Exploratory analysis of data sets with missing elements and outliers

The main goal of the presented paper was to develop a general strategy allowing exploration of contaminated data sets with missing elements, based on application of robust PLS for initial estimation of missing elements. Using robust distance, the outlying elements were identified. After their identification and replacing by missing elements, the expectation-maximization algorithm (which can be built in into different computational procedures, such as principal component analysis and its generalisation to the N-way data-the TUCKER3 model) was used for construction of the final model.     

The effects of a basic effluent on macroinvertebrate community structure in a temporary Mediterranean river

Macroinvertebrate communities and environmental variables were assessed seasonally for 1 year in a temporary river in South Portugal receiving an effluent with high conductivity, pH, sulphates, nitrates and low oxygen content. The usefulness of the ordination method canonical correspondence analysis (CCA) and the classification method cluster analysis (UPGMA) were examined to evaluate the perturbation. Macroinvertebrate samples were segregated along the first ordination axis by CCA, which in turn correlated with sulphates and nitrates. CCA produced a two-dimensional distribution of sites similar to the grouping formed by cluster analysis. In general, three or four groups were distinguished. Immediately downstream of the effluent discharge point, only taxa tolerant to low oxygen, high pH and high sulphate and nitrate concentrations were present. Further downstream, sites had a community similar to the reference sampling locations. During flowing conditions the CCA ordination axis 1 was also correlated with several classic measures of water quality (i.e. taxon richness, diversity and biotic indices). In other periods, only the percentage of Ephemeroptera, Plecoptera and Trichoptera (%EPT) and the ratio EPT/(Chironomidae + EPT) were significantly correlated with CCA axis one. This suggests that ordination methods outperform benthic indices in detecting pollution during low flows and segregated polluted from clean/recovered sites in all periods.     

Further investigation of the heavy metal content of the teeth of the bank vole as an exposure indicator of environmental pollution in Poland

The content of heavy metals in mineralised dental tissues is an indicator of the exposure of their mineral phase to heavy metals during the time of tooth development and dental tissue formation. Therefore, teeth have been used as bio-indicators which accurately reflect the environmental or dietary exposure of animals and humans to heavy metals. This study follows from the earlier work in which it was demonstrated that the teeth from bank voles inhabiting various environmentally polluted and non-polluted forests in Southern Poland were reliable indicators of exposure to heavy metals. Using analytical techniques employed in the earlier study heavy metal concentrations were obtained in the teeth of bank voles trapped in 1998-2000 to determine if efforts to clean up the environment could be detected in changes in heavy metal concentrations in the teeth. The results show that these efforts are reflected in lower concentrations of heavy metals in the teeth but that cross border contamination remains a problem.     

Online hourly determination of 62 VOCs in ambient air: system evaluation and comparison with another two analytical techniques

This paper presents results of the processing and validation of data collected by an automatic gas chromatograph (AGC). This system was used to monitor 62 volatile organic compounds (VOCs) in urban air in the Basque Country, Spain. The nonpolar compounds (C2-C10) identified-paraffins, olefins, aromatics, and chlorinated compounds-accounted for 88% of the mass of total non-methane hydrocarbons (TNMHCs) in ambient air. The evaluation of linearity, precision, detection limits (DLs), and stability of retention times (RTs) indicates that the equipment is suitable for measuring ambient air automatically for prolonged periods (6 months). The calibration of the equipment using response factors calculated on the basis of the effective carbon number (ECN) showed variations of over 10% for acetylene, isoprene, and n-hexane. The results provided by the automatic chromatograph correlated significantly with simultaneous results from other widely used techniques for determining VOCs in ambient air: (1) portable GC, equipped with photoionization detector (PID), and (2) active adsorption on Tenax-TA followed by thermal desorption and chromatographic analysis.     

