Phosphate-induced metal immobilization in a contaminated site

To assess the efficiency of P-induced metal immobilization in soils, a pilot-scale field experiment was conducted at a metal contaminated site located in central Florida. Phosphate was applied at a P/Pb molar ratio of 4.0 with three treatments: 100% of P from H3PO4, 50% of P from H3PO4+ 50% of P from Ca(H2PO4)2, and 50% of P from H3PO4+5% phosphate rock in the soil. Approximately 1 year after P application, soil and plant samples were collected to determine mobility and bioavailability of selected metals (Pb, Zn, and Cu) using sequential extraction procedure and mineralogical characterization using X-ray diffraction (XRD) and scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis. Phosphorus distribution and soil pH effects were also evaluated. Phosphate was more effective in transforming soil Pb (to 53%) from the non-residual to the residual phase than soil Zn (to 15%) and soil Cu (to 13%). This was because Pb was immobilized by P via formation of an insoluble pyromorphite-like mineral in the surface and subsurface of the soil, whereas no phosphate mineral Zn or Cu was identified. While P amendment enhanced metal uptake in the roots of St. Augustine grass (Stenotaphrum secundatum), it significantly reduced metal translocation from root to shoot, especially Pb via formation of a pyromorphite-like mineral on the membrane surface of the root. A mixture of H3PO4 and phosphate rock was effective in metal immobilization, with less soil pH reduction and less soluble P. Although H3PO4 was effective in immobilizing Pb, its use should be limited to minimize soil pH reduction and potential eutrophication risk.     

Reaction-enhanced mass transfer and transport from non-aqueous phase liquid source zones

The objective of the following research is to theoretically quantify the enhancement of interphase mass transfer of dissolved non-aqueous phase liquid (NAPL) compounds from the non-aqueous phase to the aqueous phase and the enhancement of dispersive mass transport from a NAPL zone due to destruction of dissolved NAPL compounds. For relatively slow reaction rates, such as for permanganate and perchloroethene (PCE), local-scale mass transfer enhancement is expected to be small. Dispersive mass transport with reaction from a horizontal NAPL zone can be quantified using equations derived for a mathematically equivalent falling film reactor system. In contrast to local-scale interphase mass transfer, dispersive mass transport from NAPL zones may be significantly increased by reaction. Enhancement factors due to destruction of the NAPL compound(s) are mainly dependent on NAPL solubility and oxidant concentration and to a lesser extent on reaction rate, stoichiometry, and transverse dispersion coefficients. Higher NAPL solubility and/or lower oxidant concentration reduces the maximum expected enhancement factor. Reaction enhancement factors for mass transport from NAPL zones are expected to be in the range of 5-50 for permanganate and chlorinated solvents. Theoretical results suggest that assuming instantaneous reaction rates may be appropriate for dispersive mass transport from NAPL zones.     

Bioaccumulation of the rare earth elements lanthanum, gadolinium and yttrium in carp (Cyprinus carpio)

Widespread use of the rare earth elements (REEs) in China for agricultural purposes, together with many other applications, has resulted in a remarkable increase of REE concentrations in the environment. The comparative bioaccumulations of representative light, medium and heavy REEs in a variety of tissues of carp (Cyprinus carpio L.) were investigated for an evaluation of their impacts on aquatic animals. The fish were exposed continuously to solutions containing 0.50 mg litre(-1) of each element for 45 days at pH 6.0 and sacrificed at time intervals. Skeleton, muscle, gills and internal organs were analysed for REE contents. A method using cation-exchange resin separation and ICP-AES determination was developed for the quatification of individual REEs. The results show that carp has low ability to take up the REEs under the experimental conditions. The order of REEs under the experimental conditions. The order of maximum bioconcentration factors was mostly internal organs > gills > skeleton > muscle. Neither synergistic nor antagonistic effects of the mixed REE solutions for carp were observed. The relative distributions of different REEs in the investigated tissues exhibited similar patterns. Among the selected tissues studied, the concentration of a heavy REE (Y) was the smallest, while concentrations of a medium (Gd) and a light REE (La) showed only a slight difference.     

