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In peri-urban critical zones, soil ecosystems are highly affected by increasing urbanization, causing probably an intense interaction between dissolved organic matter (DOM) and heavy metals in soil. Such interaction is critical for understanding the biogeochemical cycles of both organic matter and heavy metals in these zones. However, limited research has reported the correlative distribution of DOM and heavy metals at high seasonal and spatial resolutions in peri-urban critical zones. In this study, 160 soil samples were collected from the farmland and forestland of Zhangxi watershed, in Ningbo, eastern China during spring, summer, fall and winter four seasons. UV-visible absorption and fluorescent spectroscopy were used to explore the optical characteristics of DOM. The results indicated a mixture of exogenous and autogenous sources of DOM in the Zhangxi watershed, while DOM in farmland exhibited a higher degree of aromaticity and humification than that in forestland. Fluorescent results showed that humic acid-like, fulvic acid-like and microbial-derived humic-like fractions were mostly affected by seasons. The distribution of heavy metals was affected mainly by land-use changes and seasons. Correlation analysis between heavy metals and DOM characteristics and components suggested that aromatic and humic substances were more favorable in binding with EDTA extractable Ni, Cu, Zn and Cd. The bioavailable Cd and Pb decreased due to binding with humic fractions, indicating that DOM had great effects on the heavy metal bioavailability. Overall, these findings provide an insight into the correlative distributions of DOM and heavy metals in peri-urban areas, thereby highlighting their biogeochemical cycling in the soil environment.

Humic substances (HSs) are collections of diverse organic compounds with broad redox capacities, which directly or indirectly affect the biogeochemical behaviors and fates of almost all the pollutants in the environment. The present study investigates the relationships between the molecular characteristics of HSs and their reducing capacities or electron-donating capacities (EDCs) by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), total phenolic assay, and mediated electrochemical oxidation analysis. For decreasing the molecular heterogeneity of bulk HSs, HSs were first separated into three fractions according to their polarities. The results demonstrated that compounds in HS fractions with moderate polarity possessed a high content of total phenols and consistently had high EDCs. A strong linear correlation (R2 = 0.97) existed between EDCs and the total phenolic content, which confirmed that phenols contributed to the EDCs of HSs. Further anal...

Due to its complex composition and structure, many of the properties of natural organic matter (NOM) are poorly understood. In this study, the oxidization-induced chemiluminescence (OCL) of NOM was investigated, and a flow-injection OCL method was developed using alkaline persulfate-H

The reduction of ferric iron (Fe(III)) to ferrous iron (Fe(II)) by dissimilatory iron-reducing bacteria is widespread in anaerobic environments. The oxidation of Fe(II) in aerobic environments has been found to produce hydroxyl radicals (

Manganese (Mn) oxides are ubiquitous in the environment and have strong reactivity to induce the transformation of various contaminants. However, whether reactive oxygen species contribute to their surface reactivity remains unclear. Here, sustainable production of superoxide radicals (O2•-) by various MnO2 polymorphs in the dark was quantified and the mechanisms involved were explored. The results confirm that O2•- was produced through one-electron transfer from surface Mn(III) to adsorbed O2. In contrast, no H2O2 was detected due to its decomposition by Mn oxides to form O2•- and Mn(III), leading to the sustained production of O2•- on Mn oxide surfaces. In addition, the production of O2•- was found to make a clear contribution (4 - 28%) to the transformation of a series of halophenols by MnO2, suggesting that the O2•--mediated surface reaction is an important supplement to the direct electron-transfer mechanism in the reactivity of Mn oxides. These findings advance our understanding of the surface reactivity of Mn oxides and also reveal an important but hitherto unrecognized abiotic source of O2•- in the natural environment.

