RESUMO
Field rapid determination of soil accessible Cr(â ¥) is of great significance for on-site assessment and decision-making about the health risks of contaminated sites. When the thickness of solutions with various concentrations of Cr(â ¥) is constant, there would be a quantitative relationship between the chromogenic difference of Cr(â ¥) solutions and the concentration of Cr(â ¥). The chromogenic difference could be described by Red (R), Green (G), Blue (B) values. Based on the chromogenic reaction between 1,5-diphenylcarbazide and Cr(â ¥), this study first established the calibration curve between the chromogenic difference and the concentration of Cr(â ¥) in standard solution with or without 0.01â¯M CaCl2, using an RGB color sensor. This is the subsequent determination basis of the method for rapidly assessing accessible Cr(â ¥) in the field (M-RGB). Then, the concentration of accessible Cr(â ¥) of contaminated soil with "hand-shaking + standing" field extraction method was compared with "end-over-end shaking" laboratory extraction method. Finally, the accessible Cr(â ¥) of contaminated soil extractants was determined via M-RGB integrating the field extraction method. Results indicated there was a highly significant linear relationship between colorimetric difference value (∆E) and Cr(â ¥) concentration in the range of 0.1-3â¯mg/L (R2 > 0.99, P < 0.01), based on the Euclidean formula for calculating ∆E. The "hand-shaking + standing" field extraction method was effective in obtaining accessible Cr(â ¥) extractants with or without 0.01â¯M CaCl2, with the high extraction efficiency within 100±1%. The concentrations of accessible Cr(â ¥) in various polluted soils determined by M-RGB were consistent with that determined by the ultraviolet-visible spectrophotometry, with the relative error within ±5%, and the relative standard deviation ≤ 20%. The spiked recovery experiments showed that the recovery of M-RGB was between 95% and 105%, which means M-RGB could realize the trace analysis for accessible Cr(â ¥) in the field.
Assuntos
Cromo , Solo , Cloreto de Cálcio , Cromo/análise , Poluição Ambiental/análiseRESUMO
Field rapid determination of soil accessible Cu(â ¡) was important for environmental safety and human health risk assessment. In this study, an inexpensive red, green, and blue (RGB) color sensor was used for quantitative color difference analysis of the colored solution for soil accessible Cu(â ¡) with bis-cyclohexanone oxalydihydrazone as color reagent to develop a new method for analyzing soil accessible under field conditions. First, the calibration curve for RGB color sensor method was established in the standard solutions of Cu(II). Then the "hand shaking + standing" field extraction method for accessible Cu(â ¡) was developed. Finally, the method was applied in contaminated soils in the laboratory and in the field, and set the values determined by atomic absorption spectroscopy (AAS) as the standard ones. Results indicated that in the range of 0.1-5 mg L-1 Cu(II), the RGB Euclidean chromogenic difference values were directly linear correlated with the concentration of Cu(II) (R2 > 0.999). The interference of Fe(â ¢) and Mn(â ¡) could be eliminated by adding citric acid. The "hand shaking + standing" field extraction method could effectively extract the accessible Cu(â ¡) from soil with the high extraction rates. The concentrations of accessible Cu(II) in various polluted soils determined by RGB color sensor method were consistent with that determined by AAS, with the relative error within ±5%, the relative standard deviation ≤ 20%. The recovery of Cu(II) in RGB color sensor method was between 97% and 105%, which could meet the requirements of trace analysis of accessible Cu(â ¡) in the field. The high accuracy and precision of RGB color sensor method was reconfirmed in the rapid field quantitative assessment of soil accessible Cu(â ¡). Due to that the RGB color sensor was low cost, rechargeable, portable, mobile, ambient light resistant, the method would have a great potential for the determination of accessible Cu(â ¡) in contaminated soils.
Assuntos
Compostos Férricos , Solo , Humanos , Solo/química , Espectrofotometria AtômicaRESUMO
Diffusive gradients in thin films technique (DGT) is recognized as a more reliable method for determining labile heavy metal (HM) concentration in soil than traditional destructive methods. However, the current DGT measurement index, CDGT, theoretically underestimates the true labile concentration (Clabile) of HMs in soil and lacks direct comparability with the conventional soil HM content indices due to unit differences. Here, we proposed CDGT-W, a new simple index which is defined as the HM accumulation in the binding layer, normalized to the weight of soil (optimized water content = 100% of the maximum water holding capacity) filled in the open cavity-type DGT device over a specified deployment time (optimized time = 24 h). The procedure for measuring CDGT-W is analogous to that of CDGT but includes precise determination of water content (water/dry soil) and the mass of soil filled in the cavity. We conducted measurements of Cu, Pb, Cr(â ¥) and As(V) as CDGT-W, CDGT, solution concentration (Csoln), and CaCl2 extractable concentration (CCaCl2) on three soils with a diverse range of HM concentrations. CDGT-W showed significant linear correlations with all other tested indexes. The ratios of CDGT-W to CCaCl2 varied between 0.30 and 0.98 for all HM-soil combinations with only one exception, a range much greater than CDGT/Csoln (typically <0.1) but lower than 1. This suggested that CDGT-W may more accurately reflect Clabile than CDGT (theoretically underestimates Cliable) and CCaCl2(likely overestimates Cliable). Additionally, CDGT-W measurements for these four HMs exhibited a broad measure concentration range and a low detection limit (mg/kg level). Consequently, CDGT-W may offer a more reliable alternative to CDGT for characterizing Clabile in unsaturated soils.
