Spatial distribution of mercury and other potentially toxic elements using epiphytic lichens in Nova Scotia.

The use of naturally occurring epiphytic lichens can be an effective tool for regional monitoring of mercury (Hg) and other potentially toxic elements (PTEs). Nova Scotia, Canada is a hotspot for mercury and other trace metal accumulation in ecosystems; partially attributed to long-range transport of air pollution. The relative contribution of local and international sources of Hg to local air in Nova Scotia is unknown. This study assessed the potential of epiphytic lichens (Usnea spp.) as passive samplers for PTE air pollution in Nova Scotia. Lichens (n = 190) collected across mainland Nova Scotia were analyzed for PTEs. Results indicate that there are 3 distinct clusters of PTEs which suggest patterns and sources for each elemental cluster. Hg was correlated with longitude and prevailing wind direction, and Hg was not significantly different in site-specific hotspot sampling nor year of sampling. Our data support the hypothesis that Hg in lichens is from historical and ongoing long-range transport and diffuse emission patterns rather than localized pollution sources. PTE concentrations were shown to have median values that are similar to other remote regions (such as the Antarctic) however the maximum values were observed to be substantially higher for some elements (e.g. lead, cadmium). This research supports the use of lichens as biomonitors and provides a baseline for future monitoring efforts to identify changes in PTE distribution in Nova Scotia with ongoing industrial activity and a changing climate.

The influence of avian biovectors on mercury speciation in a bog ecosystem.

Methylmercury (MeHg) is a neurotoxin and endocrine disruptor that bioaccumulates and biomagnifies through trophic levels, resulting in potentially hazardous concentrations. Although wetlands are known hotspots for mercury (Hg) methylation, the effects of avian biovectors on these processes are poorly understood. We examined Hg speciation and distribution in shallow groundwater and surface water from a raised-bog with over 30years of avian biovector (herring gulls Larus argentatus and great black-backed gulls Larus marinus) colonization and guano input. Compared to the reference site, the avian-impacted bog had elevated concentrations of total dissolved organic carbon (TOC), total Hg, MeHg, phosphate (PO43-), and other trace metals, notably Pb, As, Cd and Ni. Spatial interpolation showed that the densest area of gull nesting was co-located with areas that had the highest concentrations of PO43-, MeHg, As and Cd, but not total mercury (THg), and models suggested that Mn, PO43-, and dissolved TOC were strong predictors of MeHg. Our findings suggest that while these gulls may not be a significant source of Hg, the excess of PO43- (a well recognised component of guano) and the subsequent changes in water chemistry due to avian biovector subsidies may increase net Hg methylation.

What is the role of obesity in the aetiology of arsenic-related disease?

Consumption of arsenic contaminated drinking water causes a large variety of adverse health outcomes. Body mass index (BMI), which is linked to diet, is positively associated with arsenic methylation capacity. We investigated the association between an obesity-related diet and arsenic body burden from exposure to naturally contaminated drinking water among Nova Scotia residents. We collected home drinking water and toenail clipping samples among 960 men and women aged 35 to 69 years in Nova Scotia, Canada from 2009 through 2010. We measured body composition and arsenic concentrations in drinking water and toenails clipping samples and collected socio-demographic, behavioural, and dietary information via standardized questionnaires. We derived an obesity-related dietary pattern score using reduced rank regression. Across quartiles of the obesity-related dietary pattern score there were no significant differences in drinking water arsenic concentrations, but there was an inverse trend in arsenic concentrations in toenails across the dietary pattern score (P=0.01). Compared with individuals in the first quartile of the dietary pattern score, those in the second through fourth quartiles had decreased likelihoods of high toenail arsenic (≥ 85 percentile). The corresponding odds ratios (95% confidence intervals [CI]) were 0.81 (95% CI, 0.49, 1.36), 0.57 (95% CI, 0.33, 0.99), and 0.55 (95% CI, 0.31, 0.98), respectively (P for trend=0.02). We conclude that given similar levels of naturally occurring arsenic exposure via drinking water, an obesity-related dietary pattern was associated with significantly lower arsenic concentrations in toenails. Further studies to investigate the underlining mechanisms are warranted.

Relationship between drinking water and toenail arsenic concentrations among a cohort of Nova Scotians.

Consumption of arsenic-contaminated drinking water is associated with increased cancer risk. The relationship between arsenic body burden, such as concentrations in human toenails, and arsenic in drinking water is not fully understood. We evaluated the relationship between arsenic concentrations in drinking water and toenail clippings among a cohort of Nova Scotians. A total of 960 men and women aged 35 to 69 years provided home drinking water and toenail clipping samples. Information on water source and treatment use and covariables was collected through questionnaires. Arsenic concentrations in drinking water and toenail clippings and anthropometric indices were measured. Private drilled water wells had higher arsenic concentrations compared with other dug wells and municipal drinking water sources (P<0.001). Among participants with drinking water arsenic levels ≥1 µg/l, there was a significant relationship between drinking water and toenail arsenic concentrations (r=0.46, P<0.0001). Given similar levels of arsenic exposure from drinking water, obese individuals had significantly lower concentrations of arsenic in toenails compared with those with a normal weight. Private drilled water wells were an important source of arsenic exposure in the study population. Body weight modifies the relationship between drinking water arsenic exposure and toenail arsenic concentrations.

A review of metal (Pb and Zn) sensitive and pH tolerant bioassay organisms for risk screening of metal-contaminated acidic soils.

