Basic considerations to minimize bias in collection and analysis of volatile methyl siloxanes in environmental samples.

Monitoring studies that aim to quantify volatile methyl siloxanes (VMS) in environmental matrices may encounter a multitude of issues, most of which relate to the unique combination of physical-chemical characteristics of VMS that distinguish them from other classes of organic compounds. These properties, which are critical to their function in various applications, also control their fate and distribution in the environment, as well as the analytical chemistry of their measurement. Polycondensation and rearrangement reactions of VMS oligomers are possible during sample storage and analysis. Thus, care should be exercised to suppress these types of reactions by avoiding any catalytic substances or surfaces in sample collection and analysis equipment. Another factor complicating sample integrity in the analysis of trace levels of VMS, is their ubiquitous presence in many common products and components of instrumentation in the laboratory. For example, some gas chromatography columns and inlet septa have been identified as sources of VMS due to surface-catalyzed transformation of silicones to VMS promoted by moisture under high temperature in some silicone-based GC columns. Possible chemical transformation of the analytes, contamination from other sources, and potential loss of analytes need to be assessed throughout all aspects of the study, from sample collection through analysis, by establishing a rigorous quality assurance and quality control program. The implementation of such a robust QA/QC program facilitates the identification and minimization of potential analytical biases and ensures the validity and usability of data generated from environmental monitoring campaigns for VMS. The objective of this paper is to focus on aspects of collection, processing, and analysis of environmental samples that may influence the quality of the VMS analytical results. This information should then be employed in the design and implementation of future monitoring studies and can used to assess the validity of analytical results from VMS monitoring studies.

Benthic invertebrate exposure and chronic toxicity risk analysis for cyclic volatile methylsiloxanes: Comparison of hazard quotient and probabilistic risk assessment approaches.

This study utilized probabilistic risk assessment techniques to compare field sediment concentrations of the cyclic volatile methylsiloxane (cVMS) materials octamethylcyclotetrasiloxane (D4, CAS # 556-67-2), decamethylcyclopentasiloxane (D5, CAS # 541-02-6), and dodecamethylcyclohexasiloxane (D6, CAS # 540-97-6) to effect levels for these compounds determined in laboratory chronic toxicity tests with benthic organisms. The concentration data for D4/D5/D6 in sediment were individually sorted and the 95th centile concentrations determined in sediment on an organic carbon (OC) fugacity basis. These concentrations were then compared to interpolated 5th centile benthic sediment no-observed effect concentration (NOEC) fugacity levels, calculated from a distribution of chronic D4/D5/D6 toxicologic assays per OECD guidelines using a variety of standard benthic species. The benthic invertebrate fugacity biota NOEC values were then compared to field-measured invertebrate biota fugacity levels to see if risk assessment evaluations were similar on a field sediment and field biota basis. No overlap was noted for D4 and D5 95th centile sediment and biota fugacity levels and their respective 5th centile benthic organism NOEC values. For D6, there was a small level of overlap at the exposure 95th centile sediment fugacity and the 5th centile benthic organism NOEC fugacity value; the sediment fugacities indicate that a negligible risk (1%) exists for benthic species exposed to D6. In contrast, there was no indication of risk when the field invertebrate exposure 95th centile biota fugacity and the 5th centile benthic organism NOEC fugacity values were compared.

Evaluating the roles of biotransformation, spatial concentration differences, organism home range, and field sampling design on trophic magnification factors.

Trophic magnification factors (TMFs) are field-based measurements of the bioaccumulation behavior of chemicals in food-webs. TMFs can provide valuable insights into the bioaccumulation behavior of chemicals. However, bioaccumulation metrics such as TMF may be subject to considerable uncertainty as a consequence of systematic bias and the influence of confounding variables. This study seeks to investigate the role of systematic bias resulting from spatially-variable concentrations in water and sediments and biotransformation rates on the determination of TMF. For this purpose, a multibox food-web bioaccumulation model was developed to account for spatial concentration differences and movement of organisms on chemical concentrations in aquatic biota and TMFs. Model calculated and reported field TMFs showed good agreement for persistent polychlorinated biphenyl (PCB) congeners and biotransformable phthalate esters (PEs) in a marine aquatic food-web. Model testing showed no systematic bias and good precision in the estimation of the TMF for PCB congeners but an apparent underestimation of model calculated TMFs, relative to reported field TMFs, for PEs. A model sensitivity analysis showed that sampling designs that ignore the presence of concentration gradients may cause systematically biased and misleading TMF values. The model demonstrates that field TMFs are most sensitive to concentration gradients and species migration patterns for substances that are subject to a low degree of biomagnification or trophic dilution. The model is useful in anticipating the effect of spatial concentration gradients on the determination of the TMF; guiding species collection strategies in TMF studies; and interpretation of the results of field bioaccumulation studies in study locations where spatial differences in chemical concentration exist.

