Different Ionization Modes in Gas Chromatography-Mass Spectrometric Determination of Organochlorine Pesticides and Polychlorinated Biphenyls in Food
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摘要: 对食品中有机氯农药和多氯联苯的气相色谱-质谱联用(GC-MS)分析方法中三种离子化方式，电子轰击电离(EI)、正化学电离(PCI)和负化学电离(NCI)进行了总结和比较。PCI-MS/MS方法和EI-MS/MS方法都有很高的选择性和较高的灵敏度；PCI方法在分析含硝基、羰基等基团的化合物时有明显优势，EI则在分析狄氏剂、异狄氏剂、硫丹及其代谢物时比PCI表现稍好，而NCI-MS的灵敏度最高，但抗干扰能力稍弱，且不适合分析滴滴涕类和多氯联苯类化合物。在食品安全分析中，三种质谱方法的准确性好，精密度高，检测限较低，都能够满足食品中农残检测的要求，在日常检测工作中可互为补充和替代。同时指出，GC在有机氯化合物分析中仍表现出明显的优越性；常规的GC-MS尤其在EI电离模式下，易受到基质干扰而使谱图变得复杂；新型离子化方式包括高选择性化学电离技术的应用，将是食品安全中GC-MS联用分析的发展方向之一。Abstract: Different modes of electron impact (EI), positive chemical ionization (PCI) and negative chemical ionization (NCI) in Gas Chromatography-Mass Spectrometry (GC-MS) determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in food are summarized and compared in this paper. Both PCI-MS/MS and EI-MS/MS have high selectivity and sensitivity. PCI-MS/MS has obvious advantages in the analysis of compounds containing nitro or carbonyl groups, while EI-MS/MS has slightly better performance when dealing with dieldrin, endrin, endosulfan and its metabolites. NCI-MS has the highest sensitivity, but weaker anti-interference ability, and is not suitable for the analysis of DDTs and PCBs. In summary, these three mass spectrometry methods, which are complementary and alternative to the routine analysis, can satisfy the requirements of pesticide residue analysis in food by providing good accuracy, good precision and low detection limits.Also it points out that Gas Chromatography showed a superiority in organochlorine compound analysis, but for traditional GC-MS, especially in the EI ionization mode, the spectrum is more complicated because of matrix interference. New ionization modes including the highly selective chemical ionization, will be one of future developments and trends of Gas Chromatography applications in the field of food safety analysis.
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关于铝土矿成矿物质来源研究，以往多用含矿层与下伏地层中化学成分、稀土、微量元素、氧同位素、锆石等副矿物特征进行对比分析[1-3]。近年来随着锆石原位微区定年技术激光剥蚀-多接收器电感耦合等离子体质谱(LA-MC-ICP-MS)及SHRIMP等高精度分析技术的发展和完善，碎屑锆石U-Pb年代学为示踪沉积物源区提供了可靠的技术手段[4]，也为沉积矿床成矿物质来源示踪提供了新的方法。
石炭纪是全球重要的铝土矿成矿期，其中90%以上的石炭纪铝土矿主要产于我国[5]。我国石炭纪铝土矿主要分布在华北地台和扬子地台，其中位于扬子地台西南部的黔中-渝南铝土矿带是石炭纪重要的成矿带之一。该成矿带内自南向北出露有早石炭世九架炉组(C1jj)和晚石炭世大竹园组(C2d)两套含矿岩系[6]，而著名的大竹园铝土矿就赋存于大竹园组中。目前，关于大竹园铝土矿的成矿物质来源问题，前人通过含矿层与下伏地层中岩石地球化学对比研究，认为成矿物源主要来自韩家店群(S1hj)[7]。本文通过对大竹园铝土矿中的铝土岩的碎屑锆石年代学研究，为铝土矿的成矿物质来源提供新的依据，并追溯成矿母岩的物质源区，探讨铝土矿成矿作用。
