Use of principal component analysis to profile temporal and spatial variations of chlorinated solvent concentration in groundwater

This work aims at evaluating spatial distribution patterns of concentration variations for chlorinated solvents in groundwater, based on principal component analysis and geographic information system (GIS) tools. The study investigates long-time series of chlorinated solvent concentrations in groundwater measured for 18 contaminated industrial sites. The characterization of contaminant plumes and delineation of pollutant sources are essential for choosing appropriate monitoring and remediation strategies, as contaminated groundwaters are characterized by complex patterns of spatial and temporal concentration variability, with wide unpredictable fluctuations over time. The present work describes the results of a new exploratory statistical method called the Variability Index Method (VIM) applied to environmental data to assess the performance of using concentration variations as molecular tracers to reveal aquifer dynamics, industrial impacts, and point sources for contamination plumes. The application of this method provides a useful assessment of controls over contaminant concentration variations as well as support for remediation techniques.     

On the limits of the air pollution predictability: the case of the surface ozone at Athens, Greece

Purpose  

The aim of this study is to investigate the potential effects of increased urbanization in the Athens city, Greece on the intrinsic features of the temporal fluctuations of the surface ozone concentration (SOC).     

Long Term Monitoring of Hydrocarbon Contamination Using Multi-Level Vapor Phase Piezometers

This study evaluated the feasibility of supplementing groundwater monitoring protocols by assessing the vadose zone for the extent of residual subsurface contamination. The study also characterized the response of the soil gas signatures with respect to different soil types and degrees of contamination. A field study was conducted at a former gasoline vending station located in Ottawa, Canada. The current state of contamination was determined by analysis of soil samples taken from boreholes. A series of 10 nested soil gas wells with monitoring depths of 0.75, 1.5, 2.25 and 3.0 m were then installed. Using these wells, soil gas surveys were performed at regular intervals over an extended period to quantify Gaseous TPH (TPH g ), oxygen and carbon dioxide concentrations in the soil gas. Results indicate that soil gas wells located near the source term exhibited characteristic soil gas signatures and significant fluctuations in TPH g , oxygen, and carbon dioxide concentrations with time. Soil gas wells located beyond the soil contamination demonstrated limited correlation between TPH g , oxygen and carbon dioxide concentrations and decreased seasonal variability.     

Growth in otter (Lutra lutra) populations in the UK as shown by long-term monitoring

European otters declined dramatically from the 1950s, disappearing from many rivers. We report here on longterm monitoring (from 1977) in 3 catchments in western Britain that were recolonized naturally and in 2 catchments in eastern England that were reinforced by captive-bred otters. A minimum of 16-years data was collected on each river until 2002. At a series of sites in each study river, the percentages which were positive for otters and the number of spraints per sprainting site were recorded and combined to produce an annual index of population. One western river, naturally recolonized, showed rapid early population growth for 5 years, followed by slower growth, while growth was steadier in 2 catchments which already held some otters at the beginning of the study. Colonization on the eastern rivers was slower, with greater fluctuations over time. Annual population growth rates were estimated at 1-7%, higher in the earlier years. A strategy for annual monitoring of otters is recommended.     

Reflectance properties and physiological responses of Salicornia virginica to heavy metal and petroleum contamination

Wetland ecosystems of California are located in highly populated areas and subject to high levels of contamination. Monitoring of wetlands to assess degrees of pollution damage requires periodic retrieval of information over large areas, which can be effectively accomplished by rapidly evolving remote sensing technologies. The biophysical principles of remote sensing of vegetation under stress need to be understood in order to correctly interpret the information obtained at the scale of canopies. To determine the potential to remotely characterize and monitor pollution, plants of Salicornia virginica, a major component of wetland communities in California, were treated with two metals and two crude oil types to study their sensitivity to pollutants and how this impacted their reflectance characteristics. Several growth and physiological parameters, as well as shoot reflectance were measured and correlated with symptoms and contamination levels. Significant differences between treatments were found in at least some of the measured parameters in all pollutants. Reflectance was sensitive to early stress levels only for cadmium and the lightweight petroleum. Pollutants that differ in their way of action also had different plant reflectance signatures. The high degree of correlation between reflectance features and stress indicators highlights the potential of using remote sensing to assess the type and degree of pollution damage.     

