Marine Birds as Indicators of Arctic Marine Ecosystem Health: Linking the Northern Ecosystem Initiative to Long-Term Studies

Marine birds are sensitive indicators of the condition of marine ecosystems in the Arctic, partly because they feed at the top of the arctic food chain. The Northern Ecosystem Initiative (NEI) recently supported four separate studies that investigated aspects of Arctic marine bird science which simultaneously addressed goals of the NEI to better understand northern ecosystems and their response to environmental stressors. The projects used both scientific and traditional knowledge to examine the relationship between sea-ice, contaminants, and the ecology of marine birds, and to transfer environmental knowledge to students. Results from these investigations confirm that changes are occurring in Arctic environments, and that these are captured through marine bird research. Collectively these studies provided new data that supported NEI objectives of monitoring the health of the Arctic ecosystem, and contributed to Canada's international obligations for Arctic science.     

Northern Rivers Ecosystem Initiative: Distribution and Effects of Contaminants

In response to a number of recommendations following the Northern Rivers Basin Studies (NRBS) contaminant program, the Northern Rivers Ecosystem Initiative (NREI) focused considerable attention on assessing contaminants from specific sources including pulp mill effluents, atmospheric transport of mercury and the Alberta oil sands operations. NRBS identified a number of major contaminants of concern including polychlorinated biphenyls, dioxins and furans, mercury and various hydrocarbons. Together, the NRBS and the NREI studies have demonstrated major declines in the levels of dioxins and furans over the last decade as pulp and paper mills have changed their process and treatment strategies in response to new Federal regulations. Polychlorinated biphenyls however, continue to be a concern for the region as their levels have not declined in fish and sediments over the course of these studies. Higher levels in sediments downstream of Grande Prairie and Hinton were identified, but the source of these contaminants remains unknown. Chlorinated pesticides were also investigated, and although toxaphene, DDT and other chlorinated organic pesticides were detected in fish tissue, they were present at very low levels. Studies on the oil sands industry in northern Alberta demonstrated limited impacts on the Athabasca River to date, although studies did identify slight to moderate impacts of natural oil seeps on fish and benthic communities in tributary streams. NREI studies also identified endocrine active compounds in the three pulp and paper mill effluents tested, but endocrine disruptive effects in wild fish were minimal. Municipal sewage effluents also contain endocrine active compounds and it is recommended that monitoring continue around these point sources.     

Northern Rivers Ecosystem Initiative: Context and Prevailing Legacy

The Northern River Ecosystem Initiative (NREI), 1997–2004, has provided new scientific knowledge in response to specific recommendations from its predecessor, the Northern River Basins Study (NRBS), 1990–1996. The two initiatives together provide a remarkable body of science which is, and will continue to be, used by resource managers responsible for economic and environmental sustainability in the northern watersheds of Alberta. The NREI focused its investigative efforts on improving our understanding related to ecological considerations of changes in river flow, effect of climate change on flow, ecological responses to pollution and cumulative effects, vulnerability of drinking water quality, and to a lesser degree, wildlife (birds) response to large scale changes within the watersheds. Key findings are briefly presented in this paper and discussed in greater detail in the other NREI papers included in this. Commensurate with the undertakings of NREI, provincial and territorial governments, First Nation and Métis communities, and other administrative organizations such as the Mackenzie River Basin Board, undertook policy, regulatory, and watershed initiatives towards achieving sustainability and providing reliable drinking water quality.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.     

Lagrangian Sampling for Emerging Contaminants Through an Urban Stream Corridor in Colorado1

