Bioconcentration of metals in the moss Scleropodium purum in the area surrounding a power plant: A geotopographical predictive model for mercury

Samples of the moss Scleropodium purum collected in 1995 and 1997 were used to biomonitor the deposition of metals in the area surrounding a thermal power plant. Significantly higher levels of Cu (p<0.05), Fe (p<0.01), As and Hg (p<0.001) were found in the 1997 samples than in the 1995 samples, due to changes in atmospheric conditions. The influence on bioconcentration of the orientation of the sampling sites relative to the source of emission was studied. It was found that the increase recorded in 1997 generally occurred in the sampling sites in the south east of the study area. Analysis of the effect of distance from the source of emission revealed that the increase in metal levels in 1997 took place close to the power station (10–30 km). Finally, multiple regression analysis was used to construct a model that related different topographical variables to the concentrations of Hg in moss. The model, constructed using the data collected in both sampling periods, included the orientation of the sampling sites relative to the source of emission as well as the height of sampling sites in 1995 and the distance from the emission point in 1997. The model allowed us to determine the extent of the area affected by deposition and to establish the magnitude of deposition.     

In-stack emissions of heavy metals estimated by moss biomonitoring method and snow-pack analysis

Data from the chemical analysis of moss growing close to a thermal power station and snowpack have been used for the estimation of heavy metal deposition close to the point pollution sources. A semi-empirical model was proposed to describe atmospheric trace metal deposition close to the point pollution source. Model parameters were derived from experimental data, and nickel and vanadium quantities, washed out with snow and rain, were calculated. Using long-term meteorological observation data of rain and snow duration and metal uptake efficiencies in moss, the average emission rates of vanadium and nickel from the stack were calculated. The coincidence between data from emission inventory and model results was within 25%. It was estimated that in the vicinity of pollution source (within 30 km) about 15% out of total emitted metals were washed out by rain and snow events. Metal concentrations in the environment become indistinguishable from the background at a distance of about 20 km from the stack.     

Organochlorine pesticides accumulation and degradation products in vegetation samples of a contaminated area in Galicia (NW Spain)

The content of 21 organochlorine pesticides were studied in vegetation samples of a highly contaminated area by isomers of hexachlorocyclohexane (HCH) located close to a former industrial area in Galicia (NW Spain). Five species of plants were collected at different points of the contaminated area and the different parts of the plants were separated in order to study differences in accumulation capabilities. Samples were extracted employing microwave energy followed by a clean-up step using solid phase extraction and finally determined by GC–ECD. The results obtained show that the most abundant pesticides are HCHs isomers, being the main isomers β-HCH and -HCH in all samples whereas δ-HCH and γ-HCH were at lower levels. Some other pesticides such as p,p′-DDT, p,p′-DDD and p,p′-DDE were also present in much lower amount in some of the samples. Several degradation products of HCH were also identified in some samples by GC–MS.     

Characterization of spatial impact of particles emitted from a cement material production facility on outdoor particle deposition in the surrounding community

The objective of this study was to estimate the contribution of a facility that processes steel production slag into raw material for cement production to local outdoor particle deposition in Camden, NJ. A dry deposition sampler that can house four 37-mm quartz fiber filters was developed and used for the collection of atmospheric particle deposits. Two rounds of particle collection (3-4 weeks each) were conducted in 8-11 locations 200-800 m downwind of the facility. Background samples were concurrently collected in a remote area located -2 km upwind from the facility. In addition, duplicate surface wipe samples were collected side-by-side from each of the 13 locations within the same sampling area during the first deposition sampling period. One composite source material sample was also collected from a pile stored in the facility. Both the bulk of the source material and the < 38 microm fraction subsample were analyzed to obtain the elemental source profile. The particle deposition flux in the study area was higher (24-83 mg/m2 x day) than at the background sites (13-17 mg/m2day). The concentration of Ca, a major element in the cement source production material, was found to exponentially decrease with increasing downwind distance from the facility (P < 0.05). The ratio of Ca/Al, an indicator of Ca enrichment due to anthropogenic sources in a given sample, showed a similar trend. These observations suggest a significant contribution of the facility to the local particle deposition. The contribution of the facility to outdoor deposited particle mass was further estimated by three independent models using the measurements obtained from this study. The estimated contributions to particle deposition in the study area were 1.8-7.4% from the regression analysis of the Ca concentration in particle deposition samples against the distance from the facility, 0-11% from the U.S. Environmental Protection Agency (EPA) Chemical Mass Balance (CMB) source-receptor model, and 7.6-13% from the EPA Industrial Source Complex Short Term (ISCST3) dispersion model using the particle-size-adjusted permit-based emissions estimates.     

