Dry deposition and foliar leaching of mercury and selected trace elements in deciduous forest throughfall

The estimated annual throughfall deposition flux of Hg in a northern mixed-hardwood forest in the Lake Huron Watershed was 10.5±1.0 μg m⁻² compared to an annual precipitation Hg flux of 8.7±0.5 μg m⁻² (June 1996–June 1997). The source of this additional Hg in throughfall is often attributed to wash-off of dry deposition, but foliar leaching of Hg may also be important. To determine the influence of both dry deposition and foliar leaching of Hg and other elements in throughfall, we measured a suite of trace elements (Hg, Al, Mg, V, Mn, Cu, Zn, As, Rb, Sr, Cd, Ba, La, Ce, and Pb) in throughfall, precipitation, and ambient air samples from a northern mixed-hardwood forest. Based on a multiple linear regression model, dry deposition had the most important influence on Hg, Al, La, Ce, V, As, Cu, Zn, Cd, and Pb fluxes while foliar leaching strongly influenced Mg, Mn, Rb, Sr, and Ba fluxes in net throughfall. The Hg dry deposition flux was estimated using gaseous and aerosol Hg measurements and modeled deposition velocities. The calculated dry deposition flux (∼12–14 μg m⁻²) of Hg to the canopy indicated that atmospheric deposition of Hg could easily account for all of the Hg deposited in net throughfall (1.9±0.1 μg m⁻²). Although there is a large uncertainty associated with these techniques, the modeling estimates indicate that atmospheric Hg may account for all of the Hg deposited in litterfall (11.4±2.8 μg m⁻²).     

Comparison of forest edge effects on throughfall deposition in different forest types

This study examined the influence of distance to the forest edge, forest type, and time on Cl⁻, SO₄²⁻, NO₃⁻, and NH₄⁺ throughfall deposition in forest edges. The forests were dominated by pedunculate oak, silver birch, or Corsican/Austrian pine, and were situated in two regions of Flanders (Belgium). Along transects, throughfall deposition was monitored at distances of 0-128 m from the forest edge. A repeated-measures analysis demonstrated that time, forest type, and distance to the forest edge significantly influenced throughfall deposition of the ions studied. The effect of distance to the forest edge depended significantly on forest type in the deposition of Cl⁻, SO₄²⁻, and NO₃⁻: the edge effect was significantly greater in pine stands than in deciduous birch and oak stands. This finding supports the possibility of converting pine plantations into oak or birch forests in order to mitigate the input of nitrogen and potentially acidifying deposition.     

Modelling trace metal partitioning in forest floors of northern soils near metal smelters

Trace metal (TM) mobility and toxicity varies with changing soil conditions. Geochemical models can account for the influence of soil characteristics on TM behaviour. We tested the effectiveness of the Stockholm humic model (SHM), and the NICA-Donnan model (NDM) to estimate partitioning coefficients (logKd) in 26 forest floor horizons of podzolic soils enriched in trace metals from deposition by metal smelters. We wanted to know if a consistent approach could be applied to model metal partitioning in forest floors without optimizing each individual soil. When optimized, the SHM reproduced the partitioning of Cd, Cu and Zn but not Pb. It was necessary to revise the affinity constants for the NDM to simultaneously simulate the partitioning of the four metals. Revised affinity constants for the NDM model based on a fixed definition of soil organic carbon, i.e., a fixed ratio of fulvic and humic acids per unit carbon, reproduced metal partitioning more effectively in an independent data set of 16 soils than the use of generic affinity constants available for these models. From the perspective of the applicability of these models to risk assessment, this result suggests geochemical models using affinity constants that have been verified and/or modified against multiple soils from a region can provide good estimates of metal partitioning on a regional scale.     

Evaluation of approaches to calculate critical metal loads for forest ecosystems

This paper evaluates approaches to calculate acceptable loads for metal deposition to forest ecosystems, distinguishing between critical loads, stand-still loads and target loads. We also evaluated the influence of including the biochemical metal cycle on the calculated loads. Differences are illustrated by examples of Cd, Cu, Pb and Zn for a deciduous forest on five major soil types in the Netherlands. Stand-still loads are generally lower than critical loads, which in turn are lower than the target loads indicating that present levels are below critical levels. Uncertainties in the calculated critical loads are mainly determined by the uncertainty in the critical limits and the chemical speciation model. Including the metal cycle has a small effect on the calculated critical loads. Results are discussed in view of the applicability of the critical load concept for metals in future protocols on the reduction in metal emissions.     

