Stability of arsenic compounds in seafood samples during processing and storage by freezing

In this study, the stability of arsenic compounds in fresh and frozen samples of raw, boiled and fried Atlantic cod (Gadhus morhua), Atlantic salmon (Salmo salar) and blue mussel (Mytilus edulis) were examined. Results show that the total arsenic concentrations of the fresh Atlantic cod and Atlantic salmon samples were not different from the frozen samples within the same seafood type. For blue mussel, the total arsenic concentration decreased significantly after storage. Inorganic arsenic was found only in blue mussels and, importantly, no significant increase of inorganic arsenic was observed after processing or after storage by freezing. The content of tetramethylarsonium ion was generally low in all samples types, but increased significantly in all fried samples of both fresh and frozen seafood. Upon storage by freezing, the arsenobetaine content was reduced significantly, but only in the samples of blue mussels.     

Incidence of Listeria species in seafood and seafood salads

A total of 128 samples of seafood on the Icelandic market were tested for the presence of Listeria monocytogenes and other Listeria species. The samples included raw, smoked and dried fish, frozen shellfish and shrimps as well as several fish salads. These products are generally consumed without heating. Listeria spp. were present in 56% of the samples of raw fish, 29% of the smoked fish, 9% of the shrimps and 32% of the salads. No Listeria spp. were present in the shellfish or dried fish. In 46% of the positive samples L. monocytogenes could be demonstrated, either alone or together with L. innocua. The other positive samples contained L. innocua and, in one sample, L. welshimeri. All products sampled had been processed and packed in Iceland, mostly for use on the domestic market. It is suggested that consuming certain fish products and fish salads may form an additional risk factor for listeriosis in humans.     

毛细管电泳-电感耦合等离子体质谱（CE-ICP-MS）联用测定干海产品中的六种砷形态化合物

采用电感耦合等离子体质谱（ICP-MS）测定了鱿鱼、银鱼、沙丁鱼、虾、牡蛎、蛤蜊、紫菜、羊栖菜、海带、浒苔10种干海产品中的砷总量,建立了毛细管电泳（CE）与ICP-MS联用测定亚砷酸盐As（III）、砷酸盐As（V）、甲基砷酸（MMA）、二甲基砷酸（DMA）、砷甜菜碱（AsB）和砷胆碱（AsC）六种砷形态化合物的分析方法。结果发现除了浒苔其余干海产品中砷总量均超出了无机砷允许限值（GB 2762-2005）,形态分析结果表明干海产品中主要是有机砷,萃取液中无机砷含量仅占砷总量的0¹5.2%。该方法简单方便、快速,样品消耗量少,而且具有较好的准确性,适用于其他生物样品中砷形态化合物的分析。      

Preserving the distribution of inorganic arsenic species in groundwater and acid mine drainage samples

The distribution of inorganic arsenic species must be preserved in the field to eliminate changes caused by metal oxyhydroxide precipitation, photochemical oxidation, and redox reactions. Arsenic species sorb to iron and manganese oxyhydroxide precipitates, and arsenite can be oxidized to arsenate by photolytically produced free radicals in many sample matrices. Several preservatives were evaluated to minimize metal oxyhydroxide precipitation, such as inorganic acids and ethylenediaminetetraacetic acid (EDTA). EDTA was found to work best for all sample matrices tested. Storing samples in opaque polyethylene bottles eliminated the effects of photochemical reactions. The preservation technique was tested on 71 groundwater and six acid mine drainage samples. Concentrations in groundwater samples reached 720 microg-As/L for arsenite and 1080 microg-As/L for arsenate, and acid mine drainage samples reached 13 000 microg-As/L for arsenite and 3700 microg-As/L for arsenate. The arsenic species distribution in the samples ranged from 0 to 90% arsenite. The stability of the preservation technique was established by comparing laboratory arsenic speciation results for samples preserved in the field to results for subsamples speciated onsite. Statistical analyses indicated that the difference between arsenite and arsenate concentrations for samples preserved with EDTA in opaque bottles and field speciation results were analytically insignificant. The percentage change in arsenite:arsenate ratios for a preserved acid mine drainage sample and groundwater sample during a 3-month period was -5 and +3%, respectively.     

