高分辨质谱+互联网+信息工程技术/地理信息（GIS） 三元融合技术提升农产品质量安全保障能力 130th AOAC INTERNATIONAL Annual Meeting and Exposition  “Facing the Analytical Challenges of Pesticide Residue Analysis- Unknowns, Difficult Pesticides/Matrices and High Resolution MS” September 21, 2016 Dallas, TX 高分辨质谱+互联网+信息工程技术/地理信息（GIS） 三元融合技术提升农产品质量安全保障能力 High-resolution MS+ Internet +Geographical Information System (GIS) Tri-Element Merged Technologies Improve Quality Assurance Capability (Pesticide residues)of Agricultural Products 高分辨质谱（HRMS）+互联网+GIS三元技术融合提高农产品质量（农药残留）安全保障能力 Guo-Fang Pang Chinese Academy Inspection and Quarantine ciqpang@163.com

①How to realize electronization for pesticide analytical techniques? Foreword With the rapid development of 21st century’s informatization technology, the world has already entered into the internet age and the prospect of pesticide residue analytical technique faces Three Major Challenges: ①How to realize electronization for pesticide analytical techniques? ②How to realize automation for the generation of the report of pesticide residue big data? ③How to realize visualization for pesticide residues risk source tracing? 随着21世纪信息化技术快速发展，世界已进入互联网时代，农药残留检测技术如何发展，面临三大挑战： ①农药残留检测如何实现电子化？ ②农药残留大数据报告生成如何实现自动化？ ③农药残留风险溯源如何实现视频化？

Challenge No.1: How to realize electronization for pesticide residue detection? Solution: Pesticide residue qualitative identification is conducted with electronic references taking place of substantial references, which may realize electronization for pesticide residue qualitative identification. 1 挑战之一：农药残留检测如何实现电子化？ 解决方案：农药残留定性鉴定以电子标准取代实物标准，可以实现农药残留鉴定电子化。

1.1Establishment of HRMS (GC-Q-TOFMS and LC-Q-TOFMS) accurate mass database and spectra library for 1200 world commonly used pesticides, laying a theoretical and methodological foundation for development of non-target detection technology Accurate mass database is used for TOFMS screening and spectra is used for QTOFMS confirmation of target pesticides, which has laid a theoretical and methodological foundation for non-target pesticide residue detection techniques. 用两种HRMS（LC-Q-TOFMS和GC-Q-TOFMS）技术评价了各种不同条件下1200多种农药的质谱特征，建立 了一级和二级精确质量数据库和谱图库

Major elements of electronic identity card for each pesticide 1.2 Electronic references developed for over 1200 pesticides to replace substantial references A unique electronic identity card (electronic identification references) is developed for each of the 1200-plus pesticides, making the identification method of using electronic references to replace the conventional pesticide substantial references as comparison come true and causing the non-target pesticide residue analytical technique to realize a frog-leap development. ①Retention time ②accurate mass of primary adduct ions ③isotope distribution ④isotope abundance ⑤ spectra library Major elements of electronic identity card for each pesticide 为1200多种农药的每一种都建立了自身独有的电子身份证，从而实现了以电子身份证代替传统的实物标准做参比的定性方法，实现了农药残留由靶向检测向非靶向筛查的跨越式发展。

1.3 Development of high throughput and high resolution GC-Q-TOFMS and LC-Q-TOFMS techniques for pesticide residues LC-QTOF 544 Compounds ① 239 pesticides GC-QTOF 722 Compounds ①242 pesticides ②209 PCBs ③271 pesticides Simultaneous determination of 1200 pesticides using both techniques with a single sample preparation Reference materials as comparison have been eliminated and accurate mass is used for identification, thus saving resources, reducing pollutions, improving the analytical speed and satisfying fully the requirements for green development, environmentally-friendliness, cleanliness and high efficiency. 从而建立了一次样品制备，LC-Q-TOFMS一次可检测544种农药；GC-Q-TOFMS可检测722种农药，两项技术共同检测的农药超过1200多种。实现了高速度、高通量、高精度、高可靠性和高度信息化和自动化，也实现了电子化。

Challenge No.2: how to realize automation for the generation of the report of pesticide residue detection big data? Solutions: HRMS+ Internet+Intelligent Analysis tri-element merged technique may realize automatic generation of the big data report of pesticide residues. 2 挑战之二：农药残留检测技术大数据报告生成如何实现自动化 解决方案：HRMS+互联网+智能分析三元融合技术可以实现农药残留大数据报告生成自动化

