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Analysis of organic and inorganic arsenic in food

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New IC-ICP-MS method enables analysis of carcinogenic arsenic species including small organoarsenic compounds with low limits of quantification

Oct 2024 (update). The actual presence of inorganic arsenic in food poses a health risk for skin cancer. This is the conclusion of the CONTAM Panel in an updated EFSA Opinion on inorganic arsenic in food published early in 2024[1]. Rice, cereals, and products thereof, as well as drinking water are identified as the main source of intake.

Starting in October 2023, the Eurofins Food & Feed Testing laboratories in Germany offer a new sensitive method for the analysis of inorganic arsenic in food according to DIN EN ISO 16802:2016. The determination by IC-ICP-MS coupling allows for the separation of the inorganic arsenic species AsIII and AsV and quantification at low limits. The method is initially available for rice, cereals, babyfood, milk products, fruit and vegetable juices, beer, sugar, legumes and fish. However, the matrix spectrum will be extended to food of marine origin such as shells and algae and feed in the near future.

NEW: Small organoarsenic species

In July 2024, EFSA extended its assessment of arsenic compounds with an opinion on small organoarsenic compounds[1a]. Main subject of this opinion are monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). In addition to the determination of inorganic arsenic, our newly implemented IC-ICP-MS coupling already enables the analysis of MMA and DMA in the above-mentioned food matrices. An extension to other food groups is in progress.

Background and toxicity

Arsenic (As) is a widespread element that occurs in soil, groundwater, plants, seawater and animals due to natural occurrence but also anthropogenic environmental contaminations. Arsenic can be present in organic and inorganic forms.

Inorganic arsenic species (iAs) are classified as carcinogenic. In food and feed, iAs are predominantly bound in the oxidation state +3 (AsIII) or +5 (AsV) in thiocomplexes or are present as oxoanions arsenite (AsIII) and arsenate (AsV).

In 2009, the European Food Safety Authority (EFSA) established a benchmark dose (BMD) of 0.3 – 8 µg iAs/kg body weight/day for an increased risk of skin, lung and bladder cancer as well as skin lesions[2]. However, in its new new opinion published early in 2024, a lower reference point (RP) of 0.06 µg iAs/kg body weight/day is already established. According to EFSA, the newly established dose already has a small but measurable adverse effect. In addition to the types of cancer already described in 2009, chronic kidney disease, respiratory disease, spontaneous abortion, stillbirths, infant mortality and neurodevelopmental effects are now attributed to iAs [1].

The small organoarsenic compounds MMA and DMA were assessed in the new EFSA opinion using the Margin of Exposure (MOE) approach. Based on the available data, no health concerns could be derived for MMA, regardless of the age and consumer group. However, DMA increases the occurrence of urinary bladder tumors in animal experiments and was also identified as probably genotoxic.

Seafood and fish are the main sources of total arsenic in the human diet and in animal feed. However, in seafood and fish, arsenic is mainly present as organic arsenobetaine and arsenocholine, which are so far considered to be of low toxicity. MMA and DMA are likewise ingested via fish and fish products, but also play a role as a source of exposure for DMA.

The main source of inorganic arsenic intake across all age groups are cereals (especially rice), cereal products, and drinking water. For infants, toddlers, and children, EFSA’s exposure assessment identifies cereal-based foods for infants and young children as well as biscuits, rusks, and cookies for children as most critical[3].

Dietary intake estimates of iAs for adult average consumers (0.03-0.15 µg iAs/kg body weight/day) are within the range of the new RP; those for adult heavy consumers (0.07-0.33 µg iAs/kg body weight/day) are even above the dose that poses an increased risk of adverse effects[1].

Regulatory provisions

Regulation (EU) 2023/915[4] sets maximum levels for inorganic arsenic as the sum of AsIII and AsV in rice, rice-based products and fruit juices as well as in food for infants and young children. Furthermore, a maximum level of total arsenic in salt is laid down. However, with its monitoring Recommendation (EU) 2015/1381[5], the European Commission continues to request its member states to monitor the levels of total arsenic and inorganic arsenic in a wide range of foods.

Maximum levels for total arsenic in certain feed products are set by Directive 2002/32/EG of the European Parliament and the Council[6] on undesirable substances in animal feed. In addition, Commission Recommendation 2002/C 206/01[7] calls for explicit monitoring of the presence of inorganic arsenic in individual and compound feed.

Analysis of organic and inorganic arsenic compounds

Our experts from the Competence Centre for Metals and Elements have many years of experience in the analysis of total arsenic and inorganic arsenic in various relevant food and feed matrices using different analytical techniques.

For the determination of inorganic arsenic the Eurofins Food & Feed Testing Laboratories in Germany now offer a new particularly sensitive method. The standard method DIN EN 16802:2016 is used in a minimally modified form. The analysis is performed by IC-ICP-MS coupling after acidic extraction without oxidation of arsenite to arsenate. Organic and inorganic arsenic species are separated by ion chromatography (IC) and detected by ICP-MS. The sum of the two separately quantified inorganic arsenic species AsIII and AsV is reported with a limit of quantification (LOQ) of 10 µg/kg. Thus, the method is ideally suited for the control of the low maximum levels of 100 µg/kg and 20 µg/kg for iAs in rice used for the production of foods for infants and young children and (cereal-based) powdered foods for infants and young children, respectively (Regulation (EU) 2023/915[4]). In addition to AsIII and AsV, the determination of MMA and DMA is possible with the same limits of quantification.

A workday measurement of calibration standards and food reference materials for the critical control of the analysis are quality standards that increase the safety and reliability of the applied method.

The method has been validated for cereal and grain products, particularly rice, wheat, and baby cereals, milk-based infant foods and complementary foods for infants and young children, milk products, juice, beer, legumes and fish. The application of the method to other types of seafood is currently in progress.

Contact us

Do you have questions regarding the analysis of organic and inorganic arsenic? Please contact your personal account manager or our expert Andreas Schaefer.

Relevant sources

[1] EFSA, 2024. Update of the risk assessment of inorganic arsenic in food
[1a] EFSA, 2024. Risk assessment of small organoarsenic species in food
[2] EFSA, 2009. Scientific Opinion on Arsenic in Food
[3] EFSA, 2021. Chronic dietary exposure to inorganic arsenic
[4] Commission Regulation (EU) 2023/915 of 25 April 2023 on maximum levels for certain contaminants in food
[5] Commission Recommendation (EU) 2015/1381 of 10 August 2015 on the monitoring of arsenic in food
[6] Directive 2002/32/EC of the European Parliament and of the Council of 7 May 2002 on undesirable substances in animal feed
[7] Commission Recommendation of 20 May 2022 on monitoring the presence of inorganic arsenic in feed 2022/C 206/01

Further EFSA recommendations

 EFSA Panel on Contaminants in the Food Chain (CONTAM), 2009. Scientific opinion on arsenic in food. EFSA Journal 2009; 7(10):1351.
 EFSA Panel on Contaminants in the Food Chain (CONTAM), 2023. Draft Scientific opinion on the update of the EFSA Scientific opinion on inorganic arsenic in food. Public Consultation PC-0590.
 Chronic dietary exposure to inorganic arsenic. EFSA Journal 2021;19(1):6380.