海产品中砷形态分析研究进展

我国是海产品的生产和消费大国,所以海产品的安全问题受到人们越来越多的关注。海产品特别是食用海藻含砷量较高,但是海产品中的砷大部分以低毒性的有机砷形态存在,而且不同种类的海产品所含有的砷形态各不相同。所以,对海产品中的不同形态砷化合物进行精准分析检测,对于科学、客观评估海产品中砷污染的健康风险以及保证海产品的安全消费具有重要意义。海产品的砷形态分析面临的困难主要是,第一在不改变砷形态的前提下把海产品中所有形态砷化合物完全提取出来;第二把各形态有机砷和无机砷在较短时间内实现基线分离、并对各形态砷化合物进行高灵敏检测。近十多年来,有关海产品中砷的形态分析得到越来越多的关注,在方法学上也取得了显著的进步。本文主要针对近十多年来有关不同海产品中不同形态砷化合物的提取方法和分析检测方法方面的研究进展进行了概述,以期为食品检测机构或食品安全研究或评估人员提供方法学上的参考。     

广州市售海产品中砷质量安全与健康风险评估

目的对广州市售海产品进行砷质量安全评价与健康风险评估。方法采用等离子体质谱仪和高效液相色谱-原子荧光联用仪分别对广州10种市售海产品中总砷和5种砷形态化合物:亚砷酸(arsenictrioxide,As(III))、砷酸(arsenicacid,As(V))、一甲基砷(monomethylarsenic,MMA)、二甲基砷(dimethylarsenic,DMA)和砷甜菜碱(arsenobetaine, AsB)的含量进行测量,根据GB 2762-2017《食品安全国家标准食品中污染物限量》海产品中砷含量的要求对海产品质量安全进行评价,利用危险熵数(hazardquotient,HQ)和致癌风险概率(carcinogenicrisk,CR)对其进行健康风险评估。结果海产品中总砷含量为1.45～42.54mg/kg,所有海产品中均能检测到5种砷化合物,其中无毒的AsB比例最高(93.45～99.96%)。在所有海产品中,贝类总砷含量最高,无毒的AsB所占比例较高;鱼类总砷含量低于贝类, AsB含量和比例较高,无机砷含量和比例较低。海产品中无机砷的含量均低于限量值,在国标要求的允许摄入范围内。海产品中无机砷的HQ均1, CR1×10~(-4)。结论广州市售海产品中砷含量处于安全水平,日常消费对人类不会造成致癌风险以及健康威胁。     

食用菌中的总砷和砷形态分布研究

研究总砷超标食用菌样品中砷的形态分布,对食用菌中总砷含量与食用安全性的关系及其限量规定进行探讨。方法从2010年深圳口岸进出口食用菌批量监测结果的各种食用菌样品中选择总砷超标的几类样品,采用液相色谱-氢化物发生原子荧光光谱联用技术(LC-HGAFS)分析了不同种类食用菌中的砷形态,准确测定了总无机砷与总砷含量。结果发现形态分析方法能够准确定性定量食用菌中的总无机砷含量,而食用菌中总砷含量和总无机砷含量并不存在对应关系,干香菇中总砷和总无机砷含量均较高,有一定食用风险,而蘑菇中总砷含量高,总无机砷含量却很低,主要以一甲基砷等其他无毒的砷形态存在,可以放心食用。结论食用菌中砷形态分布测定更能科学体现砷超标和食用安全性的关系,我国现行食用菌卫生标准仅规定总砷限量指标,建议进行修订。     

