Trace element biomonitoring using mosses in urban areas affected by mud volcanoes around Mt. Etna. The case of the Salinelle, Italy

Trace element impact was assessed using mosses in a densely inhabited area affected by mud volcanoes. Such volcanoes, locally called Salinelle, are phenomena that occur around Mt. Etna (Sicily, Italy) and are interpreted as the surface outflow of a hydrothermal system located below Mt. Etna, releasing sedimentary fluids (hydrocarbons and NaCl brines) along with magmatic gases (mainly CO(2) and He). To date, scarce data are available about the presence of trace elements, and no biomonitoring campaigns are reported about the cumulative effects of such emissions. In this study, concentrations of Al, As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, V, and Zn were detected in the moss Bryum argenteum, in soil and water. Results showed that the trace element contribution of the Salinelle to the general pollution was significant for Al, Mn, Ni, and Zn. The comparison of trace concentrations in mosses from Salinelle and Etna showed that the mud volcanoes release a greater amount of Al and Mn, whereas similar values of Ni were found. Natural emissions of trace elements could be hazardous in human settlements, in particular, the Salinelle seem to play an important role in environmental pollution.     

Analysis of selected biomonitors to evaluate the suitability for their complementary use in monitoring trace element atmospheric deposition

The biomonitoring properties of oak tree bark compared with the epiphytic moss Hypnum cupressiforme and the influence of the tree bark, as its growth substrate, on the content of heavy metals in moss were investigated. Samples of the epiphytic moss H. cupressiforme and oak tree bark (Quercus spp.) were collected in Eastern Romania at a total of 44 sampling sites. Parallel moss and bark samples were collected from the same sides of the trunk circumference. V, Cr, Ni, Cu, Zn, As, Mo, Cd, In, Tl, Sn, Pb, and Bi were determined by ICP-MS. Principal component analysis was used to identify possible sources of metals in bark and moss. Six factors explaining 87 % of the total variance in the data set were chosen. The main factors represent long-range atmospheric transport of elements (Zn, Cd, (Pb), Bi, (Mo), (Tl)), local emissions from industrial sources (As, Cr, Ni, V), road traffic (Pb, Zn) and agricultural activities (Cu, (Zn)). The element concentrations in moss and bark samples are of the same order of magnitude. For almost all the elements, higher concentrations were obtained in moss. Significant correlations between concentrations in moss and bark samples were obtained for 7 of the 13 elements: V, Ni, Cu, Zn, Cd, In, and Bi, all typical anthropogenic pollutants. The use of tree bark for monitoring purposes might be an alternative in areas where there is a scarcity of mosses.     

Biogeochemical indicators of elevated nitrogen deposition in semiarid Mediterranean ecosystems

Nitrogen (N) deposition has doubled the natural N inputs received by ecosystems through biological N fixation and is currently a global problem that is affecting the Mediterranean regions. We evaluated the existing relationships between increased atmospheric N deposition and biogeochemical indicators related to soil chemical factors and cryptogam species across semiarid central, southern, and eastern Spain. The cryptogam species studied were the biocrust-forming species Pleurochaete squarrosa (moss) and Cladonia foliacea (lichen). Sampling sites were chosen in Quercus coccifera (kermes oak) shrublands and Pinus halepensis (Aleppo pine) forests to cover a range of inorganic N deposition representative of the levels found in the Iberian Peninsula (between 4.4 and 8.1 kg N ha^?1 year^?1). We extended the ambient N deposition gradient by including experimental plots to which N had been added for 3 years at rates of 10, 20, and 50 kg N ha^?1 year^?1. Overall, N deposition (extant plus simulated) increased soil inorganic N availability and caused soil acidification. Nitrogen deposition increased phosphomonoesterase (PME) enzyme activity and PME/nitrate reductase (NR) ratio in both species, whereas the NR activity was reduced only in the moss. Responses of PME and NR activities were attributed to an induced N to phosphorus imbalance and to N saturation, respectively. When only considering the ambient N deposition, soil organic C and N contents were positively related to N deposition, a response driven by pine forests. The PME/NR ratios of the moss were better predictors of N deposition rates than PME or NR activities alone in shrublands, whereas no correlation between N deposition and the lichen physiology was observed. We conclude that integrative physiological measurements, such as PME/NR ratios, measured on sensitive species such as P. squarrosa, can provide useful data for national-scale biomonitoring programs, whereas soil acidification and soil C and N storage could be useful as additional corroborating ecosystem indicators of chronic N pollution.     

