Mengdan Gong

In situ, high-resolution evidence for iron-coupled mobilization of phosphorus in sediments

Reductive dissolution of phosphorus-bearing iron (Fe) (oxyhydr)oxides has been regarded as a primary mechanism responsible for the mobilization of phosphorus (P) in sediments for over 70 years. However, to date there is little in situ evidence to support this hypothesis. In this study, a total of 16 sites in the large eutrophic Lake Taihu were selected for investigation. Newly-developed diffusive gradients in thin films (ZrO-Chelex DGT) probes were deployed to simultaneously measure labile Fe and P mainly released from sediment solids at millimeter spatial resolution. Significantly positive correlations were observed between DGT-labile Fe and P at 14 sites, implying a release of P following reductive dissolution of Fe (oxyhydr)oxides. A coincident resupply of Fe(II) and P was observed from sediment solids to buffer their releases from DGT perturbance, further verifying the mechanism of Fe-coupled mobilization of P. The ratio of DGT-labile Fe/P was found to be positively correlated with the ratio of easily reducible (oxyhydr)oxide Fe to its associated P, indicating that this solid phase should retain P prior to its release. The results provide direct evidence for the coupling between Fe and P in sediments and further identify the easily reducible Fe (oxyhydr)oxide species involved in the coupling process.

Kinetics of phosphorus release from sediments and its relationship with iron speciation influenced by the mussel (Corbicula fluminea) bioturbation.

The effects of bivalve (Corbicula fluminea) bioturbation on the lability of phosphorus (P) in sediments were investigated. The high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were employed to obtain soluble and labile P/Fe profiles at a vertical resolution of 2 and 1mm, respectively. The bivalve bioturbation increased the concentrations of soluble reactive P (SRP) in pore water and DGT-labile P up to 116% and 833% of the control within the sediment depths from the sediment water interface (SWI) to -64 mm and -44 mm, respectively. The sediments with bioturbation had a smaller distribution coefficient than the control (1964 vs. 3010 cm(3) g(-1)), reflecting a weaker ability in retaining P. Meanwhile, the sediments with bioturbation had a greater ratio of the concentration of DGT-labile P to that of SRP (0.20 vs. 0.03), demonstrating a stronger ability to resupply pore water SRP by the sediment solids when they are affected by the bioturbation. The DGT-induced fluxes in sediments (DIFS) modeling further showed a much shorter response time (277.9 vs. 18,670 s) and a much higher rate (0.192 vs. 0.002 day(-1)) of the solids in release of P with the bioturbation. Correspondingly, the flux of P to the overlying water from the bioturbation treatment increased up to 157% of the control. The bivalve bioturbation significantly increased the concentrations of soluble Fe(II) and DGT-labile Fe up to 84% and 334% of the control from the SWI to -46 mm, respectively. The SRP and DGT-labile P were highly correlated with respective soluble and DGT-labile Fe. It was concluded that the release of P from the sediments with bioturbation to the pore water and the overlying water was promoted by the reductive dissolution of easily reducible Fe(oxyhydr)oxides due to the depletion of oxygen in the top sediments from bivalve respiration.

New holder configurations for use in the diffusive gradients in thin films (DGT) technique