嘉兴市经营环节海产品中砷的形态分布与膳食暴露风险评估

目的 了解嘉兴市经营环节海产品中砷的形态分布情况,评估食用海产品暴露的砷对人体的健康风险。方法 采用液相色谱-电感耦合等离子体质谱联用技术（HPLC-ICP-MS）对嘉兴市经营环节中采集的5种共105份海产品样品总砷及砷形态污染情况进行检测,结合嘉兴市居民水产品消费数据,对食用海产品带来的无机砷暴露的健康风险进行分析。结果 105份样品中,5种海产品中总砷平均含量范围为0.85~41.85 mg/kg,主要以无毒的砷甜菜碱或砷糖为主,有机砷含量占总砷的90%以上。无机砷的检出率为45.7%,检出浓度范围为0.015~1.169 mg/kg,中位值为0.011 mg/kg,含量较高的海产品主要为海藻类、甲壳类,其中1份样品高于GB 2762—2022的水产品限量值,超标率为0.95%。暴露边界比值（MOE）健康风险分析结果表明,嘉兴市居民食用海产品的健康风险较低（MOE值均远大于1）,城市居民风险程度略高于农村居民,女性风险程度略高于男性。结论 嘉兴市居民食用一般海产品暴露的无机砷引起的健康风险较低,但要避免长期大量摄入无机砷较高的海产品（海藻类、甲壳类）。     

X-ray absorption near-edge structure analysis of arsenic species for application to biological environmental samples

Arsenic is an element that is ubiquitous in the environment and is known to form compounds with toxic, even carcinogenic properties. Arsenic toxicity is a function of its chemical form (species). Identification of arsenic species is necessary to accurately determine the transformation and fate of arsenicals as well as the actual risk posed by arsenic contamination. We report X-ray absorption near-edge structure (XANES) measurements of 16 biologically important arsenic compounds. Solid and aqueous standards were studied for differences in XANES spectral features, white line positions, stability during exposure to the beam, and stability between two beam exposures separated by 48 h. Samples containing As(III) (11870.0-11871.7+/-0.5 eV) and As(V) (11872.6-11875.3+/-0.5 eV) were easily distinguished by white line energies and could be further subdivided into a total of seven groups. Valuable examples include As(III)-sulfur compounds (11870.0+/-0.5 eV), arsenobetaine and arsenocholine (11872.6+/-0.5 eV), and a dimethyl arsinyl riboside (11873.3+/-0.5 eV). A growing number of environmental and biological studies use X-ray absorption spectroscopy (XAS) results to complement their more traditional analyses. Results provided here are intended to help make XAS more accessible to new users interested in the study of arsenic in the environment.     

Jatropha platyphylla, a new non-toxic Jatropha species: Physical properties and chemical constituents including toxic and antinutritional factors of seeds

Local communities in Mexico consume Jatropha platyphylla seeds after roasting. The kernels of J. platyphylla contained ca. 60% oil and were free of phorbol esters. The kernel meal of this Jatropha species contained trypsin inhibitor, lectins and phytate. However, trypsin inhibitor and lectins are heat labile so this explains why the local people can eat roasted seeds without ill effects. Heat-treated J. platyphylla kernel meal (JPKM) was free of trypsin inhibitor and lectin activities. Crude protein content of JPKM was 75%. Heated JPKM and soybean meal were included in a standard diet (crude protein 36%) for Nile tilapia (Oreochromis niloticus) to replace 50% of the fish meal protein. The growth of fish in all the three groups was statistically similar and the blood biochemical parameters that serve as biomarkers for toxicity were within the normal ranges. This is the first study that confirms the non-toxic nature of J. platyphylla.     

