Determination of priority pesticides in water samples combining SPE and SPME coupled to GC–MS. A case study: Suquía River basin (Argentina)

This study reports a combined method using solid phase extraction (SPE), followed by solid phase microextraction (SPME) to concentrate different pesticides, including chlorinated, organophosphorus, triazines, pyretroids and chloroacetamides, present at trace levels in water samples. Identification and quantification was carried out by gas chromatography coupled to Mass Spectrometry (GC–MS). The optimized methodology showed LOQs at ng L^?1 levels (ranging 0.2–3.5 ng L^?1) in addition to acceptable precision and robustness (recoveries ranged 63–104%, RSD from 4% to 23%), presenting a novel method to reach trace levels, similar to that obtainable using EC detector, with structural confirmation by MS during the analysis of a wide range of environmental pollutants.This method was applied to the study of temporal and spatial distribution of pesticides in the Suquía River basin (Córdoba-Argentina). As expected, highest levels of agrochemicals were observed in areas with intensive agricultural practices, being atrazine (max. = 433.9 ng L^?1), alpha-cypermetrine (max. = 121.7 ng L^?1) and endosulfan sulfate (max. = 106.7 ng L^?1) predominant. In urban areas, the prevalent pesticide was alpha-cypermethrine. These results draw attention to the need of pesticide monitoring programs in rivers, considering both urban and rural sections.     

Mapping forest composition from the Canadian National Forest Inventory and land cover classification maps

Canada's National Forest Inventory (CanFI) provides coarse-grained, aggregated information on a large number of forest attributes. Though reasonably well suited for summary reporting on national forest resources, the coarse spatial nature of this data limits its usefulness in modeling applications that require information on forest composition at finer spatial resolutions. An alternative source of information is the land cover classification produced by the Canadian Forest Service as part of its Earth Observation for Sustainable Development of Forests (EOSD) initiative. This product, which is derived from Landsat satellite imagery, provides relatively high resolution coverage, but only very general information on forest composition (such as conifer, mixedwood, and deciduous). Here we link the CanFI and EOSD products using a spatial randomization technique to distribute the forest composition information in CanFI to the forest cover classes in EOSD. The resultant geospatial coverages provide randomized predictions of forest composition, which incorporate the fine-scale spatial detail of the EOSD product and agree in general terms with the species composition summaries from the original CanFI estimates. We describe the approach and provide illustrative results for selected major commercial tree species in Canada.     

Polar organic chemical integrative sampler (POCIS): application for monitoring organic micropollutants in wastewater effluent and surface water

In this paper, we discuss the advantages and drawbacks of POCIS (Polar Organic Chemical Integrative Sampler) for the evaluation of river water quality downstream of wastewater treatment plants. POCIS proved well adapted to sampling alkylphenols and several pharmaceuticals. Concentration factors and the decrease in limits of quantification, compared to grab water sample analyses, were significant except for hormones, β-blockers and bronchodilators. Promising preliminary results obtained in situ on deuterated atenolol used as a performance reference compound need to be confirmed in-lab. This work confirms that POCIS is a valuable tool for monitoring hydrophilic organic molecules in river and wastewaters.     

Agricultural practices in grasslands detected by spatial remote sensing

The major decrease in grassland surfaces associated with changes in their management that has been observed in many regions of the earth during the last half century has major impacts on environmental and socio-economic systems. This study focuses on the identification of grassland management practices in an intensive agricultural watershed located in Brittany, France, by analyzing the intra-annual dynamics of the surface condition of vegetation using remotely sensed and field data. We studied the relationship between one vegetation index (NDVI) and two biophysical variables (LAI and fCOVER) derived from a series of three SPOT images on one hand and measurements collected during field campaigns achieved on 120 grasslands on the other. The results show that the LAI appears as the best predictor for monitoring grassland mowing and grazing. Indeed, because of its ability to characterize vegetation status, LAI estimated from remote sensing data is a relevant variable to identify these practices. LAI values derived from the SPOT images were then classified based on the K-Nearest Neighbor (KNN) supervised algorithm. The results points out that the distribution of grassland management practices such as grazing and mowing can be mapped very accurately (Kappa index?=?0.82) at a field scale over large agricultural areas using a series of satellite images.     