This study reports two new holder configurations that can be used in the diffusive gradients in thin films (DGT) technique, including a dual-mode holder and a new flat-type holder. The dual-mode holder can be assembled as a piston type, similar to the existing one for deployments in solution/water. It can also be assembled to form a hollow cylinder (open cavity) with 10 mm depth and 20 mm diameter, in which the soil paste is placed in contact with the exposed surface of the DGT unit at the bottom of the open cavity. Tests of the open cavity-type holder showed good agreement with the existing press-type holder in measurements of P, As, Cd and Pb in soils. However, the variability in measurements has been significantly reduced in the new holder configuration by 42%. This is due to the elimination of errors caused by manual pressing of the soil paste in the existing holder configuration. Moreover, the new flat-type holder used for deployment in sediments does not have the raised bottom edge design of the existing one, which allows its exposure surface to be on the same plane as the bottom of the holder. Tests of the new flat-type holder loaded with exposed sulfide binding gel showed that the penetration depths of dissolved sulfide and sulfide-enriched sands in sediments were only 33% and 20% of those obtained using the existing holder. The DGT measurements with the new holder resulted in low-concentration sulfide distribution at a much shallower depth (2.5 mm vs. 6 mm) by preventing the seepage of oxic overlying water into the sediment. The new holder usage also caused the disappearance of an abnormal sulfide-enriched slide in the top sediment layer, which likely resulted from the sulfide-enriched fecal pellets being pushed from the sediment surface into the top layer by the existing holder. These results demonstrate that the probe insertion-induced mobilization of dissolved and particulate substances has been reduced greatly with the new holder. Thus, the use of the new holder configurations can help to obtain much more accurate DGT measurements in soils and sediments. To the best of our knowledge, this is the first report describing a significant modification of the DGT holder configurations.

Internal phosphorus loading from sediments causes seasonal nitrogen limitation for harmful algal blooms

It is proposed that the internal loading of phosphorus (P) from sediments plays an important role in seasonal nitrogen (N) limitation for harmful algal blooms (HABs), although there is a lack of experimental evidence. In this study, an eutrophic bay from the large and shallow Lake Taihu was studied for investigating the contribution of internal P to N limitation over one-year field sampling (February 2016 to January 2017). A prebloom-bloom period was identified from February to August according to the increase in Chla concentration in the water column, during which the ratio of total N to total P (TN/TP) exponentially decreased with month from 43.4 to 7.4. High-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) analysis showed large variations in the vertical distribution of mobile P (SRP and DGT-labile P) in sediments, resulting in the SRP diffusion flux at the sediment-water interface ranging from -0.01 to 6.76mg/m2/d (minus sign denotes downward flux). Significant and linear correlations existed between SRP and soluble Fe(II) concentrations in pore water, reflecting that the spatial-temporal variation in mobile P was controlled by microbe-mediated Fe redox cycling. Mass estimation showed that the cumulative flux of SRP from sediments accounted for 54% of the increase in TP observed in the water column during the prebloom-bloom period. These findings are supported by the significantly negative correlation (p<0.01) observed between sediment SRP flux and water column TN/TP during the same period. Overall, these results provide solid evidence for the major role of internal P loading in causing N limitation during the prebloom-bloom period.

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 formers high capacity and a wide tolerance to environmental interferences, together with a high efficiency in elution.

In Situ, High-Resolution Profiles of Labile Metals in Sediments of Lake Taihu

Characterizing labile metal distribution and biogeochemical behavior in sediments is crucial for understanding their contamination characteristics in lakes, for which in situ, high-resolution data is scare. The diffusive gradient in thin films (DGT) technique was used in-situ at five sites across Lake Taihu in the Yangtze River delta in China to characterize the distribution and mobility of eight labile metals (Fe, Mn, Zn, Ni, Cu, Pb, Co and Cd) in sediments at a 3 mm spatial resolution. The results showed a great spatial heterogeneity in the distributions of redox-sensitive labile Fe, Mn and Co in sediments, while other metals had much less marked structure, except for downward decreases of labile Pb, Ni, Zn and Cu in the surface sediment layers. Similar distributions were found between labile Mn and Co and among labile Ni, Cu and Zn, reflecting a close link between their geochemical behaviors. The relative mobility, defined as the ratio of metals accumulated by DGT to the total contents in a volume of sediments with a thickness of 10 mm close to the surface of DGT probe, was the greatest for Mn and Cd, followed by Zn, Ni, Cu and Co, while Pb and Fe had the lowest mobility; this order generally agreed with that defined by the modified BCR approach. Further analyses showed that the downward increases of pH values in surface sediment layer may decrease the lability of Pb, Ni, Zn and Cu as detected by DGT, while the remobilization of redox-insensitive metals in deep sediment layer may relate to Mn cycling through sulphide coprecipitation, reflected by several corresponding minima between these metals and Mn. These in situ data provided the possibility for a deep insight into the mechanisms involved in the remobilization of metals in freshwater sediments.

