Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia Usneoides (L.) in an industrialized area in Rio de Janeiro state, south east Brazil--Part I: PCDD and PCDF

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic Bromeliad species as biomonitor and measuring total deposition rates on funnels covered with polyurethane foams. Samples were collected during 78 days in V.R. and 95 days in PNI in winter (dry season, June-August 2003) and during 114 days in both areas in summer (rainy season, December 2003-February 2004). The PCDD/PCDF deposition rates ranged from 0.10 to 1.9 pg WHO-TEQ/(m2 day) in winter and from 0.11 to 2.2 pg WHO-TEQ/(m2 day) in summer. Deposition rates found in V.R. in summer were four- to ninefold higher than those measured in PNI, while in winter deposition rates in both regions were in the same range. Deposition rates in V.R. in summer were about five fold lower than those measured in 1996. PCDD/PCDF levels in biomonitor samples were between 0.95 and 14.6 ng WHO-TEQ/kg d.m. in winter and between 2.2 and 5.2 ng WHO-TEQ/kg d.m. in summer. In winter, concentrations found in V.R. were up to 11 times higher than those found in PNI, while in summer the levels measured in both areas were comparable. The homologue and isomer profiles found in the deposition as well as in the biomonitor samples from V.R. indicate that steel production is the main source of contamination in the region, whereas in PNI, the long range transport of these pollutants is the predominant contamination pathway.     

Ground laser remote sensing measurements of a Saharan dust outbreak in Central Spain. Influence on PM10 concentrations in the lower and upper Spanish plateaus

This paper presents the hourly evolution of a severe Saharan dust outbreak, (SDO), affecting Central Spain over July 23-24, 2004 measured with a laser remote sensing device at a location close to the Guadarrama mountain range foothills and its impact on PM10 levels (particles with an aerodynamic diameter below 10 microm) recorded at four contrasting monitoring stations located in the upper and lower Spanish plateau, some 170km apart. During the period of study the Saharan dust layer, (SDL), presented significant hourly variability in height (3600-1500m), depth (1500-700m) and aerosol dust loading (extinction coefficient, EC, 0.22-1.28km(-1)). Overnight layering was generally observed whereas a well mixed layer prevailed in the afternoon. The (SDO) impact on the lower levels took place approximately 12h after the (SDL) was initially observed and triggered by a descending dust enriched, evidencing the important role of subsidence over the presence of dust in lower altitudes. During the event, PM10 levels at all the stations exceeded EU air quality daily mean standards, 50 microgm(-3), on 2-4days. The maximum values ranged from 185 to 245 microgm(-3) depending on the monitoring station. The impact on PM10 spread from 2days in the upper plateau to 3-4 in the lower plateau, in agreement with the geographical location of the monitoring stations with respect to the southwest origin of the intrusion. The impact was even more dramatic on PM10 hourly concentrations, leading to maximum hourly peaks ranging from 322 to 598 microgm(-3) again depending on the monitoring station. Correlations between EC vertical profiles and PM10 hourly concentrations at the monitoring stations showed the great influence of the (SDO) on surface concentrations. The best linear fits corresponded to the extinction coefficients in the lower altitudes (close to the lower range of the device 500-650m), EC2, yielding satisfactory correlation coefficients ranging from 0.68 to 0.71. The low variability of the slope of each individual linear fit, 19.2%, shows the similar impact of (SDO) on the PM10 hourly concentrations recorded in the area under study.     

Evaluation of genotoxicity and toxicity of water and sediment samples from a Brazilian stream influenced by tannery industries

This paper reports results of genotoxicity and toxicity studies of water and sediment samples collected from the Estancia Velha stream of southern Brazil, a stream transporting both domestic sewage and effluents from regional factories working in the leather industry. Three sites were selected: in the stream headwaters (Site 1), located downstream of an urban area (Site 2), and near the basin outfall (Site 3). Results obtained with Allium cepa showed no evidence of chromosomal mutation, either in water or in sediment, during winter or summer seasons, but samples collected below Site 1 showed high toxicity. Physical and chemical analyses showed high concentrations of pollutants at these sites. Ecotoxicity tests with Daphnia magna and Ceriodaphnia dubia measured toxicity in water from Sites 2 and 3 in summer 2004. A toxic effect on Hyalella azteca was only found in sediment from Site 3 during winter 2003 and summer 2004. The results suggest that the synergy among different compounds in domestic and industrial sewage discharges can make it difficult to maintain system stability.     

Assessment of the pollution impact on biomarkers of effect of a freshwater fish

Changes in biomarkers of fish captured from stressed environments may represent a reliable tool in revealing sublethal effects of the pollutants found in aquatic ecosystems. The response patterns of selected biochemical and morphological variables biomarkers of effect were assessed in adult females of an indigenous teleost Cnesterodon decemmaculatus, caught at a polluted site (San Francisco) of the Reconquista river (Buenos Aires, Argentina). Combined field-caging experiments with controlled laboratory exposure to clean media were performed. The biochemical parameters measured were specific activities of gill (Na+ + K+)-ATPase, liver AlaAT and AspAT, and brain AChE; LSI and CF were also calculated. The changes in gill (Na+ + K+)-ATPase and liver AlaAT activities of fish captured in the field in most cases were reversible after transfer to clean media. The results were interpreted in association with the physicochemical profile of the water samples taken simultaneously with the capture of the fish. Results suggested the suitability of the test species used as tools in environmental monitoring programs of risk assessment.     

