Temporal trends in mercury concentrations in raptor flight feathers stored in an environmental specimen bank in Galicia (NW Spain) between 2000 and 2013.

Temporal trends in Hg concentrations were investigated in primary flight feathers from 319 specimens of three birds of prey: P7 in the northern goshawk (Accipiter gentilis), P6 in the common buzzard (Buteo buteo) and P5 in the tawny owl (Strix aluco). The samples were stored in a regional environmental specimen bank and belonged to specimens which died between 2000 and 2013 in Galicia (NW Spain). We would expect to see a decline in Hg concentrations across the study period, as data of atmospheric emissions show a gradual reduction of this pollutant in Europe in the last two decades. The study did not reveal any temporal pattern in Hg concentrations of feathers in any of the three species for the study period, may be due to the persistence of Hg in the environment, but showed a low level of contamination by this metal in the study area. In addition, the results show high intra-specific, as well as, inter-annual and inter-specific variability in data, mainly attributed to the level of exposure of the raptors to this pollutant and to the biomagnification process of Hg through food chains. These findings indicate that the high variability can be a limiting factor in the use of raptors for biomonitoring temporal patterns of Hg, but nevertheless, the technique provides qualitative information about the amount of Hg that reach the top of the terrestrial food chains.

Arsenic and mercury in native aquatic bryophytes: differences among species.

This study investigated the capacities of five species of aquatic bryophytes to accumulate As and Hg from their natural habitats in rivers in Galicia (NW Spain). The distributions of the concentrations of both elements in all species were skewed to the right, with a higher incidence of extreme values in the As data, which may indicate a greater degree of contamination by this metalloid. There were no significant differences in the accumulation of either of the elements between the different species studied, which justifies their combined use as biomonitors of As and Hg, at least in the study area.

Evaluation of different contour feather types for biomonitoring lead exposure in Northern goshawk (Accipiter gentilis) and tawny owl (Strix aluco).

The concentration of Pb was determined in feathers (contour feathers: mantle, pectoral, ventral, and primary- and secondary-coverts) of two sedentary species of raptors in Galicia (NW Spain): the tawny owl (Strix aluco) and the Northern goshawk (Accipiter gentilis). A high degree of intraindividual variability was observed in all types of feathers, with coefficients of variation exceeding 100 percent. The correlations between feather types were too low to enable use of a single type of body feather to predict the concentration of Pb in the other feathers. The number of body feathers required to differentiate individuals on the basis of the concentration of Pb was extremely high, in some cases higher than the number of the particular type of feather in the bird. All of this provides clear evidence that the contour and covert feathers of the raptor species considered cannot be used to biomonitor contamination by Pb, at least in this sample where the overall feather concentration were fairly uniform.

Study of the air quality in industrial areas of Santa Cruz de Tenerife (Spain) by active biomonitoring with Pseudoscleropodium purum.

A biomonitoring technique with terrestrial moss transplants (50 sampling sites in a regular grid) was used in an area of the city of Santa Cruz de Tenerife, close to an oil refinery and to an area of dense road traffic for a period of 2 months. The concentration of metals and metalloids (As, Cd, Hg, Ni, Pb and V) and 16 polycyclic aromatic hydrocarbons (PAHs) were determined. The density distribution was represented, the enrichment factors calculated and multifactorial analysis applied. In addition, contamination maps were elaborated on the basis of the bioconcentration obtained, and after confirming the existence of spatial structure, the response surfaces were represented. The results showed very high levels of contamination by Ni and V in the study area, with similar dispersal patterns observed for both. The concentrations of Cd, Hg, Pb and PAHs were lower. Active biomonitoring with terrestrial mosses was found to be a suitable technique for implementing inexpensive environmental monitoring programmes in urban and industrialized areas.

Evaluation of cations and chelating agents as extracellular extractants for Cu, Pb, V and Zn in the sequential elution technique applied to the terrestrial moss Pseudoscleropodium purum.