Use of the terrestrial moss Pseudoscleropodium purum to detect sources of small scale contamination by PAHs

Here we present a simple, economic method of identifying sources of small scale contamination by polycyclic aromatic hydrocarbons (PAHs). The method involves determining the concentrations of the contaminants in the terrestrial moss Pseudoscleropodium purum and consists of the following steps: i) testing for the existence of gradients of decreasing concentrations of PAHs in the moss in relation to distance from different emission sources; ii) measurement of the concentration of PAHs at 35 pairs of sampling sites, each separated by a distance of 1 km; iii) study of the distribution of the differences in concentration between these pairs of sampling sites and elimination of extreme values (affected by small scale sources of contamination); iv) characterization of normal distributions to determine the probability of the data being thus distributed; and v) testing the method in the surroundings of possible sources of small scale contamination by PAHs. The decrease in concentration of all of the compounds followed a steep gradient with increasing distance from the emission source; after elimination of the outliers, the distribution of the differences in concentration between the 35 pairs of sampling sites was normal for all compounds, except benzo(a)pyrene. Application of the method to 15 different types of industries provided satisfactory results and the method proved to be a very useful tool for monitoring and evaluating air quality.     

A comparison of indigenous mosses and topsoils for use in monitoring atmospheric heavy metal deposition in Galicia (northwest Spain)

Samples of moss (Scleropodium purum or, in its absence, Hypnum cupressiforme) and of topsoil (0-5 cm) were collected in the spring of 1995, from 75 sites distributed throughout Galicia (northwest Spain) in order to compare the potential usefulness of each in evaluating the atmospheric deposition of contaminants. Analysis was made of the total content of various metals in the moss and of different soil metal fractions (including total metal content, labile metals and metals bound to organic material). We found that the labile fraction most closely resembled the metal content of the moss. Calculation of enrichment factors allowed us to show that the soil was not, except in the case of Cr, the main source of contamination in the moss. By comparing contamination factors of metals in moss and soil fraction samples we found that moss samples were more useful for evaluating the degree of contamination at different sites.     

Sampling optimization, at site scale, in contamination monitoring with moss, pine and oak.

With the aim of optimizing protocols for sampling moss, pine and oak for biomonitoring of atmospheric contamination and also for inclusion in an Environmental Specimen Bank, 50 sampling units of each species were collected from the study area for individual analysis. Levels of Ca, Cu, Fe, Hg, Ni, and Zn in the plants were determined and the distributions of the concentrations studied. In moss samples, the concentrations of Cu, Ni and Zn, considered to be trace pollutants in this species, showed highly variable long-normal distributions; in pine and oak samples only Ni concentrations were log-normally distributed. In addition to analytical error, the two main source of error found to be associated with making a collective sample were: (1) not carrying out measurements on individual sampling units; and (2) the number of sampling units collected and the corresponding sources of variation (microspatial, age and interindividual). We recommend that a minimum of 30 sampling units are collected when contamination is suspected.     

