High proportions of inorganic arsenic in Laminaria digitata but not in Ascophyllum nodosum samples from Ireland.

Seaweed can accumulate inorganic arsenic (iAs) from seawater as hydrogen arsenate (HAsO42-) in place of the phosphate anion (HPO42-). While it is rapidly metabolised to organoarsenic species, predominantly arsenosugars and arsenolipids, iAs may be present in seaweed biomass and this poses a potential health concern for consumers of seaweed products. Here, the distribution of total (AsTOT) and iAs was determined in thallus parts of the kelp Laminaria digitata and the intertidal fucoid Ascophyllum nodosum (both Phaeophyceae) using inductively-coupled plasma mass spectrometry (ICP-MS) and high performance liquid chromatography - ICP-MS (HPLC-ICP-MS). AsTOT ranged from 36 to 131 mg kg-1 dry weight (DW) in L. digitata, and from 38 to 111 mg kg-1 DW in A. nodosum, with no statistically significant differences between different thallus parts. iAs was detected in all A. nodosum samples, comprising less than 1% of the AsTOT content. Concentrations of iAs in L. digitata were significantly higher, ranging from 2.2 to 87 mg kg-1, increasing through the thallus from the stipe to the decaying distal blades. iAs comprised more than 50% of AsTOT in the middle to decaying distal blades. This finding has potential implications for harvesting, processing and use of Laminaria digitata in agri-, food and health applications.

A sensitive liquid chromatography/tandem mass spectrometry method for the determination of natural and synthetic steroid estrogens in seawater and marine biota, with a focus on proposed Water Framework Directive Environmental Quality Standards.

RATIONALE: Trace levels of natural and synthetic steroid estrogens estrone (E1), 17ß-estradiol (E2) and 17α-ethynyl estradiol (EE2) have been demonstrated to exert adverse effects in exposed organisms. E2 and EE2 have been proposed for inclusion in the Water Framework Directive (WFD) list of priority pollutants; however, the detection and accurate quantification of these compounds provide significant challenges, due to the low detection limits required. METHODS: A sensitive method combining ultrasonication, solid-phase extraction (SPE) and liquid chromatography/tandem mass spectrometry, with electrospray ionisation in negative mode (LC/ESI-MS/MS), capable of determining E1, E2 and EE2 at concentrations between 0.07 and 60 ng/L for seawater and between 0.4 and 200 ng/g wet weight in Mytilus spp. is reported. Recoveries at the limit of quantification (LOQ) ranged from 95 to 102% and 88 to 100% for water and tissue, respectively. Salinity (12 to 35‰) and typical marine particulate matter loadings (between 10 and 100 mg/L) were not found to affect analyte recoveries. RESULTS: The first detection of E1 by LC/MS/MS in Irish marine waters (Dublin Bay, at 0.76 ng/L) is reported. Steroids were not detected in Galway Bay, or in any mussel samples from Dublin, Galway and Clare. The level of E2 detected in the dissolved water phase was below the proposed WFD Environmental Quality Standard (EQS) in other surface waters. CONCLUSIONS: The proposed method is suitable for the detection of E1, E2 and EE2 at biologically relevant concentrations and, due to the specificity offered, is not subject to potential interferences from endogenous E1 and E2 which often complicate the interpretation of estrogenic biomarker assays.