Are Mosses Used in Atmospheric Trace Metal Deposition Surveys Impacted by Their Substrate Soils? A National Study in Albania.

This research used moss biomonitoring to assess the atmospheric deposition of selected trace metals across the whole territory of Albania, a country of diverse lithology, and topography. Here, we assess three elements (Cr, Ni, and Co) that were identified in high concentrations compared to values reported by European moss surveys of 2010 and 2015. The possibility of element uptake by moss from substrate soils was assessed by analyzing moss and topsoil samples from the same areas. For this purpose, moss (Hypnum cupressiforme (Hedw.)) and topsoil samples were collected throughout Albania. Higher concentrations of elements in moss were found in areas of very high element content in soil characterized by no/or thin humus layer and sparse vegetation that stimulates soil dust generation. To compensate for the natural variation of the elements and to show their anthropogenic variation, geochemical normalization was conducted as the ratio of Co, Cr, and Ni concentration data to be concentration. Associations between elements in moss and soil samples, investigated by Spearman-Rho correlation analysis, indicated strong and significant correlations (r > 0.81, p = 0.000) between elements' data in moss or soil, and weak or no correlations (r < 0.4, p > 0.05) between the same data of moss and soil. Factor analysis revealed two main factors that selectively affect the elements in moss and top soil samples. Findings from this research suggested negligible interactions between moss and substrate soils, with the exception of soils with high concentrations of elements.

Regional air quality study by assessing trace metal atmospheric deposition.

This study addresses the atmospheric deposition of trace elements investigated in Albania, Croatia and Macedonia in 2010 as part of the European Moss Study. This study provides data on the concentration of ten metals (Cd, Cr, Cu, Ni, Pb, V, Zn, Fe, Al, and Li) in naturally growing mosses. In general, all concentration data follow a lognormal distribution. Cd, Cr, Ni, and Zn show strong fluctuations in the moss samples from Albania and Macedonia, and Pb, Fe, and Al in the mosses from Croatia. The concentrations of Cd, Cu, and Zn were higher in the samples from Croatia than in those from Albania and Macedonia; the concentrations of Cr, Ni, V, Fe, Al, and Li were higher in the samples from Albania than in those from Croatia and Macedonia; and a higher concentration of Pb was found in the samples from Macedonia. The observed relationship between the concentration of lithogenic elements (Al, Fe, and V) and the air quality index (AQI) confirms that moss species have a high capacity to retain atmospheric deposition particles. The anthropogenic emission sources of these elements from local and long-range transport were considered to be the most important factors affecting air quality in the studied areas.

Vanadium Contamination in Soil and Atmospheric Deposition in Albania.

By examining and evaluating the vanadium content in topsoil and moss samples, this study sought to better understand vanadium contamination in soil and atmospheric deposition. In the research area, Hypnium cupressiforme sps. moss is used. According to different distribution patterns and the lack of a link between vanadium in moss and soil samples studied by correlation analysis, no interactions between substrate soil and moss samples were investigated. Maximum vanadium concentrations (13.2 mg/kg and 250 mg/kg, respectively) were found in both moss and soil samples near the Cu mineral-rich Gjegjan area. Using lithium-normalized data on vanadium, the effect of anthropogenic activity on the vanadium in moss and soil samples is examined. There were no relationships between concentration and normalized data in moss and soil samples, showing the simultaneous effects of natural and anthropogenic sources of vanadium in the research area. Country-specific trends revealed no change for vanadium since 2010 in Albania.

The Evaluation of Air Quality in Albania by Moss Biomonitoring and Metals Atmospheric Deposition.