Multiple lines of evidence risk assessment of American robins exposed to polychlorinated dibenzofurans (PCDFS) and polychlorinated dibenzo-P-dioxins (PCDDS) in the Tittabawassee River floodplain, Midland, Michigan, USA.

Concentrations of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) in Tittabawassee River floodplain soils and biota downstream of Midland, Michigan, USA, are greater than regional background concentrations. From 2005 to 2008, a multiple lines of evidence approach was utilized to evaluate the potential for effects of PCDD/DFs on American robins (Turdus migratorius) breeding in the floodplains. A dietary-based assessment indicated there was potential for adverse effects for American robins predicted to have the greatest exposures. Conversely, a tissue-based risk assessment based on site-specific PCDD/DF concentrations in American robin eggs indicated minimal potential for adverse effects. An assessment based on reproductive endpoints indicated that measures of hatch success in study areas were significantly less than those of reference areas. However, there was no dose-response relationship between that endpoint and concentrations of PCDD/DF. Although dietary-based exposure and reproductive endpoint assessments predicted potential for adverse effects to resident American robins, the tissue-based assessment indicates minimal to no potential for adverse effects, which is reinforced by the fact the response was not dose related. It is likely that the dietary assessment is overly conservative given the inherent uncertainties of estimating dietary exposure relative to direct tissue-based assessment measures. Based on the available data, it can be concluded that exposure to PCDD/DFs in the Tittabawassee River floodplain would not likely result in adverse population-level effects to American robins.

Reproductive success of three passerine species exposed to dioxin-like compounds near Midland, Michigan, USA.

Nests of three passerine birds, house wren (HOWR), tree swallow (TRES), and eastern bluebird (EABL) were monitored daily (2005-2007) at study areas (SAs) downstream of Midland, Michigan where soil and sediment concentrations of polychlorinated dibenzofurans (PCDFs) were significantly greater than the regional background concentrations and upstream reference areas (RAs). Similarly, TRES research conducted at sites contaminated with dioxin-like compounds indicated that concentrations of polychlorinated dibenzo-p-dioxins and PCDFs, expressed as ΣPCDD/DFs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents observed in the diet and eggs of these three species would be predicted to cause significant effects on reproduction. However, site-specific reproductive parameters including hatching success and fledging success at downstream SAs were similar to or greater than those at upstream RAs. Specifically, hatching success was not significantly different among years, species, locations, or between early and late nesting attempts. Of all initiated clutches, 66% (n = 427), 73% (n = 245), and 64% (n = 122) successfully fledged at least one nestling for HOWR, TRES, and EABL, respectively. Overall reproductive performance was similar between SAs and RAs. The reason for these unexpected results is consistent with the fact that there are species-specific and congener-specific differences in sensitivities to the effects of aryl hydrocarbon receptor agonists.

Dietary- and tissue-based exposure of belted kingfisher to PCDFs and PCDDs in the Tittabawassee River floodplain, Midland, MI, USA.

Concentrations of polychlorinated dibenzofurans (PCDFs) and other dioxin-like compounds in soils and sediments of the Tittabawassee River and associated floodplains downstream of Midland, Michigan, USA, are greater than upstream sites. As a result of these concentrations, which are some of the greatest ever reported, a site-specific exposure assessment of belted kingfisher breeding in the assessment area was conducted. To reduce the uncertainty associated with predicting exposure from abiotic matrices, concentrations of residues were quantified in site-specific prey items and in eggs and nestlings of belted kingfisher. Dietary exposure, expressed as the potential average daily dose, based on site-specific concentrations of PCDFs, polychlorinated dibenzo-p-dioxins (PCDDs), and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ(WHO-Avian)) in prey items was consistently greater along the Tittabawassee River than in associated reference areas and further downstream sites in the Saginaw River. Concentrations of PCDD/DFs in eggs and nestlings of belted kingfisher varied among sampling areas, being greater in both eggs and nestlings nesting along the Tittabawassee River compared to those of belted kingfisher from upstream reference areas. Geometric mean concentrations of PCDD/DFs were 130 and 200 ng/kg wet weight in eggs and nestlings of belted kingfisher, respectively. These concentrations are the equivalent of 84 and 95 ng TEQ(WHO-Avian)/kg. Site-specific biomagnification factors for select PCDD/DF congeners ranged from <1.0 to 1.8 in belted kingfisher.

