薄膜法X射线荧光光谱对重金属铬元素检测研究

研究了重金属Cr元素薄膜法X射线荧光(XRF)光谱分析中的滤膜,结果表明亲水性聚四氟乙烯滤膜对Cr元素富集具有较好的均匀性,并且对该滤膜上Cr元素进行XRF光谱测量具有较好的灵敏度。利用亲水性聚四氟乙烯滤膜对不同浓度的Cr元素进行富集,并且利用XRF光谱进行测试,结果表明当Cr元素的面积浓度在3.84~167μg·cm-2范围内时,Cr元素XRF光谱中Kα特征谱线的积分荧光强度与Cr元素的面积浓度之间具有非常好的线性关系,线性相关系数为0.996,检测限为0.3μg·cm-2。对实验室水龙头出来的自来水水样进行加标回收实验,得到回收率在93.85%~101.95%之间,相对标准偏差小于2%。因此,以亲水性聚四氟乙烯滤膜为富集滤膜的薄膜法XRF光谱分析法,能够很好地应用于水样中重金属Cr元素的分析与检测。     

薄膜法X射线荧光测量中样品检测位置及防护铅板内衬材料的选择研究

(1)以型号316不锈钢金属板为研究对象,对薄膜法X射线荧光光谱测量中,样品检测位置的选择进行研究,确定了最佳的样品检测位置为样品距离X射线管和探测器水平基线1 cm处,并且与X射线管和探测器水平基线成16°角度。(2)以工业环境空气重金属污染物Pb,Cd,Cr为主要分析对象,在有铅板防护情况下进行薄膜法X射线荧光光谱测量研究,发现X射线会穿透样品薄膜而继续激发防护铅板,使得滤膜背景光谱中有较强的铅谱线干扰,会对实际样品中铅元素的测量产生影响。在薄样和防护铅板之间加上一层隔离材料,可有效避免防护铅板中铅谱线对样品测量产生的干扰。(3)以型号316不锈钢、黄铜、铝材、紫铜和聚四氟乙烯几种硬质隔离材料作为铅板内衬材料进行选择研究,结果表明：紫铜的X射线荧光光谱中所含元素的谱线最少,谱图中没有出现重金属Cr,Cd,Pb的谱峰,并且能量较高部分靶材散射光谱强度较弱,对实际样品中重金属元素Cr,Cd和Pb的测量不会产生干扰,作为铅板的内衬金属材料可以避免防护铅板中铅元素谱线的干扰,是最佳的薄膜法X射线荧光光谱分析中铅板的内衬金属材料。该研究为组装及搭建便携式大气及水体重金属X射线荧光光谱分析仪提供了重要的理论依据。     

薄膜法X射线荧光测量中样品检测位置及防护铅板内衬材料的选择研究

(1)以型号316不锈钢金属板为研究对象, 对薄膜法X射线荧光光谱测量中, 样品检测位置的选择进行研究, 确定了最佳的样品检测位置为样品距离X射线管和探测器水平基线1 cm处, 并且与X射线管和探测器水平基线成16°角度。(2)以工业环境空气重金属污染物Pb, Cd, Cr为主要分析对象, 在有铅板防护情况下进行薄膜法X射线荧光光谱测量研究, 发现X射线会穿透样品薄膜而继续激发防护铅板, 使得滤膜背景光谱中有较强的铅谱线干扰, 会对实际样品中铅元素的测量产生影响。在薄样和防护铅板之间加上一层隔离材料, 可有效避免防护铅板中铅谱线对样品测量产生的干扰。(3)以型号316不锈钢、黄铜、铝材、紫铜和聚四氟乙烯几种硬质隔离材料作为铅板内衬材料进行选择研究, 结果表明: 紫铜的X射线荧光光谱中所含元素的谱线最少, 谱图中没有出现重金属Cr, Cd, Pb的谱峰, 并且能量较高部分靶材散射光谱强度较弱, 对实际样品中重金属元素Cr, Cd和Pb的测量不会产生干扰, 作为铅板的内衬金属材料可以避免防护铅板中铅元素谱线的干扰, 是最佳的薄膜法X射线荧光光谱分析中铅板的内衬金属材料。该研究为组装及搭建便携式大气及水体重金属X射线荧光光谱分析仪提供了重要的理论依据。     

