Abstract
The main sources of spectral interferences in atomic emission spectral analysis (AESA) are considered, including both wide-range (bremsstrahlung and recombination continuum, radiation of hot condensed particles and electrode ends, scattered light in the spectrometer, overlapping of the analytical line by the wings of the neighbor strong spectral lines of interfering elements, imposition of the components of molecular bands with the very close lines) and narrow-band (partial or complete overlapping of the analytical line with atomic or ionic lines of the sample elements, electrodes and discharge atmosphere; superposition of spectra from higher orders of reflection in conventional diffraction spectrometers and from neighboring orders in two-dimensional echelle spectrometers). The features of their manifestation in various sources of spectrum excitation (flames, DC arc, spark discharges, arc plasma discharges, inductively coupled plasma, microwave plasma, low-pressure electric discharges, laser spark) are considered. The possibilities of reducing the level of spectral interferences or elimination of the spectral noise at the stage of design and manufacturing of AESA devices, as well as upon selecting and adjusting of operation conditions of the analysis are shown. Much attention is paid to the most easily implemented in practice off-peak correction of wide-range spectral interferences. The modern methods of background correction under the spectral peak (under-peak) using a software for atomic emission spectrometers and providing creation of various mathematical models of the background signal in the vicinity of the analytical line at the stage of developing a specific AESA technique are considered. The issues of the choice of spectral lines for analytical measurements, tables and atlases of spectral lines, electronic databases used for this purpose are considered in detail. Specific features of application of the method of inter-element correction with direct spectral overlapping of the lines are given. The operating sequence for taking into account spectral interferences when developing the analysis techniques is proposed.
Highlights
Ðàññìîòðåíû îñíîâíûå èñòî÷íèêè ñïåêòðàëüíûõ ïîìåõ â àòîìíî-ýìèññèîííîì ñïåêòðàëüíîì àíàëèçå (ÀÝÑÀ): øèðîêîäèàïàçîííûõ è óçêîäèàïàçîííûõ (÷àñòè÷íîå èëè ïîëíîå ïåðåêðûâàíèå àíàëèòè÷åñêîé ëèíèè àòîìíûìè èëè èîííûìè ëèíèÿìè ýëåìåíòîâ ïðîáû, ýëåêòðîäîâ è àòìîñôåðû ðàçðÿäà; íàëîæåíèå ñïåêòðîâ âûñøèõ ïîðÿäêîâ îòðàæåíèÿ â îáû÷íûõ äèôðàêöèîííûõ ñïåêòðîìåòðàõ è ñîñåäíèõ ïîðÿäêîâ â äâóìåðíûõ ýøåëëå-ñïåêòðîìåòðàõ)