Lichen biomonitoring of mercury emission and deposition in mining,geothermal and volcanic areas of Italy

Natural emissions of Hg are attracting increased interest both for their environmental implications and for possible applications in the exploration of mineral, petroleum and geothermal fields. However, daily and seasonal fluctuations in concentrations of Hg in the atmosphere, caused by meteorological and environmental variables, has made it very difficult to assess Hg anomalies by conventional analytical procedures. Some species of widespread foliose lichens from an abandoned cinnabar mining and smelting area (Mt. Amiata), geothermal fields (Larderello, Bagnore and Piancastagnaio, Central Italy), and active volcanic areas (Mt. Etna and Vulcano, Southern Italy) seem to be very suitable biomonitors of gaseous Hg; especially as lichen thalli have an Hg content which reflects average values measured in air samples. We discuss the advantages of quantitative biological monitoring by lichens with respect to conventional air sampling in large-scale monitoring.     

Active Moss Biomonitoring Applied to an Industrial Site in Romania: Relative Accumulation of 36 Elements in Moss-Bags

Active moss biomonitoring using the species Sphagnum girgensohnii was tested at a strongly polluted site in Romania (Baia Mare) according to a novel sampling design. Nine moss transplants from each of the two background areas (Dubna, Russia and Vitosha Mountain, Bulgaria) were deployed in parallel on balconies about 24 m above street level for 4 months. The samples were analyzed for 36 elements using instrumental neutron activation analysis (INAA). Based on the results obtained the sampling variability is discussed in relation to the analytical variability, and the relative uptake of the different elements is assessed. The moss-bags using Sphagnum girgensohnii demonstrate a high or a very high relative uptake for a majority of the 36 investigated elements, but the values depend on the initial element concentration in the moss. Moss leaves analyzed separately showed somewhat higher levels than stems for many elements. Practical considerations however still speak in favor of using the whole moss for transplants.     

Distribution, correlation, and source apportionment of selected metals in tannery effluents, related soils, and groundwater—a case study from Multan, Pakistan

The short-term responses of H₂O₂-depletion-related parameters in moss Hypnum plumaeforme to the combined stress induced by Pb and Ni were investigated. The results showed that the Pb and Ni stress induced dose-dependent accumulation of hydrogen peroxide (H₂O₂). The increase of peroxidase (POD) activity and decrease of ascorbate peroxidase (APX) activity were observed under the combined heavy metal application. The antioxidants, ascorbate (AsA) and proline content, increased significantly when the metals were applied together. The study indicated that the cell damage caused by Pb stress was higher than that caused by Ni stress, Pb and Ni had synergistic effect in inducing the oxidative stress in moss H. plumaeforme, especially under the combination of high concentration of Ni (0.1 and 1.0 mM) and Pb. Content of proline, H₂O₂ and the activity of POD, all showed a dose-dependent increase under Pb and Ni stress, suggesting their practical value as biomarkers in moss biomonitoring, especially in the case of light pollution caused by heavy metals without the changes in the appearance of mosses.     

Comparison of two metal surveys by moss Tortula ruralis in Budapest, Hungary

Moss transplants of Tortula ruralis were used as active biomonitoring organisms as part of a monitoring study to assess the metals (Al, Cd, Cu, Cr, Fe, Ni, Pb, V and Zn) associated with ambient particles on mosses in Budapest, the capital town of Hungary. The moss samples were collected in a nature conservation area from a semi-arid sand grassland (Festucetum vaginatae danubiale), less than 1 month before transplantation. Moss cushions were exposed to pollution in Budapest during October–November 1993 and February–March 1994. In the study area, 16 sites were marked out as measuring sites, in accordance with the structure of the city. A similar stand was established in the Botanical Gardens of the Szent István University in Gödöll? as a control site. ICP-AES analysis of moss for metals showed the ability of Tortula ruralis to accumulate the metals under study. Control site showed lower impact in comparison to the other sites.     

