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A universal and cost-effective method for the mitigation of interferences in inductively coupled plasma mass spectrometry 一种在电感耦合等离子体质谱中降低干扰的通用且经济有效的方法
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/j.sab.2025.107308
Michael G.A. Trolio, Diane Beauchemin
A universal and cost-effective method utilizing low sample uptake rate (50 μL min−1) combined with a mixed-gas plasma containing 1.1 % nitrogen is demonstrated to reduce oxide, carbon, and argide interferences while mitigating signal suppression from complex matrices. Low sample uptake rate also reduced nitrogen-based interferences in an argon plasma. On average, oxide interferences (ScO/Sc, YO/Y, ZrO/Zr, BaO/Ba) decreased by 94.0 % when comparing an argon plasma with 1 mL min−1 sample uptake rate to 50 μL min−1 in a mixed-gas plasma. Carbon-based, nitrogen-based and argide interferences decreased by 50.6 % to 95.5 % depending on plasma condition, sample uptake rate, and interference type. Furthermore, matrix-based signal suppression arising from 100 mg L−1 Na, Rb or Cs on 50 μg L−1 Li, Mg, Cr, Mn, Co, Sr, Y, and Pb were almost fully mitigated under both plasma conditions at low sample uptake rate, with an increase in matrix effect mitigation observed in the mixed-gas plasma. By minimizing sample waste and wear on costly instrument components, the enclosed method offers a greener solution for analytical laboratories, decreasing operational costs and increasing sample throughput without introducing significant error or uncertainty. Ultimately, this work can be universally implemented, without the need for costly instrument modifications or consideration for instrument make or model.
利用低样品吸收率(50 μL min - 1)与含有1.1%氮的混合气体等离子体相结合,证明了一种通用且具有成本效益的方法可以减少氧化物,碳和氩气干扰,同时减轻复杂基质的信号抑制。低样品吸收率也减少了氩等离子体中的氮基干扰。当样品吸收率为1 mL min - 1的氩气等离子体与样品吸收率为50 μL min - 1的混合气体等离子体相比,氧化物干扰(ScO/Sc、YO/Y、ZrO/Zr、BaO/Ba)平均降低了94.0%。碳基、氮基和氩气干扰减少了50.6%至95.5%,具体取决于等离子体条件、样品摄取率和干扰类型。此外,在低样品吸收率的两种等离子体条件下,100 mg L−1 Na、Rb或Cs对50 μg L−1 Li、mg、Cr、Mn、Co、Sr、Y和Pb产生的基于基质的信号抑制几乎完全被缓解,并且在混合气体等离子体中观察到基质效应的缓解增加。通过最大限度地减少样品浪费和昂贵仪器组件的磨损,封闭式方法为分析实验室提供了更环保的解决方案,降低了操作成本,提高了样品吞吐量,而不会引入显着的误差或不确定性。最终,这项工作可以普遍实施,而不需要昂贵的仪器修改或考虑仪器制造或型号。
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引用次数: 0
Quantitative mapping of gold nanoparticles and essential elements in plant tissue using laser ablation–single-particle inductively coupled plasma–time of flight mass spectrometry 利用激光烧蚀-单粒子电感耦合等离子体飞行时间质谱法定量定位植物组织中的金纳米粒子和必需元素
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/j.sab.2025.107379
Aline Pereira de Oliveira , Ana Lores-Padín , Thibaut Van Acker , Iker Basabe-Mendizabal , Helton Pereira Nogueira , Juliana Naozuka , Cassiana Seimi Nomura , Frank Vanhaecke
The increasing use of nanomaterials has raised concerns regarding their environmental fate and impact on food safety. Nanoparticles (NPs) can be taken up by plants, undergo biotransformation, and accumulate in edible parts. While single-particle inductively coupled plasma-mass spectrometry (spICP-MS) allows characterization of NPs in suspension, it requires their extraction from biological tissues, erasing spatial information and potentially affecting particle integrity. In contrast, laser ablation–single-particle ICP–time of flight MS (LA-spICP-ToFMS) enables spatially resolved analysis via direct solid sampling, revealing the distribution of NPs and ionic species in plant tissues. A calibration approach based on gelatin microdroplets was developed for quantitative mapping of AuNPs and essential elements in plant tissues. Microdroplets (0.015–0.100 mg) containing 30, 50, or 100 nm AuNPs (8 × 104 particles mg−1) and suitable amounts of Cu, Fe, and Mn were manually deposited on microscope slides and ablated using an ArF*excimer-based LA system equipped with a low-dispersion tube-type cell. Mapping was performed with a 20 × 20 μm spot at low fluence (0.25 J cm−2) to preserve NP integrity. The transport efficiency for AuNPs ranged from 95 to 105 % for all sizes (30–100 nm). As proof of concept, cotyledon and stem cross-sections of Phaseolus vulgaris seedlings cultivated with ionic Au or 30 ± 3 nm AuNPs (both at 1 mg L−1 Au), or without added Au, were analyzed. The method revealed AuNPs spatial distribution, particle concentration and size distribution, and effects on essential elements, proving suitable for assessing uptake, translocation, and interactions of AuNPs in plant systems.