Multiple Lines of Evidence Risk Assessment of Terrestrial Passerines Exposed to PCDFs and PCDDs in the Tittabawassee River Floodplain, Midland, Michigan, USA.

A site-specific multiple lines of evidence risk assessment was conducted for house wrens (Troglodytes aedon) and eastern bluebirds (Sialia sialis) along the Tittabawassee River downstream of Midland, Michigan, where concentrations of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) in flood-plain soils and sediments are greater compared to upstream areas and some of the greatest anywhere in the world. Lines of evidence supporting the population-level assessment endpoints included site-specific dietary- and tissue-based exposure assessments and population productivity measurements during breeding seasons 2005-2007. While a hazard assessment based on site-specific diets suggested that populations residing in the downstream floodplain had the potential to be affected, concentrations in eggs compared to appropriate toxicity reference values (TRVs) did not predict a potential for population-level effects. There were no significant effects on reproductive success of either species. The most probable cause of the apparent difference between the dietary- and tissue-based exposure assessments was that the dietary-based TRVs were overly conservative based on intraperitoneal injections in the ring-necked pheasant. Agreement between the risk assessment based on concentrations of PCDFs and PCDDs in eggs and reproductive performance in both species supports the conclusion of a small potential for population-level effects at this site.

Effects on tree swallows exposed to dioxin-like compounds associated with the Tittabawassee River and floodplain near Midland, Michigan, USA.

Concentrations of dioxin-like compounds, primarily polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs), in soils and sediments downstream of Midland, Michigan (USA) were greater than upstream sites and prompted a site-specific hazard assessment of tree swallows breeding in the associated floodplains. Potential for adverse population-level effects from site-specific contaminant exposures were evaluated at study areas (SAs) along the Tittabawassee and Saginaw rivers downstream of Midland. The site-specific multiple lines of evidence approach to hazard assessment included endpoints for dietary- and tissue-based exposures, and population productivity measurements for tree swallows ([TS]; Tachycineta bicolor) measured during the 2005, 2006, and 2007 breeding seasons. Exposure to dioxin-like compounds in TS eggs were some of the greatest recorded and were similar among all upstream and downstream study sites. Conversely, concentrations in nestlings from SAs were significantly greater compared to reference areas (RAs). The pattern of relative concentrations of PCDD/DFs in eggs and nestlings at RAs was dominated by dioxin congeners, whereas at SAs it was dominated by furan congeners. No statistically significant differences were noted in exposure to PCDD/DFs or in population-level responses when compared among locations, and total clutch failures were rare. Hatching success and fledging success were weakly negatively correlated with concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) in individual eggs and nestlings, respectively. On-site concentrations of TEQs in floodplain soils were some of the greatest ever reported in the environment, and several lines of evidence indicate potential population-level effects on TS overall reproductive productivity.

Dietary exposure of three passerine species to PCDD/DFs from the Chippewa, Tittabawassee, and Saginaw River floodplains, Midland, Michigan, USA.

Dietary exposure of house wrens (Troglodytes aedon), tree swallows (Tachycineta bicolor), and eastern bluebirds (Sialia sialis) to polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) near Midland, Michigan (USA) was evaluated based on site-specific data, including concentrations of residues in bolus samples and individual invertebrate orders and dietary compositions by study species. Site-specific dietary compositions for the three species were similar to those reported in the literature, but differed in their relative proportions of some dietary items. Oligocheata (non-depurated) and Brachycera (Diptera) contained the greatest average concentrations of ΣPCDD/DFs of the major site-specific dietary items collected via food web-based sampling. Average ingestion values of ΣPCDD/DFs from site-specific bolus-based and food web-based dietary concentrations for nestlings at study areas (SAs) were 6- to 20-fold and 2- to 9-fold greater than at proximally located reference areas (RAs), respectively. Average ingestion values of total 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ(WHO - Avian)) from site-specific bolus-based and food web-based dietary concentrations for nestlings at SAs were 31- to 121-fold and 9- to 64-fold greater than at proximally located RAs, respectively. Estimates of ΣPCDD/DFs and TEQ(WHO - Avian) tissue concentrations based on nestling dietary exposures were greater than those measured. Plausible explanations include nestling metabolism of 2,3,7,8-tetrachlorodibenzofuran and assimilation rates of less than the 70% assumed to occur over the nestling growth period. Profiles of the relative concentrations of individual PCDD/DF congeners in samples of invertebrates and bolus at SAs on the Tittabawassee River downstream of the source of contamination were dominated by 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (22% to 44%) and 2,3,7,8-tetrachlorodibenzofuran (18% to 50%).

