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Mosses as biomonitors of air pollution: 2015/2016 survey on heavy metals, nitrogen and POPs in Europe and beyond
Abstract and Figures
Here we report on the results of the 2015 moss survey, when mosses were sampled at about 5,100 sites across Europe and beyond, either in 2015, 2016 or both. In 2015, reporting for metals has greatly increased from about 28 countries in previous surveys to 36 countries, mainly due to participation of more countries in the EECCA region. Nitrogen and POPs data were reported for 14 and 8 countries respectively. As in previous surveys, mosses were sampled according to a standardised protocol and concentrations were determined in the 1 The International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops last two to three years’ growth segments using a range of analytical techniques. Pleurozium schreberi was the most frequently sampled moss species (39.6% for heavy metals), followed by Hypnum cupressiforme (23.1%), Hylocomium splendens (19.9%), Pseudoscleropodium purum (6.3%) and other species (11.2%). For quality assurance purposes moss reference material was included in the analyses and where necessary, correction factors were applied to outliers and in some cases, severe outliers were excluded from further data processing. Data were mapped for metals and nitrogen and temporal trends were determined.
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... This technique became the basis of the International Cooperative Program on Effects of Air Pollution on Natural Vegetation and Crops in the framework of the European convention on long-range transboundary air pollution (UNECE ICP). The data about concentrations of Al, Sb, As, Cd, Cr, Cu, Fe, Pb, Hg, Ni, V, and Zn in mosses are reported every five years to the UNECE ICP Vegetation program [2]. ...
... Pleurozium shreberi was chosen as it was the most frequently found species in the studied zone. It is considered the most used species for the assessment of atmospheric depositions in other countries participating in the ICP Vegetation program [2]. For the analysis, green or green-brown segments of moss corresponding to three years of growth were taken. ...
... The data for Al, V, Cr, Fe, Co, Ni, Zn, As, Sb were reported in "Mosses as biomonitors of air pollution: 2015/2016 survey on heavy metals, nitrogen, and POPs in Europe and beyond", published in 2020, without detailed analysis [2]. The results of this study could be used for further monitoring studies and for regional analysis of the ecological state of the environment. ...
The atmospheric depositions of heavy metals and other elements on the territory of Crimean Mountains in 2015 was assessed using the moss biomonitoring technique. The neutron activation analysis performed at the installation REGATA of the IBR-2 reactor was used for the determination of the mass fractions of 34 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Sb, I, Cs, Ba, La, Ce, Nd, Sm, Eu, Tb, Yb, Ta, Th, and U). Factor analysis, concentration factors, and enrichment factors were used to reveal possible sources of elements in the mosses. The main contributor to the deposition of elements on the mosses was the weathering of rock materials. The second group of elements included Br and I. The agriculture and marine sources of emissions were found to be important factors of atmospheric Br and I, respectively. The representing maps of the distribution of heavy metals and other elements revealed high levels of elements at the South coast of Crimea and near the city of Simferopol. The comparison of the obtained data with the data of biomonitoring studies performed for other mountain regions showed higher levels of Al, V, Cr, Fe, Ni, and As than in the mosses from Bulgaria, Macedonia, and Norway, but lower than in the mosses from Georgia, Turkey, Romania, and Northern Serbia. The presented results could serve as a basis for future monitoring research.
... The determination of trace elements in moss surveys was established in 1980 (Harmens et al. 2004). The European moss survey is conducted every 5 years since 1990 and the most recent survey was conducted in 2015/2016 with 36 countries participating and mosses sampled at almost 5000 sites across Europe and Asia and the concentration of Al, As, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Sb, V, and Zn in naturally growing mosses were reported (Frontasyeva et al. 2020). ...