Abstract: Recent national concerns regarding the environmental occurrence of emerging contaminants (ECs) have catalyzed a series of recent studies. Many ECs are released into the environment through discharges from wastewater treatment plants (WWTPs) and other sources. In 2005, the U.S. Geological Survey and the City of Longmont initiated an investigation of selected ECs in a 13.8‐km reach of St. Vrain Creek, Colorado. Seven sites were sampled for ECs following a Lagrangian design; sites were located upstream, downstream, and in the outfall of the Longmont WWTP, and at the mouths of two tributaries, Left Hand Creek and Boulder Creek (which is influenced by multiple WWTP outfalls). Samples for 61 ECs in 16 chemical use categories were analyzed and 36 were detected in one or more samples. Of these, 16 have known or suspected endocrine‐disrupting potential. At and downstream from the WWTP outfall, detergent metabolites, fire retardants, and steroids were detected at the highest concentrations, which commonly exceeded 1 μg/l in 2005 and 2 μg/l in 2006. Most individual ECs were measured at concentrations less than 2 μg/l. The results indicate that outfalls from WWTPs are the largest but may not be the sole source of ECs in St. Vrain Creek. In 2005, high discharge was associated with fewer EC detections, lower total EC concentrations, and smaller EC loads in St. Vrain Creek and its tributaries as compared with 2006. EC behavior differed by individual compound, and some differences between sites could be attributed to analytical variability or to other factors such as physical or chemical characteristics or distance from contributing sources. Loads of some ECs, such as diethoxynonylphenol, accumulated or attenuated depending on location, discharge, and distance downstream from the WWTP, whereas others, such as bisphenol A, were largely conservative. The extent to which ECs in St. Vrain Creek affect native fish species and macroinvertebrate communities is unknown, but recent studies have shown that fish respond to very low concentrations of ECs, and further study on the fate and transport of these contaminants in the aquatic environment is warranted.     

Depositional behaviors of plutonium and thorium isotopes at Tsukuba and Mt. Haruna in Japan indicate the sources of atmospheric dust

Monthly plutonium and thorium depositions at Tsukuba (28 m asl) and Mt. Haruna (1370 m asl) were measured during 2006 and 2007 (Jan 2006-Dec 2007 at Tsukuba, Nov 2006-Dec 2007 at Mt. Haruna). The monthly ^239,240Pu depositions ranged from 0.044 to 2.67 mBq m⁻² at Tsukuba and from 0.05 to 0.9 mBq m⁻² at Mt. Haruna during the measurement periods. Monthly ^239,240Pu deposition did not differ markedly between the two sites except in April 2007. Seasonal pattern of monthly ^239,240Pu depositions at both sites showed high in spring and low in summer, and typical of seasonal variations in northeastern Asia. Thorium deposition at Tsukuba was higher than that at Mt. Haruna except in May and June 2007. ²³⁰Th/²³²Th activity ratios were used to partition deposition samples into locally and remotely derived fractions. The results revealed that a major proportion of total ^239,240Pu and Th deposits are derived from remote sources, especially in spring.     

Molecular identification and nanoremediation of microbial contaminants in algal systems using untreated wastewater

Wastewater-algal biomass is a promising option to biofuel production. However, microbial contaminants constitute a substantial barrier to algal biofuel yield. A series of algal strains, Nannochloris oculata and Chlorella vulgaris samples (n = 30), were purchased from the University of Texas, and were used for both stock flask cultures and flat-panel vertical bioreactors. A number of media were used for isolation and differentiation of potential contaminants according to laboratory standards (CLSI). Conventional PCR amplification was performed followed by 16S rDNA sequencing to identify isolates at the species level. Nanotherapeutics involving a nanomicellar combination of natural chitosan and zinc oxide (CZNPs) were tested against the microbial lytic groups through Minimum Inhibitory Concentration (MIC) tests and Transmission Electronic Microscopy (TEM). Results indicated the presence of Pseudomonas spp., Bacillus pumilus/ safensis, Cellulosimicrobium cellulans, Micrococcus luteus and Staphylococcus epidermidis strains at a substantial level in the wastewater-fed algal reactors. TEM confirmed the effectiveness of CZNPs on the lytic group while the average MICs (mg/mL) detected for the strains, Pseudomonas spp, Micrococcus luteus, and Bacillus pumilus were 0.417, 3.33, and 1.458, respectively. Conclusively, CZNP antimicrobials proved to be effective as inhibitory agents against currently identified lytic microbial group, did not impact algae cells, and shows promise for in situ interventions.     

