CN105586321A - 一种降解农产品中残留辛硫磷的酶制剂及其方法 - Google Patents

一种降解农产品中残留辛硫磷的酶制剂及其方法 Download PDF

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CN105586321A
CN105586321A CN201510974902.XA CN201510974902A CN105586321A CN 105586321 A CN105586321 A CN 105586321A CN 201510974902 A CN201510974902 A CN 201510974902A CN 105586321 A CN105586321 A CN 105586321A
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phoxim
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胡玲
李娟�
尹若春
王林
罗学才
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Hefei Shixiandu Biotechnology Co Ltd
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Anhui University
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Abstract

本发明公开了一种降解农产品中残留辛硫磷的酶制剂及其方法，所述酶制剂的组分包括：醇脱氢酶、辣根过氧化物酶、木聚糖酶、过氧化氢酶、漆酶、多酚氧化酶中的一种或多种混合物，所述方法的步骤为：将所述酶制剂直接添加到待处理农产品上，或者在待处理农产品的加工工艺中添加上述酶制剂。本发明的降解农产品中残留辛硫磷的酶制剂及其方法能够简单快速有效地去除农产品中的辛硫磷残留，不需要进行酶的失活处理，也不需要调节pH值，降解方法简单经济，且不会造成二次污染，对农产品中残留辛硫磷的去除率达到90-99％。