越来越多地使用纳米材料引起了人们对其环境命运和对食品安全的影响的关注。纳米颗粒(NPs)可以被植物吸收,进行生物转化,并在可食用部位积累。虽然单粒子电感耦合等离子体质谱(spICP-MS)可以表征悬浮液中的NPs,但它需要从生物组织中提取NPs,从而消除空间信息并可能影响颗粒完整性。相比之下,激光烧蚀-单粒子icp -飞行时间质谱(LA-spICP-ToFMS)可以通过直接固体取样进行空间分辨分析,揭示植物组织中NPs和离子种类的分布。建立了一种基于明胶微滴的校准方法,用于植物组织中AuNPs和必需元素的定量定位。将含有30,50或100 nm AuNPs (8 × 104颗粒mg−1)和适量Cu, Fe和Mn的微滴(0.015-0.100 mg)人工沉积在显微镜载玻片上,并使用配备低色散管型细胞的ArF*准分子LA系统进行烧蚀。在低通量(0.25 J cm−2)下用20 × 20 μm点进行制图,以保持NP的完整性。在所有尺寸(30-100 nm)下,AuNPs的传输效率为95%至105%。为了证明这一概念,我们分析了在离子Au或30±3 nm AuNPs(均为1 mg L−1 Au)和未添加Au的情况下培养的Phaseolus vulgaris幼苗的子叶和茎截面。该方法揭示了AuNPs的空间分布、颗粒浓度和大小分布以及对必需元素的影响,证明该方法适用于评估植物系统中AuNPs的吸收、转运和相互作用。
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引用次数: 0
A tribute to mentor and advisor Dr. John Olesik on his 70th birthday 向导师兼顾问John Olesik博士70岁生日致敬
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/j.sab.2025.107423
Patrick J. Gray
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引用次数: 0
Fast-sequential determination of As, Bi, Cd, Ge, Hg, Sb and Sn by CVG-MIP OES using a multimode sample introduction system 多模样品导入系统CVG-MIP OES快速序列测定As、Bi、Cd、Ge、Hg、Sb和Sn
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/j.sab.2025.107446
Letícia C. Brudi, Eliana T.F. Larruscain, Andressa D.W.V. Martinez, Gustavo R. Bitencourt, Paola A. Mello, Fabio A. Duarte
The purpose of this study was to develop a method coupling chemical vapor generation (CVG) and microwave-induced plasma optical emission spectrometry (MIP OES) for the determination of As, Bi, Cd, Ge, Hg, Sb and Sn in environmental matrices, such as coal, marine, and lake sediment. The main parameters for the development of CVG-MIP OES method were the concentration of NaBH4 (0.1 to 2 % m/v) and HCl (1 to 7 mol L−1) solutions, the type (thiourea, L-cysteine, potassium iodide and hydroxylamine hydrochloride) and concentration (0.1 to 2 % m/v) of pre-reducing agents solutions, the operational conditions for MIP OES instrument, the interferences caused by transition metals (in the range of 25 to 1000 μg L−1), and the concentration of HNO3 (5 to 40 %) in the samples. The proposed method allows for achieving limit of detection (LOD) values of 199, 45.4, 112, 75.8, 89.7, 61.9, and 79.4 ng g−1 for As, Bi, Cd, Ge, Hg, Sb, and Sn, respectively. The accuracy was evaluated by the analysis of three certified reference materials: coal (NIST 1632c), marine sediment (PACS-2) and lake sediment (SUD-1), with agreement ranging from 92 to 111 %. Thus, the CVG-MIP OES method proved to be effective for As, Bi, Cd, Ge, Hg, Sb, and Sn determination in samples with different compositions, being robust regarding HNO3 concentration and interfering metals concentration. A significant reduction in the LOD of the MIP OES technique was obtained. Finally, the proposed method is a cost-effective alternative to the traditional plasma-based techniques, due to its low long-term cost and good robustness.