Long Term Monitoring of Hydrocarbon Contamination Using Multi-Level Vapor Phase Piezometers

This study evaluated the feasibility of supplementing groundwater monitoring protocols by assessing the vadose zone for the extent of residual subsurface contamination. The study also characterized the response of the soil gas signatures with respect to different soil types and degrees of contamination.A field study was conducted at a former gasoline vending station located in Ottawa, Canada. The current state of contamination was determined by analysis of soil samples taken from boreholes. A series of 10 nested soil gas wells with monitoring depths of 0.75, 1.5, 2.25 and 3.0 m were then installed. Using these wells, soil gas surveys were performed at regular intervals over an extended period to quantify Gaseous TPH (TPH_g), oxygen and carbon dioxide concentrations in the soil gas.Results indicate that soil gas wells located near the source term exhibited characteristic soil gas signatures and significant fluctuations in TPH_g, oxygen, and carbon dioxide concentrations with time. Soil gas wells located beyond the soil contamination demonstrated limited correlation between TPH_g, oxygen and carbon dioxide concentrations and decreased seasonal variability.     

Persistent organochlorine contaminants in eggs of northern goshawk and Eurasian buzzard from northeastern Spain: temporal trends related to changes in the diet

Persistent organochlorine compounds (pesticides and polychlorinated biphenyls) were determined in 24 northern goshawk (Accipiter gentilis) and eight Eurasian buzzard (Buteo buteo) samples of eggs collected between 1988 and 1999 in La Segarra (northeast Spain), in order to evaluate the changes in exposure and detrimental effects during this period. In the study area, both species exhibited similar levels of contamination, which may be related to their similar diet, mainly based on European rabbits (Oryctolagus cuniculus) in terms of biomass. The buzzard showed contamination levels similar to those found in other Spanish areas, but the levels found in the goshawk were much lower. The shell index in goshawk eggs was inversely correlated to concentration of p,p'-DDE. In late eighties, the concentrations of p,p'-DDE and heptachlor-epoxide in goshawk eggs were positively correlated to the biomass percentage of passeriforms in the diet. In goshawk samples, a decline in HCB concentration in the 1990s as compared to the 1980s was detected. Surprisingly, p,p'-DDE concentrations did not decline, as could be expected from the ban on DDT use. On the contrary, the highest p,p'-DDE concentrations were detected in some samples from the nineties, which also showed the lowest shell indices. This may be related to a severe reduction of rabbit population after 1989 that produced an increase in the consumption of passeriformes, which are known to accumulate higher levels of organochlorine compounds. Our study suggests that monitoring programs aiming to detect temporal trends in chemical contamination should take into account changes in diet composition before any conclusion can be drawn.     

Bioaugmentation of a 4-chloronitrobenzene contaminated soil with Pseudomonas putida ZWL73

The strain Pseudomonas putida ZWL73, which metabolizes 4-chloronitrobenzene (4CNB) by a partial-reductive pathway, was inoculated into lab-scale 4CNB-contaminated soil for bioaugmentation purposes in this study. The degradation of 4CNB was clearly stimulated, as indicated with the gradual accumulation of ammonium and chloride. Simultaneously, the diversity and quantity of cultivable heterotrophic bacteria decreased due to 4CNB contamination, while the quantity of 4CNB-resistant bacteria increased. During the bioaugmentation, denaturing gradient gel electrophoresis analysis showed the changes of diversity in dominant populations of intrinsic soil microbiota. The results showed that Alphaproteobacteria and Betaproteobacteria were not distinctly affected, but Actinobacteria were apparently stimulated. In addition, an interesting dynamic within Acidobacteria was observed, as well as an influence on ammonia-oxidizing bacteria population. These combined findings demonstrate that the removal of 4CNB in soils by inoculating strain ZWL73 is feasible, and that specific populations in soils rapidly changed in response to 4CNB contamination and subsequent bioaugmentation.     