Monitoring of heavy metal deposition in Northern Italy by moss analysis

A survey of heavy metal deposition in the mountainous territories of Northern Italy was carried out in 1995-96. Moss samples (mainly Hylocomium splendens) were collected in a dense network of sites (about 3.2 sites/1000 km(2)) and the data of metal concentrations in moss tissues were statistically correlated with environmental and climatic factors, as well as with bulk deposition of elements and elemental concentrations in the soil. Three main geographic patterns of metal concentration in mosses could be defined: (1) Fe, Ni, and Cr, all derived both by soil particulates and anthropogenic emissions connected with ferrous metal manufacturing, were mostly concentrated in Northwestern Italy; (2) Cu and Zn, as typical multi-source elements, showed rather high concentrations with little ranges of variation over the whole area and small peaks reflecting local source points; (3) Cd and Pb reflected long-distance transport and showed highest concentrations in the regions with highest precipitation, especially in the Eastern Alps.     

Thyroid status in juvenile alligators (Alligator mississippiensis) from contaminated and reference sites on Lake Okeechobee,Florida, USA

Exposure to environmental contaminants has been shown to alter normal thyroid function in various wildlife species, including the American alligator (Alligator mississippiensis). Abnormalities in circulating levels of the thyroid hormone thyroxine (T₄) have been reported in juvenile alligators from several contaminated lakes in Florida. To further elucidate these functional thyroid abnormalities, this study examines the structure of thyroids and circulating T₄ concentrations from juvenile alligators collected from three sites of varying contamination on Lake Okeechobee, Florida. The following variables were used to characterize thyroid morphology: epithelial cell height, width and area, percent colloid, and follicle area. These variables were compared among study sites and between genders. No difference was detected in epithelial cell height, epithelial cell area, or follicle area among the sites, whereas significant differences in epithelial cell width (p=0.02) and percent colloid (p=0.008) were found. Animals from the most contaminated site (Belle Glade) had significantly greater epithelial cell widths and significantly less colloid present in their follicles compared to animals from the reference site (West). Gender did not have a significant interaction with site for any variable measured. Thyroxine (T₄) concentrations were elevated in the intermediately contaminated site (Conservation Area 3A) compared to the other sites (p<0.0001). It is proposed that the disruptions seen in Lake Okeechobee alligators are due to disruptions at both the thyroid and extra-thyroidal tissues.     

Modeling the atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in North America

The atmospheric fate of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was simulated for the year 2000 in North America using a SMOKE/CMAQ-based chemical transport model that was modified for this purpose. The 1999 USEPA emission inventories of PCDD/Fs and criteria pollutants were used. The 1995 Canadian emission inventory of criteria pollutants and the 1995 Canadian area source emissions for PCDD/Fs were used with the 2000 Canadian point source emissions. Modifications to CMAQ involved coupling it with dual organic matter (OM) absorption and black carbon (BC) adsorption models to calculate PCDD/F gas–particle partitioning. The model satisfactorily reproduced the particle bound fractions at all rural sites for which there were measured data and across the whole domain, the modeled vs. measured differences in particle bound fractions were less than 20% for nearly all congeners. The model predicted ambient air PCDD/F concentrations were also consistent with measurements. Simulated deposition fluxes were within 58% of direct measurements. PCDD/F atmospheric depositions to each of the Great Lakes were estimated for the year 2000. The results indicate that approximately 76% of the total deposition of PCDD/Fs to the Great Lakes (in W-TEQ, or toxic equivalent units as defined by the World Health Organization) is attributed to PCDD/Fs absorbed into OM in aerosol. For all of the lakes, more than 92% of all deposition is particle phase wet deposition and only 5–8% is particle phase dry deposition. Wet deposition from the gas phase is negligible. Of the 17 toxic PCDD/F congeners, the Cl_4–5DD/F compounds contribute approximately 70% to the total atmospheric deposition to the Great Lakes. The seasonal changes in the PCDD/F deposition flux track variations in ambient temperature.     

