Chemical contaminant levels in edible seaweeds of the Salish Sea and implications for their consumption.

Despite growing interest in edible seaweeds, there is limited information on seaweed chemical contaminant levels in the Salish Sea. Without this knowledge, health-based consumption advisories can not be determined for consumers that include Tribes and First Nations, Asian and Pacific Islander community members, and recreational harvesters. We measured contaminant concentrations in edible seaweeds (Fucus distichus, F. spiralis, and Nereocystis luetkeana) from 43 locations in the Salish Sea. Metals were analyzed in all samples, and 94 persistent organic pollutants (POPs) (i.e. 40 PCBs, 15 PBDEs, 17 PCDD/Fs, and 22 organochlorine pesticides) and 51 PAHs were analyzed in Fucus spp. We compared concentrations of contaminants to human health-based screening levels calculated from the USEPA and to international limits. We then worked with six focal contaminants that either exceeded screening levels or international limits (Cd, total Hg, Pb, benzo[a]pyrene [BaP], and PCBs) or are of regional interest (total As). USEPA cancer-based screening levels were exceeded in 30 samples for the PCBs and two samples for BaP. Cadmium concentrations did not exceed the USEPA noncancer-based screening level but did exceed international limits at all sites. Lead exceeded international limits at three sites. Because there are no screening levels for total Hg and total As, and to be conservative, we made comparisons to methyl Hg and inorganic As screening levels. All samples were below the methyl Hg and above the inorganic As screening levels. Without knowledge of the As speciation, we cannot assess the health risk associated with the As. While seaweed was the focus, we did not consider contaminant exposure from consuming other foods. Other chemicals, such as contaminants of emerging concern (e.g., PFAS, pharmaceuticals and personal care products), should also be considered. Additionally, although we focused on toxicological aspects, there are cultural and health benefits of seaweed use that may affect consumer choice.

The influence of hydrous ferric oxide, earthworms, and a hypertolerant plant on arsenic and iron bioavailability, fate, and transport in soils.

Historic applications of lead arsenate pesticides and smelting activities have resulted in elevated concentrations of arsenic in Washington State soils. For example, old orchard topsoils in Washington have concentrations reaching upwards of 350 mg As/kg soil with an estimated 187,590 acres of arsenic contamination from pesticide application alone. Iron oxides have been indicated as a key factor in modulating the fate and transport of arsenic in the soil environment. We employed a factorial design to investigate the role of a specific iron oxide, hydrous ferric oxide (HFO), and terrestrial organisms on the mobility, bioavailability, and fate of arsenic and iron in locally collected soils. Earthworms in soils amended with both arsenic and HFO had 47.2 % lower arsenic tissue concentrations compared to those in soils only amended with arsenic. Similarly, arsenic leachate concentrations and plant tissue concentrations were lower when HFO was present, although this was with a reduced magnitude and was not consistently significant. A lack of significance of HFO in three of the linear models for leachate and plant bioavailability, however, indicates that the role of HFO in arsenic mobility, bioavailability, and fate is more complicated than can be explained by the simple addition or not of HFO. For example, our analyses showed that earthworms decreased pH and increased bioavailability for both arsenic and iron as demonstrated by increases in leachate and plant tissue concentrations. The mechanisms for this could include a biotransformation of earthworm-ingested arsenic combined with an earthworm-induced change in pH. We also found that arsenic amendments increased the mobility and bioavailability of iron, evidenced by increased iron concentrations in earthworms, plants, and leachate. A mechanistic explanation for this change in bioavailability is not readily apparent but does support a need for more work on bioavailability when mixtures are present. From these results, it is clear that a combination of biotic and abiotic factors influences metal/metalloid fate and transport in soils, with earthworms being one of the most important factors in our work. Study designs such as the factorial analysis can help to address the role each factor plays while efficiently generating new hypotheses and areas of inquiry; this approach can also bridge knowledge generated through reductionist and holistic approaches to complex environmental problems.

Fractionation of fulvic acid by iron and aluminum oxides--influence on copper toxicity to Ceriodaphnia dubia.

This study examines the effect on aquatic copper toxicity of the chemical fractionation of fulvic acid (FA) that results from its association with iron and aluminum oxyhydroxide precipitates. Fractionated and unfractionated FAs obtained from streamwater and suspended sediment were utilized in acute Cu toxicity tests on Ceriodaphnia dubia. Toxicity test results with equal FA concentrations (6 mg FA/L) show that the fractionated dissolved FA was 3 times less effective at reducing Cu toxicity (EC50 13 ± 0.6 µg Cu/L) than were the unfractionated dissolved FAs (EC50 39 ± 0.4 and 41 ± 1.2 µg Cu/L). The fractionation is a consequence of preferential sorption of molecules having strong metal-binding (more aromatic) moieties to precipitating Fe- and Al-rich oxyhydroxides, causing the remaining dissolved FA to be depleted in these functional groups. As a result, there is more bioavailable dissolved Cu in the water and hence greater potential for Cu toxicity to aquatic organisms. In predicting Cu toxicity, biotic ligand models (BLMs) take into account dissolved organic carbon (DOC) concentration; however, unless DOC characteristics are accounted for, model predictions can underestimate acute Cu toxicity for water containing fractionated dissolved FA. This may have implications for water-quality criteria in systems containing Fe- and Al-rich sediment, and in mined and mineralized areas in particular. Optical measurements, such as specific ultraviolet absorbance at 254 nm (SUVA254), show promise for use as spectral indicators of DOC chemical fractionation and inferred increased Cu toxicity.