Immobilization of lead in anthropogenic contaminated soils using phosphates with/without oxalic acid

Understanding the effects of oxalic acid(OA) on the immobilization of Pb(Ⅱ) in contaminated soils by phosphate materials, has considerable benefits for risk assessment and remediation strategies for the soil. A series of phosphate amendments with/without oxalic acid were applied to two anthropogenic contaminated soils. We investigated the immobilization of Pb(Ⅱ) by KH2PO4, phosphate rock(PR), activated phosphate rock(APR) and synthetic hydroxyapatite(HAP) at different phosphate:Pb(P:Pb) molar ratios(0, 0.6, 2.0 and 4.0) in the presence/absence of 50 mmol oxalic acid/kg soil, respectively. The effects of treatments were evaluated using single extraction with deionized water or Ca Cl2, Community Bureau of Reference(BCR) sequential extraction and toxicity characteristic leaching procedure(TCLP)methods. Our results showed that the concentration of water extractable, exchangeable and TCLP-Pb all decreased with incubation time. The concentration of water-extractable Pb after120 days was reduced by 100% when soils were amended with APR, HAP and HAP + OA, and the TCLP-Pb was 5 mg/L for the red soil at P:Pb molar ratio 4.0. Water-soluble Pb could not be detected and the TCLP-Pb was 5 mg/L at all treatments applied to the yellow-brown soil. BCR results indicated that APR was most effective, although a slight enhancement of water-soluble phosphate was detected at the P:Pb molar ratio 4.0 at the beginning of incubation. Oxalic acid activated phosphates, and so mixing insoluble phosphates with oxalic acid may be a useful strategy to improve their effectiveness in reducing Pb bioavailability.     

Predicted no-effect concentrations for mercury species and ecological risk assessment for mercury pollution in aquatic environment

Mercury(Hg) exists in different chemical forms presenting varied toxic potentials. It is necessary to explore an ecological risk assessment method for different mercury species in aquatic environment. The predicted no-effect concentrations(PNECs) for Hg(Ⅱ) and methyl mercury(Me Hg) in the aqueous phase, calculated using the species sensitivity distribution method and the assessment factor method, were 0.39 and 6.5 × 10-3μg/L, respectively. The partition theory of Hg between sediment and aqueous phases was considered, along with PNECs for the aqueous phase to conduct an ecological risk assessment for Hg in the sediment phase. Two case studies, one in China and one in the Western Black Sea, were conducted using these PNECs. The toxicity of mercury is heavily dependent on their forms,and their potential ecological risk should be respectively evaluated on the basis of mercury species.     

Promoting effect of vanadium on catalytic activity of Pt/Ce–Zr–O diesel oxidation catalysts

A series of Pt–V/Ce–Zr–O diesel oxidation catalysts was prepared using the impregnation method. The catalytic activity and sulfur resistance of Pt–V/Ce–Zr–O were investigated in the presence of simulated diesel exhaust. The effect of vanadium on the structure and redox properties of the catalysts was also investigated using the Brunauer–Emmett–Teller method,X-ray diffraction, H2temperature-programmed reduction, CO temperature-programmed desorption, X-ray photoelectron spectroscopy, and Energy Dispersive Spectroscopy. Results showed that the Pt particles were well dispersed on the Ce–Zr–O carrier through the vanadium isolation effect, which significantly improved the oxidation activity toward CO and hydrocarbons. An electron-withdrawing phenomenon occurred from V to Pt, resulting in an increase in the metallic nature of platinum, which was beneficial to hydrocarbon molecular activation.     

Water chemistry controlled aggregation and photo-transformation of silver nanoparticles in environmental waters

The inevitable release of engineered silver nanoparticles (AgNPs) into aquatic environments has drawn great concerns about its environmental toxicity and safety. Although aggregation and transformation play crucial roles in the transport and toxicity of AgNPs, how the water chemistry of environmental waters influences the aggregation and transformation of engineered AgNPs is still not well understood. In this study, the aggregation of polyvinylpyrrolidone (PVP) coated AgNPs was investigated in eight typical environmental water samples (with different ionic strengths, hardness, and dissolved organic matter (DOM) concentrations) by using UV–visible spectroscopy and dynamic light scattering. Raman spectroscopy was applied to probe the interaction of DOM with the surface of AgNPs. Further, the photo-transformation and morphology changes of AgNPs in environmental waters were studied by UV–visible spectroscopy, inductively coupled plasma mass spectrometry, and transmission electron microscopy. The results suggested that both electrolytes (especially Ca^2 + and Mg^2 +) and DOM in the surface waters are key parameters for AgNP aggregation, and sunlight could accelerate the morphology change, aggregation, and further sedimentation of AgNPs. This water chemistry controlled aggregation and photo-transformation should have significant environmental impacts on the transport and toxicity of AgNPs in the aquatic environments.     