Assuntos
Monitoramento Ambiental , Metais Pesados , Poluentes do Solo , Solo , Poluentes do Solo/análise , Metais Pesados/análise , Solo/química , Monitoramento Ambiental/métodos , DifusãoRESUMO
The rapid increase in soil acidity coupled with the deleterious effects of cadmium (Cd) toxicity had led to a decline in worldwide agricultural production. Rice absorbs and accumulates Cd(II) from polluted paddy soils, increasing human health risks throughout the food chain. A 35-day hydroponic experiment with four japonica and four indica (two each of them tolerant and sensitive cultivars) was conducted in this study to investigate the adsorption and absorption of Cd(II) by rice roots as related with surface chemical properties of the roots. The results showed that the three chemical forms of exchangeable, complexed, and precipitated Cd(II) increased with the increase in Cd(II) concentration for all rice cultivars. The roots of indica rice cultivars carried more negative charges and had greater functional groups and thus adsorbed more exchangeable and complexed Cd(II) than those of japonica rice cultivars. This led to more absorption of Cd(II) by the roots and greater toxicity of Cd(II) to the roots of indica rice cultivars and more inhibition of Cd(II) stress on the growth of the roots and whole plants of indica rice cultivars compared with japonica rice cultivars, which was one of the main reasons for more declines in the biomass and length of indica rice roots and shoots than japonica rice cultivars. Cd(II) stress showed more toxicity to the sensitive rice cultivars and thus greater inhibition on the growth of the cultivars due to more exchangeable and complexed Cd(II) adsorbed by their roots induced by more negative charges and functional groups on the roots compared with tolerant rice cultivar for both indica and japonica, which resulted in greater decreases in the biomass and length of roots and shoots as well as chlorophyll contents of the sensitive cultivars than the tolerant cultivars. The roots of sensitive rice cultivars also absorbed more Cd(II) than tolerant rice cultivars due to the same reasons as above. These findings will provide useful references for the safe utilization and health risk prevention of Cd-contaminated paddy fields.
Assuntos
Cádmio , Oryza , Raízes de Plantas , Poluentes do Solo , Oryza/metabolismo , Cádmio/metabolismo , Cádmio/toxicidade , Raízes de Plantas/metabolismo , Poluentes do Solo/metabolismo , Poluentes do Solo/toxicidade , Adsorção , Solo/químicaRESUMO
Lead (Pb) is one of the top metal pollutants worldwide, and its distribution between liquid and solid phases of soils is strongly controlled by its adsorption on minerals, organic matter, and their composites. This paper presented the effect of fulvic acid (FA) coexistence on the distribution of Pb(II) at the solid-liquid interface of four minerals, which provided reference for how to use humic substances to remove toxic Pb(II) in soils. The free Pb2+ of suspensions, measured by Pb ion selective electrode, was used to characterize the complexation of FA with Pb2+ at various pH. The adsorption isotherms of Pb(II) by montmorillonite, kaolinite, goethite, and gibbsite with and without FA were studied with batch experiments. Results indicated that the free Pb2+ decreased and complexed Pb(II) increased with the increase of FA concentration in Pb(II)-FA solutions, whether the initial concentration of Pb(II) was 0.1 or 1 mM. Pb2+ hydrolysis was low and the free Pb2+ concentration in pure lead solution without FA was generally unchanged with increasing solution pH at pH < 6.0. But free Pb2+ decreased with the increase of pH in the presence of FA, suggesting that the complexation ability of FA with Pb2+ increased with the increase of solution pH. The adsorption of Pb(II) by the minerals without FA followed the order: montmorillonite > kaolinite ≈ goethite > gibbsite at pH5.0. The Pb(II) adsorption by montmorillonite and kaolinite significantly enhanced with 1 g/L FA, while significantly inhibited with 3 g/L FA at low initial Pb(II) concentration. However, the effect of FA on Pb(II) adsorption by montmorillonite was greater than that of kaolinite, which was mainly related to the crystal layer structure, adsorption area, and cation exchange capacity of the minerals. The Pb(II) adsorption by goethite and gibbsite was significantly enhanced by the addition of both 1 g/L and 3 g/L FA, and the enhancement was more evident in goethite system. The effect of FA on the distribution of Pb(II) between solid and liquid phases of the minerals was determined by the factors such as the initial concentration ratio of FA to Pb(II), the adsorption capacity of minerals for FA, and the number of soluble complexes of FA with Pb2+. Therefore, the distribution of FA between solid and liquid of four minerals affected the distribution of Pb(II) between solid and liquid phases of the minerals greatly. The results can provide an important reference for understanding the distribution of Pb(II) and the dynamics and mobility of active components in polluted soils.