... In the framework of the International Cooperative Program on Effects of Air Pollution on Natural Vegetation and Crops (UNECE ICP Vegetation), in 2015, for the first time, the moss biomonitoring technique was applied in air pollution studies in the Republic of Moldova (RM). The main sources of pollution are thermoelectric plants, transport, and industry (Zinicovscaia et al. 2017;Frontasyeva et al. 2020). ...
The moss biomonitoring technique was used for the assessment of air pollution in the Republic of Moldova, in the framework of the UNECE ICP Vegetation Programme. The content of 11 chemical elements (Al, V, Cr, Fe, Ni, Zn, As, Sb, Cd, Cu, and Pb) was determined by neutron activation analysis and atomic absorption spectrometry in samples collected in spring 2020. Distribution maps were built to identify the most polluted sites. The highest concentrations of elements in mosses were determined in the north-eastern, central, and western parts of the country. The main element associations were identified using factor analysis. Three factors were determined, of which one of mixed geogenic–anthropogenic origin and two of anthropogenic origin. A comparison of the data obtained in 2020 and 2015 showed a significant decrease in the concentrations of Cr, As, Sb, Cd, Pb, and Cu in 2020. The state of the environment was assessed using Contamination Factor and Pollution Load Index values, which characterized it as unpolluted to moderately polluted. Possible air pollution sources in the Republic of Moldova are resuspension of soil particles, agricultural practices, vehicles, industry, and thermal power plants.
... Maximum concentrations of Hg and Pb were 113 and 5 times (respectively) higher than their maximum levels in Germany during 2015 (Schröder and Nickel 2019). Maximum levels of As were higher than in other countries participating in EMS, except Serbia -71.1 mg•kg -1 (Frontasyeva et al. 2020). The maximum concentrations of Zn were almost 6 times lower than registered in the Czech Republic (578 mg•kg -1 ), and 10 times lower for Cr in comparison the Russian Federation -301 mg•kg -1 (Frontasyeva et al. 2020). ...
... Maximum levels of As were higher than in other countries participating in EMS, except Serbia -71.1 mg•kg -1 (Frontasyeva et al. 2020). The maximum concentrations of Zn were almost 6 times lower than registered in the Czech Republic (578 mg•kg -1 ), and 10 times lower for Cr in comparison the Russian Federation -301 mg•kg -1 (Frontasyeva et al. 2020). Although the Rhodope Mountains are essential in terms of water supply balance and possess high biodiversity and great potential for tourism (Sabev and Yordanov 2014), this study confirmed them as a region with constantly increased toxic element levels due to the mining activities. ...
The moss Hypnum cupressiforme Hedw. was used as biomonitor in three urban and five mountain sites with different pollution loads. The concentrations of 22 macro-and microelements were determined in moss-bags and were compared with those of the same elements in moss samples naturally growing in the Rhodope Mountains area. Most of the elements had highest concentrations in moss-bags exposed in Plovdiv. Strong accumulation of Cd and Pb was registered in all moss-bags with maximum in moss-bags from Sofia, reflecting that urban activities could induce more severe air pollution than mining. Cd reached saturation at the 30th day of exposure, while Pb continued to accumulate. Analysed levels of Hg and Pb during passive monitoring confirmed the Rhodope Mountains as a region with constant high toxic element levels.
Environmental biomonitoring is an excellent supplement to instrumental methods of environmental quality assessment. The use of biological methods has many advantages (relatively low cost, independence from the source of energy in the field etc.). The limitation in the use of bioindication methods is the inability to compare the results with legal environmental pollution standards. Mosses are commonly used in air pollution monitoring. Mosses exhibit most of the characteristics attributed to effective bioindicators. The advantage of mosses over other bioindicators comes from the fact that the result depends only on-air pollution due to the lack of practical contact with the soil. Mosses are used in air pollution biomonitoring in two basic methods: naturally growing or transplanted to the researched area. They are most often used to assess air pollution by metals and other elements, but also by various organic compounds. A prerequisite for successful application of these methods is strict adherence to a recognised methodology and standardisation of all activities, such as random selection of measurement points. The article presents a critical analysis of the advantages and disadvantages of biomonitoring of air pollutants, along with a final recommendation for their use, provided that appropriate methodological rigor is maintained. An important advantage of mosses in biomonitoring is their relatively practical ease of application and interpretation of results, resulting in their widespread use.
