Fanrong Chen

Comprehensive assessment of heavy metal contamination in sediment of the Pearl River Estuary and adjacent shelf

Total metal concentrations (Cr, Ni, Cu, Zn, and Pb), acid volatile sulfide and simultaneously extracted metals (AVS-SEM), and heavy metal fractionation were used to assess the heavy metals contamination status and ecological risk in the sediments of the Pearl River Estuary (PRE) and adjacent shelf. Elevated concentrations at estuarine sites and lower concentrations at adjacent shelf sites are observed, especially for Cu and Zn. Within the PRE, the concentration of heavy metals in the western shore was mostly higher than that in the middle shore. The metals from anthropogenic sources mainly occur in the labile fraction and may be taken up by organisms as the environmental parameters change. A combination of total metal concentrations, metal contamination index and sequential extraction analysis is necessary to get the comprehensive information on the baseline, anthropogenic discharge and bioavailability of heavy metals.

Effect of pH on Aqueous Se(IV) Reduction by Pyrite

Interaction of aqueous Se(IV) with pyrite was investigated using persistently stirred batch reactors under O2-free (<1 ppm) conditions at pH ranging from 4.5 to 6.6. Thermodynamic calculations, an increase in pH during the experiments, and spectroscopic observation indicate that the reduction of aqueous Se(IV) by pyrite is dominated by the following reaction: FeS2+3.5HSeO3−+1.5H+=2SO4(2−)+Fe2++3.5Se(0)+2.5H2O. The released Fe(II) was partitioned between the bulk solution and pyrite surface at pH≈4.5 and 4.8, with the Fe2+ density at pyrite-solution interface about 4 orders of magnitude higher than that in the bulk solution, while iron oxyhydroxide precipitated at pH≈6.6, resulting in the decrease of dissolved iron. In the Se(IV) concentration range of the experiments, aqueous Se(IV) reduction rate follows the pseudofirst order which is in the form of ln mSe(IV)=−k′t+ln mSe(IV)0, where k′ is apparent rate constant combining the rate constant k and pyrite surface area to mass of solution ratio (A/M). And the aqueous Se(IV) reduction rate constant for a standard system (k) with 1 m2 pyrite surface area per 1 kg solution was obtained to be 1.65×10(−4) h(−1), 3.28×10(−4) h(−1), and 4.76×10(−4) h(−1) at pH around 4.5, 4.8, and 5.1, respectively. The positive correlation between reaction rate and pH disagrees with the theories that protons are consumed when HSeO3− is reduced to Se0, and negative charge density on pyrite surface increases as pH increases. Thus, a ferrous iron mediated electron transfer mechanism is proposed to operate during the reduction of aqueous Se(IV) by pyrite. pH and iron concentration affect significantly on Se(IV) reaction rate and reaction product.

Nanocomposite pyrite-greigite reactivity toward Se(IV)/Se(VI).

A nanopyrite/greigite composite was synthesized by reacting FeCl(3) and NaHS in a ratio of 1:2 (Wei et al. 1996). Following this procedure, the obtained solid phases consisted of 30-50 nm sized particles containing 28% of greigite (Fe(2+)Fe(3+)(2)S(4)) and 72% pyrite (FeS(2)). Batch reactor experiments were performed with selenite or selenate by equilibrating suspensions containing the nanosized pyrite-greigite solid phase at different pH-values and with or without the addition of extra Fe(2+). XANES-EXAFS spectroscopic techniques revealed, for the first time, the formation of ferroselite (FeSe(2)) as the predominant reaction product, along with elemental Se. In the present experimental conditions, at pH 6 and in equilibrium with Se(0), the solution is oversaturated with respect to ferrosilite. Furthermore, thermodynamic computations show that reaction kinetics likely played a significant role in our experimental system.

Facile preparation of hierarchically porous diatomite/MFI-type zeolite composites and their performance of benzene adsorption: the effects of NaOH etching pretreatment.

