Pollution analysis and dietary exposure risk assessment of lipophilic toxins in shellfish from Beibu Gulf seafood market in Guangxi Province
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摘要: 脂溶性贝类毒素分布广泛，会通过食物链传递，对消费者健康构成巨大威胁。广西北部湾海域是我国重要的海水养殖区，其贝类产量占比超过一半。为评估广西北部湾沿海居民因膳食贝类而引起脂溶性贝类毒素摄入风险，采用液相色谱串联质谱法 (LC-MS/MS) 分析脂溶性贝类毒素含量，24 h 膳食回顾法调查居民连续7 d海产品进食情况，应用海洋生物毒素点评估方法，计算膳食中每日毒素摄入量 (Estimated daily intake, ESI)，对照欧洲食品安全局推荐的急性参考剂量 (Acute reference dose, ARfD) 值，评价其食用安全性。结果显示：检出的4种毒素含量均低于欧盟规定的安全限量值。检出率由高到低依次为环亚胺类毒素 (Gymnodimine, GYM)(83.02%)、大田软海绵酸 (Okadaic acid, OA)(51.16%)、鳍藻毒素 (Dinophysis toxin, DTX-2)(40.91%) 和虾夷扇贝毒素 (Homo-yessotoxin, Homo-YTX)(8.6%)，检出的最高质量分数分别为105.4、31.39、38.19和159.66 μg·kg−1；毒素含量存在季节和物种差异，牡蛎秋季GYM含量最高，冬季OA含量最高。DTX-2更易在秋冬季样品中检出，Homo-YTX只在夏、秋季扇贝和贻贝样品中检出。膳食调查结果显示当地居民贝肉日平均消费量为45 g·d−1。以当地居民贝肉食用量和人体质量估算，OA组毒素ESI为0.26 μg·(kg·d)−1，小于欧盟规定的ARfD [0.3 μg·(kg·d)−1]。但若以欧盟提供的贝肉食用量和人体质量数据估算，ESI [0.34μg·(kg·d)−1]则高于ARfD。研究表明，虽然广西北部湾沿海市售贝类产品中脂溶性贝类毒素检出值低于欧盟规定的安全限量值，但当地居民存在OA组毒素膳食暴露风险。Abstract: Lipophilic shellfish toxins are widely distributed and will be transmitted to consumers through the food chain, posing a great threat to human health. The Beibu Gulf in Guangxi Province is an important mariculture area in China, accounting for more than half of the national output. To estimate the potential dietary exposure risk of coastal residents in that area, we analyzed the contents of lipophilic shellfish toxins by liquid chromatography tandem mass spectrometry. We have used a 24-hour dietary review method to investigate the consumption of marine products by coastal residents for seven consecutive days. Then we calculated the value of estimated daily intake (ESI) of toxins in the diet by using the marine biological toxin point assessment method, and evaluated the edible safety by comparing with the acute reference dose (ARfD) recommended by the European Food Safety Agency. The proportion of samples contaminated with toxins followed a descending order of gyrodimine (GYM) (83.02%), okadaic acid (OA) (51.16%), dinophysis toxin (DTX-2)(40.91%) and homo-yessotoxin (Homo-YTX) (8.6%), with the peak values of 105.4, 31.39, 38.19 and 159.6 µg·kg-1, respectively. The concentration of toxins varied with different seasons and species. Among the six kinds of shellfish, the highest content of OA and GYM was found in oyster, and the peak values were found in winter and autumn samples respectively. The contents of DTX-2 in autumn and winter samples were significantly higher than those in spring and summer samples. Homo-YTX was only detected in scallop and mussel samples in summer and autumn. Dietary survey shows that the average daily shellfish consumption of coastal residents in Beibu Gulf was 45 g·d−1. The ESI value in OA toxin was estimated to be 0.26 μg·(kg·d)−1 based on the shellfish consumption and body masses of local residents, less than the ARfD value [0.3 μg·(kg·d)−1] set by the European Union (EU). However, based on the shellfish consumption and body masses of local residents provided by the EU, the ESI value [0.34 μg·(kg·d)−1] was higher than the ARfD value. The results suggest that although the detection rate of lipophilic shellfish toxin in shellfish samples was lower than the safe limit value set by the EU, there is a risk of dietary exposure to OA toxin for the Beibu Gulf residents.