The process of globalization leads to the rapid development of industry. This
puts forward a high demand for using energy sources such as oil petroleum. As a result, an increasing amount of oil spills is observed along with pollution from
this energy source, especially oil pollution in the water environment. Oil pollution
not only negatively affects living organisms in the water bodies, but also
adversely affects the water transport, the economy, the tourism, and it is also one
of the routes of loss of the valuable source of energy [1]. Therefore, it is would be
reasonable to remove the oil pollution from the water and to regenerate lost oils.
Currently, there is a lot of procedures commonly used to solve this serious
problem. In particular, the use of adsorbents is considered one of the most
effective methods. However, adsorbents for treatment oil polluted water are
relatively expensive. Thus, creating an adsorbent with high efficiency in
cleaning up the oil pollution and, at the same time, a reasonable price, has been
the leading trend of research of scientists in recent years. To solve this problem,
we have developed a combination of the expensive and effective synthetic
sorbent - polyurethane foam (PUF) with the cheap natural material – chitin.
We applied filling PUF with 10% chitin (relative to the total mass of the
components A and B of the PUF) with particle size 1–3 mm (PPU10M) which is
reported as the most effective way for the foaming formation during the
production of sorbent and oil adsorption [2]. The effects of absorption time and
adsorbent consumption on the adsorption capacity have been evaluated on the
samples of river water and seawater [3]. The research results indicate that the
type of water does not affect the oil adsorption capacity. Therefore, the studied
adsorbent can be widely used to remove oil pollution in various water systems.
The results also show that the optimum adsorption time is 60 min for both types
of water. The sorbent consumption is estimated to be 1g per 25g oil with the oil
capacity of 13.41 g/g after 60 min adsorption.
The reuse of the adsorbent after the sorption process leads to decrease of
the amount of solid waste and, at the same time, significantly reduces the cost of
the process of removing oil pollution. The processes of mechanical regeneration
by the squeeze method and the chemical regeneration by using toluene have
been studied. The results show that in the mechanical regeneration procedure,
the PPU10M adsorbent can be used up to 20 cycles with the regenerated oil
efficiency up to 87%. The chemical regeneration method has a significantly
higher degree of oil recovery with amounts of the regenerated oil up to 97%.
338
However, its reusability is limited to 10 cycles. This result shows that the use of
an adsorbent produced from the combination between two materials: chitin and
polyurethane foam, for the process of treatment of the oil pollution not only
significantly reduces the cost of acquiring adsorbents, but also reduces the
amount of the solid waste resulted from the adsorption process.
In addition, we have studied the problem of recycling solid waste after
adsorption. To limit the discharge of solid waste into the environment, as well as
reduce the use of raw materials, the wastes after the adsorption process can be
used as a filler in the synthesis of adsorbents. The addition of the spent sorbent
into the composition of the sorbent in the amount of 5, 10 and 15% of the mass
has been investigated. It has been found that the material containing 5% of the
spent adsorbent has the higher the oil capacity (up to 12.48 g/g) in comparison
to the materials containing 10 and 15% of the filler.
The obtained results show that the material based on chitin and
polyurethane foam is a promising adsorbent for removing oil pollution from
water. It has high enough sorption ability and can be used in the different water
environment. Moreover, it is characterized by high reusability and recyclability.
Thus, the combined adsorbent based on chitin and polyurethane foam can be
considered environmentally friendly, which is suitable for the practical use to
clean up oil pollution from the water.
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.
