Absence of PCB Hot Spot Effect in Walleye Sander vitreus from Lower Green Bay of Lake Michigan.

Under certain conditions, polychlorinated biphenyl (PCB) concentration in individuals of one sex of an adult fish population may exceed that of the other sex by more than a factor of two. This phenomenon, known as the PCB hot spot effect, has been postulated to be contingent upon the following two conditions: (1) presence of a PCB hot spot in the bottom sediments of the aquatic ecosystem, such that prey PCB concentrations in the hot spot region are substantially higher than prey PCB concentrations in locations distant from the hot spot, and (2) habitat use varying between the sexes, such that individuals of one sex inhabit the hot spot region to a considerably greater degree than individuals of the other sex. To test whether PCB concentrations in walleye Sander vitreus from lower Green Bay of Lake Michigan displayed a PCB hot spot effect, whole-fish PCB concentrations were determined in ten female and ten male adult walleye from the population spawning in the Fox River, the main tributary to lower Green Bay. In addition, mark-recapture data for the Fox River walleye population were analyzed to determine differences in spatial distributions between the sexes. Results revealed that the ratio of mean PCB concentration in males to mean PCB concentration in females was only 1.13, indicating the absence of a PCB hot spot effect. This result was corroborated by the mark-recapture data analysis, which showed no significant difference in habitat use between the sexes. Thus, although condition 1 was met, condition 2 was not met. Consequently, the PCB hot spot effect was not observed in the Fox River walleye population. Lack of a significant difference in PCB congener distributions between the sexes further corroborated our conclusions.

Distributions of PCB Congeners and Homologues in White Sucker and Coho Salmon from Lake Michigan.

We tested the hypothesis of the proportion of higher chlorinated biphenyl (PCB) congeners increasing with increasing trophic level by comparing the respective PCB homologue distributions in an omnivore, white sucker ( Catostomus commersoni), and a top predator, coho salmon ( Oncorhynchus kisutch), from Lake Michigan. Adult females had the same congener and homologue proportions of total PCB concentration (ΣPCB) as adult males in both species. Hexachlorinated congeners comprised the largest proportion (32%) found in white sucker, followed by heptachlorinated (21%) and octochlorinated (18%) congeners. In contrast, pentachlorinated congeners comprised the largest proportion (33%) of ΣPCB found in coho salmon, followed by hexachlorinated (26%) and tetrachlorinated (24%) congeners. Coho salmon contained significantly higher proportions of tri-, tetra-, and pentachlorinated congeners, whereas white sucker contained significantly higher proportions of hexa- through decachlorinated congeners. Our results were opposite of the hypothesis of greater degree of PCB chlorination with increasing trophic level, and supported the contention that the PCB congener proportions in fish depends mainly on diet, and does not necessarily reflect the trophic level of the fish. Our results also supported the contention that diets do not vary between the sexes in most fish populations.

Sex differences in contaminant concentrations of fish: a synthesis.

A comparison of whole-fish polychlorinated biphenyl (PCB) and total mercury (Hg) concentrations in mature males with those in mature females may provide insights into sex differences in behavior, metabolism, and other physiological processes. In eight species of fish, we observed that males exceeded females in whole-fish PCB concentration by 17 to 43 %. Based on results from hypothesis testing, we concluded that these sex differences were most likely primarily driven by a higher rate of energy expenditure, stemming from higher resting metabolic rate (or standard metabolic rate (SMR)) and higher swimming activity, in males compared with females. A higher rate of energy expenditure led to a higher rate of food consumption, which, in turn, resulted in a higher rate of PCB accumulation. For two fish species, the growth dilution effect also made a substantial contribution to the sex difference in PCB concentrations, although the higher energy expenditure rate for males was still the primary driver. Hg concentration data were available for five of the eight species. For four of these five species, the ratio of PCB concentration in males to PCB concentration in females was substantially greater than the ratio of Hg concentration in males to Hg concentration in females. In sea lamprey (Petromyzon marinus), a very primitive fish, the two ratios were nearly identical. The most plausible explanation for this pattern was that certain androgens, such as testosterone and 11-ketotestosterone, enhanced Hg-elimination rate in males. In contrast, long-term elimination of PCBs is negligible for both sexes. According to this explanation, males not only ingest Hg at a higher rate than females but also eliminate Hg at a higher rate than females, in fish species other than sea lamprey. Male sea lamprey do not possess either of the above-specified androgens. These apparent sex differences in SMRs, activities, and Hg-elimination rates in teleost fishes may also apply, to some degree, to higher vertebrates including humans. Our synthesis findings will be useful in (1) developing sex-specific bioenergetics models for fish, (2) developing sex-specific risk assessment models for exposure of humans and wildlife to contaminants, and (3) refining Hg mass balance models for fish and higher vertebrates.