Spatial variability of throughfall fluxes in a spruce forest

The spatial variability of throughfall deposition of H(+), Ca(2+), Mg(2+), Na(+), K(+), Cl(-), NO(3)(-), NH(4)(+), O(4)(2-) to a Norway spruce (Picea abies (L.) Karst.) forest was intensively examined during the period October 1986 to October 1987. Large systematic spatial variability of the atmospheric deposition within the forest was observed. The flux of throughfall water was higher away from the trunk compared to the flux close to the trunk. In contrast to this, the deposition of all substances was considerably higher close to the trunk compared to the deposition at the periphery of the canopy. A linear decrease in deposition as a function of the distance from the nearest tree trunk was found. Further, the deposition varied quite dramatically between trees according to their size. The observed spatial variability in throughfall may be due to variabilities in the processes taking part in altering the distribution and composition of the precipitated water as it moves through the canopy. The influence of these processes of precipitation, wash-off, dry deposition and canopy exchange is discussed, and it is found that both increased dry deposition and canopy exchange in the tree tops contribute to the higher solute fluxes found close to the tree trunk.     

Monitoring historical changes in soil and atmospheric trace metal levels by dendrochemical analysis

The use of dendrochemistry for monitoring historical changes in trace metal deposition and mobilisation of metals in soils is evaluated. In experimental studies, mobilisation of trace metals in surface soil following deliberate acidification was recorded in sugar maple (Acer saccharum) tree-rings with minimal lateral movement between rings. Furthermore, positive correlations between wood (3 year section 1993-95) and foliar chemistry (mean concentration 1993-95) were found for Cd and Zn, but not for Cu and Ni, showing that mobility up the tree bole differs between metals. Even so, substantial lateral movement of elements between rings occurs in some species. Stable Pb isotope ratios in tree-rings were used to show that sacred fir (Abies religeosa) is not a useful monitor of Pb deposition because Pb accumulates in the heartwood. Numerous sophisticated analytical techniques are now used in dendrochemical studies, including laser ablation sampling in conjunction with inductively coupled plasma mass spectrometry that enable the multi-element analysis of extremely small tree-rings with low detection limits. Clearly, not all tree species are suitable for dendrochemical studies, but if careful sampling strategies are used and suitable tree species are chosen, the chemical analysis of tree-rings can provide information concerning historical changes in soil and atmospheric trace metal levels unavailable from any other source.     

Long term changes in atmospheric N and S throughfall deposition and effects on soil solution chemistry in a Scots pine forest in the Netherlands

In a Scots pine forest the throughfall deposition and the chemical composition of the soil solution was monitored since 1984. (Inter)national legislation measures led to a reduction of the deposition of nitrogen and sulphur. The deposition of sulphur has decreased by approximately 65%. The total mineral-nitrogen deposition has decreased by ca. 25%, which is mainly due to a reduction in ammonium-N deposition (−40%), since nitrate-N deposition has increased (+50%). The nitrogen concentration in the upper mineral soil solution at 10 cm depth has decreased, leading to an improved nutritional balance, which may result in improved tree vitality. In the drainage water at 90 cm depth the fluxes of NO₃⁻ and SO₄²⁻ have decreased, resulting in a reduced leeching of accompanying base cations, thus preserving nutrients in the ecosystem. It may take still several years, however, before this will meet the prerequisite of a sustainable ecosystem.     

The influence of inputs to the Firth of Forth on the concentrations of trace metals in coastal waters

The distribution of copper, lead and cadmium in dissolved and particulate phases has been investigated in the Firth of Forth, Scotland, an embayment of the North Sea. The effect of riverine and anthropogenic trace metal inputs on concentrations in the Firth of Forth and adjacent North Sea is examined. For the dissolved phase the effect of such inputs is confined to the immediate area of discharge. Concentrations in the outer Firth are indistinguishable from those in coastal waters of the North Sea, ca. Cu, 0.2 microgdm(-3) (3.1nm); Pb, 0.025 microgdm(-3) (0.12nm) and Cd, 0.020 microgdm(-3) (0.18nm). There is evidence that particulates enhanced in trace metals, relative to bottom sediments, are leaving the Forth and entering the North Sea. Predictions of the total metal concentrations in the waters of the inner Firth, based on riverine, industrial and sewage associated inputs, show reasonable agreement with observed values.     

