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.     

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.     

Distribution and potential sources of polycyclic aromatic hydrocarbons in soils around coal-fired power plants in South Africa

The distribution and potential sources of 15 polycyclic aromatic hydrocarbons (PAHs) in soils in the vicinity of three South African coal-fired power plants were determined by gas chromatography–mass spectrometry. PAH compound ratios such as phenanthrene/phenanthrene + anthracene (Phen/Phen + Anth) were used to provide reliable estimation of emission sources. The total PAH concentration in the soils around three power plants ranged from 9.73 to 61.24 μg g^?1, a range above the Agency for Toxic Substances and Disease Registry levels of 1.0 μg g^?1 for significantly contaminated site. Calculated values of Phen/Phen + Anth ratio were 0.48?±?0.08, 0.44?±?0.05, and 0.38?+?0.04 for Matla, Lethabo, and Rooiwal, respectively. Flouranthene/fluoranthene + pyrene (Flan/Flan + Pyr) were found to be 0.49?±?0.03 for Matla, 0.44?±?0.05 for Lethabo, and 0.53?±?0.08 for Rooiwal. Such values indicate a pyrolytic source of PAHs. Higher molecular weight PAHs (five to six rings) were predominant, suggesting coal combustion sources. A good correlation existed between most of the PAHs implying that these compounds were emitted from similar sources. The carcinogenic potency B[a]P equivalent concentration (B[a] Peq) at the three power plants ranged from 3.61 to 25.25 indicating a high carcinogenic burden. The highest (B[a] Peq) was found in samples collected around Matla power station. It can therefore be concluded that the soils were contaminated with PAHs originating from coal-fired power stations.     

Weather variability permitted within amphibian monitoring protocol and affects on calling Hylidae

Anuran populations are sensitive to changing environmental conditions and act as useful indicators. Presently, much information collected concerning frog populations comes from volunteers following the North American Amphibian Monitoring Protocol. Does weather variability allowed within protocol affect the abundance of calling frogs? For 10 years, Credit Valley Conservation (Ontario, Canada) has been collecting anuran data concerning nine frog species employing three frog monitoring runs. Records include frog abundance by protocol code and five weather variables. Antecedent precipitation and temperature were determined from the nearest weather station. Locations with large source populations of two Hylidae species were selected (spring peeper calling in April and gray tree frog in May). Spearman correlations suggested there were no significant relationships between calling abundance of Hylidae species and ambient wind speed or humidity. However, gray tree frogs were temperature sensitive and calling was significantly related to increased water and air temperatures as well as day time high temperatures over the previous 2 weeks. Both species of calling Hylidae were affected by the volume and timing of precipitation (though, in different ways). Gray tree frogs seem to prefer drier conditions (when temperatures are significantly warmer) while spring peepers prefer to call during, or closely following, precipitation. Monitors targeting gray tree frog should track local weather conditions and focus on evenings when it is (a) warmer than the minimum temperatures and (b) drier than suggested by the protocol. It is recommended that an additional monitoring run could be added to reduce detection variability of this species.     

Uptake of arsenic by alkaline soils near alkaline coal fly ash disposal facilities

The attenuation of arsenic in groundwater near alkaline coal fly ash disposal facilities was evaluated by determining the uptake of arsenic from ash leachates by surrounding alkaline soils. Ten different alkaline soils near a retired coal fly ash impoundment were used in this study with pH ranging from 7.6 to 9.0, while representative coal fly ash samples from two different locations in the coal fly ash impoundment were used to produce two alkaline ash leachates with pH 7.4 and 8.2. The arsenic found in the ash leachates was present as arsenate [As(V)]. Adsorption isotherm experiments were carried out to determine the adsorption parameters required for predicting the uptake of arsenic from the ash leachates. For all soils and leachates, the adsorption of arsenic followed the Langmuir and Freundlich equations, indicative of the favorable adsorption of arsenic from leachates onto all soils. The uptake of arsenic was evaluated as a function of ash leachate characteristics and the soil components. The uptake of arsenic from alkaline ash leachates, which occurred mainly as calcium hydrogen arsenate, increased with increasing clay fraction of soil and with increasing soil organic matter of the alkaline soils. Appreciable uptake of arsenic from alkaline ash leachates with different pH and arsenic concentration was observed for the alkaline soils, thus attenuating the contamination of groundwater downstream of the retired coal fly ash impoundment.     

