Although previous investigations of the trace elements in snow and ice from the Qinghai-Tibetan Plateau obtained interesting information about pollution from human activities on the plateau, most were based on traditi...Although previous investigations of the trace elements in snow and ice from the Qinghai-Tibetan Plateau obtained interesting information about pollution from human activities on the plateau, most were based on traditional acidification methods.To emphasize the influence of the different sample-preparation methods on the records of trace elements and rare earth elements, snow samples were collected from glaciers on the Qinghai-Tibetan Plateau in China and prepared using two methods: traditional acidification and total digestion. Concentrations of 18 trace elements(Al, Ti, Fe, Rb, Sr, Ba, V, Cr, Mn, Li,Cu, Co, Mo, Cs, Sb, Pb, Tl, and U), along with 14 rare earth elements(REEs: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,Tm, Yb, and Lu), Y, and Th in the snow samples, were measured using inductively coupled plasma-sector field mass spectrometry(ICP-SFMS). The results showed that the mass fraction of the trace elements(defined as ratio of concentration in the acid-leachable fraction to that in the digested sample) such as Mo, Ti, Al, Rb, and V, varied from 0.06 to 0.5. The mass fraction of other trace elements varied from about 0.6 to more than 0.9; those of the REEs, Y, and Th varied from 0.34 to0.75. Lower mass fractions will lead to an overestimated contribution of other sources, especially human activities, and the underestimated fluxes of these trace elements(especially REEs, Y, and Th, as well as dust) if the REEs are used as the proxy for the crust dust. The two sample-preparation methods exhibited different REE normalized distribution patterns,REE ratios, and provenance-tracing results. The REE normalized distribution patterns and proxies in the digested samples are more reliable and integrated than those found in traditional acidification method for dust-provenance tracing.展开更多
Inductively coupled plasma mass spectrometry （ICP-MS） is the most commonly used technique to deter- mine the abundances of trace elements in a wide range of geological materials. However, incomplete sample digestion...Inductively coupled plasma mass spectrometry （ICP-MS） is the most commonly used technique to deter- mine the abundances of trace elements in a wide range of geological materials. However, incomplete sample digestion, isobaric interferences and instrumental drift remain obvious problems that must be overcome in order to obtain precise and accurate results, For this reason, we have done many experi- ments and developed a set of simple, cost-effective and practical methods widely applicable for precise and rapid determination of trace element abundances in geological materials using ICP-MS. Commonly used high-pressure digestion technique is indeed effective in decomposing refractory phases, but this inevitably produces fluoride complexes that create new problems. We demonstrate that the fluoride complexes formed during high-pressure digestion can be readily re-dissolved using high-pressure vessel at 190 ℃ for only 2 h for 50 mg sample. In the case of isobaric interferences, although oxide （e.g., MO^＋/M^＋） and hydroxide （e.g., MO^＋/M^＋） productivity is variable between runs, the （MO^＋/M^＋）/（CeO^＋/Ce^＋） and （MOH^＋/M^＋）/（CeO^＋/Ce^＋） ratios remain constant, making isobaric interference correction for all other elements of interest straightforward, for which we provide an easy-to-use off-line procedure. We also show that mass-time-intensity drift curve is smooth as recognized previously, for which the correction can be readily done by analyzing a quality-control （QC） solution and using off-line Excel VBA procedure without internal standards. With these methods, we can produce data in reasonable agreement with rec- ommended values of international rock reference standards with a relative error of 〈8% and precision generally better than 5%. Importantly, compared to the widely used analytical practice, we can effectively save 〉60% of time （e.g., 〈24 h vs. 〉60 h）.展开更多
基金supported by grants provided by the National Natural Science Foundation of China(Grant Nos.41276194,40771046,and 40601021)
文摘Although previous investigations of the trace elements in snow and ice from the Qinghai-Tibetan Plateau obtained interesting information about pollution from human activities on the plateau, most were based on traditional acidification methods.To emphasize the influence of the different sample-preparation methods on the records of trace elements and rare earth elements, snow samples were collected from glaciers on the Qinghai-Tibetan Plateau in China and prepared using two methods: traditional acidification and total digestion. Concentrations of 18 trace elements(Al, Ti, Fe, Rb, Sr, Ba, V, Cr, Mn, Li,Cu, Co, Mo, Cs, Sb, Pb, Tl, and U), along with 14 rare earth elements(REEs: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,Tm, Yb, and Lu), Y, and Th in the snow samples, were measured using inductively coupled plasma-sector field mass spectrometry(ICP-SFMS). The results showed that the mass fraction of the trace elements(defined as ratio of concentration in the acid-leachable fraction to that in the digested sample) such as Mo, Ti, Al, Rb, and V, varied from 0.06 to 0.5. The mass fraction of other trace elements varied from about 0.6 to more than 0.9; those of the REEs, Y, and Th varied from 0.34 to0.75. Lower mass fractions will lead to an overestimated contribution of other sources, especially human activities, and the underestimated fluxes of these trace elements(especially REEs, Y, and Th, as well as dust) if the REEs are used as the proxy for the crust dust. The two sample-preparation methods exhibited different REE normalized distribution patterns,REE ratios, and provenance-tracing results. The REE normalized distribution patterns and proxies in the digested samples are more reliable and integrated than those found in traditional acidification method for dust-provenance tracing.
基金supported by National Natural Science Foundation of China(41130314 and 41630968)Chinese Academy of Sciences Innovation Grant(Y42217101L)+1 种基金Qingdao National Laboratory for Marine Science and Technology(2015ASKJ03)Marine Geological Process and Environment(U1606401)
文摘Inductively coupled plasma mass spectrometry （ICP-MS） is the most commonly used technique to deter- mine the abundances of trace elements in a wide range of geological materials. However, incomplete sample digestion, isobaric interferences and instrumental drift remain obvious problems that must be overcome in order to obtain precise and accurate results, For this reason, we have done many experi- ments and developed a set of simple, cost-effective and practical methods widely applicable for precise and rapid determination of trace element abundances in geological materials using ICP-MS. Commonly used high-pressure digestion technique is indeed effective in decomposing refractory phases, but this inevitably produces fluoride complexes that create new problems. We demonstrate that the fluoride complexes formed during high-pressure digestion can be readily re-dissolved using high-pressure vessel at 190 ℃ for only 2 h for 50 mg sample. In the case of isobaric interferences, although oxide （e.g., MO^＋/M^＋） and hydroxide （e.g., MO^＋/M^＋） productivity is variable between runs, the （MO^＋/M^＋）/（CeO^＋/Ce^＋） and （MOH^＋/M^＋）/（CeO^＋/Ce^＋） ratios remain constant, making isobaric interference correction for all other elements of interest straightforward, for which we provide an easy-to-use off-line procedure. We also show that mass-time-intensity drift curve is smooth as recognized previously, for which the correction can be readily done by analyzing a quality-control （QC） solution and using off-line Excel VBA procedure without internal standards. With these methods, we can produce data in reasonable agreement with rec- ommended values of international rock reference standards with a relative error of 〈8% and precision generally better than 5%. Importantly, compared to the widely used analytical practice, we can effectively save 〉60% of time （e.g., 〈24 h vs. 〉60 h）.
