Ash and Metal Concentrations in Peat Bogs as Indicators of Anthropogenic Activity

Stratigraphical (temporal) and physicochemical investigations of different European peat bogs confirm interrelations between increased ash and element concentrations on the one hand and human settlement (found by means of pollen analysis) on the other hand. Phases of enhanced anthropogenic activities (farming, forest clearing, forestry etc.), which can be derived from the corresponding pollen diagrams and by radiocarbon dating, agree well with the increase in soilborne elements (soil dust Pb, Si, Ti) in the peat profiles. The Pb concentrations of the investigated peat layers have been increasing since Roman Times. Changes in the Pb/Ti ratio help to discriminate between soil dust Pb and Pb from ore mining and smelting. Moreover, this approach reveals measurable Pb pollution extending as far back as the Bronze Age (approx. 2nd Millenium B.C.). Some peat bogs show increased Cu concentrations as far back as the Bronze Age.     

historical deposition rates of Cd,Cu, Pb,and Zn in Norway and Sweden estimated by 210Pb dating and measurement of trace elements in cores of peat bogs

From six ombrotrophic mires located far from distinct local sources in Sweden and Norway, a core was sampled in bog hummocks in 1988 and dated by 210_Pb. Ten slices from each core were analyzed for Cd, Cu, Pb, and Zn. Based on the datings, the accumulation rates of Cd, Cu, Pb, and Zn have been estimated for the last 150 years. A reasonable agreement exists in the comparison between the recent deposition in the peat bog and nearby bulk deposition measurements. Highest deposition has been measured in southern Norway and the western part of Sweden. Generally, deposition has increased during the last 150 years, except at a station on the east coast of Sweden. In a study in Sweden where heavy metals have been measured in mosses every five years time since 1970, significant decreases in the concentrations of heavy metals have been found. Similar decreases have not been measured in the present study, although both methods are expected to reflect atmospheric deposition. Several studies have indicated that peat bogs are not suitable for measuring the historical evolution of trace metals. However, despite the disagreement, the recent literature suggests that it can be done with reasonable accuracy when performed with samples from hummocks in the peat bog.     

Natural and anthropogenic enrichments of As,Cu, Pb,Sb, and Zn in ombrotrophic versus minerotrophic peat bog profiles,Jura Mountains,Switzerland

Peat cores were taken from two contrasting Sphagnum bogs in the Jura Mountains of Switzerland. At Etang de la Gruyere (EGr), 6.5 m of peat has accumulated during the past 10,000 years. In the first 100 cm of this profile there are several distinct peaks in ash content, but the values are well within the range for typical ombrotrophic Sphagnum bogs. There is also considerable variation in the concentrations of major and trace lithogenic metals (Al, Ti, Sc, Ca, Mg, Rb, and Sr), but most of this is simply a reflection of the natural variations in the amount of mineral matter in the peats. The Ca/Mg molar ratios in the peats at EGr are comparable to or lower than the average rainwater composition in this area, showing that this section of the peat core is ombrotrophic (i.e. rainwater-fed). In other words, the inorganic constituents in the surface peats at EGr were supplied exclusively by atmospheric deposition. This peat core, therefore, is suitable for studying the historical record of atmospheric metal deposition. Arsenic, Cu, Pb, Sb, and Zn are all more abundant in surface and near surface peat layers compared to deeper parts of the profile. Enrichment factors (EFs) for the profile were calculated conservatively by normalizing the metal/Sc ratios of individual peat samples to the average of the five lowest metal/Sc ratios in this part of the core (69–84 cm); these are tentatively assumed to represent pre-Industrial background values. The maximum EFs are approximately 5 times for Cu, 15 times for As, and 30 to 50 times for Pb, Sb, and Zn. At La Tourbière des Genevez (TGe), 1.5 m of peat represents 4,800 years of peat formation. At this site, the ash contents are higher and increase progressively with depth to values which are characteristic of minerotrophic fen peats. The concentration profiles of Al, Ti, Sc, Ca, Mg, Rb, Sr show the same general trend. The Ca/Mg molar ratios of these peats are generally twice the rainwater average, showing that this bog is essentially minerotrophic (ie groundwater-fed). Thus, the inorganic cccstituents in these peats were provided by both atmospheric and hydrospheric processes. Despite this, the Cu, Pb, Sb, and Zn concentrations are generally very similar to those at EGr, especially in the uppermost part of the profile, indicating that recent atmospheric inputs also dominate the supply of these metals to this bog. However, the minimum Pb and Sb concentrations in this profile are approximately five times higher than the corresponding values at EGr. The minerotrophic profile at TGT, therefore, could not by itself be used to calculate rates of atmospheric Pb and Sb deposition because it is impossible to distinguish between atmospheric and hydrospheric metal inputs. At TGe, As concentrations increase continuously with depth, reaching concentrations in the deeper, older peats which are more than 50 times higher than the ‘background’ As values at EGr. At this site the natural supply of As by mineral soil water completely masks the recent, elevated inputs contributed by atmospheric deposition. Thus, the peat core from TGe is also unsuitable for studying atmospheric As deposition.     