Effects of fuels, engine load and exhaust after-treatment on diesel engine SVOC emissions and development of SVOC profiles for receptor modeling.

Diesel exhaust emissions contain numerous semivolatile organic compounds (SVOCs) for which emission information is limited, especially for idling conditions, new fuels and the new after-treatment systems. This study investigates exhaust emissions of particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and sterane and hopane petroleum biomarkers from a heavy-duty (6.4 L) diesel engine at various loads (idle, 600 and 900 kPa BMEP), with three types of fuel (ultra-low sulfur diesel or ULSD, Swedish low aromatic diesel, and neat soybean biodiesel), and with and without a diesel oxidation catalyst (DOC) and diesel particulate filter (DPF). Swedish diesel and biodiesel reduced emissions of PM2.5, Σ15PAHs, Σ11NPAHs, Σ5Hopanes and Σ6Steranes, and biodiesel resulted in the larger reductions. However, idling emissions increased for benzo[k]fluoranthene (Swedish diesel), 5-nitroacenaphthene (biodiesel) and PM2.5 (biodiesel), a significant result given the attention to exposures from idling vehicles and the toxicity of high-molecular-weight PAHs and NPAHs. The DOC + DPF combination reduced PM2.5 and SVOC emissions during DPF loading (>99% reduction) and DPF regeneration (83-99%). The toxicity of diesel exhaust, in terms of the estimated carcinogenic risk, was greatly reduced using Swedish diesel, biodiesel fuels and the DOC + DPF. PAH profiles showed high abundances of three and four ring compounds as well as naphthalene; NPAH profiles were dominated by nitro-naphthalenes, 1-nitropyrene and 9-nitroanthracene. Both the emission rate and the composition of diesel exhaust depended strongly on fuel type, engine load and after-treatment system. The emissions data and chemical profiles presented are relevant to the development of emission inventories and exposure and risk assessments.

Males exceed females in PCB concentrations of cisco (Coregonus artedi) from Lake Superior.

We determined whole-fish polychlorinated biphenyl (PCB) concentrations of 25 male and 25 female age-7 ciscoes (Coregonus artedi) captured from a spawning aggregation in Thunder Bay, Lake Superior, during November 2010. We also determined PCB concentrations in the ovaries and somatic tissue of five additional female ciscoes (ages 5-22). All 55 of these ciscoes were in ripe or nearly ripe condition. Bioenergetics modeling was used to determine the contribution of the growth dilution effect toward a difference in PCB concentrations between the sexes, as females grew substantially faster than males. Results showed that the PCB concentration of males (mean = 141 ng/g) was 43% greater than that of females (mean = 98 ng/g), and this difference was highly significant (P<0.0001). Mean PCB concentrations in the ovaries and the somatic tissue of the five females were 135 and 100 ng/g, respectively. Based on these PCB determinations for the ovaries and somatic tissue, we concluded that release of eggs by females at previous spawnings was not a contributing factor to the observed difference in PCB concentrations between the sexes. Bioenergetics modeling results indicated that the growth dilution effect could explain males being higher than females in PCB concentration by only 3-7%. We concluded that the higher PCB concentration in males was most likely due to higher rate of energy expenditure, originating from greater activity and a higher resting metabolic rate. Mean PCB concentration in the cisco eggs was well below the U. S. Food and Drug Administration and Ontario Ministry of Environment guidelines of 2000 and 844 ng/g, respectively, and this finding may have implications for the cisco roe fishery currently operating in Lake Superior.