Three experiments were carried out to select the best extractant for use in the sequential elution technique, to enable extraction of Cu, Pb, V and Zn from the extracellular fraction of the terrestrial moss Pseudoscleropodium purum. The optimal concentrations of the extractants tested (CoCl(2), NiCl(2), Pb(NO(3))(2), SrCl(2), dimercaprol, EDTA, penicillamine) were determined on the basis of the maximum extraction of Zn achieved without any alteration of the plasma membrane. The capacity of these agents (at the optimal concentrations established) to extract the extracellular fractions of Cu, Pb, V and Zn was then evaluated. Extraction with 10mM EDTA is recommended for all 4 elements considered. As a second option, the use of 50mM penicillamine is recommended to extract Cu, 30 mM dimercaprol to extract Pb and V and 20 mM NiCl(2) to extract Zn. It was also concluded that these results cannot be extrapolated to other cryptogams, and that separate assays are required.

The cotton-strip assay as an environmental surveillance tool for ecological integrity assessment of rivers affected by WWTP effluents.

Environmental impact studies of rivers affected by wastewater treatment plant (WWTP) effluents have been greatly restricted by the difficulties associated with carrying out bioassays in the field and also by the complex interactions between the pollutants contained in the discharges. The cotton-strip assay (CSA) enables study of the organic matter decomposition potential, an important ecosystem process in rivers, by taking all of the factors affecting this process into account. However, the CSA has never been used for assessment of WWTP effluents. In the present study, we selected six fluvial zones affected by discharges from small WWTPs and placed cotton strips at increasing distances from the discharge points in each zone. After 17 days, we evaluated decay of the strips by measuring cotton tensile strength loss (CTSL) and cotton mass loss (CML). We then determined the relationships between these parameters and various physico-chemical and biological properties in the water, as well as the δ15N isotopic signal and metal contents of aquatic mosses transplanted in the same sampling sites and used as biomonitors. Although the WWTPs were similar, some of the discharges stimulated and others inhibited decomposition of the cotton strips. This was probably due to differences in the proportions of various types of pollutants (with trophic or toxic effects) in the discharges. The CSA proved to be a simple, practical and economic bioassay and suitable for evaluating the ecological integrity of fluvial ecosystems.

Assessing changes in the toxicity of effluents from intensive marine fish farms over time by using a battery of bioassays.

Although intensive marine fish farming is often assumed to be eco-friendly, the associated activity can lead to chronic exposure of marine organisms to potentially toxic discharges. Moreover, despite the increasing popularity of integrated multi-trophic aquaculture (IMTA), studies of the effects of fish farm effluents are almost non-existent. In the present study, the changes in the toxic potential of effluents from five land-based marine fish farms in NW Spain subjected for different lengths of time to a biodegradation procedure (for 0, 48, 120, and 240 h) were assessed in a battery of bioassays including organisms from different trophic levels (Vibrio fischeri, Isochrysis galbana, and Paracentrotus lividus). The results of the bioassays at the different times were then considered together with farm water flow in the Potential Ecotoxic Effects Probe (PEEP) index. Despite the high volumes of effluents discharged, the generally low toxicity of the effluents hinders assessment of potentially toxic effects. However, dose-response curves and statistical analysis demonstrated the existence of toxic effects during the first five days of the biodegradation procedure, especially immediately after sampling. The proposed modification of the PEEP index better reflects the changes in toxicity over time. Graphical abstract ᅟ.

Modelling spatial patterns of correlations between concentrations of heavy metals in mosses and atmospheric deposition in 2010 across Europe.

