Kunfu Pi


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Fluvial Deposition and Land Use Change Control Selenium Occurrence in Mollisols of Cold Region Agroecosystems
Kunfu Pi, Philippe Van Cappellen, Yiqun Gan, Xinlin Zhong, Lei Tong, Weitao Chen, Xun Wang, Yanxin Wang
Environmental Science & Technology, Volume 57, Issue 1

Mollisols support the most productive agroecosystems in the world. Despite their critical links to food quality and human health, the varying distributions of selenium (Se) species and factors governing Se mobility in the mollisol vadose zone remain elusive. This research reveals that, in northern mollisol agroecosystems, Se hotspots (≥0.32 mg/kg) prevail along the regional river systems draining the Lesser Khingan Mountains, where piedmont Se-rich oil shales are the most probable source of regional Se. While selenate and selenite dominate Se species in the water-soluble and absorbed pools, mollisol organic matter is the major host for Se. Poorly crystalline and crystalline Fe oxides are subordinate in Se retention, hosting inorganic and organic Se at levels comparable to those in the adsorbed pool. The depth-dependent distributions of mollisol Se species for the non-cropland and cropland sites imply a predominance of reduced forms of Se under the mildly acidic and reducing conditions that, in turn, are variably impacted by agricultural land use. These findings therefore highlight that fluvial deposition and land use change together are the main drivers of the spatial variability and speciation of mollisol Se.


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Effects of riboflavin and desferrioxamine B on Fe(II) oxidation by O2
Peng Zhang, Philippe Van Cappellen, Kunfu Pi, Songhu Yuan
Fundamental Research, Volume 2, Issue 2

Flavins and siderophores secreted by various plants, fungi and bacteria under iron (Fe) deficient conditions play important roles in the biogeochemical cycling of Fe in the environment. Although the mechanisms of flavin and siderophore mediated Fe(III) reduction and dissolution under anoxic conditions have been widely studied, the influence of these compounds on Fe(II) oxidation under oxic conditions is still unclear. In this study, we investigated the kinetics of aqueous Fe(II) (17.8 μM) oxidation by O 2 at pH 5‒7 in the presence of riboflavin (oxidized (RBF) and reduced (RBFH 2 )) and desferrioxamine B (DFOB) as representative flavins and siderophores, respectively. Results showed that the addition of RBF/RBFH 2 or DFOB markedly accelerates the oxidation of aqueous Fe(II) by O 2 . For instance, at pH 6, the rate of Fe(II) oxidation was enhanced 20‒70 times when 10 μM RBFH 2 was added. The mechanisms responsible for the accelerated Fe(II) oxidation are related to the redox reactivity and complexation ability of RBFH 2 , RBF and DFOB. While RBFH 2 does not readily complex Fe(II)/Fe(III), it can activate O 2 and generate reactive oxygen species, which then rapidly oxidize Fe(II). In contrast, both RBF and DFOB do not reduce O 2 but react with Fe(II) to form RBF/DFOB-complexed Fe(II), which in turn accelerates Fe(II) oxidation. Furthermore, the lower standard reduction potential of the Fe(II)-DFOB complex, compared to the Fe(II)-RBF complex, correlates with a higher oxidation rate constant for the Fe(II)-DFOB complex. Our study reveals an overlooked catalytic role of flavins and siderophores that may contribute to Fe(II)/Fe(III) cycling at oxic-anoxic interfaces.

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Deployment of functional DNA-based biosensors for environmental water analysis
Yichen Zhao, Kayvan Yavari, Yihao Wang, Kunfu Pi, Philippe Van Cappellen, Juewen Liu
TrAC Trends in Analytical Chemistry, Volume 153

Various functional DNA molecules have been used for the detection of environmental contaminants in water, but their practical applications have been limited. To address this gap, this review highlights the efforts to develop field-deployable water quality biosensors. The biosensor devices include microfluidic, lateral flow and paper-based devices, and other novel ideas such as the conversion of glucometers for the detection of environmental analytes. In addition, we also review DNA-functionalized hydrogels and their use in diffusive gradients in thin films (DGT) devices. We classify the sensors into one-step and two-step assays and discuss their practical implications. While the review is focused on works reported in the last five years, some classic early works are cited as well. Overall, most of the existing work only tested spiked water samples. Future work needs to shift to real environmental samples and the comparison of DNA-based sensors to standard analytical methods. • Recent development in field-deployable functional DNA based biosensors for environmental water monitoring reviewed. • Articulated the concept of one-step and two-step assays. • Microfluidic device, lateral flow device, paper, hydrogel, and glucose meter based examples reviewed.


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The Cold Region Critical Zone in Transition: Responses to Climate Warming and Land Use Change
Kunfu Pi, Magdalena Bieroza, Anatoli Brouchkov, Weitao Chen, Louis J.P. Dufour, Konstantin B. Gongalsky, Anke M. Herrmann, Eveline J. Krab, Catherine Landesman, Anniet M. Laverman, Natalia Mazei, Yuri Mazei, Mats Öquist, Matthias Peichl, S. Pozdniakov, Fereidoun Rezanezhad, Céline Roose‐Amsaleg, Anastasia Shatilovich, Andong Shi, Christina M. Smeaton, Lei Tong, Andrey N. Tsyganov, Philippe Van Cappellen
Annual Review of Environment and Resources, Volume 46, Issue 1

Global climate warming disproportionately affects high-latitude and mountainous terrestrial ecosystems. Warming is accompanied by permafrost thaw, shorter winters, earlier snowmelt, more intense soil freeze-thaw cycles, drier summers, and longer fire seasons. These environmental changes in turn impact surface water and groundwater flow regimes, water quality, greenhouse gas emissions, soil stability, vegetation cover, and soil (micro)biological communities. Warming also facilitates agricultural expansion, urban growth, and natural resource development, adding growing anthropogenic pressures to cold regions’ landscapes, soil health, and biodiversity. Further advances in the predictive understanding of how cold regions’ critical zone processes, functions, and ecosystem services will continue to respond to climate warming and land use changes require multiscale monitoring technologies coupled with integrated observational and modeling tools. We highlight some of the major challenges, knowledge gaps, and opportunities in cold region critical zone research, with an emphasis on subsurface processes and responses in both natural and agricultural ecosystems.


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A DNA-based biosensor for aqueous Hg(II): Performance under variable pH, temperature and competing ligand composition
Kunfu Pi, Juewen Liu, Philippe Van Cappellen
Journal of Hazardous Materials, Volume 385

Abstract Mercury (Hg) is a toxic metal posing major health risks to human beings and wildlife. The characterization of Hg fate and transport in aquatic environments is hindered by a lack of sensitive, selective and easily field-deployable analytical techniques. Here we assess the reliability and performance of a Hg2+ sensor based on the selective binding of Hg2+ to a thymine-rich DNA under environmentally-relevant conditions. Experimental results indicate that the interactions between the DNA and SYBR Green I, which produce the detection fluorescence signal, are significantly impacted by pH, metal ligands and natural dissolved organic matter (NDOM). These interferences are largely eliminated by immobilizing the DNA in a polyacrylamide hydrogel, although high concentrations of NDOM, such as fulvic acids, still affect the sensor’s performance due to competitive binding of Hg2+. The binding of Hg2+ to NDOM, however, can be accounted for via equilibrium speciation calculations, which also yield the complexation constant for Hg2+ binding to the DNA in the hydrogel. The equilibrium calculations reproduce the results for the entire set of experimental conditions, from simple electrolyte solutions to complex aqueous compositions mimicking natural lake waters, and across large ranges of pH (3-10) and temperature (5-50 °C).