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Development And Application Of Multi-element And Arsenic Speciation Detection Technologies In Aquatic Products

Posted on:2019-04-18Degree:MasterType:Thesis
Country:ChinaCandidate:J Q ChangFull Text:PDF
GTID:2321330545986749Subject:Agriculture
Abstract/Summary:PDF Full Text Request
With the accelerating development of the national economy,quality of people's living life has been greatly improved.As an important source of high-quality proteins,seafood is rich in nutritional value and has become an increasingly popular food.While enjoying the high-quality protein,people often ignore the potential risks caused by aquatic products consumption.A large number of research datas showed that aquatic products were rich in varieties of heavy metals or metalloid elements,some of which were much higher than the national standard limit value.How to ensure the health safety of seafood consumption has always been one of the research hotspots.The project had optimized the ICP-MS method for simultaneous determination of multiple elements such as Cr,Ni,Cu,As,Cd,Sn,Pb,and Al in various common marine products and HPLC-ICP-MS morphometry dection techniques for arsenic species.Based on the background value investigation,we mastered the current pollution status of major heavy metal elements in common seafood in Zhejiang province and got the distribution characteristics of arsenic species in four common sea crabs?Scyllaserrata,Portunustrituberculatus,Japanesesturgeonand Ovalipespunctatus?.Meanwhile,combined the dietary consumption datas with the recommended intake values of heavy metals provided by FAO,WHO and other international authoritative organizations,the health risk of exposure to heavy metal elements caused by seafood consumption was evaluated.Finally,the research on bioavailability of arsenic in mussels and crabs was conducted.The main research contents and conclusions are as follows:1.Inductively coupled plasma mass spectrometry?ICP-MS?was used to determine the content of Pb,Cd,Cr,Cu,Sn,Ni,As in 649 samples covering 38species of seafood?fish,shrimps,crabs,shellfish,and algae?.Single factor pollution index?Pi?was used for the monitoring results to evaluate the pollution degree of each element.Meanwhile,combined with the dietary data of Zhejiang residents,the point exposure method was used to calculate the exposure risk quotient?HQ?of each element.The results showed the content values of As in all seafood species,Cu and Cd in crab,Cd in shellfish and Cr in macroalgae were relatively high and the corresponding Pi values were all above 1.In terms of children the food risk evaluation showed that algae exhibited health risk of Cr,and fish,shrimp,crab,shellfish and algae exhibited health risk of As,while crabs,shellfish and algae brought Cd exposure risk.For adults,the As exposure risk HQ values caused by shrimp,crab,shellfish and algae and Cd exposure risk HQ values from crab,shellfish and algae were also above1.In particular,the Cd content in mantis shrimp were higher and the Cd exposure risk HQ values for adults and children were 11.08 and 5.54,respectively.The above results indicated that adults and children might have a higher health risk if they consumed large amounts of such seafood in one or long time.2.The distribution characteristics of five kinds of arsenic compounds including arsenobetaine?AsB?,dimethyl arsenic?DMA?,and trivalent arsenic(As3+),monomethylarsenic?MMA?and pentavalent arsenic(As5+)in seafood by high performance liquid chromatography-inductively coupled plasma mass spectrometry?HPLC-ICP-MS?in 6 minutes.The optimized chromatographic conditions were:Dionex IonPac As19 anion exchange column?250 mm×4 mm×10?m?and protection?50mm×4mm?,column temperature at 40°C,injection volume at 50?L,mobile phase was 50mmol/L ammonium carbonate solution with pH=9.5 and eluted at a flow rate of 1.0 mL/min;the optimized ICP-MS mass spectrometry conditions were:a concentric atomizer,selecting element 75As,m/z 75,acquisition mode was TRA mode,and detection mode was No Gas standard mode,carrier gas flow rate at 1.05 mL/min without compensation gas and no interference equation,while As integration time was0.3 s and peristaltic pump speed was 0.5 rps.The distribution characteristics of total arsenic and arsenic in the four common crabs including Scylla serrata,Portunus trituberculatus,Japanese sturgeon and Ovalipespunctatus were determined using an optimized method.The results showed that the sea crab was a highly enriched arsenic products.Total arsenic contents in 158 sea crabs were 1.3423.36 mg/kg,most existing in the little toxcity form of AsB accounting for 60.9%99.4%of the total arsenic.In 158 samples,poisonous inorganic arsenic content was only 00.12 mg/kg.It revealed a trend that contents of total arsenic and AsB in Ovalipespunctatus<Scylla serrata<Portunustrituberculatus<Japanesesturgeon,andgonad?female?>hepatopancre as>chest muscle>clamp meat>gill.The research suggested that sea crabs were aquatic organisms with the strong As-accumulated ability and gonad and hepatopancreas were the main arsenic enrichment organs.Meanwhile,we have used the point-estimation method to evaluate the health risks of inorganic arsenic caused by sea crabs based on the nutritional dietary data of Zhejiang residents.The results showed that the risk of inorganic arsenic exposure throughed sea crabs consumption was low.3.The inorganic arsenic content in 38 kinds of 649 seafood products from the coastal areas of Zhejiang province was further monitored and the health risk assessments were conducted.The results demonstrated that the arsenic compounds in aquatic products in coastal areas of Zhejiang province mainly existed in the form of organic arsenic,including arsenobetaine,a small amount of DMA and MMA,and the content of inorganic arsenic was relatively small.The percentage of inorganic arsenic in total arsenic in all samples was 0.03-5.79%.The inorganic arsenic content in 649samples was lower than the corresponding national limit value.The median arsenic content in all samples was 0.0286 mg/kg,and the 90th percentile was 0.084 mg/kg.We have conducted the exposure risk assessment of inorganic arsenic in coastal aquatic products in Zhejiang province based on the investigation report of the dietary structure of urban and rural residents in Zhejiang province and combined with the characteristics of the actual aquatic products consumed by coastal residents in Zhejiang Province.The assessment results showed that the amount of inorganic arsenic consumed by coastal residents?including urban and rural?in Zhejiang province was lower than the recommended value of JECFA.and the risk of inorganic arsenic ingested by residents through the consumption of aquatic products was relatively low.4.Static in vitro gastrointestinal simulation experiments were established.We have quantitatively and qualitatively researched the levels of total arsenic and the distribution of arsenic species in the samples of raw materials,cooked samples,cooking water,and the dialysates of cooked samples of the crabs and mussels,respectively.The results illustrated that 13.7%of the arsenic in the mussels and 6.1%of the arsenic in the crabs samples were removed from the sample matrix and released into the cooking water during the cooking process.Similar arsenic chromatograms were found in the analysis of arsenic species distribution in cooked samples and their cooking water.Determination of arsenic compounds in dialysate in cooked samples by HPLC-ICP-MS revealed that the dialysis process did not cause changes in arsenic species.It indicated that the acidic medium,enzyme and dialysis membrane did not cause changes in arsenic morphology.No As?III?was observed in the study sample.
Keywords/Search Tags:Multi-elements, arsenic species, HPLC-ICP-MS, risk assessment, Bioaccessibility
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