基于光谱分析的砷黄铁矿生物浸出过程中铁/砷/硫形态转化研究

基于同步辐射装置的As/S的K边及Fe的L边X射线吸收近边结构光谱(XANES)和X射线衍射(SR-XRD),结合扫描电镜(SEM)、傅里叶红外光谱(FTIR)、电感耦合等离子体发射光谱(ICP-AES)及各项浸出参数的测定,系统研究了(中度嗜热菌、嗜热硫化杆菌)浸出砷黄铁矿过程中铁、砷、硫的形态转化。结果表明,在生物作用下,砷黄铁矿的溶解速率明显高于化学浸出体系,伴随矿物溶解释放到溶液中的砷和铁在生物浸出体系中主要为As(Ⅴ)和Fe3+,而在无菌化学浸出体系则主要为As(Ⅲ)和Fe2+;细菌胞外多聚物(EPS)在细菌与硫化矿物的相互作用过程中起着至关重要的作用, FTIR的结果表明,生物浸出体系中吸附在矿物表面的吸附菌的EPS中蛋白质和多糖的含量均高于游离菌EPS;SEM的结果表明,砷黄铁矿表面在生物浸出过程中逐渐被腐蚀,且有浸出产物覆盖,而化学浸出10 d后,矿物表面依旧比较光滑;SR-XRD的结果表明,元素硫(S0)、黄钾铁矾和砷酸铁在生物浸出第4 d生成,并随时间延长逐渐累积,最终成为浸出渣中的主要成分。Fe的L边XANES结果表明,在细菌作用下矿物表面逐渐被Fe(Ⅲ)浸出产物覆盖;As的K边XANES结果表明,浸出渣中砷的价态包括As(-Ⅰ), As(Ⅲ)和As(Ⅴ),拟合结果表明,经过10 d的生物浸出,砷黄铁矿、雌黄(As2S3)和砷酸铁在矿渣中所占的比例分别为18.6%, 23.5%和57.9%,化学浸出10 d后,矿渣中除未溶解的砷黄铁矿外,仅有少量砷酸铁(6.2%)形成;S的K边XANES拟合结果表明,经过10 d的生物浸出,砷黄铁矿、 S0、硫代硫酸盐、施氏矿物和黄钾铁矾在矿渣中所占的比例分别为15.3%, 23.7%, 3.5%, 11.3%和46.2%,而在化学浸出10 d后的矿渣中,仅拟合到少量S0(7.8%)。基于上述结果可以得出,铁、砷、硫在砷黄铁矿生物作用下的形态转化过程分别为:Fe(Ⅱ)-Fe(Ⅲ), As(-Ⅰ)-As(Ⅲ)-As(Ⅴ), S-→S0→S2O■→SO■。结合溶液中的浸出参数发现,随着S0、黄钾铁矾、砷酸铁和雌黄的大量累积,砷黄铁矿的生物浸出严重受阻。硫代硫酸盐的生成表明砷黄铁矿的溶解途径与黄铁矿相似。

Fe,As and S Speciation Transformation During Arsenopyrite Bioleaching Based on Spectral Analysis Technology

In the present study, the bioleaching of arsenopyrite by the moderately thermoacidophilic strain Sulfobacillus thermosulfidooxidans YN-22 was investigated based on iron, arsenic, and sulfur speciation analysis by synchrotron radiation As/S K-, and Fe L-edge X-ray absorption near edge structure(XANES) spectroscopy, X-ray diffraction(SR-XRD), accompanied by scanning electron microscopy(SEM), Fourier transform infrared spectroscopy(FTIR), andinductively coupled plasma-atomic emission spectroscopy(ICP-AES) with the determination of the leaching parameters. The results showed that the presence of bacteria significantly promoted the dissolution of arsenopyrite, and dissolved As and Fe in the bioleaching solutions mainly existed as As(Ⅴ) and Fe3+, while were mainly As(Ⅲ) and Fe2+in the chemical leaching. Extracellular polymeric substances(EPS) plays a critical role in the interactions between bacteria and minerals during bioleaching, and the FTIR analysis of the EPS showed that the contents of protein and polysaccharides of the adhered cells were higher than those of the free cells. Results of SEM showed that the surface of the arsenopyrite was gradually corroded, and some secondary products were formed during bioleaching, while for the sterile control experiment, the mineral surface was only slightly corroded, and only a few products were found after 10 days of chemical leaching. The results of SR-XRD showed that elemental sulfur(S0), jarosite and ferric arsenate were detected after day 4, and gradually developed into the main components of the residues in the bioleaching experiment. Fe L-edge XANES analysis showed that during the bioleaching of arsenopyrite by Sulfobacillus thermosulfidooxidans, the Fe(Ⅱ) species was gradually converted to Fe(Ⅲ) species with time. As K-edge XANES analysis showed that valences of arsenic in the bioleached residues included As(-Ⅰ), As(Ⅲ) and As(Ⅴ), the fitted results of the As K-edge XANES spectra showed that the residue composition of arsenic species for the same leached time(10 days) consisted of 18.6% arsenopyrite, 23.5% orpiment and 57.9% ferric arsenate in the bioleaching assay, and of 93.8% arsenopyrite and 6.2% ferric arsenate in the chemical leaching. The fitted results of the S K-edge XANES spectra showed that after 10 days bioleaching, the residue composition of sulfur species consisted of 15.3% arsenopyrite, 23.7% S0, 3.5% thiosulfate, 11.3% schwertmannite and 46.2% jarosite, while only a small amount of S0(7.8%) was found as the sulfur intermediate at day 10 in the sterile control experiment. Based on these results, it could be concluded that the chemical speciation transformation of iron, arsenic and sulfur were performed in the pathways: Fe(Ⅱ)-Fe(Ⅲ), As(-I)-As(Ⅲ)-As(Ⅴ), and S-→S0→S2O■→SO■, respectively. Based on the observations of leaching behavior, it was found that as a massive accumulation of S0, jarosite, ferric arsenate, and As2S3 occurred the dissolution of arsenopyrite was severely hindered. Moreover, the formation of thiosulfate-like species during bioleaching indicated that arsenopyrite was dissolved in the similar way to that of pyrite.