四川青川县初榨橄榄油营养成分及油脂特性分析
2017-09-15王裕斌姚小华都卫东吕乐燕任华东
龙 伟 王裕斌 姚小华 都卫东 吕乐燕 任华东
(中国林业科学研究院亚热带林业研究所;浙江省林木育种技术研究重点实验室1,杭州 311400) (四川省青川县青源林农产品有限责任公司2,青川 628100) (四川省青川县林业和园林局3,青川 628100) (浙江同济科技职业学院4,杭州 311231)
四川青川县初榨橄榄油营养成分及油脂特性分析
龙 伟1王裕斌2姚小华1都卫东3吕乐燕4任华东1
(中国林业科学研究院亚热带林业研究所;浙江省林木育种技术研究重点实验室1,杭州 311400) (四川省青川县青源林农产品有限责任公司2,青川 628100) (四川省青川县林业和园林局3,青川 628100) (浙江同济科技职业学院4,杭州 311231)
为摸清四川青川县主栽油橄榄品种初榨橄榄油的脂肪酸组成、营养成分和挥发性物质,利用气相色谱、气质联相色谱对油脂进行检测,结果显示:平均不饱和脂肪酸为82.82%,为豆果83.30%>皮削利83.05%>鄂植8号82.1%,其中品种间油酸和油酸含量间存在显著差异;平均值维生素E含量为28.78 mg/100 g,为鄂植8号32.7 mg/100 g >皮削利27.5 mg/100 g>豆果24.4mg/100g,品种间α-维生素E存在显著差异;平均值角鲨烯含量为4 512.48 mg/kg,为皮削利6 690.95 mg/kg>鄂植8号4 386.50 mg/kg>豆果2 460.00 mg/kg,品种间角鲨烯存在极显著差异;平均值β-谷甾醇含量为849.00 mg/kg,为鄂植8号1 161.30 mg/kg>皮削利946.35 mg/kg>豆果439.35 mg/kg,品种间β-谷甾醇存在极显著差异。油脂中鉴定出25种挥发性化合物,其中醛类4个,醇类2个,酯类5个,烯烃类7个和萜烯类5个,其他2种;鄂植8号和豆果橄榄油挥发性物质的主要为醛类,占总物质的55.88%和52.58%,皮削利挥发性物质主要为烯烃类物质,占总物质的53.68%。综上所述,青川初榨橄榄油营养物质丰富,挥发性物质独特,香味浓郁,存在明显的地域特征,具有良好的开发价值。
初榨橄榄油 脂肪酸 挥发性化合物
油橄榄(OleaeuropaeaL.)作为世界上重要的木本油料树种,其果实压榨后的橄榄油富含不饱和脂肪酸、角鲨烯、维生素E等多种营养成分,具有极高的营养价植,其特殊的青草香味等受到广大消费者的欢迎,在世界范围内大面积种植[1-2]。我国自上世纪开始引种油橄榄开始,已有60多年的历史,主要分布在四川、甘肃和云南等地[3];随着人民生活水平的提高,对健康和安全的优质食用油需求日益旺盛,推动油橄榄产业的发展,国内生产的橄榄油供不应求,年进口量从2008年度的1.2万t,在2015年度达到3.1万t[4]。橄榄油脂肪酸组成、营养成分和挥发性物质(风味)等易受到品种[5]、气候[6]、地区[7-8]和加工时间[9-10]等因素的影响,使其油脂成分及相关物质发生一系列变化,引种后与原产区存在差异。目前对国内油橄榄主产区脂肪酸组成、挥发性物质等的报道多为甘肃陇南[11]和四川西昌[12]产区的果实;四川青川县白龙江流域作为油橄榄适生区,位于秦岭南麓,紧邻甘肃陇南市,种植面积有8万亩,具有较好的发展潜力[13],但对该区域橄榄油的研究报道较少;本研究对青川县油橄榄主栽的鄂植8号、皮削利和豆果3个品种进行油脂成分分析,从脂肪酸组成、营养物质和挥发性物质等角度分析橄榄油主要成分,探讨青川产橄榄油的典型地域特征,为进一步综合开发青川油橄榄资源,为引种栽培和新品种选育提供科学依据。
1 材料和方法
1.1 试验材料
在11月选取四川省广元市青川县沙洲镇油橄榄园内的鄂植8号、皮削利(Picholine)和豆果(Arbequina)的油橄榄成熟果实,进行离心压榨提取橄榄油,待澄清后取油桶上层橄榄油进行分析。
1.2 试验方法
1.2.1 脂肪酸组成及含量分析
橄榄油脂肪酸组成的测定采用气相色谱法。甲酯化处理和脂肪酸的分析分别参照GB /T 17376—2008[14]和GB /T 17377—2008[15]标准,利用美国Agilent公司的7890A 气相色谱仪进行监测分析,经数据处理系统按峰面积归一化法计算各脂肪酸组分的相对百分含量。