水体中铬、镉和铅的X射线荧光光谱同时快速分析方法研究

以氢氧化钠和硫化钠为沉淀剂采用共沉淀法同时富集水体中的Cr,Cd和Pb,通过对Cr(OH)₃,Cd(OH)₂和PbS沉淀均匀悬浮液抽滤以制成Cr,Cd和Pb均匀分布的薄膜样品并进行能量色散XRF光谱测量,以实现水体中Cr,Cd和Pb的同时快速分析与检测。研究了富集过程中的反应时间和反应物摩尔比对薄膜样品XRF光谱强度的影响,确定了富集过程的最佳反应条件为沉淀反应时间为5 min,OH-与Cr3+的最佳摩尔比为5.0,OH-与Cd2+的最佳摩尔比为5.0,S2-与Pb2+的最佳摩尔比为2;对富集后不同浓度的薄膜样品进行了均匀性检验,富集区域6个不同位置荧光强度的相对标准偏差均小于4.8%,说明富集后的薄膜样品具有较好的均匀性;将不同浓度薄膜样品的理论浓度值与ICP-MS方法测得的浓度值进行对比分析,验证了该富集方法对水样中Cr,Cd和Pb的富集率均能达到90%以上;根据薄膜样品的荧光强度与ICP-MS测得的浓度值,建立了基于该富集方法的水体中Cr,Cd和Pb的X射线荧光光谱定量分析方法,Cr,Cd和Pb校准曲线的线性相关系数分别为0.997 3,0.995 0和0.999 8,当实际采集水样体积为50 mL时,Cr,Cd和Pb的检出限分别为7.4,29.6和8.5 μg·L-1,均低于《污水综合排放标准 GB 8978-1996》中Cr,Cd和Pb的最高允许排放浓度,因此该方法能够实现工业生产及生活排放污水中Cr,Cd和Pb的同时快速分析与检测。该研究为基于X射线荧光光谱法的水体多种重金属同时快速在线监测提供依据。     

偏振X射线荧光系统测量痕量Cd元素的Geant4模拟研究

通过传统能量色散X射线荧光分析(EDXRF)对Cd元素进行痕量分析时,X光管发出的原级轫致辐射连续谱对Cd元素的分析具有严重的影响。为了减弱原级X射线对测量结果的影响,通过Geant4程序包模拟不同几何尺寸下偏振激发X射线荧光分析(P-EDXRF)中荧光靶的结构,研究其在减弱测量过程中原级X射线轫致辐射连续谱的影响。为了提高模拟效率,本文分三步进行模拟。第一步模拟不同管电压下电子打靶过程,得到不同管压下的X光管原级能谱。第二步针对Cd元素的痕量分析设置不同种类、不同几何条件的Te及BaSO₄作为荧光靶材料进行模拟。结果表明在使用K_α1能量(27.468 keV)与Cd元素吸收限26.711 keV最为接近的Te作为荧光靶材料时,随着Te靶厚度增加Te元素的特征峰强度在100 μm前快速增长,在150 μm后趋于稳定。而其信噪比(SNR)在80 μm到达最大值21.434。继续增加厚度由于荧光靶材料的自吸收作用SNR开始有些许下降,达到饱和吸收厚度后稳定。在不同应用场景时荧光靶选材应有不同,对于测量时间没有限制的条件下,应选择荧光强度更大的荧光靶厚度。而对于测量时间相对较短的条件下,则应该选择SNR更大的荧光靶厚度。第三步模拟通过荧光靶后的出射能谱激发含0.01%Cd的样品,经过Te靶后的出射能谱激发样品,得到Cd元素K_α1峰背比为8.28。相较于直接通过原级谱激发样品,Cd元素K_α1峰背比为2.29,其峰背比明显提高但Te元素的散射峰对Cd元素K_α1峰仍然有所影响。选用特征X射线能量与Cd元素K_α1相距更远的BaSO₄作为荧光靶材料,可减弱由于样品中的基体轻元素的散射作用而引起目标元素的峰背比降低情况,可将Cd元素K_α1峰背比提高至14.179。通过增大X光管管电压可进一步提高激发效果,在管电压为70 kV时对于Cd元素有最佳激发效果,峰背比为21.431。     

