Science of the Total Environment 472 (2014) 888900

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Science of the Total Environment

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The lead (Pb) isotope signature, behaviour and fate of trafc-related lead pollution in roadside soils in The Netherlands
N. Walraven a,, B.J.H. van Os b, G.Th. Klaver c, J.J. Middelburg d, G.R. Davies e
a

GeoConnect, Meester Dekkerstraat 4, 1901 PV Castricum, The Netherlands Rijksdienst voor Archeologie, Cultuurlandschap en Monumenten, P.O. Box 1600, 3800 BP Amersfoort, The Netherlands BRGM, 3 avenue Claude-Guillemin, BP 36009, 45060 Orlans Cedex 2, France d University Utrecht, Faculty of Geosciences, P.O. Box 80021, 3508 TA Utrecht, The Netherlands e VU University Amsterdam, Faculty of Earth and Life Sciences, Petrology, De Boelelaan 1085, 1081 HV Amsterdam, The Netherlands
b c

H I G H L I G H T S Lead isotope composition of litter and topsoil differs from the deeper soil samples. Litter and topsoil contain anthropogenic Pb, with gasoline Pb as main source. Anthropogenic Pb is strongly associated with organic matter in litter and topsoil. Approximately 3590% of atmospherically derived Pb migrated to groundwater. Migration is caused by low soil pH and lack of reactive phases in subsoil.

a r t i c l e

i n f o

a b s t r a c t
In this study the origin, behaviour and fate of anthropogenic Pb in sandy roadside soils were assessed by measuring soil characteristics, Pb isotope composition and content. In 1991 and 2003 samples were taken at different depth intervals at approximately 8 and 75 m from two highways in The Netherlands. The Pb isotope composition of the litter layer (206Pb/207Pb = 1.121.14) differs from the deeper soil samples (206Pb/207Pb = 1.201.21). Based on a mixing model it is concluded that the samples contain two Pb sources: natural Pb and anthropogenic Pb, the latter mainly derived from gasoline. 206 Pb/207Pb ratios demonstrate that the roadside soils were polluted to a depth of ~15 cm. Within this depth interval, anthropogenic Pb content is associated with organic matter. Although Pb pollution only reached a depth of ~ 15 cm, this does not mean that the topsoils retain all anthropogenic Pb. Due to the low pH and negligible binding capacity of soils at depths N 15 cm, anthropogenic Pb migrated towards groundwater after reaching depths of N 15 cm. The Pb isotope composition of the groundwater (206Pb/207Pb = 1.1351.185) establishes that groundwater is polluted with anthropogenic Pb. The contribution of anthropogenic Pb to the groundwater varies between ~30 and 100%. Based on the difference in soil Pb content and Pb isotope compositions over a period of 12 years, downward Pb migration is calculated to vary from 72 95 to 324 279 mg m2 y1. Assuming that the downward Pb ux is constant over time, it is calculated that 3590% of the atmospherically delivered Pb has migrated to the groundwater. 2013 Elsevier B.V. All rights reserved.

Article history: Received 12 September 2013 Received in revised form 18 November 2013 Accepted 22 November 2013 Available online 15 December 2013 Keywords: Lead Isotopes Highways Soils Groundwater Transport

1. Introduction In 1921 the anti-knock properties of tetraethyl lead (TEL) were discovered and were introduced to the market as leaded gasoline in 1923. The environmental effects are evident over the entire globe. The highest Pb contents due to the combustion of leaded gasoline
Corresponding author. E-mail addresses: n.walraven@geoconnect.nl (N. Walraven), b.vanos@rce.nl (B.J.H. van Os), g.klaver@brgm.nl (G.T. Klaver), j.b.m.middelburg@uu.nl (J.J. Middelburg), g.r.davies@vu.nl (G.R. Davies). 0048-9697/$ see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.scitotenv.2013.11.110