Input of atmospheric sulfur by dry and wet deposition to two central European forest ecosystems

The total input of atmospheric sulfur to a beech and a spruce forest in the Federal Republic of Germany has been measured over a period of 6 years. The contribution of dry deposition to the total input was determined indirectly by comparing seasonal changes in the sulfur flux coupled with precipitation beneath the canopy of the deciduous beech forest. As a result of these investigations seasonal and annual sulfur fluxes are reported corresponding to removal rates of atmospheric sulfur. The experimental data show clearly that the removal rates depend upon the quality of the atmosphere/ land interface, in forested areas from the tree species forming the canopy. The 6-years average of total deposition on bare soil is 23kg S ha⁻¹ y⁻¹, on a beech forest 47–51 kg S ha⁻¹y⁻¹, on a spruce forest 80–86 kg S ha⁻¹ y⁻¹. Based upon the experimental results the role of the forest vegetation in the removal of sulfur from the atmosphere in the area of the Federal Republic of Germany is considered. The figures indicate, that at least 50% of the total sulfur deposition takes place on forested areas which cover only 28% of the total land surface.     

Dry atmospheric inputs of trace metals at the Mediterranean coast of Israel (SE Mediterranean): sources and fluxes

This study presents the first detailed data on aerosol concentrations of trace metals (Cd, Pb, Cu, Zn, Cr, Mn, Fe and Al) at the SE Mediterranean coast of Israel, and assesses their sources and fluxes. Aerosol samples were collected at two sampling stations (Tel-Shikmona and Maagan Michael) along the coast between 1994 and 1997. Two broad categories of aerosol trace metal sources were defined; anthropogenic (Cd, Cu, Pb and Zn) and naturally derived elements (Al, Fe, Mn and Cr). The extent of the anthropogenic contribution was estimated by the degree of enrichment of these elements compared to the average crustal composition (EF_crust). High values (median >100) were calculated for Cd, Pb and Zn, minor values for Cu and relatively low values (<10) for Fe, Mn and Cr. The crustal-derived elements exhibited a statistically significant seasonal pattern of higher concentrations during spring and autumn (e.g. Al concentrations in some cases during these periods were observed to be in excess of 1500 ng m⁻³). In the eastern Mediterranean basin crustal-dominated elements are enriched by 2–3 times while others (Cd and Pb) are comparable to the northwestern Mediterranean. The Pb : Cd ratios of ∼150 are higher than in coastal European sites (60–116) or emission materials (∼50). It is speculated that these differences are attributed mainly to the mixing of crustal material with local and European emissions. At present, it is impossible to quantify the latter two fractions. Back trajectory analysis and the subsequent categorization of two main aerosol populations, ‘European’ and ‘North Africa–Arabian’, exhibited a significantly different geochemical imprint on the aerosol chemical composition. ‘European’-derived air masses indicated significantly higher EF_crust values for Cd and Pb due to the greater anthropogenic character of the aerosol population, with a dilution by crustal material of this population leading to comparatively lower EF_crust values associated with the North African–Arabian air masses.     

Dynamics of trace metals in organisms and ecosystems: prediction of metal bioconcentration in different organisms and estimation of exposure risks

Metal ions interact with biological materials and their decomposition products by ligation (coordination complex-formation with certain moieties containing O, N, S, etc.). The extent of this interaction depends on the identities of both ligand and metal ion and can be described by some equation derived from perturbation theory. Uptake of metal ions - including highly toxic ones - from soils is controlled by a competition between root exudate components and soil organic matter (SOM) for the ions. SOM consists of a variety of potential ligands which evolve during humification towards more efficient binding (retention) of metals such as Cu, Ni, Cr but also of toxicants like U, Cd. The actual way of interaction can be inferred from stoichiometry of the involved compounds and the C/N ratio in the soil, providing predictions as to which metals will be most efficiently shuttled into green plants or fungi, respectively. The latter, selective process is crucial for closing nutrient cycles and sensitively depends on C/N ratio and the extent of "forcing" by onfalling leaf or needle litter. Therefore, analytical data on the soil can be used to predict possible risks of exposition to toxic metals also for human consumption of plant parts.     

