Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).     

The fate of fipronil in modular estuarine mesocosms

The degradation and corresponding product manifold for the pesticide fipronil was determined in three replicate estuarine mesocosms. Aqueous fipronil concentrations rapidly decreased over the 672 h timescale of the experiment (95% removal). Loss was apparently first-order in fipronil, although there appeared to be a change in the removal mechanism after 96 h that corresponded to a dramatic slowdown in its disappearance. The reduction product of fipronil, fipronil sulfide, was not detected in the water column; however, it formed rapidly in sediments and was identified as the major product of fipronil degradation in the system (20% yield at 672 h, with respect to initial fipronil concentration). Fipronil sulfone is thought to form primarily via biological oxidation; and, although it was generated rapidly in the water column (10% yield), only trace amounts were detected in the sediment (1% yield). The direct photolysis product of fipronil, fipronil desulfinyl, was present in all samples; it formed rapidly in the water column (4% yield) and partitioned into the sediment phase (7% yield) over the course of the experiment. The mass balance on fipronil and associated products was 42% at 672 h.     

Competitive Retention of Lead and Cadmium on an Agricultural Soil

Lead and cadmium contamination of an agricultural soil has been studied using batch and column experiments. Thermodynamics of theretention phenomena may be represented by a Langmuir isotherm foran aqueous metal concentration up to 100 mg L^-1. First order kinetics with respect to the solid phase yield good predictabilityfor both batch and column experiments. Kinetics and thermodynamics of lead retention predominate over those ofcadmium. As a consequence, lead is preferentially retainedand can even displace sorbed cadmium. In the event of anspill involving both metals, cadmium would move further inthe soil and its aqueous concentration downstream could beeven higher than that of the influent solution, increasingpotential risks. A two-region model has been used to fit all the experimental results. Satisfactory predictions for column experiments are obtained with parameters which are consistent with those obtained for the batch experiments, for which sorption is described by a Langmuir isotherm including competitive retention.     

Effects of meteorological conditions on PM10 concentrations - A study in Macau

Review on the annual PM₁₀ concentrations over a 10-year period shows that Macau is subjected to severe fine particulate pollution. Investigations of its variation in monthly and daily time scales with the local meteorological records reveal further details. It is found that a distinct feature of the Asian monsoon climates, the changes of wind direction, mainly controls the general trend of PM₁₀ concentration in a year. The monsoon driven winter north-easterly winds bring upon Macau dry and particle enriched air masses leading to a higher concentration in that period while the summer south-westerly winds transport humid and cleaner air to the region leading to a lower PM₁₀ value. This distinct seasonal feature is further enhanced by the lower rainfall volume and frequency as well as mixing height in winter and their higher counterparts in summer. It is also found that the development of tropical cyclones near Macau could also impose episode like PM₁₀ concentration spikes due to the pre-typhoon induced stagnant air motion followed by the swing of wind direction to the northerly.     

Risk-Based Prioritization of Air Pollution Monitoring Using Fuzzy Synthetic Evaluation Technique

Air pollution monitoring programs aim to monitor pollutants and their probable adverse effects at various locations over concerned area. Either sensitivity of receptors/location or concentration of pollutants is used for prioritizing the monitoring locations. The exposure-based approach prioritizes the monitoring locations based on population density and/or location sensitivity. The hazard-based approach prioritizes the monitoring locations using intensity (concentrations) of air pollutants at various locations. Exposure and hazard-based approaches focus on frequency (probability of occurrence) and potential hazard (consequence of damage), respectively. Adverse effects should be measured only if receptors are exposed to these air pollutants. The existing methods of monitoring location prioritization do not consider both factors (hazard and exposure) at a time. Towards this, a risk-based approach has been proposed which combines both factors: exposure frequency (probability of occurrence/exposure) and potential hazard (consequence).This paper discusses the use of fuzzy synthetic evaluation technique in risk computation and prioritization of air pollution monitoring locations. To demonstrate the application, common air pollutants like CO, NO_x, PM₁₀ and SO_x are used as hazard parameters. Fuzzy evaluation matrices for hazard parameters are established for different locations in the area. Similarly, fuzzy evaluation matrices for exposure parameters: population density, location and population sensitivity are also developed. Subsequently, fuzzy risk is determined at these locations using fuzzy compositional rules. Finally, these locations are prioritized based on defuzzified risk (crisp value of risk, defined as risk score) and the five most important monitoring locations are identified (out of 35 potential locations). These locations differ from the existing monitoring locations.     

