Ronan 2017 — Inorganic vs total arsenic across thallus parts of kelp (L. digitata) and wrack (A. nodosum)

Ronan and colleagues measured total arsenic and inorganic arsenic (as As(V)) by ICP-MS and HPLC-ICP-MS across the different thallus parts of two wild Irish brown seaweeds: the kelp Laminaria digitata and the intertidal wrack Ascophyllum nodosum. Total arsenic was similar between species (36–131 mg/kg dry weight in L. digitata, 38–111 in A. nodosum), but the inorganic fraction diverged sharply: inorganic arsenic was always below 1% of total in A. nodosum (≤0.703 mg/kg DW) yet reached 2.2–87 mg/kg DW in L. digitata, rising along the thallus from the stipe to the decaying distal blades and exceeding 50% of total arsenic in the middle, distal, and decaying-distal blades. This establishes that high inorganic arsenic in edible seaweed is not confined to hijiki: kelp harvested from a clean site carried inorganic arsenic an order of magnitude above the French (3 mg/kg) and Australia–New Zealand (1 mg/kg) seaweed limits.

Key numbers

Concentrations in mg/kg dry weight (DW). Method LOD/LOQ: inorganic As 0.001/0.01; total As 0.002/0.02.

Laminaria digitata (kelp), n=5 thalli, 6 parts each:

• Total arsenic: 36–131 mg/kg DW across all parts (highest in distal blade 131 and decaying distal blade 129); mean of thalli 78 ± 24.
• Inorganic arsenic: 2.2–87 mg/kg DW, increasing from the stipe toward the distal parts; highest 87 mg/kg DW in decaying distal tips.
• Inorganic arsenic comprised >50% of total arsenic in most middle, distal, and decaying-distal blades, but <50% in stipe, meristem, and young blade.
• iAs in stipe/meristem/young blade was significantly lower than in middle/distal/decaying-distal blades (one-way ANOVA p=0.0009).
• Blade-only range (Table 1, stipe and meristem excluded, across five thalli): total As 59–114, inorganic As 30–62 mg/kg DW.

Ascophyllum nodosum (knotted wrack), n=25 thalli, annual segments:

• Total arsenic: 38–111 mg/kg DW, increasing with thallus-part age, highest (111) in 5-year-old sections; mean of thalli 64 ± 20.
• Inorganic arsenic: <1% of total throughout; 0.007–0.070 mg/kg DW across yearly sections, with two older (4- and 5-year) sections higher at 0.178 and 0.703 mg/kg DW.
• Total arsenic was significantly higher in L. digitata than A. nodosum (p=0.026); inorganic arsenic significantly higher in L. digitata (p<0.01).

Additional source-reported facts:

• The site (Galway Bay) is a routinely-monitored, relatively uncontaminated bay; seawater arsenic is typical of unpolluted Irish west-coast waters.
• Regulatory comparison: mean L. digitata inorganic arsenic in the young/middle/distal/decaying blades exceeded the French food limit (3 mg/kg DW) and the Australia–New Zealand limit (1 mg/kg) typically by an order of magnitude; A. nodosum inorganic arsenic always satisfied both. Applying the EU feed Directive 2003/100/EC basis (40 mg/kg total As at 12% moisture), mean total As in both species exceeded the limit (69 and 57 mg/kg respectively).
• The authors’ Table 1 (comparison with other studies) places this study’s L. digitata alongside Taylor & Jackson 2016 (New England: total As 50–106, iAs 2.8–20 mg/kg DW), García-Salgado 2012 (France: iAs 77 ± 3 mg/kg as As(V)), and others, confirming wide between-study variability in kelp inorganic arsenic.
• Context cited: EFSA (2014) estimated hijiki at 11 mg/kg iAs (lower than the 96 mg/kg of Rose 2007 and 117 mg/kg of Almela 2006); UK FSA (2010) and the Belgian Superior Health Council (2015) advise against hijiki consumption.

Methods (brief)

Whole thalli were collected at low tide (Spiddal, Galway Bay; 53.2409 N, −9.3095 W) in October 2015, rinsed, scraped of epiphytes, freeze-dried, and homogenised. Inorganic arsenic was determined as As(V): 0.100 g freeze-dried algae microwave-extracted (Mars 5) with 1% HNO3 + 2% H2O2 to oxidise As(III) to As(V), then HPLC-ICP-MS (Agilent 1260 HPLC + 8800 ICP-MS, Hamilton PRP-X100 anion-exchange column, 30 mM ammonium carbonate pH 8.5, germanium internal standard, O2 reaction gas, As measured as AsO+ at m/z 91). Total arsenic was determined after overnight concentrated-HNO3 pre-digestion and Ethos Up microwave digestion to 200 °C, by ICP-MS in MS/MS mode (m/z 91). Quality control used CRMs BCR-211 (rice; certified inorganic As) and ERM-CD200 (Fucus vesiculosus; certified total As): total-As recovery 90.4 ± 5.7% (BCR-211) and 96.4% (ERM-CD200); inorganic-As recovery 97.6% (BCR-211). The unequivocal determination of inorganic As as As(V) was confirmed by parallel HPLC-ICP-MS/ESI-MS showing no arsenosugar co-elution interference (acid extraction collapses arsenosugars to the aglycone-free sugar without generating inorganic As). All values are dry weight.

