Prediction models of CO, SPM and SO2 concentrations in the Campo de Gibraltar Region, Spain: a multiple comparison strategy

The 'Campo de Gibraltar' region is a very industrialized area where very few air pollution studies have been carried out. Up to date, no model has been developed in order to predict air pollutant levels in the different towns spread in the region. Carbon monoxide (CO), Sulphur dioxide (SO(2)) and suspended particulate matter (SPM) series have been investigated (years 1999-2000-2001). Multilayer perceptron models (MLPs) with backpropagation learning rule have been used. A resampling strategy with two-fold crossvalidation allowed the statistical comparison of the different models considered in this study. Artificial neural networks (ANN) models were compared with Persistence and ARIMA models and also with models based on standard Multiple Linear Regression (MLR) over test sets with data that had not been used in the training stage. The models based on ANNs showed better capability of generalization than those based on MLR. The designed procedure of random resampling permits an adequate and robust multiple comparison of the tested models. Principal component analysis (PCA) is used to reduce the dimensionality of data and to transform exogenous variables into significant and independent components. Short-term predictions were better than medium-term predictions in the case of CO and SO(2) series. Conversely, medium-term predictions were better in the case of SPM concentrations. The predictions are significantly promising (e.g., d (SPM 24-ahead) = 0.906, d (CO 1-ahead) = 0.891, d (SO2 1-ahead) = 0.851).     

Comparison of ALAD activities of Citrobacter and Pseudomonas strains and their usage as biomarker for Pb contamination

Delta-aminolevulinate dehydratase (ALAD) activity has been used in prokaryotes and eukaryotes as a biomarker for environmental lead (Pb) exposure and toxicity. Microorganisms are sensitive indicators of toxicity at the fundamental level of ecological organization, but bacterial biomarker studies are focused on the Pseudomonas strains in Group I and E coli. The objectives of the present work were to determine if Burkholderia gladioli belonging to group II, due to its 16SrRNA similarity, can be used as biomarker in metal contamination and compare its possible usage with Pseudomonas aeruginosa and Citrobacter freundii (previously known as Esherichia freundii) and Bacterium freundii which are classified in Group I. In this study, ALAD activity in an environmental strains of Burkholderia gladioli, Pseudomonas aeruginosa, Citrobacter freundii were investigated to evaluate potential inhibition by Pb and other toxic metals. When the ALAD activity of Burkholderia gladioli was tested, Co and Pb decreased activity by 27 and 71%, respectively. In addition to these findings, Zn increased the activity up to 26%. These effects were found to be statistically meaningful (p < 0.05). It was determined that the increase of lead concentration inhibites the ALAD activity at each of the three strains. There was a statistically significant dose–response relationship between ALAD activity in cells of Burkholderia gladioli and Pb (Pearson correlation coefficent = −0.665; r ² = 0.665, and p < 0.001). The strongest ALAD inhibition which was measured was 90% at Burkholderia gladioli when protein extracts were incubated with 750 μM of Pb. The relationship between Pb and ALAD activity was statistically described by [ALAD Activity] = 0.476−0.000597 × [Pb]. According to the obtained results, we suggest that the ALAD of Burkholderia gladioli can be used as a biomarker for lead contamination in the environment.     

Characteristics of atmospheric carbonyls and VOCs in Forest Park in South China

The diurnal variation of atmospheric carbonyls and VOCs in a forest in south China were studied in summer 2004. Twenty kinds of carbonyls and eight kinds of VOCs were identified and quantified. Formaldehyde and acetaldehyde were the two most abundant carbonyls, while the most abundant VOCs were isoprene, followed by o-xylene. Most C₃-C₁₀ carbonyls had higher concentrations from 09:00 to 15:00, and their levels were lower during night-time and often reached the lowest in early morning. Formaldehyde and acetaldehyde, however, showed two high levels in their diurnal patterns partly due to their different sources and sinks. The VOCs had different diurnal patterns compared to most carbonyls. The highest concentrations were observed from 03:00 to 06:00 for 1-butene, from 06:00 to 12:00 for isoprene, and from 12:00 to 15:00 for α-pinene. The highest levels for aromatic hydrocarbons occurred during midnight and the lowest in late afternoon. According to the study, emissions from vegetation and photo-oxidation of gas-phase hydrocarbons were the main sources for some carbonyls and VOCs in this region. Other compounds, such as formaldehyde, acetaldehyde and BTEX, showed anthropogenic sources.     