Dietary exposure of great blue heron (Ardea herodias) to PCDD/DFs in the Tittabawassee River floodplain, MI, USA.

Concentrations of dioxin-like compounds, primarily polychlorinated dibenzofurans (PCDFs), in soils and sediments of the Tittabawassee River (TR) and associated floodplains downstream of Midland, Michigan (USA) were greater than upstream sites and prompted a site-specific risk assessment of great blue herons (GBH). Dietary exposure of GBH to PCDFs and polychlorinated dibenzo-p-dioxins (PCDDs) was evaluated based on site-specific concentrations of residues in prey items. Concentrations of ∑PCDD/DFs and 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ(WHO-Avian)) in prey items collected from the TR were consistently greater than those collected from associated reference areas (RAs) and further downstream in the Saginaw River (SR). The average daily dose (ADD(pot)) of ∑PCDD/DFs to GBH was 45- to 54-fold greater along the TR and 12-fold greater along the SR when compared to the RA. ∑PCDD/DFs were normalized to TEQ(WHO-Avian), and fold differences in the ADD(pot) increased, being 150- to 190-fold greater along the TR and 36-fold greater along the SR than they were in the RA. Greater fold changes in the ADD(pot) based on TEQ(WHO-Avian) between the RA and the TR and SR was due to prey items from the latter reaches having a greater relative toxic potency of ∑PCDD/DFs, primarily from greater amounts of 2,3,7,8-tetrachlorodibenzofuran but also 2,3,4,7,8-pentachlorodibenzofuran. Potential for adverse population-level effects from site-specific contaminant exposures were evaluated via comparison to selected toxicity reference values. The prediction of minimal to no risk of adverse population-level effects resultant from the assessment of site-specific dietary exposure of GBH to ∑PCDD/DFs along the TR and SR is consistent with site-specific assessments of tissue-based exposures as well as population condition.

Tissue-based risk assessment of great blue heron (Ardea herodias) exposed to PCDD/DF in the Tittabawassee River floodplain, Michigan, USA.

Concentrations of dioxin-like compounds, primarily polychlorinated dibenzofurans (PCDFs), in soils and sediments of the Tittabawassee River (TR) and associated floodplains downstream of Midland, Michigan, USA, were greater than upstream sites and prompted a site-specific risk assessment of great blue herons (GBH). Tissue exposure of PCDF and polychlorinated dibenzo-p-dioxins (PCDDs) was assessed in multiple GBH tissue types, including blood plasma of adults and eggs, as well as blood plasma, adipose, liver, and muscle of nestlings. Adult GBH exposure was associated with foraging area and age class, with concentrations of PCDD/DF being greater in blood plasma of adult GBH foraging in the TR compared with those foraging in upstream reference areas and in older birds as compared with their younger cohorts. Concentrations of PCDD/DFs and dioxin-like polychlorinated biphenyls (PCBs) in eggs and nestling tissues of GBH collected from rookeries within the TR floodplain were generally similar among rookeries. Mean concentrations of PCDD/DFs in eggs of GBH ranged from 45 to 67 ng/kg, wet weight for the rookeries studied, with a maximum concentration of 210 ng/kg, wet weight observed. Adipose consistently had the greatest concentration of PCDD/DFs of all tissues collected from nestlings of GBH, ranging from 98 to 430 ng/kg, wet weight. Potential for adverse population-level effects from site-specific contaminant exposures were evaluated by comparison with selected toxicity reference values (TRVs). Minimal risk of adverse population-level effects were predicted when exposures measured in tissues of GBH collected from rookeries within the TR were compared with appropriate TRVs. This prediction is consistent with site-specific measures of population condition, which included clutch size and number of nestlings per successful nest.

Ecological risk assessment of great horned owls (Bubo virginianus) exposed to PCDD/DF in the Tittabawassee River floodplain in Midland, Michigan, USA.