This work concerns the content of selected heavy metals (Cd, Cr, Cu, Ni, Pb, and Zn), and determines the effect of absolute altitude on the content of metals in the plants of the Tatra National Park (TNP). The metals were determined in two species of plants, i.e., in the moss (Pleurozium schreberi (Willd.) Mitten) and in the Norway spruce (Picea abies (L.) H. Karst). Plant samples were collected in two test areas every 100 m of the altitude of the area, starting from 1000 m above sea level in the Lake Morskie Oko test area and from 1100 m above sea level in the Kasprowy Wierch test area, and ending at 1400 m above sea level for Lake Morskie Oko, and 1750 m above sea level (the moss) and 1550 m above sea level (the spruce) for Kasprowy Wierch. The two test areas are different from each other in terms of natural and physico-geographical conditions (geological structure, landform, climatic conditions). The conducted research showed that both plant species accumulated greater amounts of heavy metals in the Lake Morskie Oko test area than in the Kasprowy Wierch test area. The moss accumulated higher values of metals compared to the spruce. In both the moss and the spruce, the highest values, exceeding the natural content, were found for Cr, Pb, Cd, and Ni. For these metals, natural values were significantly exceeded: 20 times for Cr; 10 times for Pb; 4 times for Cd; and 3 times for Ni. For both examined areas, an increase in the quantity of accumulated metals in plants was also observed with the increase in altitude. The work focuses on the spreading around of heavy metals and their deposition on plants in protected high mountain (alpine) areas, in connection with altitude. Based on the obtained research results, Spearman's and Kendall's rank correlations were performed, and showed statistically significant relationships between the values for the content of metals and altitude. There are no heavy metal emission sources in the study area, so it is assumed that the metal content in the plants of the TNP is affected by long-range emissions.
Exposure to lead (Pb) from ammunition in scavenging and raptorial birds has achieved worldwide recognition based on incidences of lethal poisoning, but exposure implies also sublethal levels with potential harmful effects. Background and elevated Pb levels in liver from 116 golden eagles (GE, Aquila chrysaetos) and 200 white-tailed sea eagles (WTSE, Haliaeetus albicilla) from Sweden 2003–2011 are here examined, with supporting data from a previous WTSE report and eagle owl (EO, Bubu bubo) report. GE and WTSE display seasonal patterns, with no Pb level exceeding a generally accepted threshold for subclinical effects during summer but strongly elevated levels from October. Fledged juveniles show significantly lower levels than all other age classes, but reach levels found in older birds in autumn after the start of hunting seasons. Pb levels in EO (non-scavenger) show no seasonal changes and indicate no influence from ammunition, and are close to levels observed in juvenile eagles before October. In all, 15% WTSE and 7% GE were lethally poisoned. In areas with high-exposure to hunting ammunition, 24% of WTSE showed lethal Pb levels, compared to 7% in both eagle species from low-exposure areas. Lethal poisoning of WTSE remained as frequent after (15%) as before (13%) a partial ban on use of Pb-based shotgun ammunition over shallow waters (2002). Pb levels increased significantly in WTSE 1981–2011, in contrast to other biota from the same period. A significant decrease of Pb in WTSE liver occurred below a threshold at 0.25 μg/g (dry weight), exceeded by 81% of the birds. Trend patterns in Pb isotope ratios lend further support to this estimated cut-off level for environmental background concentrations. Pb from spent ammunition affects a range of scavenging and predatory species. A shift to Pb-free ammunition to save wildlife from unnecessary harm is an important environmental and ethical issue.