Where these tons of pesticide big data come from? 2.1 Loop detection conducted by 10 demonstration laboratories with the big data pesticide residues as the source and based on the internet CAIA QHDCIQ Shanghai CIQ Shenzhen CIQ Uni-Star Anhui CIQ Jiangxi CIQ Shandong CIQ Fujian CIQ Ningxia CIQ 10 demonstration laboratories execute a fully-closed operation per the integration of five steps of (1) sampling, (2) preparation, (3) detection, (4) data transmission and (5) data processing. There are quality assurance measures at each key point and there are reliable assurance for the integrity, accuracy and safety of the data. 全国选择10个示范实验室，按五统一规范操作（统一采样、统一制样、统一检测方法、统一格式数据上传，统一格式统计分析报告），封闭运行，保障数据的统一性、完整性、安全性和可靠性。

Distribution of sampling points across the country Demonstration and use of the new technique（2012-2015） 2.2 Area scope for detection:31 provincial capitals/cities directly under the Central Government ( 284 counties and regions) across the country, accounted for 25 percent of the population. Distribution of sampling points across the country ① 638 sampling points ；②146 kinds fruits and vegetables ；③12551 samples. ① 471 sampling points ；②107 kinds fruits and vegetables ；③9817 samples. LC-Q-TOFMS(2012-2015) 7561620 data GC-Q-TOFMS(2013-2015) 6968862 data 2012-2015年对方法效能进行了为期4年的验证，示范范围:全国31省会/直辖市，包括284区县600多个采样点，采集样品22000多批。消费人群占全国人口25%。

采集的样品共计18类146种，占全国果蔬标准名录的80%以上。 2.3 Scope of detection sample variety : 146 fruits and vegetables of 18 categories cover 80% of the catalogue in the national standards, revealing the universal applicability of the method. LC-Q-TOFMS GC-Q-TOFMS Category Samples(quantities） Total Vegetables 8661 1）Brassica vegetables flower Chinese cabbage (74), cabbage (74), broccoli (268), cabbage mustard (40), purple cabbage (25), cauliflower (59) 925 2solanaceous fruit vegetable tomato (621), eggplant (466), sweet pepper (549), pepper (72), cherry tomatoes (66), ginseng fruit (21) 1795 3）edible mushrooms mushroom (362), needle mushroom (35), pleurotus eryngi (7), oyster mushroom (4) 423 4）Fruiting Vegetables cucumber (591), marrow (289), white gourd (200), bitter gourd (76), bottle gourd (6), pumpkin (73), smooth loofah (32), chayote (18), winter squash (2) 1287 5）Leafy Vegetables celery (537), spinach (537), bok choy (197), garden chrysanthemum (203), lettuce (418), Chinese cabbage (350), green vegetable (144), amaranth (36), mustard greens (37), sweet potato leaves (23), boxthorn leaves (7), water spinach (84), baby Chinese cabbage (15), leaf lettuce (112), rape greens (78), Indian spinach (22), milk cabbage (1), endive (50), fennel leaf (13), celtuce (16), gynandropsis gynandra (1), rooted mustard sprout (8), spring vegetable (19), Chinese flat cabbage (2), tuberous-rooted mustard (2), taro flower (1) 2685 6）Legume Vegetables common bean (490)，cowpea (23)，garden pea (3)，sword bean (2)，podded pea (8)，soya bean (young pods) (4) 530 7）Bulb Vegetables Chinese chive (351)，green onion (41)，garlic (23)，garlic scape (58)，garlic bolt (9)，onion (33)，leek flower (3)，yellow garlic sprout (1) 519 8）Stalk Vegetables asparagus (14) 14 9）Root and tuber vegetables carrot (166)，taro (13)，potato (105)，Chinese radish (77)，yacon (5)，purple potato (19)，sweet potato (7)，ginger (18)，yam (17) 427 10）Aquatic vegetables water bamboo (6)，watercress (13)，lotus rhizome (19)，water chestnut (2)，chinese celery (1) 41 11）Sprouts Vegetables mung bean sprouts (4)，Chinese toon sprouts (1)，toothed burclover (3) 8 12）others lily (6)，bamboo shoots (1) 7 Fruits 3826 1）Citrus fruits sweet orange (284)，mandarin orange (147)，pummelo (24)，lemon (23)，kumquat (9)，tangerine (3) 490 2）Melon Fruits watermelon (237)，hami melon (32)，muskmelon (38)，honeydew (50) 357 3）Berries and other Small Fruits kiwifruit (154)，grape (411)，strawberry (114)，passion fruit (7)，concord grape (10)，blueberry (2)，mulberry (1) 699 4）Pome fruits apple (628)，pear (574)，loquat (11)，mayhaw (13) 1226 5）Assorted tropical and sub-tropical fruits pineapple (92)，banana(99)，dragon fruit (136)，litchi (46)，mango (62)，carambola (33)，mangosteen (32)，guava (23)，chinese persimmon (8)，papaya (13)，longan (8)，pomegranate (4)，syzygium samarangense (1)，red bayberry (1)，durian (1) 559 6）Stone fruits peach (310)，date (50)，apricot (24)，plum (102)，cherry (6)，nectarine (3) 495 Grains 11 1）Dry Grain maize (11) Seasoner 53 1）Leaf spices coriandre (51)，mint (2) Category Samples(quantities） Total Vegetables 6387 1）Brassica vegetables flower Chinese cabbage (93), cabbage (293), broccoli (210), cabbage mustard (24), purple cabbage (41), cauliflower (43) 704 2solanaceous fruit vegetable tomato (433), eggplant (363), sweet pepper (369), pepper (79), cherry tomatoes (65), ginseng fruit (22) 1343 3）edible mushrooms mushroom (210), needle mushroom (33), pleurotus eryngi (36), oyster mushroom (13) 327 4）Fruiting Vegetables cucumber (434), marrow (202), white gourd (39), bitter gourd (125), bottle gourd (76), pumpkin (73), smooth loofah (39), chayote (3), winter squash (2) 955 5）Leafy Vegetables celery (353), spinach (167), bok choy (134), garden chrysanthemum (111), lettuce (277), Chinese cabbage (199), green vegetable (73), amaranth (28), mustard greens (37), sweet potato leaves (25), boxthorn leaves (7), water spinach (72), baby Chinese cabbage (4), leaf lettuce (137), rape greens (72), Indian spinach (12), milk cabbage (1), endive (35), celtuce (22), rooted mustard sprout (8), spring vegetable (19) 1809 6）Legume Vegetables common bean (367)，cowpea (23)，garden pea (4) ，podded pea (4)，soya bean (young pods) (6) 429 7）Bulb Vegetables Chinese chive (223)，green onion (50)，garlic (12)，garlic bolt (19)，onion (50) 326 8）Root and tuber vegetables carrot (154)，taro (13)，potato (120)，Chinese radish (99)，purple potato (8)，sweet potato (4)，ginger (22)，yam (14) 434 9）Aquatic vegetables water bamboo (4)，watercress (13)，lotus rhizome (26) 43 10）others lily (9)，bamboo shoots (8) 17 Fruits 3404 1）Citrus fruits sweet orange (185)，mandarin orange (162)，pummelo (50)，lemon (44) 441 2）Melon Fruits watermelon (158)，hami melon (39)，muskmelon (25)，honeydew (51) 273 3）Berries and other Small Fruits kiwifruit (194)，grape (369)，strawberry (51)，passion fruit (7)，concord grape (12) 633 4）Pome fruits apple (450)，pear (437)，loquat (10)，mayhaw (4) 901 5）Assorted tropical and sub-tropical fruits pineapple (44)，banana(149)，dragon fruit (239)，litchi (56)，mango (79)，carambola (43)，mangosteen (47)，guava (23)，papaya (30)，longan (12)，pomegranate (9) 721 6）Stone fruits peach (279)，date (44)，apricot (18)，plum (91)，nectarine (3) 435 Grains 4 1）Dry Grain maize (4) Seasoner 22 1）Leaf spices coriandre (22) 146 fruits and vegetables of 18 categories cover 80% of the catalogue in the national standards, revealing the universal applicability of the method. 采集的样品共计18类146种，占全国果蔬标准名录的80%以上。