Background levels of some major,trace, and rare earth elements in indigenous plant species growing in Norway and the influence of soil acidification,soil parent material,and seasonal variation on these levels

Baseline levels of 43 elements, including major, trace, and rare earth elements (REEs) in several native plant species growing in boreal and alpine areas, are presented. Focus is placed on species metal levels at different soil conditions, temporal variations in plant tissue metal concentrations, and interspecies variation in metal concentrations. Vegetation samples were collected at Sogndal, a pristine site in western Norway, and at Risdalsheia, an acidified site in southernmost Norway. Metal concentrations in the different species sampled in western Norway are compared with relevant literature data from Norway, Finland, and northwest Russia, assumed to represent natural conditions. Except for aluminium (Al) and macronutrients, the levels of metals were generally lower in western Norway than in southern Norway and may be considered close to natural background levels. In southern Norway, the levels of cadmium (Cd) and lead (Pb) in particular appear to be affected by air pollution, either by direct atmospheric supply or through soil acidification. Levels of some elements show considerable variability between as well as within plant species. Calcium (Ca), magnesium (Mg), and potassium (K) are higher in most species at Sogndal compared to Risdalsheia, despite increased extractable concentrations in surface soil in the south, probably attributed to different buffer mechanisms in surface soil. Antagonism on plant uptake is suggested between Ca, Mg, and K on one hand and Al on the other. Tolerance among calcifuges to acid conditions and a particular ability to detoxify or avoid uptake of Al ions are noticeable for Vaccinium vitis-idaea.     

A New All Season Passive Sampling System for Monitoring Ozone in Air

A new all season passive sampling system for monitoring O₃ in the atmosphere has been developed in the laboratory and validated in the field. The unique features for this system include a newly designed passive sampler and a rain shelter, which allow the passive sampler to be installed in the field facing downwards. An equation associated with meteorological parameters is used to calculate the passive sampling rates. This system has been extensively tested in the lab (temperature from –18 to 20°C, relative humidity from 13 to 81%, and wind speed from 0.5 to 150 cm/s) and validated in the field in climates of all seasons. The accuracy of the ozone concentrations in the atmosphere obtained with the use of the new passive sampling system was higher than 85% compared to those obtained with continuous ozone analyzers. The new ozone passive sampling system can be used to measure ambient O₃ concentrations ranging from 3 ppb to 1000 ppb based on one-day exposure and 0.1 ppb to 140 ppb for a monthly exposure period. It is also reasonable to conclude that the new passive sampling system can be used for eight-hour exposure study because of the low field blanks and high sampling rates.     

The effect of absorbent grid preparation method on precision and accuracy of ambient nitrogen dioxide measurements using Palmes passive diffusion tubes

A few studies have suggested that the precision and accuracy of measurement of NO(2) by Palmes-type passive diffusion tube (PDT) are affected by the method of preparation of the triethanolamine (TEA) absorbent coating on the grids. Theses studies have been quite limited in extent and have tended to evaluate PDT accuracy as zero bias between PDT NO(2) value and the exposure-averaged NO(2) determined by co-located chemiluminescence analyser. This ignores the well-documented intrinsic systematic biases on PDT-derived NO(2), such as within-tube chemistry and exposure-duration nitrite loss, which may lead to non-zero bias values irrespective of effects of TEA absorbent preparation method on PDT accuracy. This paper reports on a statistical analysis of a large dataset comprising 680 duplicated PDT exposures spanning 146 separate exposure periods, spread over five urban exposure locations and a number of years. In each exposure period, PDTs prepared by between four and six different grid preparation methods were simultaneously compared. The preparation methods used combinations of the following: acetone or water as the TEA solvent; 20% or 50% as %TEA in the solution; and application of TEA solution by dipping grids for several minutes in the solution before drying and tube assembly, or by pipetting 50 microL of solution directly onto grids already placed in the PDT cap. These represent the range of preparation procedures typically used. Accuracy was evaluated as maximised nitrite capture within an exposure. Data were analysed by general linear modelling including examination of interaction between different aspects of grid preparation method. PDT precision and accuracy were both significantly better, on average, when the PDT grids were prepared by dipping in TEA solution, and neither solvent or %TEA used for the dipping solution were important. Where PDT preparation by pipetting TEA solution onto grids is to be used, better performance was obtained using 20% TEA in water. A systematic positive bias in PDT measure of NO(2), consistent with within-tube oxidation of NO to NO(2) and independent of preparation method, was again evident in this work.     

Monitoring human impacts on sandy shore ecosystems: a test of ghost crabs (Ocypode spp.) as biological indicators on an urban beach

This study evaluated the spatial and temporal distribution of metals in the coral reef system Cayos Arcas and Triangulos in the Campeche Bank region, off the Yucatan peninsula in Mexico. No information has been generated before for the incorporation of natural and non-natural occurring metals, some of which are possibly endowed by the oil marine station Cayo Arcas. The multivariate exploratory study of the metals on the coral skeletons, showed the formation of two distinct groups. The metals that have the highest influence on the differentiation of the groups are the metals that are natural constituents of the coral skeletons, in particular Sr can explain much of the differences between the groups, and to a much lesser extent are the metals that could be indicators of pollution. This differentiation suggests that, in our case, the environment around the corals has a higher impact than the non-naturally occurring metals (and possible indicators of pollution). The two groups formed corresponded to: the coral cores influenced by open sea variables and the coral cores in the inner part of the keys which is less exposed to open sea variables. A chronological study was made to two samples that had the longest coral section and were situated in two clearly distinctive zones: an exposed surface subjected to high wave forces and another that was less exposed. Ni and Zn show an accumulation trend in both coral samples, while Ba showed an increase in incorporation around 1980 when the Cayo Arcas oil marine station was constructed.