Spatial variance in multimedia mass balance models: comparison of LOTOS-EUROS and SimpleBox for PCB-153

The aim of this study was to determine whether nested generic box models can be used to predict spatial variance. An inter-comparison study was performed for the nested box model SimpleBox, and the spatially resolved model LOTOS-EUROS, using PCB-153 emissions in Europe as an example. We compared the two models concerning (1) average environmental concentrations, (2) spatial concentration variances, (3) spatial concentration patterns (maps), and (4) agreement with measured concentrations for the air and soil compartments. In SimpleBox, the spatial concentration variances and patterns were calculated subsequently for each separate grid cell surrounded by a regional and a continental shell with homogeneous, averaged circumstances. Average European PCB-153 concentrations calculated by LOTOS-EUROS and SimpleBox for the period 1981-2000 agree well for the air and soil compartments. Moreover, the predicted concentrations of both models are in line with the measured PCB-153 concentrations in Europe during that period. For PCB-153, the prediction of spatial concentration variances with the nested multimedia fate model SimpleBox performs adequately in most cases, except for the lower concentration boundary in the air compartment. It is concluded that SimpleBox can be used to predict the spatial maximum and average concentrations of PCB-153 in the air and soil compartments. The proposed method has to be tested systematically for different types of compounds, emission scenarios, environmental compartments and spatial scales in order to allow conclusions about the general applicability of the method.     

Comparison of different stomatal conductance algorithms for ozone flux modelling

A multiplicative and a semi-mechanistic, BWB-type [Ball, J.T., Woodrow, I.E., Berry, J.A., 1987. A model predicting stomatal conductance and its contribution to the control of photosynthesis under different environmental conditions. In: Biggens, J. (Ed.), Progress in Photosynthesis Research, vol. IV. Martinus Nijhoff, Dordrecht, pp. 221-224.] algorithm for calculating stomatal conductance (g(s)) at the leaf level have been parameterised for two crop and two tree species to test their use in regional scale ozone deposition modelling. The algorithms were tested against measured, site-specific data for durum wheat, grapevine, beech and birch of different European provenances. A direct comparison of both algorithms showed a similar performance in predicting hourly means and daily time-courses of g(s), whereas the multiplicative algorithm outperformed the BWB-type algorithm in modelling seasonal time-courses due to the inclusion of a phenology function. The re-parameterisation of the algorithms for local conditions in order to validate ozone deposition modelling on a European scale reveals the higher input requirements of the BWB-type algorithm as compared to the multiplicative algorithm because of the need of the former to model net photosynthesis (A(n)).     

Validation of predicted exponential concentration profiles of chemicals in soils

Multimedia mass balance models assume well-mixed homogeneous compartments. Particularly for soils, this does not correspond to reality, which results in potentially large uncertainties in estimates of transport fluxes from soils. A theoretically expected exponential decrease model of chemical concentrations with depth has been proposed, but hardly tested against empirical data. In this paper, we explored the correspondence between theoretically predicted soil concentration profiles and 84 field measured profiles. In most cases, chemical concentrations in soils appear to decline exponentially with depth, and values for the chemical specific soil penetration depth (d(p)) are predicted within one order of magnitude. Over all, the reliability of multimedia models will improve when they account for depth-dependent soil concentrations, so we recommend to take into account the described theoretical exponential decrease model of chemical concentrations with depth in chemical fate studies. In this model the d(p)-values should estimated be either based on local conditions or on a fixed d(p)-value, which we recommend to be 10cm for chemicals with a log K(ow)>3.     

Element fluxes through European forest ecosystems and their relationships with stand and site characteristics

This paper describes a European wide assessment of element budgets, using available data on deposition, meteorology and soil solution chemistry at 121 Intensive Monitoring plots. Input fluxes from the atmosphere were derived from fortnightly or monthly measurements of bulk deposition and throughfall, corrected for canopy uptake. Element outputs from the forest ecosystem were derived by multiplying fortnightly or monthly measurements of the soil solution composition at the bottom of the root zone with simulated unsaturated soil water fluxes. Despite the uncertainties in the calculated budgets, the results indicate that: (i) SO4 is still the dominant source of actual soil acidification despite the generally lower input of S than N, due to the different behaviour of S (near tracer) and N (strong retention); (ii) base cation removal due to man-induced soil acidification is limited; and (iii) Al release is high in areas with high S inputs and low base status.     

ARX modeling approach to leak detection and diagnosis

This work presents a time series strategy for detection, location and quantification of leaks in large pipeline systems. The technology has two active components, which operate sequentially: the Detector and the Localizer. The Detector continuously screens real-time data, searching for any anomalies such as leaks, which are detected (or not) depending on their size and position. The Detector is based on auto-regressive multi-input/multi-output (MIMO) ARX predictors with one input filter. Subsequent to successful leak detection, the Localizer is launched to diagnose the leak via estimation of its parameters – diameter and location – using recorded data on a Search Time Window that includes information in the neighborhood of the instant of detection. The Localizer is also an ARX predictor, but with two input processors, the first is a filter for dynamic plant inputs and the second filter processes “parameter signals” of active leaks. The Localizer is developed beforehand via model identification with plant data under the action of known, artificially simulated, leaks. It is, therefore, able to recognize an active pattern of leak parameters, by maximizing the adherence of its predictions to data in the Search Time Window. The proposed detection and location methods were successfully tested in simulated leak scenarios for an industrial naphtha pipeline.