Lead impact on nutrition, energy reserves, respiration and stress protein (hsp 70) level in Porcellio scaber (Isopoda) populations differently preconditioned in their habitats

The impact of lead on food consumption, energy metabolism and the stress protein (hsp 70) level was investigated in the woodlouse Porcellio scaber (Isopoda), a common representative of the saprophagous soil macrofauna. To examine possible acclimation or tolerance to lead in woodlice from a contaminated habitat, animals of two populations, one deriving from a lead-contaminated artillery range and one from an uncontaminated control stand, were exposed to a series of lead concentrations under otherwise constant laboratory conditions for a maximum of 80 days. The applied lead concentrations (at a maximum 7945 mg/kg food dry wt) did not have any significant quantitative effect on the food consumption of the isopods, although the population pre-exposed in the artillery range showed a tendency toward a higher food uptake than the control population. After 80 days of exposure, both populations showed an equal trend toward increasing their respiration as lead concentrations, that they had been fed on, were increased. Accordingly, the glycogen content of the body, in both populations, was elevated with increasing lead concentrations in the food. This effect was more pronounced in the pre-exposed isopod population than in the one from the control stand. The non-pre-exposed isopods showed a general tendency toward a lower protein content of their bodies than the pre-exposed ones, although no effect of the lead on this parameter could be statistically proven. The ability of the artillery range isopods to synthesise stress proteins (hsp 70) in response to lead contamination decreased at much lower lead concentrations in their food than in the non-pre-exposed control population, even though the artillery range isopods seemed to be equally or even slightly better equipped with energy storage products. Even though the better nutrient status of these animals might refer to some lead tolerance of the pre-exposed population, the stress protein data suggest that a metal-resistant Porcellio population did not evolve in this lead-contaminated site.     

Mercury accumulation and tissue-specific antioxidant efficiency in the wild European sea bass (Dicentrarchus labrax) with emphasis on seasonality

The main goal of this study was to assess both mercury (Hg) accumulation and organs’ specific oxidative stress responses of gills, liver and kidney of Dicentrarchus labrax with emphasis on seasonality. Fish were collected in cold and warm periods in three stations: reference, moderated and highly contaminated sites. Our results showed that seasonal factors slightly influenced Hg accumulation between year periods (cold and warm) and strongly affected organs’ response basal levels. In contrast, seasonality seemed not to influence oxidative stress responses, since similar response patterns were obtained for both year periods, and moderate degree of antioxidant responses was obtained. Moreover, the oxidative stress profile may be attributed to Hg contamination degree, which showed organ-specific response and accumulation patterns. Hence, gills showed to be able to adapt to Hg contamination, and in opposition, kidney and liver demonstrated some vulnerability to Hg toxicity. The critical Hg concentrations indicated specific threshold limits for each organ. Overall, seasonality should be taken into account in monitoring programmes, helping to characterize the individuals’ reference values of response and thus to discriminate between the effects induced by natural causes or by contamination.     

Resistance to metal contamination by historically-stressed populations of Ceriodaphnia pulchella: environmental influence versus genetic determination

Field populations of daphnids historically-stressed by metal contamination may show increased resistance to those contaminants. This study was undertaken aiming to confirm/infirm three main hypotheses: (1) field populations living in historically-impacted environments are more tolerant to metal stress than populations from reference sites; (2) resistance differences are genetically-determined, i.e., differences persist after controlling for environmental and maternal effects, by acclimating cloned lineages to similar conditions; and (3) resistance to stress in field populations living in historically-impacted environments is due to the disappearance of sensitive individuals rather than the appearance of highly resistant ones, i.e., the shift in the central tendency of resistance is linked to a decrease in the range of population resistance and not to an increased upper limit of the population resistance. Three populations of the cladoceran Ceriodaphnia pulchella Sars in Southern Portugal were sampled; one of which has been historically-stressed by acid mine drainage (AMD) from an abandoned cupric-pyrite mine and two from reference sites within the same watershed. To assess if resistance differences were genetically-determined, the three populations were acclimated for at least five generations under the same controlled conditions. Assays with AMD contaminated water samples were performed with both non-acclimated and acclimated individuals from all studied populations. Reproduction results in sub-lethal assays revealed significant differences between the reference and stressed populations. Significant differences in resistance to lethal levels of toxicity were observed for both non-acclimated and acclimated populations, individuals from population I being more resistant than those from reference populations. The existence of genetically-determined sensitivity differences was attested by the presence of significant differences in resistance to lethal levels of toxicity in acclimated individuals from reference and stressed populations. Results from cumulative mortality assays revealed that sensitive individuals were most probably present in the original population, but no conclusion could be draw about the presence of extreme resistant individuals in the historically-stressed population. Finally, it was shown that responses among populations converged from high to low levels of contamination.     