基于电极富集的水体重金属LIBS检测灵敏度研究

为了提高水体重金属LIBS检测的灵敏度以及降低元素检测限,采用LIBS结合铝电极富集方法对水体中的重金属Pb, Cd, Ni进行了分析。研究并优化了电极富集方法中关键参数—富集电压U,分析了LIBS特征谱线的光谱强度与富集电压大小之间的关系,得出重金属元素特征光强随着富集电压先增加后减小,在1.2 V处光谱强度达到最大值,选择了最优富集电压值为1.2 V。研究了Pb,Cd,Ni三种重金属元素的光谱稳定性,其特征谱线光谱强度的相对标准偏差(RSD)分别为5.98％,4.25,％和5.27％,说明该实验方法得到的谱线具有较高的稳定性。在0～ 0.13 mg·L-1范围内配制系列样品进行实验并对元素进行定量分析,得到Pb,Cd,Ni三种重金属元素的检测限分别为1.2,3.1和1.7 ppb。结果表明：LIBS结合铝电极富集方法能够有效地提高特征谱线的稳定性以及降低元素的检测限,为提高水体重金属LIBS的检测灵敏度和分析能力提供了方法支持。     

不同铅浓度土壤XRF光谱的频率域去噪及规律研究

近年来,全球工业快速发展和城市化的推进引发了一系列环境问题,其中土壤重金属铅(Pb)污染引起了科研人员的广泛关注。X射线荧光(XRF)光谱技术具有成本低、分析速度快、适合大面积监测等优势,已被广泛应用在土壤污染检测与生态环境保护等多个领域,发展前景广阔,因此充分挖掘土壤XRF光谱信息具有很强的现实意义,可为高效地进行土壤污染检测、土壤环境生态指标参量反演及矿区重金属污染早期预警等提供解决方案。目前关于XRF光谱研究大多集中在土壤重金属浓度测量结果的精度评价和环境质量评估,而对于土壤XRF光谱差异特征变化的深入分析研究较少。时频分析可将时域复杂信号变换到频率域空间,从频率域角度检测光谱、信号中存在的异常信息,是一种有效的谱差异特征变化检测方法,其中,谐波分析(HA)可用于电磁信号去噪;平滑伪魏格纳分布(SPWVD)可筛选合适的基函数,突出信号时频局域性细节特征。首先采用HA方法探究不同Pb浓度土壤XRF光谱的去噪效果,然后利用光谱的SPWVD研究实地采样土壤样品的去噪XRF光谱局部规律。研究结果表明:当谐波分解次数为400时,土壤XRF光谱去燥效果较好并节省了时间,且保留了光谱的特征。土壤样品Pb浓度与XRF光谱的SPWVD在400和600～700波段序列上的频率峰值的分布具有一定的规律性,根据此规律性可识别该地区土壤的Pb浓度超标:全部实地采样土壤中,能够识别75%的Pb浓度不超标的样品,在波段序列为400附近有1个较高的频率峰(频率小于400 Hz)或有2个很强的频率峰值(频率大于400 Hz);全部实地采样土壤中,能够识别79.17%的Pb浓度超标的样品,在波段序列为400附近有1个很强的频率峰(频率大于400 Hz),且在600～700波段序列之间有3个层次明显的频率峰分布,据此推断该地区土壤Pb浓度超标的XRF光谱特征波段区间为6.42和9.42～10.92 keV。因此,研究通过引入时频分析法实现了对土壤XRF光谱频域甄析和可视化显现,为深度挖掘Pb污染谱规律特征及异常信息提供一种新思路。     

内标法在土壤重金属镍元素X荧光分析中的应用研究

利用能量色散型XRF重金属实验平台,在实验室自然大气环境下获取土壤的X射线荧光,通过X射线荧光光谱法定量分析了国家标准土壤样品中元素Ni的含量。实验研究了土壤中Ni元素的X荧光特征分析谱线,采用加入内标法测定了Ni元素定标曲线,并依据实验结果分析了内标元素选取方法。实验结果表明,对土壤样品进行内标法分析时,可选取基体中适宜元素作为内标元素;使用Pb的Lα线,Cu和Fe的Kα线作内标线时相对标准偏差(RSD)分别为6.24%,5.24%和5.22%,说明选择合适基体主量元素的特征谱线作为内标线,可有效提高测量结果的准确性。     