Lead in Three Peat Bog Profiles,Jura Mountains,Switzerland: Enrichment Factors,Isotopic Composition,and Chronology of Atmospheric Deposition

One metre cores were taken from three peat bogs in the Jura Mountains of Switzerland: Etang de la Gruère (EGr), La Tourbière des Genevez (TGe), and Praz Rodet (PRd). Dried peat samples were analyzed for lead (Pb) using the EMMA XRF and scandium (Sc) using INAA. Enrichment factors (EF) were calculated by normalizing to the background Pb/Sc ratio at EGr. Age dates were obtained using 210Pb (CRS Model) and confirmed using pollen chronostratigraphic markers in replicate cores. The isotopic composition of Pb in selected peat samples from EGr and TGe was determined using TIMS. Two pronounced peaks in Pb EF occur in the uppermost sections of all three bogs: the upper one corresponds to the late 1960's to late 1970's and the lower one to approximately 1900 to 1920. At EGr, sample 2f5 (11 cm, 86 µg/g Pb, EF = 91, and dated at A.D. 1967 ± 2) has an isotopic composition similar to that of leaded gasoline used in Berne in the 1970's. For comparison, the older peak at EGr (sample 2fl 1 at 29 cm, 84 µg/g Pb, EF = 79 and dated at A.D. 1905 ± 6) is significantly different. In contrast to these two samples, the isotopic composition of sample 2fl 5 (41 cm, 30 µg/g Pb, EF = 13 and pre-dating ca. A.D. 1800) approaches the present day "average terrestrial lead" and is likely to be predominately lithogenic. Therefore, the isotopic data show that the Pb introduced to the bog from leaded gasoline has not penetrated to this depth in the profile. A simple mass balance using the measured Pb concentrations and the isotopic compositions shows that vertical migration of gasoline Pb cannot explain the deeper, older peak in Pb EF. A more likely explanation is that the older peak reflects the rates of atmospheric Pb deposition during the first two decades of the 20th century. Taken together, the Pb concentrations, age dates, and isotopic data suggest that these peat profiles have preserved the record of changing rates of atmospheric Pb deposition. In addition, the results indicate that the isotopic composition of Pb deposited on the surface of the bogs gradually shifted away from lithogenic ratios as long ago as the middle of the 19th century, a change which clearly pre-dates the introduction of leaded gasoline.     

A Comparison of the Historical Lead Pollution Records in Peat and Freshwater Lake Sediments from Central Scotland

The concentrations, inventories, fluxes and isotopic composition of Pb in four 210Pb-dated cores from the raised Flanders Moss peat bog are compared with corresponding data for two sediment cores from Loch Lomond, also in central Scotland. Although the inventories and fluxes of Pb revealed by the peat record for the past few hundred years are generally lower, the isotopic records are in good agreement, confirming a prevailing 206Pb/207Pb ratio of 1.17 for anthropogenic ("industrial") Pb in the atmosphere prior to the introduction of leaded petrol in the 1920s. The 206Pb-depleted nature of the latter has resulted in a decline of about -0.04 to -0.05 in the 206Pb/207Pb ratio of deposited Pb for both peat and lake sediments. Despite the time-resolution limitations of the peat record, car exhaust emissions of Pb appear to have contributed 35-50% over the past 20 years, 15-30% over the past 75 years, but no more than 27% overall to the peat Pb burden. The finding that 67-85% of anthropogenic Pb in the peat was apparently deposited post-1900 compared with 51% for the Loch Lomond sediments could be due to geographical variations in atmospheric deposition of Pb, other additional inputs to the sediments, or perhaps to some post-depositional loss of Pb from peat, although the integrity of the 206Pb/207Pb record does argue against any significant vertical mobility of Pb in peat.     

