Accumulation of polycyclic aromatic hydrocarbons and heavy metals in lettuce grown in the soils contaminated with long-term wastewater irrigation

Accumulation of polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs) by crop plants from contaminated soils may pose health risks. A greenhouse pot experiment using lettuce (Lactuca satuva L.) as a representative vegetable was conducted to assess the concentrations of PAHs and HMs in vegetables grown in wastewater-contaminated soils. The concentrations of total PAHs were ranged from 1.5 to 3.4 mg kg(-1) in the contaminated soils, while 1.2 mg kg(-1) in the reference soil. Linear regression analyses showed that the relationships between soil and shoot PAH concentrations were stronger for LMW-PAHs (R(2) between 0.51 and 0.92) than for HMW-PAHs (R(2) 0.02 and 0.60), suggesting that translocation for LMW-PAHs is faster than HMW-PAHs. Furthermore, the data imply that root uptake was the main pathway for HMW-PAHs accumulation. The plant shoots were also highly contaminated with HMs, particularly Cd (0.4-0.9 mg kg(-1)), Cr (3.4-4.1 mg kg(-1)), Ni (11.7-15.1 mg kg(-1)) and Pb (2.3-5.3 mg kg(-1)), and exceed the guidance limits set by State Environmental Protection Administration (SEPA), China and the World Health Organization (WHO). This study highlights the potential health risks associated with cultivation and consumption of leafy vegetables on wastewater-contaminated soils.     

Kinetics as a tool to assess the immobilization of soil trace metals by binding phase amendments for in situ remediation purposes

Many soil remediation techniques consist in decreasing the mobility of trace metals by means of adding trace metal binding phases. For this study, whose aim is to assess the efficiency of soil remediation method by binding phase amendment, a kinetic fractionation method that provides the labile and slowly labile trace metal amounts in soil has been introduced. Manganese oxides (vernadite) and insolubilized humic acids (IHA) have been used as binding phases for the remediation of four heavily polluted soils. Vernadite amendments are effective for lead and cadmium remediation, whereas IHA amendments are only effective for copper remediation. In most cases, the labile metal fractions decrease dramatically in amended soils (up to 50%); on the other hand, the amounts of total extracted metal near the point of thermodynamic equilibrium often show no significant difference between the amended soil and the control soil. These results highlight the utility of kinetic fractionation in assessing the efficiency of soil remediation techniques and, more generally, in evaluating trace metal mobility in soils and its potential advantages compared to extraction schemes performed under equilibrium conditions. In the future, this kinetic method could be considerably simplified so as to consume much less time allowing its routine use.     

Investigation of the transport and fate of Pb, Cd, Cr(VI) and As(V) in soil zones derived from moderately contaminated farmland in Northeast, China

Some farmland in Shenyang had been irrigated with industrial wastewater since 1962. Although wastewater irrigation was ceased in 1992, soil had been heavily polluted by heavy metals, especially by Cd. For better understanding processes of soil-heavy metal interactions, in particular, the mobility and retention mechanism of heavy metal in soil, a study on the transport and fate of heavy metals in soil zones from Shenyang suburb was carried out by column leaching tests in laboratory. Breakthrough curves of Pb, Cd, Cr(VI) and As(V) fitted by Thomas model and Yoon–Nelson model. The results of fitted breakthrough curves showed that transport rates of the four heavy metals in the soil zones followed the order: Cr(VI) > As(V) > Cd > Pb, which indicated that Cr(VI) was much more mobile, and Pb was comparatively unmovable. Cr in effluents and As were almost entirely Cr(VI) and As(V), respectively, and no Cr(III) and As(III) was ever detected during the leaching tests. The contents of Pb, Cd, Cr and As in leached soils decreased in the order of Pb > Cd > Cr > As, which suggested that adsorption ability of soil to Pb was greatest and to As was least. The methods of selective sequential extraction and solvent extraction were used to determine the fractions of Pb, Cd, Cr, As and the valent states of Cr, As [Cr(VI) or Cr(III), As(V) or As(III)] in original soils and in leached soils. After leaching tests, the relative and absolute concentrations of exchangeable, carbonate, Fe–Mn oxide and organic fraction of each element were all increased, which enhanced the potential mobility and risk of Pb, Cd, Cr and As to soil/groundwater system. The relative concentrations of Cr(III) and As(III) in different depth of the soil zones after leaching tests were increased by about 6.0% and 5.6%, respectively. Cr(III) and As(III) tended to be adsorbed by soils, which reduced the mobility of them into groundwater.     

