This work presents the quantitation of the effects that different chemical environments induced in the transition probabilities of their L and M series spectra working in the particular geometrical and analytical conditions imposed by the Total-reflection X-Ray Fluorescence (TXRF) spectrometry. The evaluated chemical environments were metallic Au(0) and chloride Au(3+) phases, with different oxidation states and different crystal field surroundings. Lines Ll, Lα, Lη, Lβ, Lγ and the overlapped Mα and Mβ, named as Mαβ, were evaluated. Transition probabilities and production cross-section ratios were calculated for both gold environments. The absolute transition probabilities were evaluated as the intensity of each line versus the sum of the set of intensities investigated, i.e. Au L and M lines. Achieved results show significant differences between both gold chemical states and environments higher than uncertainties. TXRF has proven to be sensitive to the transition probabilities induced by different atomic environments. Intensity variations with decrements of −7.3% for Lβ line and increments of 96% for Mαβ lines were measured. In parallel, the same phenomenon observed for gold has been observed qualitatively and for the first time by TXRF in three different phases of lead, metallic Pb(0), nitrate Pb(2+) and sulfide Pb(2+). The achieved results corroborate the ability of TXRF to investigate the, different oxidation states, differents crystalline phases, different environments and in a general way, the different chemical surrounding effect. Finally, the existence of a possible enhancement effect in the Au Mαβ line due to a secondary excitation by the presence of Cl Kα secondary excitation was also checked. Results indicate that the observed change of Mαβ intensities between metallic gold and gold chloride are not due to the Cl Kα enhancement effect.

这项工作提出了在全反射X射线荧光（TXRF）光谱法施加的特定几何和分析条件下，不同化学环境在其L和M系列光谱的跃迁概率中引起的影响的定量分析。评估的化学环境是金属Au（0）和氯化物Au（3+）相，具有不同的氧化态和不同的晶体场环境。线L1，Lα，Lη，Lβ，Lγ以及重叠的Mα和Mβ（称为Mαβ）被评估。计算了两种黄金环境的转变概率和生产横截面比率。将绝对跃迁概率评估为每条线的强度与所研究强度集（即Au L和M线）的总和。取得的结果表明，金的化学状态与环境之间的显着差异高于不确定性。事实证明，TXRF对不同原子环境引起的跃迁几率很敏感。Lβ线的强度变化为-7.3 ％的降低，Mαβ的强度变化为96％测量线。同时，TXRF在铅，金属Pb（0），硝酸盐Pb（2+）和硫化物Pb（2+）的三个不同相中首次定性观察到了金的相同现象。所获得的结果证实了TXRF研究不同的氧化态，不同的结晶相，不同的环境以及总体上不同的化学周围效应的能力。最后，在金的可能的增强效应的存在Mαβ线由于通过氯的存在下，二次激励Kα二次激发也被检查。结果表明，所观察到的变化Mαβ金属和金的氯化金之间强度是不是由于氯Kα 增强效果。