PAHs (polycyclic aromatic hydrocarbons), nitro-PAHs, and hopane and sterane biomarkers in sediments of southern Lake Michigan, USA.

PAHs in the Great Lakes basin are of concern due to their toxicity and persistence in bottom sediments. Their nitro derivatives, nitro-PAHs (NPAHs), which can have stronger carcinogenic and mutagenic activity than parent PAHs, may follow similar transport routes and also are accumulated in sediments. Limited information exists regarding the current distribution, trends and loadings of these compounds, especially NPAHs, in Lake Michigan sediments. This study characterizes PAHs, NPAHs, and biomarkers steranes and hopanes in surface sediments collected at 24 offshore sites in southern Lake Michigan. The ΣPAH14 (sum of 14 compounds) ranged from 213 to 1,291 ng/g dry weight (dw) across the sites, levels that are 2 to 10 times lower than those reported 20 to 30 years earlier. Compared to consensus-based sediment quality guidelines, PAH concentrations suggest very low risk to benthic organisms. The ΣNPAH5 concentration ranged from 2.9 to 18.6 ng/g dw, and included carcinogenic compounds 1-nitropyrene and 6-nitrochrysene. ΣSterane6 and ΣHopane5 concentrations ranged from 6.2 to 36 and 98 to 355 ng/g dw, respectively. Based on these concentrations, Lake Michigan is approximately receiving 11, 0.16, 0.25 and 3.6 metrictons per year (t/yr) of ΣPAH14, ΣNPAH5, ΣSterane6 and ΣHopane5, respectively. Maps of OC-adjusted concentrations display that concentrations decline with increasing off-shore distance. The major sources of PAHs and NPAHs are pyrogenic in nature, based on diagnostic ratios. Using chemical mass balance models, sources were apportioned to emissions from diesel engines (56 ± 18%), coal power plants (27 ± 14%), coal-tar pavement sealants (16 ± 11%), and coke ovens (7 ± 12%). The biomarkers identify a combination of petrogenic and biogenic sources, with the southern end of the lake more impacted by petroleum. This first report of NPAH levels in sediments of Lake Michigan reveals several carcinogenic compounds at modest concentrations, and a need for further work to assess potential risks to aquatic organisms.

PAHs, nitro-PAHs, hopanes, and steranes in lake trout from Lake Michigan.

The present study examines concentrations and risks of polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), steranes, and hopanes in lake trout collected in Lake Michigan. A total of 74 fish were collected in 2 seasons at 3 offshore sites. The total PAH concentration (Σ9 PAH) in whole fish ranged from 223 pg/g to 1704 pg/g wet weight, and PAH concentrations and profiles were similar across season, site, and sex. The total NPAH (Σ9 NPAH) concentrations ranged from 0.2 pg/g to 31 pg/g wet weight, and carcinogenic compounds, including 1-nitropyrene and 6-nitrochrysene, were detected. In the fall, NPAH concentrations were low at the Illinois site (0.2-0.5 pg/g wet wt), and site profiles differed considerably; in the spring, concentrations and profiles were similar across sites, possibly reflecting changes in fish behavior. In the fall, the total sterane (Σ5 Sterane) and total hopane (Σ2 Hopane) levels reached 808 pg/g and 141 pg/g wet weight, respectively, but concentrations in the spring were 10 times lower. Concentrations in eggs (fall only) were on the same order of magnitude as those in whole fish. These results demonstrate the presence of target semivolatile organic compounds in a top predator fish, and are consistent with PAH biodilution observed previously. Using the available toxicity information for PAHs and NPAHs, the expected cancer risk from consumption of lake trout sampled are low. However, NPAHs contributed a significant portion of the toxic equivalencies in some samples. The present study provides the first measurements of NPAHs in freshwater fish, and results suggest that additional assessment is warranted.