Assessment of trace metals and porphyrins in excreta of Humboldt penguins (Spheniscus humboldti) in different locations of the northern coast of Chile

To add data on trace metal contamination of Humboldt penguins in the South Pacific, levels of trace metals (As, Hg, Pb, Cu, Zn, and Cd) and porphyrins (copro-, uro-, and proto-) in excreta of Humboldt penguins that inhabit some important nesting sites on the northern coast of Chile were determined. Fresh excreta were collected on Pan de Azúcar Island, Chañaral Island, and Cachagua Island, from December 2011 to January 2012. Concentration of metals was determined by flame atomic absorption spectrophotometry, whereas porphyrins levels were measured by fluorimetric analysis. Concentrations (dry weight) of Cu (199.67 μg g^?1), As (7.85 μg g^?1), and Pb (12.78 μg g^?1) were higher (p?≤?0.05) in Cachagua Island. Colonies from Pan de Azúcar Island showed the highest levels of Hg (0.76 μg g^?1), Cd (47.70 μg g^?1), and Zn (487.10 μg g^?1). Samples from Cachagua Island showed the highest (p?≤?0.05) levels of copro- (2.16 nmol g^?1), uro- (2.20 nmol g^?1), and protoporphyrins (2.23 nmol g^?1). There was a positive correlation between the metals As, Pb, and Cu with uro-, copro-, and protoporphyrins. The results indicated that penguin colonies from Cachagua Island are more exposed to metal contamination than penguin colonies from Pan de Azúcar and Chañaral Islands, thus being more likely to develop certain diseases caused by contamination with metals. Considering biomagnification, the metals detected in the excreta of Humboldt penguins can be a source of contamination from marine environments to terrestrial ecosystems, which could also affect other living organisms.     

Assessment of potential health risk for inhabitants living near a former lead smelter. Part 2: site-specific human health risk assessment of Cd and Pb contamination in kitchen gardens

Metal contamination of urban soils and homegrown products has caused major concern. In Part 1, we investigated the long-term effects of a former smelter on the degree of kitchen garden-soil contamination and the quality of the homegrown vegetables from these gardens. The results showed that the soils retained a high level of contamination and that a large proportion of the vegetables produced did not comply with the legislation on the levels of metals allowed for human consumption. The present study aims to assess the associated potential health risk to local inhabitants through consumption of homegrown vegetables and ingestion of soil particles using a land use-based approach. For lead (Pb), the standard hazard quotient (HQ)-based risk assessment method was used to determine the HQ. For cadmium (Cd), the approach consisted of calculating the HQs and then deriving site-specific assessment criteria (SSAC) using the SNIFFER method. The results suggested that the exposure pathways considered should not engender any form of deleterious health effects for adults. For children, Pb was the main concern and induced a relatively high health risk through soil particle ingestion, and most total soil Cd concentrations exceeded the derived SSAC, in particular, through consumption of vegetables. The metal bioaccessibility in soils was incorporated into the methods to establish more realistic risk assessment measures. This study proposes an approach to integrate different human health risk assessment methods. Further investigations should complete the assessment to improve risk determination, e.g., the determination of metal bioaccessibility in vegetables.     

Cytotoxic and genotoxic effects of silver nanoparticle/carboxymethyl cellulose on <Emphasis Type="Italic">Allium cepa</Emphasis>

Several mutagenic agents may be present in substances released in the environment, which may cause serious environmental impacts. Among these substances, there is a special concern regarding the widespread use of silver nanoparticles (AgNP) in several products due to their widely known bactericidal properties, including in the medical field and the food industry (e.g., active packaging). The assessment of the effects of AgNP released in the environment, having different concentrations, sizes, and being associated or not to other types of materials, including polymers, is therefore essential. In this research, the objective was to evaluate the genotoxic and cytotoxic effects of AgNP (size range between 2 and 8 nm) on root meristematic cells of Allium cepa (A. cepa). Tests were carried out in the presence of colloidal solution of AgNP and AgNP mixed with carboxymethylcellulose (CMC), using distinct concentrations of AgNP. As a result, when compared to control samples, AgNP induced a mitotic index decrease and an increase of chromosomal aberration number for two studied concentrations. When AgNP was in the presence of CMC, no cytotoxic potential was verified, but only the genotoxic potential for AgNP dispersion having concentration of 12.4 ppm.     