a new high-pressure squeezing technique for pore fluid extraction from terrestrial soils

A core consisting of minerogenic peat and organic-rich mineral sediments was collected at an altitude of 4275 m in the Ovejuyo valley, 100 km NE of La Paz in Bolivia. Age dating with 210Pb showed that the core represents approximately three centuries of sediment accumulation. None of the peats are ombrotrophic. Despite this, the Cd/Al, Cu/Al, Zn/Al, and Pb/Al ratios are all significantly higher in the surface layers, particularly in the top 6 cm: natural, abiological geochemical processes, therefore, cannot account for these elevated heavy metal/Al ratios. There are two possible explanations for the metal enrichments, relative to Al, in the surface layers: bioaccumulation by living plants, and anthropogenic atmospheric metal deposition. While the living plant layer may be responsible for the Cd, Cu, and Zn enrichments, this is an unlikely explanation for the Pb profile. In contrast to the other metals, the concentration of Pb in the first sample (dating from 1985-1994) is less than that of the second sample (dating from 1970-1985). The Pb/Al profile is consistent with the well documented, rapid increase in atmospheric Pb emissions during the present century (which accelerated following the introduction of leaded gasoline), and the decline in Pb pollution during the past 20 years (as a result of the introduction of unleaded gasoline). Thus, the Ovejuyo Valley mire has provided one of the first records of atmospheric Pb pollution in South America.     

Atmospheric Lead Deposition from 12,400 to ca. 2,000 yrs BP in a Peat Bog Profile,Jura Mountains,Switzerland

The bog at Etang de la Gruère (Jura Mountains, Switzerland) consists of 420 cm of Sphagnum-dominated bog peat overlying 230 cm of Carex-dominated fen peat. One hundred cm below the bog surface, there is a pronounced peak in lead (Pb) concentration (approx. 10 µg/g) which has been dated at 2110 ± 30 BP and can be attributed to Roman Pb mining and smelting. Lead concentrations in peats from deeper, much older layers were measured using ICP-MS and found to be low and relatively constant (0.28 ± 0.04 µg/g, n = 17) from 405 cm to 235 cm which corresponds to the period from approx. 8,000 and 5,500 years before present (BP). In this same interval, scandium (Sc) concentrations (measured using INAA) were 0.07 ± 0.02 µg/g, yielding an average Pb/Sc ratio of 4.1 ± 1.2. These values are assumed to represent the true "background" Pb and Sc concentrations and Pb/Sc ratios of pre-anthropogenic aerosols. At 205 cm the Pb concentrations began to increase by 2 to 3 times, but these are proportional to the increases in aluminum (Al), titanium (Ti), silicon (Si), and Sc, and reflect an increase in Pb deposition supplied by silicate-derived soil dust. This depth, dated at 5,230 BP, coincides with the development of agriculture and indicates the impact of soil cultivation on metal fluxes to the air. At 115 cm, however, the Pb concentrations increase out of proportion with Sc; this point was dated at 3,000 BP and reflects the beginning of Pb contamination by mining and metallurgy in Europe and the Middle East. There are two pronounced peaks in Pb concentrations centered at 435 cm and 555 cm, corresponding with local maxima in ash and ash-forming major elements at the same depths. These samples have been dated at 8,230 BP and 10,590 BP, respectively, indicating the Vasset/Killian volcanic events (Massif Central, France) and Younger-Dryas cold phase as the most likely explanations.     

Role of cation exchange in preventing the decay of anoxic deep bog peat

The major bog systems in northern areas are dominated by Sphagnum species, the partially decomposed remains of which form the bulk of deep peat. By adding mono- and di-valent cations to deep peat cores (2.0-2.5 m) and measuring CH₄ and CO₂ concentrations in the manipulated peat cores using quadrupole mass spectrometry (QMS) we demonstrate that the lack of availability to microorganisms of essential cations is limiting decay in deep peat. The cations with the highest binding strength displaced the most cations and stimulated decay. Decay in deep peat cores was also stimulated by a C source (acetate), but not by NH₄⁺. The addition of cations and acetate resulted in a less than additive stimulation of decay. The stimulatory effect of acetate and copper decreased in the presence of ammonium. The addition of EDTA to surface bog peat (where cations are conserved) decreased decay rates in surface peat (0.0-0.5 m) to that of the untreated deep peat (2.0-2.5 m). Deep peat was unaffected by treatment with EDTA. The effect of adding Cu²⁺differed with the depth from which the peat was collected. Cu²⁺ did not stimulate decay in surface bog peat (0.0-1.5 m) but stimulated decay in peat from 1.5-3.5 m. Below 3.5 m to the bottom of the profile (5.0 m) no positive effect was observed. By comparing deep peat with surface peat we have shown that cation limitation because of high cation exchange capacity is specific to the main mass of deep bog peat and may explain differences in decay rates between anoxic surface peat and deep peat.     