Monitoring of the ecotoxicological hazard potential by polar organic micropollutants in sewage treatment plants and surface waters using a mode-of-action based test battery

We propose and evaluate a mode-of-action based test battery of low-complexity and in-vitro bioassays that can be used as a routine monitoring tool for sewage treatment efficiency and water quality assessment. The test battery comprises five bioassays covering five different modes of toxic action. The bioluminescence inhibition test with Vibrio fischeri and a growth rate inhibition test with the green algae Pseudokirchneriella subcapitata are measures of non-specific integrative effects. A second endpoint in the algae test, the specific inhibition of the efficiency of photosynthesis, gives an account of the presence of herbicides. An enzymatic assay covers an important aspect of insecticidal activity, the inhibition of the acetylcholine esterase activity. Estrogenic effects are assessed with the yeast estrogen screen (YES) and genotoxicity with the umuC test. Three field studies, each lasting six to seven consecutive days, were undertaken at a sewage treatment plant (STP) in Switzerland. Samples were collected in summer and late autumn, under dry and rainy conditions. None of the bioassays gave positive results with raw water in whole effluent toxicity testing. Therefore, water samples from various sites during wastewater treatment and from surface water were enriched with solid-phase extraction. The focus was on non-volatile compounds of average to moderate hydrophobicity, a range that includes most pesticides, biocides and pharmaceuticals. Various polar solid phases were evaluated for their extraction efficiency, disturbance by matrix components and overall performance. We finally selected a mixture of a polymeric sorbent and a C18-sorbent, Lichrolut EN and RP-18 or, alternatively, Empore SDB-RPS disks. All bioassays gave clear and robust responses with the SPE extracts. With the bioassay data the treatment efficiency of the STP can be assessed with respect to different modes of toxic action and accordingly different groups of micropollutants. Furthermore, the data allowed for a comparison between the effluent and the receiving river. In all bioassays the primary effluent had a strong effect and this effect was reduced after passing the STP. Treatment efficiency was high (typically over 90%) but varied from bioassay to bioassay, which is expected because each bioassay detects different types of micropollutants and therefore we cannot expect a common answer.     

Design and evaluation of an inlet conditioner to dry particles for real-time particle sizers

Real-time particle sizers provide rapid information about atmospheric particles, particularly peak exposures, which may be important in the development of adverse health outcomes. However, these instruments are subject to erroneous readings in high-humidity environments when compared with measurements from filter-based, federal reference method (FRM) samplers. Laboratory tests were conducted to evaluate the ability of three inlet conditioners to dry aerosol prior to entering a real-time particle sizer for measuring coarse aerosols (Model 3321 Aerodynamic Particle Sizer, APS) under simulated highly humid conditions. Two 30 day field studies in Birmingham, AL, USA were conducted to compare the response of two APSs operated with and without an inlet conditioner to that measured with FRM samplers. In field studies, the correlation of PM(10-2.5) derived from the APS and that measured with the FRM was substantially stronger with an inlet conditioner applied (r2 ranged from 0.91 to 0.99) than with no conditioner (r2 = 0.61). Laboratory experiments confirmed the ability of the heater and desiccant conditioner to remove particle-borne moisture. In field tests, water was found associated with particles across the sizing range of the APS (0.5 microm to 20 microm) when relative humidity was high in Birmingham. Certain types of inlet conditioners may substantially improve the correlation between particulate mass concentration derived from real-time particle sizers and filter-based samplers in humid conditions.     