The air quality of Albania is evaluated by trace metals atmospheric deposition using moss biomonitoring method. Bryophyte moss (Hypnum cupressiforme Hedw.) samples were collected during August and September 2015 from 55 sampling points distributed over the entire territory of Albania. The concentrations of Cr, Cu, Fe, Ni, Pb, V, and Zn in moss samples was determined by ICP-AES, ETAAS (As and Cd), and CVAAS (Hg) analysis. Spatial distribution and temporal trend of the moss elements is discussed in this study. Different variability was found in moss metal concentrations that may reflect their spatial distribution patterns and may identify the location of the areas with high contamination of each element. Compared with the measurements of moss collected in 2010, significant differences were found in the concentrations of As, Cr, Cu, Hg, Ni, Pb, and Zn. The differences between two moss surveys may reflect changes in the bioavailability of the elements resulting from wet and dry deposition respectively during 2015 and 2010 moss biomonitoring survey. The pollution loading index that was applied to judge the content of metal contamination indicated moderate pollution throughout Albania. Examination of the potential ecological risk found that As, Cd, Cr, Hg, Ni, and Pb pose the highest potential ecological risks particularly in the areas with high metal contents. Factor analysis applied to investigate the probable sources of metals in the environment suggested that Al and Fe likely originated from natural sources. As, Cd, Hg, Pb, Cu, Zn, Ni, and Cr likely originated from anthropogenic sources associated with long-range transport, transboundary pollution and local emission sources.

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.

Origin and spatial distribution of metals in moss samples in Albania: A hotspot of heavy metal contamination in Europe.

This study presents the spatial distribution of 37 elements in 48 moss samples collected over the whole territory of Albania and provides information on sources and factors controlling the concentrations of elements in the moss. High variations of trace metals indicate that the concentrations of elements are affected by different factors. Relations between the elements in moss, geochemical interpretation of the data, and secondary effects such as redox conditions generated from local soil and/or long distance atmospheric transport of the pollutants are discussed. Zr normalized data, and the ratios of different elements are calculated to assess the origin of elements present in the current moss samples with respect to different geogenic and anthropogenic inputs. Factor analysis (FA) is used to identify the most probable sources of the elements. Four dominant factors are identified, i.e. natural contamination; dust emission from local mining operations; atmospheric transport of contaminants from local and long distance sources; and contributions from air borne marine salts. Mineral particle dust from local emission sources is classified as the most important factor affecting the atmospheric deposition of elements accumulated in the current moss samples. The open slag dumps of mining operation in Albania is probably the main factor contributing to high contents of Cr, Ni, Fe, Ti and Al in the moss. Enrichment factors (EF) were calculated to clarify whether the elements in the present moss samples mainly originate from atmospheric deposition and/or local substrate materials.

Biomonitoring of water quality of the Osumi, Devolli, and Shkumbini rivers through benthic macroinvertebrates and chemical parameters.

Environmental monitoring of river water quality in Albania, using biological and chemical parameters, is a fast and effective way to assess the quality of water bodies.The aim of this study was to investigate Ephemeroptera, Plecoptera and Trichoptera (EPT), Biotic index-Richness using macroinvertebrates to assess the water quality, with special reference to nutrient (phosphorus and nitrogen) levels in the Devolli, Shkumbini and Osumi rivers. Our objective was to investigate the relationships between the measures of benthic macroinvertebrate communities and nutrient concentrations to assess water quality. The rivers' benthic macroinvertebrates were collected during different seasons in 2012. The biological and chemical parameters used in the current study identified them as quick indicators of water quality assessment. The total number of macroinvertebrate individuals (n = 15,006) (Osumi river: n = 5,546 organisms; Devolli river: n = 3,469 organisms; and Shkumbini river: n = 5,991 organisms), together with the EPT group (Ephemeroptera, Plecoptera, and Trichoptera), showed that the water quality at the river stations during the above-mentioned period belonged to Classes II and III (fair water quality and good water quality, respectively). The classification of the water quality was also based on the nitrogen and total phosphorus contents. The pollution tolerance levels of macroinvertebrate taxa varied from the non-tolerating forms encountered in environments with low pollution levels to the tolerating forms that are typical of environments with considerable pollution levels.

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.