本研究的目的是建立一种耦合化学蒸汽产生(CVG)和微波诱导等离子体光学发射光谱(MIP OES)的方法,用于测定煤、海洋和湖泊沉积物等环境基质中的As、Bi、Cd、Ge、Hg、Sb和Sn。CVG-MIP OES的发展方法的主要参数是NaBH4的浓度(m / v 0.1 - 2%)和盐酸(1 - 7摩尔L−1)解决方案,类型(硫脲,半胱氨酸,碘化钾和盐酸羟胺)和浓度(0.1米/ v) 2%的pre-reducing代理解决方案,MIP海洋能仪器,操作条件造成的干扰过渡金属(在25到1000μg L−1),和硝酸的浓度(5 - 40%)的样品。该方法对As、Bi、Cd、Ge、Hg、Sb和Sn的检测限(LOD)分别为199、45.4、112、75.8、89.7、61.9和79.4 ng g−1。准确度通过分析三种认证标准物质进行评估:煤(NIST 1632c),海洋沉积物(PACS-2)和湖泊沉积物(SUD-1),一致性范围为92%至111%。因此,CVG-MIP OES法对不同成分样品的As、Bi、Cd、Ge、Hg、Sb、Sn的测定是有效的,对HNO3浓度和干扰金属浓度的测定是稳健的。MIP OES技术的LOD显著降低。最后,该方法长期成本低,鲁棒性好,是传统等离子体技术的一种经济有效的替代方法。
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引用次数: 0
Enhanced repeatability and reproducibility in lunar analog material analysis using LIXS compared to LIBS 与LIBS相比,LIXS在月球模拟物质分析中的可重复性和再现性增强
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/j.sab.2025.107306
Nivethika Komathinathan , Kevin Kraft , Philipp Schuetz , Florian Kehl , Davide Bleiner
In-situ resource identification on extraterrestrial bodies is pivotal for space exploration and necessitates precise material characterization techniques. This study evaluates the comparative performance of Laser-Induced Soft X-ray and Extreme Ultraviolet (XUV) Spectroscopy (LIXS) and conventional Laser-Induced Breakdown Spectroscopy (LIBS) for this purpose. LIXS, designed to operate at shorter wavelengths and to detect signals in vacuum, aims to enhance extraplanetary exploration tools along with its environmental compatibility, particularly on the lunar surface. A key hypothesis of our study is that LIXS is more repeatable and reproducible compared to LIBS, which are known limitations of LIBS. This analysis includes the evaluation of repeatability and reproducibility for three prominent emission lines from lunar analogue samples as well as for the emission of aluminum from the same samples using both detection methods. The investigation reveals that a maximum relative standard deviation (RSD) for aluminum emission intensities of 11.1 % is achieved by LIXS and of 208.2 % by LIBS at equivalent energies, signifying notably enhanced repeatability. Additionally, LIXS exhibits up to eight times better reproducibility of aluminum emission intensities in diverse experimental setting conditions compared to LIBS. Signal-to-noise ratio analysis further underscores the advantages of noise reduction by LIXS, contributing to its better performance, establishing LIXS as a superior alternative with enhanced repeatability and reproducibility for resource identification in space exploration.