Epiphytic lichens as sentinels for heavy metal pollution at forest ecosystems (central Italy)

The results of a study using epiphytic lichens (Parmelia caperata) as sentinels for heavy metal deposition at six selected forest ecosystems of central Italy are reported. The woods investigated are characterized by holm oak (Quercus ilex), turkey oak (Quercus cerris) and beech (Fagus sylvatica) and represent the typical forest ecosystems of central Italy at low, medium and high elevations, respectively. The results showed that levels of heavy metals in lichens were relatively low and consequently no risk of heavy metal air pollution is expected for the six forest ecosystems investigated. However, for two of them there are indications of a potential risk: the beech forest of Vallombrosa showed signs of contamination by Pb as a consequence of vehicle traffic due to the rather high touristic pressure in the area, and the holm oak forest of Cala Violina showed transboundary pollution by Mn, Cr and Ni originating from the steel industry in Piombino. Epiphytic lichens proved to be very effective as an early warning system to detect signs of a changing environment at forest ecosystems.     

Oribatid mite communities and metal bioaccumulation in oribatid species (Acari, Oribatida) along the heavy metal gradient in forest ecosystems

The responses of oribatid communities to heavy metal contamination were studied. Concentration of cadmium, copper and zinc in nine oribatid species along a gradient of heavy metal pollution was measured. Oribatid mites were sampled seasonally during two years in five forests located at different distances from the zinc smelter in the Olkusz District, southern Poland. The most numerous and diverse oribatid communities were found in the forest with moderate concentrations of heavy metals. Analysis by atomic absorption spectrophotometry revealed large differences in metal body burdens among species. All studied oribatid species appeared to be accumulators of copper with Oppiella nova, Nothrus silvestris and Adoristes ovatus characterized by the highest bioaccumulation factors. Most species poorly accumulate cadmium and zinc. The accumulation of heavy metals in the body of oribatids was not strictly determined by their body size or the trophic level at which they operate.     

Eutrophication: impacts of excess nutrient inputs on freshwater, marine, and terrestrial ecosystems

In the mid-1800s, the agricultural chemist Justus von Liebig demonstrated strong positive relationships between soil nutrient supplies and the growth yields of terrestrial plants, and it has since been found that freshwater and marine plants are equally responsive to nutrient inputs. Anthropogenic inputs of nutrients to the Earth's surface and atmosphere have increased greatly during the past two centuries. This nutrient enrichment, or eutrophication, can lead to highly undesirable changes in ecosystem structure and function, however. In this paper we briefly review the process, the impacts, and the potential management of cultural eutrophication in freshwater, marine, and terrestrial ecosystems. We present two brief case studies (one freshwater and one marine) demonstrating that nutrient loading restriction is the essential cornerstone of aquatic eutrophication control. In addition, we present results of a preliminary statistical analysis that is consistent with the hypothesis that anthropogenic emissions of oxidized nitrogen could be influencing atmospheric levels of carbon dioxide via nitrogen stimulation of global primary production.     

Rain and throughfall chemistry in a Norway spruce forest in the Western Prealps

From January 1987 to December 1989 precipitation was collected in an open field in a forested area of the Western Prealps. The site faces the intensely industrialized area of the Po Valley. In a Norway spruce plantation, next to the open field sampler, throughfall was collected from January 1987 to August 1989 for a period of 32 months. In the common sampling period median pH values of the open field precipitation and throughfall were 4.28 and 4.19 respectively. Open field precipitation has yearly deposition rates of acidity, Ca, S, and N of 0.81, 9.82, 24.83 and 32.81 kg/ha(-1) respectively. The throughfall showed significant increases in the deposition rates for Ca, Mg, K, N and S, due to abundant dry deposition and, probably, to nutrient leaching contributed by the canopies of the spruce. On the basis of available data, an initial approach to atmosphere-canopy interaction was made.     

Coarse atmospheric aerosol: size distributions of trace elements

A sampler, employing nine single stage impactors placed in parallel within a portable wind tunnel, has been used to determine the metal content of coarse atmospheric aerosol. The wind tunnel maintains a constant flow environment for the collectors housed inside it, so that representative sampling conditions are achieved compared to the varied ambient wind conditions. At a flow rate of 8 m s⁻¹ the 50% cut-off diameters of the impactors ranged from 7.8 to 38.8 μm. Measurements were conducted at a rural and urban site near Colchester in south east England. The samplers were analysed by PIXE for P, K, Ca, Fe, Ti, Mn, Cu, V, Co, Cr, Br, Zn, Ni, Sc and Pb. It is found that the sampler can be employed to quantitatively characterise the elemental mass size distribution for aerosol larger than 10 μm. The results indicate that a small fraction of the above earth and trace elements’ metal mass is present in particles greater than 10 μm. This fraction for earth metals (Ca, K, Ti) is comparatively greater in the rural site than the urban site, while for trace metals (Mn, V, Cu, Cr) this fraction constitutes a more significant part of the coarse mass at the urban site. Trace element concentrations were of a similar order of magnitude to earlier literature reports. Although the number of measurements was limited it can be concluded that the size distributions obtained were characteristic of an unpolluted area.     

