Reply to the comments on "A novel approach to peatlands as archives of total cumulative spatial pollution loads from atmospheric deposition of airborne elements complementary to EMEP data: Priority pollutants (Pb, Cd, Hg)" by V. De Vleeschouwer et al.

In the comments by De Vleeschouwer et al. (2020) on a recent paper by Miszczak et al. (2020), two major issues were critically discussed: (1) the behavior of lead in ombrotrophic peatlands, with particular regard to the possible lead vertical mobility/immobility; (2) lead data use to accurately reconstruct historical contamination. The authors stated that "some of the conclusions reached by Miszczak et al. (2020) are based on misinterpretation or incorrect sampling and data analyses approaches". A reply to comments emphasises that these topics are not an issue of the paper. Its major idea was to use the unique natural systems (that are ombrotrophic peat bogs) as complete and reliable inventories for the assessment of cumulative loads of airborne element deposition independently upon its chronology. The results of a study conducted on ten ombrotrophic peat bogs in Norway and Poland showed a striking quantitative precision of such assessment. This has led to the idea of including ombrotrophic peat bogs into the EMEP network as tools for the completion of spatial distribution data on the fugitive element deposition. It would be helpful if a bigger number of experienced and widely recognized researchers take part in such project. Simultaneously, the analysis of source data, own results and case studies makes clear that the information regarding ombrotrophic peat properties is still insufficient to reconstruct precisely the chronology of metal contamination records, despite the development of high resolution sampling and analytical techniques and interpretational approaches. The clarification of some seemingly biased records would help to elucidate unexplained or unusual lead behavior in some outstanding cases. These cases demonstrate also that despite over 40 years of studies there are still the substantial gaps in our knowledge that need to be filled up.

Heavy metal and nitrogen concentrations in mosses are declining across Europe whilst some "hotspots" remain in 2010.

In recent decades, naturally growing mosses have been used successfully as biomonitors of atmospheric deposition of heavy metals and nitrogen. Since 1990, the European moss survey has been repeated at five-yearly intervals. In 2010, the lowest concentrations of metals and nitrogen in mosses were generally found in northern Europe, whereas the highest concentrations were observed in (south-)eastern Europe for metals and the central belt for nitrogen. Averaged across Europe, since 1990, the median concentration in mosses has declined the most for lead (77%), followed by vanadium (55%), cadmium (51%), chromium (43%), zinc (34%), nickel (33%), iron (27%), arsenic (21%, since 1995), mercury (14%, since 1995) and copper (11%). Between 2005 and 2010, the decline ranged from 6% for copper to 36% for lead; for nitrogen the decline was 5%. Despite the Europe-wide decline, no changes or increases have been observed between 2005 and 2010 in some (regions of) countries.

Influence of chemical composition of precipitation on migration of radioactive caesium in natural soils.

The aim of the present work was to study the impact of the chemical composition of precipitation on radiocaesium mobility in natural soil. This was done through column studies. Three types of precipitation regimes were studied, representing a natural range found in Norway: Acidic precipitation (southernmost part of the country); precipitation rich in marine cations (highly oceanic coastal areas); and low concentrations of sea salts (slightly continental inland areas). After 50 weeks and a total precipitation supply of ∼10 000 L m(-2) per column, results indicate that acidic precipitation increased the mobility of (134)Cs added during the experiment. However, depth distribution of already present Chernobyl fallout (137)Cs was not significantly affected by the chemical composition of precipitation.

Distributions of (137)Cs and (210)Pb in moss collected from Belarus and Slovakia.

In the present work, moss samples collected in Slovakia and Belarus were assayed with respect to gamma-emitting radionuclides. The results for (137)Cs and (210)Pb are discussed. Moss was used for the first time in Belarus, as a biological indicator of radioactive environmental pollution in consequence of the Chernobyl accident in 1986. In Belarus, the maximum activity of (137)Cs was observed in the Gomel region near Mazyr (6830 Bq/kg) and the minimum activity in the Vitebsyevsk Region near Luzhki-Yazno (5 Bq/kg). "Hot spots" were also observed near the towns Borisow and Yuratsishki. The results of measurements of (137)Cs in moss samples collected in 2000, 2006 and 2009 in the same localities of Slovakia are presented and compared with the results of air monitoring of (137)Cs carried out in Slovakia from 1977 until 2010. Measurements of the (210)Pb concentration in moss samples collected over the territory of Slovakia showed, that the median value exceed 2.3 times median value of (210)Pb obtained for Belarus moss. For that reason, the inhalation dose for man from (210)Pb and (137)Cs in Slovakia is more than twice as high as in Belarus, in spite of the initially very high (137)Cs exposure in the latter country.