Relationship between two consecutive lactations and fat level in persistent organochlorine compound concentrations in human breast milk

An attempt was made to understand how consecutive deliveries and the following lactations have an impact on the organochlorine compound levels detected in human milk. The other goal of the study was to check for a possible dependence between fat content and the levels of the studied compounds in milk samples from the same lactations. 199 milk samples were examined for the presence of p,p'-DDT, p,p'-DDE, p,p'-DDD, alpha-, beta-, gamma-HCH and sigmaPCBs. Moreover, in 87 milk samples the fat content was additionally determined. This study has indicated that, for the mother with a shorter interval between lactations, mean concentrations of the examined compounds were higher in the milk of the first lactation than that of the second. For the other donor whose second lactation began after 2 years, the mean levels of HCB, beta-HCH, p,p'-DDD, and PCBs in her milk were higher during the first lactation. At the same time, the concentrations of p,p'-DDT and p,p'-DDE after the second delivery were slightly higher. The correlation coefficients between the two data sets (fat content in milk, concentrations of the compounds studied in milk) showed no interrelationship between them.     

The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 microg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.     

Interaction of limestone grains and acidic solutions from the oxidation of pyrite tailings

To characterise the coatings formed and to analyse element partitioning between the aqueous and solid phase, suspensions were prepared with four grain sizes of limestone and three different amounts of acidic solution from oxidized pyrite tailings. In all cases, red coatings with three different layers covered the grain surface, sealing off the acidic solution. The inner layer was composed mainly of basaluminite, the middle layer of schwertmannite, and the outer layer of gypsum and jarosite. Zn, Cd and Tl were co-precipitated by Fe and Al; As and Pb were co-precipitated almost completely by Fe; and Cu formed mainly Cu sulphates. All trace elements reached almost total precipitation at pH 6.3, but the precipitation of As and Pb tended to decrease as the pH rose. Consequently, liming should be calculated so that the soil pH does not exceed 6.3. This calculation should take into account that the armouring of the limestone grains can cause underestimations in the amount of liming material needed.     

Competitive sorption of heavy metal by soils. Isotherms and fractional factorial experiments

Competing ions strongly affect heavy metal sorption onto the solid surfaces of soil. This study evaluated competitive sorption of Cd, Cu, Ni, Pb and Zn on three soils: Calcixerollic Xerochrept, Paralithic Xerorthent and Lithic Haplumbrept. Monometal and competitive sorption isotherms were obtained at 25 degrees C. The individual effect of ions on retention of the others was ascertained by a fractional factorial analysis design. Most of the sorption isotherms belonged to type L subtype 2 in the classification of Giles. In competitive sorption the initial linear part was shorter and the knee sharper when compared with monometal sorption isotherms. Parameters related to sorptive capacity, such as Point B, Langmuir monolayer and Freundlich distribution coefficient, were higher in monometal than in competitive sorption, and in basic soils than in acidic soil. Calcium desorbed at different points of the sorption isotherms indicated that cationic exchange with Ca was the main retention mechanism in calcareous soils. For Pb, the ratio Ca desorbed/Pb sorbed was close to one; for Cu, Ni and Zn the ratio ranged from 1.20 to 1.37, probably due to partial dissolution of calcium carbonates by hydrolytic processes during retention. On the other hand, Cd had a ratio around 0.6 reflecting another additional retention mechanism, probably surface complexation. Fractional factorial design confirmed that the presence of the cations investigated reduced the amount of the five metals retained, but the presence of Cu and Pb in the system depressed Ni, Cd and Zn sorption more than the inverse. Cation mobility was enhanced when equilibrium concentration increased and the effect was higher in Ca-saturated soils.     

Oxygen levels versus chemical pollutants: do they have similar influence on macrofaunal assemblages? A case study in a harbour with two opposing entrances

Generally, harbours are polluted zones characterised by low values of hydrodynamism and oxygen in the water column and high concentrations of pollutants in sediments. The harbour of Ceuta, North Africa, has an unusual structure; it is located between two bays connected by a channel, which increases the water movement and exchange in the harbour, maintaining moderate oxygen levels in the water-sediment interface. Nevertheless, high concentration of organic matter, nutrients and heavy metals were measured in sediments from this harbour. Under these unusual conditions (high levels of pollution but total saturation of oxygen in the water column) we studied the responses of soft-bottom macrobenthic communities using uni and multivariate analyses. The number of species was similar inside and outside the harbour but the species composition differed between internal and external stations; oxygen levels seem to control the "quantity" of species whereas pollutants control the "quality" of them.