BACKGROUND: This paper aims to investigate the correlations between the concentrations of nine heavy metals in moss and atmospheric deposition within ecological land classes covering Europe. Additionally, it is examined to what extent the statistical relations are affected by the land use around the moss sampling sites. Based on moss data collected in 2010/2011 throughout Europe and data on total atmospheric deposition modelled by two chemical transport models (EMEP MSC-E, LOTOS-EUROS), correlation coefficients between concentrations of heavy metals in moss and in modelled atmospheric deposition were specified for spatial subsamples defined by ecological land classes of Europe (ELCE) as a spatial reference system. Linear discriminant analysis (LDA) and logistic regression (LR) were then used to separate moss sampling sites regarding their contribution to the strength of correlation considering the areal percentage of urban, agricultural and forestry land use around the sampling location. After verification LDA models by LR, LDA models were used to transform spatial information on the land use to maps of potential correlation levels, applicable for future network planning in the European Moss Survey. RESULTS: Correlations between concentrations of heavy metals in moss and in modelled atmospheric deposition were found to be specific for elements and ELCE units. Land use around the sampling sites mainly influences the correlation level. Small radiuses around the sampling sites examined (5 km) are more relevant for Cd, Cu, Ni, and Zn, while the areal percentage of urban and agricultural land use within large radiuses (75-100 km) is more relevant for As, Cr, Hg, Pb, and V. Most valid LDA models pattern with error rates of < 40% were found for As, Cr, Cu, Hg, Pb, and V. Land use-dependent predictions of spatial patterns split up Europe into investigation areas revealing potentially high (= above-average) or low (= below-average) correlation coefficients. CONCLUSIONS: LDA is an eligible method identifying and ranking boundary conditions of correlations between atmospheric deposition and respective concentrations of heavy metals in moss and related mapping considering the influence of the land use around moss sampling sites.

Use of an environmental specimen bank for evaluating the impact of the Prestige oil spill on the levels of trace elements in two species of Fucus on the coast of Galicia (NW Spain).

In the present study we investigated possible contamination by trace elements due to the oil slick caused by the shipwreck of the Prestige oil tanker, in two species of brown macroalgae (Fucus vesiculosus and Fucus ceranoides) collected from the coastal area most severely affected by the spill (Galicia, NW Spain). The oil slick apparently did not cause significant increases in the concentrations of the trace elements studied, except vanadium. It appears that the magnitude of terrestrial inputs to coastal waters is sufficiently high to mask the inputs of trace elements from the fuel. The observed exception of V suggests that bioaccumulation of this element by the two species of Fucus may be used to indicate exposure to petrochemical products similar to the Prestige fuel. The findings of the study are another example of the importance of the existence of Environmental Specimen Banks for studies of this type.

Design of an aquatic biomonitoring network for an environmental specimen bank.

The aim of the present study was to establish an aquatic biomonitoring network for the Galician Environmental Specimen Bank (BEAG) (NW Spain). For this, a sampling system was designed that comprised of 121 points distributed throughout Galician rivers, from which samples of water and of three species of bryophytes were collected. The results obtained allowed selection of 74 sampling points and 2 species (Fontinalis antipyretica Hedw. and F. squamosa Hedw.) as the most suitable for use in future BEAG sampling surveys. The two species selected showed a strong similarity in their capacity to accumulate the 17 elements determined (Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Pb, Se and Zn), as well as in their ecological preferences. Furthermore, the levels of contamination of epicontinental waters were lower than those observed in previous surveys.

Evergreen or deciduous trees for capturing PAHs from ambient air? A case study.

Tree canopies play a key role in the cycling of polycyclic aromatic hydrocarbons (PAHs) in terrestrial ecosystems, as leaves can capture PAHs from the air. In this study, accumulation of PAHs was compared in an evergreen species, P. pinaster, and in a deciduous species, Q. robur, in relation to some physio-morphological characteristics. For this purpose, pine needles and oak leaves collected from different sites across Galicia (NW Spain) were analysed to determine PAH contents, specific leaf area, stomatal density and conductance. Leaves and needles contained similar total amounts of PAHs. The major contribution of particle-bound PAHs in oak (the concentrations of 4- and 5-ring PAHs were two times higher, and those of 6-ring PAHs five times higher in oak than in pine) may be related to the higher specific leaf area (13 and 4 cm2 g-1 dry mass in respectively oak and pine). However, the major contribution of vapor-phase PAHs in pines may be affected by the stomatal conductance (two times higher in pine than in oak). Moreover, an increase in the diameter at breast height of trees led to an increase in accumulation of PAHs, with pine capturing higher amounts of low and medium molecular weight PAHs. The study findings underline the potential role of trees in improving air quality, taking into account the canopy biomass and life cycle.

Contribution of atmospheric deposition to tissue concentrations of mercury in aquatic bryophytes.