Spatiotemporal distribution of airborne elements monitored with the moss bags technique in the Greater Thriasion Plain, Attica, Greece.

The well-known moss bags technique was applied in the heavily polluted Thriasion Plain region, Attica, Greece, in order to study the spatiotemporal distribution, in the atmosphere, of the following 32 elements: Na, Al, Cl, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Co, Zn, As, Se, Br, Sr, Mo, Sb, I, Ba, La, Ce, Sm, Tb, Dy, Yb, Hf, Ta, Hg, Th, and U. The moss bags were constituted of Sphagnum girgensohnii materials. The bags were exposed to ambient air in a network of 12 monitoring stations scattered throughout the monitoring area. In order to explore the temporal variation of the pollutants, four sets of moss bags were exposed for 3, 6, 9, and 12 months. Instrumental neutral activation analysis was used for the determinations of the elements. The data were analyzed using the Pearson correlations, the partial redundancy analysis, and the biplot statistical methods. Some pairs of elements were highly correlated indicating a probable common source of origin. The levels of the measured pollutants were unevenly distributed throughout the area and different pollutants exhibited different spatial patterns. In general, higher loads were observed in the stations close to and within the industrial zone. Most of the measured elements (e.g., Al, Ca, Ni, I, Zn, Cr, and As) exhibited a monotonic accumulation trend over time. Some elements exhibited different dynamics. The elements Mn, Mo, and Hg showed a decreasing trend, probably due to leaching and/or volatilization processes over time. Na and Br initially showed an increasing trend during the winter and early spring periods but decreased drastically during the late warm period. The results further suggest that the moss bags technique would be considered valuable for the majority of elements but should be used with caution in the cases of elements vulnerable to leaching and/or volatilization. It also suggests that the timing and the duration of the exposure of moss materials should be considered in the interpretation of the results.

Distribution and turnover of (137)Cs in birch forest ecosystems: influence of precipitation chemistry.

The aim of the present work was to study radioactive caesium in soil and plants from birch forests subject to different chemical climate. Four areas and three types of precipitation regimes were considered, representing a natural climatic range found in Norway: (A) acidic precipitation (southernmost part of the country); (B) precipitation rich in "sea salts"/marine cations (coastal areas); and (C) + (D) low concentrations of sea salts (inland areas). The results showed significant regional differences in plant uptake between the investigated areas. For instance the aggregated soil-to-plant transfer coefficients (Tag) were generally up to 7-8 times higher for the area receiving acid rain. Differences in caesium speciation partly explained the regional variability - e.g. the exchangeable fraction ranged from 1 to 40% (with the largest fraction of exchangeable caesium found in southernmost Norway). Transfer coefficients estimated on the basis of exchangeable fractions showed no significant differences between the areas of highest (A) and lowest (C) Tags. However, exchangeable fractions taken into consideration, the uptake of (137)Cs in plants in the acid rain-influenced area is still about twice that in the sea salt influenced area B. A significantly lower concentration of soluble base cations and a higher share of acid components in soils in area A is a likely explanation for this observation.

Country-specific correlations across Europe between modelled atmospheric cadmium and lead deposition and concentrations in mosses.

Previous analyses at the European scale have shown that cadmium and lead concentrations in mosses are primarily determined by the total deposition of these metals. Further analyses in the current study show that Spearman rank correlations between the concentration in mosses and the deposition modelled by the European Monitoring and Evaluation Programme (EMEP) are country and metal-specific. Significant positive correlations were found for about two thirds or more of the participating countries in 1990, 1995, 2000 and 2005 (except for Cd in 1990). Correlations were often not significant and sometimes negative in countries where mosses were only sampled in a relatively small number of EMEP grids. Correlations frequently improved when only data for EMEP grids with at least three moss sampling sites per grid were included. It was concluded that spatial patterns and temporal trends agree reasonably well between lead and cadmium concentrations in mosses and modelled atmospheric deposition.

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 (r(2) = 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.

Mosses as biomonitors of atmospheric heavy metal deposition: spatial patterns and temporal trends in Europe.