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图 1 贝类样品中脂溶性贝类毒素质量分数
Figure 1. Mass fractions of lipophilic shellfish toxins in different shellfish samples
图 2 不同季节脂溶性贝类毒素质量分数
注：同一图中标有不同字母表示有显著性差异 (P<00.5)。
Figure 2. Mass fractions of lipophilic shellfish toxins in shellfish in four seasons
Note: Different letters within the same figure indicate significant difference (P<0.05).
图 3 广西北部湾沿海居民海产品摄入种类分布
Figure 3. Distribution of seafood species intake by residents in Beibu Gulf in Gangxi Province
图 4 广西北部湾沿海居民贝肉日均消费量
Figure 4. Mean daily shellfish meat consumption of residents in Beibu Gulf in Guangxi Province
表 1 9种脂溶性贝类毒素检测参数
Table 1. MRM of nine lipophilic shellfish toxins
毒素
Toxin电离模式
ESI mode母离子
Precursor ion/(m/z)子离子
Product ion/(m/z)碰撞电压
Collision energy/eV大田软海绵酸
OA[M+H]− 803.4 255, 563.2 −65, −55 鳍藻毒素1
DTX-1[M+H]− 817.5 255.1, 113.1 −65, −100 鳍藻毒素2
DTX-2[M+H]− 803.5 255.1, 563.2 −65, −55 虾夷扇贝毒素
YTX[M+H]− 1 141.5 1 061.5, 855.5 −65, −50 Homo-虾夷扇贝毒素
Homo-YTX[M+H]− 1 155.5 1 075.5, 869.5 −65, −50 环亚胺毒素
GYM[M+H]+ 508.3 174.3, 490.3 50, 35 螺环内酯毒素
SPX1[M+H]+ 692.5 444.4, 674.4 45, 45 原多甲藻酸1
AZA1[M+H]+ 842.5 806.5, 824.5 40, 50 原多甲藻酸3
AZA3[M+H]+ 828.5 810.4, 792.5 40,50 
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表 2 贝中脂溶性贝类毒素检出率及含量
Table 2. Detection rates and contents of lipophilic shellfish toxins in shellfish samples
脂溶性贝类毒素
Lipophilic shellfish
toxin检出值范围
Detection range/
(μg·kg−1)平均检出值
Mean/
(μg·kg−1)检出率
Detection
rate/%环亚胺毒素
GYM0.12~105.54 33.1 83.02 螺环内酯毒素
SPX1ND ND ND 大田软海绵酸
OA0.34~31.39 7.97 51.16 鳍藻毒素1
DTX-1ND ND ND 鳍藻毒素2
DTX-20.29~38.19 7.65 40.91 原多甲藻酸1
AZA1ND ND ND 原多甲藻酸3
AZA3ND ND ND 虾夷扇贝毒素
YTXND ND ND Homo-虾夷扇贝毒素
Homo-YTX3.83~159.66 47.97 8.60 注：ND表示未检出。 Note: ND. Non detected.
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表 3 脂溶性贝类毒素的毒性等效因子与急性参考值
Table 3. Toxic equivalent factors and ARfD of some shellfish toxins
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表 4 广西北部湾沿海居民脂溶性贝类毒素急性暴露评估
Table 4. Acute dietary exposure to some shellfish toxins of residents in Beibu Gulf in Guangxi Province
毒素
Toxin贝肉日P99消费量
P99 daily shellfish consumption/g毒素检出的最大值
Max/(μg·kg−1)每日摄入量
ESI/[μg·(kg·d)−1]急性参考剂量
ARfD/[μg·(kg·d)−1]第一组
First group第二组
Second group大田软海绵酸
OA205 31.39 0.26 0.34 0.3 38.19 虾夷扇贝毒素
YTX159.66 0.6 1.1 25
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表 5 广西北部湾沿海居民脂溶性贝类毒素慢性暴露评估
Table 5. Chronic dietary exposure to some shellfish toxins of residents in Beibu Gulf in Guangxi Province
毒素
Toxin贝肉日均消费
Daily shellfish consumption/g毒素检出的均值
Mean detected value/(μg·kg−1)贝肉日P99消费量
P99 daily shellfish consumption/g每日摄入量
ESI//[μg·(kg·d)−1]第一组
First group第二组
Second group大田软海绵酸
OA45 7.97 205 6.58×10−3 0.03 鳍藻毒素2
DTX-27.65 3.79×10−3 0.017 Homo-虾夷扇贝毒素
Homo-YTX47.97 0.04 0.18
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