1.2.2 橄榄油营养成分测定
维生素E含量测定参照GB/T 5009.82—2003标准[16],角鲨烯和β-谷甾醇测定参考汤富彬等[17]的方法,利用美国Agilent公司的 5975B气质联用仪进行检测分析。
1.2.3 挥发性物质测定
挥发性物质测定参照龙奇志等[18]报道进行提取。利用气相色谱操作美国Agilent公司的6890N气相色谱仪和美国Waters公司的2 695 FLD荧光检测器高效液相色谱仪进行分析。气质联用操作条件采用美国Aglient公司的5 975B气质联用仪。色谱条件同分离化合物的鉴定经计算机谱图库NIST 98 检索匹配, 并结合标样的保留时间、质谱图, 并参考有关文献数据确认。以上测定由国家林业局经济林产品质量检验检测中心(杭州)完成。
2 结果和分析
2.1 橄榄油脂肪酸组成成分分析
对获得的初榨橄榄油成分进行方差分析(表1),结果显示品种间亚麻酸、花生酸和二十碳烯酸成分无显著差异;棕榈酸、棕榈烯酸和硬脂酸存在显著差异;油酸和亚油酸存在极显著差异。经过多重比较分析(表2),棕榈酸和硬脂酸在鄂植8号和豆果间无差异,与皮削利存在显著差异;棕榈烯酸在豆果和鄂植8号存在显著差异,与皮削利无显著差异,表明皮削利的饱和脂肪酸含量上与其他品种存在差异;不饱和脂肪酸成分里油酸和亚油酸在品种间存在显著差异,其他成分无显著差异。
表1 橄榄油脂肪酸组成方差分析
注:*表示P<0.05 存在显著差异;**表示P<0.01存在极显著差异。
表2 橄榄油脂肪酸组成多重比较分析
注:abc表示P<0.05 存在显著差异。
从平均数值来看,皮削利、鄂植8号和豆果的不饱和脂肪酸质量分数分别为皮削利83.30%,鄂植8号83.05%和豆果82.10%,其中油酸为皮削利78.10%>豆果72.80%>鄂植8号71.70%;亚油酸质量分数鄂植8号9.95%>豆果7.50%>皮削利3.75%;亚麻酸含量豆果为0.8%,其他品种为0.9%。饱和脂肪酸质量分数为豆果17.90%,鄂植8号16.95%和皮削利16.70%,其中棕榈酸为豆果14.25%>鄂植8号13.90%>皮削利13.10%;棕榈烯酸为豆果2.15%>皮削利1.70%>鄂植8号1.45%;硬脂酸为皮削利1.90%>鄂植8号1.60%>豆果1.50%。与已报道的甘肃陇南[19]等主产区橄榄油脂肪酸含量和成分较一致,表明青川所产橄榄油在脂肪酸组成与其他产区无差别。
2.2 橄榄油油脂营养成分分析
对橄榄油各营养成份进行方差分析(表3),品种间α-维生素存在显著差异,角鲨烯和β-谷甾醇存在极显著差异。经过多重比较分析(表4),α-维生素在皮削利和豆果间无显著差异,与鄂植8号存在显著差异;角鲨烯和β-谷甾醇在品种间存在极显著差异,表明两种物质含量受到品种因素影响。从平均值看,维生素E含量平均值为28.78 mg/100 g,鄂植8号32.7 mg/100 g>皮削利27.5 mg/100 g>豆果24.4 mg/100 g;角鲨烯含量平均值为4 512.48 mg/kg,皮削利6 690.95 mg/kg>鄂植8号4 386.50 mg/kg>豆果2 460.00 mg/kg;β-谷甾醇平均值为849.00 mg/kg,鄂植8号1 161.30 mg/kg>皮削利946.35 mg/kg>豆果439.35 mg/kg。根据任传义等[19]和柏云爱[20]等对橄榄油营养物质研究结果,青川所产橄榄油内营养物质含量高于油茶、核桃和香榧物种;角鲨烯和谷甾醇平均含量高于陇南地区所产橄榄油,维生素E含量低于该地区。
表3 橄榄油营养物质组成方差分析
注:*表示P<0.05存在显著差异;** 表示P<0.01存在极显著差异。
表4 橄榄油营养物质多重比较分析
注:abc表示P<0.05 存在显著差异。
2.3 橄榄油挥发性物质组成分析
如表5和图1所示,利用GS-MS在初榨橄榄油共鉴定出25种挥发性化合物,其中醛类4个,醇类2个,酯类5个,烯烃类7个和萜烯类5个,十三烷和甲基萘2种;各品种挥发性物质数量鄂植8号16种,皮削利19种,豆果17种;鄂植8号和豆果橄榄油挥发性物质的主要为醛类,占总物质的55.88%和52.58%;皮削利挥发性物质主要为烯烃类物质,占总挥发性物质的53.68%。
图1 橄榄油挥发性物质