2.4 Intelligent analyzing system of pesticide residue detection data Intelligent analyzing system consists of presentation tier, business tier, visit tier and data tier, including: Presentation tier Data tier consists of databases, four major fundamental databases and other relative documents, providing databases and document services. Visit tier is to provide the data in the databases for the business tier through the visit by the visit components of databases to the data in the database. Business tier is to provide a multi-dimensional statistical analysis of the sampling points, pesticides, levels of pollutions, etc. on the basis of statistical analysis model. Presentation tier is to churn out an intelligent analytical report with different pictures and illustrations as requested for the 18 conditions by the customer. Business tier Visit tier 10 League Laboratory Detection Databases Pesticide information databases MRL databases agricultural products classification databases Geographical information databases Data tier 采用浏览器/服务器三层结构，即Web展现层、业务逻辑层和数据访问层，依托10个示范实验室循环农药残留检测，根据四大基础数据库的技术支持，完成了海量农药残留数据的智能分析。

2.5 HRMS + internet + informatization engineering technology are conducive to realizing “one-click download”, with a report with pictures and illustrations generated within 30 minutes for one province. The 1st -2nd Quarter of 2016 Pesticide residue detection report for fruits and vegetables available on the market in Beijing, Tianjin and Hebei Province (about 5 million words) a pesticide residue detection report for each province for fruits and vegetables in 31 provincial capitals/cities directly under the Central Government (about 20 million words) HRMS+Internet+信息工程技术实现了“一键按下”一个省会的农药残留侦测报告30分钟自动生成。