1. 区域地质特征
黔中-渝南铝土矿带位于扬子地台西南部，呈北北东向展布，延长约370 km，自南向北依次包括修文、息烽、遵义、正安和道真五个铝土矿带[3, 8]。大竹园铝土矿位于道真铝土矿带的东段，是贵州省地矿局106地质大队于上世纪90年代初发现的一大型铝土矿。目前，对大竹园铝土矿的地质概况、成矿时代、成因类型、成矿物质来源、形成的气候环境等一系列问题进行了不同程度的研究，认为晚石炭世黔中-渝南一带位于靠近赤道的湿热气候区，沉积基底——韩家店群(S1hj)泥、页岩，经风化、搬运，沉积在低洼滨海-沼泽区，再经后期成矿-改造-成熟-保存，最终形成沉积型铝土矿[6-13]。但是关于韩家店群的沉积物质源前人并未开展研究。
大竹园组(C2d)分布于贵州遵义以北的桐梓、湄潭、绥阳、凤冈、务川、正安、道真、习水及四川南川、武隆、彭水等地，其下伏地层主要是下志留统韩家店群。该组厚度较小，一般4~8 m，最厚19 m，由北向南厚度逐渐减薄。岩性变化较大，可分为两个岩性段： 下段为黏土岩－铁质岩段，一般厚1～5 m，主要岩性为绿泥石黏土岩、绿泥石岩、铁质黏土岩、伊利石黏土岩等，岩石常具碎屑结构，不显层理，其中普遍可见植物化石碎片。上段为铝质岩段，一般厚2～6 m，主要岩性为铝土矿、铝土质黏土岩和黏土岩，时夹炭质黏土岩和煤，均不显层理。上覆地层为下二叠统梁山组炭质页岩和栖霞组含炭质条带和隧石条带、团块的石灰岩[10]。
大竹园矿区内出露最老的地层为下志留统韩家店群(S1hj)，之上不整合覆盖上石炭统黄龙组石灰岩(C2hl)和大竹园组(C2d)。大竹园组被中二叠统梁山组炭质页岩(P2l)和栖霞组石灰岩(P2q)覆盖。矿区内还出露有下三叠统夜郎组(T1y)、茅草铺组(T1m)及第四系(图 1)。铝土矿矿体分布于栗园向斜北段两翼的上石炭统大竹园组中，呈层状、似层状产出，产状与地层产状基本一致，厚0~13.2 m。以栗园向斜轴线为界，分为两个矿段，东部位白岩塘矿段，西部为木海坨矿段。
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图 1 大竹园铝土矿区地质简图Figure 1. Geological map of the Dazhuyuan bauxite deposit,Northern Guizhou2. 样品特征及定年分析
2.1 样品采集
样品WDK322采自大竹园铝土矿栗园向斜东翼的QJ964号浅井2.5~3.0 m处(图 2)，为大竹园组铝土岩，样品呈褐黄色、半土状，下伏地层为土状或半土状铝土矿，上覆地层为二叠统梁山组(P1l)。
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图 2 样品采集剖面图Figure 2. Profile image of the shallow well QJ964,showing the distribution of sample2.2 样品定年分析
样品的测试工作是在中国地质科学院矿产资源研究所MC-ICP-MS实验室完成，所用仪器为Finnigan Neptune型MC-ICP-MS及Newwave UP213激光剥蚀系统。实验中激光剥蚀斑束直径为25 μm，频率为10 Hz，能量密度为2.5 J/cm2，以He
为载气。锆石年龄谐和图用Isoplot 3.0程序完成，测试数据误差为1σ。对于年轻锆石(< 800 Ma)采用206Pb/238Pb年龄，而对于较老锆石(>800 Ma)采用207Pb/206Pb年龄。详细的实验测试过程参见侯可军等(2009)[14]。
3. 碎屑锆石U-Pb测年结果
对样品WDK322进行了87个测试点分析，获得了84个谐和年龄(表 1)。所测锆石粒径部分在80~150 μm之间，部分在150~200 μm之间，Th/U比值介于0.16~5.55，除了个别锆石的Th/U比值小于0.4外，其余大部分均大于0.4。
表 1 大竹园铝土岩的LA-MC-ICP-MS碎屑锆石的U-Pb测试结果Table 1. Detrital zircon U-Pb dating results of aluminous from the Dazhuyuan bauxite deposit点号 w(Pb)/(μg·g-1) 
207Pb/206Pb 207Pb/235U 206Pb/238U 207Pb/206Pb 207Pb/235U 206Pb/238U 比值 1σ 比值 1σ 比值 1σ 年龄/Ma 1σ 年龄/Ma 1σ 年龄/Ma 1σ DZY-1 260 1.6 0.084000 0.001007 2.260308 0.040370 0.195187 0.002734 1292 24 1200 13 1149 15 DZY-2 207 2.6 0.080895 0.000909 1.844509 0.028984 0.165561 0.002143 1220 22 1061 10 988 12 DZY-3 295 1.9 0.067737 0.000867 1.145260 0.020446 0.122606 0.001541 861 26 775 10 746 9 DZY-4 152 1.9 0.075818 0.000965 1.618283 0.026876 0.155245 0.002223 1100 26 977 10 930 