Geochemical characteristics of zinc in soil and prediction of Zn−rich wheat cultivating areas in Weining Plain, Northwest China
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摘要:研究目的
大部分粮食作物锌含量较低，人体难以从正常的膳食结构中获取足够的锌元素。通过开展土地质量地球化学调查，探寻种植富锌作物的适宜区域，是基于自然途径使作物达到富锌标准的最优方案。
研究方法本研究以宁夏卫宁平原农业用地为研究区，基于土地质量地球化学调查所获取的农用地表层土壤、小麦籽实及其根系土中元素地球化学数据，研究了表层土壤、小麦籽实Zn地球化学特征，探究了小麦籽实富集Zn的影响因素；以中国健康膳食营养结构与居民膳食营养素参考摄入量为基准，推算出富锌小麦锌含量区间值。
研究结果研究区表层土壤Zn含量范围25.1~102.0 mg/kg，背景值61.4 mg/kg；研究区小麦籽实Zn含量范围13.34~37.78 mg/kg，平均值24.72 mg/kg，生物富集系数（BCF）平均值0.41；富锌小麦Zn含量取值范围为26.5~50.0 mg/kg，研究区小麦籽实的富锌比例为36.7%；基于神经网络模型预测出卫宁平原适宜种植富锌小麦的农用地面积为242.86 km2。
结论研究区表层土壤Zn空间分布较为均匀且主要受到成土母质控制；小麦籽实富集Zn的能力为中等，土壤Zn、Fe2O3、K2O、SiO2/Al2O3与小麦籽实Zn具有显著相关关系；神经网络模型能构建出可靠的预测模型，可以作为基于地球化学调查数据探寻有益微量元素富集作物种植适宜区的方法。
创新点:基于中国健康膳食营养结构与居民膳食营养素参考摄入量，推算出富锌小麦Zn含量区间值；运用神经网络模型构建了小麦籽实Zn含量预测模型，通过预测小麦籽实Zn含量，划分出适宜种植富锌小麦的区域。
Abstract:This paper is the result of agricultural geological survey engineering.
ObjectiveMost of the food crops are low in zinc and it is difficult for humans to obtain sufficient zinc through the normal diet. Land quality geochemical survey, as nature−based solutions, is the best scheme to find the suitable region for cultivating zinc−rich crops.
MethodsThis study takes agricultural land in Weining Plain of Ningxia as the research region, geochemical data of surface soils, wheat seeds and rhizosphere soils of agricultural lands were obtained through land quality geochemical survey, the geochemical characteristics of zinc in surface soil and wheat seed were studied, and the influencing factors of zinc enrichment in wheat seed were explored. The interval value of zinc content in zinc−rich wheat was calculated based on the nutritional structure of healthy diet in China and the reference intake of dietary nutrients in residents.
ResultsIn the research region, the range of zinc content in surface soils was 25.1 mg/kg to 102.0 mg/kg, and the background value of surface soil was 61.4 mg/kg. The range of zinc content in wheat seeds was 13.34 mg/kg to 37.78 mg/kg, the average content was mg/kg, and the averagebio−enrichment coefficient was 0.41. The range of zinc content in Zn−enriched wheat was 26.5 to 50.0 mg/kg, and the proportion of zinc enriched wheat seeds in the research region was 36.7%.Based on the neural network model, we predicted that the region of agricultural lands, which were suitable for cultivating zinc enriched wheat in Wei Ning Plain, was 242.86 km2.
ConclusionsThe spatial distribution of zinc in the surface soil of the research region was relatively uniform and was mainly controlled by soil parent materials. The zinc enrichment ability of wheat seeds was medium. The zinc enrichment ability of wheat seeds is significantly correlated with Zn, Fe2O3, K2O, SiO2/Al2O3 in rhizosphere soils. Neural network model can construct a reliable prediction model, which can be used as a method to explore suitable cultivating regions for beneficial micronutrient enrichment crops through geochemical survey data.
Highlights:Based on the healthy nutrition structure of Chinese diet and the reference intake of dietary nutrients, the interval value of zinc content in zinc enrichment wheat seeds was calculated. A prediction model of zinc content in wheat seeds was established through neural network model.