Limited downward migration of pollutant metals (Cu,Zn, Ni,and Pb) in acidic virgin peat soils near a smelter

The distribution of pollutant heavy metals (Cu, Zn, Ni, Cd, and Pb) was determined in 11 acidic virgin peat profiles located along two transects moving away from a smelter plant in the Noranda region of Quebec. The levels of all five metals were found highest in the 0 to 15 cm layer at site near the smelter, and decreased progressively with the distance from the smelter, up to 42 km. Copper had the highest concentrations (5525 μg g^?1) followed by Pb and Zn. The maximum levels of total metals built up in the peat surface near the smelter were high, approximately reaching the threshold limits for phytotoxicity in peat soils. The amounts of heavy metals moving down and accumulating in the anaerobic zone of the peat profiles were limited. The distribution and enrichment ratios in the profiles showed that Cu, Zn, and Cd would have relatively higher mobility than Pb.     

Fens in Karst Sinkholes – Archives for Long Lasting `Immission' Chronologies

Fens in karst sinkholes are excellent archives for the reconstruction of vegetation, land use and emission rates over millennia. The reasons are the usually good preservation of pollen, the high portion of low density organic material with very low background concentrations of heavy metals, and the circum-neutral pH-values in most of these mires preventing migration of heavy metals. Immissions of dust and of harmful elements can easily be correlated with changes in vegetation (`immission' is a synonym for the deposition or impact of pollutants from the atmosphere on a receptor surface).One 13 m core from a ～5000 yr old karst sinkhole fen (Silberhohl, western margin of the Harz Mountains, central Germany) was investigated by geochemical analysis, pollen analysis and dated by ¹⁴C and palynological data. The core consists of organic material with a few percent of CaCO₃ precipitated from groundwater and a small amount of atmospheric detritus. As early as the Iron Age (first pre-Christian millennium), slight but significant enrichments of Pb, Zn, Cu and Cd are observed. After 400 AD stronger enrichments occurred culminating in the High Middle Ages (～1200–1300 AD). Maximum values are 1250 μg g^-1 Pb, 214 μg g^-1 Cu, 740 μg g^-1 Zn, and 3.8 μg g^-1 Cd. The enrichments are caused by emissions during smelting of sulfidic lead-zinc ores from the adjacent Hercynian deposits to extract Ag and Cu. Except for cadmium, these values were never exceeded in modern times. Since the Iron Age 23 g technogenic Pb, 5.3 g Cu, 27 g Zn and 0.2 g Cd have been deposited per square meter.Palynological investigations show a strong correlation between decreasing red beech pollens (Fagus sylvatica) and increasing demand on woodfor smelting in the Middle Ages. Simultaneously, the pollen share of pioneer trees such as birch (Betula pubescens) and of cereal grains (e.g. Secale) increases. Since the beginning of the 14th century, the decline of agriculture and population is reflected in the decreasing contents of Secale and heavy metals in the fen deposits.     

Losses of Soil Carbon upon a Fire on a Drained Forested Raised Bog

We studied the consequences of a fire that affected 29 ha of a drained forested raised bog in Tver oblast, Central European Russia. The drainage network consisted of open 1-m-deep ditches with 60 to 160 m ditch spacing. The groundwater level (GWL) varied within the studied drained bog. We used the method of assessing the loss of soil carbon (C) based on the difference between the ash concentration in the burnt peat of the upper layer and underlying unburnt layers. The carbon loss was higher near the drainage ditches than in the sites remote from ditches. The sample median values of carbon loss (kg C/m²) were estimated at 0.37 near the drainage ditches and at 0.22 for the remote sites with a distance of 160 m between ditches. They increased to 2.23 and 0.79 near and far from the drainage ditches for 106 m ditch spacing, and ranged from 1.13 to 2.10 near the drainage ditches and were equal to 0.45 at the remote sites for 60 m ditch spacing. The maximum loss of C was at the bog margin with the 70-cm-deep GWL; the sample median was equal to 2.97 kg C/m². The results obtained for C loss from the wildfire on the raised bog agree with the estimates obtained by other authors (1.45–4.90 kg C/m²) and confirm the importance of taking such loss into account in the estimates of the carbon budget of peat soils (Histosols).     

