Classification and ordination of DDT and HCH in soil samples from the Guanting Reservoir, China

Organochlorine pesticides (OCPs) have been a major environmental issue, drawing much scientific and public attention due to their bioaccumulation potential, persistence and toxicity. Soil samples from three villages around the Guanting Reservoir, one of Beijing's five major water systems located to the northwest of the city, were collected in 2003 and analyzed to determine DDT and HCH-concentrations. The samples were also analyzed for soil texture, pH, and concentrations of total carbon, nitrogen and phosphorus to investigate their possible relationship to current OCP-concentrations. Hierarchical Cluster Analysis (HCA) and Principal Component Analysis (PCA) were used to study the distribution and contamination levels of OCPs within the study area. Classification splits were made to divide the 30 samples into three groups. The first group contained samples in soils from village C; the second group contained all of the samples in village B and most of the samples in village A; and the third group contained just three samples from village A, and the three samples had a relatively high concentration of OCPs. Ordination plots of the first two axes from PCA (cumulative percentage 80.91%) were constructed to explore the HCH and DDT-distribution patterns as well as the degradation ratios between the parent substances and their isomers.     

Levels of polychlorinated biphenyls in Patella piperata from the coast of Fuerteventura (Canary Islands, Spain)

Concentration of 51 PCB congeners were determined in the visceral mass of the endemic limpet Patella piperata, sampled in four stations in the coast of Fuerteventura (Canary Islands, Spain) during 1991-1995, and evaluated in order to assess the origin of their contamination and the possibility of this limpet being used as a bioindicator organism for PCB contamination. PCB extracted from samples were fractionated on Florisil columns and analysed by capillary gas chromatography with flame ionisation detector. Principal Component, Factor and Cluster Analysis were used to study the patterns and relationships among PCBs.     

A chemometric approach to the evaluation of atmospheric and fluvial pollutant inputs in aquatic systems: the Guadalquivir River estuary as a case study

To establish the quality of waters it is necessary to identify both point and non-point pollution sources. In this work, we propose the combination of clean analytical methodologies and chemometric tools to study discrete and diffuse pollution caused in a river by tributaries and precipitations, respectively.During a two-year period, water samples were taken in the Guadalquivir river (selected as a case study) and its main tributaries before and after precipitations. Samples were characterized by analysing nutrients, pH, dissolved oxygen, total and volatile suspended solids, carbon species, and heavy metals. Results were used to estimate fluvial and atmospheric inputs and as tracers for anthropic activities.Multivariate analysis was used to estimate the background pollution, and to identify pollution inputs. Principal Component Analysis and Cluster Analysis were used as data exploratory tools, while box-whiskers plots and Linear Discriminant Analysis were used to analyse and distinguish the different types of water samples.     

Groundwater characterization and potential impacts of agricultural activities in the Sers El Kef plain

Tunisia has very limited potential of surface and groundwater resources which are subject to different quantitative and qualitative forms of degradation. The risk of groundwater pollution results from the interaction between the vulnerability of aquifers to pollution and anthropogenic activities. Our research focuses on the study of the Sers water table water quality (northwest Tunisia) following the inputs used for agricultural activities in the region. Water samples were extracted from 40 wells to analyze the main physicochemical parameter indicators of the groundwater quality. The results obtained show that these waters have two major facies: Na-Cl and Ca-Mg-SO₄. The nitrate contents are relatively high suggesting that the agricultural activities are probably the most important anthropogenic source of water contamination. The results of the Standardized Principal Component Analysis (SPCA) confirm the geochemical methods and results and provide further information about the water quality of the Sers El Kef aquifer. In addition, the pollution degree differs from one site to another depending on the spreading rate of nitrogen fertilizers and the distance from the pollution source.     

