Abstract: When X-ray fluorescence spectrometry(XRF) is applied to the analysis of high-manganese iron ore,the abnormal manganese content(w(MnO)>2%) will cause negative deviation in Fe₂O₃ determination results.In addition,the conventional fusion preparation with a dilution ratio of 10∶1 easily leads to cracking of fused bead and poor molding difficulty.To address these issues,the calibration method,sample preparation conditions and interference correction were systematically optimized in this study.Firstly,a series of gradient calibration samples were prepared by proportionally mixing national first-grade certified reference materials of manganese ore and iron ore,which expanded the linear determination ranges for MnO and Fe₂O₃,and filled the calibration blank for high-manganese(w(MnO)>0.5%) and high-iron(w(Fe₂O₃)>30%) content intervals.Secondly,by optimizing the fusion preparation conditions such as dilution ratio,fusion temperature and time,the optimal fusion procedure was determined:a dilution ratio of 14∶1,addition of LiBr solution and NH₄I solution as release agents,and fusion at 1 050 ℃ for 10 min.This procedure significantly improved the preparation quality and success rate of fused bead.Finally,the combination of theoretical α coefficient method and empirical coefficient method was adopted to correct the matrix effect.The overlapping interference of Mn Kβ spectral line on Fe Kβ spectral line was deducted,which effectively eliminated the distortion of Fe₂O₃ measurement results caused by high-manganese under high-iron background.The proposed method was used to determine 10 major components in high-manganese iron ore sample,including SiO₂,Al₂O₃,Fe₂O₃,CaO,MgO,K₂O,Na₂O,TiO₂,P₂O₅ and MnO.The relative standard deviations (RSD,n=6) of the results ranged from 0.29% to 8.3%.The RSD for the low-content Na₂O component was relatively high,but all determination results could meet the requirements of DZ/T 0130-2006 The Specification of Testing Quality Management for Geological Laboratories.The trueness was further verified using reference materials iron ore.The determined values of each component were in good agreement with the standard values,and the relative errors could meet the specification requirements.Additionally,two high-iron high-manganese iron ore samples from a mining area were analyzed,and the results were compared with those obtained by national standard methods(gravimetry for SiO₂;titrimetry for Al₂O₃,CaO,and MgO;spectrophotometry for Fe₂O₃,TiO₂,and P₂O₅;atomic absorption spectrometry for Na₂O,K₂O,and MnO).The results showed good consistency between the two methods,and all errors conformed to the allowable range specified in DZG 93-07 Analytical Procedures for Iron Ores.The XRF analysis method for high-manganese iron ores established in this study successfully overcame the challenges of high-manganese matrix interference and sample preparation difficulties,and it was suitable for the analysis of actual samples.