Assessment of Atmospheric Deposition of Heavy Metals and Other Elements in Belgrade Using the Moss Biomonitoring Technique and Neutron Activation Analysis

This study aimed at assessing atmospheric deposition of heavy metals and other elements using the moss genera Brachythecium sp. (B. rutabulum and B. salebrosum) and Eurhynchium sp. (E. hians and E. striatum) collected in autumn 2004 in the urban area of Belgrade. The concentrations of 36 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Mo, Sb, I, Cs, Ba, La, Ce, Sm, Tb, Dy, Hf, Ta, W, Hg, Th, U) were determined in moss and local topsoil samples by instrumental neutron activation analysis. The concentration of elements in moss positively correlated to those obtained for topsoil. High enrichment factors for As, Zn, Mo, Br, Sb, Se, Hg and Cl, calculated to continental crust composition, gave an evidence for anthropogenic impact on urban area, mainly due to intensive vehicular traffic and fossil fuel combustion. The concentration of elements in moss, characteristic for fossil fuel combustion, obtained in this study were substantially lower than in the previous investigation (2000) conducted in the area of Belgrade. The level of concentrations for V, Cr, Ni, and As in moss from this study correlated to those measured for neighboring countries, and were several times higher than the base-level data from low polluted areas. The level of accumulated elements in both investigated moss genera were similar and all studied species could be combined for biomonitoring purposes in urban areas.     

Assessing the influence of altitude and temperature on biological monitoring of freshwater quality: A preliminary investigation

The effect of altitude and water temperature on biomonitoring of freshwater quality was examined along an unpolluted area (36 km in length) of the upper Río Tajo (central Spain). The macrobenthic and fish communities were studied, and the Biological Monitoring Water Quality (BMWQ) method was applied. As expected, values of altitude and temperature respectively decreased and increased with increasing distance from the river source; these two physical parameters exhibited a negative and significant (P<0.05) correlation coefficient between them. However, despite evident changes in the functional structure of both aquatic communities along the study area, BMWQ scores were similar at all sampling sites. Pearson correlation coefficients between physical and biological parameters were not significant (P>0.05). The BMWQ index only exhibited significant (positive) correlation coefficients with macrobenthic and fish biomasses, indicating that freshwater quality could affect the biological production of fluvial ecosystems. It is concluded that biomonitoring of freshwater quality may be independent of the influence of altitude and water temperature at local spatial scales. Nonetheless, further investigations would be needed to clearly differentiate between the effects of anthropogenic and natural causes on biological monitoring at larger spatial scales.     

Biomonitoring of cadmium, chromium, nickel and arsenic in general population living near mining and active industrial areas in Southern Tunisia

The human health impact of the historic and current mining and industrial activities in Tunisia is not known. This study assessed the exposure to metals in the population of Southern Tunisia, using biomonitoring. The aim of this pilot study was to evaluate metal exposure on 350 participants living near mining and active industrial areas in the South of Tunisia. Blood specimens were analyzed for metals (Cd, Cr, As, and Ni) by Atomic Absorption Spectrometer equipped with Zeeman background correction and AS-800 auto sampler by graphite furnace and graphite tubes with integrated L'vov platform. The sample population was classified according to different age groups, sex, smoking habit, sea food and water drinking consumption, occupational exposure, amalgam fillings and place of residence. The blood As, Cd, Cr and Ni values expressed as mean?±?SD were 1.56?±?2.49, 0.74?±?1.15, 35.04?±?26.02 and 30.56?±?29.96 μg/l, respectively. Blood Cd and Ni levels in smokers were 2 and 1.2 times, respectively, higher than in non-smokers. Blood Cd levels increase significantly with age (p?=?0.002). As, Cd and Ni were significantly correlated with gender and age (p?<?0.05). Cd level in blood samples of subjects occupationally exposed was 1.3 times higher than that of non-exposed. Blood metals were not significantly affected by amalgam fillings, place of living and sea food and drinking water consumption. This first biomonitoring study of metal exposure in the South of Tunisia reveals a substantial exposure to several metals. The pathways of exposure and health significance of these findings need to be further investigated.     