Hierarchically porous diatomite/MFI-type zeolite (Dt/Z) composites with excellent benzene adsorption performance were prepared. The hierarchical porosity was generated from the microporous zeolite coated at the surface of diatom frustules and from the macroporous diatomite support. A facile NaOH etching method was employed for the first time to treat the frustule support, followed by hydrothermal growth of MFI-type zeolite at the surface of frustules previously seeded with nanocrystalline silicalite-1 (Sil-1). NaOH etching enlarged the pores on diatom frustules and further increased the coated zeolite contents (W(z)). The central macropore size of the diatom frustules increased from approximately 200-500 nm to 400-1000 nm after NaOH etching. The W(z) could reach 61.2%, while the macroporosity of the composites was largely preserved due to more voids for zeolite coating being formed by NaOH etching. The Dt/Z composites exhibited higher benzene adsorption capacity per unit mass of zeolite and less mass transfer resistance than Sil-1, evaluated via a method of breakthrough curves. These results demonstrate that etching of a diatomite support is a facile but crucial process for the preparation of Dt/Z composites, enabling the resulting composites to become promising candidates for uses in volatile organic compounds emission control.

Removal of antibiotics and antibiotic resistance genes from domestic sewage by constructed wetlands: Optimization of wetland substrates and hydraulic loading.

This study aimed to assess removal potential of antibiotics and antibiotic resistance genes (ARGs) in raw domestic wastewater by various mesocosm-scale horizontal subsurface-flow constructed wetlands (CWs) planted Cyperus alternifolius L. with different design parameters. Twelve CWs with three hydraulic loading rates (HLR 10, 20 and 30cm/day) and four substrates (oyster shell, zeolite, medical stone and ceramic) were set up in order to select the best optimized wetland. The result showed that 7 target antibiotics compounds including erythromycin-H2O, lincomycin, monensin, ofloxacin, sulfamerazine, sulfamethazine and novobiocin were detected, and all selected 18 genes (three sulfonamide resistance genes (sul1, sul2 and sul3), four tetracycline resistance genes (tetG, tetM, tetO and tetX), two macrolide resistance genes (ermB and ermC), three quinolone resistance genes (qnrB, qnrD and qnrS) and four chloramphenicol resistance genes (cmlA, fexA, fexB and floR)) and two integrase genes (int1 and int2) were positively detected in the domestic wastewaters. The aqueous removal rates of the total antibiotics ranged from17.9 to 98.5%, while those for the total ARGs varied between 50.0 and 85.8% by the mesocosm-scale CWs. After considering their aqueous removal rates in combination with their mass removals, the CW with zeolite as the substrate and HLR of 20cm/day was selected as the best choice. Combined chemical and biological analyses indicate that both microbial degradation and physical sorption processes were responsible for the fate of antibiotics and ARGs in the wetlands. The findings from this study suggest constructed wetlands could be a promising technology for the removal of emerging contaminants such as antibiotics and ARGs in domestic wastewater.

Surface silylation of natural mesoporous/macroporous diatomite for adsorption of benzene.

Naturally occurring porous diatomite (Dt) was functionalized with phenyltriethoxysilane (PTES), and the PTES-modified diatomite (PTES-Dt) was characterized using diffuse reflectance Fourier transform infrared spectroscopy, nitrogen adsorption, nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. After silylation, a functional group (-C6H5, phenyl) was successfully introduced onto the surface of Dt. PTES-Dt exhibited hydrophobic properties with a water contact angle (WCA) as high as 120°±1°, whereas Dt was superhydrophilic with a WCA of 0°. The benzene adsorption data on both Dt and PTES-Dt fit well with the Langmuir isotherm equation. The Langmuir adsorption capacity of benzene on PTES-Dt is 28.1 mg/g, more than 4-fold greater than that on Dt. Moreover, the adsorption kinetics results show that equilibrium was achieved faster for PTES-Dt than for Dt, over the relative pressure range of 0.118-0.157. The excellent benzene adsorption performance of PTES-Dt is attributed to strong π-system interactions between the phenyl groups and the benzene molecules as well as to the macroporosity of the PTES-Dt. These results show that the silylated diatomite could be a new and inexpensive adsorbent suitable for use in benzene emission control.

Temporal trends of hydrocarbons in sediment cores from the Pearl River Estuary and the northern South China Sea

Concentrations and fluxes of unresolved complex mixture of hydrocarbons (UCM) and polycyclic aromatic hydrocarbons (PAHs) were analyzed for two (210)Pb dated sediment cores from the Pearl River Estuary (PRE) and the adjacent northern South China Sea (NSCS). Compound-specific stable carbon isotopic compositions of individual n-alkanes were also measured for identification of the hydrocarbon sources. The historical records of PAHs in the NSCS reflected the economic development in the Pearl River Delta during the 20th century. PAHs in the NSCS predominantly derive from combustion of coal and biomass, whereas PAHs in the PRE are a mixture of petrogenic and pyrogenic in origins. The isotopic profiles reveal that the petrogenic hydrocarbons in the PRE originate predominantly from local spillage/leakage of lube oil and crude oils. The accumulation rates of pyrogenic PAHs have significantly increased, whereas UCM accumulation has slightly declined in the NSCS in the recent three decades.

