Naphthenic acid fraction compounds reduce the reproductive success of wood frogs (Rana sylvatica) by affecting offspring viability.

Understanding the toxicity of organic compounds in oil sands process-affected water (OSPW) is necessary to inform the development of environmental guidelines related to wastewater management in Canada's oil sands region. In the present study, we investigated the effects of naphthenic acid fraction compounds (NAFCs), one of the most toxic components of OSPW, on mating behaviour, fertility, and offspring viability in the wood frog (Rana sylvatica). Wild adult wood frogs were exposed separately from the opposite sex to 0, 5, or 10 mg/L of OSPW-derived NAFCs for 24 h and then combined in outdoor lake water mesocosms containing the same NAFC concentrations (n = 2 males and 1 female per mesocosm, n = 3 mesocosms per treatment). Mating events were recorded for 48 h and egg masses were measured to determine adult fertility. NAFC exposure had no significant effect on mating behaviour (probability of amplexus and oviposition, amplexus and oviposition latency, total duration of amplexus and number of amplectic events) or fertility (fertilization success and clutch size). Tadpoles (50 individuals per mesocosm at hatching, and 15 individuals per mesocosm from 42 d post-hatch) were reared in the same mesocosms under chronic NAFC exposure until metamorphic climax (61-85 d after hatching). Offspring exposed to 10 mg/L NAFCs during development were less likely to survive and complete metamorphosis, grew at a reduced rate, and displayed more frequent morphological abnormalities. These abnormalities included limb anomalies at metamorphosis, described for the first time after NAFC exposure. The results of this study suggest that NAFCs reduce wood frog reproductive success through declines in offspring viability and therefore raise the concern that exposure to NAFCs during reproduction and development may affect the recruitment of native amphibian populations in the oil sands region.

A preparative method for the isolation and fractionation of dissolved organic acids from bitumen-influenced waters.

The surface mining of oil sands north of Fort McMurray, Alberta produces considerable tailings waste that is stored in large tailings ponds on industrial lease sites. Viable strategies for the detoxification of oil sands process affected water (OSPW) are under investigation. In order to assess the toxic potential of the suite of dissolved organics in OSPW, a method for their extraction and fractionation was developed using solid phase extraction. The method successfully isolated organic compounds from 180 L of an aged OSPW source. Using acidic- or alkaline-conditioned non-polar ENV+ resin and soxhlet extraction with ethyl acetate and methanol, three fractions (F1-F3) were generated. Chemical characterization of the generated fractions included infusion to electrospray ionization ultrahigh-resolution mass spectrometry (ESI-UHRMS), liquid chromatography quadrupole time-of-flight mass spectrometry, gas chromatography triple quadrupole time-of-flight mass spectrometry, and synchronous fluorescence spectroscopy (SFS). Additionally, ESI-UHRMS class distribution data and SFS identified an increased degree of oxygenation and aromaticity, associated with increased polarity. Method validation, which included method and matrix spikes with surrogate and labelled organic mono carboxylic acid standards, confirmed separation according to acidity and polarity with generally good recoveries (average 76%). Because this method is capable of extracting large sample volumes, it is amenable to thorough chemical characterization and toxicological assessments with a suite of bioassays. As such, this protocol will facilitate effects-directed analysis of toxic components within bitumen-influenced waters from a variety of sources.

Neonicotinoid insecticide mixtures: Evaluation of laboratory-based toxicity predictions under semi-controlled field conditions.