X射线荧光光谱中散射效应对荧光强度的贡献研究

采用理论计算和实验测定的方法研究了在纯元素样品、BaB二元样品及熔融片样品中三种散射效应对荧光强度的贡献(包括相干散射X射线激发的荧光强度、非相干散射X射线激发的荧光强度以及其他方向的一次荧光X射线被散射进探测方向的强度)大小及其变化规律。研究结果表明,三种散射效应对荧光强度的贡献大小与所研究元素原子特征谱线的能量及样品的基体有关,元素原子的特征谱线能量越高,散射效应对荧光强度的贡献越大;轻基体样品中散射效应对荧光的贡献比重基体样品大。实验证明,将散射效应包括在基本参数法的理论计算中可以有效地提高理论计算的准确度。     

基于多谱线内标法的不规则铜合金样品中 Pb元素成分检测研究

原位分析和在线检测是激光诱导击穿光谱(LIBS)技术的一大优势,但是,在野外环境中,人们无法对样品进行统一预处理,面对各种形态的待测样品如何保证LIBS的检测精度是函待解决的一大难题。提出一种多谱线内定标的方法来解决上述问题,即通过求解多条分析谱线的强度和与内标元素谱线的强度比值来建立定标曲线,进而降低光谱信号波动带来的误差,提高线性相关性和检测精度。实验中以铅黄铜合金样品为例,采用LIBS对厚度不一（最大变化值为±2 mm）的铅黄铜样品中的Pb元素进行了定量检测研究,并分别采用传统定标法和多谱线内定标法对这种不规则样品进行校正和建立定标曲线。实验发现,对于不规则样品,传统定标法的检测精度大大降低,定标曲线没有明显的线性关系。当采用单条谱线的内定标方法时,定标曲线线性相关度大大提高,校正决定系数达到0.724 89。而采用多条谱线内标方法（考虑多条分析谱线的相对强度总和）计算发现,当选取5条Pb谱线（Pb 261.42 nm,Pb 280.20 nm,Pb 368.35 nm,Pb 405.78 nm和Pb 520.14 nm）进行计算时,定标曲线线性拟合度达到0.984 6,由此可见该方法消除了样品不规则所带来的光谱强度波动误差,显著提高了测量精度。虽然继续增加分析谱线数目可以进一步提升线性相关度,但是也会增加计算的复杂度,所以选择合适的分析谱线是十分重要的。此外,通过多谱线内标法也能一定程度上消除基体效应和光谱干扰等影响,是一种简单有效且具备普适性的数据处理方法。当然,该方法也存在一定的局限性（如样品成分分布极不均匀、样品表面极不规则致使激光能量低于击穿阈值等）,不过通过调整和优化检测装置方案（例如增大激光能量、增大聚焦光斑、采用长焦距聚焦透镜等）可以更好的发挥该方法的优势。该研究内容可以为LIBS原位检测和在线检测的应用提供一种新思路。     

土壤重金属铅元素的X射线荧光光谱测量分析

在实验室条件下,利用NITON XLt793型便携式X射线荧光光谱重金属分析仪测量并分析土壤中铅元素的X射线荧光光谱特性。分别以铅的L_α(10.55 keV)和L_β(12.61 keV)特征谱线作为分析线,分析了不同基体元素对分析线的影响;测定在不同铅浓度下的特征谱线强度变化。结果表明铅的质量分数在10×10-6～1 800×10-6范围内,元素的光谱强度与浓度之间呈现较好的线性关系;建立了铅元素的定标曲线,并计算得到铅的检出限为7.89×10-6。     

Sample thickness considerations for quantitative X‐ray fluorescence analysis of the soft and skeletal tissues of the human body – theoretical evaluation and experimental validation

A good estimation of the matrix composition and the areal mass of the sample is critical for quantitative X‐ray fluorescence (XRF) analysis. Integrated aspects of the XRF quantitative analysis of various human body organs are presented. Special emphasis is placed on the determination of the sample thicknesses at which the specimen can be regarded as thin, thick, or intermediate thickness depending on the element under consideration. Moreover, a method for a fully quantitative analysis allowing the determination of the masses per unit area of chemical elements in thin, thick, and intermediate thickness samples is discussed. It was found that for an incident beam of 17 keV energy, a 15 µm thick sample is of intermediate thickness for all elements between P and Ca and becomes thin from Fe for most human body tissues in a natural form. Dried samples of soft tissues excluding these of low water content can be regarded as thin for all elements from phosphorus to strontium. The use of thin sample approach in quantification of intermediate thickness specimen may result in about 30–45% discrepancy in areal mass (weight fraction) of phosphorus, 20–35% of sulfur, 15–25% of chlorine, 8–15% of potassium, and 5–10% of calcium. Theoretical evaluations presented in the work are verified experimentally. The analysis of human brain samples (white and gray matter) and bovine liver (National Institute of Standards and Technology standard reference materials 1577b) confirms high accuracy of the XRF quantification on the basis of the described procedures. Copyright © 2012 John Wiley & Sons, Ltd.     