地外天体的原位资源识别是空间探索的关键,需要精确的材料表征技术。本研究评估了激光诱导软x射线和极紫外光谱(LIXS)和传统激光诱导击穿光谱(LIBS)在这方面的比较性能。LIXS的设计目的是在更短的波长下工作,并在真空中探测信号,旨在增强行星外探测工具及其环境兼容性,特别是在月球表面。我们研究的一个关键假设是LIXS比LIBS具有更高的可重复性和可重复性,这是LIBS已知的局限性。该分析包括评估来自月球模拟样品的三个突出发射线的可重复性和再现性,以及使用两种检测方法从相同样品中发射铝。结果表明,在等效能量下,LIXS法测得铝发射强度的最大相对标准偏差(RSD)为11.1%,LIBS法测得的最大相对标准偏差为208.2%,重复性显著提高。此外,与LIBS相比,LIXS在不同实验环境条件下对铝发射强度的再现性提高了8倍。信噪比分析进一步强调了LIXS降噪的优势,使其性能更好,确立了LIXS作为空间探索中资源识别的可重复性和再现性增强的优越替代方案。
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引用次数: 0
Enhancement of LIBS plasma in air with organic solvent vapors 有机溶剂蒸气对空气中LIBS等离子体的增强作用
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/j.sab.2025.107309
Yi You , Boyang Xue , Jens Riedel
Laser-induced breakdown spectroscopy (LIBS) offers versatile, field-deployable elemental analysis; however, compact, high-repetition-rate nanosecond laser systems typically face constraints in power consumption and size, often compromising emission intensity and thus analytical performance. We demonstrate a significant improvement in LIBS signals through the controlled introduction of common organic solvent vapors into a sheath gas, with a diode-pumped solid-state laser (1064 nm, 2–28 kHz repetition rate, 450–600-μJ pulse energy). Optical and acoustic diagnostics reveal up to ca. 40-fold enhancement of the N II emission line at 567 nm when ambient air serves as the analyte. Maximal enhancement occurs at intermediate repetition rates of ca. 15 kHz, particularly at pulse energies approaching the optical breakdown threshold; this observation suggests a viable strategy for operating LIBS at lower pulse energies and higher repetition rates. Enhancement effects scale jointly with both vapor pressure and ionization energy of the organic species, with acetone and toluene markedly outperforming methanol and isopropanol. These findings provide a rational foundation for significantly improving the analytical performance of portable LIBS instruments without exceeding platform-specific constraints.
激光诱导击穿光谱(LIBS)提供多功能、可现场部署的元素分析;然而,紧凑、高重复率的纳秒激光系统通常面临功耗和尺寸的限制,通常会影响发射强度,从而影响分析性能。利用二极管泵浦固体激光器(1064 nm, 2-28 kHz重复频率,450-600 μ j脉冲能量),将常见的有机溶剂蒸汽引入鞘气中,可以显著改善LIBS信号。光学和声学诊断显示,当环境空气作为分析物时,在567 nm处的N II发射线增强了约40倍。最大增强发生在大约15 kHz的中间重复频率,特别是在脉冲能量接近光学击穿阈值时;这一观察结果提示了在低脉冲能量和高重复率下操作LIBS的可行策略。强化效果与有机组分的蒸汽压和电离能共同作用,其中丙酮和甲苯的强化效果明显优于甲醇和异丙醇。这些发现为在不超出特定平台限制的情况下显著提高便携式LIBS仪器的分析性能提供了合理的基础。
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引用次数: 0
Size detection limits in single particle inductively coupled plasma mass spectrometry: Reconsidering the selection of dwell times 单粒子电感耦合等离子体质谱法的尺寸检测限:重新考虑停留时间的选择
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/j.sab.2025.107307
Isabel Abad-Alvaro, Eduardo Bolea, Francisco Laborda
Performance of single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) methods is constrained by the characteristics of the instrumentation. The commercial availability of fast data acquisition quadrupole instruments, which allow the use of dwell times in the microsecond range rather than being restricted to milliseconds, was expected to improve the performance of the technique. When data acquisition frequency is increased, individual particles are recorded as transient signals consisting of multiple-reading events instead of one-reading pulses. Since particle events must be detected above the baseline noise, the highest intensity reading of a transient signal becomes a relevant parameter whose value decreases with decreasing dwell time, as the total intensity of a particle event is independent of the number of readings per event and thus of the selected dwell time. In this work, the effect of dwell time on the attainable size detection limits has been reconsidered, achieving minimum size detection limits when dwell times in the range of 200500 μs were used, regardless of the baseline level. At such dwell times, particle events from small nanoparticles (e.g., 23 times the size detection limit) were recorded within 12 readings despite the duration of particle events, which was modified working in both standard and gas reaction modes. Under these conditions, free and proprietary software capable of handling multiple-reading events allowed to process successfully the SP-ICP-MS data independently of the dwell time applied.