A new approach to Assess Atmospheric Nitrogen Deposition by Way of Standardized Exposition of mosses

A standardized method of moss exposition for assessing variations in nitrogen deposition was tested in the western part of Germany. Six pleurocarpous moss species were transplanted to two sites differing in their deposition rates but being comparable as to their climatic conditions. The mosses were exposed in standardized containers over a period of 12 months; the focus of interest was the effect of N deposition on nitrogen content and on ¹⁵N natural abundance (δ¹⁵N-values). Within the first nine months only trends could be observed. However, after one year all species tested showed significantly higher N concentrations at the highly polluted site. Besides, more negative δ¹⁵N-values possibly reflecting the higher ammonium input were detected at this site. Surprisingly, most of the plants though being kept in plastic containers without a favourable substratum did not show any conspicuous deficiency symptoms. The potential advantages of a standardized moss exposition for N monitoring purposes are discussed. It is concluded that the method presented here can yield significant results in particular if the number of testing sites is increased.     

Use of Stable Nitrogen Isotopes and Permeable Membrane Devices to Study what Factors Influence Freshwater Mollusk Survival in the Conasauaga River

Recent biological inventory data shows severe declines in freshwater mussel abundance and biodiversity in the Conasauga River Basin in Northwest Georgia, USA. Based on assessments of habitat conditions, mussel populations should be sustainable. We conducted a study of sediment and water quality to evaluate the impact of anthropogenic contamination on mussel populations. Permeable membrane devices (PMD), polar organic chemical integrative samplers (POCIS™), conventional water and sediment quality analyses, and stable nitrogen isotope ratio analyses (δ¹⁵N) of snails and sediments were used to assess sediment and water quality at target sites throughout the basin. Ambient concentrations of organic contaminants in water were well below any aquatic life criteria; concentrations of some nutrients were detected above aquatic life criteria levels. Most mussel species in the river are endangered or threatened; therefore, snails were collected for δ¹⁵N analyses. Mean δ¹⁵N values for snails collected at forested upper watershed sites (national forest areas) were significantly lower than δ¹⁵N values from snails in agricultural areas. δ¹⁵N values for raw cow manure and manure-treated soil were similar to δ¹⁵N values for snails collected in agricultural areas. Dissolved nitrate from water samples had elevated δ¹⁵N values similar to the upper range of δ¹⁵N values for snails in agricultural areas. Data, particularly stable nitrogen isotope data, indicates that a land use change from national forest land to agriculture alters nitrogen sources to the basin and snails. Implications of nutrient release on freshwater molluscan reproduction, growth, and survival are discussed.     

A geographical approach to tracking Escherichia coli and other water quality constituents in a Texas coastal plains watershed

Diffuse sources of surface water pathogens and nutrients can be difficult to isolate in larger river basins. This study used a geographical or nested approach to isolate diffuse sources of Escherichia coli and other water quality constituents in a 145.7-km² river basin in south central Texas, USA. Average numbers of E. coli ranged from 49 to 64,000 colony forming units (CFU) per 100 mL depending upon season and stream flow over the 1-year sampling period. Nitrate-N concentrations ranged from 48 to 14,041 μg?L^?1 and orthophosphate-P from 27 to 2,721 μg?L^?1. High concentrations of nitrate-N, dissolved organic nitrogen, and orthophosphate-P were observed downstream of waste water treatment plants but E. coli values were higher in a watershed draining an older part of the city. Total urban land use explained between 56 and 72 % of the variance in mean annual E. coli values (p?<?0.05) in nine hydrologically disconnected creeks. Of the types of urban land use, commercial land use explained most of the variance in E. coli values in the fall and winter. Surface water sodium, alkalinity, and potassium concentrations in surface water were best described by the proportion of commercial land use in the watershed. Based on our nested approach in examining surface water, city officials are able to direct funding to specific areas of the basin in order to mitigate high surface water E. coli numbers and nutrient concentrations.     

