A statistic comparison of multi-element analysis of low atmospheric fine particles (PM2.5) using different spectroscopy techniques

Over the past few decades, the metal elements (MEs) in atmospheric particles have aroused great attention. Some well-established techniques have been used to measure particle-bound MEs. However, each method has its own advantages and disadvantages in terms of complexity, accuracy, and specific elements of interest. In this study, the performances of inductively coupled plasma–optical emission spectrometry (ICP-OES) and total reflection X-ray fluorescence spectroscopy (TXRF) were evaluated for quality control to analyze data accuracy and precision. The statistic methods (Deming regression and significance testing) were applied for intercomparison between ICP-OES and TXRF measurements for same low-loading PM_2.5 samples in Weizhou Island. The results from the replicate analysis of standard filters (SRM 2783) and field filters samples indicated that 10 MEs (K, Ca, V, Cr, Mn, Fe, Ni, Cu, Zn, and Pb) showed good accuracies and precision for both techniques. The higher accuracy tended to the higher precision in the MEs analysis process. In addition, the interlab comparisons illustrated that V and Mn all had good agreements between ICP-OES and TXRF. The measurements of K, Cu and Zn were more reliable by TXRF analysis for low-loading PM_2.5. ICP-OES was more accurate for the determinations for Ca, Cr, Ni and Pb, owing to the overlapping spectral lines and low sensitivity during TXRF analysis. The measurements of Fe, influenced by low-loading PM_2.5, were not able to determine which instrument could obtain more reliable results. These conclusions could provide reference information to choose suitable instrument for the determination of MEs in low-loading PM_2.5 samples.     

Size distribution and source of heavy metals in particulate matter on the lead and zinc smelting affected area

In order to understand the size distribution and the main kind of heavy metals in particulate matter on the lead and zinc smelting affected area, particulate matter(PM) and the source samples were collected in Zhuzhou, Hunan Province from December 2011 to January 2012 and the results were discussed and interpreted. Atmospheric particles were collected with different sizes by a cascade impactor. The concentrations of heavy metals in atmospheric particles of different sizes, collected from the air and from factories, were measured using an inductively coupled plasma mass spectrometry(ICP-MS). The results indicated that the average concentration of PM, chromium(Cr), arsenic(As), cadmium(Cd) and lead(Pb) in PM was177.3 ± 33.2 μg/m~3, 37.3 ± 8.8 ng/m~3, 17.3 ± 8.1 ng/m~3, 4.8 ± 3.1 ng/m~3 and 141.6 ± 49.1 ng/m~3,respectively. The size distribution of PM displayed a bimodal distribution; the maximum PM size distribution was at 1.1–2.1 μm, followed by 9–10 μm. The size distribution of As, Cd and Pb in PM was similar to the distribution of the PM mass, with peaks observed at the range of1.1–2.1 μm and 9–10 μm ranges while for Cr, only a single-mode at 4.7–5.8 μm was observed. PM(64.7%), As(72.5%), Cd(72.2%) and Pb(75.8%) were associated with the fine mode below 2.1 μm,respectively, while Cr(46.6%) was associated with the coarse mode. The size distribution characteristics, enrichment factor, correlation coefficient values, source information and the analysis of source samples showed that As, Cd and Pb in PM were the typical heavy metal in lead and zinc smelting affected areas, which originated mainly from lead and zinc smelting sources.