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Lorenc et al. 2020 - arsenic species in marine algae products

Lorenc and colleagues developed and validated a combined HPLC/ICP-MS and UPLC/ESI-MS/MS workflow for arsenic in algae products. The occurrence-relevant data are the total arsenic and arsenic-speciation values in Table 2 for five algae/seaweed materials, including a commercial cooked/dried hijiki product, nori sheets, serrated wrack, and two reference materials. Unknown arsenic and arsenosugar species are kept separate from inorganic arsenic.

Key numbers

Table 2 reports total arsenic before extraction as mg kg-1 (c ± SD) and extracted/speciated arsenic as mg kg-1 (c ± U, k = 2). No unit conversion was performed.

SampleNative tAsExtractionExtracted tAsAsBAs(III)DMAAs(V)uAs
Sample 1, NMIJ CRM 7405-a Hijiki34.38 ± 0.99Water, UAE17.88 ± 0.68<LOD0.853 ± 0.056<LOD2.83 ± 0.1479%
Sample 1, NMIJ CRM 7405-a Hijiki34.38 ± 0.99Water:methanol, UAE9.12 ± 0.23<LOD<LOD<LOD6.59 ± 0.3228%
Sample 1, NMIJ CRM 7405-a Hijiki34.38 ± 0.99Water, MAE16.52 ± 0.34<LOD<LOD<LOD7.39 ± 0.3655%
Sample 1, NMIJ CRM 7405-a Hijiki34.38 ± 0.99Water:methanol, MAE26.76 ± 0.70<LOD<LOD<LOD7.37 ± 0.3572%
Sample 2, Hijiki cooked/dried, milled72.6 ± 2.7Water, UAE66.0 ± 1.5<LOD0.952 ± 0.063<LOD5.64 ± 0.2790%
Sample 2, Hijiki cooked/dried, milled72.6 ± 2.7Water:methanol, UAE36.54 ± 0.73<LOD1.468 ± 0.0970.766 ± 0.0405.94 ± 0.2978%
Sample 2, Hijiki cooked/dried, milled72.6 ± 2.7Water, MAE48.94 ± 0.087<LOD1.147 ± 0.075<LOD5.48 ± 0.2686%
Sample 2, Hijiki cooked/dried, milled72.6 ± 2.7Water:methanol, MAE57.99 ± 0.93<LOD1.168 ± 0.077<LOD5.95 ± 0.2988%
Sample 2a, Hijiki cooked/dried, mortar-groundnot separately reportedWater, UAE59.6 ± 1.2<LOD2.63 ± 0.170.669 ± 0.0354.87 ± 0.2386%
Sample 2a, Hijiki cooked/dried, mortar-groundnot separately reportedWater:methanol, UAE11.29 ± 0.16<LOD1.233 ± 0.081<LOD4.81 ± 0.2346%
Sample 2a, Hijiki cooked/dried, mortar-groundnot separately reportedWater, MAE60.7 ± 2.0<LOD1.195 ± 0.079<LOD4.12 ± 0.2091%
Sample 2a, Hijiki cooked/dried, mortar-groundnot separately reportedWater:methanol, MAE55.1 ± 1.5<LOD1.248 ± 0.0820.596 ± 0.0314.71 ± 0.2388%
Sample 3, Nori sheets for sushi19.28 ± 0.45Water, UAE11.85 ± 0.43<LOD7.88 ± 0.52<LOD<LOD34%
Sample 3, Nori sheets for sushi19.28 ± 0.45Water:methanol, UAE16.51 ± 0.77<LOD<LOD<LOD<LOD100%
Sample 3, Nori sheets for sushi19.28 ± 0.45Water, MAE13.83 ± 0.65<LOD8.97 ± 0.59<LOD<LOD35%
Sample 3, Nori sheets for sushi19.28 ± 0.45Water:methanol, MAE14.96 ± 0.70<LOD<LOD<LOD<LOD100%
Sample 4, Serrated Wrack19.37 ± 0.51Water, UAE2.82 ± 0.12<LOD1.292 ± 0.085<LOD<LOD54%
Sample 4, Serrated Wrack19.37 ± 0.51Water:methanol, UAE10.37 ± 0.30<LOD1.291 ± 0.085<LOD<LOD88%
Sample 4, Serrated Wrack19.37 ± 0.51Water, MAE5.35 ± 0.16<LOD1.098 ± 0.072<LOD<LOD79%
Sample 4, Serrated Wrack19.37 ± 0.51Water:methanol, MAE11.40 ± 0.35<LOD1.252 ± 0.082<LOD<LOD89%
Sample 5, NIST SRM 3232 Kelp Powder45.4 ± 1.4Water, UAE4.649 ± 0.069<LOD<LOD<LOD<LOD100%
Sample 5, NIST SRM 3232 Kelp Powder45.4 ± 1.4Water:methanol, UAE14.59 ± 0.59<LOD0.911 ± 0.060<LOD<LOD94%

The abstract summarizes edible algae tAs as (19.28 ± 0.45) mg kg-1 to (72.6 ± 2.7) mg kg-1, As(III) as <LOD to (8.97 ± 0.59) mg kg-1, As(V) as <LOD to (5.95 ± 0.29) mg kg-1, DMA as <LOD to (0.766 ± 0.040) mg kg-1, and unknown arsenic species as 28% to 100% of extracted tAs.

