Assessment of Arctic community wastewater impacts on marine benthic invertebrates.

This study sought to understand the performance of arctic treatment systems and the impact of wastewater effluent on benthic invertebrate communities in arctic receiving water habitats. Effluent quality and benthic impacts were monitored in the receiving water of five communities across Nunavut that differed in the type and level of treatment achieved by wastewater infrastructure, the volume of effluent and receiving water mixing environment. We detected minimal impacts to benthic communities (<225 m linear distance from the effluent source) in four out of the five communities (Grise Fiord, Kugaaruk, Pond Inlet, and Pangnirtung), where the population was <2000 people. In these small communities impacts were characterized by increases or decreases in species richness, diversity, evenness, and density, and some differences in benthic species composition. This was in contrast to benthic sediments in Iqaluit (population 6699), which were devoid of benthic fauna up to 580 m from the effluent source in response to sediment anoxia. Variation in benthic community response between sampling locations was attributed primarily to differences in effluent volume, with effluent quality and receiving water hydrodynamics playing secondary roles. The results of this study will help to inform the development of northern specific treatment performance standards which will aid in prioritizing community wastewater system upgrades in arctic communities.

An enhanced capillary electrophoresis method for characterizing natural organic matter.

Natural organic matter (NOM) is ubiquitous and is one of the most complex naturally occurring mixtures. NOM plays an essential role in the global carbon cycle; atmospheric and natural water photochemistry; and the long-range transport of trace compounds and contaminants. There is a dearth of separation techniques capable of resolving this highly complex mixture. To our knowledge, this is the first reported use of ultrahigh resolution counterbalance capillary electrophoresis to resolve natural organic matter. The new separation strategy uses a low pH, high concentration phosphate buffer to reduce the capillary electroosmotic flow (EOF). Changing the polarity of the electrodes reverses the EOF to counterbalance the electrophoretic mobility. Sample stacking further improves the counterbalance separation. The combination of these conditions results in an electropherogram comprised up to three hundred peaks superimposed on the characteristic "humic hump" of NOM. Fraction collection, followed by three-dimensional emission excitation spectroscopy (EEMs) and UV spectroscopy generated a distinct profile of fluorescent and UV absorbing components. This enhanced counterbalance capillary electrophoresis method is a potentially powerful technique for the characterization and separation of NOM and complex environmental mixtures in general.

Investigating aggregation in Suwannee River, U.S.A., dissolved organic matter using diffusion-ordered nuclear magnetic resonance spectroscopy.

Aggregation of the Suwannee River (USA) dissolved organic matter (SRDOM) is studied using nuclear magnetic resonance spectroscopy. Diffusion-ordered spectroscopy identifies two distinct bands, one corresponding to smaller components and the other to larger components. At lower concentrations (500 ppm), the dissolved organic matter (DOM) is present mainly as small components; however, with increasing concentration, the larger components become more pronounced as a result of aggregation. Calibrations indicate the small materials behave in a manner similar to that of maltodextrins of approximately 180 to 950 Da or proteins of 100 to 1000 Da. The aggregated species show behavior similar to that of maltodextrins of approximately 1000 to 21,000 Da or proteins of 1050 to 70,000 Da. The mean diffusivity of the aggregated components in SRDOM is consistent with that of maltodextrins of approximately 4500 Da and proteins of approximately 8000 Da at the highest concentration measured. At the lowest concentration (closest to environmental concentrations), little to no aggregation is observed. Diffusion profiles show an increase in large-molecular-weight material, with a simultaneous decrease in small-molecular-weight components with increasing DOM concentration. This suggests aggregates in SRDOM may be weak dispersive associations of low-molecular-weight material. Additionally, with a decrease in temperature, aggregates show faster diffusion, suggesting a tighter, more condensed arrangement. Further evidence supports DOM aggregation as conglomerations of numerous components in DOM rather than a more organized self-association. Carboxyl-rich alicyclic molecules (CRAM) play a prominent role in aggregation of SRDOM and, to a lesser extent, material-derived from linear terpenoids (MDLT). The role of lignin and carbohydrates is less clear, although at least some of the lignin is present as macromolecules and tends to show interactions with both the MDLT and CRAM components.

