[Characteristics of Heavy Metals and Other Elements in Atmospheric Dry and Wet Deposition and Health Risk Assessment of a Typical Industrial and Mining City in Central Yunnan].

In order to study the characteristics of atmospheric dry and wet deposition elements and the health risks of typical industrial and mining cities in central Yunnan, the atmospheric dry and wet depositions collected from June 2019 to July 2020 in Anning city were selected as the research object and measured. The contents of the 11 indexes TN, F, Cr, Ni, Cu, Zn, Cd, Pb, P, As, and Hg were determined, the annual atmospheric deposition flux was calculated, and the exposure risk model was used to assess the risk to human health. The results showed that:1 In addition to Cr, Ni, and As in the atmospheric dry sediments, the average contents of the elements F, Cu, Zn, Cd, Pb, and Hg were significantly higher than those of the surface soil in Anning City, which were 5.82, 3.00, 28.27, 57.53, 2.83, and 1.08 times higher, respectively. The average contents of F and total nitrogen in wet deposition exceeded the standard value of surface water V-class water. 2 The annual atmospheric deposition flux of total nitrogen was the highest, and the annual deposition flux of eight heavy metal elements from smallest to largest was Hg

Water quality characteristics, sources, and assessment of surface water in an industrial mining city, southwest of China.

This study analyzed the physiochemical factors, spatial-seasonal variations, and correlations of main pollutants, water quality evaluation and possible sources of nitrogen in the surface water of Anning, an industrial mining city, southwest of China. Seventy surface water samples were examined through an analysis of 41 physiochemical indices in the dry and wet seasons in April and July 2019, respectively, while a part of water site samples collected in July 2020 was taken for isotope detections. To identify the water quality, single-factor pollution index (SI), Nemerow pollution index (NPI), and water quality comprehensive pollution index (CPI) were calculated based on 13 pollutants using GB 3838-2002 class III water standard values. Results pointed to typical pollutants of TN, TP, and F with ranges of l.d.-44.8 (2.00 ± 3.69) mg/L, l.d.-250 (2.07 ± 15.35) mg/L, and l.d.-11 (1.48 ± 7.34) mg/L respectively with high spatial variability. The concentrations of heavy metals present in the water samples followed the sequence: Zn > Ni > Cu > As > Pb > Cd > Hg, and most of the samples showed low values relative to the standard permissible limits. In three methods, the water quality evaluation results of SI method were obviously worse than NPI and CPI methods. The NPI and CPI values had ranges of 0.116-887.40 (8.12 ± 74.89) and 0.03-111.54 (1.17 ± 9.40), respectively; consequently, the water quality was considered generally well, with more than 65% of sites classified as "cleanness" or "sub-cleanness." Most of the values of δ15N and δ18O had ranges of 6.62-20.05‰ and - 6.53-4.70‰, which suggested the livestock manure resources were the possible sources of nitrogen that entered the surface water causing more pollution in the wet season. Part of sites with serious water pollution had very high concentrations of P, F, or heavy metals and might be closely correlated with the point source pollution of phosphate chemical industry or iron ore mining and smelting. The results of this study can provide the basic data for efficient water management and human health protection for local government.

Solution Cathode Glow Discharge Based on Charge Coupled Device Detector.

In 21st century, many countries pay much attention to lithium because lithium is an ideal material for green energy and light alloys as well as an important kind of strategic resources. The main source of lithium is from salt lake brine. China has rich resources of salt lake brine, but these brine resources are mainly distributed in the remote western region, which are in urgent need of portable analytical instrument for on-site exploration and exploitation. However, the available experimental techniques at present can not achieve the target of on-site analysis. Over the past decade, based on atmospheric pressure solution cathode glow discharge-atomic emission spectrometry (SCGD-AES) has been paid attention to analytical researchers because it runs without common air conditions such as fuel gas, carrier gas and vacuum environment. On the basis of previous studies of other researchers, we have developed a portable SCGD based on a charge coupled device (CCD) detector by ourselves, which is short for Li-K analyzer. The length, width, height and weight of the portable Li-K analyzer is 35 cm, 19 cm, 27 cm and 10 kg, respectively, which is very conducive to carry. This work selected the wavelength of 670.78 nm as the characteristic spectral line of Li and has established a rapid analytical method for Li in salt lake brine based on two different types of brines from Tibet. Under the optimum operating conditions, the detection limit of Li was 4 ng·mL-1 and the measured precision (RSD) was better than 2%. The analytical results of Li were much different from those obtained by inductively coupled plasma-mass spectrometry (ICP-MS) with different dilution ratios by standard curve method, which may be related to the matrix effect of solution. However, the analytical results of Li agreed well with the results obtained by ICP-MS using standard addition method, which showed that standard addition method can effectively reduce the matrix effect and improve the analytical accuracies. A great deal of experimental results showed that standard addition method could obtain accurate results of Li using only two points and can greatly reduce the workloads. This work laid a methodological foundation for on-site determination of Li in salt lake brine by the portable Li-K analyzer.

[On-Site Analysis of Heavy Metals in Water with Handheld X-Ray Fluorescence and Pre-Concentration Device without External Power Supply].