Seabird eggs as bioindicators of chemical contamination in Chile

Seabird eggs were used as bioindicators of chemical contamination in Chile. Brown-hooded Gull (Larus maculipennis), Kelp Gull (Larus dominicanus), Trudeau's Tern (Sterna trudeaui), Neotropic Cormorant (Phalacrocorax brasilianus), and Pink-footed Shearwater (Puffinus creatopus) eggs were sampled at different breeding sites during the 1990s. Mercury and organochlorines (PCBs, DDT, HCB, HCH, and PCP) were quantified to reveal the interspecific differences, spatial and temporal trends in contamination levels. Trudeau's Tern displayed the highest levels of mercury (486 ng g(-1) wet weight). The highest sumDDT concentrations were measured in Brown-hooded Gulls (726 ng g(-1)). PCB levels were similar among the species (102-236 ng g(-1)), but the composition of the PCB mixture was different in Pink-footed Shearwaters. With the exception of the Brown-hooded Gull, all species studied presented similar and low levels of organochlorines (sumOHa). Residues of PCB and related compounds were not detected in any of the seabird eggs analyzed in Chile. Geographical variation was low, although levels of industrial chemicals were slightly higher in eggs from Concepción Bay, and agricultural chemicals in eggs from Valdivia. Also interannual variation was low, but some evidence was found of decreasing levels in gull eggs throughout the time of the study. The causes of the low levels and small variability in space and time of environmental chemicals in Chilean seabirds are discussed. We propose the use of seabirds in future monitoring of the development of chemical contamination in Chile.     

Temporal variations in PAH concentrations in Quercus ilex L. (holm oak) leaves in an urban area

Temporal variations of polycyclic aromatic hydrocarbon (PAH) concentrations in leaves of a Mediterranean evergreen oak, Quercus ilex L., were investigated in order to assess the suitability of this species to biomonitor PAH air contamination. Leaf samples were collected at six sites of the urban area of Naples (Italy) and at a control site in the Vesuvius National Park, in May and September 2001, and in January and May 2002. PAH extraction was conducted by sonication in dichloromethane-acetone and quantification by GC-MS. In winter, leaf total PAH concentrations showed, at all the urban sites, values 2-fold higher than in all the other samplings, reflecting the temporal trend reported for PAH air contamination in the Naples urban area. Moreover, leaf PAH concentrations showed, at all the urban sites, a decrease in May 2002 after the winter accumulation. At the control site leaf PAH concentrations showed lower values and smaller temporal variations than at the urban sites. The findings support the suitability of Q. ilex leaves to monitor temporal variations in PAH contamination. The highest winter concentrations of total PAHs were due to the medium molecular weight PAHs that increased with respect to both low and high molecular weight PAHs. The medium molecular weight PAHs showed the same temporal trend both at the urban and remote sites.     

An appraisal of soil diffuse contamination in an industrial district in northern Italy

