Comment 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 Ewa Miszczak, Sebastian Stefaniak, Adam Michczynski, Eiliv Steinnes and Irena Twardowska.

A recent paper by Miszczak et al. (2020) examines metal contamination of mires in Poland and Norway. The authors conclude that lead (Pb) records in ombrotrophic peatlands cannot be used to reconstruct the chronological history of anthropogenic activities due to post-depositional mobility of the metal. We contest this general conclusion which stands in contrast with a significant body of literature demonstrating that Pb is largely immobile in the vast majority of ombrotrophic peatlands. Our aim is to reaffirm the crucial contribution that peat records have made to our knowledge of atmospheric Pb contamination. In addition, we reiterate the necessity of following established protocols to produce reliable records of anthropogenic Pb contamination in environmental archives.

Geochemistry and pH control of seepage from Ni-Cu rich mine tailings at Selebi Phikwe, Botswana.

Acid mine drainage from mine tailings at Selebi Phikwe, eastern Botswana, has been investigated using a combination of total decomposition, sequential extraction, X-ray diffraction, Mössbauer spectroscopy, and SEM analyses of solid phase samples, water analyses, isotopic analyses, and geochemical modeling. The principal ferric phases in the seepage stream sediments are jarosite and goethite, which incorporate Ni and Cu. The Mössbauer spectroscopy (MS) indicated exclusively 3+ oxidation state of iron with typical features of ferric hydroxides/sulfates. A fraction of dissolved sulfate is also sequestered in gypsum which precipitates further downstream. Significant portions of Fe, Ni, and Cu are transported in suspension. Values of pH decreased downstream due to H+ generated by the precipitation of jarosite. Values of δ2H and δ18O indicate evaporation of pore water in the mine tailings before seepage. Values of δ34S(SO4) are consistent with the oxidation of sulfides, but sample from the seepage face is affected by dissolution of gypsum. No minerals of Ni and Cu were detected and the principal attenuation processes seem to be adsorption and co-precipitation with jarosite. Higher contents of Cu are sequestered in solid phases compared to Ni, in spite of much higher dissolved Ni concentrations. Based on the speciation calculations, seepage water is undersaturated with respect to all Ni and Cu phases and adsorption and co-precipitation with jarosite seems to be the principal attenuation processes. Direct geochemical modeling was able to reproduce downstream pH trends, thus confirming the precipitation of jarosite as the principal pH-controlling process.

Geochemical sources, forms and phases of soil contamination in an industrial city.

This study examines current soil contamination in an Australian industrial city, Newcastle. Public (roadside verges and parks) and private (homes) surface soils (n=170) contained metal(loid)s elevated above their respective Australian Health Investigation Levels (HIL). Lead (Pb), the most common contaminant in the city, exceeds the HIL for residential soils (HIL-A, 300mg/kg) in 88% of private soils (median: 1140mg/kg). In-vitro Pb bio-accessibility analysis of selected soils (n=11) using simulated gastric fluid showed a high affinity for Pb solubilisation (maximum Pb concentration: 5190mg/kg, equating to 45% Pb bio-accessibility). Highly soluble Pb-laden Fe- and Mn-oxides likely contribute to the bio-accessibility of the Pb. Public and private space surface soils contain substantially less radiogenic Pb (range: 208Pb/207Pb: 2.345-2.411, 206Pb/207Pb: 1.068-1.312) than local background soil (208Pb/207Pb: 2.489, 206Pb/207Pb: 1.198), indicating anthropogenic contamination from the less radiogenic Broken Hill type Pb ores (208Pb/207Pb: 2.319, 206Pb/207Pb: 1.044). Source apportionment using Pb isotopic ratio quantification and soil mineralogy indicate the city's historic copper and steel industries contributed the majority of the soil contaminants through atmospheric deposition and use of slag waste as fill material. High-temperature silicates and oxides combined with rounded particles in the soil are characteristic of smelter dust emissions. Additionally, a preliminary investigation of polycyclic aromatic hydrocarbons in soils, sometimes associated with ferrous metal smelting, coal processing or burning of fossil fuels, shows that these too pose a health exposure risk (calculated in comparison to benzo(a)pyrene: n=12, max: 13.5mg/kg, HIL: 3mg/kg).

Geochemistry of mine tailings and behavior of arsenic at Kombat, northeastern Namibia.

The mine tailings at Kombat, in semiarid northeastern Namibia, were investigated by the combination of solid-phase analyses, mineralogical methods, leaching tests, and speciation modeling. Dissolution of the most abundant primary sulfides, chalcopyrite and galena, released copper and lead which were adsorbed onto ferric oxyhydroxides or precipitated in the form of malachite, Cu2CO3(OH)2, and cerussite, PbCO3, respectively. Arsenic released from arsenopyrite was incorporated into ferric oxyhydroxides. Based on sequential extraction and (57)Fe Mössbauer spectroscopy, a large amount of ferric iron is present as low solubility hematite and goethite formed rapidly (<10 years) under warm semiarid climatic conditions, and arsenic in these phases is relatively tightly bound. It seems that Cu and especially Pb in carbonate minerals represent a more serious environmental risk. Immobilization of As in hematite has implications for other mining sites in regions with similar climatic conditions because this process results in long-term immobilization of As.

