For the routine determination of metals in environmental samples, we require microwave-assisted digestion methods that yield 'total' or 'near-total' recoveries while avoiding the use of HF acid. As inductively coupled plasma mass spectrometry (ICP-MS) is the method of detection, it is desirable to minimize the use of HCl to avoid spectral interferences caused by high Cl- concentrations. Using certified reference materials, we performed a series of modifications to the US EPA method 3051 which included: increasing the temperature and durations of microwave digestion, varying the ratio of sample mass to acid volume, and alterations to the compositions of the acid digestion mixture. The experiments were conducted using urban particulate matter (NIST-1648), coal fly ash (NBS-1633) and six CANMET certified reference materials (Till-2, Till-3, Till-4, LKSD-1, LKSD-2 and LKSD-4), in two laboratories (Health Canada and Environment Canada) using different microwave digestion systems and different ICP-MS instruments. Our modified microwave-assisted nitric acid digestion method improved recoveries for Pb, Zn, V, Fe and Cu approaching 'total' recoveries in the same matrices determined using X-ray fluorescence (XRF) and instrumental neutron activation analysis (INAA) as reported in the certificates of analysis. Recoveries for other elements such as Cr and Ni compared well with 'near-total' recoveries yielded by traditional (non-assisted) acid digestion methods.

The use of vegetated wetlands for accelerating pesticide removal from agricultural runoff is gaining acceptance as a best management practice. In this study, the dissipation of five cotton pesticides – endosulfan, chlorpyrifos, aldicarb, prometryn and diuron – was quantified in cotton field runoff water contained in glasshouse columns, under light or dark conditions. Two water samples sourced from large, non-vegetated storage dams were compared with two other water samples obtained from vegetated wetlands receiving runoff from cotton fields. All pesticides studied except chlorpyrifos dissipated significantly faster from the storage dam samples than the vegetated wetland samples. Suggested reasons include a greater number of pesticide-degrading microorganisms in the storage dam waters and/or the presence of more organic matter in the wetland samples, limiting contaminant volatilisation and hydrolysis. Exposure to light significantly reduced the rate of endosulfan removal, whereas light increased the rate of chlorpyrifos removal. Half-lives are presented for each pesticide where appropriate.

The potential for colloid-facilitated migration in contaminated sites is well known, and remediation techniques such as ultrafiltration are often considered for contaminant removal. Although this approach could be successful, the stability of the contaminant species in groundwater and the removal efficiency need to be investigated to ensure proper decontamination of moving aquifers. In our study, we have sampled contaminated groundwater near a former radioactive liquid disposal area at Chalk River, Ontario, Canada. Samples were taken in 2002 and 2004 to determine the behaviour of radiocontaminants by size fractionation using ultrafiltration, with emphasis on ⁶⁰Co and ¹³⁷Cs. The contaminant concentrations varied significantly for both contaminants in the two samples (34.5 and 25.5 Bq/l for ⁶⁰Co, 25.5 and 97.2 Bq/l for ¹³⁷Cs). On the other hand, the size fractionation (5,000 Daa nominal cut-off) remained consistent between the 2002 and 2004 samples, as most of the ⁶⁰Co (72%-83%) remained in the filtrate, while almost all of the ¹³⁷Cs (>98%) was retained along with the colloidal-sized material. Release of ⁶⁰Co and ¹³⁷Cs from the colloidal material yielded desorption coefficients (K D₋des) of 7.8 x 10⁵ and 1.7 x 10⁸ ml/g for ⁶⁰Co and ¹³⁷Cs, respectively.

Suspended particulate matter is significantly related to the degradation of air quality in urban agglomerations, generating adverse health effects. Therefore, the ability to make accurate predictions of particulate ambient concentrations is important in order to improve public awareness and air quality management. This study aims at developing models using multiple regression and neural network (NN) methods that might produce accurate 24-h predictions of daily average (DA) value of PM10 concentration and at comparatively assessing the above mentioned techniques. Pollution and meteorological data were collected in the urban area of Volos, a medium-sized coastal city in central Greece, whose population and industrialization is continuously increasing. Both models utilize five variables as inputs, which incorporate meteorology (difference between daily maximum and minimum hourly value of ground temperature and DA value of wind speed), persistency in PM10 levels and weekly and annual variation of PM10 concentration. The validation of the models revealed that NN model showed slightly better skills in forecasting PM10 concentrations, as the regression and the NN model can forecast 55 and 61% of the variance of the data, respectively. In addition, several statistical indexes were calculated in order to verify the quality and reliability of the developed models. The results showed that their skill scores are satisfying, presenting minor differences. It was also found that both are capable of predicting the exceedances of the limit value of 50 μg/m³ at a satisfactory level.

Samples of pig slurry, as well as dairy and poultry manures collected in Brittany (western France) were analysed to test the ability of sterol profiles to provide a fingerprint of pig slurry contribution to soil organic matter. The data show that the 5β-stanol, known as coprostanol, is the most abundant sterol present in pig slurry, whereas this compound occurs only in minor amounts in both poultry and dairy manures. Moreover, systematic variations of (campesterol + sitosterol)/cholesterol (i.e., C₂₈₊₂₉/C₂₇) and (coprostanol + epi-coprostanol)/cholesterol (i.e., 5β/C₂₇) ratios allow to discriminate clearly pig slurry from poultry and dairy manures. The robustness of the pig slurry “sterol fingerprint” was tested by analysing the sterol profiles of soil samples from an experimental field that had received a massive pig slurry input between 10 to 14 years ago. The results indicate that the specific sterol profile of pig slurry is conservative once the slurry has been incorporated into the soil. In particular, the diagnostic 5β/C₂₇ ratio proves to be constant with time in soils having received pig slurry application, even 10 years after the end of the application. The “sterol fingerprint” of pig slurry is thus sufficiently distinctive from dairy and poultry manures, and also sufficiently time-resistant, to be of diagnostic value in determining whether a soil sample was once contaminated by pig slurry.