Assessing the organic composition of urban surface films using nuclear magnetic resonance spectroscopy.

Recently it has been shown that urban surfaces are covered with a thin film which mediates the fate, distribution and accumulation of semi-volatile organic compounds in the environment. In this study we apply a combination of solution, semi-solids, and solid state nuclear magnetic resonance (NMR) methods to provide a general overview of the organic constituents. In surface film collected from 30 m2 of outside windows over an area of 12 km2 in downtown Toronto, we roughly estimate that the organic carbon is approximately 35% carbohydrate, approximately 35% aliphatics, approximately 20% aromatics, and approximately 10% carbonyl groups. Various aliphatic groups can be identified including a number of acids, alcohols, alkanes, and alkenes. Also, numerous intact aliphatic esters are apparent that have not been observed before, as well as carbohydrates. The aromatic species include a small portion that appears to be derived from a polymer of styrene, in addition a larger fraction is consistent with polyhydroxylated PAH derived material, although this assignment is tentative and based solely on 1-D NMR data only. In addition, signals from polybutadiene are present and while accurate quantification is not possible, it appears that this polymer may be up to a few percents by weight of the total organic material.

The role of lipids on sorption characteristics of freshwater- and wastewater-irrigated soils.

The soil lipid fraction can play an important role in the sorption of organic compounds. In this study, the impact of the lipid fraction of freshwater- and wastewater-irrigated soils on the sorption of non- and relatively polar compounds was assessed. Lipid analyses revealed a clear difference between the two lipid fractions. The lipid extract from the wastewater-irrigated soil was consistent with mainly straight paraffinic chain materials; the lipid extract from freshwater-irrigated soil, on the other hand, exhibited stronger signals of aromatics, double bonds, ester, ether, and methyl, in addition to a smaller contribution from methylene protons. Our data suggest that lipid removal induced a stronger increase in the soil's sorption affinity for solutes capable of polar interactions such as atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and chlorotoluron (N'-(3-chloro-4-methylphenyl)-N,N-dimethylurea) as compared to phenanthrene. Moreover, the level of increase in sorption affinities due to lipid removal was much higher for the freshwater-irrigated soil than for its wastewater-irrigated counterpart, even though the level of lipids in the freshwater-irrigated soil was half that in the wastewater-irrigated one (6 vs. 11% of the total organic C). The higher level of polar functionalities, such as ether and ester moieties, in the lipid fraction from the freshwater-irrigated soil suggests that these extractable compounds compete successfully with the polar solutes (atrazine and chlorotoluron) for specific binding sites in the soil organic matter (SOM). It appears that the composition of the lipid fraction may be a key consideration in unraveling the sorption of organic molecules in soils.

Direct (1)H NMR spectroscopy of dissolved organic matter in natural waters.

Nuclear magnetic resonance (NMR) spectroscopy arguably provides the greatest insight into the overall chemical composition of dissolved organic matter (DOM). However, in a standard 5 mm NMR probe, a sample of sea water at natural abundance only contains ca. 500-600 ng of organic matter, distributed among the heterogeneous components of DOM. Additionally, the intensity of the water signal, which may be many orders of magnitude greater than the signals from DOM, makes the detection and analysis of DOM at natural abundance extremely demanding. Here, we demonstrate, that although challenging, the application of an improved water suppression technique allows NMR spectra of DOM to be obtained directly (i.e without pre-concentration) for major bodies of water, including rivers, lakes and the ocean. The technique described here provides a compositional overview of an intact sample, permitting researchers to investigate and assess the impact of concentration, isolation and extraction procedures that are employed routinely. Also the technique permits NMR to be performed on 'precious' samples for which traditional isolations are not possible, for example, water from ice cores and pore water, which are key in hydrology and for paleoclimatic reconstruction.