Identifying the origin of atmospheric inputs of trace elements in the Prades Mountains (Catalonia) with bryophytes, lichens, and soil monitoring

The biomonitors Hypnum cupressiforme and Xanthoria parietina were used to assess the deposition of trace elements and their possible origin in the Prades Mountains, a protected Mediterranean forest area of NE Spain with several pollution sources nearby. Al, As, Cd, Co, Cu, Cr, Ni, Pb, Sb, Ti, V, and Zn were determined in 16 locations within this protected area. Soil trace element concentrations were also ascertained to calculate enrichment factors (EF) and use them to distinguish airborne from soilborne trace element inputs. In addition, lichen richness was measured to further assess atmospheric pollution. EF demonstrated to be useful not only for the moss but also for the lichen. Cd, Cr, Cu, Ni, and Zn presented values higher than three in both biomonitors. These trace elements were also the main ones emitted by the potential sources of pollutants. The distance between sampling locations and potential pollution sources was correlated with the concentrations of Cu, Sb, and Zn in the moss and with Cr, Ni, and Sb in the lichen. Lichen richness was negatively correlated with lichen Cu, Pb, and V concentrations on dry weight basis. The study reflected the remarkable influence that the pollution sources have on the presence of trace elements and on lichen species community composition in this natural area. The study highlights the value of combining the use of biomonitors, enrichment factors, and lichen diversity for pollution assessment to reach a better overview of both trace elements’ impact and the localization of their sources.     

Mussel isotope signature as indicator of nutrient pollution in a freshwater eutrophic lake: species, spatial, and seasonal variability

Stable nitrogen isotope ratios of five mussel species from littoral and pelagic areas were investigated with different trophic states in the eutrophic Lake Taihu, the third largest lake in China. Interpopulation variability for these mussels was relatively small in foot tissues because of the slow turnover time. Seasonal and spatial variations among the δ ¹⁵N values of mussels might be due in part to the natural variation in δ ¹⁵N values of potential food sources and the variation in the amount of human pollutions discharged into various locations of the lake. Although the increase of mussel δ ¹⁵N values was accompanied by the increase of nutrient concentrations in most situations in this study, statistically significant correlations were only 22% of the total correlations in this survey, which might be attributed to the different time-scale variations in nutrient concentrations and isotope signatures and the unknown details of the trophic pathways and metabolism for incorporation of these nutrients.     

Estimating the importance of natural and anthropogenic sources on N and P emission to estuaries along the Ceará State Coast NE Brazil

The Northeastern semi-arid Brazilian region is experiencing rapid social and economic development based on improving water management and even in areas of low human occupation, anthropogenic emissions of N and P surpass natural emissions in at least one order of magnitude and these additional loads can alter the water quality of the receiving estuaries. This study estimates, using an emission factor approach, the annual emissions of N and P from natural processes and anthropogenic sources for estuaries along the Ceará State, NE Brazil. Emission factors from natural sources are one to two orders of magnitude lower than those for anthropogenic sources. Among the anthropogenic activities, the aquaculture is responsible for most N emission (0.52 t km⁻² year⁻¹) followed by waste water and husbandry. For P, the largest average emission factors are from husbandry (0.30 t km⁻² year⁻¹), waste water and agriculture.     

Assessing the Relative Importance of Spatial Variability in Emissions Versus Landscape Properties in Fate Models for Environmental Exposure Assessment of Chemicals

Multimedia mass balance models differ in their treatment of spatial resolution from single boxes representing an entire region to multiple interconnected boxes with varying landscape properties and emission intensities. Here, model experiments were conducted to determine the relative importance of these two main factors that cause spatial variation in environmental chemical concentrations: spatial patterns in emission intensities and spatial differences in environmental conditions. In the model, experiments emissions were always to the air compartment. It was concluded that variation in emissions is in most cases the dominant source of variation in environmental concentrations. It was found, however, that variability in environmental conditions can strongly influence predicted concentrations in some cases, if the receptor compartments of interest are soil or water—for water concentrations particularly if a chemical has a high octanol–air partition coefficient (K _oa). This information will help to determine the required level of spatial detail that suffices for a specific regulatory purpose.     