Persistent organic pollutant in a fish community of a sub-alpine lake

This study investigated the presence of organochlorine pollutants in abiotic and biotic samples from Lake Como (Italy). DDTs and PCBs were found to be the major contaminants, ranging from 0.04 to 4.25 and from 0.25 to 40.8 μg/g lipid respectively. Evidence of biomagnification according to the trophic role of the investigated organisms was highlighted by means of Stable Isotope Analysis. A Trophic Magnification Factor (TMF) was calculated for the chemicals of interest and the applicability of the method for global use was confirmed. Statistically significant correlation has been found between the calculated trophic level and the concentrations of more lipophilic compounds, while for the less lipophilic (e.g., HCH, 3CBs) the relationship is no statistically significant and the TMF is close to 1.The role of the foraging area in affecting PCB and DDT concentrations within aquatic ecosystems has been highlighted by a Principal Component Analysis (PCA).     

The application of positive matrix factorization in the analysis, characterisation and detection of contaminated soils

Multivariate factor analytical techniques are widely used for the approximation, in terms of a linear combination of factors, of multivariate experimental data. The chemical composition of soil samples are multivariate in nature and provide datasets suitable for the application of these statistical techniques. Recent developments of multivariate factor analytical techniques have led to the approach of Positive Matrix Factorization (PMF), a weighted least squares fit of a data matrix in which the weights are determined depending on the error estimates of each individual data value. This approach relies on more physically significant assumptions than methods like Principal Components Analysis which is frequently used in the analysis of soil datasets. In this paper we apply PMF to characterise the pollutant source in a set of geographically referenced soil samples taken within a 200 m radius of a site characterised by a high concentration of heavy metals. Each sample has been analysed for major and minor elements (using wavelength-dispersive X-ray fluorescence spectrometry), carbon, hydrogen and nitrogen (using a CHN elemental analyzer) and mercury (using cold-vapour atomic absorption spectrometry). Analysis of the soils using PMF resulted in a successful partitioning of variances into sources related to background soil geochemistry, organic influences and those associated with the contamination. Combining these results with a geostatistical approach successfully demarcated the main source of the combined organic and heavy metal contamination.     

3-Way pattern-recognition of PAHs from Galicia (NW Spain) seawater samples after the Prestige's wreck

In November 2002 the oil tanker ‘Prestige’ released 65 000 tons of a heavy fuel oil throughout the Galician coastline (NW Spain), causing extensive damage to marine life, natural resources and economic activities at Northern Portugal, Spain and SW France. To evaluate the impact of the oil spill on the aquatic system, 30 polycyclic aromatic hydrocarbons (PAHs), including alkylated derivatives, were analyzed in seawater on five different sampling campaigns from 2002 to 2004. Sampling was made along the Galician continental shelf. In each station three samples were collected at three different depths (surface, mid-depth and bottom). Four different approaches for 3-way analyses (Catenated-PCA, Matrix-Augmented Principal Components Analysis, Parallel Factor Analysis and Procrustes rotation) have been used to asses the major sources of PAHs into the seawater. They revealed two main pollution patterns: one related to oil spillages and discharge of petroleum products, and another more associated with a diffuse anthropogenic origin.     

Heavy metal levels and solid phase speciation in street dusts of Delhi,India

Street dust samples were collected from three different localities (industrial, heavy traffic and rural) situated in the greater Delhi area of India. The samples analyzed for Cd, Zn, Pb, Ni, Cu, and Cr indicated remarkably high levels of Cr, Ni, and Cu in the industrial area, whilst Pb and Cd did not show any discernible variations between the three localities. A multivariate statistical approach (Principal Component Analysis) was used to define the possible origin of metals in dusts. The street dusts were sequentially extracted so that the solid pools of Cd, Zn, Pb, Ni, Cu, Cr could be partitioned into five operationally defined fractions viz. exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. Metal recoveries in sequential extractions were +/- 10% of the independently measured total metal concentrations. Cd was the only metal present appreciably (27.16%) in the exchangeable fraction and Cu was the only metal predominantly associated (44.26%) with organic fraction. Zn (45.64%) and Pb (28.26%) were present mainly in the Fe-Mn oxide fraction and the residual fraction was the most dominant solid phase pool of Cr (88.12%) and Ni (70.94%). Assuming that the mobility and bioavailability are related to the solubility of geochemical forms of the metals and decrease in order of extraction, the apparent mobility and potential metal bioavailability for these highly contaminated street dust samples is: Cd>Zn approximately equal Pb>Ni>Cu>Cr.     