海产品致病菌检测考核样品的制备研究

目的 结合我国现行食品卫生标准, 探索优化海产品致病菌检测考核样品的制备方法, 并检验样品的均匀性与稳定性。方法 以海虾酱为主要基质, 添加目标菌后制成人工污染样品, 通过样品的均匀性与稳定性研究, 优化样品中各基质的组分来配制出合格的质控考核样品。结果 海虾酱中加入枸橼酸钠、吐温-80、氟康唑等介质, 在一定的pH值条件下, 目标菌在样品中可以均匀分布, 将样品密封储存5~22 ℃环境中下, 14 d后样品外观无明显变化, 目标菌可以正常检出且无其他致病菌的生长, 样品均匀性、稳定性均满足考核样的使用要求。结论 建立的海产品致病菌检测质控考核样品的制备方法与程序有效, 适用于考核与评估实验室的检测能力, 可以为构建复杂的微生物能力验证样品奠定基础、搭建平台。     

Fast extraction methodologies for the determination of toxic arsenic in meat

A nonchromatographic analytical procedure has been developed for the determination of arsenic in meat samples including the major toxic arsenic species arsenite, arsenate, monomethylarsonic acid (MMA) and dimetylarsinic acid (DMA). The method is based on the extraction of arsenic species in mild conditions, selective trivalent hydride formation and final determination by hydride generation atomic fluorescence spectroscopy (HG‐AFS). Different extractant agents and two different procedures, microwave‐assisted extraction (MAE) and ultrasound assisted extraction at room temperature, were evaluated for As species extraction. The method provided a limit of detection of 0.013 ng mL^?1 and a mean relative standard deviation in actual samples of 0.3%. Data found for toxic As in meat samples varied from 0.42 ng g^?1 in chicken muscle to 68 ng g^?1 in pork liver. Percentage of toxic As respect to total As varied in the 9–46% range depending on the meat product.     

Prevalence of potentially pathogenic Vibrio species in the seafood marketed in Malaysia

Seafood samples obtained in seafood markets and supermarkets at 11 sites selected from four states in Malaysia were examined for the presence of nine potentially pathogenic species from the genus Vibrio between July 1998 and June 1999. We examined 768 sample sets that included shrimp, squid, crab, cockles, and mussels. We extensively examined shrimp samples from Selangor State to determine seasonal variation of Vibrio populations. Eight potentially pathogenic Vibrio species were detected, with overall incidence in the samples at 4.6% for V. cholerae, 4.7% for V. parahaemolyticus, 6.0% for V. vulnificus, 11% for V. alginolyticus, 9.9% for V. metschnikovii, 1.3% for V. mimicus, 13% for V. damsela, 7.6% for V. fluvialis, and 52% for a combined population of all of the above. As many as eight Vibrio species were detected in shrimp and only four in squid and peel mussels. The overall percent incidence of any of the eight vibrios was highest (82%) in cockles (Anadara granosa) among the seafoods examined and was highest (100%) in Kuching, Sarawak State, and lowest (25%) in Penang, Pulau Penang State, among the sampling sites. Of 97 strains of V. cholerae isolated, one strain belonged to the O1 serotype and 14 to the O139 serotype. The results indicate that the various seafood markets in Malaysia are contaminated with potentially pathogenic Vibrio species regardless of the season and suggest that there is a need for adequate consumer protection measures.     

Comparative evaluation of non-toxic and toxic varieties of Jatropha curcas for chemical composition,digestibility, protein degradability and toxic factors