Implications

• Certification (HMTc): direct-evidence speciation data for the Category 6 seaweed-kelp-foods row (iAs/tAs platform), and the most consequential finding so far for that row’s structure — kelp (Laminaria digitata), a primary component of “kombu”/sea-vegetable products, can itself carry inorganic arsenic up to 87 mg/kg DW (>50% of total in the blades), comparable to hijiki and an order of magnitude above the French and ANZ seaweed limits, even from a clean site. This argues that the within-row high-iAs concern is not hijiki-exclusive and that kelp/Laminaria warrants explicit treatment in the row’s clean/dirty structuring. The strong intra-thallus gradient (stipe low → decaying distal high) and species contrast (A. nodosum negligible) are processing/sourcing-relevant signals. All on the dry-weight, as-harvested basis.
• App: contributes to the seaweed ingredient contamination_profile for total and inorganic arsenic, with the species- and thallus-part-specific caveats (kelp blades high; knotted wrack low).

Verification notes

• raw_handle MFK_ronan2017 from the PDF filename; raw_path under “raw/Manual Fetch Kimi /June 8 Inorganic Arsenic Seaweed/“. DOI 10.1016/j.chemosphere.2017.07.076 confirmed on the accepted-manuscript cover. This is the accepted-manuscript version (Chemosphere, CHEM 19609).
• Evidence tier A: peer-reviewed, HPLC-ICP-MS speciation with CRM-based QC and ESI-MS confirmation of inorganic As as As(V).
• Speciation: total As and inorganic As (measured as As(V) after As(III)→As(V) oxidation) both reported and kept distinct; lifted to frontmatter as tAs and iAs. No mercury/cadmium/lead/chromium measured.
• Units/basis preserved exactly (mg/kg dry weight). Inorganic-As ranges (2.2–87 for L. digitata; 0.007–0.703 for A. nodosum) and total-As ranges (36–131; 38–111) taken from the Results text; per-thallus-part mean values shown only graphically (Figure 2) and in supplementary Table S1 (not reproduced numerically here beyond the text-stated ranges and gradient, to avoid reading approximate values off a bar chart). The blade-only ranges (total As 59–114, iAs 30–62) are the source’s Table 1 “this study” row, footnoted as blades of five thalli with stipe and meristem excluded.
• sample_n=30 reflects the L. digitata thallus-part samples (5 thalli × 6 parts); the 25 A. nodosum thalli (annual-segment pooled samples) are described in sample_population — recorded this way because L. digitata is the food-relevant (kelp/kombu) subject for the seaweed-kelp-foods row.
• Matrix fit: L. digitata is harvested as a sea vegetable/kombu and for feed; A. nodosum is mainly feed/fertiliser/alginate but is edible macroalgae. Both are in-scope for the seaweed/macroalgae ingredient and the seaweed-kelp-foods product row as wild-harvested raw material; this is a wild intra-thallus distribution study, not a retail-product survey (noted for the occurrence-extraction pass, which may weight retail surveys differently).
• Brand firewall: not engaged (wild-harvested specimens; no commercial products or brands).
• Jurisdiction IE; sampling_locations records the Galway Bay (Spiddal) site; sampling_year_range 2015.
• matrices [edible-seaweed, macroalgae, kelp, dry-weight] per corpus convention; kelp is directly warranted (L. digitata).
• Instrument/CRM/vendor names (Agilent, Hamilton, Mars 5/Ethos Up, BCR-211, ERM-CD200) retained in Methods as permitted scientific reporting.
• Audit subagent (2026-06-08, fresh-context) returned PROMOTE on all five checks; speciation fidelity (tAs vs iAs-as-As(V) by species and thallus part) verified exact with no transposition. One ⚠️ applied: intro prose understated the A. nodosum inorganic-As maximum as “≤0.70”; verified against source (0.703 mg/kg DW, Results) and corrected to “≤0.703”. Matrices-vocabulary ⚠️ left as-noted (corpus convention, documented above).

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