Microbial dissimilatory iron reduction and aerobic oxidation affect the biogeochemical cycles of many elements. Although the processes have been widely studied, the underlying mechanisms, and especially how the surface structures of iron oxides affect these redox processes, are poorly understood. Therefore, {001} facet-dominated hematite nanoplates (HNP) and {100} facet-dominated hematite nanorods (HNR) were used to explore the effects of surface structure on the microbial dissimilatory iron reduction and aerobic oxidation processes. During the reduction stage, the production of total Fe(II) normalized by specific surface area (SSA) was higher for HNP than HNR due to steric effects and the ligand-bound conformation of the connection between iron on different exposed facets and electron donors from microorganisms. However, during the aerobic oxidation stage, both the SSA- and Fe(II)-normalized reactive oxygen species (ROS), including hydrogen peroxide (H2O2) and hydroxyl radical (•OH), were higher for HNR than HNP. Theoretical calculation results showed that the {100} facets exhibited a lower activation energy barrier for oxygen reduction reaction than {001} facets, supporting the experimental observation that {100} facet-dominated HNR had a higher ROS production efficiency than {001} facet-dominated HNP. These results indicated that surface characteristics not only mediated the microbial reduction of Fe(III) but also affected the aerobic oxidation of microbially reduced Fe(II). Accessibility of electron donors to surface iron atom determined the reduction of Fe(III), and activation energy barrier for oxygen reduction by surface Fe(II) dominated the ROS production during the redox processes. This study advances our understanding of the mechanisms through which ROS are produced by iron (oxyhydr)oxides during microbial dissimilatory iron reduction and aerobic oxidation processes.

Interactions between dissolved organic matter (DOM) and iron oxyhydroxides have important environmental and geochemical implications. The present study employed two hematite nanocrystals to investigate the adsorption and molecular fractionation of two typical humic substances (HSs) using electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Hematite with a predominant exposure of {100} facets induced more pronounced adsorption and molecular fractionation of HSs than {001} facets, indicating that the interfacial adsorptive fractionation process of HSs was mediated by exposed facets of hematite. Further exploration of the surface OH groups of the two hematite nanocrystals confirms that the facet-mediated molecular fractionation of HSs was attributable to the abundance of singly iron-atom coordinated -OH sites on the hematite surfaces. Molecules with a high oxidation state and high aromaticity such as oxidized black carbon, polyphenol-like, and tannic-like compounds preferentially formed ligand-exchange complexes with singly coordinated -OH groups on the hematite surfaces, inducing the selective binding and molecular fractionation of HSs at the mineral-water interface. These results demonstrate that singly iron-atom coordinated -OH sites determine DOM adsorption and mediate molecular fractionation on hematite surfaces, and this contributes substantially to our understanding of the molecular mechanisms of iron oxyhydroxide-mediated molecular exchange of DOM in soils and/or sediments.

A novel biosensor was fabricated based on hemoglobin (Hb) immobilized onto cuprous sulfide (Cu2S) nanorods/nafion nanocomposite film for the detection of polyphenols in the presence of hydrogen peroxide (H2O2). The nanostructured inorganic–organic hybrid material formed by Cu2S nanorods and nafion provided a biocompatible microenvironment for Hb and increased the sensitivity for polyphenols detection. The modified electrodes were characterized by electrochemical impedance spectroscopy and linear sweep voltammetry. Parameters such as pH, H2O2 concentration, and the applied potential were optimized. Under optimum conditions, the biosensor gave linear response ranges of 7.0–110, 0.6–10, and 8–100 μM for catechol, hydroquinone, and resorcin, with the detection limits of 0.5, 0.03, and 0.6 μM (S/N = 3), respectively. The developed biosensor exhibited a short response time within only 8 s with good stability and reproducibility. Such a novel biosensor showed great promise for rapid, simple analysis of polyphenols contents in real samples.

A sensitive electrochemical method for the detection of avian influenza virus (AIV) H5N1 gene sequence using a DNA aptamer immobilized onto a hybrid nanomaterial-modified electrode was developed. To enhance the selectivity and sensitivity, the modified electrode was assembled with multi-wall carbon nanotubes (MWNT), polypyrrole nanowires (PPNWs) and gold nanoparticles (GNPs). This electrode offered a porous structure with a large effective surface area, highly electrocatalytic activities and electronic conductivity. Therefore, the amount of DNA aptamer immobilized onto the electrode was increased while the accessibility of the detection target was maintained. The biosensor is based on the hybridization and preferred orientation of a DNA aptamer immobilized onto a modified electrode surface with its target (H5N1 specific sequence) present in solution. It is selective for the H5N1 specific sequence, and the signal of the indicator was approximately linear to log(concentration) of the H5N1 specific sequence from 5.0 × 10−12 to 1.0 × 10−9 M (R = 0.9863) with a detection limit of 4.3 × 10−13 M. These studies showed that the new hybrid nanomaterial (MWNT/PPNWs/GNPs) and the DNA aptamer could be used to fabricate an electrochemical biosensor for gene sequence detection. Furthermore, this design strategy is expected to have extensive applications in other biosensors.