12 DZY-6 94 0.6 0.069599 0.000884 1.202590 0.019919 0.125385 0.001472 917 21 802 9 761 8 DZY-7 95 0.8 0.067264 0.001133 1.103268 0.024196 0.118768 0.001353 856 35 755 12 723 8 DZY-8 272 0.9 0.199825 0.000799 14.228608 0.156894 0.516527 0.005492 2825 6 2765 10 2684 23 DZY-10 132 0.2 0.075508 0.001289 1.621806 0.032441 0.155825 0.001737 1083 35 979 13 934 10 DZY-11 77 0.9 0.071191 0.001545 1.198367 0.031455 0.122166 0.002030 963 44 800 15 743 12 DZY-13 57 0.4 0.073617 0.000615 1.491785 0.019922 0.146894 0.001507 1031 17 927 8 884 8 DZY-14 489 2.9 0.058975 0.000583 0.673348 0.008737 0.082827 0.000808 565 20 523 5 513 5 DZY-15 102 0.6 0.065508 0.000726 1.058949 0.016945 0.117107 0.001221 791 22 733 8 714 7 DZY-16 167 0.9 0.070580 0.000562 1.209501 0.014258 0.124310 0.001258 946 16 805 7 755 7 DZY-18 181 1.0 0.077919 0.000694 1.907179 0.027073 0.177389 0.002083 1146 17 1084 9 1053 11 DZY-19 166 0.8 0.072197 0.000574 1.394698 0.018628 0.140011 0.001628 991 17 887 8 845 9 DZY-20 47 0.8 0.109638 0.001580 4.390446 0.092671 0.290256 0.004961 1794 26 1711 17 1643 25 DZY-21 195 1.3 0.072962 0.000702 1.480085 0.022914 0.146963 0.001822 1013 19 922 9 884 10 DZY-22 89 0.6 0.068301 0.000496 1.311950 0.016046 0.139231 0.001509 877 16 851 7 840 9 DZY-23 252 1.1 0.084394 0.000544 2.332440 0.027475 0.200323 0.002152 1302 7 1222 8 1177 12 DZY-24 240 1.0 0.073769 0.000432 1.574996 0.016611 0.154795 0.001495 1035 11 960 7 928 8 DZY-26 86 0.2 0.077246 0.000504 1.868713 0.021403 0.175345 0.001706 1128 13 1070 8 1041 9 DZY-27 289 1.5 0.161607 0.000903 9.217397 0.108260 0.413519 0.004689 2473 9 2360 11 2231 21 DZY-28 59 0.4 0.076754 0.001545 1.549058 0.036503 0.146472 0.002367 1115 39 950 15 881 13 DZY-29 129 1.2 0.075106 0.000782 1.587368 0.023608 0.153283 0.001769 1072 21 965 9 919 10 DZY-32 20 0.5 0.064730 0.001126 0.873646 0.017577 0.097982 0.001314 765 236 638 10 603 8 DZY-34 76 0.8 0.080735 0.000911 2.014581 0.031292 0.180936 0.002033 1217 22 1120 11 1072 11 DZY-35 174 0.6 0.074616 0.000576 1.598876 0.017891 0.155407 0.001463 1057 16 970 7 931 8 DZY-36 1565 2.8 0.164166 0.001958 9.776507 0.169227 0.431454 0.004886 2499 20 2414 16 2312 22 DZY-37 356 1.7 0.073101 0.001031 1.480363 0.030063 0.146534 0.001611 1017 34 922 12 882 9 DZY-38 340 0.6 0.073916 0.000478 1.623477 0.018845 0.159216 0.001653 1039 13 979 7 952 9 DZY-40 262 0.8 0.060733 0.000509 0.703043 0.010105 0.083888 0.001025 