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The objective of this study is to investigate the extent and degree of heavy metal contamination of paddy fields influenced by metalliferous mining activity. Paddy soils, rice plants and irrigation waters were sampled along six traverse lines in the vicinity of the mine and nearby control site. Soil samples were taken 30, 80 and 150 days after rice transplanting, to study seasonal variation of their chemical properties and heavy metal concentrations. Sampling of rice plants and irrigation waters was also undertaken with seasons. The analysis of the samples were carried out using ICP-AES for 25 elements including Cd, Cu, Pb and Zn. Physical and chemical properties of soils (pH, loss-on-ignition, cation exchange capacity and texture) and waters (pH, Eh and temperature) were also measured. The properties of soils were similar to the average Korean soils, with the exception of some samples taken in the vicinity of the mine. Concentrations of Cd, Cu, Pb and Zn in paddy soils, rice plants and irrigation waters sampled in the immediate vicinity of the mine were relatively high due to the seepage of metals from mining dump sites. Although there was variation between sampling sites, soil pH values under reducing conditions were on average higher than those under oxidising conditions. Relatively low content of organic matter and low cation exchange capacity of soils were found at 80 days after rice transplanting (P < 0.05). No seasonal variations in metal concentrations were found in paddy soils throughout the period of the rice growing, in which soils ranged from flooded reducing conditions through most of the growing season to drained oxidising conditions before and at harvest. Relatively high metal concentrations were found in the rice stalks and leaves under oxidising conditions. The sequential extraction analysis of selected soil samples confirmed that high proportions of exchangeable fractions of the metals were found under oxidising conditions. It was shown that Cd and Zn concentrations in rice leaves and stalks and rice grain increased with increasing metal concentrations in paddy soils to a greater extent than for Cu and Pb. This difference in uptake is in agreement with the greater proportions of Cd and Zn, compared with Cu and Pb, in the exchangeable soil fraction extracted with MgCl2. Average daily intake from locally grown rice by the residents was estimated to be 121 micrograms Cd and 126 micrograms Pb. Thus, long-term metal exposure by regular consumption of the rice poses potential health problems to residents in the vicinity of the mine, although no adverse health effects have as yet been observed.
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PMID:Environmental contamination and seasonal variation of metals in soils, plants and waters in the paddy fields around a Pb-Zn mine in Korea. 916 64

A combined method of electrothermal vaporization and low-pressure helium ICP-MS was developed for the determination of traces of arsenic in chloride solutions, because serious spectral interference occurred in conventional argon ICP-MS. On a tungsten filament was placed 5 microl of a sample and heated electrothermally to remove the solvent. The resulting residue on the filament was covered with a vaporization chamber, and after reducing the pressure to ca. 5 Torr, it was rapidly heated by discharging a high-capacity condenser (0.22 F). The vapor of arsenic was transferred to a helium plasma with a stream of carrier gas for the determination. The background was not observed at m/z of 75, which allowed the determination of arsenic at ng/ml levels in chloride solutions. Sodium chloride significantly enhanced the intensity of the arsenic signal, whereas other chlorides, including KCl, MgCl2, CaCl2 and NH4Cl, suppressed the analytical signals. This enhancement due to sodium ions seems to be a peculiar phenomenon to the helium ICP. The proposed method can be applied to direct determinations of as low as 0.9 ng/ml of arsenic in seawater.
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PMID:Electrothermal vaporization on a tungsten filament for the determination of arsenic in chloride solutions by low-pressure helium ICP-MS. 1199 58

Three treatment media, used for the removal of arsenic from drinking water, were sequentially extracted using 10 mM MgCl2(pH 8), 10 mM NaH2PO4(pH 7) followed by 10 mM (NH4)2C2O4(pH 3). The media were extracted using an on-line automated continuous extraction system which allowed the arsenic in each of the extraction fluids to be speciated on-line using IC-ICP-MS. The 10 mM MgCl2 preferentially extracted As(III) from each of the media. The percentage of the arsenic extracted by the MgCl2, relative to a HNO3/H2O2 digestion of the media, ranged from 0.1-2.3% for the three solids. The next sequential extraction fluid, 10 mM NaH2PO4, extracted some of the residual As(III) remaining on each of the media but the predominant species extracted was As(V). The 10 mM NaH2PO4 extracted 15.3 to 42.8% of the total arsenic relative to a total digested concentration for each of the media. The As(III) and As(V) stability studies conducted in these two extraction fluids indicated that conversion between As(III) and As(V) was not significant for the short extraction fluid sample contact time associated with the on-line continuous flow extraction cell. Finally, the 10 mM (NH4)2C2O4 extraction fluid was utilized in an off-line analysis mode because the Fe and As concentrations extracted from the media were not compatible with direct ICP-MS detection. The (NH4)2C2O4 extracted 2.9-29% As(III) for all three media and caused an oxidation of As(III) to As(V) during the extraction period for one of the three media. The sum of the arsenic from each of the three extraction fluids represented 92%, 44% and 53% of the available total arsenic for the three media, respectively. The speciation results for each media were obtained by adding all the speciation results from all three extraction fluids together and the resulting distribution of As(III)/As(V) compared well with the speciation results obtained via XANES.
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PMID:Investigation of arsenic speciation on drinking water treatment media utilizing automated sequential continuous flow extraction with IC-ICP-MS detection. 1625 57

To realize the simultaneous removal and recovery of phosphate and partial nitrogen from stale human urine, a series of lab-scale jar tests, adopting MgCl2 x 6H2O as precipitant, were conducted to study the influence of the molar ratio of Mg/PO4(3-)-P, pH, mixing speed, reaction time and precipitation time on MAP precipitation. The experiment results showed that the molar ratio of Mg/PO4(3-)-P was found to be a very important operating parameter to affect phosphorus recovery efficiency. When the molar ratio of Mg/PO4(3-)-P was above 1.3:1, the phosphorus recovery efficiency was above 95% and the residual phosphorous was less than 10 mg/L in the solution. Increasing pH with 10 mol/L NaOH solution could not increase the recovery phosphorus efficiency obviously. Without pH control, the optimal parameters of reaction time, precipitation time and mixing speed could be set at 20 min, 2.0 h and 120 r/min, respectively. To reveal the chemical characteristics of MAP products from human urine, three MAP product samples, with no pH adjustment and under the above optimal operation condition, were obtained at different Mg/PO4(3-)-P molar ratios of 1:1, 1.3:1 and 1.5:1, respectively, and analyzed with SEM, XRD and ICP instrumentation. These precipitates were identified as nearly pure struvite (12.62% of P, 5.71% of N and 9.91% of Mg) with the presence of trace calcium, potassium and sodium. The contents of phosphorus, nitrogen and magnesium in the precipitates were 13.54%, 5.34% and 9.01% (Mg/PO4(3-)-P = 1:1), 13.78%, 5.23% and 9.36% (Mg/PO4(3-)-P = 1.3:1), as well as 13.34%, 5.12% and 9.15% (Mg/PO4(3-)-P = 1.5:1), respectively.
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PMID:[Phosphorus removal and recovery from human urine with MAP crystallization]. 1826 83