White birch (Betula papyrifera Marshall) foliar litter decomposition in relation to trace metal atmospheric inputs at metal-contaminated and uncontaminated sites near Sudbury, Ontario and Rouyn-Noranda, Quebec, Canada

Decomposition of white birch (Betula papyrifera Marshall) foliar litter was examined at metal-contaminated and uncontaminated sites established along gradients of soil Cu, Ni, Pb and Zn concentrations near Sudbury, Ontario and Rouyn-Noranda, Quebec. Over an 18-month study period, a significantly lower rate of litter mass loss was observed at the Sudbury contaminated site (S1) than at the uncontaminated site (S2). This result was not duplicated at corresponding sites (RN1, RN2) in Rouyn-Noranda, despite similar levels of soil metal contaminants and atmospheric inputs. Concentrations of metals in litter increased at all sites with time. However, the greatest litter Cu and Ni concentrations were observed at S1 (188 and 192 microg/g, respectively), a result of substantial net gains of these elements from atmospheric inputs. On a per hectare basis, Cu accumulation in litter at S1 approached recommended application rates of Cu as copper sulphate for control of fungal diseases in agricultural operations, indicating that the current rate of Cu smelter emissions in Sudbury may cause the observed impairment of decomposition.     

兰州市冬季细颗粒中微量金属元素及无机可溶性离子来源分析

通过对兰州市区4个在线大气监测点冬季细颗粒成分进行测定,测得微量金属元素和无机可溶性离子分别占细颗粒浓度的1%、52%。微量金属元素中Pb的检出量最高,占本文所测微量金属元素总含量的39.3%;无机可溶性离子含量最高的是SO2-4,其次为NO-3、Na+,分别占本文所测9种无机可溶性离子的23.3%、20.5%和19.7%。采用富集因子法与因子分析法对微量金属元素来源进行分析,结果表明,微量金属元素的来源为燃煤源、风沙土壤源、金属加工,燃煤源成因率最高,为61.2%;采用因子分析法对无机可溶性离子来源进行分析,结果表明,无机可溶性离子的来源为二次转化、人为排放、土壤源(包括风沙土壤尘和道路扬尘),土壤源成因率最高,为49.5%。     

Water balances in intensively monitored forest ecosystems in Europe

A soil hydrological model based on Darcy's law was used to calculate hydrological fluxes for 245 intensively monitored forest plots in Europe. Local measured input data for the model were rather limited and input was partly based on generic data. To obtain the best results, the model was calibrated on measured throughfall at the plots. Median transpiration fluxes are 350 mm; median leaching fluxes are 150 mm yr(-1) with the highest values in areas with high rainfall. Uncertainty analyses indicate that the use of local meteorological data instead of generic data leads to lower leaching fluxes at 70% of the plots due to an overestimation of the wind speed on basis of main meteorological stations. The underestimation of the leaching fluxes is confirmed by the median Cl fluxes which were slightly positive for the considered plots.     

Study of the trace metal ion influence on the turnover of soil organic matter in cultivated contaminated soils

The role of metals in the behaviour of soil organic matter (SOM) is not well documented. Therefore, we investigated the influence of metals (Pb, Zn, Cu and Cd) on the dynamic of SOM in contaminated soils where maize (C4 plant) replaced C3 cultures. Three pseudogley brown leached soil profiles under maize with a decreasing gradient in metals concentrations were sampled. On size fractions, stable carbon isotopic ratio (delta13C), metals, organic carbon and nitrogen concentrations were measured in function of depth. The determined sequence for the amount of C4 organic matter in the bulk fractions: M3 (0.9)>M2 (0.4)>M1 (0.3) is in agreement with a significant influence of metals on the SOM turnover. New C4 SOM, mainly present in the labile coarser fractions and less contaminated by metals than the stabilised C3 SOM of the clay fraction, is more easily degraded by microorganisms.