A new electrochemical biosensor for directly detecting DNA damage induced by acrylamide (AA) and its metabolite was presented in this work. The graphene-ionic liquid-Nafion modified pyrolytic graphite electrode (PGE) was prepared, and then horseradish peroxidase (HRP) and natural double-stranded DNA were alternately assembled on the modified electrode by the layer-by-layer method. The PGE/graphene-ionic liquid-Nafion and the construction of the (HRP/DNA) n film were characterized by electrochemical impedance spectroscopy. With the guanine signal in DNA as an indicator, the damage of DNA was detected by differential pulse voltammetry after PGE/graphene-ionic liquid-Nafion/(HRP/DNA) n was incubated in AA solution or AA + H 2 O 2 solution at 37 °C. This method provides a new model to mimic and directly detect DNA damage induced by chemical pollutants and their metabolites in vitro. The results indicated that, in the presence of H 2 O 2 , HRP was activated and catalyzed the transformation of AA to glycidamide, which could form DNA adducts and induce more serious damage of DNA than AA. In order to further verify these results, UV–vis spectrophotometry was also used to investigate DNA damage induced by AA and its metabolites in solution and the similar results were obtained.

A novel bio-composite film which contains multi-walled carbon nanotube (MWNT)-chitosan (Chit)/poly(amidoamine) (PAMAM) nanocomposite along with the incorporation of DNA modified Au electrode as a biosensor for determination of dopamine(DA) and uric acid (UA) under coexistence of ascorbic acid (AA) was fabricated by layer-by-layer modification. Electrochemical impedance spectroscopy (EIS) and Cyclic Voltametry (CV) were used to characterize the electrochemical properties of the modified electrodes. The biosensor was applied to detect DA and UA in the presence of AA. It not only exhibited strong catalytic activity toward the oxidation of DA and UA but also separated the originally overlapped signals of UA, DA and AA oxidation at the bare electrode into three well-defined peaks. The peak separation between AA and DA, AA and UA was 179 mV and 288 mV, respectively. In the presence of 1.0 mM AA, two linear relationships were obtained for DA over the concentration range from 0.2 to 10 μM (R = 0.9984) and 10–100 μM (R = 0.9957) with a detection limit of 0.03 μM (s/n = 3). The anodic peak current of UA was also a linear relationship in the concentration range 0.5–100 μM (R = 0.9971) with a detection limit of 0.07 μΜ. Moreover, the modified electrode surface has very good reproducibility and stability.

A tyrosinase (Tyr) biosensor has been constructed by immobilizing tyrosinase on the surface of Mg–Al–CO3 hydrotalcite-like compound film (HTLc) modified glassy carbon electrode (GCE) for the determination of polyphenols. The negatively charged tyrosinase was adsorbed firmly on the surface of a positively charged HTLc/GCE by electrostatic interactions and retained its activity to a great degree. The modified electrode was characterized by cyclic voltammetry and AC impedance spectra. Polyphenols were determined by a direct reduction of biocatalytically generated quinone species. The different parameters, including pH, temperature, and enzyme loading were investigated and optimized. Under the optimum conditions, Tyr/HTLc electrode gave a linear response range of 3–300, 0.888–444, and 0.066–396 μM with a detection limit (S/N = 3) of 0.1, 0.05, and 0.003 μM for catechol, caffeic acid, and quercetin, respectively. In addition, the repeatability and stability of the enzyme electrode were estimated. Total polyphenol contents of real samples were also determined to study the potential applicability of the Tyr/HTLc/GCE biosensor.

