The Use of Semipermeable Membrane Devices to Concentrate Chemicals in Oil Refinery Effluent on the Mackenzie River

To concentrate natural and refinery-derived inducers of mixed function oxygenase (MFO), semipermeable membrane devices (SPMDs) were deployed for 11-12 days in Norman Wells refinery effluent and upstream and downstream on the Mackenzie River, Northwest Territories, Canada. SPMDs, which are layflat polyethylene membrane tubes containing a thin film of purified triolein, absorb freely dissolved neutral organic chemicals that diffuse through the polyethylene membrane. Fish liver cells (Poeciliopsis lucida hepatoma; PLHC-1) were dosed with SPMD extracts; then MFO activity was determined. SPMDs from the effluent contained potent MFO inducers, equivalent to 4830-8700 pg 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin (TCDD)/g SPMD. SPMDs from the site 0.5 km downstream of the refinery outfall also induced MFO, but downstream extracts were about 1/40 as potent as those from effluent-exposed SPMDs. Comparing sites on the Mackenzie River, extracts of SPMDs from downstream of the refinery outfall were over 20 times as potent as those from upstream SPMDs. Polyaromatic hydrocarbons (PAHs) and C1- to C3-substituted PAHs were abundant in extracts of SPMDs from the effluent and, to a lesser degree, in extracts of SPMDs from 0.5 km downstream. In effluent-exposed and downstream SPMDs, concentrations of parent PAHs were lower than those of C1-substituted PAHs. The highest concentrations were those of C2- and C3-substituted PAHs. It is unknown which compounds in the SPMDs caused the MFO induction, but there was a very strong correlation between the concentration of total C3-phenanthrene/anthracene in the SPMD extracts and MFO-induction potency. The study shows both the use of SPMDs as concentrators of neutral organic compounds in harsh environments (such as high temperature effluents and fast-flowing rivers) and the utility and sensitivity of the fish liver cell line for ranking MFO-inducing potencies of environmental SPMD extracts.Afin de concentrer les inducteurs naturels et dérivés de raffinerie de l'oxygénase à fonction mixte (OFM), on a déployé de l'équipement à membrane semi-perméable pendant une durée de 11 à 12 jours dans les effluents de l'usine de raffinage de Norman Wells, de même qu'en amont et en aval dans les eaux du Mackenzie (Territoires du Nord-Ouest, Canada). Ces systèmes, formés de tubes de membrane en polyéthylène aplatis contenant une mince pellicule de trioléine purifiée, absorbent abondamment les produits chimiques organiques neutres en solution qui se diffusent dans toute la membrane de polyéthylène. On a mis des extraits de cette membrane en contact avec des cellules de foie de poisson (hépatocarcinome de Poeciliopsis lucida; HCPL-1), puis on a déterminé l'activité de l'OFM. Les membranes provenant des effluents contenaient de puissants inducteurs d'OFM, équivalents à 4830-8700 pg de tétrachlorodibenzodioxine-p 2,3,7,8 (TCDD)/g de membrane. Les membranes provenant du lieu situé à 0,5 km en aval du déversoir étaient aussi des inducteurs d'OFM, mais environ quarante fois moins puissants que ceux provenant des membranes exposées directement aux effluents. En comparant les sites sur le Mackenzie, les extraits des membranes situées en aval du déversoir de la raffinerie étaient environ 20 fois plus puissants que ceux des membranes situées en amont. Les hydrocarbures aromatiques polycycliques (HAP) et les HAP de remplacement de formule C1 à C3 se trouvaient en abondance dans les extraits de membrane provenant des effluents et, à un degré moindre, dans les extraits de membrane provenant du lieu situé à 0,5 km en aval. Dans les membranes exposées aux effluents et aux eaux situées en aval, les concentrations des HAP mères étaient inférieures à celles des HAP de remplacement de formule C1. Les concentrations les plus fortes étaient celles des HAP de remplacement de formule C2 et C3. On ne sait pas quels composés présents dans les membranes ont causé l'induction de l'OFM, mais il existait une très forte corrélation entre la concentration totale de phénanthrène/anthracène dans les extraits de membrane et la puissance d'induction de l'OFM. L'étude démontre à la fois l'utilisation des membranes comme concentrateurs des composés organiques neutres dans un environnement difficile (tel celui d'effluents à haute température et de cours d'eau rapides) ainsi que l'utilité et la sensibilité de la lignée cellulaire de foie de poisson pour classer les extraits de membrane environnementale selon leur puissance d'induction de l'OFM

Long-term impacts of invasive species on a native top predator in a large lake system