Successful control of internal phosphorus loading after sediment dredging for 6 years: A field assessment using high-resolution sampling techniques

The effectiveness of sediment dredging for the control of internal phosphorus (P) loading, was investigated seasonally in the eutrophic Lake Taihu. The high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were used to measure the concentrations of soluble Fe(II) and soluble reactive P (SRP) as well as DGT-labile Fe/P in the non-dredging and post-dredging sediments. The P resupply kinetics from sediment solids were interpreted using DGT Induced Fluxes in Sediments (DIFS) modeling. The results showed no obvious improvement in water and sediment quality after dredging for 6years, due to their geographical proximity (a line distance of approximately 9km). However, dredging significantly decreased the concentrations of soluble Fe(II)/SRP and DGT-labile Fe/P in sediments, with effects varying at different depths below the sediment-water interface; More pronounced effects appeared in January and April. The diffusive flux of pore water SRP from sediments decreased from 0.746, 4.08 and 0.353mg/m2/d to 0.174, 1.58 and 0.048mg/m2/d in April, July and January, respectively. DIFS modeling indicated that the P retention capability of sediment solids was improved in April in post-dredging site. Positive correlations between pore water soluble Fe(II) and SRP as well as between DGT-labile Fe and P, reflect the key role of Fe redox cycling in regulating dredging effectiveness. This effect is especially important in winter and spring, while in summer and autumn, the decomposition of algae promoted the release of P from sediments and suppressed dredging effectiveness. Overall, the high-resolution HR-Peeper and DGT measurements indicated a successful control of internal P loading by dredging, and the post-dredging effectiveness was suppressed by algal bloom.

NUCLEATE POOL BOILING HEAT TRANSFER OF BINARY MIXTURES WITH DIFFERENT BOILING RANGES

The nucleate pool boiling heat transfer data on a smooth flat surface were measured for three binary mixtures of HC600a/HFC134a, HC600a/HC290, and HC600a/HFC23. Much effort was made to investigate the influence of the boiling range on the pool-boiling heat transfer performance. From the experimental results, the HC600a/HFC23 mixture with a wide boiling range showed lower heat transfer coefficients (HTCs) than the mixture with a narrow boiling range such as HC600a/HFC134a and HC600a/HC290 systems. The measured data were also compared with the results predicted by five well-known correlations. It can be found that the average deviation is less than 25% for mixtures with narrow boiling ranges, but a larger deviation for mixtures with wide boiling ranges.

Submillimeter-scale heterogeneity of labile phosphorus in sediments characterized by diffusive gradients in thin films and spatial analysis

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 Morans 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.

High resolution spatiotemporal sampling as a tool for comprehensive assessment of zinc mobility and pollution in sediments of a eutrophic lake

To assess zinc (Zn) pollution risk from sediments, this study investigated the monthly changes of dissolved Zn and labile Zn in sediment-overlying water profiles in a eutrophic bay (Meiliang Bay) of Lake Taihu (China) using high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) at a 4 mm vertical resolution. In February and March, Mn oxides reduction caused high concentrations of DGT-labile Zn (14 ∼ 235 μg L-1), as evidenced by the significant correlation between DGT-labile Zn and DGT-labile Mn in sediments. In June and July, algal blooms reduced concentrations of dissolved Zn via algal assimilation. From August through October, concentrations of dissolved Zn in overlying water (338 ∼ 1023 μg L-1) exceeded the water quality limit for fisheries in China (100 μg L-1). This was attributed to reductive dissolution of Mn oxides in sediments caused by algal degradation followed by complexation of dissolved organic matter (DOM), which was identified in a simulated algal bloom experiment. In the winter, decreased Zn mobility was mainly attributed to adsorption by Mn oxides. It was concluded that enhanced Zn pollution risk from sediments is worthy of concern especially during algal degradation in eutrophic lakes.