showed that although long-term (23 yrs) organic fertilization treatment caused the accumulation of Cd (over 3 times) in soils when compared to no fertilization and chemical fertilization treatments, it significantly (p<0.05) reduced the Cd concentration in wheat grain. The 2D COS analyses demonstrated that soil functional groups controlling Cd binding were modified by fertilization treatments, providing implications for the reduced bioavailability of heavy metals in organic fertilized soils. Furthermore, correlative micro X-ray fluorescence spectromicroscopy, electron probe micro-analyzer mapping, and synchrotron-radiation-based FTIR spectromicroscopy analysis showed that Cd, minerals, and organic functional groups were heterogeneously distributed at the micro-scale in soil colloids. Only minerals, rather than organic groups, had a similar distribution pattern with Cd. Together, this strategy has a potential to explore the interactions and binding sites among heavy metals, minerals and organic components in soil.

A diffusive gradients in thin-films technique for the assessment of bisphenols desorption from soils

Desorption/adsorption of bisphenols (BPs) in soils affects their mobility and availability. However, the kinetics of these processes have not been well studied, due to the lack of appropriate means of measurement. Diffusive gradients in thin-films (DGT) technique can assess kinetic processes in soils and have recently been developed for measuring three BPs (BPA, BPB and BPF). DGT was deployed for 2.5h to 20 d in five soils with different soil properties. Non-linear increase in mass accumulation by DGT with time indicated poor resupply of BPs from soil solid to solution phase. By fitting the data with DIFS (DGT-induced fluxes in soils) model, values for the labile partition coefficient (Kdl), response time (tc) and rates of exchange (k1 and k-1) of BPs between soil solid and solution phases were obtained. The derived values of Kdl showed that most of the BPs in the soil could participate in labile exchange. Average response times of 1-2h implied that the supply of BPs to DGT was limited by their desorption rate. Soils with more binding sites (higher DOM, CEC and Fe oxides) could resupply BPs more quickly, highlighting the danger of just considering partition effects.

In situ measurement of perfluoroalkyl substances in aquatic systems using diffusive gradients in thin-films technique

To better understand the environmental impact of ubiquitous perfluoroalkyl substances (PFASs) in waters, reliable and robust measurement techniques are needed. As one of the most widely used passive sampling approaches, diffusive gradients in thin-films (DGT) is not only easy to handle but also provides time-weighted analyte concentrations. Based on DGT with XAD18 as a binding agent, we developed a new methodology to measure two frequently detected PFASs in surface waters and wastewaters, i.e. perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Their diffusion coefficients in the diffusive gel, measured using an independent diffusion cell, were 4.37 × 10-6 and 5.08 × 10-6 cm2 s-1 at 25 °C, respectively. DGT had a high capacity for PFOA and PFOS at 196 and 246 μg per gel disk, suggesting the DGT sampler was suitable for deployment of several weeks. Time-integrated concentrations of PFOA and PFOS in a natural lake and river, and a municipal wastewater treatment plant effluent using DGT samplers deployed in situ for 12-33 d were comparable to those measured by a solid-phase extraction method coupled with high-frequency grab sampling. This study demonstrates that DGT is an effective tool for in situ monitoring of PFASs in natural waters and wastewaters.

Contrasting effects of photochemical and microbial degradation on Cu(II) binding with fluorescent DOM from different origins

Effects of photochemical and microbial degradation on variations in composition and molecular-size of dissolved organic matter (DOM) from different sources (algal and soil) and the subsequent influence on Cu(II) binding were investigated using UV-Vis, fluorescence excitation-emission matrices coupled with parallel factor analysis, flow field-flow fractionation (FlFFF), and metal titration. The degradation processes resulted in an initial rapid decline in the bulk dissolved organic carbon and chromophoric and fluorescent DOM components, followed by a small or little decrease. Specifically, photochemical reaction decreased the aromaticity, humification and apparent molecular weights of all DOM samples, whereas a reverse trend was observed during microbial degradation. The FlFFF fractograms revealed that coagulation of both protein- and humic-like DOM induced an increase in molecular weights for algal-DOM, while the molecular weight enhancement for allochthonous soil samples was mainly attributed to the self-assembly of humic-like components. The Cu(II) binding capacity of algal-derived humic-like and fulvic-like DOM consistently increased during photo- and bio-degradation, while the soil-derived DOM exhibited a slight decline in Cu(II) binding capacity during photo-degradation but a substantial increase during microbial degradation, indicating source- and degradation-dependent metal binding heterogeneities. Pearson correlation analysis demonstrated that the Cu(II) binding potential was mostly related with aromaticity and molecular size for allochthonous soil-derived DOM, but was regulated by both DOM properties and specific degradation processes for autochthonous algal-derived DOM. This study highlighted the coupling role of inherent DOM properties and external environmental processes in regulating metal binding, and provided new insights into metal-DOM interactions and the behavior and fate of DOM-bound metals in aquatic environments.