Terry Kolic

Identification and screening analysis of halogenated norbornene flame retardants in the Laurentian Great Lakes: Dechloranes 602, 603, and 604.

Dechlorane (Dec) 602, Dechlorane (Dec) 603, Dechlorane (Dec) 604, and Dechlorane Plus (DP) are flame retardant substitutes for mirex. Dec 602, 603, and 604 were detected in sediment and fish from the Laurentian Great Lakes. Lake Ontario surface sediments had the highest concentrations of Dec 602 and 604 at 6.0 and 4.0 ng/g dry weight, respectively. Temporal analysis of a Lake Ontario sediment core indicates that Dec 602 and 604 trends are similar to DP peaking in the early 1980s. Lake trout and whitefish from Lake Ontario also had the highest concentrations of Dec 602 and 604 at 34 and 1.2 ng/g lipid. Concentrations of Dec 602 were higher than those of DP in all fish samples, indicating that Dec 602 is likely more bioavailable and/or more readily bioaccumulates than DP. Spatial trends for Dec 602 and 604 in sediment and fish indicate that manufacturing plants along the Niagara River upstream of Lake Ontario were important sources of Dec 602 and 604 to the Great Lakes, while Dec 603 in the Great Lakes is likely from atmospheric deposition. The findings of this first report of Dec 602, 603, and 604 in the Laurentian Great Lakes basin suggests further investigation of halogenated norbornene flame retardants in the environment is merited.

Historic trends of dechloranes 602, 603, 604, dechlorane plus and other norbornene derivatives and their bioaccumulation potential in lake ontario.

Temporal trends and seasonal variation of Dechloranes (Dec) 602, 603, 604, and Chlordene Plus (CP) in Niagara River suspended sediment, a Lake Ontario sediment core, and Lake Ontario lake trout were investigated, with Mirex and Dechlorane Plus (DP) included for comparison. Temporal concentration trends were generally consistent in each of the media for all compounds with the lowest concentrations observed in or after the late 1990s. In Niagara River suspended sediments, all compounds showed seasonal variation over a year with distinct profiles observed. The relative concentration patterns observed were total DP > Mirex > Dec 602 and Dec 604 > Dec 603 > CP in suspended sediments and sediment cores, whereas Mirex was highest in lake trout, followed by Dec 602 and DP. Dec 602 concentrations were 50 to 380 times greater than those of DP in lake trout, indicating Dec 602 has a greater bioaccumulation potential. The estimated biota-sediment accumulation factor (BSAF) for Dec 602 was much greater than for DP in Lake Ontario, and was greater than those calculated for PBDEs, indicating that assessment of some dechlorane compounds is merited if use is ongoing or planned.

Surficial Sediment Contamination in Lakes Erie and Ontario: A Comparative Analysis

Abstract Sediment surveys were conducted in Lakes Erie and Ontario to characterize spatial trends in contamination, to assist in elucidation of possible sources of contamination, and for identification of areas where contamination exceeded Canadian sediment quality guidelines for protection of aquatic biota. Sediment levels of metals including nickel, lead, zinc, chromium, and copper were compared to pre-colonial concentrations, and sediment enrichment factors, defined as the ratio of surficial concentrations to background concentrations determined from benthos cores, were calculated. Sediments in Lake Ontario exhibited elevated contamination compared to Lake Erie. The average enrichment factor for Lake Ontario (2.6) was comparable to the western basin in Lake Erie but greater than those for the central (1.3) and eastern (1.0) basins. There was a gradient toward decreasing sediment contamination from the western basin to the eastern basin of Lake Erie, and from the southern to the northern area of the central basin. Sediment contamination in Lake Ontario was similarly distributed across the three major depositional basins. The spatial distribution of metals was similar to those of other contaminants including mercury, polychlorinated biphenyls (PCBs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs). Lake-wide averages of sediment mercury, PCBs and PCDDs/PCDFs in Lake Erie were 0.185 μg/g, 96.5 ng/g, and 18.8 pg/g TEQs, respectively. Lake-wide averages of sediment mercury, PCBs and PCDDs/PCDFs in Lake Ontario were 0.586 μg/g, 100 ng/g, and 101 pg/g TEQs, respectively.

Liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry for analysis of 36 halogenated flame retardants in fish.

A comprehensive, sensitive and high-throughput liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry (LC-APPI-MS/MS) method has been developed for analysis of 36 halogenated flame retardants (HFRs). Under the optimized LC conditions, all of the HFRs eluted from the LC column within 14min, while maintaining good chromatographic separation for the isomers. Introduction of the pre-heated dopant to the APPI source decreased the background noise fivefold, which enhanced sensitivity. An empirical equation was proposed to describe the relation between the ion intensity and dopant flow. The excellent on-column instrument detection limits averaged 4.7pg, which was similar to the sensitivity offered by gas chromatography-high-resolution mass spectrometry (GC-HRMS). This method was used to analyze a series of fish samples. Good agreement was found between the results for PBDEs from LC-APPI-MS/MS and GC-HRMS.

Dechloranes 602, 603, 604, Dechlorane Plus, and Chlordene Plus, a newly detected analogue, in tributary sediments of the Laurentian Great Lakes.

A chlorinated compound (Chlordene Plus, CP), structurally related to Dechloranes (Dec) 602, 603, 604, and Dechlorane Plus (DP), was identified, and concentrations and spatial trends of Dec 602, 603, 604, CP, and DP in tributary sediments of the Laurentian Great Lakes are reported. The dechloranes were widely detected with their concentrations varying considerably across the Great Lakes basin. Spatial trends of Dec 602, 604, and DP in Canadian tributary sediments were similar to that of BDE 209, which suggested these flame retardant chemicals in tributaries were associated with industrial and urban areas. The highest concentrations of Dec 602, 604, and DP observed in tributaries of the Niagara River confirmed that past or ongoing manufacturing of these compounds at plants along the river were important sources to Lake Ontario. Dec 603 was detected in technical products of aldrin and dieldrin, and its spatial trend was consistent with historic pesticide usage. Similarly, CP was detected in technical products of chlordene and chlordane, and it was found in higher concentrations in sediments near urban areas, possibly related to past chlordane use in home termite control.

Temporal trends and spatial distribution of dioxins and furans in lake trout or lake whitefish from the Canadian Great Lakes.

Concentrations of the seventeen 2,3,7,8-substituted, most toxic congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were measured in lake trout (Salvelinus namaycush) or lake whitefish (Coregonus clupeaformis) collected between 1989 and 2003 from the Canadian Great Lakes as a part of the on-going Sport Fish Contaminant Monitoring Program of the Ontario Ministry of the Environment. These monitoring data were used to assess temporal trends and spatial variations of these compounds in the Canadian Great Lakes. Toxic equivalents (TEQs) were calculated using the measured congener concentrations and toxicity equivalency factors (TEFs) published by the World Health Organization in 1998. Five congeners, namely 2,3,7,8-TCDD, 2,3,7,8-TCDF, 1,2,3,7,8-PeCDD, 1,2,3,7,8-PeCDF, and 2,3,4,7,8-PeCDF, were the most dominant congeners among the 17 congeners analyzed. The highest TEQs were found for Lake Ontario lake trout (22-54 pg g(-1)) while the TEQs for the other Canadian Great Lakes were 60-95% lower. Non-parametric Mann-Kendall and Sens tests performed on TEQs and PCDD/Fs standardized at a mean lake trout length of 60 cm suggest a linearly decreasing trend for PCDD/Fs in lake trout from Lakes Ontario and Huron. There was no monotonously increasing or decreasing trend found for Lake Superior lake trout. The ratios of 2,3,7,8-TCDD to 2,3,7,8-TCDF concentrations were generally constant during the 1989-2003 period with the values being in the order of Lakes Superior (0.05-0.3) <or= Huron (0.16-0.25)<<Ontario (0.56-0.88). These spatial differences observed in the relative abundance of TCDD and TCDF suggest that the sources of dioxins and furans differ between the upper and lower Great Lakes.