Enhancement of source traceability of atmospheric PM by elemental chemical fractionation

During a 1-year study (“Fine dust” Project) funded by the Lazio regional government (Italy), about 1000 daily PM₁₀ and PM_2.5 samples collected from six sites in the region were subjected to chemical fractionation based on differences in elemental solubility. In this way, it was possible to achieve meaningful characterization of the elemental composition of individual samples. For most of the investigated elements, we found significant differences between the extracted and the mineralized residual fraction. In general, fine particulate was best characterized by the composition of the extracted fraction, while coarse particles from traffic-related sources were best characterized using residues. For several metals (Cd, Pb, Sn, Sb and V) having a critical environmental impact, this result was particularly clear.The application of Principal Component Analysis (PCA) and receptor modelling (PCR) to the data set allowed us to evidence the enhancement of selectivity towards different emission sources that is obtained when chemical fractionated data are considered instead of total element content. Chemical fractionation seems to generate very selective markers for specific emission sources and in particular for re-suspended road dusts, one of the main factors responsible for the increase of elemental concentrations in urban areas.     

Patterns and concentration levels of polybrominated diphenyl ethers (PBDEs) in placental tissue of women in Denmark

The levels and congener patterns of PBDEs were investigated in human placental samples in Denmark. The median concentrations of ∑PBDE_tri-hepta and BDE-209 in the 50 samples were 1.22 and 1.14 ng g⁻¹ lw, respectively, with the total sum ranging from 0.51 to 17.1 ng g⁻¹ lw, which is similar to previous placental studies. The PBDE content in placental tissue was dominated by BDE-209, which accounted for approximately 50% of the total amount of PBDEs. BDE-47, -99, and -153 were detected in all samples. Approximately equal amounts of BDE-47 and BDE-153 were observed in the placental tissue, which is in agreement with previous European studies of human serum. Principal Component Analysis (PCA) was performed to analyze congener patterns within and between mothers. The loading plot showed groupings of the measured PBDE variables in three groups, representative of Penta-, Octa- and Deca-BDE technical mixtures. Congeners representing the individual technical mixtures were close to orthogonal or inversely correlated, indicating variation in the congener patterns of internal exposure corresponding to the patterns of technical mixtures used in products. Visualisation of the participant objects according to body mass index (BMI), revealed inherent congener patterns (19% X-variance) showing increased frequency for participants within the highest BMI group to have elevated concentrations of BDE-209 in the placental tissue.     

Polychlorinated biphenyls in two mollusc species from the coast of Tenerife (Canary Islands, Spain)

Levels of PCBs were determined in two marine organisms, limpets (Patella ullisiponensis aspera) and winkles (Ossilinus atratus), sampled in three stations in the south east coast of Tenerife during 1993. Winkles and limpets exhibited different PCB patterns. Principal Component Analysis (PCA) was used to study the patterns and the relationships among PCBs.     

Correlation patterns of metals in the epiphytic moss Hypnum cupressiforme in Bavaria

Since 1981, the Bavarian State Office for Environmental Protection (LfU) has been operating a bioindication network of epiphytic mosses Hypnum cupressiforme located on a regular grid with distances 16 km, in order to observe immission-derived metal accumulation in plant material. About 300 specimens are collected yearly (since 1991 every second year) at the end of the growth period, and the concentration of trace metals is determined. In order to gain insight into predominant sources of metal pollution in Bavaria, correlation patterns between Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Sb, Hg, and Pb are analyzed by Principal Component Analysis. Detailed results are presented for the 1984 and 1995 data. At least 80% of the variance can be explained by five components. The following factors are extracted from both data sets by varimax rotation: factor 1 with similar loadings of Al, Ti, V, Cr, Fe, and As; factor 2 representing Cd and Zn; factor 3 with loadings of Sb, Pb, and Cu; factor 4 representing Mn; factor 5 being nearly identical with the Hg variable. For comparison, published region-specific correlation matrices from the 1991 moss survey performed by the German Federal Environmental Agency (UBA) – observing epigeic mosses Pleurozium schreberi – were submitted to Principal Component Analysis. With respect to the first factor, our 1991 results from Bavaria are similar to those from the Southern former GDR, but different from those from Western Germany (including Bavaria). Possible common and specific sources are discussed.     