Composition and Integrity of PAHs, Nitro-PAHs, Hopanes and Steranes In Diesel Exhaust Particulate Matter.

Diesel exhaust particulate matter contains many semivolatile organic compounds (SVOCs) of environmental and health significance. This study investigates the composition, emission rates, and integrity of 25 SVOCs, including polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and diesel biomarkers hopanes and steranes. Diesel engine particulate matter (PM), generated using an engine test bench, three engine conditions, and ultra-low sulfur diesel (ULSD), was collected on borosilicate glass fiber filters. Under high engine load, the PM emission rate was 0.102 g/kWh, and emission rate of ΣPAHs (10 compounds), ΣNPAHs (6 compounds), Σhopanes (2 compounds), and Σsteranes (2 compounds) were 2.52, 0.351, 0.02 ~ 2 and 1µg/kWh, respectively. Storage losses were evaluated for three cases: conditioning filters in clean air at 25 °C and 33% relative humidity (RH) for 24 h; storing filter samples (without extraction) wrapped in aluminum foil at 4 °C for up to one month; and storing filter extracts in glass vials capped with Teflon crimp seals at 4 °C for up to six months. After conditioning filters for 24 h, 30% of the more volatile PAHs were lost, but lower volatility NPAHs, hopanes and steranes showed negligible changes. Storing wrapped filters and extracts at 4 °C for up to one month did not lead to significant losses, but storing extracts for five months led to significant losses of PAHs and NPAHs; hopanes and steranes demonstrated greater integrity. These results suggest that even relatively brief filter conditioning periods, needed for gravimetric measurements of PM mass, and extended storage of filter extracts can lead to underestimates of SVOC concentrations. Thus, SVOC sampling and analysis protocols should utilize stringent criteria and performance checks to identify and limit possible biases occurring during filter and extract processing.

Concentrations and speciation of polybrominated diphenyl ethers in human amniotic fluid.

Polybrominated diphenyl ethers (PBDEs) are persistent organic chemicals used as flame retardants in textiles, plastics, and consumer products. Although PBDE accumulation in humans has been noted since the 1970s, few studies have investigated PBDEs within the gestational compartment, and none to date has identified levels in amniotic fluid. The present study reports congener-specific brominated diphenyl ether (BDE) concentrations in second-trimester clinical amniotic fluid samples collected in 2009 from fifteen women in southeast Michigan, USA. Twenty-one BDE congeners were measured by GC/MS/NCI. The average total PBDE concentration was 3795 pg/ml amniotic fluid (range: 337-21,842 pg/ml). BDE-47 and BDE-99 were identified in all samples. Based on median concentrations, the dominant congeners were BDE-208, 209, 203, 206, 207, and 47 representing 23, 16, 12, 10, 9 and 6%, respectively, of the total detected PBDEs. PBDE concentrations were identified in all amniotic fluid samples from southeast Michigan, supporting a need for further investigations of fetal exposure pathways and potential impacts on perinatal health.

Polybrominated diphenyl ethers in human gestational membranes from women in southeast Michigan.