醛类物质包含(E)-2-己烯醛(质量分数为16.25%~48.55%),壬醛(2.90%~3.81%),己醛(0.05%~0.32%)在各品种都含有,含量己烯醛和壬醛较高,2-甲基-3-苯基,2-丙烯醛(1.06%)仅存在与鄂植8号的挥发性物质中;(E)-2-己烯醛和己醛作为青草香味的主要来源[21-22],测试结果中鄂植8号和豆果质量分数分别为51.87%和48.55%,皮削利为16.25%,表明鄂植8号和豆果的香味为青草香味为主。
醇类物质主要为(E)-(Z)-2-戊烯-1-醇和(E)-(E)-3-己烯-1-醇,其中(E)-(Z)-2-戊烯-1-醇(0.05%~0.15%)在各品种都检测出;(E)-(E)-3-己烯-1-醇在鄂植8号和豆果中占比22%和0.5%。可以看出醇类也是鄂植8号挥发性物质的主要来源。
作为青草味和香蕉味来源的酯类化合物[22],(Z)-乙酸-3-己烯酯质量分数为皮削利9.91%和豆果1.96%;苯甲酸乙酯仅在鄂植8号检出,苯甲酸甲酯、邻苯二甲酸二异丁酯仅在豆果检出含量分别为1.17%和0.11%,法呢烯酯仅在皮削利检出质量分数为0.28%。酯类物质除(Z)-乙酸己烯酯类所含较多外,其他物质在挥发性物质中含量较低,也说明不是挥发性物质的主要成分。
表5 橄榄油挥发性物质组成
含量较高的烯烃类和萜烯类化合物被检出,其中烯烃类1-壬烯(6.11%~35.02%),4-甲基-1,5-庚二烯(1.29%~4.6%),(Z)-3,7-二甲基,1,3,6-辛三烯(1.19%~2.65%),2-庚烯(1.44%~1.98%),戊二烯(0.07%~0.13%)在各品种含量较高,甘菊环仅存于皮削利(2.23%)和豆果(0.76%)中,4,8-二甲基,1,7-壬二烯仅存在于皮削利(12.38%)挥发性物质中。萜烯类化合物如法呢烯(7.53%~16.65%),衣兰油烯(0.84%~2.22%),可巴烯存在于鄂植8号0.30%和皮削利0.91%,β-水芹烯在皮削利和豆果中分别为0.92%和0.09%,香木兰烯仅存在于豆果为0.34%。萜烯类物质的所占比例常受品种因素的影响,常被作为橄榄油产地和品种的特征性物质[23]。
十三烷和1-甲基萘分别在鄂植8号和皮削利中检测出,但其所占比例较低,可能为试验试剂带入。
3 讨论与结论
油脂成分作为评价油脂价值的重要指标,不仅可以用于评价植物价值也能作为识别品种的特征[24]。作为原产于地中海区域的物种,被世界范围内大量引种,有研究发现油橄榄脂肪酸组成常受到品种[25]、气候[26]、海拔[27]、地形[28]等因素的影响,油脂脂肪酸成分与主产区发生变化,如海拔越高,不饱和脂肪酸含量上升[27],这些因素影响着橄榄油的品质。本研究对青川县主栽的鄂植8号、皮削利和豆果的油脂脂肪酸成分分析,结果显示平均饱和脂肪酸和平均不饱和脂肪酸分别为17.18%和82.82%,与朱万泽等[12]对四川广元利州区产橄榄油测试结果相近,高于西昌,低于开江,同时与任传义等[19]甘肃陇南橄榄油的报道结果相近;表明青川县产橄榄油脂肪酸组成可能受到地理因素的影响,相距越近(陇南和利州区),变化幅度越小,随距离增加(西昌和开江),变化幅度越大。
橄榄油作为一种高档食用油,除含有较好的脂肪酸组成外,其含有丰富的生物活性的物质如谷甾醇、角鲨烯和维生素E等营养成分,也是其受到重视的原因之一;这些物质广泛存在于植物油中,但物种间含量差距较大,如角鲨烯含量最高的橄榄油[29]和苋属植物的种子[30],其含量在品种间易受到品种和果实成熟度的影响,随成熟度上升而增加[31]。本研究结果显示平均角鲨烯含量为4 512.48 mg/kg,平均维生素E含量为28.78 mg/100 g和平均谷甾醇含量为849 mg/kg,与甘肃[19]和云南[31]等地同品种的角鲨烯和β-谷甾醇含量相比较高,ɑ-维生素E含量持平,说明青川县橄榄油含有较高的营养物质。