To improve risk estimates at the screening stage of Ecological Risk Assessment (ERA), short duration bioassays tailored to undisturbed soil cores from the contaminated site could be useful. However, existing standardized bioassays use disturbed soil samples and often pH sensitive organisms. This is a problem as naturally acidic soils are widespread. Changing soil properties to suit the test organism may change metal bioavailability, leading to erroneous risk estimates. For bioassays in undisturbed soil cores to be effective, species able to withstand natural soil properties must be identified. This review presents a critical examination of bioassay species' tolerance of acidic soils and sensitivity to metal contaminants such as Pb and Zn. Promising organisms include; Dendrobaena octaedra, Folsomia candida, Caenorhabditis elegans, Oppia nitens, Brassica rapa, Trifolium pratense, Allium cepa, Quercus rubra and Acer rubrum. The MetSTICK test and the Bait lamina test were also identified as suitable microorganism tests.

Utility of bioassays (lettuce, red clover, red fescue, Microtox, MetSTICK, Hyalella, bait lamina) in ecological risk screening of acid metal (Zn) contaminated soil.

The objective of this study was to assess selected bioassays and ecological screening tools for their suitability in a weight of evidence risk screening process of acidic metal contaminated soil. Intact soil cores were used for the tests, which minimizes changes in pH and metal bioavailability that may result from homogenization and drying of the soil. Soil cores were spiked with ZnCl(2) or CaCl(2). Leachate collected from the soil cores was used to account for the exposure pathways through pore water and groundwater. Tests assessed included MetSTICK in soil cores and Microtox in soil leachate, lettuce (Lactuca sativa), red fescue (Festuca rubra) and red clover (Trifolium pratense) in the soil cores and lettuce and red clover in soil leachate, Hyallella azteca in soil leachate, and an ecological soil function test using Bait Lamina in soil cores. Microtox, H. azteca, lettuce and red fescue showed higher sensitivity to low pH than to Zn concentrations and are therefore not recommended as tests on intact acidic soil cores and soil leachate. The Bait Lamina test appeared sensitive to pH levels below 3.7 but should be investigated further as a screening tool in less acidic soils. Among the bioassays, the MetSTICK and the T. pratense bioassays in soil cores were the most sensitive to Zn, with the lowest nominal NOEC of 200 and 400mg Zn/kg d.w., respectively. These bioassays were also tolerant of low pH, which make them suitable for assessing hazards of metal contaminated acid soils.

Ecotoxicological risk assessment of undisturbed metal contaminated soil at two remote lighthouse sites.

Ecotoxicological risk assessments of contaminated soil are commonly completed using guideline values based on total concentrations. However, only certain fractions of contaminants are bioavailable and pose a hazard to the environment. This paper investigates the relationship between measured metal concentrations in soil and soil leachate, and the effects in organisms exposed to intact, undisturbed soil cores (wheat, Tricum aestivum) and soil leachate (lettuce, Lactuca sativa, and water flea, Daphnia magna). Despite the samples containing metal concentrations significantly above guideline values, metals of concern (e.g. Pb and Zn) did not have a significant toxic effect on wheat or D. magna. During weeks with low leachate pH, an effect on lettuce root elongation was observed in the most contaminated samples. This study has shown that bioassays with intact soil cores can indicate metal bioavailability and provide a better estimate of ecological risk than total metal concentrations in the soil.

Kinetic study of uranium speciation in model solutions and in natural waters using Competitive Ligand Exchange Method.

Kinetic speciation of uranium in model solutions containing uranium and humic acid (HA) and in natural waters has been investigated by Competitive Ligand Exchange Method (CLEM). In alkaline freshwaters, most of uranium species were uranium-carbonate species, which were labile in the CLEM experiment. The uranium speciation of every sample was characterized either as "labile" or "non-labile" uranium complexes depending on the dissociation rate coefficients of the complexes. The results showed that as the U(VI)/HA ratio was decreased, the dissociation rate coefficients decreased and the labile fraction decreased as well. When the U(VI)/HA ratio was 0.1, the labile fraction of the U(VI)-HA increased with increasing pH; however, there was no pH effect on the dissociation of U(VI)-HA complexes at lower U(VI)/HA ratios. Chelex-100 had some limitations in its use for the study of dissociation of U(VI)-HA complex at very low U(VI)/HA ratios. By developing an analytical method and procedure for quantitative determination of kinetic parameters for the dissociation of uranium-HA complexes in model solutions and natural waters, this work has made a substantial contribution to analytical chemistry.

Cascade ultrafiltration and competing ligand exchange for kinetic speciation of aluminium, iron, and nickel in fresh water.

Kinetic speciation of nickel, aluminium, and iron in fresh water has been investigated by cascade ultrafiltration followed by competing ligand exchange of the ultrafiltered fractions. Graphite furnace atomic absorption spectrometry was used to measure the kinetics of metal complex dissociation. Dissolved metal species were fractionated by cascade ultrafiltration. Metal speciation in each ultrafiltered fraction was then characterized as free metal ions, "labile" metal complexes (with dissociation rate constants >/=10(-3) s(-1)), "slowly labile" metal complexes (with dissociation rate constants >10(-6) s(-1)), and "inert" metal complexes (with dissociation rate constants <10(-6) s(-1)). The experimental results were compared with the predictions of a computer-based equilibrium speciation model, the Windermere humic aqueous model (WHAM) V. Cascade ultrafiltration coupled with kinetic speciation of the metal species in each molecular weight cut-off (MWCO) fraction provided a more comprehensive picture and insight into the physical and the chemical characteristics of the metal species than either ultrafiltration or measurement of dissociation kinetics alone.