A total of nine sediment cores were collected from the five deep basins of Kejimkujik Lake, located in southwestern Nova Scotia, Canada, in order to track changes related to surface-water acidification and to test reproducibility of results between sediment cores from different basins in a large lake. Present-day and pre-industrial (c. 1850) samples were analyzed from all cores and detailed diatom profiles were undertaken on three cores to determine the timing of acidification. All three detailed diatom profiles show declines in inferred pH starting in the early 1930-1940s. Since the 1940s, diatom-inferred lakewater pH has declined from a background pH of ~5.8 (± 0.4) to a current diatom-inferred pH of ~4.9 (± 0.1). This corresponds to the current (2001-2002) range of measured lakewater pH = 4.7-5.2 with a mean pH = 4.9. Species diversity of diatoms also declines markedly in all cores with the Hill's N2 index decreasing from ~5 to near 1. The pre-impact diatom assemblages were dominated by Aulacoseira spp. and have since changed to dominance by Asterionella ralfsii var. americana (>45 μm). All nine sediment cores showed similar changes in diatom assemblages, diatom-inferred pH, and timing of the onset of acidification. Thus, paleolimnological inferences from deepwater sediment cores were highly reproducible in this large, morphometrically complex lake system.

Concentration levels of 11 lower carbonyls were studied at Montelibretti, a semi-rural area near Rome, Italy, over July-September 2005 and February 2006. In both periods the most abundant carbonyls were acetone and formaldehyde, followed by methylglyoxal, acetaldehyde and hexanal. Monthly variation was apparent with maximum values observed in July, when levels at least a factor two higher compared to the successive months were observed. In summer all carbonyls except acetone were reasonably well correlated among themselves and with ozone. In addition very high formaldehyde/benzene concentration ratios were measured in the summer months compared to February. These findings indicated that photochemical reactions should be the major source of carbonyls in summer. Ranking of carbonyls respect to ozone production potential emphasized the predominance of formaldehyde and methylglyoxal, followed at a distance by glyoxal and acetaldehyde.

Naturally high total dissolved solids and upstream agricultural runoff often mask the influence of urban land cover on stream chemistry and biology. We examined the influence of headwater urbanization on the water chemistry, microbiology, and fish communities of the Big Brushy Creek watershed, a 96 km² drainage basin in the piedmont of South Carolina, USA. Concentrations of most major anions and cations (especially nitrate, sulfate, chloride, sodium, potassium, and calcium) were highest in the urban headwaters and decreased downstream. Generally, the highest concentrations of suspended coliform bacteria occurred in the urban headwaters. In contrast, stream habitat quality and the abundance, species richness, and species diversity of fishes did not differ significantly between urban and rural sites. Discharge of wastewater treatment plant effluent at one rural location caused an increase in concentrations of many solutes and possibly the abundance of benthic algae. We hypothesize that atmospheric dry deposition and domestic animal wastes are important sources of stream solutes and of coliform bacteria, respectively, in the urban headwaters. The lack of significant differences in fish abundance and diversity between urban and rural sites may indicate that urban development in the Big Brushy Creek watershed has not yet degraded habitat conditions greatly for stream fishes. Alternatively, agriculture or other land uses may have degraded stream habitat quality throughout the watershed prior to urbanization.

Clinoptilolite is investigated as a possible regenerable sorbent for acid rock drainage based on its adsorption capacity for Zn, adsorption kinetics, effect of pH, and regeneration performance. Adsorption of Zn ions depends on the initial concentration and pH. Adsorption/Desorption of Zn reached 75% of capacity after 1–2 h. Desorption depended on pH, with an optimum range of 2.5 to 4.0. The rank of desorption effectiveness was EDTA > NaCl > NaNO₃ > NaOAc > NaHCO₃ > Na₂CO₃ > NaOH > Ca(OH)₂. For cyclic absorption/desorption, adsorption remained satisfactory for six to nine regenerations with EDTA and NaCl, respectively. The crystallinity and morphology of clinoptilolite remained intact following 10 regeneration cycles. Clinoptilolite appears to be promising for ARD leachate treatment, with significant potential advantages relative to current treatment systems.

The determination of stomatal ozone fluxes is essential to assess the potential damage to plants due to ozone uptake. This parameter is not accessible directly with measurements, but can be deduced through algorithms using observational data. Total ozone fluxes and water vapour fluxes are generally used. Water vapour fluxes give an indication on stomatal aperture, which is the controlling factor of ozone uptake by vegetation. In this work, a series of observations made during the growing season over an onion field are used to show the equivalence of two algorithms found in the literature to derive ozone stomatal fluxes and both based on the similarity between ozone stomatal fluxes and water vapour stomatal fluxes. One of these algorithms uses the Penman-Monteith approach, where the water vapour pressure deficit is calculated using air temperatures; the second calculates, with another formulation, the water vapour deficit from the leaf temperature. The two approaches lead to the same results if applied properly, as shown in this work, both theoretically and numerically.