Rongliang Qiu

Relative distribution of Pb2+ sorption mechanisms by sludge-derived biochar

Lead sorption capacity and mechanisms by sludge-derived biochar (SDBC) were investigated to determine if treatment of acid mine drainage (AMD) containing metals with SDBC is feasible. It was found that the biochar derived from pyrolysis treatment of sewage sludge could effectively remove Pb(2+) from acidic solution with the capacities of 16.11, 20.11, 24.80, and 30.88mgg(-1) at initial pH 2, 3, 4 and 5, respectively. Lead sorption processes were pseudo-second order kinetic and faster at a higher pH. Furthermore, the relative contribution of both inorganic mineral composition and organic functional groups of SDBC for Pb(2+) removal mechanisms, was quantitatively studied at pH 2-5. The results showed that Pb sorption primarily involved the coordination with organic hydroxyl and carboxyl functional groups, which was 38.2-42.3% of the total sorbed Pb varying with pH, as well as the coprecipitation or complex on mineral surfaces, which accounted for 57.7-61.8% and led to a bulk of Ca(2+) and Mg(2+) release during sorption process. A new precipitate was solely observed on Pb-loaded SDBC as 5PbO·P(2)O(5)·SiO(2)(lead phosphate silicate) at initial pH 5, confirmed by XRD and SEM-EDX. The coordination of Pb(2+) with carboxyl and hydroxyl functional groups was demonstrated by FT-IR, and the contribution of free carboxyl was significant, ranging from 26.1% to 35.5%. Results from this study may suggest that the application of SDBC is a feasible strategy for removing metal contaminants from acid solutions.

The study of operating variables in soil washing with EDTA

This study discusses the operating variables for removal of metals from soils using EDTA, including the type of EDTA, reaction time, solution pH, dose, temperature, agitation, ultrasound and number of extractions. For As, Cd, Cu, Pb and Zn, the removal efficiency order was: H(4)-EDTA > Na(2)EDTA > (NH(4))(2)EDTA. At low EDTA concentrations the removal increased progressively with increasing dose while above 0.4 mmol/g only small increases in extraction efficiency were observed. EDTA induced a two-step process including a rapid desorption within the first hour, and a gradual release in the following hours. The extraction efficiency of metals decreased with increasing pH in the range of 2-10. Consecutive extractions using low concentrations were more effective than a single extraction with concentrated EDTA if the same dose of EDTA was used.

Influence of EDTA washing on the species and mobility of heavy metals residual in soils

Aiming to estimate the potential risk of ethylenediaminetetraacetic acid (EDTA)-enhanced soil washing, the heavy metal species and their mobility in the washed soil under different combinations were investigated by batch leaching tests and the sequential extraction procedure. Results demonstrate that the metal removal efficiency was rather low (less than 12%), partially due to the significant Ca dissolution and strong bonding between metals and the soil as well as the insufficient EDTA dosage. The washing combination of 0.0005 M EDTA and half-an-hour washing can enhance the instant mobility of Ni, Zn and Pb possibly owing to the slow detachment of EDTA-destabilized metals. Metal fractionation also exhibits the corresponding increase in their labile exchangeable fractions. Therefore, a more concentrated EDTA solution for a longer duration often decreased their mobility. The increase in some fractions of a curtain metal implies the redistribution of this metal during the EDTA soil washing. The pathway of such a redistribution may vary for different metals, but the redistribution to organic matter is often a slow process, while that to carbonates or Fe/Mn oxides is a faster one and even may occur in a half hour washing with 0.0005 M EDTA solution. These redistribution processes may also increase the metal chemical availability. Therefore, we should prudently control the chelating reagent concentration and washing duration to finally minimize the mobility and availability of the remaining heavy metals when designing the soil washing for the remediation of metal-contaminated soils.

Photocatalytic activity of polymer-modified ZnO under visible light irradiation

Photocatalytic removal of phenol, rhodamine B, and methyl orange was studied using the photocatalyst ZnO/poly-(fluorene-co-thiophene) (PFT) under visible light. After 2 h irradiation with three 1 W LED (light-emitting diode) lights, about 40% removal of both phenol and methyl orange was achieved; rhodamine B was completely degraded to rhodamine. Diffuse reflectance spectra showed that the absorbance range of PFT/ZnO was expanded from 387 nm (ZnO) to about 500 nm. Photoluminescent spectra and photoluminescent quantum efficiency indicated that electrons were transferred from PFT to the conduction band of ZnO. Electron spin resonance (ESR) signals of spin-trapped paramagnetic species with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) evidenced that the OH* radicals were indeed formed in the PFT/ZnO system under visible light irradiation. A working mechanism involving excitation of PFT, followed by charge injection into the ZnO conduction band is proposed.

Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40gkg(-1)) and steel slag (3 and 6gkg(-1)) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils.

Role of oxygen active species in the photocatalytic degradation of phenol using polymer sensitized TiO2 under visible light irradiation

The role of dissolved oxygen, and of active species generated by photo-induced reactions with oxygen, in the photocatalytic degradation of phenol was investigated using polymer [poly-(fluorene-co-thiophene) with thiophene content of 30%, so-called PFT30] sensitized TiO2 (PFT30/TiO2) under visible light irradiation. The photoluminescent (PL) quantum yield of PFT30/TiO2 was about 30% of that of PFT30/Al(2)O(3), proving that electron transfer took place between the polymer and TiO2. The result that photocatalytic degradation of phenol was almost stopped when the solution was saturated with N(2) proved the importance of O(2). Addition of NaN(3), an effective quencher of singlet oxygen ((1)O(2)), caused about a 40% decrease in the phenol degradation ratio. Addition of alcohols caused about a 60% decrease in the phenol photodegradation ratio, indicating that the hydroxyl radicals (OH), whose presence was confirmed by electron spin resonance (ESR) spectroscopy, was the predominant active species in aqueous solution. In anhydrous solution, singlet oxygen ((1)O(2)) was the predominant species. These results indicate that oxygen plays a very important role in the photocatalytic degradation of phenol.