Polybrominated diphenyl ethers (PBDEs) have been incorporated into many consumer products as flame retardants. Due to their persistence and ability to bioaccumulate, PBDEs are ubiquitous in human blood and breast milk samples from industrialized nations. Although there exists a potential for environmental pollutants such as PBDEs to adversely impact birth outcomes and perinatal health, reports of PBDE levels in human reproductive tissues are limited. The aim of the current study is to evaluate the total levels and congener-specific profiles of PBDEs from human extraplacental gestational membranes. Gestational membranes from five term pregnancies were obtained from nonlaboring caesarian deliveries at the University of Michigan Women's Hospital Birth Center. Duplicate samples were extracted and analyzed by GC-MS for twenty-one PBDE congeners. Total PBDE loading was 17.4 +/- 3.9 pg/g tissue (5.62 +/- 1.28 ng/g lipid). Seventy-eight percent of the total measurable PBDE loading was due to BDEs 47, 49, 99, 100, and 153, with measured values of 3.63, 3.15, 3.05, 1.74, and 1.90 pg/g tissue (1170, 1018, 983, 561, and 612 pg/g lipid), respectively. The remaining 28% comprised BDEs 17, 28, 66, 71, 85, and 154. No octa-, nona-, or deca-BDEs were identified. Although previously unreported in the human gestational compartment BDE 49 comprised 17% of the total PBDE level. This work establishes baseline accumulated levels of PBDEs in gestational membranes of women in Southeast Michigan.

Sexual difference in PCB concentrations of walleyes (Sander vitreus) from a pristine lake.

We determined polychlorinated biphenyl (PCB) concentrations in 15 adult female walleyes (Sander vitreus) and 15 adult male walleyes from South Manistique Lake (Michigan, United States), a relatively pristine lake with no point source inputs of PCBs. By measuring PCB concentration in gonads and in somatic tissue of the South Manistique Lake fish, we also estimated the expected change in PCB concentration due to spawning for both sexes. To determine whether gross growth efficiency differed between the sexes, we applied bioenergetics modeling. Results showed that, on average, adult males were 34% higher in PCB concentration than adult females in South Manistique Lake. Results from the PCB determinations of the gonads and somatic tissues revealed that shedding of the gametes led to 1% and 5% increases in PCB concentration for males and females, respectively. Therefore, shedding of the gametes could not explain the higher PCB concentration in adult male walleyes. Bioenergetics modeling results indicated that the sexual difference in PCB concentrations of South Manistique Lake walleyes was attributable, at least in part, to a sexual difference in gross growth efficiency (GGE). Adult female GGE was estimated to be up to 17% greater than adult male GGE.

Effects of selected polybrominated diphenyl ether flame retardants on lake trout (Salvelinus namaycush).

Polybrominated diphenyl ether (PBDE) flame-retardants have been identified as an emergent contaminants issue in many parts of the world. In vitro analyses were conducted to test the hypothesis that selected PBDEs congeners affect viability, apoptosis, and necrosis of thymocytes from laboratory-reared lake trout (Salvelinus namaycush). At current environmental levels (< 1 mg/L), effects of the tested PBDEs on thymocytes were negligible. However, at 100 mg/L, major effects were seen for congener brominated diphenyl ether 47 (BDE-47) and minor effects were seen for congener BDE-99.

Time trends (1983-1999) for organochlorines and polybrominated diphenyl ethers in rainbow smelt (Osmerus mordax) from Lakes Michigan, Huron, and Superior, USA.

The U.S. Geological Service Great Lakes Science Center has archived rainbow smelt (Osmerus mordax) collected from the early 1980s to the present. These fish were collected to provide time- and site-dependent contaminant residue data needed by researchers and managers to fill critical data gaps regarding trends and behavior of persistent organic contaminants in the Great Lakes ecosystem. In the present study, data are presented for concentrations of several organochlorine (OC) contaminants in the archived smelt, including DDT, polychlorinated biphenyls (PCBs), toxaphene, and chlordanes in Lakes Michigan and Huron (MI, USA) and in Lake Superior (MN, USA). The trends for all the OCs were declining as a first-order decay over the sampled time series (1983/1985-1993/1999) with the exception of toxaphene in Lake Superior and PCBs at the Charlevoix/Little Traverse Bay site in Lake Michigan. Concentration of the emerging contaminant, polybrominated diphenyl ethers (PBDEs), also was traced from its apparent entry into this ecosystem in approximately 1980 until 1999. Time trends for the PBDEs were increasing exponentially at all sites, with concentration-doubling times varying from 1.58 to 2.94 years.