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO₄ (OMS-2-SO₄) and Mn(CH₃COO)₂ (OMS-2-AC) as precursors. SO₄^2 −-doped OMS-2-AC catalysts with different SO₄^2 − concentrations were prepared next by adding (NH₄)₂SO₄ solution into OMS-2-AC samples to investigate the effect of the anion SO₄^2 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO₄ catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO₄^2 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO₄^2 − (SO₄/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH₃-TPD and H₂-TPR techniques. The results showed that the presence of a suitable amount of SO₄^2 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO₄ compared to OMS-2-AC is due to the presence of some residual SO₄^2 − species in OMS-2-SO₄ samples.     

Ozone concentrations, flux and potential effect on yield during wheat growth in the Northwest-Shandong Plain of China

Ozone (O₃) concentration and flux (F_o) were measured using the eddy covariance technique over a wheat field in the Northwest-Shandong Plain of China. The O₃-induced wheat yield loss was estimated by utilizing O₃ exposure-response models. The results showed that: (1) During the growing season (7 March to 7 June, 2012), the minimum (16.1 ppbV) and maximum (53.3 ppbV) mean O₃ concentrations occurred at approximately 6:30 and 16:00, respectively. The mean and maximum of all measured O₃ concentrations were 31.3 and 128.4 ppbV, respectively. The variation of O₃ concentration was mainly affected by solar radiation and temperature. (2) The mean diurnal variation of deposition velocity (V_d) can be divided into four phases, and the maximum occurred at noon (12:00). Averaged V_d during daytime (6:00–18:00) and nighttime (18:00–6:00) were 0.42 and 0.14 cm/sec, respectively. The maximum of measured V_d was about 1.5 cm/sec. The magnitude of V_d was influenced by the wheat growing stage, and its variation was significantly correlated with both global radiation and friction velocity. (3) The maximum mean F_o appeared at 14:00, and the maximum measured F_o was − 33.5 nmol/(m²·sec). Averaged F_o during daytime and nighttime were − 6.9 and − 1.5 nmol/(m²·sec), respectively. (4) Using O₃ exposure-response functions obtained from the USA, Europe, and China, the O₃-induced wheat yield reduction in the district was estimated as 12.9% on average (5.5%–23.3%). Large uncertainties were related to the statistical methods and environmental conditions involved in deriving the exposure-response functions.     

Enhanced CO2 adsorptive performance of PEI/SBA-15 adsorbent using phosphate ester based surfactants as additives

In this study,a series of polyetherimide/SBA-15: 2-D hexagonal P6 mm,Santa Barbara USA(PEI/SBA-15) adsorbents modified by phosphoric ester based surfactants(including tri(2-ethylhexyl)phosphate(TEP),bis(2-ethylhexyl) phosphate(BEP) and trimethyl phosphonoacetate(TMPA))were prepared for CO_2 adsorption.Experimental results indicated that the addition of TEP and BEP had positive effects on CO_2 adsorption capacity over PEI/SBA-15.In particular,the CO_2 adsorption amount could be improved by around 20% for 45PEI–5TEP/SBA-15 compared to the additive-free adsorbent.This could be attributed to the decrease of CO_2 diffusion resistance in the PEI bulk network due to the interactions between TEP and loaded PEI molecules,which was further confirmed by adsorption kinetics results.In addition,it was also found that the cyclic performance of the TEP-modified adsorbent was better than the surfactant-free one.This could be due to two main reasons,based on the results of in situ DRIFT and TG-DSC tests.First and more importantly,adsorbed CO_2 species could be desorbed more rapidly over TEP-modified adsorbent during the thermal desorption process.Furthermore,the enhanced thermal stability after TEP addition ensured lower degradation of amine groups during adsorption/desorption cycles.     