Description

一种降解农产品中残留辛硫磷的酶制剂及其方法
技术领域
本发明涉及的是农药残留降解的技术领域，尤其涉及的是一种适用于农产品辛硫磷降解的酶制剂及其方法。
背景技术
辛硫磷又名肟硫磷、倍腈松，化学名为O-二乙基硫代磷酸酯。辛硫磷是一种广谱杀虫剂，击倒力强，以触杀和胃毒作用为主，无内吸作用，对鳞翅目幼虫很有效，目前已广泛用于防治多种作物害虫，包括地下害虫和仓库害虫。在中性及酸性介质中稳定，在碱性介质中易分解；高温下易分解，光解速度快，在黑暗或遮光条件下分解慢，残留期可达2-3个月。
辛硫磷作为有机磷农药中的一种，因其具有光敏性强，降解速度快，在环境中不稳定的特点而被广泛使用。但是辛硫磷的过量使用会造成水污染、土壤污染，进而通过生物富集作用而影响到动物及人类的健康。有研究表明，长期接触辛硫磷会对心脏、肝脏等器官及生殖系统造成伤害。因此，辛硫磷残留超标问题不容忽视。在我国国家标准中(GB14869—1994)，对辛硫磷在食品中的残留量做出明确规定：粮食(原粮)、蔬菜、水果最大残留量每公斤不得超过0.05mg。
辛硫磷等有机磷杀虫剂在作物不同部位的残留情况有所差异，如在根类或块茎类作物比在叶菜类或豆类的豆荚部分的残留时间长。辛硫磷等有机磷杀虫剂主要残留在谷粒和叶菜类的外皮部分，故粮食经加工后，残留的辛硫磷主要存留在用作饲料的加工副产品部分如麦麸和米糠等。
发明内容
本发明的目的在于克服现有技术的不足，提供了一种降解农产品中残留辛硫磷的酶制剂及其方法，以简单快速的方法降解辛硫磷，农产品中残留辛硫磷的降解率高达90％～99％，且不会造成二次污染。
本发明是通过以下技术方案实现的：
本发明提供了一种降解农产品中残留辛硫磷的酶制剂，所述酶制剂的组分包括：纯脱氢酶、辣根过氧化物酶、木聚糖酶、过氧化氢酶、漆酶、多酚氧化酶中的一种或多种混合物。
优选地，对于粮食作物类农产品中残留辛硫磷的降解，所述酶制剂中各组分与农产品的质量百分比分别为：醇脱氢酶0.01％～0.15％，辣根过氧化物酶0.001％～0.02％，木聚糖酶0.08％～0.25％，超氧化物歧化酶0.01％～0.05％，过氧化氢酶0.03％～0.23％，漆酶0.01％～0.25％，多酚氧化酶0.02％～0.5％。
优选地，对于初级加工类农产品中残留辛硫磷的降解，所述酶制剂中各组分与农产品的质量百分比分别为：醇脱氢酶0.05％～0.25％，辣根过氧化物酶0.01％～0.2％，木聚糖酶0.05％～0.5％，超氧化物歧化酶0.01％～0.35％，过氧化氢酶0.05％～0.15％，漆酶0.05％～0.45％，多酚氧化酶0.05％～0.35％。
优选地，所述酶制剂中的各组分均为食品级。
本发明还提供了一种降解农产品中残留辛硫磷的方法，将上述酶制剂直接添加到待处理农产品上，或者在待处理农产品的加工工艺中添加上述酶制剂。
优选地，对于果蔬类农产品，将农产品直接浸泡在所述酶制剂的水溶液中10-60min，即可去除果蔬类农产品中残留辛硫磷，进一步优选地，所述酶制剂的水溶液的质量浓度为0.01-0.5％，酶制剂的水溶液与农产品的质量比为1.5：1。
优选地，对于粮食作物类农产品，直接在该农产品表面喷洒所述酶制剂的水溶液，然后在20-40℃下恒温保持1-12h。
优选地，对于初级加工的农产品，在农产品的加工过程中直接添加所述酶制剂，进一步优选地，所述酶制剂的添加量为农产品总质量的0.001-0.5％。
本发明相比现有技术具有以下优点：本发明提供了一种降解农产品中残留辛硫磷的酶制剂及其方法，该酶制剂和方法对农产品中残留辛硫磷的去除率达到90-99％，且所用的酶制剂均为食品级，可直接喷洒在农作物产品表面，或直接在加工过程中添加，而不需要对原有加工工艺做出调整，且不需要另外添加新的仪器设备；本发明能够简单快速有效地去除农产品中的辛硫磷残留，不需要进行酶的失活处理，也不需要调节pH值，降解方法简单经济，且不会造成二次污染。
附图说明
图1是辛硫磷标准样品的HPLC图谱；
图2是实施例1中处理后样品中残留辛硫磷的HPLC图谱；
图3是实施例2中处理后样品中残留辛硫磷的HPLC图谱；
图4是实施例3中处理后样品中残留辛硫磷的HPLC图谱；
图5是实施例4中处理后样品中残留辛硫磷的HPLC图谱；
图6是实施例5中处理后样品中残留辛硫磷的HPLC图谱；
图7是实施例6中处理后样品中残留辛硫磷的HPLC图谱；
图8是实施例7中处理后样品中残留辛硫磷的HPLC图谱。
具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
本实施例提供的一种酶制剂及其降解农产品中残留辛硫磷的方法，适用于初级农产品中残留辛硫磷的去除，本实施例以叶类蔬菜白菜为例，包括以下步骤：
(1)将白菜浸泡在酶制剂中，所述酶制剂与白菜的质量比为1.5：1，所述酶制剂的组分(食品级)及其质量浓度为：木聚糖酶0.2％，醇脱氢酶0.06％，多酚氧化酶0.05％，超氧化物歧化酶0.03％，余量为水；
(2)浸泡20min后，取出白菜；
(3)检测处理前后白菜中残留辛硫磷的含量分别为2mg/kg和0.1mg/kg，并计算降解率为95％。
实施例2
本实施例提供的一种酶制剂及其降解农产品中残留辛硫磷的方法，适用于初级农产品中残留辛硫磷的去除，本实施例以小麦为例，包括以下步骤：
(1)将20000U/L的醇脱氢酶(食品级)水溶液和1000U/L的过氧化氢酶(食品级)水溶液喷洒到小麦上，醇脱氢酶水溶液、过氧化氢酶水溶液和小麦的质量比为1:1:10；
(2)30℃下保持4h后，取出小麦；
(3)检测处理前后小麦中残留辛硫磷的含量，分别为2mg/kg和0.2mg/kg，并计算降解率为90％。
实施例3
本实施例提供了一种酶制剂及其降解农产品中残留辛硫磷的方法，适用于初级加工的农产品，本实施例以谷朊粉为例，包括以下步骤：
(1)按照常规方法用小麦面粉提取谷朊粉，在和面过程中随水冲入酶制剂，所述酶制剂的组分(食品级)及其与小麦面粉的质量浓度为：木聚糖酶0.05％、漆酶0.01％、过氧化氢酶0.1％。
(2)检测小麦面粉中残留辛硫磷的含量为3.2mg/kg，提取后的谷朊粉中残留辛硫磷含量为0.26mg/kg，并计算谷朊粉中辛硫磷的降解率为92％。
实施例4
本实施例提供了一种酶制剂及其降解农产品中残留辛硫磷的方法，适用于初级加工类农产品，本实施例以花生壳为例，包括以下步骤：
(1)将酶制剂配制成水溶液直接喷洒在花生壳上，所述酶制剂为过氧化氢酶，其与花生壳的质量百分比为0.1％；
(2)30℃下保持3h后，取出花生壳即可；
(3)检测处理前后花生壳中残留辛硫磷的含量分别为5mg/kg和0.35mg/kg，并计算降解率为93％。
实施例5
本实施例提供了一种酶制剂及其降解农产品中残留辛硫磷的方法，适用于粮食作物类农产品，本实施例以玉米棒为例，包括以下步骤：
(1)将酶制剂配制成水溶液直接喷洒在玉米棒上，所述酶制剂的组分及其与玉米棒的质量百分比为：超氧化物歧化酶0.05％，过氧化氢酶0.23％，漆酶0.25％，多酚氧化酶0.5％；
(2)25℃下保持12h后，取出农作物；
(3)检测处理前后玉米棒中残留辛硫磷的含量分别为4.2mg/kg和0.27mg/kg，并计算降解率为93.5％。
实施例6
本实施例提供了一种酶制剂及其降解农产品中残留辛硫磷的方法，适用于初级加工类农产品，本实施例以苹果浓缩汁加工为例，包括以下步骤：
(1)在苹果汁的加工过程中直接添加酶制剂，所述酶制剂的组分及其与处理前苹果的质量百分比为：木聚糖酶0.05％，超氧化物歧化酶0.01％，过氧化氢酶0.05％；
(2)检测处理前苹果中残留辛硫磷的含量为2.75mg/kg，处理后苹果浓缩汁中辛硫磷的含量为0.15mg/kg，并计算降解率为94.5％。
实施例7
本实施例提供了一种酶制剂及其降解农产品中残留辛硫磷的方法，适用于初级加工类农产品，本实施例以土豆粉为例，包括以下步骤：
(1)在土豆粉的加工过程中，打芡过程中添加酶制剂，所述酶制剂的组分及其与处理前土豆的质量百分比为：醇脱氢酶0.25％，辣根过氧化物酶0.2％，漆酶0.45％，多酚氧化酶0.35％；
(2)检测处理前后土豆粉中残留辛硫磷的含量分别为3mg/kg和0.09mg/kg，并计算降解率为97％。
利用高效液相色谱HPLC法测定实施例1-7中处理后样品中辛硫磷的含量，其中，HPLC的检测条件为：色谱柱SunFireC18Column，5μm，4.6×150mm，流动相A为水，流动相B为乙睛，流速0.8ml/min，柱温25℃，检测波长263nm，进样量15μl，非梯度洗脱，检测时间为15min。
结果如图1-8所示，图中可以看出：辛硫磷标样的出峰时间为9.6min，每个实施例中辛硫磷含量均明显降低。