Catalytic removal of bisphenol A from aqueous solution with hemoglobin immobilized on amino-modified magnetic nanoparticles as an enzyme catalyst was reported. The amino-modified magnetite nanoparticles were firstly prepared by the coprecipitation of Fe2+ and Fe3+ with NH3·H2O and then modified by 3-aminopropyltriethoxysilane. The immobilization process was optimized by examining enzyme concentration, glutaraldehyde concentration, cross-link time, and immobilization time. The optimum conditions for the removal of bisphenol A with immobilized hemoglobin were also investigated. Under the optimality conditions, the removal efficiency of bisphenol A was about 80.3%. The immobilization had a beneficial effect on the stability of hemoglobin and conversions of bisphenol A. According to the proposed breakdown pathway and the intermediates, the enzyme-catalytic removal of bisphenol A by the immobilized hemoglobin is considered to be an effective method.

A novel electrochemical method of detecting DNA hybridization is presented based on the change in flexibility between the single and double stranded DNA. A recognition surface based on gold nanoparticles (GNPs) is firstly modified via mixing self-assembled monolayer of thiolated probe DNA and 1,6-hexanedithiol. The hybridization and electrochemical detection are performed on the surface of probe-modified GNPs and electrode, respectively. Here in our method the charge transfer resistance ( R ct ) signal is enhanced by blocking the surface of electrode with DNA covered GNPs. The GNPs will be able to adsorb on the gold electrode when covered with flexible single stranded DNA (ssDNA). On the contrary, it will be repelled from the electrode, when covered with stiff double stranded DNA (dsDNA). Therefore, different R ct signals are observed before and after hybridization. The hybridization events are monitored by electrochemical impedance spectroscopy (EIS) measurement based on the R ct signals without any external labels. This method provides an alternative route for expanding the range of detection methods available for DNA hybridization.

Environmental contextNotwithstanding the environmental and geochemical significance of soil dissolved organic matter (DOM), its molecular components are still not well characterised. This study investigates chemical similarities and differences between two widely used forms of soil DOM: water-extractable organic matter and fulvic acids. The findings will guide appropriate extraction and purification protocols in future studies related to soil DOM. AbstractDissolved organic matter (DOM) is the most active fraction of soil organic matter (SOM), which has both environmental and geochemical importance. However, the extraction of DOM from soils is still ambiguous. Instead, operational concepts, such as fulvic acid (FA) and water-extractable organic matter (WEOM), are widely used in practice. In this study, the molecular components of FA and WEOM extracted from two standard soils were investigated by using electrospray ionisation coupled with Fourier-transform ion cyclotron resonance mass spectrometry and proton nuclear magnetic resonance (1H NMR) spectroscopy to clarify the molecular similarities and differences between them. The results revealed that WEOM and FA shared many of the same molecules, which accounted for 64% and 82% of the total numbers of molecules for WEOM and FA respectively. However, WEOM displayed higher chemical and molecular diversities than FA. Detailed analysis revealed that the extraction and desalination procedure of FA led to the loss of lignin, protein and carbohydrate compounds, but induced preferential release of some tannin-like molecules from the aggregate- or organic mineral-associated SOM. Based on the results of the present study, water extraction combined with desalination through a functionalised styrene divinylbenzene polymer-based solid phase extraction is more reliable to retain the molecular diversity of soil DOM.

An electrochemical method for the detection of DNA hybridization using a novel electroactive, cationic, and water-soluble branched polyethyleneimine (BPEI)–cobalt(III)–phenanthroline(phen) polymeric indicator and single-stranded neutral peptide nucleic acid (PNA) probe on the Au electrode was developed. The indicator possesses some free amine groups, as well as cationic cobalt complexes in the polymer chain. It does not bind to neutral PNA capture probe alone. However, the indicator strongly interacts with the negatively charged backbone of the complementary oligonucleotide bound to the PNA probe through electrostatic interactions. The coordination spherical moieties also interact with the probe by embedding into the double-helix structure of PNA–DNA. These two interactions enable transduction of hybridization, producing a clear electrical signal in differential pulse voltammetry (DPV). The correlation against non-complementary DNA, three-base and one-base mismatch DNA was sharp, and the signal of indicator for the target DNA demonstrated a linear relationship within the concentration range of 5.0 × 10−9 to 2.5 × 10−7 M (R = 0.9940) with a detection limit of 5.6 × 10−10 M. These studies showed that the novel polymeric indicator and single-stranded PNA probe could be used to fabricate an electrochemical biosensor for DNA detection. This technique can provide an alternative route for expanding the range of detection methods available for DNA hybridization.