Oxidation of Cr(III) on birnessite surfaces: The effect of goethite and kaolinite

Oxidation of Cr(III) by manganese oxides may pose a potential threat to environments due to the formation of toxic Cr(VI) species. At present, it was still unclear whether the extent of Cr(III) oxidation and fate of Cr(VI) would be changed when manganese oxides co-exist with other minerals, the case commonly occurring in soils. This study investigated the influence of goethite and kaolinite on Cr(III) oxidation by birnessite under acidic pH condition (pH 3.5) and background electrolyte of 0.01 mol/L NaCl. Goethite was found not to affect Cr(III) oxidation, which was interpreted as the result of overwhelming adsorption of cationic Cr(III) onto the negatively-charged birnessite (point of zero charge (PZC) < 3.0) rather than the positively-charged goethite (PZC = 8.8). However, more Cr(VI) would be retained by the surface with the increase in addition of goethite because of its strong ability on adsorption of Cr(VI) at low pH. Moreover, either Cr(III) oxidation or distribution of the generated Cr(VI) between the solid and solution phases was not affected by kaolinite (PZC < 3.0), indicating its low affinity for Cr species. Reactions occurring in the present mixed systems were suggested, which could be partly representative of those in the soils and further indicates that the mobility and risk of Cr(VI) would be decreased if goethite was present.     

Responses of soil ammonia oxidizers to a short-term severe mercury stress

The responses of soil ammonia-oxidizing archaea(AOA) and ammonia-oxidizing bacteria(AOB) to mercury(Hg) stress were investigated through a short-term incubation experiment.Treated with four different concentrations of Hg(CK,Hg25,Hg50,and Hg100,denoting 0,25,50,and 100 mg Hg/kg dry soil,respectively),samples were harvested after 3,7,and 28 day incubation.Results showed that the soil potential nitrification rate(PNR) was significantly inhibited by Hg stress during the incubation.However,lower abundances of AOA(the highest in CK: 9.20 × 10~7 copies/g dry soil; the lowest in Hg50: 2.68 × 10~7 copies/g dry soil) and AOB(the highest in CK: 2.68 × 10~7 copies/g dry soil; the lowest in Hg50:7.49 × 10~6 copies/g dry soil) were observed only at day 28 of incubation(P 0.05).Moreover,only the community structure of soil AOB obviously shifted under Hg stress as seen through DGGE profiles,which revealed that 2–3 distinct AOB bands emerged in the Hg treatments at day 28.In summary,soil PNR might be a very useful parameter to assess acute Hg stress on soil ecosystems,and the community structure of soil AOB might be a realistic biological indicator for the assessment of heavy metal stress on soil ecosystems in the future.     

Effect of AlCl3 concentration on nanoparticle removal by coagulation

In recent years, engineered nanoparticles, as a new group of contaminants emerging in natural water, have been given more attention. In order to understand the behavior of nanoparticles in the conventional water treatment process, three kinds of nanoparticle suspensions, namely multi-walled carbon nanotube-humic acid (MWCNT-HA), multi-walled carbon nanotube-N,N-dimethylformamide (MWCNT-DMF) and nanoTiO₂-humic acid (TiO₂-HA) were employed to investigate their coagulation removal efficiencies with varying aluminum chloride (AlCl₃) concentrations. Results showed that nanoparticle removal rate curves had a reverse “U” shape with increasing concentration of aluminum ion (Al^3 +). More than 90% of nanoparticles could be effectively removed by an appropriate Al^3 + concentration. At higher Al^3 + concentration, nanoparticles would be restabilized. The hydrodynamic particle size of nanoparticles was found to be the crucial factor influencing the effective concentration range (ECR) of Al^3 + for nanoparticle removal. The ECR of Al^3 + followed the order MWCNT-DMF > MWCNT-HA > TiO₂-HA, which is the reverse of the nanoparticle size trend. At a given concentration, smaller nanoparticles carry more surface charges, and thus consume more coagulants for neutralization. Therefore, over-saturation occurred at relatively higher Al^3 + concentration and a wider ECR was obtained. The ECR became broader with increasing pH because of the smaller hydrodynamic particle size of nanoparticles at higher pH values. A high ionic strength of NaCl can also widen the ECR due to its strong potential to compress the electric double layer. It was concluded that it is important to adjust the dose of Al^3 + in the ECR for nanoparticle removal in water treatment.