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.

Influence of various water quality parameters on passive sampler accumulation kinetics of different metal valencies in freshwater.

Stabilized liquid membrane devices (SLMDs) have been used for passive integrative sampling of metals in freshwater systems. Field measurements of metal accumulation on SLMDs can provide a time-weighted average mass of labile metals over the deployment period. We exposed SLMDs in the laboratory to 0.5 µM solutions of silver, zinc, or aluminum as nitrate salts at three levels of water hardness, measuring metal accumulation every 4 days for 32 days. We saw linear accumulation in all experimental treatments, except for silver in high hardness (345.9 mg/L as CaCO3). The time-accumulation relationships indicated that metal sorption rates vary across valency with the lower valency metals generally accumulating at greater rates. Water hardness also affected accumulation rates and accumulated mass with greater rates as hardness increased for zinc and aluminum. The accumulated zinc mass at 32 days in soft water was 78% of the mass in hard water for zinc, and accumulated aluminum mass was 29% of the mass in hard water. Factors such as oleate formation on the SLMD surface and solution chemistry, including pH and chemical speciation, were evaluated in explaining our results. Our work supports that SLMDs have utility for sampling metals in freshwater over extended time periods, which may be beneficial when there is limited access to sites; it also provide important interpretive guidance for the use of SLMDs.

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.

The effects of chronological age and size on toxicity of zinc to juvenile brown trout.

A series of toxicity tests were conducted to investigate the role of chronological age on zinc tolerance in juvenile brown trout (Salmo trutta). Four different incubation temperatures were used to control the maturation of the juveniles before zinc exposures. These 96-h exposures used flow-through conditions and four chronological ages of fish with weights ranging from 0.148 to 1.432 g. Time-to-death (TTD) data were collected throughout the exposure along with the final mortality. The results indicate that chronological age does not play a predictable role in zinc tolerance for juvenile brown trout. However, a relationship between zinc tolerance and fish size was observed in all chronological age populations, which prompted us to conduct additional exploratory data analysis to quantify how much of an effect size had during this stage of development. The smallest fish (0.148-0.423 g) were shown to be less sensitive than the largest fish (0.639-1.432 g) with LC50 values of 868 and 354 µg Zn/L, respectively. The Kaplan-Meier product estimation method was used to determine survival functions from the TTD data and supports the LC50 results with a greater median TTD for smaller fish than larger juvenile fish. These results indicate that fish size or a related characteristic may be a significant determinant of susceptibility and should be considered in acute zinc toxicity tests with specific attention paid to the expected exposure scenario in the field.

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.