Persistent organic pollutants in Detroit River suspended sediments: polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like polychlorinated biphenyls and polychlorinated naphthalenes

Suspended sediments from the Detroit River were collected in 1999 and 2000 using sediment traps at sites ranging from western Lake Erie to southern Lake St. Clair and analyzed to determine the spatial distributions of contaminants including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), dioxin-like PCBs (DLPCBs) and polychlorinated naphthalenes (PCNs). Concentrations of all three contaminant classes were clearly elevated at sites in the lower reaches of the river in the Trenton Channel. The potential influence of the Trenton Channel as a source of contamination to western Lake Erie was further evidenced by PCDD/PCDF homologue profiles, which indicated a contribution from chemical manufacturing in addition to the normal background combustion profile. Toxic equivalents (TEQs) for PCDDs/PCDFs generally exceeded those for DLPCBs; combined total TEQs in July 2000 for these two compound classes ranged from 2.30 pg/g in southern Lake St. Clair to 306 pg/g at a station just downstream of the outflow of Monguagon Creek in the Trenton Channel. The spatial distribution of PCN contamination was similar to that of PCDDs/PCDFs and DLPCBs, with the highest level of total PCNs (8200 ng/g) detected at a site in the Trenton Channel near Elizabeth Park; TEQs for PCNs in the Trenton Channel ranged from 73 to 3300 pg/g. The data indicate that PCNs represent a significant contribution to dioxin-like biological activity in Detroit River suspended sediments.

Occurrence and sources of polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in surficial sediments of Lakes Superior and Huron.

Concentrations and congener profile patterns of 2378-substituted PCDD/Fs and DLPCBs in offshore, nearshore and tributary sediments of Lakes Superior and Huron are reported, and spatial trends and source contributions assessed. PCDD/F concentrations ranged from 5 to 18,000 pg/g dw (Lake Superior) and 3 to 6100 pg/g dw (Lake Huron); DLPCBs ranged from 9 to 11,000 pg/g dw (Lake Superior) and 9 to 27,000 pg/g dw (Lake Huron). Our analysis indicated atmospheric deposition is a primary source to depositional areas of both lakes; however, greater PCDD/F and DLPCB concentrations were observed at several nearshore and tributary sites, and were attributed to corresponding land use in the watershed. Statistical analysis and pattern comparison suggested that industrial inputs mainly associated with wood treatment plants, pulp and paper mills, mining operations, and chlorine-based chemical manufacturing also contributed to contamination by PCDD/Fs and DLPCBs in certain nearshore and offshore areas of Lakes Superior and Huron.

Patterns and sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in surficial sediments of Lakes Erie and Ontario

This study determines spatial trends and congener patterns of 2378-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surficial sediments of Lakes Erie and Ontario. Sediments are enriched in 2378-PCDFs in Lake Ontario, and the PCDD/F concentrations increased from shallow near-shore sediments towards deep-water depositional zone sediments. In Lake Erie, sediments were dominated by octachlorodibenzo-p-dioxin, and the highest PCDD/F concentrations were observed in the western basin and the southern shoreline of the central basin with a decrease towards the eastern basin and the northern shoreline of the central basin. Principal components analysis revealed that chemical manufacture and disposal of chemical waste along the Niagara River has been a major PCDD/F source to Lake Ontario; while PCDD/Fs in Lake Erie are from multiple sources including industrial sources along the Detroit River, major tributaries along the southern shoreline of the lake, and atmospherically-derived material from the upper lakes and connecting channels.

Potential of groundwater contamination by polybrominated diphenyl ethers (PBDEs) in a sensitive bedrock aquifer (Canada)