Four varieties of Jatropha curcas which originated from Nicaragua (Cape Verde and Nicaragua toxic varieties cultivated in Managua), Nigeria (a wild variety from Ife; toxicity unknown) and Mexico (a wild non-toxic variety collected from Papantla) were studied. The average seed weight was 0.69, 0.86, 0.53 and 0.65 g for Cape Verde, Nicaragua, Ife-Nigeria and non-toxic Mexico varieties, respectively. The kernel to shell ratio in seeds was relatively similar (62.7:37.3 for both Cape Verde and Nicaraguan, 60:40 for Ife-Nigerian and 63.5:36.5 for non-toxic Mexican). The shell of the seeds composed mainly of fiber (>83% neutral detergent fiber) and very little crude protein (CP < 6%). The kernels were rich in CP (22.2–27.7%) and lipid (53.9–58.5%). The meal (defatted kernels) had a CP content of 57.3, 61.9, 56.1 and 64.4% for Cape Verde, Nicaragua, Ife-Nigeria and non-toxic Mexico varieties, respectively, and about 90% of this CP was true protein. The pepsin insoluble nitrogen was from 5.5 to 7%. The amino acid composition of meals from Cape Verde, Nicaragua and non-toxic Mexico varieties was similar. The levels of essential amino acids except lysine were higher than that for the FAO reference protein. The meal from the toxic variety (Cape Verde) did not have any anti-fermentative activity on rumen microbes. The estimated digestible organic matter (DOM) and metabolizable energy (ME) for the shells were low (26.2–27.1% and 2.4–2.8 MJ kg⁻¹), whereas these values for Jatropha meals were 77.3–78.4% and 10.7–10.9MJ kg⁻¹. For commercially available (heat-treated) soyabean meal, DOM and ME were 87.9% and 13.3MJ kg⁻¹, respectively. The in-vitro rumen degradable nitrogen (% of total nitrogen) for meals from Cape Verde, Nicaragua, Ife-Nigeria and non-toxic Mexico varieties was 43.3, 37.7, 38.7 and 28.9, respectively, and for the soyabean meal it was 80.9%. Tannins, cyanogens, glucosinolates and amylase inhibitors were not detected in meals of any of the four varieties. A small amount of tannins were present in shells (2.0–2.9% as tannic acid equivalent). High levels of trypsin inhibitor activity (18.4–26.5 mg trypsin inhibited g⁻¹), lectin (51–102; inverse of the minimum amount in mg ml⁻¹ of the assay which produced haemagglutination in presence of 10 mM Mn²⁺) and phytate (7.2–10.1%) were observed in the meals. The concentrations of phorbol esters in kernels of Cape Verde, Nicaragua and Ife-Nigeria varieties were 2.70, 2.17 and 2.30mg g⁻¹, whereas kernels of non-toxic Mexican had a very low level (O.11 mg g⁻¹) of phorbol esters.     

Determination of total arsenic, inorganic and organic arsenic species in wine

Forty-five wine samples from the south of Spain of different alcoholic strength were analysed for total arsenic and its inorganic [As(III), As(V)] and organic (monomethylarsonic acid [MMAA], dimethylarsinic acid [DMAA]) species. The As levels of the wine samples ranged from 2.1 to 14.6 µg l^-1. The possible effect of the alcoholic fermentation process on the levels of the total arsenic and arsenical species was studied. The average total arsenic levels for the different samples were very similar, without significant differences between all types of wines. In table wines and sherry, the percentages of total inorganic arsenic were 18.6 and 15.6%, with DMAA or MMAA being the predominant species, respectively. In most samples, DMAA was the most abundant species, but the total inorganic aresenic fraction was considerable, representing 25.4% of the total concentration of the element. The estimated daily intakes of total arsenic and total inorganic arsenic for average Spanish consumers were 0.78 and 0.15 µg/person day^-1, respectively. The results suggest that the consumption of these types of wines makes no significant contribution to the total and inorganic arsenic intake for normal drinkers. However, wine consumption contributes a higher arsenic intake than through consumption of beers and sherry brandies.     

不同前处理对原子荧光法测定海产品总砷的影响

对氢化物-原子荧光法测定海产品中总砷的前处理进行研究,探讨了微波消解、干法灰化、湿法消解、微波-湿法消解四种前处理方法对原子荧光法测定海产品中总砷结果的影响。实验证明不同的前处理方法对样品结果有很大影响:微波消解不适于海产品总砷的前处理,干法灰化不适用紫菜类植物性海产品的前处理,硝酸-高氯酸-硫酸体系的湿法消解、微波-湿法消解(加高氯酸、硫酸)可以作为一般海产品的前处理,且两种前处理的回收率均大于90%。     