Pattern recognition and classification of sediments according to their metal content using chemometric tools. A case study: the estuary of Nerbioi-Ibaizabal River (Bilbao, Basque Country)

Chemometrics are increasingly used in environmental monitoring studies, but are still far from being accepted as routine tools by field specialists. The multivariate character of usually highly correlated environmental data recommends the use of advanced chemometrics as part of the analytical methodology in order to get information on the basic structure of data. In this work, we have applied a battery of non-supervised (Principal Component Analysis (PCA)) and supervised (k-Nearest Neighbour (k-NN), Soft Independent Modelling of Class Analogies (SIMCA), Linear Discriminant Analysis (LDA) and Artificial Neural Networks (ANNs)) multivariate techniques on a specific environmental dataset. The dataset consists on the concentration of 14 elements (Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V and Zn) in 95 sediments collected at eight different locations of the estuary of the Nerbioi-Ibaizabal River (Bilbao, Basque Country) during 12 sampling campaigns conducted every 3 months between 2005 and 2008. The study aims to present a simple methodology of general applicability which may result in a flexible and practical tool to assess chemical pollution in sediments of a given specific site.     

Dioxin and dibenzofuran concentrations in adipose tissue of a general population from Tarragona, Spain

Polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) levels were determined in adipose tissue of 15 autopsied subjects who at the time of death had lived in the city of Tarragona (Catalonia, Spain) and surroundings during at least the last 10 years. PCDD/F concentrations ranged between 13.37 and 69.37 ng I-TEQ/kg fat, with mean and median values of 30.98 and 26.30 ng I-TEQ/kg fat, respectively. PCDD/F concentrations were higher (p < 0.01) in women (mean value: 44.95 ng I-TEQ/kg fat) than in men (mean value: 24.00 ng I-TEQ/kg fat). Although individuals living in industrial areas showed higher PCDD/F levels than those living Tarragona downtown the difference was not statistically significant. When Principal Component Analysis was applied to the concentrations of PCDD/Fs found in the 15 adipose tissue samples together with those found in 20 blood samples collected in a previous study, a single two-dimensional model was obtained, which would explain 62.9% of the variance in the data. The PCDD/F concentrations in adipose tissue found in the current study are of the same order of magnitude than those reported for most industrialized countries.     

Disposition of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in two Norwegian epibenthic marine food webs

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a group of halogenated hydrocarbons, comprising 210 different, theoretically possible congeners. They are relatively hydrophobic and persistent to biodegradation, thereby rendering them subject to bioaccumulation. This study was conducted in Frierfjord and Eidangerfjord in the Grenland fjord system, Norway, heavily polluted by PCDD/PCDF discharges from the magnesium production at Herøya from 1951 to 2001. Pooled samples of surface-sediments and the following organisms were collected for the Frierfjord and Eidangerfjord study areas: common shrimp (Crangon crangon), polychaetes (mainly Nereis diversicolor), shore crab (Carcinus maenas), cod (Gadus morhua), flounder (Platichthys flesus), trout (Salmo trutta), herring (Clupea harengus), benthic amphipods and zooplankton. Concentrations of 2,3,7,8-PCDD/Fs were quantified in pooled samples for all species. The relative abundances of stable isotopes of nitrogen (δ¹⁵N) were evaluated in the organisms as a measure of chemically-derived trophic level. Contrary to earlier studies on other persistent organochlorines, it was found that the concentrations of PCDD/Fs declined with increasing trophic level. Principal Component Analysis (PCA) also showed differences between species in the pattern of PCDD/Fs. Higher chlorinated congeners constituted lower percentages of the PCDD/F-concentrations higher in the food chain as compared to lower trophic levels. In general, congener patterns did not differ between fjords. Infauna (polychaetes) and zooplankton had congener patterns most similar to the pollution source. The results indicate lower accumulation of higher chlorinated congeners in species at higher trophic levels (fish), presumably due to low membrane permeability (high molecular size) and possibly slow transport through intestinal aqueous phases because of low aqueous solubility.     