632 21 541 6 519 6 DZY-41 248 1.1 0.076908 0.000771 1.630058 0.026862 0.153534 0.001875 1120 20 982 10 921 10 DZY-43 620 2.1 0.075872 0.000435 1.709532 0.018790 0.163368 0.001617 1092 12 1012 7 975 9 DZY-44 6 2.3 0.056663 0.000929 0.621263 0.011361 0.079672 0.000854 480 40 491 7 494 5 DZY-45 711 1.0 0.167249 0.000780 10.084893 0.097107 0.437307 0.003892 2531 7 2443 9 2339 17 DZY-46 164 0.7 0.075159 0.000706 1.666796 0.022720 0.160912 0.001766 1072 23 996 9 962 10 DZY-47 182 0.7 0.081148 0.000778 2.107716 0.027541 0.188494 0.001907 1225 19 1151 9 1113 10 DZY-48 111 0.9 0.067859 0.000800 1.211085 0.019137 0.129521 0.001476 865 25 806 9 785 8 DZY-49 249 2.1 0.066580 0.000745 1.141188 0.018037 0.124400 0.001434 833 176 773 9 756 8 DZY-51 13 0.2 0.059551 0.001950 0.666104 0.020931 0.081475 0.001737 587 68 518 13 505 10 DZY-52 67 0.8 0.080306 0.001035 1.990364 0.034553 0.180070 0.002586 1206 21 1112 12 1067 14 DZY-53 14 1.2 0.068711 0.000902 1.340879 0.022225 0.141664 0.001613 900 27 864 10 854 9 DZY-54 94 0.2 0.068099 0.000633 1.198079 0.015587 0.127665 0.001269 872 23 800 7 775 7 DZY-57 155 1.7 0.128224 0.001170 6.397771 0.106391 0.361751 0.004915 2074 21 2032 15 1990 23 DZY-58 42 0.2 0.076858 0.000527 1.826559 0.023355 0.172387 0.001936 1118 13 1055 8 1025 11 DZY-59 200 1.3 0.077241 0.000494 1.911900 0.023192 0.179511 0.001878 1128 13 1085 8 1064 10 DZY-60 45 0.7 0.070234 0.001422 1.554264 0.036972 0.160851 0.002580 1000 41 952 15 962 14 DZY-61 228 0.8 0.107760 0.000405 3.849682 0.042295 0.259082 0.002703 1762 7 1603 9 1485 14 DZY-62 35 0.5 0.064992 0.000571 0.933599 0.012350 0.104162 0.001009 774 19 670 6 639 6 DZY-64 5 0.5 0.060956 0.001332 0.725323 0.017349 0.086403 0.001169 639 46 554 10 534 7 DZY-65 82 1.5 0.077967 0.000946 1.702053 0.027783 0.158373 0.001822 1146 24 1009 10 948 10 DZY-67 18 1.7 0.062302 0.001436 1.047273 0.026834 0.122294 0.001959 683 48 728 13 744 11 DZY-68 18 0.2 0.063945 0.000886 0.849563 0.014983 0.096315 0.000938 739 30 624 8 593 6 DZY-69 84 1.6 0.060050 0.000955 0.743041 0.015131 0.089712 0.001058 606 33 564 9 554 6 DZY-70 86 1.0 0.059172 0.000537 0.614267 0.008920 0.075280 0.000823 572 20 486 6 468 5 DZY-71 17 0.6 0.076427 0.001184 1.745434 0.032973 0.165859 0.002305 1106 30 1025 12 989 13 DZY-72 78 1.0 0.072534 0.000655 1.537240 0.019483 0.153755 0.001480 1011 19 945 8 922 8 DZY-73 190 0.7 0.104721 0.000314 4.382576 0.039884 0.303540 