Antioxidative response to Cd in a newly discovered cadmium hyperaccumulator, Arabis paniculata F.

A hydroponic experiment was carried out to study the effect of cadmium (Cd) on growth, Cd accumulation, lipid peroxidation, reactive oxygen species (ROS) content and antioxidative enzymes in leaves and roots of Arabis paniculata F., a new Cd hyperaccumuator found in China. The results showed that 22-89 microM Cd in solution enhanced the growth of A. paniculata after three weeks, with 21-27% biomass increase compared to the control. Cd concentrations in shoots and roots increased with increasing Cd supply levels, and reached a maximum of 1662 and 8670 mg kg(-1) Cd dry weight at 178 microM Cd treatment, respectively. In roots, 22-89 microM Cd reduced the content of malondialdehyde (MDA), superoxide (O(2)(-1)) and H(2)O(2) as well as the activities of superoxide dismutase (SOD), guaiacol peroxidase (GPX), ascorbate peroxidase (APX) and glutathione reductase (GR). In leaves, the contents of MDA, O(2)(-1) and H(2)O(2) remained unaffected by 22-89 microM Cd, while 178 microM Cd treatment significantly increased the MDA content, 69.5% higher than that of the control; generally, the activities of SOD, catalase (CAT), GPX and APX showed an increasing pattern with increasing Cd supply levels. Our present work concluded that A. paniculata has a great capability of Cd tolerance and accumulation. Moderate Cd treatment (22-89 microM Cd) alleviated the oxidative stress in roots, while higher level of Cd addition (178 microM) could cause an increasing generation of ROS, which was effectively scavenged by the antioxidative system.

Pb(II) and Cr(VI) sorption by biochars pyrolyzed from the municipal wastewater sludge under different heating conditions

To optimize the pyrolysis process of municipal wastewater sludge for metal sorption, this study investigated the characteristics of the produced biochar under different heating conditions with particular interest in Pb(II) or Cr(VI) sorption. Results indicate that the biochar pyrolyzed at 400 °C for 2 h obtained the largest BET surface area and was rich of organic functional groups, owning the highest Pb(II) (at pH 5.0) and Cr(VI) (at pH 2.0) sorption capacity. The Pb sorption is dominated by the rate-limited chemical processes, and a longer residence during pyrolysis significantly reinforces its sorption bonds. The Cr(VI) sorption is highly pH-dependent, and the optimal occurs at pH 2, where the transformation of Cr(VI) to Cr(III) makes a significant contribution as confirmed by the XPS spectra. Similarly, a longer residence during pyrolysis also facilitates the Cr(VI) sorption in terms of capacity and affinity, likely due to the greater reducing potential of biochar.

Visible light induced photocatalytic reduction of Cr(VI) over polymer-sensitized TiO2 and its synergism with phenol oxidation

In this study, both Cr(VI) reduction and phenol oxidation induced by polymer-sensitized TiO(2) were investigated under visible light. Study of the reaction mechanism indicated that poly(fluorene-co-thiophene) (PFT) acted as a semiconductor and was by itself able to reduce Cr(VI) under visible light irradiation. When coupled with TiO(2), PFT served not only as the electron donor for Cr(VI) reduction, but also as a sensitizer. Upon irradiation by visible light, electrons in the sensitizing PFT polymer are excited and are transferred to the conduction band of TiO(2). PFT-catalyzed reduction of Cr(VI) was significantly promoted by the presence of phenol, and synergism between Cr(VI) reduction and phenol degradation was demonstrated both by analysis of the FT-IR spectrum of PFT/TiO(2) and by measuring the effect of repeated use of PFT/TiO(2) on its photocatalytic efficiency. The results provide a cost-effective method to remove organic and inorganic pollutants simultaneously in the complex wastewater.

Cadmium tolerance of carbon assimilation enzymes and chloroplast in Zn/Cd hyperaccumulator Picris divaricata.

To better understand the photosynthesis under stress, the effect of cadmium on carbon assimilation and chloroplast ultrastructure of a newly found Zn/Cd hyperaccumulator Picris divaricata in China was investigated in solution culture. The shoot and root Cd concentrations increased with increase in Cd supply, reaching maxima of 1109 and 5604mgkg(-1) dry weight at 75microM Cd, respectively. As Cd supply to P. divaricata increased, the shoot and root dry weight, leaf water content (except 75microM Cd), concentrations of chlorophyll a and b, chlorophyll a/b ratio and the concentration of carotenoids were not depressed at high Cd. However, the stomatal conductance, transpiration rate, net photosynthetic rate and intercellular CO(2) concentration were significantly affected when the Cd concentration reached 10, 10, 25 and 75microM, respectively. Meanwhile, carbonic anhydrase (CA; EC 4.2.1.1) activity and Rubisco (EC 4.1.1.39) content reached maxima in the presence of 50 and 5microM Cd, respectively. In addition, CA activity correlated positively with shoot Cd in plants treated with Cd at a range of 0-50microM. Moreover, the activities of NADP(+)-glyceraldehyde-3-phosphate dehydrogenase (EC 1.2.1.13), Rubisco and fructose-1, 6-bisphosphatase (EC 3.1.3.11) were not significantly suppressed by increased Cd supply. Although the mesophyll cell size was reduced, chloroplast ultrastructure remained intact at the highest Cd treatment. Our finding revealed that P. divaricata chloroplast and the enzymes of carbon assimilation tolerate high levels of Cd, demonstrating its potential in possible application in phytoremediation.