橄榄油挥发性物质的组成和含量易受多种因素影响,如品种和地理环境[32]、成熟度[33]、水分[34-35]和栽培[36-37],加工[38]等因素的影响,如欧洲产区橄榄油挥发性物质多为2-己烯醛[39-41],澳大利大产区为马烯酮和醛类等[42],国内甘肃主产区橄榄油挥发性物质的研究也表明受到品种和产地的影响[43]。本研究对青川县橄榄油挥发性物质的研究结果显示鄂植8号和豆果挥发性物质主要为醛类和醇类,与甘肃产区同品种的主要挥发性物质相同,但种类和数量存在差异,使香味成分复杂;皮削利主要挥发性物质为烯烃类,与甘肃产区的皮削利醛类为主要挥发性物质不同,使其香味具有独特的地域特色。萜烯类物质的出现,其在含量和种类的差异,可以作为产地和品种独特标记进行识别。综上所述在青川县白龙江流域独特的气候、土壤和光照条件下,同品种的油橄榄在青川县具有不同其他产区的独特味道,其相关成分可以作为青川橄榄油特殊标识。
有研究表明脂肪酸对橄榄油气味产生影响,随单饱和脂肪酸含量升高,青草味和涩味越浓,多不饱和脂肪酸越高,苦杏味越浓[42],且脂肪酸组成比例对橄榄油气味也有着显著影响,各种气味间相互作用,从而影响橄榄油的香味[43]。本研究中3个品种的脂肪酸组成比例不同,其在挥发性物质含量和种类上也表现出较大差异;皮削利烯烃类挥发性物质为主,其单不饱和脂肪酸含量在品种间最高,4,8-二甲基,1,7-壬二烯和(Z)-乙酸-3-己烯酯是其特有成分。鄂植8号和豆果挥发性物质以醛类为主,在多不饱和脂肪酸中的亚油酸等含量上豆果最高,其次为鄂植8号;豆果挥发性物质成分中金合欢烯含量高于鄂植8号和皮削利,酯类种类较多,鄂植8号己烯-1-醇含量高于皮削利和豆果。综上所述,橄榄油挥发性物质成分较为复杂,可能受品种、加工等多种因素影响,使油脂的挥发性物质产生较大的差别,其与脂肪酸成分的关联性及其产生相关机制还有待与进一步研究。
世界橄榄油主要分布在地中海区域,占世界产量的90%,由于受地理环境等因素影响,地中海各国的初榨橄榄油在挥发性物质、营养成分上存在差异,如突尼斯、阿尔巴尼亚产橄榄油香味平淡,多用于混合其他国家产橄榄油后用于出口[44]。随着美国、阿根廷、智利、印度和伊朗等地的不断地引种,橄榄油来源已逐渐不仅仅局限于地中海区域,也使橄榄油的油脂成分、营养和挥发性物质在不同地区产生较大变化,具有引种地的特色。我国油橄榄种植从西部四川,云南等到东部的安徽、浙江等省,面积不断扩大,在充分考虑生长结实能力的同时,还需要在引种过程中保持品种原产地橄榄油品质的基础上,加强在土壤、水分和肥力等因素的管理,形成具有引种地特色的橄榄油。结合开展油橄榄杂交育种或者加大区域试验范围,筛选出适应不同气候带和风味的油橄榄品种。本研究研究只是针对一个成熟阶段的分析,后续对果实成熟各个阶段内的变化情况有待于进一步研究,以其获得最佳品质的橄榄油。
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Analysis of Composition of Nutritions and Characteristic for Virgin Oil ofOleaeuropaeaL from Qingchuan Country in Sichuan Province
Long Wei1Wang Yubing2Yao Xiaohua1Du Weidong3Lü Leyan4Ren Huadong1
(Zhejiang Provincial Key laboratory of TreeBreeding Research Institute of Subtropical Forestry,Chinese Academy of Forestry1, Hangzhou 311400) (Qingyuan Forestry Product Limited Liability Company of Qingchuan County2, Qingchuan 628100) (Forestry and GardenBureau of Qingchuan County3, Qingchuan 628100)
(Department of Hydraulic, ZhejiangTongji Vocational College of Science and Technology4, Hangzhou 311231)