A simple effective procedure for the determination of adenosine triphosphate in soils

A simple method for the extraction and determination of adenosine 5′-triphosphate (ATP) in soil is described. ATP was extracted by stirring with dimethyl sulphoxide (DMSO), followed by adding 0.01 M trisodium phosphate (Na₃PO₄) buffer solution for a further dispersion. The ATP content was quantitatively measured by luciferin-luciferase system employing a standard addition technique. The method was most efficient in comparison with 7 other extraction procedures. The recoveries of ATP in spiked soil were found to be approximately 100 %. ATP contents in 16 selected soils were in ranges of 0.76±0.05 – 7.79±0.83 μg/g (dry weight). A significant correlation between ATP amounts and biomasses in these soils was also observed.     

Antioxidative responses to arsenic in the arsenic-hyperaccumulator Chinese brake fern (Pteris vittata L.)

This study measured antioxidative responses of Chinese brake fern (Pteris vittata L.) upon exposure to arsenic (As) of different concentrations. Chinese brake fern was grown in an artificially-contaminated soil containing 0 to 200 mg As kg(-1) (Na2HAsO4) for 12 weeks in a greenhouse. Soil As concentrations at < or =20 mg kg(-1) enhanced plant growth, with 12-71% biomass increase compared to the control. Such beneficial effects were not observed at >20 mg As kg(-1). Plant As concentrations increased with soil As concentrations, with more As being accumulated in the fronds (aboveground biomass) than in the roots and with maximum frond As concentration being 4675 mg kg(-1). Arsenic uptake by Chinese brake enhanced uptake of nutrient elements K, P, Fe, Mn, and Zn except Ca and Mg, whose concentrations mostly decreased. The contents of non-enzymatic antioxidants (glutathione, acid-soluble thiol) followed similar trends as plant As concentrations, increasing with soil As concentrations, with greater contents in the fronds than in the roots especially when exposed to high As concentrations (>50 mg kg(-1)). The activities of enzymatic antioxidants (superoxide dismutase, catalase, ascorbate peroxidase, guaiacol peroxidase) in Chinese brake followed the same trends as plant biomass, increasing with soil As up to 20 mg kg(-1) and then decreased. The results indicated though both enzymatic and non-enzymatic antioxidants played significant roles in As detoxification and hyperaccumulation in Chinese brake, the former is more important at low As exposure (< or =20 mg kg(-1)), whereas the latter is more critical at high As exposure (50-200 mg kg(-1)).     

Photochemical degradation of 1,3-dinitrobenzene in aqueous solution in the presence of hydrogen peroxide

A study on the destruction of 1,3-dinitrobenzene (1,3-DNB) in aqueous solution was carried out under ultraviolet (UV) irradiation alone and UV irradiation in the presence of hydrogen peroxide (H2O2). The combination of UV and H2O2 is significantly effective in degrading 1,3-DNB in terms of initial reaction rate and the mineralization of organic carbons. The photodegradation process can be influenced in certain extent by increasing the content of H2O2 and the acidity of reaction matrices. It was found that a variety of phenolic intermediates and inorganic acid were formed via hydroxyl radicals attacking the parent compound. The UV/H2O2 oxidation of 1,3-DNB was characterized by pseudo-zero order reaction for the degradation of 1,3-DNB with a 20 times enhanced rate constant of 1.36 x 10(-7) Ms(-1) and the initial rate constant was dependent on the initial concentration of 1,3-DNB.     

Mechanisms of nitrite accumulation occurring in soilnitrification

Because low concentration of nitrite could be toxic to biological systems and high amounts of nitrite have been observed in a river of northern China since 1990, nitrite from agricultural soil sources should be investigated. In this paper, effects of levels of ammonium-N (NH4+-N), soil pH and nitrification inhibitors on NO2- accumulation, and duration of nitrite in soils were studied. Application of 11.2 mg of nitrapyrin kg(-1) soil or 11.2 mg of sodium azide kg(-1) soil dramatically suppressed nitrite occurrence. Within all incubation times and at all levels of ammonium-N input, we did not detect any measurable NO2-N accumulation in samples of Yellow-brown earth (pH 5.67), but observed huge accumulation in the 2 alkaline soils, Fluvo-aquic loam (pH 7.89) and Fluvo-aquic sand (pH 8.20). The concentrations of nitrite in both alkaline soils were related to ammonium-N levels. The effect of pH on nitrite accumulation was demonstrated by using slurries of Fluvo-aquic sand under continuous aeration and buffers of different pH. Data showed that nitrite concentration increased with the elevated pH, yet that ammonia oxidizers from the original soil (pH 8.2) could adapt to the new medium of low pH (pH 5.35). Dynamic changes of nitrite in soils amended with different rates of nitrite-N were also measured in 6 days. Thereby, we concluded that nitrite was unstable in acid soils, but durable in alkaline soils. The authors suggested that NO2- accumulation in field soils and its subsequent environmental impact should receive more attention.     