0.002651 1710 6 1709 8 1709 13 DZY-74 3 0.6 0.063917 0.001518 0.857877 0.022722 0.097468 0.001521 739 50 629 12 600 9 DZY-75 40 1.4 0.074713 0.000967 1.635913 0.029262 0.158835 0.002112 1061 26 984 11 950 12 DZY-76 71 0.8 0.065345 0.000431 1.084570 0.011616 0.120359 0.001073 787 13 746 6 733 6 DZY-77 124 1.4 0.072840 0.000416 1.664695 0.017832 0.165692 0.001549 1009 11 995 7 988 9 DZY-78 176 0.6 0.161478 0.000544 9.525714 0.096541 0.427694 0.004288 2472 6 2390 9 2295 19 DZY-80 26 0.9 0.077469 0.001274 1.843364 0.042371 0.172400 0.002689 1133 32 1061 15 1025 15 DZY-81 229 5.6 0.074130 0.000618 1.619865 0.021603 0.158434 0.001809 1056 17 978 8 948 10 DZY-82 48 0.4 0.061894 0.000417 0.871391 0.009967 0.102080 0.001023 672 13 636 5 627 6 DZY-83 144 0.8 0.070845 0.000381 1.544302 0.015089 0.158097 0.001451 954 11 948 6 946 8 DZY-84 208 0.6 0.072324 0.000283 1.619648 0.014881 0.162346 0.001431 994 8 978 6 970 8 DZY-85 165 0.7 0.071079 0.000363 1.552787 0.016050 0.158316 0.001430 961 10 952 6 947 8 DZY-86 135 0.3 0.070318 0.000412 1.391468 0.016968 0.143412 0.001530 939 12 885 7 864 9 DZY-87 190 0.8 0.067188 0.000375 1.214271 0.013071 0.131028 0.001289 843 12 807 6 794 7 DZY-88 385 1.4 0.079307 0.000350 2.177104 0.019869 0.198968 0.001651 1189 8 1174 6 1170 9 DZY-89 342 0.4 0.130696 0.000425 6.497753 0.058526 0.360360 0.003174 2107 6 2046 8 1984 15 DZY-90 2878 2.0 0.163223 0.000562 10.287660 0.098524 0.456865 0.004321 2500 6 2461 9 2426 19 DZY-91 298 0.6 0.081009 0.000424 2.065544 0.022167 0.184787 0.001728 1222 9 1137 7 1093 9 DZY-92 64 0.5 0.074309 0.000623 1.715894 0.020356 0.167448 0.001572 1050 50 1014 8 998 9 DZY-93 179 1.1 0.059593 0.000576 0.702914 0.008460 0.085555 0.000726 587 20 541 5 529 4 DZY-94 141 1.0 0.063734 0.000536 0.919265 0.009410 0.104686 0.000872 731 17 662 5 642 5 DZY-95 61 0.3 0.063679 0.000590 0.947262 0.011796 0.107828 0.000911 731 14 677 6 660 5 DZY-96 65 0.8 0.075073 0.000871 1.609097 0.022041 0.155585 0.001663 1072 19 974 9 932 9 DZY-97 133 1.6 0.059992 0.001060 0.732299 0.015136 0.088467 0.000900 611 39 558 9 546 5 DZY-98 81 0.5 0.056545 0.000514 0.559911 0.007414 0.071780 0.000676 472 20 451 5 447 4 DZY-99 125 1.4 0.065139 0.000657 1.174023 0.015973 0.130782 0.001342 789 17 789 7 792 8 DZY-100 133 1.0 0.189506 0.001124 13.606214 0.248462 0.520381 0.008834 2739 10 2723 17 2701 37 测定结果显示(表 1)，锆石年龄分布在447~2825 Ma之间，即从晚奥陶世到太古代。