Claims (10)

1.一种降解农产品中残留辛硫磷的酶制剂，其特征在于，所述酶制剂的组分包括：醇脱氢酶、辣根过氧化物酶、木聚糖酶、过氧化氢酶、漆酶、多酚氧化酶中的一种或多种混合物。
2.根据权利要求1所述的一种降解农产品中残留辛硫磷的酶制剂，其特征在于，对于粮食作物类农产品中残留辛硫磷的降解，所述酶制剂中各组分与农产品的质量百分比分别为：醇脱氢酶0.01％～0.15％，辣根过氧化物酶0.001％～0.02％，木聚糖酶0.08％～0.25％，超氧化物歧化酶0.01％～0.05％，过氧化氢酶0.03％～0.23％，漆酶0.01％～0.25％，多酚氧化酶0.02％～0.5％。
3.根据权利要求1所述的一种降解农产品中残留辛硫磷的酶制剂，其特征在于，对于初级加工类农产品中残留辛硫磷的降解，所述酶制剂中各组分与农产品的质量百分比分别为：醇脱氢酶0.05％～0.25％，辣根过氧化物酶0.01％～0.2％，木聚糖酶0.05％～0.5％，超氧化物歧化酶0.01％～0.35％，过氧化氢酶0.05％～0.15％，漆酶0.05％～0.45％，多酚氧化酶0.05％～0.35％。
4.根据权利要求1所述的一种降解农产品中残留辛硫磷的方法，其特征在于，所述酶制剂中的各组分均为食品级。
5.一种降解农产品中残留辛硫磷的方法，其特征在于，将如权利要求1-3所述的酶制剂直接添加到待处理农产品上，或者在待处理农产品的加工工艺中添加上述酶制剂。
6.根据权利要求5所述的一种降解农产品中残留辛硫磷的方法，其特征在于，对于果蔬类农产品，将农产品直接浸泡在所述酶制剂的水溶液中10-60min。
7.根据权利要求6所述的一种降解农产品中残留辛硫磷的方法，其特征在于，所述酶制剂的水溶液的质量浓度为0.01-0.5％，酶制剂的水溶液与农产品的质量比为1.5：1。
8.根据权利要求5所述的一种降解农产品中残留辛硫磷的方法，其特征在于，对于粮食作物类农产品，直接在该农产品表面喷洒所述酶制剂的水溶液，然后在20-40℃下恒温保持1-12h。
9.根据权利要求5所述的一种降解农产品中残留辛硫磷的方法，其特征在于，对于初级加工的农产品，在农产品的加工过程中直接添加所述酶制剂。
10.根据权利要求9所述的一种降解农产品中残留辛硫磷的方法，其特征在于，所述酶制剂的添加量为农产品总质量的0.001-0.5％。
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