 àòîìíî-ýìèññèîííîì ñïåêòðàëüíîì àíàëèçå (ÀÝÑÀ) íàáëþäàþòñÿ ñëåäóþùèå îñíîâíûå ñïåêòðàëüíûå ïîìåõè, ðàçëè÷àþùèåñÿ âèäîì ïðîÿâëåíèÿ â ñïåêòðå è ñïîñîáàìè èõ óñòðàíåíèÿ è ó÷åòà: øèðîêîäèàïàçîííûå; óçêîäèàïàçîííûå (÷àñòè÷íîå èëè ïîëíîå ïåðåêðûâàíèå àíàëèòè÷åñêîé ëèíèè àòîìíûìè èëè èîííûìè ëèíèÿìè ýëåìåíòîâ ïðîáû, ýëåêòðîäîâ è àòìîñôåðû ðàçðÿäà; íàëîæåíèå ñïåêòðîâ âûñøèõ ïîðÿäêîâ îòðàæåíèÿ â îáû÷íûõ äèôðàêöèîííûõ ñïåêòðîìåòðàõ è ñîñåäíèõ ïîðÿäêîâ â äâóìåðíûõ ýøåëëå-ñïåêòðîìåòðàõ)
Ïðîãðàììíîå îáåñïå÷åíèå ñîâðåìåííûõ ïðèáîðîâ ñîäåðæèò ýëåêòðîííûå áàçû äàííûõ ñïåêòðàëüíûõ ëèíèé, â êîòîðûõ ïðåäñòàâëåíû è âûÿâëåííûå ïîòåíöèàëüíûå ñïåêòðàëüíûå ïîìåõè ëèíèé ýëåìåíòîâ è ìîëåêóëÿðíûõ êîìïîíåíò
Summary
Ðàññìîòðåíû îñíîâíûå èñòî÷íèêè ñïåêòðàëüíûõ ïîìåõ â àòîìíî-ýìèññèîííîì ñïåêòðàëüíîì àíàëèçå (ÀÝÑÀ): øèðîêîäèàïàçîííûõ (òîðìîçíîé è ðåêîìáèíàöèîííûé êîíòèíóóì; èçëó÷åíèå ãîðÿ÷èõ êîíäåíñèðîâàííûõ ÷àñòèö è êîíöîâ ýëåêòðîäîâ; ðàññåÿííûé ñâåò â ñïåêòðîìåòðå; ïåðåêðûâàíèå àíàëèòè÷åñêèõ ëèíèé êðûëüÿìè ñîñåäíèõ ñèëüíûõ ñïåêòðàëüíûõ ëèíèé ìåøàþùèõ ýëåìåíòîâ; íàëîæåíèå êîìïîíåíò ìîëåêóëÿðíûõ ïîëîñ ñ î÷åíü áëèçêèìè ëèíèÿìè) è óçêîäèàïàçîííûõ (÷àñòè÷íîå èëè ïîëíîå ïåðåêðûâàíèå àíàëèòè÷åñêîé ëèíèè àòîìíûìè èëè èîííûìè ëèíèÿìè ýëåìåíòîâ ïðîáû, ýëåêòðîäîâ è àòìîñôåðû ðàçðÿäà; íàëîæåíèå ñïåêòðîâ âûñøèõ ïîðÿäêîâ îòðàæåíèÿ â îáû÷íûõ äèôðàêöèîííûõ ñïåêòðîìåòðàõ è ñîñåäíèõ ïîðÿäêîâ â äâóìåðíûõ ýøåëëå-ñïåêòðîìåòðàõ). Ïîêàçàíû âîçìîæíîñòè ñíèæåíèÿ óðîâíÿ è óñòðàíåíèÿ äàííûõ ñïåêòðàëüíûõ ïîìåõ ïðè êîíñòðóèðîâàíèè è èçãîòîâëåíèè ïðèáîðîâ äëÿ ÀÝÑÀ, ïîäáîðå è ðåãóëèðîâàíèè îïåðàöèîííûõ óñëîâèé àíàëèçà. Ðàññìîòðåíû ñîâðåìåííûå ñïîñîáû êîððåêöèè ôîíà ïîä ñïåêòðàëüíûì ïèêîì (under-peak) ñ ïîìîùüþ ïðîãðàììíîãî îáåñïå÷åíèÿ àòîìíî-ýìèññèîííûõ ñïåêòðîìåòðîâ ïóòåì ñîçäàíèÿ ðàçëè÷íûõ ìàòåìàòè÷åñêèõ ìîäåëåé ôîíîâîãî ñèãíàëà â îêðåñòíîñòè àíàëèòè÷åñêîé ëèíèè íà ýòàïå ðàçðàáîòêè êîíêðåòíîé ìåòîäèêè ÀÝÑÀ. Ïðèâåäåíû îñîáåííîñòè ïðèìåíåíèÿ ñïîñîáà ìåæýëåìåíòíîé êîððåêöèè ïðè ïðÿìîì ñïåêòðàëüíîì íàëîæåíèè ëèíèé. Êëþ÷åâûå ñëîâà: àòîìíî-ýìèññèîííûé ñïåêòðàëüíûé àíàëèç; êîíòèíóóì; íåïðåðûâíûé è äèñêðåòíûé ôîí; ìîëåêóëÿðíûå ïîëîñû; ðàññåÿííûé ñâåò; òåïëîâîå èçëó÷åíèå; êîíòóð è êðûëüÿ ñïåêòðàëüíûõ ëèíèé; êîððåêöèÿ ñïåêòðàëüíûõ ïîìåõ
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