Removal of antibiotics from piggery wastewater by biological aerated filter system: Treatment efficiency and biodegradation kinetics

This study aimed to investigate the removal efficiency and mechanism for antibiotics in swine wastewater by a biological aerated filter system (BAF system) in combination with laboratory aerobic and anaerobic incubation experiments. Nine antibiotics including sulfamonomethoxine, sulfachloropyridazine, sulfamethazine, trimethoprim, norfloxacin, ofloxacin, lincomycin, leucomycin and oxytetracycline were detected in the wastewater with concentrations up to 192,000ng/L. The results from this pilot study showed efficient removals (>82%) of the conventional wastewater pollutants (BOD5, COD, TN and NH3-N) and the detected nine antibiotics by the BAF system. Laboratory simulation experiment showed first-order dissipation kinetics for the nine antibiotics in the wastewater under aerobic and anaerobic conditions. The biodegradation kinetic parameters successfully predicted the fate of the nine antibiotics in the BAF system. This suggests that biodegradation was the dominant process for antibiotic removal in the BAF system.

Incorporation of neptunium(V) and iodate into a uranyl phosphate: implications for mitigating the release of 237Np and 129I in repositories.

The simultaneous incorporation of IO3(-) and NpO2+ into Ba3(UO2)2(HPO4)2(PO4)2 (BaUP), which serves as a model for uranyl alteration phases, was investigated. LA-ICP-MS data demonstrate that the incorporation of both of these species is significantly enhanced when they are present together. The most probable explanation is that charge balance is obtained by the coupled substitutions of NpO2+ <--> UO2(2+) and IO3(-) <--> HPO4(2-). According to the LA-ICP-MS results, in the absence of iodate as much as 2.91 +/- 0.14 to 3.44 +/- 0.25% of the uranium in BaUP can be replaced by neptunium. When iodate is present in the reaction, the amount of uranium substitution by neptunium increases to 6.05 +/- 0.65% to 7.93 +/- 0.83%. The net increase for neptunium is 116 +/- 0.30% to 225 +/- 0.25%. Similarly, in the absence of NpO2+, iodate incorporation into BaUP reaches an I/U level of 0.0021 +/- 0.0004 to 0.0038 +/- 0.0005; whereas in its presence there is an increase to as much as 100 +/- 0.11% to 0.0042 +/- 0.0008.

Removal of antibiotics and antibiotic resistance genes from domestic sewage by constructed wetlands: Effect of flow configuration and plant species.

This study aims to investigate the removal of antibiotics and antibiotic resistance genes (ARGs) in raw domestic wastewater by various mesocosm-scale constructed wetlands (CWs) with different flow configurations or plant species including the constructed wetland with or without plant. Six mesocosm-scale CWs with three flow types (surface flow, horizontal subsurface flow and vertical subsurface flow) and two plant species (Thaliadealbata Fraser and Iris tectorum Maxim) were set up in the outdoor. 8 antibiotics including erythromycin-H2O (ETM-H2O), monensin (MON), clarithromycin (CTM), leucomycin (LCM), sulfamethoxazole (SMX), trimethoprim (TMP), sulfamethazine (SMZ) and sulfapyridine (SPD) and 12 genes including three sulfonamide resistance genes (sul1, sul2 and sul3), four tetracycline resistance genes (tetG, tetM, tetO and tetX), two macrolide resistance genes (ermB and ermC), two chloramphenicol resistance genes (cmlA and floR) and 16S rRNA (bacteria) were determined in different matrices (water, particle, substrate and plant phases) from the mesocosm-scale systems. The aqueous removal efficiencies of total antibiotics ranged from 75.8 to 98.6%, while those of total ARGs varied between 63.9 and 84.0% by the mesocosm-scale CWs. The presence of plants was beneficial to the removal of pollutants, and the subsurface flow CWs had higher pollutant removal than the surface flow CWs, especially for antibiotics. According to the mass balance analysis, the masses of all detected antibiotics during the operation period were 247,000, 4920-10,600, 0.05-0.41 and 3500-60,000μg in influent, substrate, plant and effluent of the mesocosm-scale CWs. In the CWs, biodegradation, substrate adsorption and plant uptake all played certain roles in reducing the loadings of nutrients, antibiotics and ARGs, but biodegradation was the most important process in the removal of these pollutants.