A Comparison of Temporal Patterns in Trace Metal Concentration in Tree Rings of Four Common European Tree Species Adjacent to a Cu-Cd Refinery

Metal processing at a Cu-Cd refinery at Prescot in N.W. England has led to severe contamination of the surrounding soils and vegetation, although Cu and Cd in bulk deposition declined dramatically between 1975 and 1990. Despite high spatial and temporal variability in metal deposition, mean Cd concentrations in annual tree rings of sycamore (Acer pseudoplatanus L.), lime (Tilia europaea L.) and beech (Fagus sylvatica L.) at Prescot were correlated with annual bulk Cd deposition. In contrast, mean Cd concentrations in ash (Fraxinus excelsior L.) were unrelated to Cd deposition and there was no significant relationship between mean Cu concentrations in tree rings and Cu deposition in any species. Mean Pb concentrations in sycamore, lime and beech at Prescot and the reference site also decreased over time. At Prescot however, Cd concentrations in tree rings formed in the mid 1990s were up to 10-fold higher than the reference site despite Cd deposition values during this period that were typical of levels expected for urban areas in the UK. The high Cd concentrations in wood during this period indicate that the majority of Cd in tree rings at Prescot is derived from soil, limiting the usefulness of dendrochemistry for monitoring temporal changes in metal deposition. It appears that trees are not simply passive recorders of metal deposition and other possibilities, in addition to decreasing atmospheric deposition, may explain the patterns of Cd and Pb found in sycamore, lime and beech. More research on the physiology of metal cycling in trees is required before dendrochemical techniques can be applied with confidence in environmental monitoring programs.     

Multi-element analysis of an english peat bog soil

Nineteen elements were quantitatively determined by atomic emission spectroscopy with inductively coupled plasma in peat profiles in Ringinglow Bog, Derbyshire, England. For the elements Ba, Ca, Cd, Co, Cr, Fe, La, Mn, Ni, Ti, and Zn an enrichment in the upper 5 cm of the peat bogs was found probably caused by anthropogenic influences. The elements Al, Be, Cu, and Pb showed a different distribution pattern with maximum concentration in the 5 to 15 cm layer. The elements Mg, Na, and Sr showed no enrichment in the upper 55 cm of the peat reflecting the constant input of these elements from the sea during the last few centuries. Upper parts (leaves and stems) of the plants investigated (Calluna vulgaris and Eriophorum vaginatum) only represent higher values of Pb compared with the normal element content in other plants. Compared with the results of peat profiles in a Norwegian bog, the concentrations of the comparable elements (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) are much higher in the English peat. Ringinglow Bog seem to be very suitable for further investigations within the scope of a global monitoring programme.     

Flüssebilanzen und aktuelle Änderungsraten der Schwermetall-Vorräte in Wald-Ökosystemen des Soiling

Flux balances and current rates of change of heavy metal stores in forest ecosystems of the Soiling The inventory of the heavy metals Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb is calculated for a beech and a spruce forest ecosystem in the Soiling mountains on the basis of measured concentrations in the vegetation and soil compartments and their dry mass per hectare. The inventory is compared with measured heavy metal fluxes coupled with precipitation above and below the canopy, with seepage water fluxes below the rooting zone (50 cm depth), with litterfall, and with the current increment to biomass. The ratios between heavy metal stores in the forest floor layers (table 3) and the annual flux with litterfall (table 4) show decreasing tendency for liberation of the elements by decomposition of organic matter (OM) in the following order: Mn>OM>Ni>Cd>Cu>Cr ≈? Zn>Co ≈? Fe ≈? Pb Manganese is set free faster than total organic matter. The flux balances for the total ecosystems (table 4) show input > output in the case of Cr, Fe, Cu, Cd, and Pb; input ≈? output for Ni and Zn; input < output for Mn and Co. Heavy metal stores in mineral soil are decreasing by percolation losses and increment to biomass (mainly wood) in the case of all elements investigated, except Zn (under beech), Cd and Pb (table 4). The concentrations of Cu and Pb in the forest floor layers have reached levels at which deleterious effects on microorganisms and litter decomposition are to be expected.     