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1. 研究目的（Objective）
湘中坳陷作为南方复杂构造区页岩气勘探的热点地区之一，也是中国油气勘探久攻未克的地区。前期在湘中地区北部的涟源凹陷泥盆系和石炭系获得了页岩气突破和发现，证实了湘中地区上古生界页岩气资源丰富。但对湘中地区南部的邵阳凹陷调查程度较为薄弱，针对邵阳凹陷二叠系仅开展了少量基础地质调查工作，页岩气资源潜力评价方面的工作尤为欠缺。本次研究依托邵阳湘邵地1井（XSD1井）钻探工程建立了邵阳凹陷二叠系地层层序序列，揭示了主要含气页岩层系的分布特征，获取了含气性评价参数，对湘中地区二叠系页岩气勘探开发和重新评价湘中坳陷页岩气资源潜力具有重要的现实意义。
2. 研究方法（Methods）
中国地质调查局武汉地质调查中心在收集分析区域地质相关资料的基础上，结合邵阳凹陷短陂桥向斜的煤田浅钻、非震物探等资料开展页岩气地质综合评价，采用页岩埋深500~4500 m，页岩有机碳含量≥1.0%，页岩厚度≥15 m，页岩有机质热演化程度1.0%~3.5%的评价参数在短陂桥向斜区优选页岩气远景区，论证部署了1口小口径页岩气地质调查井—XSD1井，湖南煤田地质勘查有限公司组织实施钻探（图 1a）。该井采样全井段取心钻井工艺，测井选取PSJ-2数字测井系统，录井采用SK-2000G气测录井，钻获二叠系大隆组156.05 m（暗色硅质页岩、钙质泥岩94.48 m），龙潭组349.95 m（暗色泥岩216.93 m，粉砂质泥岩36.9 m），对这两套层系共采集暗色泥岩样品33件，进行解析气含量测定分析，落实了含气性评价参数。
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图 1 湘邵地1井构造位置图（a）、主要含气层段岩性和含气性参数柱状图（b）、以及富集模式图（c）Figure 1. Structural location of Xiangshaodi 1 well (a), lithology and gas-bearing parameters of main gas bearing zones (b), and enrichment mode (c)3. 结果（Results）
本次样品分析工作由武汉地质调查中心古生物与生命-环境协同演化重点实验室完成，采用YSQ-IIIA岩石解析气测定仪（燃烧法）对含气段岩心共计33件样品进行分析。该井钻获二叠系大隆组厚度156.05 m，为一套硅质岩、硅质页岩、炭质钙质泥岩地层。其中在井深842~930.2 m硅质页岩、钙质泥岩段，气测全烃值从1.06%上升至16.54%，甲烷值从1.01%上升至14.04%，13件大隆组硅质页岩现场解析总含气量为1.29~9.97 m3/t，平均4.85 m3/t。实现了湘中坳陷二叠系页岩气新发现，有效拓展了华南地区大隆组勘探范围。
钻获龙潭组厚度349.95 m，上段为一套细砂岩、粉砂岩夹泥岩潮坪相沉积地层，下段为一套炭质泥岩、粉砂质泥岩夹薄层细砂岩泻湖相沉积地层。在井深1013.4~1048 m泥岩与粉砂岩互层段气测全烃值最高可达19.87%，甲烷值最高为16.94%，7件泥岩与粉砂岩样品现场解析总含气量0.57~3.42 m3/t，平均1.78 m3/t；井深1088.10~1199.75 m泥岩夹泥质粉砂岩含气层111.6 m，气测全烃值最高可达28.2%，甲烷值最高为23.6%，13件泥岩、粉砂质泥岩样品现场解析总含气量0.90~4.55 m3/t，平均2.01 m3/t（图 1b），首次查明了湘中坳陷二叠系龙潭组非常规油气分布特点。
通过区域地质背景分析，并结合煤田区域地质资料，本研究认为滑脱断裂（F9）上下盘具有不同的页岩气聚集条件。滑脱断裂之上由一系列的同向逆断层形成的逆冲推覆体，地层变形强烈，且裂缝发育，导致页岩气保存条件变差。滑脱断裂下盘是页岩气主要富集区，地层平缓，不发育次级通天断裂，与下盘地层形成反向遮挡，易形成封闭，保存条件良好（图 1c）。
4. 结论（Conclusions）
（1）二叠系大隆组岩性以硅质岩、硅质页岩为主，夹少量灰岩。主要含气段存在于上段硅质页岩段，厚88.2 m，含气量平均为4.85 m3/t，含气性优越，资源潜力大。
（2）二叠系龙潭组上段以致密砂岩气为主，含气量平均为1.78 m3/t；下段以页岩气为主，泥岩厚达177.47 m，含气量平均为2.01 m3/t，具有泥岩厚度大，含气性好等特征。
（3）保存条件是页岩气富集关键，构造改造弱的封闭演化环境有利于页岩气保存，研究区滑脱断裂下盘是页岩气主要富集区，易形成封闭，保存条件良好。
（4）湘邵地1井在二叠系大隆组和龙潭组获得良好的页岩气显示，证实了湘中地区二叠系具有良好的页岩气资源潜力，对湘中地区页岩气资源潜力评价具有重要意义。
5. 基金项目（Fund support）
本文为中国地质调查局项目“中扬子地区油气页岩气调查评价”（DD20221659）资助的成果。
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图 4 小麦籽实Zn与根系土Zn含量散点图
