花园土壤氟的形态分布特征及降低水溶态氟措施研究
摘要
饮茶是人类摄取氟的重要来源,适量的氟有利于预防龋病和骨组织的强化,但过量的氟会对人体造成不可逆转的伤害,如关节疼痛、活动受限、驼背、跛行等氟骨症。茶叶中的氟主要来源于土壤,目前针对我国土壤氟的含量和茶叶氟的累积分布规律已有大量研究,但有关茶园土壤氟的形态分布规律及其与茶叶氟含量相互关系的报道较少。而水溶态氟是茶树吸收氟的主要形态,是土壤-水-植物-动物氟环境的枢纽。因此,研究茶园土壤氟的分组及降低土壤水溶态氟的措施,对于调控茶叶氟含量,提高茶叶品质,保护人类健康具有重要意义。
本文以湖北省14个茶园土壤样和对应的茶叶样品为对象,研究了茶叶的氟含量、土壤氟分组及其与土壤理化性质间的相互关系。另外,以湖北英山、大悟、竹山、赤壁和浙江杭州茶园土壤为研究对象,通过施加一定量的含钙化合物(CaCO3、CaO、Ca3(PO4)2、CaCl2和CaSO4)、固体吸附物质(人造沸石、硅藻土和活性炭)和生物材料(枇杷叶和竹叶)来调控土壤中水溶性氟含量。研究结果表明：
湖北茶园老叶氟含量为321～2274 mg/kg,嫩叶氟含量为57～1806 mg/kg。同一茶园内老叶氟含量高于嫩叶,老叶氟积累明显。随着土壤深度的增加,总氟含量降低,而各形态氟含量变化不一。土壤氟含量均表现为：残渣态>>有机结合态>铁锰结合态>水溶态>交换态,残渣态氟是茶园土壤中氟的主要形态。全氟含量与总P呈显著正相关,水溶性氟含量与土壤PH、CEC和交换性Ca含量呈显著正相关。交换态氟含量与粘粒、CEC、游离Al和游离Fe都呈极显著正相关关系。铁锰结合态氟与pH、交换性Ca和全P呈极显著正相关,而与无定形Al和游离A1呈显著负相关。有机结合态与交换性Ca和全P呈极显著正相关。土壤有机质和无定形Fe对土壤中各形态氟的含量没有显著影响。
英山、大悟和竹山茶园土壤中施加一定量的CaCl2或CaSO4均可降低土壤中水溶性氟含量,且施用CaCl2的效果均比CaSO4好,但施加CaCO3、CaO和Ca3(PO4)2则显著增加土壤中水溶性氟含量。英山和大悟茶园土壤中可施加1-2g/kg的CaCl2或CaSO4,竹山茶园土壤中可施加3-5g/kg的CaCl2或CaSO4。赤壁和杭州茶园土壤中施加一定量的CaCO3、CaO或Ca3(PO4)2均可降低土壤中水溶性氟含量,赤壁茶园土壤中可施加1.5-2 g/kg的CaCO3或CaO,也可施加3-4g/kg的Ca3(PO4)2。杭州茶园土壤中可施加4-5g/kg的CaCO3或CaO或Ca3(PO4)2。赤壁和杭州茶园土壤中施用CaCO3的效果均比CaO和Ca3(PO4)2好,而这些土壤中施加CaCl2和CaSO4则显著增加土壤中水溶性氟含量。活性炭、人造沸石、硅藻土、枇杷叶和竹叶加入英山、大悟、竹山、赤壁和杭州茶园土壤后,土壤水溶性氟含量增加,故不适宜施用。
Tea is an important source for people to intake fluoride, which, with a right amount, is helpful for avoiding dental caries and strengthening bone tissue, but, with an excessive amount, is harmful by causing irreversible damage, such as joint pain, limited mobility, humpbacked, lame and so on. Fluorine in tea maily comes from soil. There have been many reports about contents of fluorine in tea garden soils and the cumulative distribution of tea fluoride. But there have been few reports about the form distribution of fluorine in soil and the correlation between floride in tea and fluorine in soil. Fluorine adsorbed by tea plants is of the water-soluble fluorine, which is the hub of soil, water, plant and animal for fluorine circulation. Consequently, it has theoretical and practical significance to study the distribution of fluorine in soil and methodology of reducing soil water soluble fluorine content for improving the quality of tea, decreasing contents of fluoride in tea and ensuring health of human.
Taking 14 tea leave samples and the 14 corresponding soils of tea gardens in Hubei province as research objects, this study researched the content of fluorine in tea, distribution of fluorine in soil and the relationship between the distribution of fluorine in soil and the physical-chemical properties of soils. Calcium-containing materials(CaCO3, CaO, Ca3(PO4)2, CaCl2, CaSO4), solid sorbent(active carbon, zeolite, diatomite) and biomass materials(loquat and bamboo leaves) were used to regulate water-soluble fluoride in tea garden soils collected from Yingshan, Dawu, Zhushan, Chibi of Hubei province and Hangzhou of Zhejiang province.