Moss biomonitoring is a widely used technique for monitoring the accumulation of trace elements in airborne pollution. A total of one hundred and five samples, mainly of the Hypnum cupressiforme Hedw. moss species, were collected from the Northern Greece during the 2015/2016 European ICP Vegetation (International Cooperative Program on Effects of Air Pollution on Natural Vegetation and Crops) moss survey, which also included samples from the metalipherous area of Skouries. They were analyzed by means of neutron activation analysis, and the elemental concentrations were determined. A positive matrix factorization (PMF) model was applied to the results obtained for source apportionment. According to the PMF model, five sources were identified: soil dust, aged sea salt, road dust, lignite power plants, and a Mn-rich source. The soil dust source contributed the most to almost all samples (46% of elemental concentrations, on average). Two areas with significant impact from anthropogenic activities were identified. In West Macedonia, the emissions from a lignite power plant complex located in the area have caused high concentrations of Ni, V, Cr, and Co. The second most impacted area was Skouries, where mining activities and vehicular traffic (probably related to the mining operations) led to high concentrations of Mn, Ni, V, Co, Sb, and Cr.
Background: The collection of atmospheric deposition by technical samplers and validated deposition modelling using chemical transport models is spatially complemented by using mosses as bioindicator: since 1990, the European moss survey has been providing data on element concentrations in moss every 5 years at up to 7300 sampling sites. In the moss specimens, heavy metals (since 1990), nitrogen (since 2005) and persistent organic pollutants (since 2010) were determined. Germany participated in all surveys with the exception of that in 2010. In this study, the spatial structures of element concentrations in moss collected in Germany between 1990 and 2015 were comparatively investigated by using Moran’s I statistics and Variogram analysis and mapped by use of Kriging interpolation. This is the precondition to spatially join the moss survey data with data collected at other locations within different environmental networks and to validate spatial patterns of atmospheric deposition as derived by technical sampling and modelling.
Results: The calculated maps reveal a clear and statistically significant decrease of most heavy metals, but not of nitrogen, in moss. Due to decreasing element concentrations and the unchanged application of the element concentration classification for the mapping, the heavy metal maps for the survey 2015 do no longer depict much spatial variation.
Conclusions: Therefore, in an upcoming study, this analysis needs to be complemented for the heavy metals by calculating maps that depict the spatial structure of survey-specific percentile statistics 1990, 1995, 2000, 2005 and 2015.
Background:
Since 1990, every 5 years, moss sampling is conducted within the European moss monitoring programme to assess the atmospheric deposition of airborne pollutants. Besides many other countries, Germany takes regularly part at these evaluations. Within the European moss monitoring 2015, more than 400 moss samples across Germany were taken according to a harmonized methodology for the assessment heavy metal and nitrogen input. In a pilot programme, eight of these sites were chosen for additional investigations on a broad range of organic contaminants to evaluate their accumulation in moss and thereby their presence in atmospheric deposition in Germany. Target compound classes comprised polycyclic aromatic hydrocarbons (PAH), polychlorinated dibenzodioxins and -furans (PCDD/F), dioxin-like and non-dioxin-like polychlorinated biphenyls (dl-PCB, ndl-PCB), polyfluorinated alkyl substances, classical flame retardants as well as emerging chlorinated and brominated flame retardants. In total, 120 target compounds were analysed. For some analytes, comparisons of accumulation in moss and tree leave samples were possible.
Results:
Except for certain flame retardants, PFAS, and ndl-PCB, substances of all other compound classes could be quantified in moss samples of all sites. Concentrations were highest for PAH (40-268 ng g-1) followed by emerging flame retardants (0.5-7.7 ng g-1), polybrominated diphenyl ethers (PBDE; 0.3-3.7 ng g-1), hexabromocyclododecane (HBCD; 0.3-1.2 ng g-1), dl-PCB (0.04-0.4 ng g-1) and PCDD/F (0.008-0.06 ng g-1).
Conclusions:
Results show the widespread atmospheric distribution and deposition of organic contaminants across Germany as well as the suitability of moss as bioaccumulation monitor for most of these compound classes. Compared to nearby tree leaf samples, accumulation potential of moss appeared to be higher for pollutants of high octanol-air partition coefficient (KOA) and octanol-water partition coefficient (KOW).