Natural attenuation in a slag heap contaminated with cadmium: the role of plants and arbuscular mycorrhizal fungi

A field study of the natural attenuation occurring in a slag heap contaminated with high available cadmium was carried out. The aims of this research were: to determine plants colonizing this slag heap; to analyze colonization and morphological biodiversity of spores of arbuscular mycorrhizal fungi (AMF); to determine spore distribution in undisturbed samples; to know mycelium and glomalin abundance in the rhizosphere of these plants, and to investigate glomalin participation in Cd-stabilization. Forming vegetal islands, 22 different pioneering plant species from 11 families were colonizing the slag heap. The most common plants were species of Fabaceae, Asteraceae and Poaceae. Almost all plants were hosting AMF in their roots, and spores belonging to Gigaspora, Glomus, Scutellospora and Acaulospora species were observed. Micromorphological analysis showed that spores were related to decomposing vegetal residues and excrements, which means that mesofauna is contributing to their dispersion in the groundmass. Mycelium mass ranged from 0.11 to 26.3 mg/g, which contained between 13 and 75 mg of glomalin/g. Slag-extracted total glomalin was between 0.36 and 4.74 mg/g. Cadmium sequestered by glomalin extracted from either slag or mycelium was 0.028 mg/g. The ecological implication of these results is that organisms occupying vegetal patches are modifying mine residues, which contribute to soil formation.     

Effect of a sulfonated azo dye and sulfanilic acid on nitrogen transformation processes in soil

Introduction of organic dyes into soil via wastewater and sludge applications has been of increasing concern especially in developing or under-developed countries where appropriate management strategies are scarce. Assessing the response of terrestrial ecosystems to organic dyes and estimating the inhibition concentrations will probably contribute to soil remediation studies in regions affected by the same problem. Hence, an incubation study was conducted in order to investigate the impact of a sulfonated azo dye, Reactive Black 5 (RB5) and sulfanilic acid (SA), a typical representative of aromatic sulfonated amines, on soil nitrogen transformation processes. The results apparently showed that nitrogen related processes in soil can be used as bioindicators of anthropogenic stress caused by organic dyes. It was found that urease activity, arginine ammonification rate, nitrification potential and ammonium oxidising bacteria numbers decreased by 10–20% and 7–28% in the presence of RB5 (>20 mg/kg dry soil) and SA (>8 mg/kg dry soil), respectively. Accordingly, it was concluded that organic dye pollution may restrict the nitrogen-use-efficiency of plants, thus further reducing the productivity of terrestrial ecosystems. Furthermore, the response of soil microbiota to SA suggested that inhibition effects of the organic dye may continue after the possible reduction of the parent dye to associated aromatic amines.     

Novel modeling concept for evaluating the effects of cadmium and copper on heterotrophic growth and lysis rates in activated sludge process

A new modeling concept to evaluate the effects of cadmium and copper on heterotrophic growth rate constant (μ_H) and lysis rate constant (b_H) in activated sludge was introduced. The oxygen uptake rate (OUR) was employed to measure the constants. The results indicated that the μ_H value decreased from 4.52 to 3.26 d⁻¹ or by 28% when 0.7 mg L⁻¹ of cadmium was added. Contrarily the b_H value increased from 0.31 to 0.35 d⁻¹ or by 11%. When adding 0.7 mg L⁻¹ of copper, the μ_H value decreased to 2.80 d⁻¹ or by 38%. The b_H value increased to 0.42 d⁻¹ or by 35%. After regression, the inhibitory effect was in a good agreement with non-competitive inhibition kinetic. The inhibition coefficient values for cadmium and copper were 1.82 and 1.21 mg L⁻¹, respectively. The relation between the b_H values and heavy metal concentrations agreed with exponential type well. The heavy metal would enhance b_H value. Using these data, a new kinetic model was established and used to simulate the degree of inhibition. It was evident that not only the inhibitory effect on μ_H but also that the enhancement effect on b_H should be considered when heavy metal presented.     