Distributions and sources of polycyclic aromatic hydrocarbons in surface sediments from the Cross River estuary,S.E. Niger Delta,Nigeria

Polycyclic aromatic hydrocarbon (PAH) analyses of surface sediments from the Cross River estuary by gas chromatography–mass spectrometry indicated natural diagenetically derived PAHs in the upper estuary, with minor and variable amounts of petrogenic and combustion-derived PAHs from human activities (lower estuary). The occurrence of significant amounts of perylene (average 23% of all PAHs) with the diagenetic natural PAHs in the middle estuary bordered by mangrove forests supports its origin from terrestrial organic matter. The natural PAHs represent the highest percentage (average 76%) of the total PAHs in this tropical environment. The traditional geochemical parameters, including the petrogenic PAHs, confirmed trace petroleum contamination in the estuary. Specific PAH ratios such as Fl/Py and Fl/(Fl+Py) also support this source contribution.     

Atmospheric deposition and storm induced runoff of heavy metals from different impermeable urban surfaces

Contaminants deposited on impermeable surfaces migrate to stormwater following rainfall events, but accurately quantifying their spatial and temporal yields useful for mitigation purposes is challenging. To overcome limitations in current sampling methods, a system was developed for rapid quantification of contaminant build-up and wash-off dynamics from different impervious surfaces. Thin boards constructed of concrete and two types of asphalt were deployed at different locations of a large carpark to capture spatially distributed contaminants from dry atmospheric deposition over specified periods of time. Following experimental exposure time, the boards were then placed under a rainfall simulator in the laboratory to generate contaminant runoff under controlled conditions. Single parameter effects including surface roughness and material composition, number of antecedent dry days, rain intensity, and water quality on contaminant build-up and wash-off yields could be investigated. The method was applied to quantify spatial differences in deposition rates of contaminants (TSS, zinc, copper and lead) at two locations varying in their distance to vehicle traffic. Results showed that boards exposed at an unused part of the carpark >50 m from vehicular traffic captured similar amounts of contaminants compared with boards that were exposed directly adjacent to the access route, indicating substantial atmospheric contaminant transport. Furthermore, differences in contaminant accumulation as a function of surface composition were observed. Runoff from asphalt boards yielded higher zinc loads compared with concrete surfaces, whereas runoff from concrete surfaces resulted in higher TSS concentrations attributed to its smoother surfaces. The application of this method enables relationships between individual contaminant behaviour and specific catchment characteristics to be investigated and provides a technique to derive site-specific build-up and wash-off functions required for modelling contaminant loads from impermeable surfaces.     

Design to monitor trend in abundance and presence of American beaver (Castor canadensis) at the national forest scale

Wildlife conservationists design monitoring programs to assess population dynamics, project future population states, and evaluate the impacts of management actions on populations. Because agency mandates and conservation laws call for monitoring data to elicit management responses, it is imperative to design programs that match the administrative scale for which management decisions are made. We describe a program to monitor population trends in American beaver (Castor canadensis) on the US Department of Agriculture, Black Hills National Forest (BHNF) in southwestern South Dakota and northeastern Wyoming, USA. Beaver have been designated as a management indicator species on the BHNF because of their association with riparian and aquatic habitats and its status as a keystone species. We designed our program to monitor the density of beaver food caches (abundance) within sampling units with beaver and the proportion of sampling units with beavers present at the scale of a national forest. We designated watersheds as sampling units in a stratified random sampling design that we developed based on habitat modeling results. Habitat modeling indicated that the most suitable beaver habitat was near perennial water, near aspen (Populus tremuloides) and willow (Salix spp.), and in low gradient streams at lower elevations. Results from the initial monitoring period in October 2007 allowed us to assess costs and logistical considerations, validate our habitat model, and conduct power analyses to assess whether our sampling design could detect the level of declines in beaver stated in the monitoring objectives. Beaver food caches were located in 20 of 52 sampled watersheds. Monitoring 20 to 25 watersheds with beaver should provide sufficient power to detect 15–40% declines in the beaver food cache index as well as a twofold decline in the odds of beaver being present in watersheds. Indices of abundance, such as the beaver food cache index, provide a practical measure of population status to conduct long-term monitoring across broad landscapes such as national forests.