In this study, the canopy drip effect on the exposure of forests to atmospheric deposition of potentially toxic metals and nitrogen (N) and element accumulation was investigated. Thereby, the respective element concentrations of metals and N in moss specimens were investigated by example of North-Western Germany. To this end, on the one hand, the concentrations of Al, As, Cd, Cr, Cu, Fe, Hg, Pb, Ni, Sb, V, Zn, and N in mosses sampled under, outside, and at the edge of forest canopies were examined for statistical significant differences. On the other hand, vegetation structures parameterizing the canopy drip effect were quantified by use of information collected, in addition to the element data, at each moss sampling site. The statistical relations between ratios of vegetation parameters and ratios of element concentrations were modeled by regression analysis, and the respective element concentration in moss was geostatistically estimated and mapped for unsampled locations throughout Germany. This article tackles regression models with R2 > 0.5 (Cu, Hg, Pb, Sb, and N) to adapt the element concentrations measured at the 400 sites of the European Moss Survey (EMS) to three different features of hypothetical vegetation structures. To this end, the continuum of vegetation structures were represented as follows: open land (meadows) described by a leaf area index (LAI) value of 2.96 and under canopy sites in coniferous forests represented by a LAI value of 11. The arithmetic mean of LAI values at 400 EMS sites throughout Germany amounts to 5.1. The element concentrations for these target LAIs representing three site categories were calculated and mapped. Then, these LAI-dependent element concentration maps were compared with the maps depicting the spatial patterns of "pure" element concentrations. Spatial differences were evaluated and supposed to be of great value for the validation of atmospheric deposition modeling.
Concentrations of eight metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn and V) and nitrogen were determined during a nationwide biomonitoring survey using Pleurozium schreberi moss in Latvia. Particular concentrations of heavy metals were clearly associated with local emission point sources in Liepāja (Cd, Cr, Cu, Fe, Pb, V, Zn), Brocēni (Ni), Riga (Cr, Cu) and Daugavpils (Cr, Cu, Fe, Ni, Zn). Increased concentrations in the western part of Latvia (Cd, Cr, Cu, Ni, Pb, V, Zn) were due to the long-range transboundary transport of pollution from Europe and local metallurgical and other factories sources in Liepāja City. Higher concentrations near the Lithuanian border were associated with the impact of pollution from the cement industry of Naujoji Akmene (Cu, Fe, Ni) and the oil refinery of Mažeikiai (Ni, V). In general, concentrations of heavy metals were lower in Latvia compared to the background levels in Europe. In comparison to the previous monitoring results, the concentration of heavy metals in moss has decreased in Latvia. The higher N concentrations in the southwestern part of Latvia were due to the long-range transboundary transport of pollution, territories with intensive agriculture and areas close to the industrial cities.
Multi-element epithermal neutron activation analysis (ENAA) applied to different moss species collected over the territory of Tula Region (Russia) determined the level of their ability to accumulate heavy metals and metalloids from wet and dry atmospheric depositions. Moss species were revealed with accumulating ability close to that one for moss species recommended for moss biomonitoring purposes (Pleurozium schreberi, etc): Abietinella abietina, Atrichum undulatum, Rhytidiadelphus triquetrus, as well those which are characterized by high accumulation ability of toxic element from the environment: Brachythecium rutabulum, Brachythecium salebrosum, Eurhynchium angustirete, Plagiomnium ellipticum, Orthotrichum speciosum, Oxyrrhynchium hians. These species can be recommended for use in passive moss biomonitoring of atmospheric deposition of trace elements. The species with low accumulating ability of heavy metals and metalloids were also revealed: Climacium dendroides, Plagiomnium undulatum, Sphagnum sp., Using the method of passive moss biomonitoring, air pollution of Tula region (Central Russia) was studied. A high content of a number of elements of anthropogenic origin V, Fe, Zn, As, Sm, Tb, Hf, W, Th, and U in the air compared to other regions of Russia and high content of As, Cd, Cr, Fe, V, Zn and Al compared to the CIS countries and Europe were revealed. The reason for such high level of anthropogenic air pollution in the region is the activity of enterprises of metallurgical, defense, engineering and chemical industries.