Degradation of polycyclic aromatic hydrocarbons (PAHs) in contaminated soils by Fenton's reagent: a multivariate evaluation of the importance of soil characteristics and PAH properties

In this study, we investigated how the chemical degradability of polycyclic aromatic hydrocarbons (PAHs) in aged soil samples from various contaminated sites is influenced by soil characteristics and by PAH physico-chemical properties. The results were evaluated using the multivariate statistical tool, partial least squares projections to latent structures (PLS). The PAH-contaminated soil samples were characterised (by pH, conductivity, organic matter content, oxide content, particle size, specific surface area, and the time elapsed since the contamination events, i.e. age), and subjected to relatively mild, slurry-phase Fenton's reaction conditions. In general, low molecular weight PAHs were degraded to a greater extent than large, highly hydrophobic variants. Anthracene, benzo(a)pyrene, and pyrene were more susceptible to degradation than other, structurally similar, PAHs; an effect attributed to the known susceptibility of these compounds to reactions with hydroxyl radicals. The presence of organic matter and the specific surface area of the soil were clearly negatively correlated with the degradation of bi- and tri-cyclic PAHs, whereas the amount of degraded organic matter correlated positively with the degradation of PAHs with five or six fused rings. This was explained by enhanced availability of the larger PAHs, which were released from the organic matter as it degraded. Our study shows that sorption of PAHs is influenced by a combination of soil characteristics and physico-chemical properties of individual PAHs. Multivariate statistical tools have great potential for assessing the relative importance of these parameters.     

模拟酸雨对土壤中Zn的释放与缓冲作用研究

研究了模拟酸雨淋溶过程中南方主要土壤锌释放量与缓冲机理。结果表明,土壤中存在两个缓冲体系,pH值高于3.0时,土壤以初级缓冲体系为主;pH值低于3.0,尤其是离子淋溶量高于或接近CEC值后,次级缓冲体系成为主要的质子缓冲源。淋溶液pH值的降低可加速Zn的释放,从而促进土壤中Zn的淋溶,但Zn的淋溶同时受到吸附、沉淀与转化过程及土壤初始条件的影响。     

Effect of thermal cycling on the damping behavior in alumina borate whisker with and without Bi2O3 coating reinforced pure aluminum composites

Alumina borate whiskers with and without Bi₂O₃ coatings reinforced pure aluminum composites were fabricated by squeeze casting. The damping behavior of the composites was described. Samples had undergone thermal cycling during the damping measurement. For the Al₁₈B₄O₃₃w/Al composite, two damping peaks are present either in the heating or in the cooling process. For the Al₁₈B₄O₃₃w/Al composite with whisker coatings, there are also two damping peaks in the heating process, but there are three damping peaks in the cooling process. The research results indicate that a distinct difference presents in the damping-temperature curves for the Al₁₈B₄O₃₃w/Al composite with and without whisker coatings. The damping behavior and damping mechanism in the composites during thermal cycling are explained through dislocation motion, interfacial and grain boundary slip.     

Study on solid phase extraction and graphite furnace atomic absorption spectrometry for the determination of nickel, silver, cobalt, copper, cadmium and lead with MCI GEL CHP 20Y as sorbent

A solid phase extraction and graphite furnace atomic absorption spectrometry (GFAAS) for the determination of nickel, silver, cobalt, copper, cadmium and lead with MCI GEL CHP 20Y as sorbent was studied. Trace amounts of chromium, nickel, silver, cobalt, copper, cadmium and lead were reacted with 2-(2-quinolinil-azo)-4-methyl-1,3-dihydroxidobenzene (QAMDHB) followed by adsorption onto MCI GEL CHP 20Y solid phase extraction column, and 1.0molL(-1) HNO(3) was used as eluent. The metal ions in 300mL solution can be concentrated to 1.0mL, representing an enrichment factor of 300 was achieved. The recoveries of analytes at pH 8.0 with 1.0g of resin were greater than 95% without interference from alkaline, earth alkaline and some metal ions. When detected with graphite furnace atomic absorption spectrometry, the detection limits in the original samples were 1.4ngL(-1) for Cr(III), 1.0ngL(-1) for Ni(II), 0.85ngL(-1) for Ag(I), 1.2ngL(-1) for Co(II), 1.0ngL(-1) for Cu(II), 1.2ngL(-1) for Cd(II) and 1.3ngL(-1) for Pb(II). The validation of the procedure was performed by the analysis of the certified standard reference materials, and the presented procedure was applied to the determination of analytes in biological, water and soil samples with good results (recoveries range from 89 to 104%, and R.S.D.% lower than 3.2%. The results agreed with the standard value or reference method).     