In recent decades, mosses have been used successfully as biomonitors of atmospheric deposition of heavy metals. Since 1990, the European moss survey has been repeated at five-yearly intervals. Although spatial patterns were metal-specific, in 2005 the lowest concentrations of metals in mosses were generally found in Scandinavia, the Baltic States and northern parts of the UK; the highest concentrations were generally found in Belgium and south-eastern Europe. The recent decline in emission and subsequent deposition of heavy metals across Europe has resulted in a decrease in the heavy metal concentration in mosses for the majority of metals. Since 1990, the concentration in mosses has declined the most for arsenic, cadmium, iron, lead and vanadium (52-72%), followed by copper, nickel and zinc (20-30%), with no significant reduction being observed for mercury (12% since 1995) and chromium (2%). However, temporal trends were country-specific with sometimes increases being found.

Monitoring of trace element atmospheric deposition using dry and wet moss bags: accumulation capacity versus exposure time.

To clarify the peculiarities of trace element accumulation in moss bags technique (active biomonitoring), samples of the moss Sphagnum girgensohnii Rusow were exposed in bags with and without irrigation for 15 days up to 5 months consequently in the semi-urban area of Belgrade (Serbia) starting from July 2007. The accumulation capacity for 49 elements determined by ICP-MS in wet and dry moss bags was compared. The concentration of some elements, i.e. Al, V, Cr, Fe, Zn, As, Se, Sr, Pb, and Sm increased continuously with exposure time in both dry and wet moss bags, whereas concentration of Na, Cl, K, Mn, Rb, Cs, and Ta decreased. Irrigation of moss resulted in a higher accumulation capacity for most of the elements, especially for Cr, Zn, As, Se, Br, and Sr. Principal component analysis was performed on the datasets of element concentrations in wet and dry moss bags for source identification. Results of the factor analysis were similar but not identical in the two cases due to possible differences in element accumulation mechanisms.

Atmospheric deposition of trace element pollutants in Macedonia studied by the moss biomonitoring technique.

For the first time the atmospheric deposition of trace metals was studied over the entire territory of the Republic of Macedonia. Samples of the terrestrial mosses Hypnum cupressiforme, Camptothecium lutescens, and Homalothecium sericeum were collected in September-October 2002 at 73 sites evenly distributed over the country, and a total of 43 elements were determined by instrumental neutron activation analysis and atomic absorption spectrometry. Principal component factor analysis was used to identify the most polluted areas and characterize different pollution sources. The most important sources of trace metal deposition are ferrous and non-ferrous smelters, oil refineries, fertilizer production plants, and central heating stations. Four areas appear to be particularly exposed to metal pollution: Veles, Skopje, Tetovo, and Kavadarci-Negotino, whereas the predominantly agricultural regions in the south, southwest, and southeast show levels closer to European median values for most elements of mainly pollution origin.

Estimation of diffusive boundary layer thickness in studies involving diffusive gradients in thin films (DGT).

Recent laboratory experiments and field investigations involving diffusive gradients in thin films (DGT) have shown that the thickness (delta) of the diffusive boundary layer (DBL), which can affect the accuracy of the technique, is generally not negligible. Accordingly, the determination of delta has become a matter of considerable practical importance. Though the problem has been addressed in the recent literature, there is room for some improvement. An expression for estimation of delta is presented here, and a practical procedure for determining delta and the concentration of DGT-labile species from sparse experimental data is proposed and illustrated by analyzing data from four experiments with DGT samplers of different diffusive gel thicknesses.

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.

Transfer of (85)Sr and (134)Cs from diet to reindeer foetuses and milk.

Sr-85 and (134)Cs in aqueous solution of the chlorides were administered daily to four pregnant reindeer during the last part of gestation. Radionuclide concentrations were determined in calves sacrificed at birth, and secretion of the nuclides was measured in milk. Although the gastrointestinal absorption of (85)Sr was low, an apparently higher transfer of the absorbed fraction of (85)Sr than (134)Cs from the mother to the foetus led to similar accumulation of (85)Sr and (134)Cs in foetuses. At birth 1.4-1.6 and 1.5-2.5% of the total administered activities of (85)Sr and (134)Cs, respectively, were present in the calves' bodies. Transfer coefficients (F (m)) for (85)Sr and (134)Cs from feed to milk were estimated at 0.0218+/-0.0026 and 0.185+/-0.025 day kg(-1), respectively, and the observed ratio (OR(milk-diet)) for (85)Sr was 0.124+/-0.037. Transfer of radiostrontium to reindeer milk was in agreement with previously reported relationships between Ca intake and radiostrontium transfer in ruminants. These relationships suggest that the transfer of radiostrontium to foetuses and milk of free-ranging reindeer can be 3-4 times higher than observed in this experiment (due to lower Ca intake with natural forage), but the transfer to milk will not be as high as that of ionic (134)Cs. The concentrations of (85)Sr in milk suggested that the does mobilized skeletal stores of Ca and (85)Sr for milk production, although the diet appeared to satisfy the Ca requirements. In reindeer with radiostrontium intake during the whole year, radiostrontium concentrations in milk will therefore be higher than indicated by the F (m) value observed in our study. No differences in half-times for (85)Sr and (134)Cs secretion in milk were detected. Both nuclides were secreted with short- and long-term half-times of 1-2 and 12-19 days, respectively. For (85)Sr, 80-90% of the activity was excreted with the short half-time, whereas the corresponding value for (134)Cs was 30-50%.