Moss bags as sentinels for human safety in mercury-polluted groundwaters

An equation to estimate Hg concentrations of <4 μg/L in groundwaters of a polluted area in NE Italy was set out by using transplants of the aquatic moss Rhynchostegium riparioides as trace element bioaccumulators. The equation is derived from a previous mathematical model which was implemented under laboratory conditions. The work aimed at (1) checking the compliance of the uptake kinetics with the model, (2) improving/adapting the model for groundwater monitoring, (3) comparing the performances of two populations of moss collected from different sites, and (4) assessing the environmental impact of Hg contamination on a small river. The main factors affecting Hg uptake in the field were—as expected—water concentration and time of exposure, even though the uptake kinetics in the field were slightly different from those which were previously observed in the lab, since the redox environmental conditions influence the solubility of cationic Fe, which is a negative competitor of Hg²⁺. The equation was improved by including the variable ‘dissolved oxygen concentration’. A numerical parameter depending on the moss collection site was also provided, since the differences in uptake efficiency were observed between the two populations tested. Predicted Hg concentrations well fitted the values measured in situ (approximately ±50 %), while a notable underestimation was observed when the equation was used to predict Hg concentration in a neighbouring river (?96 %), probably due to the organic pollution which hampers metal uptake by mosses.     

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model’s ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year^?1 of elemental Hg.     

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.     

Mosses and lichens as biomonitors of trace metals. A comparison study on Hypnum cupressiforme and Parmelia caperata in a former mining district in Italy.

Samples of the moss Hypnum cupressiforme and the epiphytic lichen Parmelia, caperata were collected during the summer of 1999 in an area (Colline Metallifere, central Italy) intensively exploited in the past for metals (Cu, Fe, Pb, Zn) and currently for geothermal resources. Lichens were more sensitive than mosses to emissions of S compounds near geothermal fields and abandoned sulphide ore smelting plants. Comparison of elemental compositions of the two cryptogamic species from the same sampling sites showed significantly higher concentrations of lithophile elements (Al, Cr, Fe, Mn, Ni, Ti) in the moss and atmophile elements (Hg, Cd. Pb, Cu, V, Zn) in the lichen. Patterns of bioaccumulation of elements throughout the study area were quite similar for widespread pollutants such as S, B, As, Zn, Cr and Ni, but the lichen and the moss showed different distribution patterns of Hg, Cd and other elements subject to long-range atmospheric transport. These results are due to differences in the morphology and ecophysiology of mosses and lichens and indicate that these organisms cannot be used interchangeably as biomonitors of metals in areas with mineral deposits.     

Active moss biomonitoring of trace elements with Sphagnum girgensohnii moss bags in relation to atmospheric bulk deposition in Belgrade, Serbia

Active biomonitoring with wet and dry moss bags was used to examine trace element atmospheric deposition in the urban area of Belgrade. The element accumulation capability of Sphagnum girgensohnii Russow was tested in relation to atmospheric bulk deposition. Moss bags were mounted for five 3-month periods (July 2005-October 2006) at three representative urban sites. For the same period monthly bulk atmospheric deposition samples were collected. The concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, and Pb were determined by instrumental neutron activation analyses and atomic absorption spectrometry. Significant accumulation of most elements occurred in the exposed moss bags compared with the initial moss content. High correlations between the elements in moss and bulk deposits were found for V, Cu, As, and Ni. The enrichment factors of the elements for both types of monitor followed the same pattern at the corresponding sites.     

Observations of mercury wet deposition in Mexico

We provide a longer-term record of Hg wet deposition at two tropical latitude monitoring sites in Mexico, selected to provide regionally representative data. Weekly wet deposition samples were collected over 2 years, from September 2003 to November 2005. Based on this data set, we discuss the magnitude and seasonal variation of Hg in wet deposition and compare the results to other measurement sites and to several model estimates. With precipitation-weighted mean (PWM) concentrations of 8.2 and 7.9 ng L^?1, respectively, during the sampling period from Sep 30 2003 to Oct 11 2005, and median weekly concentrations of 9.4?±?1 ng L^?1 for both sites, the wet Hg concentrations and deposition at HD01 were much lower than those observed at the US Gulf Coast MDN sites while the wet Hg deposition at OA02 was much lower than most MDN sites, but somewhat similar to US MDN sites along the Pacific Coast. Based on the limited available data, we conclude that the approximately 30 % higher average precipitation at HD01 and roughly equal PWM concentrations lead to the higher deposition at HD01 versus OA02. We believe that these observations may offer scientists and modelers additional understanding of the depositional fluxes in the lower latitudes of North America.     