Neonicotinoid insecticide mixtures are frequently detected in aquatic environments in agricultural regions. Recent laboratory studies have indicated that neonicotinoid mixtures can elicit greater-than-additive toxicity in sensitive aquatic insects (e.g. Chironomus dilutus). However, this has yet to be validated under field conditions. In this study, we compared the chronic (28- and 56-day) toxicity of three neonicotinoids (imidacloprid, clothianidin, and thiamethoxam) and their mixtures to natural aquatic insect communities. Using experimental in-situ enclosures (limnocorrals), we exposed wetland insects to single-compounds and binary mixtures at equitoxic concentrations (1 toxic unit under the principle of Concentration Addition). We assessed the composition of all emerged insect taxa and the cumulative Chironomidae emergence and biomass over time. In treated limnocorrals, there were subtle shifts in community composition, with greater mean proportions of emergent Trichoptera and Odonata. Cumulative emergence and biomass increased over time and there was a significant interaction between time and treatment. At 28 days, cumulative Chironomidae emergence and biomass were not significantly different between neonicotinoid treatments and controls. However, cumulative emergence in the imidacloprid, clothianidin, and clothianidin-thiamethoxam treatments were 42%, 20%, and 44% lower than predicted from applied doses. At 56 days, effects on cumulative emergence and biomass were significant for imidacloprid, clothianidin, and the clothianidin-thiamethoxam mixture. Contrary to laboratory predictions, mixtures were not more toxic than single compounds under semi-controlled field settings. Furthermore, only clothianidin significantly shifted sex-ratios towards female-dominated populations. Results showed that the responses of natural Chironomidae populations to neonicotinoids and their mixtures cannot be adequately predicted from laboratory-derived single-species models, and although occasional overdosing may have influenced the magnitude of effects, reductions in Chironomidae emergence and biomass can occur at average neonicotinoid concentrations below some current water quality guidelines. Therefore, neonicotinoid guidelines should be revised to ensure that Chironomidae and other sensitive aquatic insects inhabiting agricultural wetlands are adequately protected.

Can chronic exposure to imidacloprid, clothianidin, and thiamethoxam mixtures exert greater than additive toxicity in Chironomus dilutus?

Widespread agricultural use of neonicotinoid insecticides has resulted in frequent detection of mixtures of these compounds in global surface waters. Recent evidence suggests that neonicotinoid mixtures can elicit synergistic toxicity in aquatic insects under acute exposure conditions, however this has not been validated for longer exposures more commonly encountered in the environment. Therefore, we aimed to characterize the chronic (28-day) toxicity of imidacloprid, clothianidin, and thiamethoxam mixtures under different doses and mixture ratios to determine if the assumption of synergistic toxicity would hold under more environmentally realistic exposure settings. The sensitive aquatic insect Chironomus dilutus was used as a representative test species, and successful emergence was used as a chronic endpoint. Applying the MIXTOX modeling approach, predictive parametric models were fitted using single-compound toxicity data and statistically compared to observed toxicity in subsequent mixture tests. Imidacloprid-clothianidin, clothianidin-thiamethoxam and imidacloprid-clothianidin-thiamethoxam mixtures did not significantly deviate from concentration-additive toxicity. However, the cumulative toxicity of the imidacloprid-thiamethoxam mixture deviated from the concentration-additive reference model, displaying dose-ratio dependent synergism and resulting in up to a 10% greater reduction in emergence from that predicted by concentration addition. Furthermore, exposure to select neonicotinoid mixtures above 1.0 toxic unit tended to shift sex-ratios toward more male-dominated populations. Results indicate that, similar to acute exposures, the general assumption of joint additivity cannot adequately describe chronic cumulative toxicity of all neonicotinoid mixtures. Indeed, our observations of weak synergism and sex-ratio shifts elicited by some mixture combinations should be considered in water quality guideline development and environmental risk assessment practices for neonicotinoid insecticides, and explored in further investigations of the effects of neonicotinoid mixtures on aquatic communities.

Meltwater from snow contaminated by oil sands emissions is toxic to larval fish, but not spring river water.

To assess the toxicity of winter-time atmospheric deposition in the oil sands mining area of Northern Alberta, embryo-larval fathead minnow (Pimephales promelas) were exposed to snowmelt samples. Snow was collected in 2011-2014 near (<7km) oil sands open pit mining operations in the Athabasca River watershed and at sites far from (>25km) oil sands mining. Snow was shipped frozen back to the laboratory, melted, and amended with essential ions prior to testing. Fertilized fathead minnow eggs were exposed (<24h post-fertilization to 7-16days post-hatch) to a range of 25%-100% snowmelt. Snow samples far from (25-277km away) surface mining operations and upgrading facilities did not affect larval fathead minnow survival at 100%. Snow samples from sites near surface mining and refining activities (<7km) showed reduced larval minnow survival. There was some variability in the potencies of snow year-to-year from 2011 to 2014, and there were increases in deformities in minnows exposed to snow from 1 site on the Steepbank River. Although exposure to snowmelt from sites near oil sands surface mining operations caused effects in larval fish, spring melt water from these same sites in late March-May of 2010, 2013 and 2014 showed no effects on larval survival when tested at 100%. Snow was analyzed for metals, total naphthenic acid concentrations, parent PAHs and alkylated PAHs. Naphthenic acid concentrations in snow were below those known to affect fish larvae. Concentrations of metals in ion-amended snow were below published water quality guideline concentrations. Compared to other sites, the snowmelt samples collected close to mining and upgrading activities had higher concentrations of PAHs and alkylated PAHs associated with airborne deposition of fugitive dusts from mining and coke piles, and in aerosols and particles from stack emissions. CAPSULE: Snow collected close to oil sands surface mining sites is toxic to larval fathead minnows in the lab; however spring melt water samples from the same sites do not reduce larval fish survival.