Unraveling the structural components of soil humin by use of solution-state nuclear magnetic resonance spectroscopy.

Humin is the most recalcitrant and least understood fraction of soil organic matter. By definition, humin is that fraction not extracted by traditional aqueous alkaline soil extractants. Here we show that > or = 70% of the traditional humin fraction is solubilized when 0.1 M NaOH + 6 M urea and dimethyl sulfoxide (DMSO) + 6% H2SO4 are used in series after conventional extraction. Multidimensional solution-state NMR is applied in this study to gain an understanding of the major constituents present in these "solubilized humin fractions". The spectra indicated strong contributions from five main categories of components, namely, peptides, aliphatic species, carbohydrates, peptidoglycan, and lignin. Diffusion edited spectroscopy indicated that all species are present as macromolecules (or stable aggregate species). Although the distribution of the components is generally similar, peptidoglycan is present at significant levels supporting a higher microbial contribution to humin than to humic and fulvic fractions. The abundance of plant- and microbial-derived materials found does not exclude "humic" materials (e.g., oxidized lignin) or the presence of novel compounds at lower concentrations but suggests that a large proportion of humin is formed from classes of known compounds and parent biopolymers.

Major structural components in freshwater dissolved organic matter.

Dissolved organic matter (DOM) contains a complex array of chemical components that are intimately linked to many environmental processes, including the global carbon cycle, and the fate and transport of chemical pollutants. Despite its importance, fundamental aspects, such as the structural components in DOM remain elusive, due in part to the molecular complexity of the material. Here, we utilize multidimensional nuclear magnetic resonance spectroscopy to demonstrate the major structural components in Lake Ontario DOM. These include carboxyl-rich alicyclic molecules (CRAM), heteropolysaccharides, and aromatic compounds, which are consistent with components recently identified in marine dissolved organic matter. In addition, long-range proton-carbon correlations are obtained for DOM, which support the existence of material derived from linear terpenoids (MDLT). It is tentatively suggested that the bulk of freshwater dissolved organic matter is aliphatic in nature, with CRAM derived from cyclic terpenoids, and MDLT derived from linear terpenoids. This is in agreement with previous reports which indicate terpenoids as major precursors of DOM. At this time it is not clear in Lake Ontario whether these precursors are of terrestrial or aquatic origin or whether transformations proceed via biological and/ or photochemical processes.

Passive sampler for dissolved organic matter in freshwater environments.

A passive sampler for the isolation of dissolved organic matter (DOM) from freshwater environments is described. The sampler consists of a molecular weight selective membrane (1000 kDa) and an anion exchange resin (diethylaminoethylcellulose (DEAE-cellulose)). NMR indicates the samplers isolate DOM that is nearly indistinguishable from that isolated using the batch DEAE-cellulose procedure. In a comparative study DOM isolated from Lake Ontario cost approximately 0.30 dollars/mg to isolate using the passive samplers while DOM isolated using the traditional batch procedure cost approximately 8-10 dollars/mg. The samplers have been shown to be effective in a range of freshwater environments including a large inland lake (Lake Ontario), fast flowing tributary, and wetland. Large amounts (gram quantities of DOM) can be easily isolated by increasing the size or number of samplers deployed. Samplers are easy to construct, negate the need for pressure filtering, and also permit a range of temporal and spatial experiments that would be very difficult or impossible to perform using conventional approaches. For example, DOM can be monitored on a regular basis at numerous different locations, or samplers could be set at different depths in large lakes. Furthermore, they could potentially be deployed into hard to reach environments such as wells, groundwater aquifers, etc., and as they are easy to use, they can be mailed to colleagues or included with expeditions going to difficult to reach places such as the Arctic and Antarctic.