In this biomonitoring study, we measured the temporal variations in concentrations of mercury in samples of aquatic bryophytes from rivers in a region that received large inputs of the metal via atmospheric deposition. In the first year of sampling, the presence of an important source of atmospheric deposition of Hg (a lignite-fired power plant) led, during the rainy season, to elevated concentrations of the metal in catchments situated downwind of the prevailing winds. High concentrations of the metal were even detected in samples from apparently clean rivers in isolated mountain sites within the downwind catchments. Substitution of the type of fuel (high quality imported carbon instead of brown coal) used in the power plant greatly reduced Hg emissions in subsequent years. Application of spatial interpolation techniques to dense monitoring networks with aquatic bryophytes, without taking into consideration the catchment borders, appears suitable for studying extensive atmospheric pollution derived from a large scale source of contamination. This study also demonstrates the importance of environmental specimen banks in retrospective studies of contamination, as they enable posterior analysis of contaminants that for various reasons cannot be analyzed at the time of sampling.

Spatially valid data of atmospheric deposition of heavy metals and nitrogen derived by moss surveys for pollution risk assessments of ecosystems.

For analysing element input into ecosystems and associated risks due to atmospheric deposition, element concentrations in moss provide complementary and time-integrated data at high spatial resolution every 5 years since 1990. The paper reviews (1) minimum sample sizes needed for reliable, statistical estimation of mean values at four different spatial scales (European and national level as well as landscape-specific level covering Europe and single countries); (2) trends of heavy metal (HM) and nitrogen (N) concentrations in moss in Europe (1990-2010); (3) correlations between concentrations of HM in moss and soil specimens collected across Norway (1990-2010); and (4) canopy drip-induced site-specific variation of N concentration in moss sampled in seven European countries (1990-2013). While the minimum sample sizes on the European and national level were achieved without exception, for some ecological land classes and elements, the coverage with sampling sites should be improved. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010. In contrast, hardly any changes were observed for N in moss between 2005, when N was included into the survey for the first time, and 2010. In Norway, both, the moss and the soil survey data sets, were correlated, indicating a decrease of HM concentrations in moss and soil. At the site level, the average N deposition inside of forests was almost three times higher than the average N deposition outside of forests.

Interannual changes in δ¹5N values in Fucus vesiculosus L.

The natural abundance of (15)N (δ(15)N) has been widely used to detect anthropogenically derived N loads in environmental impact studies. The present study involved retrospective analysis of subsamples of Fucus vesiculosus L. collected during a period of three years (2008-2010) from two sites: a control site, within a coastal reference area, and an area affected by the effluents of a marine land-based fish farm. The isotopic signal in different subsamples of the macroalgae thalli (tissue that has grown during the same period) varied depending on the age of the tissue. Moreover, the isotopic signal decreased significantly with the age of the frond to within a certain range. The δ(15)N of F. vesiculosus is temporally unstable; therefore, measurement of the δ(15)N of macroalgal tissues does not allow reliable retrospective biomonitoring of environmental pollution. Further knowledge about the growth and other biological aspects of this species is required.

Assessing the effects of heavy metal contamination on the proteome of the moss Pseudoscleropodium purum cross-transplanted between different areas.

Protein expression was assessed in samples of Pseudoscleropodium purum cross-transplanted between one unpolluted (UNP) and two polluted (POLL) sites. Firstly, the level of expression (LE) of 17 proteins differed between native mosses from both types of sites, but differences were only maintained throughout the experiment for 5 of them. The LE of these five proteins changed over time in mosses transplanted from UNP to POLL and vice versa, becoming similar to that in autotransplants. However, these changes occurred slower than changes in the heavy metal concentrations measured in the same samples, and therefore they were not related to atmospheric pollution. Although the proteins identified were associated with moss metabolism, the expected growth reduction in samples autotransplanted within POLL (as a result of the down-regulation of photosynthesis-related proteins), did not occur. This supports the hypothesis that mosses growing in polluted areas adapt to heavy metal pollution and are able to reduce/overcome their toxic effects (i.e., reduced growth). Nevertheless, further specific research must be carried out to identify the proteins involved in this type of response, as lack of information on the bryophyte genome precludes us from reaching further conclusions.

Assessing the tolerance of the terrestrial moss Pseudoscleropodium purum to high levels of atmospheric heavy metals: a reciprocal transplant study.