This paper presents a novel electroenzymatic method for the treatment of bisphenol A (BPA) in a membraneless electrochemical reactor. The electrochemical reactor was arranged with a stainless steel and an enzymatic film as anode and cathode, respectively. The enzymatic film was formed by immobilizing hemoglobin (Hb) on carbon fiber. In the membraneless electrochemical reactor, hydrogen peroxide (H(2)O(2)) was generated in situ in cathode and BPA was oxidated and removed by the combining Hb with H(2)O(2). The experimental conditions for electrogeneration of H(2)O(2) and electroremoval of BPA were optimized. Experimental results showed that in supplied voltage 2.4 V, pH 5.0 and oxygen flow rate 25 mL/min, the electrogeneration of H(2)O(2) and the electroenzymatic removal of BPA were highest. Under optimal operation conditions, the removal efficiency of BPA reached 50.7% in 120 min and then kept constant when further prolonging the period of reaction. Compared with electrochemical and biochemical methods, the removal of BPA through electroenzymatic method was comparatively favorable.

A glassy carbon electrode was modified with dsDNA and a nanocomposite composed of multi-walled carbon nanotubes and chitosan (MWNT-chit). The electrode was applied to the electrochemical detection of DNA damage as induced by in situ generated bisphenol A (BPA) radicals through electro-oxidation. The modified electrode was characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The results indicate that MWNT-chit nanocomposite represents a viable platform for the immobilization of DNA that effectively promotes electron transfer between DNA and the electrode. The mode of interaction between DNA and BPA was investigated by differential pulse voltammetry and UV-vis spectrophotometry, indicating that the dominant interaction is intercalation. In order to explore the mechanism of damage caused by BPA radicals, the electro-oxidation of BPA at the modified glass electrode was investigated. Based on the signal for guanine without any other external indicator, DNA damage was investigated through the electro-oxidation of BPA.

This study presents a detailed kinetic investigation on the uptake, acropetal translocation and transformation of BDE-47, 6-OH-BDE-47 and 6-MeO-BDE-47 in maize (Zea mays L.) by hydroponic exposure. Root uptake followed the order: BDE-47 > 6-MeO-BDE-47 > 6-OH-BDE-47, while 6-OH-BDE-47 was the most prone to acropetal translocation. Debromination rates of BDE-47 were 1.31 and 1.46 times greater than the hydroxylation and methoxylation rates, respectively. Transformation from BDE-47 to lower brominated OH/MeO-PBDEs occurred mainly through debromination first followed by hydroxylation or methoxylation. There was no transformation from 6-OH-BDE-47 or 6-MeO-BDE-47 to PBDEs. Methylation rate of 6-OH-BDE-47 was twice as high as that of 6-MeO-BDE-47 hydroxylation, indicating methylation of 6-OH-BDE-47 was easier and more rapid than hydroxylation of 6-MeO-BDE-47. Debromination and isomerization were potential metabolic pathways for 6-OH-BDE-47 and 6-MeO-BDE-47 in maize. This study provides important information for better understanding the mechanism on plant uptake and transformation of PBDEs.

Electro-enzymatic processes, which are enzyme catalysis combined with electrochemical reactions, have been used in the degradation of many environment pollutants. For some pollutants, the catalytic mechanisms of the electrochemical-enzyme reaction are still poorly understood. In this paper, the degradation of chlorpyrifos by a combination of immobilized hemoglobin and in situ generated hydrogen peroxide is reported for the first time. Hemoglobin was immobilized on graphite felts to catalyze the removal of chlorpyrifos in an electrochemical-enzyme system. Under the optimal conditions, more than 98% of the chlorpyrifos was degraded. Furthermore, the degradation products of chlorpyrifos were also studied and identified using liquid chromatography-mass spectrometry analysis. The results suggest a possible degradation mechanism for chlorpyrifos with low power and high efficiency, reveal the feasibility of hemoglobin as a substitute for some expensive natural enzymes, and demonstrate the application of an electro-enzymatic process in the treatment of organophosphorus compounds in wastewater.