Changes in the heavy metal and nutrient contents of dried feather mosses during long-term storage

This study measured heavy metal and nutrient concentrations of two feather mosses during the periods of dry storage. Samples (Hylocomium splendens, Pleurozium schreberi) were collected in the nationwide moss surveys carried out on the permanent sample plots of the 8th Finnish National Forest Inventory in 1985–86, 1990, 1995 and 2000. A small amount of each moss sample was analyzed soon after collection, and the remainder was dried and stored at the Paljakka environmental specimen bank (ESB). The 108 stored samples from 27 plots were reanalyzed in 2008. Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) and nutrients (Ca, K, Mg, P) were determined and compared for each survey year. Overall, Fe, Pb and Cr concentrations decreased, and Cu concentrations increased significantly during storage. The greatest decrease was observed in samples from plots where their initial concentrations were the highest. Changes in the concentrations of Cd, Ni and Zn were less pronounced. The loss of heavy metals is likely due to drying when cell membranes rupture and some of the surface material is lost. K, P and, to some extent, Mg concentrations increased during storage, whereas Ca did not change significantly. Nutrient increase is probably due to their movement from older to younger growths during the initial phase of drying. Ca is mostly bound to cell walls and is not easily released. Results emphasize the importance of establishing the intended use of a stored moss prior to sampling, in order to select and optimize an appropriate storage technique.     

Occurrence and distribution of polycyclic aromatic hydrocarbons in surface microlayer and subsurface seawater of Lagos Lagoon,Nigeria

Polycyclic aromatic hydrocarbons (PAHs) in surface microlayer (SML) and subsurface water (SSW) of Lagos Lagoon were investigated using gas chromatography-electron capture detector (GC-ECD) technique to ascertain their occurrence and spatial distribution, origin, enrichment, and carcinogenicity. Total PAH (ΣPAH) concentrations ranged from 9.10 to 16.20 μg L^?1 in the SML and 8.90 to 13.30 μg L^?1 in the SSW. ΣPAH concentrations were relatively higher in the SML than the underlying SSW samples. The enrichment factors (EFs) of ΣPAHs ranged from 0.76 to 1.74 while the EFs of the individual PAHs varied from 0.50 to 2.09. In general, the EFs values calculated in this study were consistent or slightly less than the EFs reported for similar coastal seawater ecosystems. A correlation between the EFs of fluoranthene and pyrene indicated a positive significant value (R?=?0.9828, p?<?0.0001, n?=?6). Source analyses using the phenanthrene/anthracene and fluoranthene/pyrene ratios indicated the dominance of petrogenic-derived PAHs. Furthermore, enhanced concentrations of BaP (strong carcinogenicity) in SML and SSW samples, which resulted in higher EFs, could pose serious ecological and human health risks.     

Use of three bivalve species for biomonitoring a polluted estuarine environment

Estuaries are marine areas at great contamination risk due to their hydrodynamic features. PAH are wide and ubiquitous contaminants with a high presence in these marine environments. Chemical analysis of sediments can provide information, although it does not give a direct measure of the toxicological effect of such contaminants in the biota. Samples of Venerupis pullastra, Cerastoderma edule, and Mytilus galloprovincialis were collected from two locations in Corcubión estuary (Norhwest of Spain). The level of PAH in sediment and biota, and its possible origin were assessed. A moderate level of contamination was observed with a predominance of PAH of a pyrogenic origin. Genotoxic damage, measured as single-strand DNA breaks with the comet assay, was evaluated in gill tissue and in hemolymph. The values of DNA damage obtained showed a higher sensitivity of clams and cockles to the pollution load level. These differences among species make us suggest the use of some other species coupled with mussels as an optimal tool for biomonitoring estuarine environments.