Functioning of microbial complexes in aerated layers of a highmoor peat bog

Monitoring was carried out using the luminescent-microscopic method of the abundance parameters of different groups of microorganisms in a monolith and in the mixed layers of a highmoor peat bog (oligotrophic residual-eutrophic peat soil) in a year-long model experiment. The increase of the aeration as a result of mixing of the layers enhanced the activity of the soil fungi. This was attested to by the following changes: the increase of the fungal mycelium length by 6 times and of the fungal biomass by 4 times and the double decrease of the fraction of spores in the fungal complex. The response of the fungal complex to mixing was different in the different layers of the peat bog. The maximal effect was observed in the T1 layer and the minimal one in the T2 layer. The emission of CO₂ in the mixed samples was 1.5–2 times higher than that from the undisturbed peat samples. In contrast with the fungi, the bacteria and actinomycetes were not affected by the aeration of the highmoor layers.     

Four Thousand Years of Atmospheric Pb,Cd and Zn Deposition Recorded by the Ombrotrophic Peat Bog of Penido Vello (Northwestern Spain)

The Northwestern Iberian Peninsula is a mid-latitude oceanic region with areas where different types of bogs are frequent or abundant. The ombrotrophic nature of some bogs make them suitable for the study of accumulation patterns of heavy metals. One of these bogs, Penido Vello, was sampled to a depth of 2.5 m and analyzed in detail for its physico-chemical properties and Pb, Zn and Cd concentrations. Ash and organic carbon content, Ca/Mg molar ratios and a number of other characteristics support an ombrotrophic interpretation of the core. Concentrations of Pb, Zn and Cd were measured, showing important variations in the core. While Zn and Cd are concentrated mainly in the upper sections of the core with minor changes with depth, the Pb profile shows significant peaks in the deeper layers suggesting pre-industrial atmospheric pollution. Enrichment factors (EFs) calculated by normalising to Al correlate well with those calculated by normalising to Ti. Maximum EFs are 33, 56 and 52 for Pb, Zn and Cd respectively. While for Pb these values are comparable to those obtained by other authors, maximum Zn EFs are greater than those mentioned in the literature and may be attributed to the emissions of a nearby coal-burning power plant. At least for Pb the accumulation pattern suggests that atmospheric pollution can be dated back some 2800 years, and that pollution increased steadily since the Iron Age to reach considerably elevated levels, up to 5 times the ‘background’, during the Roman Empire. Changes in Pb emissions through time are in good accord with the prehistorical and historical record of the Iberian Peninsula.     

Die räumliche Variabilität von Schwermetall-Konzentrationen in Niederschlägen und Sickerwasser von Waldstandorten des Sollings

Local variability in the heavy metal concentrations of precipitation and seepage water from forest sites in the Solling Concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in precipitation and seepage water have been measured continuously with local replicates during a 6-months period at a beech and a spruce forest site. Variation coefficients of the avarage concentrations were, in most cases, well below 30 %, being mainly caused by local differences. Comparison of means showed a significant increase of heavy metal concentration in the canopy drip of beech (Mn, Fe, Pb) and spruce (Cr, Mn, Fe, Ni, Zn, Pb) compared to bulk precipitation measured in the open field. Concentration of Mn, Co, Ni, Zn and Cd in the seepage water is significantly higher under spruce compared to beech. These results point at higher filter efficiency of the spruce canopy, compared with beech, for air pollutants, but a smaller retention capacity of the soil under spruce for heavy metals.     

An Air-Pollution History of Metallurgical Innovation in Iron- and Steel-Making: A Geochemical Archive of Sheffield