Distribution of 90Sr and 137Cs in Arctic soil profiles polluted by heavy metals.

Effects of industrial pollution on the behaviour of radionuclides in spruce forest ecosystems were studied along a gradient from of a copper-nickel smelter in Monchegorsk, NW Russia. A reference site was situated in Lapland, Finland, 152 km west of Monchegorsk. Most of the total 137Cs activity in soil was in mineral (E and B) horizons, except at the reference site where the major part was still in the organic surface layer. Most of the total 90Sr activity still remaining in the soil profile was found in the surface layer, but the relative amount decreased with increasing level of industrial pollution. Pollutants from the smelter clearly affected the chemical speciation of radionuclides. Smaller amounts of exchangeable radionuclides were present in the organic surface layer at the most polluted sites. The decline of 137Cs with decreasing distance from the smelter correlated strongly with a similar depletion in exchangeable K and Mg. Total concentrations of 137Cs and 90Sr showed high correlations with exchangeable cations, particularly in the E and upper B horizon. A sudden change in behaviour of 137Cs in the lower B horizon may be associated with changes in clay mineralogy along the soil profile caused by weathering.

Physiological parameters that affect the transfer of radiocaesium to ruminants.

Recently there has been a renewed interest in biological scaling relationships between parameters, such as those between, for example, body mass, dry matter intake and biological half-times of radionuclides that are useful in predicting the transfer of radiocaesium to different animal species, particularly to wild animals. However, there is still a considerable unexplained variability in transfer coefficient estimates between individuals of the same species. This paper discusses the physiological parameters that affect the transfer of radiocaesium to ruminants, and it shows how a better understanding of these parameters may help to reduce the within-species variability in radiocaesium transfer coefficients. In light of the improved understanding during the past 10-15 years of the importance of source-dependent bioavailability on absorption of radiocaesium from the gastrointestinal tract, it is concluded that further studies are required on the effects of feed digestibility and physiological factors on absorption and endogenous faecal excretion of radiocaesium to better understand the variability in transfer coefficients.

Atmospheric supply of trace elements studied by peat samples from ombrotrophic bogs.

Concentrations of Fe and 12 trace elements in peat from ombrotrophic bogs were used to estimate the atmospheric deposition of these elements on a temporal and spatial scale. Peat samples were collected at 21 different sites in Norway encompassing large geographical differences in marine influence and air pollution. The study demonstrates that surface peat is an excellent medium to study geographical differences in heavy metal deposition, provided that effects of the surface plant cover are properly considered. Long-range atmospheric transport of pollutants is the main source for As, Cd, Pb, Sb, and Zn, and to a lesser extent for Cu and Se. Biogenic emissions from the ocean appear to be the main source of Se to the peat. The metals Co, Cr, Fe, and Ni are mainly associated with wind-blown local soil dust. Surface enrichment of Mn, and in part Zn, is mainly caused by nutrient circulation between the surface peat and vascular plants growing on it. Deposition of marine salts appears to be the main reason for lower Mn concentrations in the peat near the coast.

Atmospheric deposition of lead in Norway: spatial and temporal variation in isotopic composition.

Moss samples collected from 22 sites all over Norway at five different times during 1977-2000 were analysed for stable lead isotope ratios. These data together with total lead concentrations and relevant literature lead isotope data from UK, western/central Europe and eastern Europe/Russia were used to elucidate major source regions for lead deposited in different parts of the country at different times. The southernmost part of the country was most affected from western/central Europe around 1975, but the deposition declined rapidly and UK became a more significant source region in the 1980s. Recently, the influence is mostly from Eastern Europe. In the west, UK was the dominant source region during the whole period. In the middle and northern regions, the deposition was low but also decreasing regularly, and the main source region was probably the North Atlantic. In the far north-east, influence from Russia and eastern Europe was dominant during the whole period.