根据样品年龄及频率分布特征大致可以划分为四组： ① 207Pb/206Pb年龄集中在2474~2531 Ma(n=5)，如测试点27、89、90(图 3)，锆石呈长条状，均被磨圆，环带结构明显，Th/U=0.62~2.76，显示岩浆锆石特征。 ② 207Pb/206Pb年龄集中在900~1302 Ma，峰值年龄为(1075±30) Ma(n=41)，如测试点96和75等(图 3)，锆石有长条状、短柱状，多被磨圆，多环带结构明显，除了个别Th/U比值< 0.4外，大多大于0.4，多数显示岩浆锆石特征。 ③ 206Pb/238U年龄集中在714~794 Ma，峰值年龄为(755±16) Ma(n=13)，锆石颗粒大小不均一，个别未被磨圆，如测试点49(图 3)，大部分为岩浆锆石； ④ 206Pb/238U年龄集中在505~660 Ma，峰值年龄为(576±6) Ma(n=14)，锆石颗粒普遍较小，有不同程度的磨圆化，个别呈椭圆状，如51号测试点(图 3)。51号测试点(503 Ma)、68号测试点(593 Ma)的Th/U比值小于0.4。样品中最小的年龄为447 Ma、468 Ma。
4. 铝土矿物源区示踪及对成矿的指示意义
关于大竹园组的沉积时代，刘平(1996)[10]按地层产出层位和孢子化石认为属上石炭统马平阶。本文对大竹园组铝土岩的碎屑锆石测年，显示最小的锆石年龄为447 Ma，多数集中在505~1302 Ma之间(图 4)，并未记录志留纪-早石炭世的岩浆事件。这可能是因为区域上并未有志留纪-早石炭世的岩浆活动，也可能说明碎屑锆石来自早志留世沉积地层，即为再循环锆石。
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图 4 (a)—锆石的U-Pb年龄谐和图,(b)—锆石的U-Pb加权平均年龄图Figure 4. (a)—Concordia diagram of zircon U-Pb isotopes,(b)—Weight mean diagram of zircon U-Pb age近年来对华南新元古代-古生代的变质岩系及沉积岩进行了较多的碎屑锆石年代学研究，积累了一批可靠的年代学资料，为大竹园组铝土岩的物质来源提供了丰富的信息。新元古代-寒武纪，扬子地块鄂东发育莲沱组(Pt3l)，其碎屑锆石年龄具有约2489 Ma、约2045 Ma和785~893 Ma三期峰值年龄[15-16](图 5)。华夏地块出露的潭溪片麻岩[17]和桂东寒武纪沉积岩的碎屑锆石具有约2500 Ma、约1000 Ma的峰值年龄[18](图 5)，华夏地块变质岩系中的碎屑锆石同样具有一致的年龄峰值[19-22]。可见，自成冰期Rodinia超大陆裂解[23]至寒武纪初期扬子和华夏地块为独立的块体，独自供给沉积物质。
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早古生界碎屑锆石年龄资料显示，华夏地块赣南爵山沟组(O1j)[23]和中扬子崇阳茅山组(S1m)碎屑锆石[15]具有相似的年龄频谱，均有约2500 Ma和500~1200 Ma的年龄段(图 5)，暗示早奥陶世华夏和扬子地块已成统一陆块。这与扬子地块至珠江盆地奥陶纪生物相和岩相呈连续渐变一致[24]，与晚奥陶世华夏和扬子地块构造开始反转、沉积格局开始调整一致[25]，也与华夏地块发育约460 Ma的后碰撞花岗岩一致[26-27]。区域上泥盆系的碎屑锆石年龄显示物源具有多样性，赣南跳马涧组(D2t)[23]和鄂东南曾定高家边组(S1g)[15]的碎屑锆石具有相似的年龄频谱，与华南奥陶纪-志留纪地层中的碎屑锆石相比明显记录了430~450 Ma的岩浆事件。而四川桂溪镇平驿铺组(D1p，具有化石依据)碎屑锆石年龄集中在850~1000 Ma、680~800 Ma、500~650 Ma三个年龄区间，最小的锆石年龄为507 Ma(图 5)[28]。桂北莲花山组(D1l)石英砂岩的碎屑锆石显示约1700 Ma、约900 Ma和84~104 Ma的年龄段。物源的多样性与各自局部地区的岩浆-变质事件息息相关。如华南400~500 Ma的岩浆岩主要分布在华夏地块和扬子地块北缘，华夏地块内的加里东期花岗岩广泛分布于武夷山和云开大山地区，时代集中在400~470 Ma[27, 29-30]。扬子地块北缘也发育428~460 Ma的岩浆岩[31-32]，云开大山地区普遍受燕山期-印支期热改造事件的影响[18, 20]。
黔北晚石炭世大竹园组铝土岩的碎屑锆石与爵山沟组(O1j)、茅山组(S1m)和平驿铺组(D1p)碎屑锆石具有相似的年龄频谱。大竹园矿区含矿岩系下伏地层为韩家店群(S1hj)，锆石均被磨圆，显示远距离搬运的特征，碎屑锆石可能为下伏地层中的再循环锆石，韩家店群(S1hj)为铝土矿的成矿母岩。加里东造山事件使扬子和华夏陆块最终拼合成统一的华南陆块，沉积岩具有统一的物源区。志留纪，华夏地块除了在广西钦州-防城一带有沉积外，大部分地区发生褶皱及隆升成陆缺失沉积；扬子地块成为隆后盆地，晚奥陶世-早志留世大部分为局限浅海环境，沉积褐色炭质页岩以及粉砂岩[25, 33]，快速隆升、被剥蚀的华夏地块为扬子地块上稳定展布的下志留统提供了大量的沉积物质，为铝土矿及新近发现的钨和锂[35]等的形成提供了物质基础。
5. 结语
大竹园铝土矿中铝土岩的碎屑锆石年代学资料为铝土矿的成矿物质来源提供了新的依据，证实其成矿母岩为下伏韩家店群(S1hj)，也为成矿母岩的物质来源提供了可靠信息。碎屑锆石测年技术为沉积型矿床成矿物质来源的研究提供了新的技术手段。
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