The effect of oil sands tailings pond sediments on embryo-larval walleye (Sander vitreus).

Walleye (Sander vitreus) are a commercially important North American fish species that inhabit the Athabasca River. This river flows through the Athabasca oil sands where natural sources of bitumen erode from the McMurray formation. Little information is available on responses of walleye embryos to oil sands tailings pond sediments in a laboratory setting. The current study describes the design and implementation of a daily-renewal bioassay to assess the potential effects of tailings pond sediments from the Athabasca oil sands area on walleye development. Developing walleye embryos were exposed to increasing concentrations of two tailings pond sediments (collected in the Athabasca oil sands area) until the completion of yolk absorption in control fish. Sediments from the tailings pond represent a mixture of polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs. During the 31 day exposure, the walleye were examined for mortalities, weight, length and developmental abnormalities to provide an initial evaluation of the effects of the oil sands tailings pond sediments. Walleye embryo survival differed between the tailings pond sediments, and survival decreased with increasing sediment concentration. Alkylated PAH content differed between the two tailings pond sediments and lower embryo survival corresponded to higher total and alkylated PAH content. Tailings pond sediment-exposed walleye exhibited a delay in development, as well as increased percentages of larvae with heart and yolk sac edema, and cranial and spinal malformations. These abnormalities in development are often associated with PAH and alkylated PAH exposure. This study provides an exposure design that can be used to assess sediment toxicity to early developmental stages of a fish species not commonly tested in the lab, and lays the groundwork for future studies with this and other difficult-to-culture species. These results offer information on the potential effects of tailings pond sediments containing PAH/alkylated PAH mixtures on walleye development and survival.

Chemical fingerprinting of naphthenic acids and oil sands process waters-A review of analytical methods for environmental samples.

This article provides a review of the routine methods currently utilized for total naphthenic acid analyses. There is a growing need to develop chemical methods that can selectively distinguish compounds found within industrially derived oil sands process affected waters (OSPW) from those derived from the natural weathering of oil sands deposits. Attention is thus given to the characterization of other OSPW components such as oil sands polar organic compounds, PAHs, and heavy metals along with characterization of chemical additives such as polyacrylamide polymers and trace levels of boron species. Environmental samples discussed cover the following matrices: OSPW containments, on-lease interceptor well systems, on- and off-lease groundwater, and river and lake surface waters. There are diverse ranges of methods available for analyses of total naphthenic acids. However, there is a need for inter-laboratory studies to compare their accuracy and precision for routine analyses. Recent advances in high- and medium-resolution mass spectrometry, concomitant with comprehensive mass spectrometry techniques following multi-dimensional chromatography or ion-mobility separations, have allowed for the speciation of monocarboxylic naphthenic acids along with a wide range of other species including humics. The distributions of oil sands polar organic compounds, particularly the sulphur containing species (i.e., OxS and OxS2) may allow for distinguishing sources of OSPW. The ratios of oxygen- (i.e., Ox) and nitrogen-containing species (i.e., NOx, and N2Ox) are useful for differentiating organic components derived from OSPW from natural components found within receiving waters. Synchronous fluorescence spectroscopy also provides a powerful screening technique capable of quickly detecting the presence of aromatic organic acids contained within oil sands naphthenic acid mixtures. Synchronous fluorescence spectroscopy provides diagnostic profiles for OSPW and potentially impacted groundwater that can be compared against reference groundwater and surface water samples. Novel applications of X-ray absorption near edge spectroscopy (XANES) are emerging for speciation of sulphur-containing species (both organic and inorganic components) as well as industrially derived boron-containing species. There is strong potential for an environmental forensics application of XANES for chemical fingerprinting of weathered sulphur-containing species and industrial additives in OSPW.