It was aimed to check out composition of fatty acid, nutritionand volatile substances by GC and GC-MS in virgin olive oil of three varieties which were planted in Qingchuan County, Sichuan Province. The results showed that the average content of unsaturated fatty acid in virginal oil was 82.82%, and they were be ranked asArbequina 83.30%>Picholine 83.05%>E’Zhi 8# 82.1%. There weresignificant difference in oleic acid and linoleicacid of varieties. The average content of ɑ-vitamin E in virginal oil was 28.78 mg/100 g, andthey were be ranked as E’Zhi 8# 32.7 mg/100 g>Picholine 27.5 mg/100 g>Arbequina 24.4 mg/100g. There were significant difference in ɑ-vitamin E of varieties. The average content of squalene in virginal oil was 4512.48 mg/kg, and it was ranked as Picholine 6 690.95 mg/kg>E’Zhi 8# 4 386.50 mg/kg>Arbequina 2 460.00 mg/kg.; There were very significant differences in squalene of varieties. The average content of β-sitosterol in virginal oil was 849.00 mg/kg,andthey were beranked asE’Zhi 8# 1 161.30 mg/kg>Picholine 946.35 mg/kg>Arbequina439.35 mg/kg. There were very significant differences in β-sitosterol of varieties. Volatile compounds were be identified 25 kinds in virginal oil, including four aldehydes, two alcohols, five esters, seven alkenes and five terpenes and two others. Aldehydes were main composition of volatile substances in E’Zhi 8# and Arbequina, accounting for the total material 55.88% and 52.58%. Alkene hydrocarbon were main compositionof volatile substances in Picholine, accounting for the total material of 53.68%. To sum up, there were many specialcharacteristics in virginal oil of Qingchuan, including abundant nutrition, unique volatile substances and flavor. Sothey had obviously geographical characteristics and great value of development.
virginal oil ofOleaeuropaeaL, fatty acid, volatile substance
林业公益性行业科研专项(201104052)
2016-06-07
龙伟,男,1981年出生,助理研究员,经济林遗传育种与良种繁育
姚小华,男,1962年出生,研究员,经济林遗传育种与栽培
TQ646
:A
:1003-0174(2017)08-0077-07