Figure 4. Scatter plots of Zn content in wheat seed and rhizosphere soil
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图 5 神经网络预测模型拟合效果图
a—训练集拟合；b—验证集拟合：c—测试集拟合；d—总拟合
Figure 5. Fitting effect diagram of neural network prediction model
a–Training set fitting; b–Validation set fitting; c–Test set fitting; d–Total fitting
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图 6 研究区富锌小麦种植适宜区范围
Figure 6. Suitable regions of Zn−enriched wheat cultivating in the study area
表 1 土壤样品分析项目及其测试方法和检出限
Table 1 Analysis items and its testing method and detection limits of samples
样品类型 元素或指标 分析方法 分析方法检出限 准确度 精密度/% 土壤 Al2O3/% XRF 0.05 0.01 3.82 CaO/% 0.02 0.02 3.97 Fe2O3/% 0.02 0.01 3.55 K2O/% 0.03 0.01 3.17 SiO2/% 0.05 <0.01 2.86 有机质/% VOL 0.034 <0.01 6.19 Zn/% ICP−MS 1 <0.01 3.29 pH ISE 0.1 0.01 3.51 小麦籽实 Zn/(mg/kg) ICP−MS 1 0.01 10.53 
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表 2 研究区小麦籽实及其根系土Zn含量
Table 2 Zn content of wheat seeds and their rhizosphere soils
样品分布区域 样品量 类别 含量范围 平均值 标准偏差 变异系数/% 黄河
冲洪积平原38（件） 小麦籽实/(mg/kg) 13.34~37.78 27.15 6.04 22.26 根系土/(mg/kg) 43.38~92.43 67.80 10.74 15.84 富集系数(BCF) 0.28~0.51 0.40 0.06 15.56 洪积倾斜台地 22（件） 小麦籽实/(mg/kg) 16.77~26.25 21.41 2.81 13.11 根系土/(mg/kg) 36.34~56.31 49.76 5.15 10.34 富集系数(BCF) 0.34~0.53 0.43 0.05 12.08 研究区 60（件） 小麦籽实/(mg/kg) 13.34~37.78 24.72 5.68 22.98 根系土/(mg/kg) 36.34~92.43 60.17 12.55 20.86 富集系数(BCF) 0.28~0.53 0.41 0.06 14.63
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表 3 Zn生物富集系数与土壤理化指标相关系数
Table 3 Correlation analysis of BCF with soil physicochemical properties
SiO2/Al2O3 CaO Fe2O3 K2O 有机质 根系土Zn pH 小麦籽实 Zn −0.77** 0.41* 0.73** 0.67** 0.38 0.79** −0.25 注：*代表在0.05水平显著；**代表在0.01水平显著。
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表 4 居民平衡膳食结构Zn供应量及富锌谷类锌含量下限值
Table 4 The supply of Zn in residents balanced dietary and the lower limit of zinc content in zinc-rich crops
食物 推荐食用量/(g/d) Zn含量
/(mg/kg)Zn摄入量
/(mg/d)推荐范围 本文取值 奶 300~500 400 4.50 1.80 动物性食物 120~200 160 25.80 4.13 蔬菜 300~500 400 2.21 0.88 水果 200~350 225 1.68 0.38 谷类 200~300 250 X Y 除富锌谷类外其他普通食物（奶、动物性食品、蔬菜、水果）每日Zn供应量 7.19 成年人每日Zn推荐摄入量(RNI) 12.5 富锌谷类每日Zn最低供应量(Y) 5.31 X = (5.31 mg/d)/(250 g/d)= 21.24 mg/kg
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