Functional biodiversity of microbial communities in aerobic selector slaughterhouse wastewater.

The biodiversity of the microbial communities of an aerobic selector and a conventional system treating slaughterhouse wastewater were evaluated using the Biolog technique (Biolog Inc., Hayward, California). Principal components analysis of patterns and level of microbial activity indicate that microbial communities statistically differentiate between the selector and conventional system. Biolog data indicated that there was seasonal variation in the structure and function of the microbial community in conventional samples, which may be a useful indicator of wastewater community disturbance and unsteadiness, while, for the selector system, there were no recognizable statistical differences between winter and summer data communities, Biodiversity indices indicated that the selector system maintained a high functional diversity (Shannon-Weaver diversity index [H'] from 3.8 to 4.6) than the conventional system (H' from 1.8 to 2.8). The high values in the selector system were a reflection of the fact that most of the carbon sources were used, contributing to the very high Shannon indices. In addition, the high substrate equitability values (J) obtained for the selector samples indicated that the microbial communities between the summer and winter samples used the carbon sources in the same proportion. In contrast, differences in the equitability of the microbial communities within the conventional system were observed. This indicated a pattern representing unevenness.     

Temporal variability of airborne bacterial community structure in an urban area

Temporal airborne bacterial genetic community structure and meteorological factors were analysed above an urban area in the northwest of France from December 2003 to April 2004 with a sampling strategy considering different time intervals (from an hour to a month). Principal component analysis (PCA) of B-ARISA (Bacterial-Automated Ribosomal Intergenic Spacer Analysis) profiles revealed a hierarchy in the temporal variability of bacterial community: daily<weekly<seasonal. Co-inertia analysis between B-ARISA data and meteorological factors demonstrated the correlation between the seasonal variability in the bacterial community and climatic conditions such as temperature and relative humidity, whereas daily and weekly variability seemed likely to be managed by other factors such as anthropogenic activities.     

Temporal trends of elements in Turin (Italy) atmospheric particulate matter from 1976 to 2001

The temporal trends of major, minor and trace elements in the total atmospheric particulate sampled in the urban area of Turin (Italy) were determined for the following years: 1976, 1986, 1996 and 2001. The wavelength dispersive X-ray fluorescence (WD-XRF) technique was adopted to determine the concentrations of Ba, Br, Ca, Cl, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, S, Ti and Zn. A smaller number of samples was also analysed by ICP atomic emission spectroscopy (ICP-AES) and the results were compared with those obtained by WD-XRF to confirm their validity. A clear seasonal pattern with higher concentrations of the aforementioned elements in the cold periods was observed. Moreover, a change in the chemical composition of atmospheric particulate matter was evidenced, particularly between the first (1976 and 1986) and the last (1996 and 2001) years. This change can be attributed both to the greater contribution of Pb and Br to atmospheric pollution in the past and, in recent years, to the higher level of pollutants associated with increased vehicular traffic and industrial activities. The application of chemometric techniques (Principal Component Analysis and Cluster Analysis) allowed us to speculate about the main emitting sources influencing the total atmospheric particulate in these years.     

One-year study of the elemental composition and source apportionment of PM10 aerosols in Florence, Italy

An extensive investigation was carried out for the characterisation of the air particulate composition in Florence. The aim was to determine the aerosol elemental concentrations, as well as to identify pollution sources. For our investigation, the external Particle-Induced X-Ray Emission-Particle-Induced gamma-Ray Emission beam facility of the Istituto Nazionale di Fisica Nucleare, Van de Graaff accelerator at the Physics Department of the Florence University was used. We report the results of the analysis of a long temporal series (approximately 1 yr) of PM10 particulate samples, collected on Millipore filters on a daily basis in three different sites (characterised by different urban settings). Daily concentrations of more than 20 elements were detected. The long sampling period (approximately 1 yr) allowed a comparison with the air quality recommended values and the identification of seasonal variations. Four main sources (traffic, oil-combustion, soil-dust, and wind transported sea-salt) were extracted with the help of Principal Component Analysis (PCA). An absolute PCA showed traffic to be the major source both in the high traffic site and in the urban background site.