1. Declining abundances of forage fish and the introduction and establishment of non-indigenous species have the potential to substantially alter resource and habitat exploitation by top predators in large lakes. 2. We measured stable isotopes of carbon (δ13C) and nitrogen (δ15N) in field-collected and archived samples of Lake Ontario lake trout (Salvelinus namaycush) and five species of prey fish and compared current trophic relationships of this top predator with historical samples. 3. Relationships between δ15N and lake trout age were temporally consistent throughout Lake Ontario and confirmed the role of lake trout as a top predator in this food web. However, δ13C values for age classes of lake trout collected in 2008 ranged from 1.0 to 3.9‰ higher than those reported for the population sampled in 1992. 4. Isotope mixing models predicted that these changes in resource assimilation were owing to the replacement of rainbow smelt (Osmerus mordax) by round goby (Neogobius melanostomus) in lake trout diet and increased reliance on carbon resources derived from nearshore production. This contrasts with the historical situation in Lake Ontario where δ13C values of the lake trout population were dominated by a reliance on offshore carbon production. 5. These results indicate a reduced capacity of the Lake Ontario offshore food web to support the energetic requirements of lake trout and that this top predator has become increasingly reliant on prey resources that are derived from nearshore carbon pathways

The astrobiology primer: An outline of general knowledge - Version 1, 2006

Peer reviewe

Halogenated Flame Retardants in Predator and Prey Fish from the Laurentian Great Lakes: Age-Dependent Accumulation and Trophic Transfer

The identification, persistence, accumulation and trophic transfer of 25 polybrominated diphenyl ether (PBDE) congeners, 23 non-PBDE halogenated flame retardants (NPHFRs), 4 polybrominated-diphenoxybenzenes (PB-DiPhOBzs) and 6 methoxylated (MeO-) PB-DiPhOBzs were investigated in predator and prey fish collected in 2010 from sites in the North American Great Lakes of Ontario (n = 26) and Erie (n = 39). Regardless of locations or species, 20 PBDEs and 12 NPHFRs were quantifiable in at least one of the 65 analyzed samples, and polybrominated-1,4-diphenoxybenzenes (PB-DiPhOBzs) and MeO-PB-DiPhOBzs were not detectable in any of analyzed samples. Among the FRs, the greatest concentrations were the -PBDE, ranging from 1.06 (Rainbow Smelt, Lake Erie) to 162 (Lake Trout, Lake Ontario) ng/g wet weight (ww), which was followed by mean HBCDD concentrations ranging ND to 17.3 (Lake Trout, Lake Ontario) ng/g ww. The remaining FRs were generally not detectable or at sub-ppb levels. In most of cases, FR concentrations in samples from Lake Ontario were greater than those from Lake Erie. Strong and significant positive linear relationships occurred between log-normalized FR concentrations (ww or lipid weight (lw)) and ages of the top predator Lake Trout (n = 16, from Lake Ontario), and the estimated FR doubling ages (T2) were 2.9-6.4 years. For Walleye from Lake Erie, significantly positive linear relationships were also observed for some FRs, but the linear relationships generally became negative after FR concentrations were normalized with lipid weight. This study provides novel information on FR accumulation in aquatic organisms, and for the first time, significant positive linear relationships are reported between log-normalized FR concentrations (lw or ww) and ages of Lake Trout from the Great Lakes

Spatial trends and bioaccumulation of organochlorine pollutants in marine zooplankton from the Alaskan and Canadian Arctic

Planktonic copepods (Calanus glacialis and C. hyperboreus; n = 37) and water (n = 19) were collected to examine the spatial distribution and bioaccumulation of organochlorine contaminants (OCs) in the Alaskan and Canadian Arctic. The rank order of total OC (∑ OC) group concentrations in Calanus samples was toxaphene ≥ ∑ polychlorinated biphenyls (PCBs) \u3e ∑ hexachlorcyclohexane (HCH) \u3e ∑ DDT \u3e ∑ chlordane-related compounds (CHLOR) \u3e ∑ chlorobenzenes (ClBz). The dominant analyte was α-HCH in all water and zooplankton samples. The most abundant toxaphene congener in water and zooplankton samples was the hexachlorobornane B6-923. Organochlorine contaminant group concentrations in Alaskan zooplankton and water samples were lower than those in samples collected from sites in the eastern Canadian Arctic. Comparison of PCB and toxaphene congener profiles in zooplankton and water samples suggests that biotransformation by cytochrome P-4502B isozymes is low in Calanus, and limited phase I metabolism may occur. The log relationship of bioaccumulation factor (log BAF) versus octanol-water partition coefficient (log KOW) relationship was near 1:1 for OCs within the log KOW range of 3 to 6. A curvilinear model provided a better relationship between these two variables when OC compounds with log KOW \u3e 6 were included. These results suggest that hydrophobic OCs (log KOW 3-6) in Calanus species are at equilibrium with the water concentrations and that physical partitioning, rather than biotransformation, is the major factor governing OC profiles in marine zooplankton

A New Fluorinated Surfactant Contaminant in Biota: Perfluorobutane Sulfonamide in Several Fish Species