The content of fluorine in Hubei tea leaves varied from 321 to 2274 mg/kg for old leaves and from 57 to 1806 mg/kg for young leaves. The content of fluorine in old leaves was higher than that in young leaves, which shows that the accumulation of fluorine in old leaves increased significantly. The total fluorine decreased with the increased soil depth, but the content of other forms of fluorine changed with the increase of soil depth. The content of fluorine in different layers of soils were all in the order of residual F (Res-F)>>rganic bound F (Or-F)>Fe(Mn) oxides bound F (Fe/Mn-F)>water soluble F (Ws-F)>extractable F (Ex-F), and the residual fluorine is the main form in tea garden soils. Total F (T-F) was positively correlated with total phosphorus at a statistically significant level. Ws-F was positively correlated with pH, CEC and exchangeable Ca content significantly. Ex-F was positively correlated with clay content, CEC, free Al and free Fe contents. Fe/Mn-F was positively correlated with pH, contents of exchangeable Ca and total phosphorus, but it was negatively correlated with contents of amorphous Al and free Al significantly. Or-F was positively correlated with contents of exchangeable Ca and total phosphorus. The different form of fluorine was not significantly correlated with organic matter and amorphous Fe.
The results indicated that the content of water-soluble fluoride in soils of Yingshan, Dawu and Zhushan decreased after application of CaCl2 and CaSO4, and the effect of applying CaCl2 was better than that of CaSO4. However, the content of water-soluble fluoride in these three soils increased by applying CaCO3, CaO or Ca3(PO4)2. The appropriate amount was 1～2 g/kg of CaCl2 or CaSO4 in soils of Yingshan and Dawu, and 3～5 g/kg of CaCl2 or CaSO4 in the soil of Zhushan, respectively. The content of water-soluble fluoride in soils of Chibi and Hangzhou decreased by applying CaCO3, CaO or Ca3(PO4)2, and the appropriate amount for soil of Chibi was 1.5～2 g/kg of CaCO3 or CaO or 3-4 g/kg of Ca3(PO4)2, while for the soil of Hangzhou was 4-5 g/kg of CaCO3, CaO or Ca3(PO4)2. The effect of applying CaCO3 was better than that of CaO and Ca3(PO4)2 on the soils of Chibi and Hangzhou, however, the content of water-soluble fluoride in these two soils increased by applying CaCl2 or CaSO4. The content of water-soluble fluoride in soils of Yingshan, Dawu, Zhushan, Chibi and Hangzhou increased by applying activated carbon, zeolite, diatomite, loquat or bamboo leaves, so these can not be applicable.
本文以湖北省14个茶园土壤样和对应的茶叶样品为对象,研究了茶叶的氟含量、土壤氟分组及其与土壤理化性质间的相互关系。另外,以湖北英山、大悟、竹山、赤壁和浙江杭州茶园土壤为研究对象,通过施加一定量的含钙化合物(CaCO3、CaO、Ca3(PO4)2、CaCl2和CaSO4)、固体吸附物质(人造沸石、硅藻土和活性炭)和生物材料(枇杷叶和竹叶)来调控土壤中水溶性氟含量。研究结果表明：
湖北茶园老叶氟含量为321～2274 mg/kg,嫩叶氟含量为57～1806 mg/kg。同一茶园内老叶氟含量高于嫩叶,老叶氟积累明显。随着土壤深度的增加,总氟含量降低,而各形态氟含量变化不一。土壤氟含量均表现为：残渣态>>有机结合态>铁锰结合态>水溶态>交换态,残渣态氟是茶园土壤中氟的主要形态。全氟含量与总P呈显著正相关,水溶性氟含量与土壤PH、CEC和交换性Ca含量呈显著正相关。交换态氟含量与粘粒、CEC、游离Al和游离Fe都呈极显著正相关关系。铁锰结合态氟与pH、交换性Ca和全P呈极显著正相关,而与无定形Al和游离A1呈显著负相关。有机结合态与交换性Ca和全P呈极显著正相关。土壤有机质和无定形Fe对土壤中各形态氟的含量没有显著影响。
英山、大悟和竹山茶园土壤中施加一定量的CaCl2或CaSO4均可降低土壤中水溶性氟含量,且施用CaCl2的效果均比CaSO4好,但施加CaCO3、CaO和Ca3(PO4)2则显著增加土壤中水溶性氟含量。英山和大悟茶园土壤中可施加1-2g/kg的CaCl2或CaSO4,竹山茶园土壤中可施加3-5g/kg的CaCl2或CaSO4。赤壁和杭州茶园土壤中施加一定量的CaCO3、CaO或Ca3(PO4)2均可降低土壤中水溶性氟含量,赤壁茶园土壤中可施加1.5-2 g/kg的CaCO3或CaO,也可施加3-4g/kg的Ca3(PO4)2。杭州茶园土壤中可施加4-5g/kg的CaCO3或CaO或Ca3(PO4)2。赤壁和杭州茶园土壤中施用CaCO3的效果均比CaO和Ca3(PO4)2好,而这些土壤中施加CaCl2和CaSO4则显著增加土壤中水溶性氟含量。活性炭、人造沸石、硅藻土、枇杷叶和竹叶加入英山、大悟、竹山、赤壁和杭州茶园土壤后,土壤水溶性氟含量增加,故不适宜施用。