Separation of heavy metal from water samples--The study of the synthesis of complex compounds of heavy metal with dithiocarbamates.

The toxicity and persistence of heavy metal (HM) ions may cause several problems to marine organisms and human beings. For this reason, it is growing the interest in the chemistry of sulphur donor ligands such as dithiocarbamates (DDTC), due to their applications particularly in analytical chemistry sciences. The aim of this work has been the study of heavy metal complexes with DDTC and their application in separation techniques for the preconcentration and/or removing of heavy metals from the water solutions or the water ecosystems prior to their analysis. The HM-DDTC complexes were prepared and characterized by elemental analysis, FTIR and UV-Vis spectroscopic methods. The elemental analysis and the yield of the synthesis (97.5-99.9%) revealed a good purity of the complexes. High values of complex formation yields of HM-DDTC complexes is an important parameter for quantitatively removing/and or preconcentration of heavy metal ions from water solution even at low concentration of heavy metals. Significant differences founded between the characteristic parameters of UV/Vis (λmax and ϵmax) and FTIR absorption spectra of the parent DDTC and HM-DDTC complexes revealed the complex formation. The presence of the peaks at the visible spectral zone is important to M(nd(10-m))-L electron charge transfer of the new complexes. The (C=N) (1450-1500 cm(-1)) and the un-splitting (C-S) band (950-1002 cm(-1)) in HM-DDTC FTIR spectra are important to the identification of their bidentate mode (HM[S2CNC4H10]2). The total CHCl3 extraction of trace level heavy metals from water samples after their complex formation with DDTC is reported in this article.

First survey of atmospheric heavy metal deposition in Kosovo using moss biomonitoring.

Bryophytes act as bioindicators and bioaccumulators of metal deposition in the environment. The atmospheric deposition of Cd, Cr, Cu, Fe, Hg, Ni, Mn, Pb, and Zn in Kosovo was investigated by using carpet-forming moss species (Pseudocleropodium purum and Hypnum cupressiforme) as bioindicators. This research is part of the European moss survey coordinated by the ICP Vegetation, an International Cooperative Programme reporting on the effects of air pollution on vegetation to the UNECE Convention on Long-range Transboundary Air Pollution. Sampling was performed during the summer of 2011 at 25 sampling sites homogenously distributed over Kosovo. Unwashed, dried samples were digested by using wet digestion in Teflon tubes. The concentrations of metal elements were determined by atomic absorption spectrometry (AAS) equipped with flame and/or furnace systems. The heavy metal concentration in mosses reflected local emission sources. The data obtained in this study were compared with those of similar studies in neighboring countries and Europe (2010-2014 survey). The geographical distribution maps of the elements over the sampled territory were constructed using geographic information system (GIS) technology. The concentrations of Cr, Ni, Pb, and Zn were higher than the respective median values of Europe, suggesting that the zones with heavy vehicular traffic and industry emission input are important emitters of these elements. Selected zones are highly polluted particularly by Cd, Pb, Hg, and Ni. The statistical analyses revealed that a strong correlation exists between the Pb and Cd content in mosses, and the degree of pollution in the studied sites was assessed.

The effect of sampling scheme in the survey of atmospheric deposition of heavy metals in Albania by using moss biomonitoring.

The atmospheric deposition of heavy metals in Albania was investigated by using a carpet-forming moss species (Hypnum cupressiforme) as bioindicator. Sampling was done in the dry seasons of autumn 2010 and summer 2011. Two different sampling schemes are discussed in this paper: a random sampling scheme with 62 sampling sites distributed over the whole territory of Albania and systematic sampling scheme with 44 sampling sites distributed over the same territory. Unwashed, dried samples were totally digested by using microwave digestion, and the concentrations of metal elements were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and AAS (Cd and As). Twelve elements, such as conservative and trace elements (Al and Fe and As, Cd, Cr, Cu, Ni, Mn, Pb, V, Zn, and Li), were measured in moss samples. Li as typical lithogenic element is also included. The results reflect local emission points. The median concentrations and statistical parameters of elements were discussed by comparing two sampling schemes. The results of both sampling schemes are compared with the results of other European countries. Different levels of the contamination valuated by the respective contamination factor (CF) of each element are obtained for both sampling schemes, while the local emitters identified like iron-chromium metallurgy and cement industry, oil refinery, mining industry, and transport have been the same for both sampling schemes. In addition, the natural sources, from the accumulation of these metals in mosses caused by metal-enriched soil, associated with wind blowing soils were pointed as another possibility of local emitting factors.

