http://chineseinput.net/에서 pinyin(병음)방식으로 중국어를 변환할 수 있습니다.
변환된 중국어를 복사하여 사용하시면 됩니다.
김영민(Yeongmin Kim),이인성(Insung Lee),James Farquhar,강지숙(Jisuk Kang),Igor M. Villa,김형범(Hyoungbum Kim) 대한지질학회 2021 대한지질학회 학술대회 Vol.2021 No.10
서울 지역 강수의 다중 황 동위원소(δ<SUP>34</SUP>Ssulfate, Δ<SUP>33</SUP>Ssulfate & Δ <SUP>36</SUP>Ssulfate), 질소 동위원소(δ<SUP>15</SUP>Nnitrate & δ<SUP>18</SUP>Onitrate) 및 스트론튬 동위원소(<SUP>87</SUP>Sr/<SUP>86</SUP>Sr)의 조성을 분석하였다. δ<SUP>34</SUP>Ssulfate 값은 1.9~14.6‰ (with a median of 4.7‰)의 범위를 보이며, δ<SUP>15</SUP>Nnitrate 값은 -2.0~13.3‰ (with a median of 1.0‰)의 범위를 보인다. 이러한 값은 화석연료의 사용이 황과 질소의 주요 공급원임을 지시하며, DMS 및 해수기원 황산염 등의 자연발생 공급원의 기여 역시 있었음을 확인할 수 있다. 겨울철에 높은 값을 보이는 δ<SUP>34</SUP>Ssulfate 및 δ<SUP>15</SUP>Nnitrate 값은 중국 지역에서 가정용 난방을 위해 사용되는 석탄의 사용 증가와 연관되어 있는 것으로 여겨진다. δ<SUP>18</SUP>Onitrate 값은 계절 변화를 보이며, 이는 NOx 산화 과정의 변화에 의한 것으로 생각된다. <SUP>87</SUP>Sr/<SUP>86</SUP>Sr 비는 0.70988~0.71487 (with a median of 0.71073)의 범위를 보이며, 최소 세 가지 공급원(규산염질 입자, 탄산염질 입자 및 인간활동 기원 물질)의 영향이 있었음을 지시한다.
Sulfur versus Iron Oxidation in an Iron−Thiolate Model Complex
McDonald, Aidan R.,Bukowski, Michael R.,Farquhar, Erik R.,Jackson, Timothy A.,Koehntop, Kevin D.,Seo, Mi Sook,De Hont, Raymond F.,Stubna, Audria,Halfen, Jason A.,Mü,nck, Eckard,Nam, Wonwoo,Que, American Chemical Society 2010 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.132 No.48
<P>In the absence of base, the reaction of [Fe<SUP>II</SUP>(TMCS)]PF<SUB>6</SUB> (<B>1</B>, TMCS = 1-(2-mercaptoethyl)-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane) with peracid in methanol at −20 °C did not yield the oxoiron(IV) complex (<B>2</B>, [Fe<SUP>IV</SUP>(O)(TMCS)]PF<SUB>6</SUB>), as previously observed in the presence of strong base (KO<SUP>t</SUP>Bu). Instead, the addition of 1 equiv of peracid resulted in 50% consumption of <B>1</B>. The addition of a second equivalent of peracid resulted in the complete consumption of <B>1</B> and the formation of a new species <B>3</B>, as monitored by UV−vis, ESI-MS, and Mössbauer spectroscopies. ESI-MS showed <B>3</B> to be formulated as [Fe<SUP>II</SUP>(TMCS) + 2O]<SUP>+</SUP>, while EXAFS analysis suggested that <B>3</B> was an O-bound iron(II)−sulfinate complex (Fe−O = 1.95 Å, Fe−S = 3.26 Å). The addition of a third equivalent of peracid resulted in the formation of yet another compound, <B>4</B>, which showed electronic absorption properties typical of an oxoiron(IV) species. Mössbauer spectroscopy confirmed <B>4</B> to be a novel iron(IV) compound, different from <B>2</B>, and EXAFS (Fe?O = 1.64 Å) and resonance Raman (ν<SUB>Fe?O</SUB> = 831 cm<SUP>−1</SUP>) showed that indeed an oxoiron(IV) unit had been generated in <B>4</B>. Furthermore, both infrared and Raman spectroscopy gave indications that <B>4</B> contains a metal-bound sulfinate moiety (ν<SUB>s</SUB>(SO<SUB>2</SUB>) ≈ 1000 cm <SUP>−1</SUP>, ν<SUB>as</SUB>(SO<SUB>2</SUB>) ≈ 1150 cm <SUP>−1</SUP>). Investigations into the reactivity of <B>1</B> and <B>2</B> toward H<SUP>+</SUP> and oxygen atom transfer reagents have led to a mechanism for sulfur oxidation in which <B>2</B> could form even in the absence of base but is rapidly protonated to yield an oxoiron(IV) species with an uncoordinated thiol moiety that acts as both oxidant and substrate in the conversion of <B>2</B> to <B>3</B>.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2010/jacsat.2010.132.issue-48/ja1045428/production/images/medium/ja-2010-045428_0015.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja1045428'>ACS Electronic Supporting Info</A></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja1045428'>ACS Electronic Supporting Info</A></P>
Kim, Yeongmin,Lee, Insung,Seo, Jung Hun,Lee, Jong Ik,Farquhar, James Elsevier 2017 Chemical geology Vol.466 No.-