Reference-material checks and method figures:

  • NMIJ CRM 7405-a Hijiki tAs was (34.38 ± 0.99) mg kg-1 versus certified (35.8 ± 0.9) mg kg-1.
  • NIST SRM 3232 Kelp Powder tAs was (45.4 ± 1.4) mg kg-1 versus certified (38.3 ± 1.34) mg kg-1; the source states this was not in as good accordance as the NMIJ CRM.
  • The source reports LODs of 0.041 mg kg-1 for tAs, 0.12 mg kg-1 for extracted tAs, 0.55 mg kg-1 for AsB, 0.61 mg kg-1 for As(III), 0.57 mg kg-1 for DMA, 0.64 mg kg-1 for MMA, and 0.55 mg kg-1 for As(V).
  • MMA was not detected in any sample. AsB was detected only in one Fucus serratus extract.

UPLC-HRMS identification context from Table 4 includes DMA(V), arsenate(V), MMMTA(V), MTA(V), DMAE, DMDTA(V), MMDTA(V), DMAA, pentylarsonic acid, dimethylarsinoylribose, multiple methylated arsenosugars, and one unknown arsenic compound. The authors report a high variety of As-sugars (12 compounds) and eight additional simple organic arsenic compounds; these organoarsenic identifications are not collapsed into inorganic arsenic.

Methods (brief)

The study analyzed five seaweed materials: NMIJ CRM 7405-a Hijiki, a cooked/dried Sargassum fusiforme hijiki product, Pyropia yezoensis nori sheets for sushi, Fucus serratus serrated wrack, and NIST SRM 3232 Kelp Powder. Nori and hijiki were ground before digestion/extraction; NMIJ CRM, NIST SRM, and serrated wrack were not further ground. Total arsenic used microwave-assisted digestion with nitric acid and hydrogen peroxide at 200 °C, followed by ICP-DRC-MS monitoring 91AsO+ with 73Ge+ internal standard.

Speciation used ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) with water or water:methanol (1:1, v/v) after nitric-acid extraction was discarded because it changed As speciation. For each extraction, 200 mg algae material was extracted with 20 mL extracting agent for 30 min; MAE was at 60 °C and UAE at room temperature. HPLC/ICP-DRC-MS used a Hamilton PRP-X100 anion-exchange column. UPLC/ESI-MS/MS was used for unknown arsenic-species identification.

Implications

This source provides a method-centered but routeable arsenic-speciation dataset for algae/seaweed products. It supports seaweed/kelp food and algae/seaweed supplement context with total arsenic and source-measured As(III), As(V), DMA, and unknown-organoarsenic fractions. Because the source’s conclusion emphasizes arsenosugars and other unknown organoarsenic species, downstream extraction must preserve speciation and must not treat total arsenic or arsenosugars as inorganic arsenic.

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Verification notes

  • Identity checks before writing found no existing source page for DOI 10.1016/j.talanta.2020.121384, raw handle MFK_lorenc2020, title text, or cite key lorenc2020-marine-algae-arsenic-species.
  • All Key numbers were rechecked against /tmp/hmi-seaweed-043.txt, extracted with pdftotext -layout. Table 2 was transcribed as available in the extracted text; NIST SRM 3232 appears with two UAE rows in the text layer, while the prose states its MAE signals were broad and could not be assigned to specific compounds.
  • Units and bases are preserved as mg kg-1, %, mg, mL, min, and °C; no unit conversion was performed.
  • Speciation check: As(III), As(V), DMA, AsB, MMA, unknown arsenic, and arsenosugar/organic species remain separate. No tAs value or arsenosugar identification is promoted to iAs.
  • Brand firewall: the source does not name consumer brands; the page records product forms/material types and CRM/SRM identities only.
  • Missing-slug check: no missing product or ingredient slug blockers. Exact nori, hijiki, serrated wrack, Fucus, and kelp powder terms remain in source text while frontmatter uses broad seaweed/kelp and algae/seaweed supplement slugs.

Page history

The five most recent substantive edits to this page. The full version history lives in git; when DOI minting comes online (see schema docs), each entry below will also link to a version-pinned DataCite DOI.

CommitDateDescription
4039d202026-06-10scope: broaden ingest to the full upstream+downstream literature (marine, atmospheric, attribution, exposure, toxicology) — inclusion is the default