Preliminary fingerprinting of Athabasca oil sands polar organics in environmental samples using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

There is a growing need to develop analytical methods that can distinguish compounds found within industrially derived oil sands process water (OSPW) from those derived from natural weathering of oil sands deposits. This is a difficult challenge as possible leakage beyond tailings pond containments will probably be in the form of mixtures of water-soluble organics that may be similar to those leaching naturally into aquatic environments. We have evaluated the potential of negative ion electrospray ionization high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) for comparing oil sands polar organics from tailing ponds, interceptor wells, groundwater, river and lake surface waters. Principal component analysis was performed for all species observed. which included the O(2) class (often assumed to be monocarbxoylic naphthenic acids) along with a wide range of other species including humic substances in the river and lake samples: O(n) where n=1-16; NO(n) and N(2)O(n) where n=1-13; and O(n)S and O(n)S(2) where n=1-10 and 1-8, respectively. A broad range of species was investigated because classical naphthenic acids can be a small fraction of the 'organics' detected in the polar fraction of OSPW, river water and groundwater. Aquatic toxicity and environmental chemistry are attributed to the total organics (not only the classical naphthenic acids). The distributions of the oil sands polar organics, particularly the sulfur-containing species, O(n)S and O(n)S(2), may have potential for distinguishing sources of OSPW. The ratios of species containing O(n) along with nitrogen-containing species: NO(n), and N(2)O(n), were useful for differentiating organic components derived from OSPW from those found in river and lake waters. Further application of the FTICRMS technique for a diverse range of OSPW of varying ages and composition, as well as the surrounding groundwater wells, may be critical in assessing whether leakage from industrial sources to natural waters is occurring.

Assessment of metals in bed and suspended sediments in tributaries of the Lower Athabasca River.

Several oil sands mines and refineries are currently recovering oil from the Athabasca River region near Fort McMurray, Alberta. Planning and construction of additional oil sands mines are in various stages of completion. Due to environmental concerns for aquatic life in areas downstream from current and future oil sands activities, surveys were conducted between 1998 and 2000 to determine whether the quality of water and sediments in tributaries of the Athabasca River are affected by flowing through reaches with exposure to natural oil sand deposits. This paper presents the results for metals in bed and suspended sediments collected from the Mackay, Steepbank, and Ells rivers during those surveys. The suspended sediments had a clay content (n = 7) ranging from 36.2% to 65.0%, while bed sediments, which consisted of a predominant sand fraction, had percent clay (n = 39) ranging from 0.0% to 38.1%. A Mann-Kendall non-parametric analysis to assess the longitudinal trend of the metals in the bed sediments found no significant (alpha = 0.05) downstream trend in the Mackay or Steepbank rivers; however, the Ells River displayed a generally decreasing tend from upstream to downstream. The results provide no indication that metal concentrations in the bed sediments and/or suspended sediments of the Mackay, Steepbank, and Ells rivers increase significantly as the three tributaries flow through reaches that have natural oil sand exposures (McMurray Formation).

Persistence of the sulfonylurea herbicides thifensulfuron-methyl, ethametsulfuron-methyl, and metsulfuron-methyl in farm dugouts (ponds).

Sulfonylurea herbicides are applied at relatively low rates (3 to 40 g ha(-1)) to control weeds in a variety of crops across the Canadian prairies. Because of their high phytotoxicity and the likelihood of their transport in surface runoff, there is concern about their possible impact to aquatic ecosystems. Little is known, however, about their persistence and behavior in aquatic ecosystems. To assess persistence in aquatic ecosystems, three prairie farm dugouts (ponds) were fortified with either thifensulfuron-methyl {methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate}, ethametsulfuron-methyl {methyl 2-[[[[[4-ethoxy-6-(methylamino)-1,3,5-triazin-2-yl]amino]carbonyl]amino]sulfonyl]benzoate} or metsulfuron-methyl {methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazinyl)amino]carbonyl]amino]sulfonyl]benzoate}. The decreasing order of persistence of environmentally relevant concentrations (1 to 4.6 microg L(-1)) of these herbicides in dugout water over the June to October period was metsulfuron-methyl>ethametsulfuron-methyl>thifensulfuron-methyl. The corresponding dissipation half-lives (DT(50)) of 84, 30, and 16 d, respectively, are in the same relative order as the recropping intervals for these herbicides. Thifensulfuron-methyl showed a biphasic dissipation with slower dissipation during the winter months. In contrast, the dissipation of metsulfuron-methyl, the sulfonylurea herbicide with the longest DT(50), was somewhat enhanced under winter conditions. One of the major routes of sulfonylurea herbicide dissipation was removal from the water column when dugout water was lost during hydrological discharge. The relatively long persistence of these herbicides in water indicates that partitioning into sediments was minimal, the sulfonylurea and methyl ester linkages in these compounds were resistant to hydrolysis in weakly alkaline waters, and that microbial and photolytic degradation in dugout waters were slow.