Soils and sediments downstream of Midland, Michigan, USA have elevated polychlorinated dibenzofuran (PCDF) and polychlorinated dibenzo-p-dioxin (PCDD) concentrations. To determine if the PCDD/DF concentrations have the potential to adversely affect terrestrial avian predators, a site-specific, multiple lines of evidence risk assessment was conducted for the great horned owl (Bubo virginianus; GHO). As long-lived resident top predators, the GHO has the potential to be exposed to relatively great concentrations of bioaccumulative compounds such as PCDD/DF. From 2005 to 2008, concentrations of PCDD/DF were measured in blood plasma of adult and nestling GHOs and addled eggs. Indicators of the condition of the population, including abundance and reproductive success, were collected along 115 km of river corridor. Fifty-five active 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) equivalents (TEQ(WHO-Avian)) nests were monitored in 21 breeding territories from 2005 to 2008. The geometric mean concentration in blood plasma of GHOs was greater in the study area (SA) than in the reference area (RA) for both adults (RA: 3.1; SA: 9.4 ng TEQ(WHO-Avian)/kg) and nestlings (RA: 0.82 ng TEQ(WHO-Avian)/kg, SA: 2.1 ng TEQ(WHO-Avian)/kg) GHOs, but less than concentrations expected to cause adverse effects based on laboratory studies. Concentrations of TEQ(WHO-Avian) in addled GHO eggs were also greater in the SA than the RA (50 and 7.3 ng/kg, wet weight, respectively), but were less than concentrations expected to cause adverse effects. The GHO population condition and productivity were both greater in the study area than in the reference area and were similar to other GHO populations. This result suggests the GHO population in the Tittabawassee River floodplain is consistent with what would be expected for this area.

Great horned owl (Bubo virginianus) dietary exposure to PCDD/DF in the Tittabawassee River floodplain in Midland, Michigan, USA.

Soils and sediments in the floodplain of the Tittabawassee River downstream of Midland, Michigan, USA contain elevated concentrations of polychlorinated dibenzofurans (PCDF) and polychlorinated dibenzo-p-dioxins (PCDD). As a long-lived, resident top predator, the great horned owl (Bubo virginianus; GHO) has the potential to be exposed to bioaccumulative compounds such as PCDD/DF. Site-specific components of the GHO diet were collected along 115 km of the Tittabawassee, Pine, Chippewa, and Saginaw Rivers during 2005 and 2006. The site-specific GHO biomass-based diet was dominated by cottontail rabbits (Sylvilagus floridanus) and muskrats (Ondatra zibethicus). Incidental soil ingestion and cottontail rabbits were the primary contributors of PCDD/DF to the GHO diet. The great horned owl daily dietary exposure estimates were greater in the study area (SA) (3.3 to 5.0 ng 2,3,7,8-TCDD equivalents (TEQ(WHO-avian))/kg body wt/d) than the reference area (RA) (0.07 ng TEQ(WHO-Avian)/kg body wt/d). Hazard quotients (HQs) based on central tendency estimates of the average daily dose and no-observable-adverse effect level (NOAEL) for the screech owl and uncertainty factors were <1.0 for both the RA and the SA. Hazard quotients based on upper end estimates of the average daily dose and NOAEL were <1.0 in the RA and up to 3.4 in the SA.

Passerine exposure to primarily PCDFs and PCDDs in the river floodplains near Midland, Michigan, USA.

House wren (Troglodytes aedon), tree swallow (Tachycineta bicolor), and eastern bluebird (Sialia sialis) tissues collected in study areas (SAs) downstream of Midland, Michigan (USA) contained concentrations of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo-p-dioxins (PCDDs) greater than in upstream reference areas (RAs) in the region. The sum of concentrations of PCDD/DFs (SigmaPCDD/DFs) in eggs of house wrens and eastern bluebirds from SAs were 4- to 22-fold greater compared to those from RAs, whereas concentrations in tree swallow eggs were similar among areas. Mean concentrations of SigmaPCDD/DFs and sum 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (SigmaTEQs(WHO-Avian)), based on 1998 WHO avian toxic equivalency factors, in house wren and eastern bluebird eggs ranged from 860 (430) to 1500 (910) ng/kg wet weight (ww) and 470 (150) to 1100 (510) ng/kg ww, respectively, at the most contaminated study areas along the Tittabawassee River, whereas mean concentrations in tree swallow eggs ranged from 280 (100) to 760 (280) ng/kg ww among all locations. Concentrations of SigmaPCDD/DFs in nestlings of all studied species at SAs were 3- to 50-fold greater compared to RAs. Mean house wren, tree swallow, and eastern bluebird nestling concentrations of SigmaPCDD/DFs and SigmaTEQs(WHO-Avian) ranged from 350 (140) to 610 (300) ng/kg ww, 360 (240) to 1100 (860) ng/kg ww, and 330 (100) to 1200 (690) ng/kg ww, respectively, at SAs along the Tittabawassee River. Concentrations of SigmaTEQs(WHO-Avian) were positively correlated with SigmaPCDD/DF concentrations in both eggs and nestlings of all species studied. Profiles of relative concentrations of individual congeners were dominated by furan congeners (69-84%), primarily 2,3,7,8-tetrachlorodibenzofuran and 2,3,4,7,8-pentachlorodibenzofuran, for all species at SAs on the Tittabawassee and Saginaw rivers but were dominated by dioxin congeners at upstream RAs.