Mercury accumulation in peatbogs at Czech sites with contrasting pollution histories.

Mercury (Hg) concentrations and accumulation patterns were studied in (210)Pb-dated peat cores from three ombrotrophic sites in the Czech Republic with contrasting emission histories (Novodomské raseliniste, ND, and Bílá Smedá, BS, in the polluted northern parts of the country, and Jezerní slat, JS, in a relatively pristine southern part of the Czech Republic). The Hg concentration varied significantly between sites. Whereas the sites in the northern part of the Czech Republic yielded a range of higher Hg concentrations (50-750 µg kg(-1) for ND and 30-600 µg kg(-1) for BS), a Hg concentration range of 40-220 µg kg(-1) was reported at JS. At the northern localities, the highest Hg concentrations were detected at depths of 5-10 cm, corresponding to the period between the early 1960s until the late 1980s. In contrast, the highest Hg values at JS were observed at a depth of 10-15 cm, corresponding to the period between the early 1950s and the early 1970s. The maximum Hg accumulation rates were approximately 2× higher at the northern localities (ND: 106 µg m(-2)yr(-1), BS: 90 µg m(-2)yr(-1), JS: 43 µg m(-2)yr(-1)). Although a decrease in the Hg concentration can be observed in the youngest segments of all the peat cores, a slight increase in Hg accumulation rates in the most recent peat segments (living Sphagnum moss) has been reported for all three sites (40-44 µg m(-2)yr(-1)), which is approximately 2× higher than in peat bogs in western and northern Europe. This observation may either be related to a real recent increase in Hg emissions in Central Europe (active coal mining and burning and limited Hg pollution control in thermal power plants) or could indicate a preferential Hg binding mechanism in the living moss at the surface of the peat.

Lead fluxes, isotopic and concentration profiles in a peat deposit near a lead smelter (Príbram, Czech Republic).

The content and the isotopic composition of lead (Pb) were studied in a peat deposit on the ridge of the Brdy Hills, in the vicinity of the Príbram metallurgical works, in the Czech Republic. Quadrupole ICP MS was employed to determine the elemental composition and (206)Pb/(207)Pb and (208)Pb/(206)Pb isotope ratios. The individual layers were dated using alpha spectrometric measurement of the (210)Pb activity. The historical time period covered by the studied cores reached back to the 18th century. The Pb concentration in the studied profiles varied from 10 to 550 mg kg(-1). The (206)Pb/(207)Pb ratio varied in the range from 1.154 to 1.194 in the individual parts of the profile. The metallurgy of the Pb ores ((206)Pb/(207)Pb approximately 1.16), lithogenic Pb ((206)Pb/(207)Pb approximately 1.2), metallurgical processing of automobile batteries ((206)Pb/(207)Pb approximately 1.17) and the combustion of coal ((206)Pb/(207)Pb approximately 1.17-1.19) yield isotopic signatures that determine the isotope compositions of the individual profiles. Deposition rates between 15 mg m(-2) year(-1) at the beginning of the 19th century and 320 mg m(-2) year(-1) in the 1980s were determined in the dated profiles. The increased deposition rates determined on the dated profiles correspond to the increasing production of Pb ores in the Príbram mining area at the turn of the 19th and 20th centuries. The maximum for metallurgical production corresponds to the highest deposition rates recorded in 1960s and 1970s. The current deposition rate of 5-89 mg m(-2) year(-1) Pb is related to erosion of contaminated soils and waste dumps.

A comparison of sequential extraction techniques for determining arsenic fractionation in synthetic mineral mixtures.

The sequential extraction methods according to Tessier et al., Borovec et al., Zhang and Moore and Hall et al. have been tested for their suitability for arsenic fractionation in samples of artificially prepared mineral mixtures. Mixtures containing different amounts of As-containing phases were prepared so that their compositions corresponded to weathering products on As-bearing ore deposits. A comparison of different procedures on simple mineral mixtures containing calcium arsenate (CaHAsO(4).H(2)O), As-bearing goethite (FeOOH) and arsenopyrite (FeAsS) showed that only the results of the Hall method satisfactorily correspond to the expected arsenic distribution. A detailed verification of the Hall method was subsequently carried out on most complex synthetic mineral mixtures with varying amounts of As-containing kaolinite and carbonate, calcium arsenate, As-bearing goethite and arsenopyrite. The results confirm that the Hall method cannot be fully employed for an accurate As speciation but may be applied for a route identification of As distribution between "labile", "medium-labile" and "residual" forms in heavily polluted soils.