激光诱导Ti等离子体电子温度的实验研究

室温,常压下,利用Nd∶YAG脉冲激光器产生的波长为1 064 nm, 脉宽12 ns,能量分别180, 230和280 mJ的脉冲激光冲击Ti靶,使用中阶梯光栅光谱仪检测了三种激光能量下对应的光谱。调节延时器DG645的延迟时间,检测了延迟0～500 ns时间范围内Ti等离子体对应激光能量下的发射光谱,分析光谱,可以得到了九条不同的的TiⅠ 和TiⅡ等离子体谱线,证明在该实验条件下,Ti靶能够充分吸收能量电离且离子谱线具有不同的演化速率,利用Saha-Boltzmann法计算并分析Ti等离子体电子温度,实验结果表明：相同的延迟时间,激光能量越大,谱线相对强度越大,电子温度越高,谱线相对强度的变化量随激光能量的变化量增大而增大;在延时0～150 ns内,三种激光能量下的等离子体电子温度和谱线的相对强度都随延迟时间的增加而快速下降,其中280 mJ激光能量下的等离子体电子温度和谱线强度下降速率较快;在150～250 ns范围内,电子温度和谱线强度均随延迟时间的增加有一个缓慢的上升,180 mJ激光能量下的等离子体电子温度和谱线强度的上升速率较快。250～500 ns范围内,三种激光能量下的电子温度和谱线强度均随延迟时间的增加而缓慢下降。     

Characterization and application in XRF of HfO_2-coated glass monocapillary based on atomic layer deposition

Coating a glass monocapillary x-ray optics with high-density film is a promising way to improve transmission characteristics. For a long time, it has been a challenge to coat a high-density film in the inside of monocapillary with an extremely high length-to-diameter ratio. In this work, Hf O2 film is deposited on the inner wall of a tapered glass monocapillary with length 9.9 cm, entrance diameter 596.4 μm, and exit diameter 402.3 μm by atomic layer deposition. The coated and uncoated monocapillaries are studied by the transmission process of x-rays with energy from 5 ke V to 100 ke V and the x-ray fluorescence(XRF) spectra of a Mo sample are detected. Improved transmission characteristics have been obtained for the Hf O_2-coated monocapillary. The energy upper limit of focused x-rays increases from 18.1 ke V to 33.0 ke V and the ‘penetration halo' is suppressed to some extent. The XRF spectrum presents two stronger peaks at ～ 17.4 ke V and～ 19.6 ke V which are considered as the characteristic x-rays of Mo K_α and Mo K_β. These results reveal that more higher energy x-rays from the W x-ray tube are totally reflected on the inner wall of the Hf O_2-coated glass monocapillary due to the increase of total reflection critical angle. This work is significant for more applications of monocapillary in higher energy x-ray field.     

杂质元素特征X射线对氢气放电源打靶新谱线的影响

 在氢气放电源打靶的实验中,测到了系列能量恒定不变的低能X射线新谱线,这些新谱线的能量分别为(1.70±0.10) keV, (2.25±0.07) keV,(2.56±0.08) keV,(3.25±0.10) keV和（3.62±0.11） keV,与Si,Ta,S,Cl,K和Ca等元素的特征X射线能量相近,但靶中所含的杂质或来自放电室的杂质元素可能会产生这些能量的X射线谱峰,证实新谱线是否由这些元素的特征X射线干扰所致显得尤为重要。分析了本实验系统中各种杂质的可能来源,论证了放电室端杂质对新谱线的影响,及靶材料中体杂质和面杂质对新谱线的影响;用X射线光电子能谱仪对靶做了表面分析。研究结果表明：杂质元素的特征X射线不会对氢气放电源打靶产生的新谱线有影响。这些新谱线的性质有待进一步的实验研究。     

