Study on distribution characteristics and storage variation of semicarbazide in Macrobrachium rosenbergii
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摘要: 氨基脲 (Semicarbazide, SEM) 为一种有毒物质，是判断呋喃西林是否违规使用的标记性残留物。为探讨甲壳类水产品中氨基脲的检出情况，采用高效液相色谱-串联质谱联用法 (High performance liquid chromatography-mass spectrometry, HPLC-MS/MS) 对罗氏沼虾 (Macrobrachium rosenbergii) 中的SEM进行了检测。结果显示，罗氏沼虾不同部位均检出SEM，其中头胸甲和虾壳等甲壳部位SEM检出值较高 [平均 (32.02±3.75) 和 (26.85±13.90) μg·kg−1]，肌肉和肝脏的SEM检出值较低 [平均 (1.35±0.67) 和 (5.56±0.87) μg·kg−1]，均超过我国现行规定的残留限量标准 (1 μg·kg−1)；罗氏沼虾虾壳和虾肉中的SEM检出值随贮藏时间的增加而减小，甲壳组织中SEM检出值始终高于1.0 μg·kg−1，而不同贮藏温度对罗氏沼虾中SEM检出值影响较小。因此，以SEM为标志物对罗氏沼虾进行呋喃西林残留检测时，应考虑样品贮藏时间及本底含量因素，以避免误判；同时为确保检测结果的真实性和准确性，在制备样品时应避免将碎壳混入虾肉中。Abstract: Semicarbazide (SEM) is a toxic substance, which is a marker residue to determine whether Nitrofurazone is used illegally or not. To explore the detection of SEM in Crustacean aquatic products, we detected the SEM content of M. rosenbergii by High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS/MS). The results show that SEM was detected in different parts of M. rosenbergii, higher in the cephalothorax and shrimp shell [Average: (32.02±3.75) and (26.85±13.90) μg·kg−1], but lower in the muscle and liver [Average: (1.35±0.67) and (5.56±0.87) μg·kg−1], and all exceeded the residue limit standards in China (1 μg·kg−1). The SEM content in the shrimp shell and shrimp meat increased with the prolongation of storage time, but that in the shrimp shell was higher than 1.0 μg·kg−1. Different storage temperatures had a little effect on the SEM content of M. rosenbergii. Therefore, when taking SEM as a marker for Nitrofurazone residue detection of M. rosenbergii, the detection time and background content factors should be considered so as to avoid false judgment; and in order to ensure the authenticity and accuracy of the test results, the crushed shell should be avoided in preparing samples.
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图 3 罗氏沼虾不同部位SEM检出值的分布情况
Figure 3. Distribution of SEM values in different parts of M. rosenbergii
图 4 罗氏沼虾贮藏期间SEM检出值变化
注：不同大写字母表示不同贮藏时间下罗氏沼虾SEM检出值差异显著 (P<0.05)；不同小写字母表示不同贮藏温度下罗氏沼虾SEM检出值差异显著 (P<0.05)。
Figure 4. Changes of SEM contents during storage of M. rosenbergii
Note: Different uppercase letters indicate significant difference in the SEM content of M. rosenbergii at different storage times (P<0.05); different lowercase letters indicate significant difference in the SEM content of M. rosenbergii at different storage temperatures (P<0.05).
表 1 液相色谱梯度洗脱条件
Table 1. Program of gradient elution
时间
t/min流速
Flow rate/(mL·min−1 )流动相 A
Mobile phase A/%流动相 B
Mobile phase B/%0 0.35 75 25 3.0 0.35 70 30 4.0 0.35 30 70 4.5 0.35 75 25 6.0 0.35 75 25 
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表 2 呋喃西林代谢物及其内标的质谱条件
Table 2. Nitrofurazone metabolites and their internal target mass spectrometry conditions
被测物
Analyte母离子
Precursor ion/
(m/z)子离子
Product ion/
(m/z)锥孔电压
DP/V碰撞能量
CE/V氨基脲 SEM 209.1 166.1* 24 9 192.1 24 10 氨基脲内标
SEM-15N2-13C212.1 168.1 24 9 注：*. 定量离子。 Note: *. Quantitative ion.
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表 3 样品中SEM的加标回收率和精密度
Table 3. Standard recovery and precision of SEM in samples
加标量
Added amount/(μg·kg−1)回收率
Recovery rate/%相对标准偏差
RSD/%1 96.00 8.84 5 92.20 6.11 10 97.30 2.02
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表 4 罗氏沼虾不同部位SEM检出值
Table 4. SEM content in different parts of M. rosenbergii
样品
Sample样品数
Number of samplesSEM检出值
SEM content/(μg·kg−1)均值±标准差
$ \overline { X}\pm { \rm {SD}} $/(μg·kg−1)检出率
Detection rate/%头胸甲 Cephalothorax 8 26.31~37.54 32.02±3.75 100 虾壳 Shrimp shell 8 10.80~50.17 26.85±13.90 100 尾扇 Shrimp tail 8 16.45~30.11 23.97±4.11 100 肢足 Shrimp foot 6 17.45~24.15 21.03±2.51 100 肝 Shrimp liver 6 4.59~7.31 5.56±0.87 100 虾肉 Shrimp meat 8 ND~2.72 1.35±0.67 87.5 注：ND. 检测结果小于0.50 μg·kg−1。 Note: ND. The result is less than 0.50 μg·kg−1.
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表 5 罗氏沼虾虾壳和虾肉中SEM的检出值
Table 5. Detection of SEM in shrimp shell and meat of M. rosenbergii
样品
SampleSEM检出值 SEM content/(μg·kg−1) 平行样1
Replicate 1平行样2
Replicate 2平行样3
Replicate 3平行样4
Replicate 4平均值
Mean虾壳 Shrimp shell 31.80±1.11 27.63±1.67 29.18±2.03 32.23±1.76 30.21±1.64 虾肉 Shrimp meat 1.93±0.17 1.63±0.09 1.38±0.13 1.73±0.29 1.66±0.17 比值 Ratio 16.47 16.95 21.14 18.63 18.19
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