This paper explores the degree to which palaeoecological analyses can determine the history of metallurgical innovation and complex technological developments that took place in the iron- and steel industries of the City of Sheffield, Yorkshire, England. A knowledge of the key scientific breakthroughs as well as documentary evidence of industrial growth and decline in Sheffield are used as base-line historical data with which to interpret the palaeoecological and geochemical evidence presented here as a result of investigations of peats and clays collected from the Tinsley Park Bog in the Lower Don Valley of Sheffield. These deposits were analysed for charcoal, pollen, mineral magnetic properties and some trace elements (Ti, V, Fe, Co, Ni, Zn, and Pb). Metal concentrations (measured using AAS) were as high as 320 ppm Ni, 472 ppm Cu, 613 ppm Zn, and 827 ppm Pb. Compared to the typical concentrations found in crustal rocks, Ni is enriched in the peats and sediments by as much as a factor of 5 times, Cu and Zn by a factor of 10, and Pb by more than 60 times. The lowest concentrations of Cu, Ni, Zn and V were found in the basal peats of Tinsley Park Bog arguing against a natural geochemical source as the cause of the enrichments. The greatest Cu and Zn enrichments are found in the peats in the top 0.1 m of the bog, possibly an indication of a large Special Steels Plant which began production nearby in 1963. Below these levels in the peat, in contrast, Ni and V are relatively abundant. They are believed to reflect the manufacture of complex steels during the earlier part of the twentieth century. Lead is most abundant in samples from depths in the peat which are though to post-date the onset of coal utilisation at the nearby Rothervale Mine. Interpretation is hampered because at present there is no independent evidence of the antiquity of the peat deposits studied. Neither is there any clear understanding of the significance of the taphonomic processes which have influenced the geochemical and paleoecological records obtained from the deposits. Nevertheless, our present interpretation of the data presented here indicates that to a suprising extent, it is possible to detect in the peat monolith (i) evidence of the expansion and relative decline of the adjacent steel industry; (ii) the impact of this manufacturing economy and associated coal-mining upon the adjacent vegetation; and (iii) the introduction of trace elements in pure forms or as alloys, as steel-making processes developed through the 19th and 20th centuries.     

Stable Isotope and Concentration Records of Atmospheric Lead Pollution in Peat and Lake Sediments in Sweden

We compare lead concentration and stable lead isotope analyses from three peat bog and three lake sediment records in Sweden. Radiocarbon dated stratigraphies give evidence that trends in the concentration of Pb in the peat and sediment cores are very similar, and follow the general outline of historical global Pb production over several thousand years. Due to the large difference in the 206Pb/207Pb ratio between Sweden, about 1.5, and continental Europe (excluding Fennoscandia), ≤1.2, it is possible to distinguish external sources of Pb to Sweden. In the lake sediments, profiles of 206Pb/207Pb ratio mirror the Pb concentration until 1000 AD; increasing concentration is accompanied by decreasing ratios. After 1000 AD the ratio varies little at about 1.2 in sediments, because of the near total dominance of pollutant Pb. There is a further decline in the Pb ratio to about 1.14 in this century as a result of the addition of alkyl-Pb in petrol. The Pb concentration profiles in the peat match the lakes, but the isotope profiles do not. During the fen-to-bog transition there is a rapid decline in the 206Pb/207Pb ratio from >1.3 to about 1.2, and the ratio continues to decline to the present. We hypothesise that this is because externally-derived Pb from long-range transport of soil dust and atmospheric pollution has always been more important in the ombrotrophic peat than in lakes, which have a greater influx of catchment-derived Pb.     

Polycyclic aromatic hydrocarbons (PAHs) in peat and plants from selected peat‐bogs in the north‐east of Poland

The concentrations of polycyclic aromatic hydrocarbons (PAHs) were analyzed in samples of peat and of two plant species (Pinus sylvestris and Ledum palustre) overgrowing peat‐bogs in the north‐east of Poland. Peat samples were collected from different depths according to the stratigraphic profile of the peat bogs. The total concentrations of the 16 anthropogenic PAHs (15 from the US EPA list and benzo[e]pyrene) in all peat samples were between 70 and 439 ng g^—1. The concentration for the same compounds in pine needles (Pinus sylvestris) and Dutch Myrthe leaves (Ledum palustre) varied between 194 and 1039 ng g^—1. A noticeably high fluorene concentration in Dutch Myrthe leaves was found at some sites. In all peat samples 3‐ring compounds were predominant (55 to 319 ng g^—1). There were less 4‐ring PAHs (15 to 110 ng g^—1) and the least common PAHs were 5‐ring and 6‐ring compounds (0 to 81 ng g^—1 for both groups). In some peat samples, the perylene concentration largely exceeds of the total concentration of all the other PAHs investigated. The high content of perylene in bottom layers could result from the processes of perylene sorption from water during peat‐bog formation or from biogenic formation of perylene.