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.     

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.     

Environmental behaviors of phoxim with two formulations in bamboo forest under soil surface mulching

Phoxim (emulsifiable concentrate (EC) and granules (G)) has been widely used in bamboo forests. The persistence and magnitude of phoxim residues in the crop and soil must be investigated to ensure human and environmental safety. The environmental behaviors of the two formulations were investigated in a bamboo forest under soil surface mulching conditions (CP) and non-covered cultivation conditions (NCP). The half-lives of phoxim in soil under the two conditions in soil were 4.1–6.2 days (EC) and 31.5–49.5 days (G), respectively. Phoxim in EC could be leached from the topsoil into the subsoil. A minimized leaching effect was observed for G under NCP. Inversely, an enhanced leaching effect was observed for G under CP. The G formulation resulted in more parent compound (in bamboo shoots) and metabolite (in soil) residues of phoxim than in the case of EC, especially under CP conditions. In addition, the intensity and duration of the formulation effect on soil pH adjustment from G were more obvious than that from EC. Results showed that the environmental behaviors (distribution, degradation, residue) of phoxim in the bamboo forest were significantly influenced by the type of formulation. The prolongation effect from phoxim G might cause persistence and long-term environmental risk. However, bamboo shoot consumption could be considered relatively safe after applying the recommended dose of the two phoxim formulations.     

Insights into metals in individual fine particles from municipal solid waste using synchrotron radiation-based micro-analytical techniques

Excessive inter-contamination with heavy metals hampers the application of biological treatment products derived from mixed or mechanically-sorted municipal solid waste(MSW). In this study, we investigated fine particles of 2 mm, which are small fractions in MSW but constitute a significant component of the total heavy metal content, using bulk detection techniques. A total of 17 individual fine particles were evaluated using synchrotron radiation-based micro-X-ray fluorescence and micro-X-ray diffraction. We also discussed the association, speciation and source apportionment of heavy metals. Metals were found to exist in a diffuse distribution with heterogeneous intensities and intense hot-spots of 10 μm within the fine particles. Zn–Cu, Pb–Fe and Fe–Mn–Cr had significant correlations in terms of spatial distribution. The overlapped enrichment, spatial association, and the mineral phases of metals revealed the potential sources of fine particles from size-reduced waste fractions(such as scraps of organic wastes or ceramics) or from the importation of other particles. The diverse sources of heavy metal pollutants within the fine particles suggested that separate collection and treatment of the biodegradable waste fraction(such as food waste) is a preferable means of facilitating the beneficial utilization of the stabilized products.     

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.     

Applying a new method for direct collection,volume quantification and determination of N2 emission from water

The emission of N2 is important to remove excess N from lakes, ponds, and wetlands. To investigate the gas emission from water, Gao et al.(2013) developed a new method using a bubble trap device to collect gas samples from waters. However, the determination accuracy of sampling volume and gas component concentration was still debatable. In this study, the method was optimized for in situ sampling, accurate volume measurement and direct injection to a gas chromatograph for the analysis of N2 and other gases. By the optimized new method, the recovery rate for N2 was 100.28% on average; the mean coefficient of determination(R2) was 0.9997; the limit of detection was 0.02%. We further assessed the effects of the new method, bottle full of water, vs. vacuum bag and vacuum vial methods, on variations of N2 concentration as influenced by sample storage times of 1,2, 3, 5, and 7 days at constant temperature of 15°C, using indices of averaged relative peak area(%) in comparison with the averaged relative peak area of each method at 0 day.The indices of the bottle full of water method were the lowest(99.5%–108.5%) compared to the indices of vacuum bag and vacuum vial methods(119%–217%). Meanwhile, the gas chromatograph determination of other gas components(O2, CH4, and N2O) was also accurate. The new method was an alternative way to investigate N2 released from various kinds of aquatic ecosystems.     

Sulfide elimination by intermittent nitrate dosing in sewer sediments

The formation of hydrogen sulfide in biofilms and sediments in sewer systems can cause severe pipe corrosions and health hazards, and requires expensive programs for its prevention. The aim of this study is to propose a new control strategy and the optimal condition for sulfide elimination by intermittent nitrate dosing in sewer sediments. The study was carried out based on lab-scale experiments and batch tests using real sewer sediments. The intermittent nitrate dosing mode and the optimal control condition were investigated. The results indicated that the sulfide-intermittent-elimination strategy by nitrate dosing is advantageous for controlling sulfide accumulation in sewer sediment. The oxidation–reduction potential is a sensitive indicator parameter that can reflect the control effect and the minimum N/S(nitrate/sulfide)ratio with slight excess nitrate is necessary for optimal conditions of efficient sulfide control with lower carbon source loss. The optimal control condition is feasible for the sulfide elimination in sewer systems.     

Piriformospora indica confers cadmium tolerance in Nicotiana tabacum

Piriformospora indica, a root-colonizing endophytic fungus of Sebacinales, promotes plant growth and confers resistance against biotic and abiotic stresses. In order to confirm the influence of P. indica on growth, proline, malondialdehyde (MDA), chlorophyll, and cadmium (Cd) amounts in Nicotiana tabacum under Cd stress, hydroponics, pot and field trials were conducted. The results showed that P. indica can store Cd in plant roots and reduce leaf Cd content, reduce the concentration of MDA, and increase the proline and chlorophyll content and the activities of catalase, peroxidase, and superoxide dismutase under hydroponic Cd stress. RT-PCR analysis showed that the relative expression level of genes Gsh2, TaPCS1, oas1, GPX, and Hsp70 in colonized plants was 4.3, 1.4, 2.9, 1.7, and 6.9 fold higher than in un-colonized plants respectively. Cd exposure significantly reduced un-colonized plants'' agronomic traits compared to P. indica-colonized ones. Our results suggested that P. indica can sequester Cd in roots, so that much less cadmium was transported to leaves, and the increased concentrations of antioxidant enzymes, pigments and proline contents, as well as the higher expression of stress-related phytochelatin biosynthesis genes in P. indica-inoculated plants, may also serve to protect N. tabacum plants against oxidative damage, enhancing Cd tolerance.