Effects of inoculation of biosurfactant-producing Bacillus sp. J119 on plant growth and cadmium uptake in a cadmium-amended soil

A biosurfactant-producing Bacillus sp. J119 isolated from heavy metal contaminated soils was investigated for its effects on the plant growth-promoting characteristics and heavy metal and antibiotic resistance. A pot experiment was conducted for investigating the capability of the biosurfactant-producing bacterial strain Bacillus sp. J119 to promote the plant growth and cadmium uptake of rape, maize, sudangrass and tomato in soil artificially contaminated with different levels of cadmium (Cd) (0 and 50 mg kg⁻¹). The strain was found to exhibit different multiple heavy metal (Pb, Cd, Cu, Ni and Zn) and antibiotic (kanamycin, streptomycin, ampicillin, tetracycline and rifampin) resistance characteristics. The strain had the capacity to produce indole acetic acid (IAA) and siderophores. Cd treatment did not significantly decreased growth of tomato, maize and rape plants, but Cd treatment significantly decreased growth of sudangrass (p < 0.05). In the Cd-added soil, above-ground biomass and root dry weights of tomatoes were increased by 24 and 59%, respectively, in live bacterial inoculation compared to dead bacterial inoculation control. There were no obvious differences in the above-ground tissue and root dry weight of maize and sudangrass between live bacterial inoculation and dead bacterial inoculation. In the soil treated with 50 mg Cd kg⁻¹, increase in above-ground tissue Cd content varied from 39 to 70% in live bacterium-inoculated plants compared to dead bacterium-inoculated control. In addition, among the inoculated plants, tomato was the greatest Cd accumulator. The bacterial strain was also able to colonize and develop in the rhizosphere soils after root inoculation.     

A simple methodology to evaluate influence of H2O2 and Fe(2+) concentrations on the mineralization and biodegradability of organic compounds in water and soil contaminated with crude petroleum

Simple measurements of H2O2 concentration or CO2 evolution were used to evaluate the effectiveness of the use of Fenton's reagent to mineralize organic compounds in water and soil contaminated by crude petroleum. This methodology is suitable for application in small treatment and remediation facilities. Reagent concentrations of H2O2 and Fe(2+) were found to influence the reaction time and temperature, as well as the degree of mineralization and biodegradability of the sample contaminants. Some H2O2/Fe(2+) combinations (H2O2 greater than 10% and Fe(2+) greater than 50mM) resulted in a strong exothermic reaction, which causes peroxide degradation and violent gas liberation. Up to 75% TOC removal efficiency was attained in water and 70% in soil when high H2O2 (20%) and low Fe(2+) (1mM) concentrations were used. Besides increasing the degree of mineralization, the Fenton's reaction enhances the biodegradability of petroleum compounds (BOD5/COD ratios) by a factor of up to 3.8 for contaminated samples of both water and soil. Our experiments showed that low reagent concentrations (1% H2O2 and 1mM Fe(2+)) were sufficient to start the degradation process, which could be continued using microorganisms. This leads to a decrease in reagent costs in the treatment of petroleum-contaminated water and soil samples. The simple measurements of H2O2 concentration or CO2 evolution were effective to evaluate the Fenton's reaction efficiency.     

Structural and optical properties of ZnO films grown on silicon and their applications in MOS devices in conjunction with ZrO<Subscript>2</Subscript> as a gate dielectric

Photoluminescence (PL) properties of undoped ZnO thin films grown by rf magnetron sputtering on silicon substrates have been investigated. ZnO/Si substrates are characterized by Rutherford backscattering (RBS), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). ZrO₂ thin films have been deposited on ZnO using microwave plasma enhanced chemical vapour deposition at a low temperature (150°C). Using metal insulator semiconductor (MIS) capacitor structures, the reliability and the leakage current characteristics of ZrO₂ films have been studied both at room and high temperatures. Schottky conduction mechanism is found to dominate the current conduction at a high temperature. Good electrical and reliability properties suggest the suitability of deposited ZrO₂ thin films as an alternative as gate dielectric on ZnO/n-Si heterostructure for future device applications.     

A new features on S-waves propagation in a nonhomogeneous anisotropic incompressible medium under influence of gravity field and initial stress with and without electromagnetic field and rotation

The present article is concerned with the investigation of the propagation of shear waves in a nonhomogeneous anisotropic incompressible medium under the effect of the electromagnetic field, gravity field, rotation, and initial stress taking into account a comparison between presence and absence of magnetic field, initial stress, and rotation. Analytical analysis reveals that the velocity of propagation of the shear waves depends upon the direction of propagation, the anisotropy, magnetic field, rotation, gravity field, nonhomogeneity of the medium, and the initial stress. The frequency equation that determines the velocity of the shear waves has been obtained. Some special cases are also deduced from the present investigation. In fact, these equations are an agreement with the corresponding classical results when the medium is isotropic. Numerical results have been given and illustrated graphically in each case considered. The results indicate that the effects of gravity field, initial stress, magnetic field, electric field, anisotropy, and rotation are very pronounced. Also, the absence of initial stress, magnetic field, and rotation tends to increasing of the S-waves velocity compared with presence of them.