Quality of "sachet" waters in the Cape Coast municipality of Ghana.

To determine the quality of sachet water samples in the Cape Coast municipality of Ghana, random sampling procedures were used to collect 180 samples from 29 brands produced in the municipality from 1999 to 2004. For any particular year, each tested brand was sampled three times at intervals of not less than 2 weeks (usually monthly) between the months of March to June. Forty-five percent (45%) of the brands subjected to bacteriological examination contained coliform bacteria for one sampling period or another during the period of investigation. The coliform contamination seemed to be more prevalent with some particular brands. Three out of seven brands examined in 2004 also recorded the presence of E. coli. Exceedances were recorded for WHO drinking water quality guidelines for pH (6.25-7.93) in 2002 and for conductivity (67-306 microS cm(-1)) in 2002 and 2004. Total hardness values for all sachet water brands were less than 100 mg/l CaCO(3) and therefore below the WHO limit for potable water. None of the samples seems to pose any health dangers as far as the major cations; sodium (17.4-19.1 mg/l), potassium (5.7-6.2 mg/l), calcium (8.0-24.0 mg/l) and magnesium (19.9-50 mg/l) are concern. Apart from nitrite, for which some exceedances were recorded and phosphate which does not have an established WHO guideline, the measured major anions (i.e., chloride: 1.57-37.7 mg/l, sulfate: 0.33-44.33 mg/l and nitrates: 0.005-0.70 mg/l) were within the WHO drinking water guideline. No exceedances were also recorded for iron and lead. In general, the high quality claimed for sachet waters could not be confirmed based on the measured physico-chemical and bacteriological properties. The variable quality and in some cases, poor water quality observed, likely reflects the fact that the sachets are not always bagged under scrutinized sanitary conditions.

Is biodegradation of bitumen a source of recalcitrant naphthenic acid mixtures in oil sands tailing pond waters?

Carboxylic acids are transient metabolites during the mineralization of petroleum hydrocarbons. Crude oils, however, vary in their proportion of the hydrocarbon components. Depending on structure, some carboxylic acid metabolites resist further biodegradation and persist in aquatic systems. During the extraction of oil sands bitumen, recalcitrant carboxylic acid mixtures, collectively referred to as naphthenic acids (NAs), are released into the wastewaters. These waters also contain unrecovered bitumen from the oil sands. The unextracted bitumen is often overlooked as a possible source of the petroleum acids. The present article discusses the literature data on the biotransformation of hydrocarbons in bitumen from oil sands to the corresponding petroleum carboxylic acids. Some insight is given on the mechanism of the biodegradation process. The susceptibility to biodegradation is affected by differences in alicyclic carboxylic acids such as carbon chain length, chain branching, and the oddness or evenness of carbon chain containing the carboxylic group, positions where alkyl groups are substituted on the cyclic ring, geometrical isomerism, and number of cyclic rings.

In situ bioremediation of naphthenic acids contaminated tailing pond waters in the athabasca oil sands region--demonstrated field studies and plausible options: a review.

Currently, there are three industrial plants that recover oil from the lower Athabasca oil sands area, and there are plans in the future for several additional mines. The extraction procedures produce large volumes of slurry wastes contaminated with naphthenic acids (NAs). Because of a "zero discharge" policy the oil sands companies do not release any extraction wastes from their leases. The process-affected waters and fluid tailings contaminated with NAs are contained on-site primarily in large settling ponds. These fluid wastes from the tailing ponds can be acutely and chronically toxic to aquatic organisms, and NAs have been associated with this toxicity. The huge tailings containment area must ultimately be reclaimed, and this is of major concern to the oil sands industry. Some reclamation options have been investigated by both pioneering industries (Syncrude Energy Inc. and Suncor Inc.) with mixed results. The bioremediation techniques have limited success to date in biodegrading NAs to levels below 19 mg/L. Some tailing pond waters have been stored for more than 10 years, and it appears that the remaining high molecular weight NAs are refractory to the natural biodegradation process in the ponds. Some plausible options to further degrade the NAs in the tailings pond water include: bioaugmentation with bacteria selected to degrade the more refractory classes of NAs; the use of attachment materials such as clays to concentrate both the NA and the NA-degrading bacteria in their surfaces and/or pores; synergistic association between algae and bacteria consortia to promote efficient aerobic degradation; and biostimulation with nutrients to promote the growth and activity of the microorganisms.