Multi-elements atmospheric deposition study in Albania.

For the first time, the moss biomonitoring technique and inductively coupled plasma-atomic emission spectrometric (ICP-AES) analytical technique were applied to study multi-element atmospheric deposition in Albania. Moss samples (Hypnum cupressiforme) were collected during the summer of 2011 and September-October 2010 from 62 sites, evenly distributed over the country. Sampling was performed in accordance with the LRTAP Convention-ICP Vegetation protocol and sampling strategy of the European Programme on Biomonitoring of Heavy Metal Atmospheric Deposition. ICP-AES analysis made it possible to determine concentrations of 19 elements including key toxic metals such as Pb, Cd, As, and Cu. Cluster and factor analysis with varimax rotation was applied to distinguish elements mainly of anthropogenic origin from those predominantly originating from natural sources. Geographical distribution maps of the elements over the sampled territory were constructed using GIS technology. The median values of the elements in moss samples of Albania were high for Al, Cr, Ni, Fe, and V and low for Cd, Cu, and Zn compared to other European countries, but generally were of a similar level as some of the neighboring countries such as Bulgaria, Croatia, Kosovo, Macedonia, and Romania. This study was conducted in the framework of ICP Vegetation in order to provide a reliable assessment of air quality throughout Albania and to produce information needed for better identification of contamination sources and improving the potential for assessing environmental and health risks in Albania, associated with toxic metals.

TXRF analysis of soils and sediments to assess environmental contamination.

Total reflection x-ray fluorescence spectroscopy (TXRF) is proposed for the elemental chemical analysis of crustal environmental samples, such as sediments and soils. A comparative study of TXRF with respect to flame atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy was performed. Microwave acid digestion and suspension preparation methods are evaluated. A good agreement was found among the results obtained with different spectroscopic techniques and sample preparation methods for Cr, Mn, Fe, Ni, Cu, and Zn. We demonstrated that TXRF is suitable for the assessment of environmental contamination phenomena, even if the errors for Pb, As, V, and Ba are ingent.

Determination of the different states of mercury in seawater near the Vlora and Durres Bays.

Because of the toxicity and mobility of organic mercury, there is a need for determination of organic and inorganic mercury at very low concentrations in the environment, especially in seawater. A procedure for extraction and determination of low concentrations of the different states of mercury - total, inorganic, and organic - in seawater, by cold vapour atomic absorption spectroscopy (CVAAS) is described. Inorganic mercury only was directly reduced to the Hg(0) state by tin(II) chloride under strongly acid conditions (H(2)SO(4)) and mercury metal (Hg(0)) was determined by cold vapour atomic absorption spectroscopy. Organic and inorganic mercury were extracted, with toluene, as the bromide derivatives and re-extracted, together, into ammonium chloride solution. Organic mercury was converted into inorganic mercury by thermal digestion at 80-90 degrees C in the presence of strong oxidants. These two states of mercury were determined together as total mercury. Inorganic mercury was measured directly after pre-concentration of the sample by toluene extraction. Toluene dissolved in aqueous phase after re-extraction of the sample was removed by heating for 30 min at 80-90 degrees C. Organic mercury was calculated as the difference between total and inorganic mercury. The sensitivity of the method is 0.0001 ng mL(-1) Hg, depending on sample volume.