单粒子电感耦合等离子体质谱(SP-ICP-MS)方法的性能受到仪器本身特性的制约。快速数据采集四极杆仪器的商业可用性,允许使用停留时间在微秒范围内,而不是局限于毫秒,预计将提高该技术的性能。当数据采集频率增加时,单个粒子被记录为由多个读取事件组成的瞬态信号,而不是单读取脉冲。由于必须在基线噪声之上检测粒子事件,因此瞬态信号的最高强度读数成为一个相关参数,其值随着停留时间的减少而减小,因为粒子事件的总强度与每个事件的读数数量无关,因此与所选择的停留时间无关。在这项工作中,重新考虑了停留时间对可达到的尺寸检测限的影响,当停留时间在200-500 μs范围内时,无论基线水平如何,都可以获得最小的尺寸检测限。在这样的停留时间内,小纳米颗粒(例如,2-3倍于检测极限大小)的颗粒事件在1-2个读数内被记录下来,尽管颗粒事件持续时间很长,但在标准和气体反应模式下都进行了修改。在这些条件下,能够处理多个读取事件的免费专有软件允许独立于应用的停留时间成功处理SP-ICP-MS数据。
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引用次数: 0
Improved signal stability in inductively coupled plasma–atomic emission spectrometry through use of tandem spray chambers and surfactant addition 通过使用串联喷雾室和添加表面活性剂改善电感耦合等离子体-原子发射光谱的信号稳定性
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/j.sab.2025.107339
George C.-Y. Chan , Gary M. Hieftje
A search for causes of intermittent mid-term (about two hours) instability in emission signals from an inductively coupled plasma led to adoption of a tandem spray-chamber arrangement and subsequently to use of a surfactant (Triton X-100) to mitigate the remaining and newly found instabilities. Through a series of investigations, abrupt signal excursions in the tandem setup were traced to droplet coagulation and drainage inside the glass tube that connected the two spray chambers. However, the signal shifts were not the result of sample-solution release directly but rather to the influence of the underlying factors on plasma behavior. Experiments tailored to the study included not only examination of temporal signal behavior but also collection of long-term videos and measurement of radiofrequency characteristics of the plasma. The addition of a surfactant, Triton X-100, for signal-stability improvement is applicable not only to systems that employ tandem spray chambers but also to conventional single Scott-type chamber arrangements. Further, use of the surfactant was unsuccessful in overcoming “acid effects”, either of the steady-state or transient nature, and did not alter plasma background or analyte signals significantly.