The characterization and distribution of inorganic chemicals in tributary waters of the lower Athabasca river, Oilsands region, Canada.

At present, there are two large industrial plants recovering oil from the lower Athabasca oil sands area and there are plans for several more mines in the area. There are environmental concerns for aquatic life in areas downstream of current and future oil sands activities. To assess and predict potential impacts of industrial activities, it is important to separate impacts from those produced by naturally occurring oil sands deposit. Studies were therefore conducted to determine whether the water quality of tributaries to the Athabasca River, which have not been impacted by anthropogenic activities, is affected by inorganic constituents resulting from flowing through reaches with natural oilsands deposit. Three tributaries, Steepbank River, Mackay River, and Ells River at upstream and downstream locations on each stream were investigated during four surveys from 1998 to 2000. In addition to some physical parameters such as pH, conductance and hardness and the major ions (calcium, magnesium, sodium, potassium, bicarbonate, chloride, sulfate, and silicates), seventeen trace metals were investigated. Some of these metals, especially iron and manganese, were of high concentrations and in some instances, particularly in a survey conducted during the spring freshets in April 1999, exceeded guidelines for the protection of aquatic life. The observed concentrations of metals seem to be of natural origin and can be used as base-line data for future assessment of anthropogenic activities in the oil sand region.

Abatement of gas-condensate hydrocarbons in a natural wetland.

Results of a five-year research study on natural attenuation processes in a wetland, located downgradient of a sour gas processing plant in central Alberta, Canada, show that natural attenuation may present a favourable remedial solution. Both free-phase and dissolved phase condensate have been discharging to the wetland since 1984. This condensate is primarily composed of C5 to C12 hydrocarbons, including BTEX compounds. The condensate enters the base of the wetland at 1 m below ground surface, resulting in contamination of the wetland peat and underlying clay till. The lateral extent of contamination in the wetland has remained stable, and apparent free product thickness and BTEX concentrations have decreased over time. Sorption, aerobic biodegradation, volatilization, and anaerobic biodegradation were identified as active attenuation processes at this site. Sorption and desorption processes were evaluated by laboratory testing of site soils using 14C-benzene. Linear sorption coefficients (Kd) for the surface and subsurface peat were similar (4.48-4.62 l/kg), while the Kd for the underlying silt was 0.096 l/kg. The significantly higher Kd values for the peat are attributed to the peat's higher organic content (40%), relative to the clayey silt (1%). No significant resistance to desorption was observed, however, indicating that benzene would remain mobile and bioavailable over time. Aerobic biodegradation and volatilization appear to be the main removal processes. They are enhanced by a seasonal drop in the water level from surface down to 1 m depth, resulting in an aerobic unsaturated zone. Respiration testing in the peat indicates a significant aerobic biodegradation rate of 27 mg/kg/day, equating to an estimated hydrocarbon removal rate of 5 kg/day across the 3600 m2 plume area. Surface vapour measurements indicate hydrocarbon volatilization is occurring at a rate of 3 x 10(-4) kg/m2/day, equating to a mass removal of 1 kg/day across the plume. Anaerobic biodegradation is occurring primarily in the clayey silt, based on geochemical indicator parameters, microbial analyses, and soil vapour sampling. Overall, natural attenuation appears to be a feasible remedial solution for this wetland, by providing continued removal and degradation of condensate components before they reach the downgradient surface water receptor.

Sorption and metabolism of selected herbicides in river biofilm communities.

In the present study, biofilms were grown in rotating annular bioreactors with river water as inoculum and sole source of nutrients. The herbicides atrazine and diclofop methyl were applied to the bioreactors, while an identical reactor acted as a control. Biofilm structure was visualized using specific fluorescent probes in conjunction with confocal laser scanning microscopy. The concentration of both herbicides in the bulk water phase followed the pattern of application. Atrazine and metabolites were detected in biofilm samples using direct insertion probe tandem mass spectrometry (DIP-MS/MS) and only trace levels were detected after the addition phase. Monoclonal antibody (MAb) studies indicated that sorption of atrazine was associated with a unique microcolony type. In contrast, diclofop and metabolites reached a maximum level in the biofilm at the end of the addition phase and persisted in the biofilm. Experiments with 14C-labeled atrazine and diclofop methyl indicated that mineralization of these compounds to CO2 (<1%) occurred in the river biofilms. Thus, both herbicides were sorbed and metabolized by the river biofilm community and detected in biofilms when they were not detected in the bulk water phase. These results indicate that biofilms and specific community members may act as a sink for herbicides, and that this should be taken into account in terms of both sampling and studies of the environmental chemodynamics of contaminants.