Pesticides residues in the Prochilodus costatus (Valenciennes, 1850) fish caught in the São Francisco River,Brazil

The objective of this study was to determine the levels of pesticides in the fish Prochilodus costatus caught in São Francisco River, one of most important rivers in Brazil. Thirty-six fish were captured in three different areas, and samples of the dorsal muscle and pooled viscera were collected for toxicological analysis. We evaluated the presence of 150 different classes of insecticides, fungicides, herbicides and acaricides by multiresidue analysis technique using liquid chromatography-tandem mass spectrometry (LC-MS/MS), with the limit of detection of 5 ppb. In this study, organophosphorus and carbamate pesticides were detected at the highest levels in the caught fish. Among the 41 organophosphorus pesticides surveyed, nine types were detected (chlorpyrifos, diazinon, dichlorvos, disulfoton, ethion, etrimfos, phosalone, phosmet and pyrazophos) in the muscle, viscera pool, or both in 22 (61.1%) fish. Sampled tissues of 20 (55.6%) fish exhibited at least one of the eight evaluated carbamate pesticides and their metabolites: aldicarb, aldicarb sulfoxide, carbaryl, carbofuran, carbosulfan, furathiocarb, methomyl and propoxur. Fungicides (carbendazim, benalaxyl, kresoxim-methyl, trifloxystrobin, pyraclostrobin and its metabolite BF 500 pyraclostrobin), herbicides (pyridate and fluasifop p-butyl), acaricide (propargite) and pyrethroid (flumethrin) were also detected. In conclusion, P. costatus fish caught in the São Francisco River contained residues of 17 different pesticides, in both muscles and the viscera pool, indicating heavy environmental contamination by pesticides in the study area.     

Oxyanion flux characterization using passive flux meters: development and field testing of surfactant-modified granular activated carbon

We report here on the extension of Passive Flux Meter (PFM) applications for measuring fluxes of oxyanions in groundwater, and present results for laboratory and field studies. Granular activated carbon, with and without impregnated silver (GAC and SI-GAC, respectively), was modified with a cationic surfactant, hexadecyltrimethylammonium (HDTMA), to enhance the anion exchange capacity (AEC). Langmuir isotherm sorption maxima for oxyanions measured in batch experiments were in the following order: perchlorate>chromate>selenate, consistent with their selectivity. Linear sorption isotherms for several alcohols suggest that surfactant modification of GAC and SI-GAC reduced (approximately 30-45%) sorption of alcohols by GAC. Water and oxyanion fluxes (perchlorate and chromate) measured by deploying PFMs packed with surfactant-modified GAC (SM-GAC) or surfactant-modified, silver-impregnated GAC (SM-SI-GAC) in laboratory flow chambers were in close agreement with the imposed fluxes. The use of SM-SI-GAC as a PFM sorbent was evaluated at a field site with perchlorate contamination of a shallow unconfined aquifer. PFMs packed with SM-SI-GAC were deployed in three existing monitoring wells with a perchlorate concentration range of approximately 2.5 to 190 mg/L. PFM-measured, depth-averaged, groundwater fluxes ranged from 1.8 to 7.6 cm/day, while depth-averaged perchlorate fluxes varied from 0.22 to 1.7 g/m2/day. Groundwater and perchlorate flux distributions measured in two PFM deployments closely matched each other. Depth-averaged Darcy fluxes measured with PFMs were in line with an estimate from a borehole dilution test, but much smaller than those based on hydraulic conductivity and head gradients; this is likely due to flow divergence caused by well-screen clogging. Flux-averaged perchlorate concentrations measured with PFM deployments matched concentrations in groundwater samples taken from one well, but not in two other wells, pointing to the need for additional field testing. Use of the surfactant-modified GACs for measuring fluxes of other anions of environmental interest is discussed.     

Molecular indicators for pollution source identification in marine and terrestrial water of the industrial area of Kavala city, North Greece

Eight terrestrial and four marine water samples were collected from the industrial section of the city of Kavala in northern Greece to determine the occurrence and distribution of organic contaminants, as well as to identify the molecular markers of different emission sources. The samples were analyzed by means of non-target screening analyses. The analytical procedure included a sequential extraction of the samples, GC-FID, GC/MS analyses, and additional quantitative analyses of selected pollutants. The results show a wide variety of compounds including halogenated compounds, technical additives and metabolites, phosphates, phthalates, benzothiazoles, etc. A close relationship between many of the contaminants and their emission sources was determined based on their molecular structures and information on technical applications.