Band reject filtration of the excitation spectrum at energy dispersive X-ray spectroscopy of weak signals

The possibility of the efficient band reject filtration of the continuous X-ray excitation spectrum in the energy range E ≥ 8 keV is demonstrated. This makes it possible to strongly increase the sensitivity of energy dispersive X-ray spectroscopy at detecting of weak fluorescence lines. Spectral rejection is implemented by transmitting a primary beam through highly oriented pyrolytic graphite with given structural parameters. Diffraction extinction in pyrolytic graphite ensures the possibility of reducing the intensity by more than 20 dB and rejecting the spectral band with a width of ~1 keV. The reduction of statistical fluctuations of the background of elastically scattered radiation is achieved when the bottom of the formed spectral valley is adjusted to the analyzed fluorescence line. The proposed scheme of band reject filtration also allows the suppression of intense characteristic lines in the primary and scattered radiation spectra.     

Local thickness measurement through scattering contrast and electron energy-loss spectroscopy

Scattering contrast measurements were performed on thin films of amorphous carbon and polycrystalline Au, as well as single-crystal MgO nanocubes. Based on the exponential absorption law, mass-thickness can be obtained within 10% accuracy by measuring the incident and transmitted intensities in the same image. For mass-thickness measurement of a thin amorphous specimen, a small collection semiangle improves the measurement sensitivity, whereas for the measurement of polycrystalline or single-crystal specimens, a large collection semiangle should be used to reduce diffraction-contrast effects. EELS thickness measurements on MgO nanocubes suggest that the Kramers-Kronig sum-rule method (with correction for plural and surface scattering) gives 10% accuracy at medium collection semiangles but overestimates the thickness at small collection semiangles, due to underestimation of the surface-mode scattering. The log-ratio method, with a formula for inelastic mean free path proposed by Malis et al. (1988), provides 10% accuracy at small collection semiangle, while that proposed by Iakoubovskii et al. (2008a) is preferable for medium and large collection semiangles. As a result of this work, we provide recommendations of preferred methods and conditions for local-thickness measurement in the TEM.     

Improving signal-to-noise ratio for the forensic analysis of glass using micro X-ray fluorescence spectrometry

Micro X-ray fluorescence spectrometry (μXRF) is a standard technique used for the elemental analysis of glass fragments in forensic casework. The glass specimens encountered in casework are usually small (<1 mm), thin fragments that are partially transparent to the exciting X-ray beam. In addition to providing fluorescence from the small glass fragments, the primary beam X-rays can scatter within the chamber and provide noise in the measurements. To reduce scatter from the sample stage, the fragments are typically mounted on a thin plastic film and raised on an XRF sample cup (≤3 cm in height). However, at these heights, there may still be significant scatter from the sample stage, which adversely affects the signal-to-noise ratio (SNR) and the limit of detection (LOD). A plastic mount was designed and 3D-printed in-house to allow fragments to be raised as high as possible from the sample stage, thereby minimizing stage scatter. Most elements detected in glass showed an improvement in the SNR when using the 3D-printed mount for analyses. The greatest improvement (>30%) was observed for lower atomic number elements (Na and Mg) and higher atomic number elements (Sr and Zr). Another simple method to improve SNR is the use of primary beam filters; when using primary beam filters during analyses, elements with characteristic lines in the high-energy range (Rb, Sr, and Zr) showed the greatest improvement (>70%) in SNR. The impact of both strategies for the improvement of SNR is presented here.     

Determination of the reduction depth of tungsten oxide thin films under the effect of proton irradiation

This work is devoted to experimental determination of the limiting reduction depth of tungsten oxide to metal by the measurement of volumetric variations in a thin film of WO₃ under the effect of proton irradiation with an energy of 1.5 keV. The method of radiation-induced reduction of tungsten from WO₃ can be used for preparation of conducting structures in a dielectric matrix and obtaining an inorganic mask for carrying out different ion-beam processes. It is shown experimentally that the effect of a proton beam with an energy of 1.5 keV provides complete reduction of a tungsten oxide layer up to 138 nm thick. The experimental ratio of the thickness of the reduced layer to the thickness of the starting oxide film was 0.31. It is shown that the limiting reduction depth of tungsten oxide is determined by the path of protons in tungsten.