Environmental contamination and regulation of longer-chain perfluoroalkyl substances (PFASs) such as perfluorooctanesulfonate (PFOS) has given rise to the increased use of shorter-chain PFASs as alternatives in new products, although confirmation of their presence in the environment remains limited. In this study, the PFAS alternative, perfluoro-1-butane-sulfonamide (FBSA), was identified for the first time in biota in homogenate samples of fish by liquid chromatography-quadrupole time-of-flight mass spectrometry (LC-Q-ToF-MS) and quantified by ultra high performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-QQQ-MS/MS). In one flounder (Platichthys flesus) muscle sample from the Western Scheldt, The Netherlands, FBSA concentration was at 80.12 ng/g wet weight (w.w.) and was exceeded only by PFOS. FBSA was also detected in 32 out of 33 samples of freshwater fish collected (2009–2010) from water bodies across Canada. In lake trout (Salvelinus namaycush) from northern Canada (e.g., Lake Kusawa (Yukon Territory), Great Bear Lake (Northwest Territories and in the Arctic), and Lake Athabasca (northern Alberta)), the concentrations of FBSA ranged from below method detection limit (<0.01 ng/g w.w) to 0.44 ng/g w.w. and were much lower than those reported for lake trout from the more urbanized and industrialized Laurentian Great Lakes sites (3.17 ± 1.53 ng/g w.w.). In three species of fish purchased from a supermarket in Ottawa (ON, Canada), FBSA concentrations were the lowest of all fish and ranged from < MLOD to 0.29 ng/g w.w. and 0.03 to 0.76 ng/g w.w. in muscle and liver, respectively. FBSA is a bioaccumulative contaminant in fish in Canada and possibly in The Netherlands. It is likely sourced from new alternative perfluorobutane-based products, as well as other shorter chain perfluoroalkyl-based products

Mercury and other trace elements in a pelagic Arctic marine food web (Northwater Polynya, Baffin Bay)

Total mercury (THg), methylmercury (MeHg) and 22 other trace elements were measured in ice algae, three species of zooplankton, mixed zooplankton samples, Arctic cod (Boreogadus saida), ringed seals (Phoca hispida) and eight species of seabirds to examine the trophodynamics of these metals in an Arctic marine food web. All samples were collected in 1998 in the Northwater Polynya (NOW) located between Ellesmere Island and Greenland in Baffin Bay. THg and MeHg were found to biomagnify through the NOW food web, based on significant positive relationships between log THg and log MeHg concentrations vs. δ15N muscle and liver . The slope of these relationships for muscle THg and MeHg concentrations (slope = 0.197 and 0.223, respectively) were similar to those reported for other aquatic food webs. The food web behavior of THg and δ15N appears constant, regardless of trophic state (eutrophic vs. oligotrophic), latitude (Arctic vs. tropical) or salinity (marine vs. freshwater) of the ecosystem. Rb in both liver and muscle tissue and Zn in muscle tissue were also found to biomagnify through this food web, although at a rate that is approximately 25% of that of THg. A number of elements (Cd, Pb and Ni in muscle tissue and Cd and Li in seabird liver tissue) were found to decrease trophically through the food web, as indicated by significantly negative relationships with tissue-specific δ15N. A diverse group of metals (Ag, Ba, La, Li, Sb, Sr, U and V) were found to have higher concentrations in zooplankton than seabirds or marine mammals due to bioconcentration from seawater. The remaining metals (As, Co, Cu, Ga, Mn, Mo and Se in muscle tissue) showed no relationship with trophic position, as indicated by δ15N values, although As in liver tissue showed significant biomagnification in the seabird portion of the food web

Hydroxylated PCBs and other chlorinated phenolic compounds in lake trout (Salvelinus namaycush) blood plasma from the Great Lakes region

Recently, there has been an increase in studies focusing on an emerging class of organic contaminants, hydroxylated PCBs (OH-PCBs) and chlorinated phenolic compounds (CPCs) in the environment, particularly in northern regions of Europe and Canada. Since information for fish from the Great Lakes are scarce, we determined the blood plasma concentrations of OH-PCB congeners, pentachlorophenol (PCP), 2,3,4,5-tetrachlorophenol (TCP), and 4-hydroxyheptachlorostyrene (4-OH-HpCS) for lake trout (Savelinus namaycush) collected from two of the Great Lakes, Lake Ontario and Lake Superior, and two regional lakes, Lake Champlain and Lake Opeongo. PCP was the dominant CPC in lake trout (105-658 pg/g of plasma). Detectable concentrations of 2,3,4,5-TCP and 4-OH-HpCS were found in all lake trout (2.6-101 and 0.4-27 pg/g, respectively). Highest concentrations were found in trout from Lake Ontario and Lake Superior. Sixteen OH-PCBs were quantified, with 4-OH-CB187 having the highest concentration in all samples (10-173 pg/g of plasma). Unexpectedly, highly chlorinated OH-PCBs such as 4′-OH-CB199 (mean 21.4 and 74.4 pg/g), 4,4′-diOH-CB202 (18.3 and 27.7 pg/g), and 4′-OH-CB208 (24.5 and 34.7 pg/g) were found in lake trout from Lake Ontario and Lake Superior, respectively. Future studies to delineate the sources and impacts of CPCs in the Great Lakes catchment are needed