Higher Plants As Bioindicators Of Sulphur Dioxide Emissions In Urban Environments

The evaluation of certain vascular plants that grow in the city of Madrid as biomonitors of SO₂ air pollution in urban environments has been carried out. Total concentration of sulphur in leaves of the chosen higher plants as well as other parameters in close relation to this contaminant (visible injury symptoms, chlorophyll a- and b-content and peroxidase activity) have been determined in order to study the spatial distribution and temporal changes in SO₂ deposition. Results obtained show that coniferous species such as Pinus pinea, were more sensitive to SO₂ atmospheric concentration than leafy species as Quercux ilex subspecies ballota and, in the same way, bush species, such asPyracantha coccinea and Nerium oleander, were more sensitive than wooded species, such as Cedrus deodaraandPinus pinea, respectively. There is a higher accumulation of sulphur in vegetable species located near highways and dense traffic incidence roads and near areas with high density of population. The minimum values for accumulation of SO₂ were registered in winter and spring seasons (from January to April) due to the vegetative stop; while maximum values are obtained during the summer season (from June to September), due to the stoma opening. The highest increments in sulphur concentration, calculated as the difference between two consecutive months, are obtained in May and June for all considered species except forCedrus deodara and Pyracantha coccinea, both species have few seasonal changes during the whole year. Some species are more sensitive to natural washing than others, showing a decrease in sulphur concentration after rainfall periods.     

Using Wet-FGD systems for mercury removal

A plan to control mercury emissions to the atmosphere and to establish mercury emission limits has recently been elaborated by the European Commission, making it necessary to devise an efficient and cost effective mercury removal technology. Towards this end wet flue gas desulfurization units appear as a promising option for multi-pollutant control. However, more investigation on mercury removal and a greater mercury removal efficiency are required to achieve this objective. In the present work scrubber chemistry and the application of various solid additives to enhance mercury removal in wet scrubbers is evaluated. The results obtained show a significant correlation between mercury removal efficiency and the pH of the scrubber slurry and SO2 concentration. A weaker correlation was observed between oxygen or slurry concentration and removal efficiency. Finally several solid oxides were found to be effective additives for enhancing mercury capture in wet scrubbers.     

Degradability and Sediment Sorption of an Alcohol Polyglycol Ether Surfactant Putatively Useful for the Control of Red Swamp Crayfish in Rice Fields

This work reports studies of the degradation rates of a fattyalcohol polyglycol ether non-ionic surfactant, Genapol OXD-080, putatively useful for the control of red swamp crayfish (Procambarus clarkii Girard) in rice fields under laboratory and field conditions. The influence of temperature,sediment site specificity and sorption were taken into account.The degradation kinetics of the surfactant depends on the experimental conditions: type of inocula and temperature. Thedistribution of this chemical in aquatic systems was also examined. Genapol OXD-080 was removed into the sedimentsreadily after application, and sorption was considered the majorpath of removal from the water phase. Data suggest that furtherstudies are required regarding the effects of Genapol OXD-080 in aquatic organisms resident in rice fields, in parallelwith the development of technologies related with the use ofsurfactants to control P. clarkii populations.     

Optimization of a multielement sequential extraction method employing an experimental design approach for metal partitioning in soils and sediments

The optimisation of a simple multielement extraction method employing an experimental design approach is described. The method uses centrifugation to pass one extractant solution at varying pH through a contaminated soil sample. The nature and concentration of the acid, rate of centrifugation and time, number of sequential leachates and the ratio of extractant volume: sample weight have been studied in order to obtain the optimum conditions for extraction. A fractional factorial experimental design was performed, and the results were used to identify significance which was then evaluated by carrying out a central composite experimental approach. Once optimum conditions had been obtained, sequential leaches were analysed by ICP-AES and chemometrics were employed to identify the composition of each component. Comparisons have been made with previous studies and tentative assignments, based on well defined separated fractions and percentage compositions for individual elements, used to identify the different physico-chemical components in the sample.