Heavy metal air pollution in Romania was investigated by using passive moss biomonitoring. The research is a part of international programme UNECE ICP Vegetation programme - moss surveys. A total of 330 moss samples, Pleurozium schreberi, Hylocomium splendens, Hypnum cupressiforme, and other species, were collected on the Romanian territory during the dry seasons of summer and autumn of 2010. The content of Al, V, Cr, Fe, Ni, Cu, Zn, Cd and Pb was determined by two complementary methods: instrumental neutron activation analysis and graphite furnace/flame atomic absorption spectrometry. The obtained data were statistically processed and the spatial distribution maps of factor scores based on elemental concentrations together with the spatial distribution maps of heavy metals in moss were drawn. Median values for some heavy metals in moss samples collected in Romania, such as Cd (1.20 mg/kg dw) and Pb (30.8 mg/kg dw) are high compared to other European countries. The results revealed that the atmospheric deposition of these metals is a considerable problem in the northern and north-western parts of Romania.
Moss biomonitoring using the species Hypnum cupressiforme (Hedw.) and Pleurocarpous sp was applied to study air pollution in the Republic of Moldova. A total of 41 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Cd, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb, Hf, Ta, W, Pb, Th, and U) were determined by instrumental epithermal neutron activation analysis and atomic absorption spectrometry. Principal component analysis was used to identify and characterize different pollution sources. Geographical distribution maps were prepared to point out the regions most affected by air pollution and relate this to potential sources of contamination. Median values of the elements studied were compared with data from the European moss biomonitoring program. The cities of Chisinau and Balti were determined to experience particular environmental stress.
Monitoring and mapping of atmospheric deposition can be achieved by use of chemical transport models, technical sampling devices and/or bio-accumulators such as mosses, lichens, etc. Within the European Moss Survey programme, since 1990 every 5 years mos specimens have been collected and analysed for heavy metals, nitrogen and persistent organic pollutants according a harmonised methodology. Calculation and geostatistical mapping of percentile statistics of element concentration in moss is in the focus of this paper. Thereby, elementand survey-specific as well as heavy metals and surveys integrating statistical evaluations and GIS-mapping were performed. Cr, Sb and Zn show contrary to Fe and Pb, no constant decrease of element concentrations, but an intermediate increase between 2000 and 2005, which did not continue until 2015. Cd, Hg, Pb and N which are of priority according to the Convention on Long-Range Transboundary Air Pollution are in focus in this paper. Additionally, Cr is regarded as representing those elements with an intermediate increase between the years 2000 and 2005 as is also true for Sb and Zn. Surveys integrating percentile statistics depict the spatial patterns of,
in most cases, declining element concentrations across time. Survey-specific statistical analyses corroborate that the spatial patterns of element concentrations in moss are changing element-specifically across time. The longterm information on the percentile statistics of bioaccumulation of atmospheric deposition in moss is essential
for further scientific evaluation as well as for measurements and reporting of nature protection and environmental management.
The determination of atmospheric deposition in forests can be accomplished using technical sampling devices (bulk samplers, wet only samplers), biomonitors or modelling. In Europe, since 1990 moss sampled every five years at up to 7300 places in up to 35 countries was used as biomonitor. In the moss specimens, heavy metals (HM), nitrogen (N, since 2005) and persistent organic pollutants (POPs, since 2010) were determined. Germany participated in all surveys with the exception of that in 2010. For the moss survey 2015, the biomonitoring network applied in the 2005 campaign should be reorganized. To this end, a complex statistically based methodology including a decision support system was developed and implemented. Its application yielded a network with a reduction of sample points from 726 to 402. By use of the data collected in 2005 the performance of the reorganized network did not reveal significant loss of statistical validity.