Currently, increasing importance has been attached to heavy metal pollution of water environment. In order to help geologist and environmentalist to obtain on-site experimental data, there is an urgent need to develop portable analysis techniques of water quality, which can be used to give an timely and accurate assessment of water quality of the contaminated area with low cost and to monitor water environment conveniently in daily preventing and controlling work of water pollution. Based on adsorption with Purolite S930 chelating resin at pH 4 and thin-film sample preparation technique, a rapid and simple on-site-oriented analysis method of heavy metal ions, namely Mn, Fe, Ni, Cu, Zn and Pb in aqueous solutions, was developed utilizing a handheld energy-dispersive X-ray fluorescence in this paper. The correlation coefficients of the calibration curves were greater than 0.992 for all six metal ions, the lower limits of detection were between 5.8 and 18.6 µg·L-1. Precision tests carried out on multi-element mixed solutions showed that the relative standard deviations (RSD, n=10) were better than 15%. The method has been used on-site to analysis 21 water samples collected from different river or well sites near a mining area northeast China. Out of the five underground water samples one was found contaminated by Cu and Zn (Class Ⅲ), one by Zn and Fe (Class Ⅱ), and one by Fe(in between Class Ⅱ to Ⅲ). Surface water samples showed better qualities. But two out of the sixteen were found to be contaminated by Mn heavily (Class Ⅳ). Laboratory ICPMS was used to analyze the same samples. The results for Cu, Ni and Pb were coincident with the on-site data in general. But for Zn and Mn with higher concentrations, on-site data were lower than that by ICPMS. The reason for that might be the inclusion of the fine suspending particles in the samples by ICPMS. We conclude that the on-site data were effective. With the described method, an overall data acquisition time, including sampling, processing and measuring, can be within 12 hours for a batch of 10 samples. The pre-concentration device and the XRF instrument are both small, light, portable and can operate without external power supply. So, the method is suitable for on-site water sample analysis, especially in remote areas.

[Characterization of matrix effects in microanalysis of sulfide minerals by laser ablation-inductively coupled plasma-mass spectrometry based on an element pair method].

Matrix effect between reference materials and samples is one of the major factors affecting the accuracy of analytical results by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). However, there is no method or calculation formula to quantify matrix effect between standards and samples up to date. In this paper, the linear correlation coefficient r of the Ii/I(is-Ci)/Cis graphs of element pairs were used to characterize the matrix effect, which took the ratios of concentrations (ci/ c(is)) and intensities (Ii/Iis) of the analytical element and internal standard element as x-axis and gamma-axis, respectively. Matrix effects of 6 element pairs in 13 glass reference materials, 2 sulfide reference materials and 2 sulfide minerals using Fe as internal standard was studied, with the linear correlation coefficient r of Fe-Cu, Fe-Zn element pairs both less than 0. 999 and trace Fe--Mn, Fe--Co, Fe--Ga, Fe--Pb element pairs all better than 0.999. Matrix effects of 3 major element pairs in 2 sulfide ref- erence materials and 6 sulfide minerals using S as internal standard was also studied, with the linear correlation coefficient r of S--Fe, S--Cu, S--Zn all less than 0.999. The great majority of relative errors of EMPA analytical results for major elements in sulfide minerals were greater than 10%, whether analyzed using Fe as internal standard with glass reference materials as external standard, or S as internal standard with sulfide reference materials MASS-1, IMER-1 as external standard, respectively. But the most analytical results for trace elements calibrated by glass reference materials using Fe as internal standard were well agreed with sulfide standard MASS-1, with the relative errors less than 15%. The results showed that matrix effects existed in glass reference materials, sulfide reference materials and sulfide minerals, and it also proved a certain rationality and practicability for quantification of matrix effect using the linear correlation coefficient r of the Ii/Iis-Ci/Cis graphs by this element pair method. This study also indicated that trace elements in sulfide minerals could be calibrated using Fe as internal standard with non-matrix matched glass reference materials as external standard, especially for NIST610 contained nearly all the trace elements in sulfide minerals and with relative high concentrations of each element, which obtained analytical results agreed well with sulfide standard MASS-1.

[The evaluation of uncertainty in the results for elements rubidium, strontium, yttrium and zirconium in silicate geological samples by polarized energy dispersive X-ray fluorescence spectrometry].

A method for evaluation of uncertainty was established with standard deviation of relative error. Utilizing a polarized energy dispersive X ray fluorescence spectrometer (P-EDXRF)X-lab 2000 with pressed polyethylene-backed pellets, 76 national reference materials and 89 geological examination samples were analyzed, the results indicated that the relative errors consist with the normal distribution with confidence level 95%. The section standard deviations of relative errors acted as method global relative uncertainty and expanded factor was 2. The section relative uncertainty caused by precision was analyzed and relative uncertainty caused by accuracy based on the error transfer formula was isolated. The ratio of relative uncertainty caused by accuracy to the global relative uncertainty was different with different levels and elements. Two methods validated that the evaluation of global uncertainty is reasonable, with the first method being the formula of audited results in laboratory, and the second being the comparison of standard value with expanded uncertainty and a revised value with expanded uncertainty.