Nitrogen concentrations in mosses indicate the spatial distribution of atmospheric nitrogen deposition in Europe

In 2005/6, nearly 3000 moss samples from (semi-)natural location across 16 European countries were collected for nitrogen analysis. The lowest total nitrogen concentrations in mosses (<0.8%) were observed in northern Finland and northern UK. The highest concentrations (≥1.6%) were found in parts of Belgium, France, Germany, Slovakia, Slovenia and Bulgaria. The asymptotic relationship between the nitrogen concentrations in mosses and EMEP modelled nitrogen deposition (averaged per 50 km × 50 km grid) across Europe showed less scatter when there were at least five moss sampling sites per grid. Factors potentially contributing to the scatter are discussed. In Switzerland, a strong (r² = 0.91) linear relationship was found between the total nitrogen concentration in mosses and measured site-specific bulk nitrogen deposition rates. The total nitrogen concentrations in mosses complement deposition measurements, helping to identify areas in Europe at risk from high nitrogen deposition at a high spatial resolution.     

Mercury exposure in terrestrial birds far downstream of an historical point source

Mercury (Hg) is a persistent environmental contaminant found in many freshwater and marine ecosystems. Historical Hg contamination in rivers can impact the surrounding terrestrial ecosystem, but there is little known about how far downstream this contamination persists. In 2009, we sampled terrestrial forest songbirds at five floodplain sites up to 137 km downstream of an historical source of Hg along the South and South Fork Shenandoah Rivers (Virginia, USA). We found that blood total Hg concentrations remained elevated over the entire sampling area and there was little evidence of decline with distance. While it is well known that Hg is a pervasive and long-lasting aquatic contaminant, it has only been recently recognized that it also biomagnifies effectively in floodplain forest food webs. This study extends the area of concern for terrestrial habitats near contaminated rivers for more than 100 km downstream from a waterborne Hg point source.     

Critical remarks on the use of terrestrial moss (Hylocomium splendens and Pleurozium schreberi) for monitoring of airborne pollution

Duplicate samples of the two terrestrial moss species Hylocomium splendens and Pleurozium schreberi, which are widely used to monitor airborne heavy metal pollution, have been collected from eight catchments spread over a 1,500,000 km2 area in northern Europe. These were analysed for a total of 38 elements by inductively coupled plasma-mass spectrometry, inductively coupled plasma-atomic emission spectrometry and cold vapour-atomic absorption spectometry techniques. Results show that the moss species can be combined without interspecies calibration for regional mapping purposes. For the majority of elements the observed within-catchment variation is large--big composite samples over a large area should thus be collected when moss is to be used for monitoring purposes. For the majority of elements the input of dust governs moss chemistry. For a reliable 'contamination' signal over a sizeable area a major source is needed. Some elements show a dependence on climate/vegetation zone. In coastal areas the input of marine aerosols will alter the chemical signal obtained from moss samples.     

Current multi-element distribution in forest epigeic moss in the Czech Republic--a survey of the Czech national biomonitoring programme 2000

The content of 35 elements was determined in moss samples collected at 250 sites in the Czech Republic (CZ) in 2000. Four main areas of increased element contents in moss were revealed in the CZ (southern Moravia, Czech part of the former Black Triangle I territory, industrial northeastern Moravia, and the surroundings of a smelting town in southwestern Bohemia). The bioindicated high levels of Al, Ce, Co, Ga, La, Li, Pr, S, Th, U, V and Y atmospheric deposition loads in southern Moravia have never been reported in any paper before. Correlations were found in element content in moss vs. altitude, precipitation sums and bedrock types of the moss sampling plots. The current variability of element content in the CZ moss samples can be explained by the operation of not more than six factors.