Soil diffuse contamination is one the major soil threats, especially in regions with a high population density and strong industrialization. In this work agricultural, natural, and periurban soils of an Italian Province (858 km(2)) were sampled and analyzed. Overall, 140 samples were taken at two depths and analyzed for 10 trace elements, 13 rare earth elements and for organic contaminants (PCBs, PCDDs and PAHs). The aim of this work was to obtain an appraisal of soil diffuse contamination in a large Italian Province by applying and validating available tools to quantify background values and evaluate the intensity of contamination. Data were processed, background values estimated, and enrichment and contamination factors calculated. For some contaminants the results allowed a discrimination between natural or anthropic-derived contaminants. Some contaminants revealed clear trends of enrichment in function of the land use (in particular for periurban soils). REEs were found to mostly derive from parent material. The results obtained in this study show the importance of merging the quantification of contaminants with the elaboration of indices of contamination. These require an accurate quantification of background values to be able to discriminate the anthropic contribution. Enrichment factor resulted to be more accurate than contamination factor but it cannot be applied to organic contaminants and requires a careful selection of the reference element to be adopted. This study revealed that some contaminants - Sb, Sn, Pb, and organic contaminants - can be used as tracers of diffuse contamination, and should be therefore always included in similar studies.     

Assessment of the Mediterranean sediments contamination by persistent organic pollutants

A compilation of information about levels of selected persistent organic pollutants, namely polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroetane and its degradation products (DDTs) and hexachlorobenzene (HCB), in Mediterranean sediments, including data published from 1971 to 2005, has been conducted in order to assess their main drivers and pressures in the environment. The application of mapping tools (GIS) and statistical instruments enabled the assessment of geographical and temporal trends. Chemical contamination mainly originates from land-based sources, and decreases significantly when moving off-shore. Contamination hot spots are generally located along the Northern coastline. The data for open sea sediments enabled the establishment of background levels of contamination for the region. A decreasing temporal trend in concentrations was found, more evident in the case of DDTs probably due to a more efficient regulation of this chemical. Finally, some gaps in reliable data were also identified which were related to the lack of information in the southern and eastern parts of the Mediterranean as well as the variety of analytical methodologies used.     

Reindeer in the Swedish mountains: an assessment of grazing impacts

During the last decade, several well-publicized grazing-related incidents of vegetation degradation have helped to form an official opinion of overutilization of some mountain areas and a concern that Swedish reindeer husbandry may not be ecologically sustainable. We examine these examples in a temporal and management perspective to assess the scale of impact on summer grazing grounds in the Swedish mountains. Long-term data on population dynamics of reindeer show no trend with fluctuations around 225 000 animals for the last century. Data on grazing effects from L?ngfj?llet (Dalarna) and Mitt?kl?ppen (H?rjedalen) are discussed in detail. We compare these data to the situation in Finnmark, Norway, and in northern Finland where reindeer husbandry in recent decades does not seem to have been ecologically sustainable. We conclude that large-scale overexploitation by reindeer in the Swedish mountains is not evident. However, strong grazing and trampling effects may be found around enclosures and fences.     

Temporal trends of polycyclic aromatic hydrocarbons (PAHs) in Dreissena polymorpha specimens from Lake Maggiore (Northern Italy)

The Lake Maggiore (Northern Italy) has been recognized as an aquatic environment heavily contaminated by persistent organic pollutants, mainly organochlorine compounds, but to date limited information is available regarding another class of widespread and hazardous pollutants, such as the polycyclic aromatic hydrocarbons (PAHs). The aim of this study was to investigate seasonal and temporal trends of 18 PAHs accumulated in native Dreissena polymorpha specimens during a 5-year biomonitoring program, as well as to identify the possible PAH emission sources by using isomeric diagnostic ratios. Zebra mussels were sampled both in their pre- (May) and post-reproductive (September) stage over the 2008–2012 period in eight sampling stations covering the whole lake shoreline. PAH concentrations were measured through gas chromatography coupled to mass spectrometry. A notable PAH contamination following an increasing temporal trend was noticed in bivalves from all the sampling stations, with the benzo(α)anthracene as the predominant compound. An overall increase in PAH levels was found in the post-reproductive surveys, indicating a marked seasonality of this contamination probably due to the increase in touristic activity during spring–summer months.     