Challenge No.3: how to realize visualization for pesticide residue risk source tracing? Solution: HRMS + Internet + GIS tri-element technique may realize visualization for risk source tracing. 3 挑战之三：农药残留风险溯源如何实现视频化？ 解决方案：HRMS+互联网+GIS三元融合技术可以实现风险溯源视频化

3. Development of pesticide residue risk tracing video system of HRMS +Internet+GIS 3.1 Development of two products First product: Horizontal Map Atlas of Pesticide Residues in Fruits and Vegetables Currently Available in 31 Provincial Capitals and Cities Directly under the Central Government (hard copy) With one atlas of pesticide residue map in hand, one may have an entire view of all the pesticide residues across the country. HRMS+Internet+GIS三元技术融合，实现了农药残留风险溯源视频化。现已形成两个产品：第一个产品：中国第一部全国农药残留地图集，已绘制完成，实现了中国农药残留地图集一书在手，全国农药残留概览无余！

Tracing can be conducted in the following three aspects. 3.2 The second product: the video software of Online Drafting System of Pesticide Residues of Chinese Agricultural Products Map Module Pesticide Pesticide data Module Interconnection & Interconnectivity Tracing can be conducted in the following three aspects. With one video in hand, one may have, at a glance, an entire view of all the pesticide residues across the country. 第二个产品：农产品农药残留视频溯源软件，已研究开发成功，实现了一册视频软件在手，全国农药残留一目了然！

3.3 Visualized tracing demonstration （1）Tracing by origins The pesticide residue features of farm crops are expressed with multi-space resolutions—multi-dimensions like nation, province and county, which constitutes a multi-scale open map frame of “nation-province-country”, being convenient for both collection of the current data and dynamic addition and real-time updating of future data. ① nation ②Shandong Province ③Jinnan City A wisdom map for pesticide detection and control may provide scientific data support for enterprise self-discipline, government control and the supervision form a third party in the society. （1）可视化农药残留溯源例证：按产地多维度溯源：国家尺度、省区尺度和市县尺度。

（2）Tracing by pesticides Pesticide varieties ranking top 10 in nationwide detection (LC-Q-TOFMS): imidacloprid, difenconazole, thiophanate-methyl, propamocarb, dimethomorph, metalaxyl, tebuconazole, acetamiprid, pyrimethanil （2）按农药溯源：使用量排前10的农药。

(3) Tracing by categories of agricultural products (vegetables) Vegetables ranking top 10 in nationwide pesticide detection: celery, green pepper, tomato, cucumber, green beans, lettuce, chrysanthemum coronarium, spinach, Chinese cabbage and leek （3）按产品溯源：农药污染排前10的蔬菜溯源。

Conclusion: the construction of big databases for pesticide residues has already begun to take shape. The three-element merging technology of HRMS + internet + GIS improves the monitoring and control capability of food safety (pesticide residues), prompt the four strictest policies implementation, and guarantee safety of agricultural produce without  pesticide residue. Construction of pesticide residue detection result databases Pesticide residue detection result databases have now been stored in the 10 demonstration laboratories in 31 provincial capitals/cities directly under the Central Government (including 284 counties and regions), and there are 638 sampling points with 22368 lots of samples of over 140 kinds of fruits and vegetables, from which 13.74 million detection data have been generated, with 0.145 billion high-resolution MS photos and a 25-million-word pesticide residue detection report. Structural Sketch of Pesticide Residue Detection Result Database Note：①②③④⑤⑥⑦⑧…… detection result databases from demonstration laboratories A report with pictures can be generated automatically with “one-click download”. On the basis of five major fundamental databases, inter-connection and inter-connectivity are realized through the internet and informationatization engineering technology and pesticide residue detection result database are initially constructed. Pesticide Residue Detection Result Database 农药残留大数据库构建已具雏形:①31省会/直辖市284个区县，600多个采样点；②18类146种水果蔬菜20000多批样品；③400多种检出农药；④13.74 million data; ⑤1.4 亿张残留农药质谱图；⑥2500万字文图并茂侦测报告。

Call for collaborators We are planning to organize an AOAC collaborative study on “Non-Target Detection of Over 1200 Pesticides in Fruits and Vegetables by GC-Q-TOFMS and LC-Q-TOFMS” to be an AOAC Official Method in 2018, and experts who are interested are kindly advised to join us!   Join Us Guo-Fang Pang Chinese Academy of Inspection and Quarantine Address:No.11 South Ronghua Road, Yizhuang Zone, Beijing, P. R. China Email: ciqpang@163.com Telephone:+86-10-53898011

Chinese Academy Inspection and Quarantine Thank you Chinese Academy Inspection and Quarantine ciqpang@163.com