It is necessary to understand the presence, movement, and persistence of contaminants in aquifers to develop adequate groundwater protection plans. Fractured bedrock aquifers with thin overburden cover are very sensitive to contamination, and little is known about transport processes from the ground surface to depth in this setting. This study was undertaken to investigate the potential of groundwater contamination by polybrominated diphenyl ethers (PBDEs), which are flame retardants, in a natural fractured bedrock aquifer in Canada proven to be sensitive to contamination. PBDEs, which had not been previously measured in groundwater in detail, were detected in the study aquifer at concentrations greater than those observed in surface-water bodies. Potential sources include manure, septic tanks, and the atmosphere. From this scoping study, it is evident that additional surveys of PBDE concentrations in groundwater are warranted, especially in settings with high potential source concentrations coupled with sensitive aquifers.RésuméIl est nécessaire de comprendre la présence, les mouvements et la persistance des polluants dans les aquifères afin de développer des plans de protection adaptés à la protection des eaux souterraines. Les aquifères d’un socle fracturé recouvert d’une couverture peu épaisse sont très sensibles à la pollution et on sait peu sur les processus de transfert de la surface du sol vers la profondeur dans cette configuration. On a entrepris cette étude pour reconnaître le degré de pollution par des polybromodiphényl éthers (PBDE) retardateurs de flamme d’un aquifère du socle fracturé naturellement reconnu comme vulnérable à la pollution au Canada. Les PBDE, qui n’avaient pas été précédemment dosés de façon précise dans la nappe, ont été détectés dans l’aquifère objet de l’étude à des concentrations supérieures à celles observées dans les eaux de surface. Les sources potentielles incluent les engrais, les fosses septiques et l’atmosphère. Suivant cette étude cadre, il est évident que des campagnes complémentaires de mesure des concentrations de PBDE dans l’eau souterraine sont justifiées, particulièrement dans des configurations où de hautes concentrations de sources potentielles sont couplées avec des aquifères vulnérables.ResumenEs necesario entender la presencia, movimiento y persistencia de los contaminantes en los acuíferos para desarrollar planes de protección adecuados de las aguas subterráneas. Los acuíferos en rocas de basamento fracturado con una delgada cubierta son muy sensibles a la contaminación, y poco es conocido acerca de los procesos de transporte desde la superficie del terreno a la profundidad en esta configuración. Este estudio se llevó a cabo para investigar el potencial de la contaminación de agua subterránea por polibromodifeniléteres (PBDEs), que son retardantes del fuego, en un acuífero de basamento fracturado natural en Canadá que se conoce como sensible a la contaminación. Los PBDEs, que no habían sido previamente medidos detalladamente en el agua subterránea, fueron detectados en el estudio del acuífero en concentraciones mayores que aquellas observadas en los cuerpos de agua superficial. Las fuentes potenciales incluyen estiércol, tanques sépticos, y la atmósfera. A partir este estudio observacional, es evidente que mediciones adicionales de concentraciones de PBDE en aguas subterráneas están justificadas, especialmente en configuraciones con fuentes potenciales de altas concentraciones acopladas con acuíferos sensibles.摘要为发展适宜的地下水保护计划, 理解含水层中污染物的存在、运移及持久性是必要的。具有薄层表土层的裂隙基岩含水层对污染及其敏感, 但对此背景下从地表面到深部的运移过程了解较少。本文利用多溴二苯醚 (PBDEs)调查地下水污染的可能性, PBDEs是一种阻燃剂, 在加拿大天然裂隙基岩含水层中被证明对污染物是敏感的。PBDEs在之前的地下水中没有具体的监测过, 在研究区含水层中观测到的浓度大于在地表水体中观测到的。可能的污染源包括粪肥、化粪池以及大气。从本次范围界定研究中明白对于地下水中PBDE浓度的额外调查是有保证的, 尤其是在高可能污染源浓度以及敏感含水层背景下。ResumoÉ necessário perceber a presença, o movimento e a persistência de contaminantes em aquíferos de forma a desenvolver planos adequados de proteção das águas subterrâneas. Aquíferos fraturados com uma pequena espessura de recobrimento são muito sensíveis à contaminação e neste cenário pouco se sabe sobre os processos de transporte a partir da superfície até ao meio subterrâneo. Este estudo foi realizado para investigar o potencial de contaminação das águas subterrâneas por difenil éteres polibromados (PBDEs), que são retardantes de chama, num aquífero fraturado no Canadá o qual provou ser sensível à contaminação. PBDEs, que não tinham previamente sido medidos com detalhe nas águas subterrâneas, foram detetados no estudo do aquífero em concentrações superiores às observadas nas massas de água superficial. As fontes potenciais incluem o estrume, fossas séticas, e a atmosfera. Com base no âmbito deste estudo, é evidente que estão justificadas pesquisas adicionais das concentrações de PBDEs nas águas subterrâneas, especialmente em ambientes com fontes potenciais com altas concentrações associadas aquíferos sensíveis.