Correlations between cadmium and mineral nutrients in absorption and accumulation in various genotypes of rice under cadmium stress

The absorption and accumulation of Cd2+, Fe3+, Zn2+, Mn2+, Cu2+ and Mg2+ in the roots and leaves of 20 rice cultivars (Oryza sativa L.) with different genotypes under cadmium (Cd) stress were investigated with pot experiments. The results showed that there existed significant differences among the rice cultivars in the contents of six mineral elements in both roots and leaves at both heading and ripening periods. The statistical analysis showed that, for their contents in roots, significant and positive correlations between Cd2+ and Fe3+, Cd2+ and Zn2+, Cd2+ and Mn2+, Cd2+ and Cu2+ existed, but no significant correlation between Cd2+ and Mg2+, at the two periods. In the leaves, Cd also showed significant and positive correlations with Fe3+, Zn2+ and Cu2+ at the both periods, but a significant and negative correlation with Mn2+ and no significant correlation with Mg2+ at heading, a significant and positive correlation with Mg2+ and no significant correlation with Mn2+ at ripening. These results suggested that there were cooperative absorption between Cd2+ and Fe3+, Mn2+, Cu2+, Mn2+ in rice plants. Genotypic differences in Cd uptake and translocation among the rice cultivars suggested that paddy field of some rice cultivars may be irrigated with partially treated sewage water.     

Interactions between organic flocculant PAN-DCD and dyes

Organic flocculant polyacrylonitrile-dicyandiamide (PAN-DCD) was characterized by IR, 1H NMR and 13C NMR spectra. Polar groups, such as triazine, carboxyl, amidine, carbonamide and non-polar groups, such as methylene were identified in the macromolecular chain of PAN-DCD. The flocculant effectively decolorized the examined dyes in their aqueous solutions under acid condition. By comparing the IR spectra of dyes with that of PAN-DCD and that of flocs formed, weak chemical interactions between amino in PAN-DCD side chain and sulfonic acid group in the dye molecules were observed through the formation of -NH3+ SO3(-)-, NH2+ SO3(-)- or/and =NH+ SO3(-)-. By using equilibrium dialysis technique, the hydrophobic interactions between PAN-DCD and the dyes in the binding process were also observed from the experimental results. The binding extent of PAN-DCD to dye KN-R was greater than that of MO. The addition of urea into the binding system of KN-R by PAN-DCD reduced the first binding constant K from 12.2 x 10(5) (without urea) to 3.48 x 10(5) (with urea).     

The role of citric acid on the phytoremediation of heavy metal contaminated soil

Adsorption and hydroponics experiments were conducted to study the role of citric acid on the phytoremediation of heavy metal contaminated soil. The results show that addition of citric acid decreased the adsorption of both lead and cadmium, such an effect was bigger for cadmium than for lead. The decrease in the adsorption of Pb and Cd was mainly due to a decrease of pH in the presence of citric acid. The presence of citric acid could alleviate the toxicity of Pb and Cd to radish, and stimulate their transportation from root to shoot. The studies of heavy metal forms using sequential extraction demonstrated that lead was mainly existed as FHAC (a lower bioavailable form) in the root, while F(HCl) was the dominant form in the leaf. The addition of citric acid to the soil changed the concentration and relative abundance of all the forms. The detoxifying effect of citric acid to Pb in shoots might result from the transformation of higher toxic forms into lower toxic forms. Cadmium was mainly present as F(NaCl), therefore, it had higher toxicity than lead. The addition of citric acid increased the abundance of F(H2O) + F(NaCl), indicating that citric acid treatment could transform cadmium into more transportable forms.