为了寻找电感耦合等离子体发射信号中间歇性中期(约两小时)不稳定的原因,采用了串联喷射室布置,随后使用表面活性剂(Triton X-100)来减轻剩余的和新发现的不稳定性。通过一系列的研究,在串联装置中突然的信号偏移被追踪到液滴在连接两个喷雾室的玻璃管内的凝固和排出。然而,信号移位不是样品-溶液释放的直接结果,而是潜在因素对等离子体行为的影响。为研究量身定制的实验不仅包括对时间信号行为的检查,还包括收集长期视频和测量等离子体的射频特性。添加表面活性剂Triton X-100可以改善信号稳定性,不仅适用于采用串联喷雾室的系统,也适用于传统的单scott型喷雾室布置。此外,表面活性剂的使用无法克服“酸效应”,无论是稳态还是瞬态性质,并且没有显着改变等离子体背景或分析物信号。
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引用次数: 0
Outside Front Cover - Journal name, Cover image, Volume issue details, ISSN, Cover Date, Elsevier Logo and Society Logo if required 外部封面-期刊名称,封面图片,卷刊细节,ISSN,封面日期,爱思唯尔标志和学会标志(如果需要)
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-24 DOI: 10.1016/S0584-8547(25)00322-2
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引用次数: 0
Arc discharge-assisted enhancement of femtosecond LIBS for improved sensitivity in trace Cu detection in aqueous solutions 电弧放电辅助增强飞秒LIBS对水溶液中痕量铜检测的灵敏度
IF 3.8 2区 化学 Q1 SPECTROSCOPY Pub Date : 2025-12-23 DOI: 10.1016/j.sab.2025.107445
Xin Yu , Yuanfei Jiang , Hongxia Qi , Jianhui Han , Anmin Chen , Mingxing Jin
This study combines arc discharge with femtosecond laser-induced breakdown spectroscopy (fs-LIBS) to investigate the time-integrated and time-resolved spectra of aluminum atoms and AlO molecules in aluminum targets. A dried droplet method was further employed to analyze the emission spectra and calibration curves of Cu in aqueous solutions. Under arc-assisted fs-LIBS, at a laser energy of 0.5 mJ, the spectral enhancement factors reached up to 14 and 5 for Al and AlO, respectively. Vibrational temperatures of AlO were calculated as functions of laser energy and detection delay, showing consistently higher values in the presence of arc discharge. For Cu detection, the results revealed that, at a laser energy of 1 mJ, arc-assisted fs-LIBS reduced the limit of detection (LOD) of Cu (I) at 324.75 nm from 187 ng/mL to 25 ng/mL, and at 327.40 nm from 191 ng/mL to 31 ng/mL—corresponding to an improvement of ∼7 and 6-fold respectively over conventional fs-LIBS. The correlation coefficient (R2) of the calibration curve also improved, from 0.949 to 0.951 at 324.75 nm and from 0.896 to 0.957 at 327.40 nm. These results indicate that at relatively low laser energy, arc discharge-assisted fs-LIBS not only enhances the detection sensitivity of Al and AlO species, but also significantly improves the analytical performance of trace Cu in liquids, thereby expanding the applicability of femtosecond LIBS in high-sensitivity spectroscopic analysis.
本研究将电弧放电与飞秒激光诱导击穿光谱(fs-LIBS)相结合,研究了铝靶中铝原子和AlO分子的时间积分和时间分辨光谱。采用干滴法分析了水溶液中Cu的发射光谱和标定曲线。在电弧辅助fs-LIBS下,激光能量为0.5 mJ时,Al和AlO的光谱增强因子分别达到14和5。计算了激光能量和检测延迟对AlO振动温度的影响,结果表明电弧放电时的振动温度始终较高。对于Cu的检测,结果表明,在激光能量为1 mJ时,电弧辅助fs-LIBS将Cu (I)在324.75 nm处的检出限(LOD)从187 ng/mL降低到25 ng/mL,将327.40 nm处的检出限(LOD)从191 ng/mL降低到31 ng/mL,分别比传统fs-LIBS提高了约7倍和6倍。校正曲线的相关系数(R2)在324.75 nm处由0.949提高到0.951,在327.40 nm处由0.896提高到0.957。这些结果表明,在相对较低的激光能量下,电弧放电辅助fs-LIBS不仅提高了Al和AlO的检测灵敏度,而且显著提高了液体中痕量Cu的分析性能,从而扩大了飞秒LIBS在高灵敏度光谱分析中的适用性。
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引用次数: 0
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Spectrochimica Acta Part B: Atomic Spectroscopy
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