<P><B>Abstract</B></P> <P>Oxygen (<SUP>16</SUP>O, <SUP>17</SUP>O and <SUP>18</SUP>O) and sulfur (<SUP>32</SUP>S, <SUP>33</SUP>S, <SUP>34</SUP>S and <SUP>36</SUP>S) isotope ratios of and major ion (Na<SUP>+</SUP>, Ca<SUP>2+</SUP>, Cl<SUP>−</SUP>, NO<SUB>3</SUB> <SUP>−</SUP> and SO<SUB>4</SUB> <SUP>2−</SUP>) concentrations in lakes, ponds and creeks from Deception Island, Antarctic Peninsula were analyzed to study the sources of sulfate, its oxidation, and the surficial processes of the dissolved sulfate. The positive relationship between the δ<SUP>34</SUP>S<SUB>sulfate</SUB> (8.1‰ to 17.3‰) and the Cl<SUP>−</SUP>/SO<SUB>4</SUB> <SUP>2−</SUP> molar ratio suggests mixing of sulfate from atmospheric deposition and from oxidation of sulfide minerals. The average sea salt fraction (28%) and δ<SUP>34</SUP>S<SUB>nss</SUB> values (from 5.6‰ to 15.9‰) indicate that a combination of sea salt and marine biogenic sulfide provide the high δ<SUP>34</SUP>S end-member of the dissolved sulfates. The relatively low δ<SUP>18</SUP>O<SUB>sulfate</SUB> (from −4.6‰ to 0.7‰) of Deception Island water suggests a role of local water in the formation of sulfate. Slightly negative but mass-dependent Δ<SUP>17</SUP>O<SUB>sulfate</SUB> values imply that atmospheric oxidation by O<SUB>3</SUB> and H<SUB>2</SUB>O<SUB>2</SUB> are negligible, while these values might suggest a significant role of oxidation by molecular oxygen and OH. The distinctly low δ<SUP>34</SUP>S<SUB>sulfate</SUB> value of two samples (DCW-2 and DCW-3) suggests the input of sulfate from sulfide oxidation. Slight elevation of δ<SUP>34</SUP>S<SUB>sulfate</SUB> values up to 17.3‰ compared to a typical atmospheric value indicates a minimal role for dissimilatory microbial sulfate reduction of Deception Island water and sediments. Both Δ<SUP>33</SUP>S<SUB>sulfate</SUB> and Δ<SUP>36</SUP>S<SUB>sulfate</SUB> values are homogeneous and near zero, implying that the dominant atmospheric oxidation process is tropospheric and that there are minimal to no contributions of stratospheric sulfate to Deception Island water.</P>
Yildirim, N.,Donmez, C.,Kang, J.,Lee, I.,Pirajno, F.,Yildirim, E.,Gunay, K.,Seo, J.H.,Farquhar, J.,Chang, S.W. Elsevier 2016 Ore geology reviews Vol.79 No.-
The Ortaklar VMS deposit is hosted in the Kocali Complex consisting of basalts and deep sea pelagic sediments, which formed by rifting and continental break-up of the southern Neotethyan in Late Triassic. The basalts are of NMORB-type without notable crustal contamination. From the surface to depth, the Ortaklar deposit consists of a gossan zone, a thick massive ore zone and a poorly developed stockwork zone. Primary mineralisation is characterised by distinctive facies including sulphide breccias (proximal), graded beds (distal), stockworks and chimney fragments. Ore mineral abundances decrease in the order of pyrite, magnetite, chalcopyrite, and sphalerite. Two distinct phases of mineralisation, massive magnetite and massive sulphide, are present in the Ortaklar deposit. Textural evidence (e.g., magnetite replacing sulphides) and the spatial relationships with the host rocks indicate that magnetite and sulphide minerals were generated in different stages. The transition from sulphide to magnetite mineralisation is interpreted to relate to variation in H<SUB>2</SUB>S content of ore fluids. The 1st stage massive sulphide ore might have formed by early hydrothermal fluids rich in Fe and H<SUB>2</SUB>S. The 2nd stage massive magnetite might have formed by later neutral hydrothermal fluids rich in Fe but poor in H<SUB>2</SUB>S, replacing the pre-existing sulphide ore. The alteration patterns, mineral paragenesis, lithological features (massive ore-stockwork ore-gossan) of the Ortaklar deposit together with its trace elements, Cu-Pb-Zn-Au-Ag and REE signatures are all consistent with a Cyprus-type VMS system. The δ<SUP>34</SUP>S values in pyrite and chalcopyrite samples range from 2.6 to 5.7%%, indicating that the hydrothermal fluids were associated with sub-seafloor igneous activity, typical of Cyprus-type VMS deposits. However, magnetite formed later than sulphide minerals in the Ortaklar deposit, contrasting with typical Cyprus-type VMS deposits where magnetite generally occurs in lower sections. Consequently, although the Ortaklar deposit generally conforms to Cyprus-type deposits, it is distinguished from them by its late stage and high magnetite concentration. Thus, the Ortaklar deposit is thought to be an exceptional and perhaps unique Cyprus-type VMS deposit.