We measured the concentrations of Cd, Cu, Hg, Pb and Zn in samples of the terrestrial moss Pseudoscleropodium purum reciprocally transplanted between an unpolluted and two polluted sampling sites. At the beginning of the experiment, the concentrations of all these elements differed significantly between mosses from the unpolluted site and mosses from the polluted sites. In general, the concentrations of the heavy metals in mosses from both polluted sites transplanted to the unpolluted site decreased until they reached the same levels as in autotransplants at this site (after 480-840 days). However, the concentrations of all heavy metals in mosses transplanted from the unpolluted site to both polluted sites increased to higher levels than in the autotransplants (except for Cu, Hg and Pb at one of the sampling sites). These results led us to conclude that mosses that have been continuously exposed to high atmospheric deposition of heavy metals undergo an adaptive response (probably genotypic) to such conditions. We therefore recommend active rather than passive biomonitoring of air quality in industrial environments because atmospheric deposition could be underestimated, and also recommend further investigation into the mechanisms involved in this response.

A meta-analysis approach to the effects of fish farming on soft bottom polychaeta assemblages in temperate regions.

Marine fish farms could cause environmental disturbances on the sediment due to uneaten food and fish faeces that impact the marine benthos. Polychaete assemblages are considered good indicators of environmental perturbations. The present study aimed to establish groups of polychaetes as potential indicators of fish farm pollution. This study was carried out in ten fish farms along the Spanish coast. Changes in polychaete assemblage were analyzed with meta-analysis and multivariate techniques. Abundance, richness and diversity showed significant decreases under fish farm conditions. Distribution patterns of polychaetes responded to combinations of physicochemical variables. The main ones are sulfide concentration, silt and clays percentage, and stable nitrogen isotope ratio. The results showed that some families are tolerant, Capitellidae, Dorvilleidae, Glyceridae, Nereididae, Oweniidae and Spionidae; while others are sensitive to fish farm pollution, Magelonidae, Maldanidae, Nephtyidae, Onuphidae, Paralacydoniidae, Paraonide, Sabellidae and also Cirratulidae in spite of being reported as a tolerant family.

Selection of flight feathers from Buteo buteo and Accipiter gentilis for use in biomonitoring heavy metal contamination.

The concentrations of Hg were determined in all primary flight feathers from 20 specimens of Buteo buteo and 49 specimens of Accipiter gentilis, which had died in various Wildlife Recovery Centres in Galicia (NW Spain) between 2001 and 2009. The aim of the study was to standardize the feather or feathers that should be analyzed in each species to enable inter-individual comparison of the levels of contamination, taking into consideration any variability in the concentrations of Hg caused by the birds' molting patterns. For both species the results show a high degree of both inter (e.g. an individual of A. gentilis showed 426 ng g(-1) of Hg as median and 568 ng g(-1) as median absolute deviation, MAD) and intra-individual variability (e.g. primary feather number seven - P7 - of all the A. gentilis individuals showed 537 ng g(-1) of Hg as median and 1129 ng g(-1) as MAD). Although molting did not have a clear effect on the concentrations of Hg in the flight feathers, it was possible to identify the most representative feather in each individual, taking into account the amount of metal excreted in each feather and the intra-individual variability. For B. buteo use of flight feather P6 is recommended for Hg biomonitoring studies; the amount of Hg excreted to this feather was 509 ng as median, which represents the 14% (from 10 to 20%) of the total Hg present in all the primary feathers. For A. gentilis the recommended feather is P7, which has a median of 86 ng of Hg (corresponding to 12%, and varying between 5 and 22%).

Substituting missing data in compositional analysis.

Multivariate analysis of environmental data sets requires the absence of missing values or their substitution by small values. However, if the data is transformed logarithmically prior to the analysis, this solution cannot be applied because the logarithm of a small value might become an outlier. Several methods for substituting the missing values can be found in the literature although none of them guarantees that no distortion of the structure of the data set is produced. We propose a method for the assessment of these distortions which can be used for deciding whether to retain or not the samples or variables containing missing values and for the investigation of the performance of different substitution techniques. The method analyzes the structure of the distances among samples using Mantel tests. We present an application of the method to PCDD/F data measured in samples of terrestrial moss as part of a biomonitoring study.