Tea is an important source for people to intake fluoride, which, with a right amount, is helpful for avoiding dental caries and strengthening bone tissue, but, with an excessive amount, is harmful by causing irreversible damage, such as joint pain, limited mobility, humpbacked, lame and so on. Fluorine in tea maily comes from soil. There have been many reports about contents of fluorine in tea garden soils and the cumulative distribution of tea fluoride. But there have been few reports about the form distribution of fluorine in soil and the correlation between floride in tea and fluorine in soil. Fluorine adsorbed by tea plants is of the water-soluble fluorine, which is the hub of soil, water, plant and animal for fluorine circulation. Consequently, it has theoretical and practical significance to study the distribution of fluorine in soil and methodology of reducing soil water soluble fluorine content for improving the quality of tea, decreasing contents of fluoride in tea and ensuring health of human.
Taking 14 tea leave samples and the 14 corresponding soils of tea gardens in Hubei province as research objects, this study researched the content of fluorine in tea, distribution of fluorine in soil and the relationship between the distribution of fluorine in soil and the physical-chemical properties of soils. Calcium-containing materials(CaCO3, CaO, Ca3(PO4)2, CaCl2, CaSO4), solid sorbent(active carbon, zeolite, diatomite) and biomass materials(loquat and bamboo leaves) were used to regulate water-soluble fluoride in tea garden soils collected from Yingshan, Dawu, Zhushan, Chibi of Hubei province and Hangzhou of Zhejiang province.
The content of fluorine in Hubei tea leaves varied from 321 to 2274 mg/kg for old leaves and from 57 to 1806 mg/kg for young leaves. The content of fluorine in old leaves was higher than that in young leaves, which shows that the accumulation of fluorine in old leaves increased significantly. The total fluorine decreased with the increased soil depth, but the content of other forms of fluorine changed with the increase of soil depth. The content of fluorine in different layers of soils were all in the order of residual F (Res-F)>>rganic bound F (Or-F)>Fe(Mn) oxides bound F (Fe/Mn-F)>water soluble F (Ws-F)>extractable F (Ex-F), and the residual fluorine is the main form in tea garden soils. Total F (T-F) was positively correlated with total phosphorus at a statistically significant level. Ws-F was positively correlated with pH, CEC and exchangeable Ca content significantly. Ex-F was positively correlated with clay content, CEC, free Al and free Fe contents. Fe/Mn-F was positively correlated with pH, contents of exchangeable Ca and total phosphorus, but it was negatively correlated with contents of amorphous Al and free Al significantly. Or-F was positively correlated with contents of exchangeable Ca and total phosphorus. The different form of fluorine was not significantly correlated with organic matter and amorphous Fe.
The results indicated that the content of water-soluble fluoride in soils of Yingshan, Dawu and Zhushan decreased after application of CaCl2 and CaSO4, and the effect of applying CaCl2 was better than that of CaSO4. However, the content of water-soluble fluoride in these three soils increased by applying CaCO3, CaO or Ca3(PO4)2. The appropriate amount was 1～2 g/kg of CaCl2 or CaSO4 in soils of Yingshan and Dawu, and 3～5 g/kg of CaCl2 or CaSO4 in the soil of Zhushan, respectively. The content of water-soluble fluoride in soils of Chibi and Hangzhou decreased by applying CaCO3, CaO or Ca3(PO4)2, and the appropriate amount for soil of Chibi was 1.5～2 g/kg of CaCO3 or CaO or 3-4 g/kg of Ca3(PO4)2, while for the soil of Hangzhou was 4-5 g/kg of CaCO3, CaO or Ca3(PO4)2. The effect of applying CaCO3 was better than that of CaO and Ca3(PO4)2 on the soils of Chibi and Hangzhou, however, the content of water-soluble fluoride in these two soils increased by applying CaCl2 or CaSO4. The content of water-soluble fluoride in soils of Yingshan, Dawu, Zhushan, Chibi and Hangzhou increased by applying activated carbon, zeolite, diatomite, loquat or bamboo leaves, so these can not be applicable.
引文
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