A study on PCB, PCDD/PCDF industrial contamination in a mixed urban-agricultural area significantly affecting the food chain and the human exposure. Part I: soil and feed

This study deals with a PCB, PCDD and PCDF contamination in Brescia, a city in the North-West of Italy, affecting an area with about 11000 inhabitants. The area is close to an industrial plant that produced, in total, some 31,000 ton of PCB. A relevant part of the polluted area is agricultural soil, where cattle were fed with polluted forage and farmers were consuming their own products, so that contamination led eventually to human exposure. Total levels of PCDD/Fs varied from 8 to 592 pgTE(WHO)/g for soil samples and when the dioxin-like PCBs (dl-PCBs) are included, the levels varied from 14.6 to 1033.7 pgTE(WHO)/g. In several cases, the legal limit was exceeded by more than one order of magnitude, with the highest contamination in some agricultural areas and in the surrounding zones. For the forage samples, total levels of PCDD/Fs varied from 0.29 to 2.04 pgTE(WHO)/g and, when dl-PCBs are included, this range increased from 2.04 to 4.75 pgTE(WHO)/g. PCB contamination of the forage through vapor condensation seemed to be relevant. The toxic contribution of dl-PCBs is always relevant and must be considered for risk management. The main component of the contamination source is probably a heavy PCB mixture, such as Aroclor 1262. The study dealt generally with the contamination transfer of PCBs, PCDDs and PCDFs from soil up to humans across the food chain. Results on soils and forages are shown, while measurements concerning the contamination of the animals fed with contaminated forage, and the exposure of the farmers (through human serum analyses), as compared to general population, will be reported in a dedicated paper.     

Comparison of solid-phase bioassays and ecoscores to evaluate the toxicity of contaminated soils

Five bioassays (inhibition of lettuce germination and growth, earthworm mortality, inhibition of springtail population growth, avoidance by springtails) were compared, using four coke factory soils contaminated by PAHs and trace elements, before and after biotreatment. For each bioassay, several endpoints were combined in an ‘ecoscore’, a measure of test sensitivity. Ecoscores pooled over all tested bioassays revealed that most organisms were highly sensitive to the concentration of 3-ring PAHs. When four soils were combined, behavioural tests using the springtail Folsomia candida showed higher ecoscores, i.e. they were most sensitive to soil contamination. However, despite overall higher sensitivity of behavioural tests, which could be used for cheap and rapid assessment of soil toxicity, especially at low levels of contamination, some test endpoints were more sensitive than others, and this may differ from a soil to another, pointing to the need for a battery of bioassays when more itemized results are expected.     

Large-scale spatial pollution patterns around the North Sea indicated by coastal bird eggs within an EcoQO programme

To categorize the marine environmental health status, the Oslo and Paris commissions have recently formulated Ecological Quality Objectives (EcoQOs) for many ecological features including the contamination of coastal bird eggs with mercury and organochlorines. In this study, we describe spatial and temporal patterns of egg contamination around the North Sea and compared them to the EcoQOs. Concentrations of mercury, polychlorinated biphenyl (??PCB) congeners, dichlorodiphenyltrichloroethane (??DDT) and derivatives, hexachlorobenzene (HCB) and hexachlorocyclohexane (??HCH) isomers were analysed in two tern species (Sterna hirundo and Sterna paradisaea) and Oystercatcher (Haematopus ostralegus) eggs collected between 2008 and 2010 in a total of 21 sites in seven countries surrounding the North Sea. Hg, ??PCB and HCB were highest in the southern sites, while ??DDT and ??HCH concentrations were greatest in eggs from the western North Sea and the Elbe estuary. There were rarely any consistent decreases over time for any compounds. In the terns, Hg, HCB and ??HCH increased at most sites, ??PCB and ??DDT in Sweden and Norway. In the Oystercatcher, HCB and ??HCH increased at more than the half of the sites, ??PCB, ??DDT and Hg at several German sites. In the terns, Hg, ??PCB and ??DDT exceeded the EcoQO in all, HCB in most years and sites. At most sites, ??HCH fulfilled the EcoQO in some study years. In the Oystercatcher, Hg, ??PCB and ??DDT exceeded the EcoQO in all or most years and sites. HCB and ??HCH fulfilled the EcoQO in some or all years at most sites. The EcoQO was exceeded most frequently in estuaries. We conclude that EcoQOs are suitable for drawing contamination patterns of the coastal North Sea in an easily understandable manner, offering the opportunity to harmonize the EcoQOs with coordinated environmental monitoring programmes.