Toxic equivalent concentrations (TEQs) for baseline toxicity and specific modes of action as a tool to improve interpretation of ecotoxicity testing of environmental samples

The toxic equivalency concept is a widely applied method to express the toxicity of complex mixtures of compounds that act via receptor-mediated mechanisms such as induction of the arylhydrocarbon or estrogen receptors. Here we propose to extend this concept to baseline toxicity, using the bioluminescence inhibition test with Vibrio fischeri, and an integrative ecotoxicity endpoint, algal growth rate inhibition. Both bioassays were validated by comparison with literature data and quantitative structure-activity relationships (QSARs) for baseline toxicity were developed for all endpoints. The novel combined algae test, with Pseudokirchneriella subcapitata, allows for the simultaneous evaluation of specific inhibition of photosynthesis and growth rate. The contributions of specific inhibition of photosynthesis and non-specific toxicity could be differentiated by comparing the time and endpoint pattern. Photosynthesis efficiency, measured with the saturation pulse method after 2 h of incubation, served as indicator of specific inhibition of photosynthesis by photosystem II inhibitors. Diuron equivalents were defined as toxicity equivalents for this effect. The endpoint of growth rate over 24 h served to derive baseline toxicity equivalent concentrations (baseline-TEQ). By performing binary mixture experiments with reference compounds and complex environmental samples from a sewage treatment plant and a river, the TEQ concept was validated. The proposed method allows for easier interpretation and communication of effect-based water quality monitoring data and provides a basis for comparative analysis with chemical analytical monitoring.     

Quantitative arsenic speciation in two species of earthworms from a former mine site

The relationship between the total arsenic concentration and the chemical speciation of arsenic in two species of earthworm (Lumbricus rubellus and Dendrodrilus rubidus) in relation to the host soil, was investigated for 13 sites of varying arsenic content, including a background level garden soil and a former mine site at the Devon Great Consols, UK. Earthworms were collected with the host soil (As soil concentration range 16-12, 466 mg kg(-1) dry weight) and measured for their total arsenic (concentration range 7-595 mg kg(-1) dry weight) using inductively coupled plasma mass spectrometry (ICP-MS). A methanol-water mixture was used to extract arsenic species from the earthworms prior to determination of the individual arsenic species by a combination of anion and cation exchange high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A gradient elution anion exchange method is presented whereby nine arsenic species could be measured in one sample injection. Arsenic species were identified by comparison of retention times and sample spiking with known standards and a fully characterised seaweed extract. Arsenic was generally present in the earthworm as arsenate (As(V)) or arsenite (As(III)) and arsenobetaine (AB). Methylarsonate (MA), dimethylarsinate (DMA) and three arsenosugars (glycerol, phosphate, sulfate) were present as minor constituents. These results are discussed in relation to the mechanisms for coping with exposure to soil bound arsenic.     

Origin and characterisation of microparticles in an ice core from the Central Dronning Maud Land, East Antarctica

The scanning electron microscopy-energy dispersive spectroscopic (SEM-EDS) study of selected samples from an ice core collected from Central Dronning Maud Land (CDML), East Antarctica, revealed several microparticles. They are mainly siliceous and carbonaceous particles and have distinct variations in their shape and composition. The morphology and major element chemistry of the particles suggest their origin from either volcanic eruptions or continental dust. The EDS analysis revealed that the volcanic particles are enriched in silica (average SiO2 62%), compared to the continental dust particle (average SiO2 56%). We found that the tephra relating to Agung (1963) and Karkatau (1883) volcanic eruptions, as recorded, in the ice core harbored microbial cells (both coocoid and rods). The occurrence of organic and inorganic particles which bear relation to volcanic eruption and continental dust implies significant environmental changes in the recent past.     

Cross-border response of mosses to heavy metal atmospheric deposition in Southeastern Bulgaria and European Turkey

First cross-border atmospheric pollution of 11 heavy metals and toxic elements assessed by Hypnum cupressiforme was reported for a part of Southeastern Europe (Southeastern Bulgaria and European Turkey). Moss monitoring technique followed the main requirements of European Moss Survey. Moss samples were collected in April 2006 both in Bulgaria and Turkey. Concentration of Al, As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, V, and Zn were determined by ICP-AES. Interlaboratory parallel calibration (exchanged four moss samples from each country), standard reference moss materials (M2 and M3) results ensured the study. ANOVA showed no differences between measured results in both laboratories at the 99% confidence level. Principle Component Analyze proved two factors: F1 group of Al, As, Cd, Cr, Fe, Ni, and V and F2 of Cu, Pb, and Zn as main atmospheric pollutants. Results obtained showed approximately Cu and Pb high concentrations around Istanbul and Burgas and Zn pollution in Istanbul district. Arsenic cross-border atmospheric pollution in the study area of Southeastern Europe was found.