Liquid chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry determination of N-methylpyrrolidinone in riverine biofilms.

A rugged procedure utilizing reversed-phase liquid chromatography with positive-ion electrospray ionization mass spectrometry (LC-MS) along with tandem MS is described for the quantification and confirmation of N-methylpyrrolidinone (NMP) in methanolic extracts of riverine biofilm. The LC-MS method provided a 100-fold improvement in detection limits (2 ng g(-1) with a repeatability of 80-95% based on triplicate analyses) compared to a conventional LC-UV detection procedure and was applicable to quantitative analysis of biofilm samples with little or no clean up. Under low-energy collision induced dissociation (CID) conditions (17 V, laboratory frame of reference, with argon as the collision gas), two product-ions of the [M+H]+ ion were formed at m/z 69 [MH-CH3NH2]+ and m/z 58 [MH-CH3NCH]+ with relative abundances of 30% and 5%, respectively. These CID transitions were used to demonstrate that biofilm uptake of a photocatalytically-generated mixture of NMP was rapid once acclimation was achieved.

Riverine fluxes of the persistent organochlorine pesticides hexachlorcyclohexane and DDT in the Russian Federation.

The contribution of gross riverine organochlorine pesticide (OCP) transport to estuaries of Russian seas and Lake Baikal was determined to help understand OCP transboundary transfer and to provide a basis for estimating Russia's contribution to global pollution by these pesticides. The official OGSNK/GSN data ranks sea/ocean/lake basins in the following order based upon the amounts of total OCPs received from agricultural use: Eastern Arctic>Western Arctic>Pacific>Baltic>Caspian>Azov/Black>Baikal. A similar ranking was obtained using an independent set of data: Eastern Arctic>Pacific>Caspian>Western Arctic>Baltic>Azov/Black. In terms of riverine flow-associated discharge of HCH isomers (i.e., sum of alpha-, beta- and gamma-HCH) estuaries of the Kara, Okhotsk and Beloye (White)/Barents seas received more pesticides than other seas. No HCH was discharged to estuaries of the Eastern Siberian and Bering seas. For DDT and its derivative (DDE), estuaries of the Kara, Caspian, Okhotsk and Baltic seas received the greatest amounts. During our study period (1988-1996), HCH transport was more prevalent in the majority of rivers reflecting both the official ban on the use of DDT in the former Soviet Union and the greater popularity of HCH as a pesticide. In general, it appears that Russian rivers play a significant role in OCP contamination of some estuaries of regional seas, especially those of the eastern Arctic basin, such as the Kara Sea.

Optimization of solid-phase microextraction for the gas chromatographic-mass spectrometric determination of synthetic musk fragrances in water samples.

Described is a solid-phase microextraction-gas chromatography-mass spectrometric procedure for the determination of three polycyclic musk fragrances (galaxolide, tonalide, celestolide) and a nitro musk fragrance (musk ketone) in natural river water. Both classes of the musk fragrances could be extracted reproducibly from water samples with a recovery in the range of 45-50% and relative standard deviation of 11-18% for fragrances at 25-260 ng/l levels. Detection limits were between 14 and 22 ng/l. To achieve this reproducibility it was necessary to use an internal standard, pentachloronitrobenzene, for all substances. Best recoveries were achieved with polydimethylsiloxane (PDMS)-divinylbenzene fibers (compared to recoveries obtained with PDMS, polyacrylate or carboxen fibers) and extraction times of 45 min at 30 degrees C, with no need for attainment of equilibrium conditions. The latter was achieved at about 2 h. For Elbe River water, in the vicinity of Magdeburg, no matrix effects were observed. While the average levels of celestolide and musk ketone for samples investigated were below the detection limits, 14 and 22 ng/l, respectively, and for tonalide below the limit of quantification, 22 ng/l, the ambient levels of galaxolide in the Elbe River were 117 ng/l.