湿法消解-原子荧光光谱法同时检测海产品中的总砷与总汞

目的建立湿法消解-原子荧光光谱法同时测定海产品中总砷、总汞含量的分析方法。方法采取硝酸、高氯酸和硫酸混合体系的冷消解及热消解结合的方法,并采用电炉高温短时间加热的优化条件进行消解样品,利用氢化物原子荧光光谱法同时进行总砷、总汞的测定。结果砷在0～40μg/L浓度范围内呈良好线性关系,汞在0～12μg/L浓度范围内呈良好线性关系,相关系数均大于0.999。砷的检出限为0.037μg/L,回收率为94.36%～96.62%,精密度为0.86%～1.36%,汞的检出限为0.048μg/L,回收率为93.33%～95.28%,精密度为0.88%～2.62%。通过对能力验证HMRL1601海鱼粉中总汞、总砷的检测,检测结果总汞为0.30 mg/kg,总砷为2.06 mg/kg,均为满意结果,黄鱼、紫菜质控样的检测值均在参考值允许范围内。结论该方法操作简便、准确灵敏,适用于每一个实验室开展海产品中总砷总汞的同时测定。     

Assessment of lectin activity in a toxic and a non-toxic variety of Jatropha curcas using latex agglutination and haemagglutination methods and inactivation of lectin by heat treatments

Lectin activity in a toxic (Cape Verde) and non-toxic (Mexico) variety of Jatropha curcas seed meal was investigated using latex agglutination and haemagglutination assays. Lectin activity expressed as reciprocal of the minimum quantity (in mg) of Jatropha meal per ml of the assay mixture which produced agglutination with the latex beads was 2·88 ± 0·57 and 1·71 ± 0·00 (mean ± SD, n = 3) for the toxic and the non-toxic varieties, respectively, which did not differ significantly (P > 0·05), while with the haemagglutination assay these values were 102 and 51, respectively, and differed significantly (P < 0·05). The lectins were inactivated by heating and moist heat was more effective than dry heat. The results suggest that lectins may not be responsible for short term toxicity caused by consumption of raw Jatropha meal. © 1998 SCI.     

Mercury,lead, arsenic,and cadmium in Norwegian seafood products and consumer exposure

ABSTRACT

Seafood can be a source of contaminants, which may raise health concerns. The aim of this study was to analyse the levels of inorganic contaminants in commercially available seafood products and assess consumer exposure. Commercially available samples were collected from 2015–2018 and analysed as composite samples for mercury, lead, arsenic, and cadmium, using accredited methods. Levels of cadmium, lead, and arsenic were low and human exposure of these metals would be minimal from consumption of the analysed seafood products. Mercury levels were well below the EU maximum limit for mercury in fish. However, children, who are high consumers, might be at risk of exceeding the tolerable weekly intake for methyl mercury, when eating products with the highest mercury levels. The collected data can be used for future risk-benefit assessments as intake of processed seafood products represent a large proportion of the populations' seafood intake in Europe.     

Histamine levels in seventeen species of fresh and processed South African seafood

Histamine levels were determined in fresh and processed seafood from a representative range of 10 outlets after several incidents of scombroid seafood poisoning occurred. Species included seventeen fresh and processed scombroid- and non-scombroid fish, marine mollusks and crustaceans. Histamine levels in fresh seafood were generally low (0–9 ppm) with the exception of one sample of snoek (scombroid fish; >50 ppm) and one sample of yellowtail (non-scombroid fish; >50 ppm). Both species are rich in free histidine (1.5–5.3 ppb), a precursor of histamine. Processed seafood had, in general, low histamine concentrations (0–3 ppm) with the exception of fish meal (76 ppm), salted herring (47 ppm), one sample of smoked snoek (>50 ppm) and dried tuna (8000 ppm). In total, 5 of 80 examined samples (6%) contained histamine concentrations above the legal limit of 50 ppm. Experimental formation of histamine was demonstrated to be strongly temperature- and time-dependent. Samples were not contaminated with Vibrio spp., Pseudomonas spp., Klebsiellas spp. or Enterobacteria.