have been measured in roadside soils (up to 3000 mg/kg: e.g. Chow, 1970; Milberg et al., 1980; Banin et al., 1987; Goyer, 1988; Groot and van Swinderen, 1993; Othman et al., 1997; Emmanuel and Erel, 2002; Fakayode and Olu-Owolabi, 2003; Bakirdere and Yaman, 2008; Chen et al., 2010; Khan et al., 2011). Elevated Pb contents have also been measured in remote parts of the globe, including Greenland snow (Boutron et al., 1991; Rosman et al., 1993, 1994) and the remote ice cap of Antarctica (e.g. Wolff and Suttie, 1994; Barbante et al., 1997; Vallelonga et al., 2002). For years it was thought that the topsoil horizon was an almost permanent sink for anthropogenic Pb (Siccama and Smith, 1978).

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Early reports suggested that the residence time of Pb in forest oors could be in the order of several hundred years (Benninger et al., 1975; Tyler, 1978; Friedland and Johnson, 1985; Turner et al., 1985). If these estimates are correct, then despite the reduction in Pb deposition due to legislative measures starting in the 1970s to curtail gasoline Pb, the Pb content in soils should continually increase to potentially toxic levels (Watmough et al., 2004). However, it has been observed that Pb levels in soil proles have reacted to the decline in Pb emission and deposition. This suggests that the residence time of Pb in these reservoirs is shorter than previously estimated (Herrick and Friedland, 1990; Miller and Friedland, 1994; Steinmann and Stille 1997; Erel, 1998; Teutsch et al., 2001; Klaminder et al., 2006). Erel (1998) calculated that the Pb inltration velocity in Israeli soils is 0.5 cm/y, implying residence times of 100 to 200 years for 50 to 100 cm deep soils. Not all soils are permanent sinks for Pb, potentially leading to groundwater pollution. Previous workers demonstrated that stable Pb isotopes can be used to 1) distinguish natural and anthropogenic Pb sources and 2) determine transport rates of gasoline Pb (e.g. Petit et al., 1984; Facchetti, 1989; Krause et al., 1993; Erel, 1998). Regional variations in Pb isotope ratios in gasoline, however, imply that Pb isotope measurements cannot simply be used to estimate the contribution of gasoline Pb in the environment. In Belgium, for example, automobile exhaust had a 206Pb/207Pb ratio of 1.121.14 (Petit et al., 1984) while in northern Italy leaded gasoline had a 206Pb/207Pb ratio of around 1.19 (Facchetti, 1989). Lead pollution in roadside soils in The Netherlands has been little studied. In 1991 Pb contents in several roadside soils in The Netherlands were determined (Groot and van Swinderen, 1993). These samples were stored at the Dutch National Institute of Public Health and the Environment (RIVM) and were available for Pb isotope analysis. Combined with samples collected in 2003, these samples offer a unique possibility to study changes in Pb isotope composition and content in roadside soils over a 12-year period. If the isotopic composition of roadside soils polluted with gasoline Pb differs measurably from natural background Pb, it can be used to determine 1) transport rates of anthropogenic Pb through the soil and 2) if groundwater near the selected highways is (already) polluted with gasoline Pb. 2. Background information

rangiferina) and heather (o.a. Calluna vulgaris) (Groot and van Swinderen, 1993). The site is located in an inltration area with average highest groundwater levels at depths N 80 cm-g.l. and average lowest groundwater levels at depth N 160 cm-g.l. Samples were taken at 8 m and 74 m from the highway A28 (Appendix 1). Eight metres was the closest point to the highway where the soil was undisturbed and situated within the forest. Seventy-four metres from the highway was the farthest accessible point from the highway where the soil was undisturbed and still situated in the forest. The soil at 8 m from the highway is a humic podzolic soil with hydromorphic characteristics (suborder xeropodzol soil), consisting of loam-poor ne sand with a low pH (pH-H 2 O 3.6; Groot and van Swinderen, 1993). The soil at 74 m from the highway is a vague soil with hydromorphic characteristics (suborder xerovague soils), consisting of coarse sand with a low pH (pH-H2 O 3.6; Groot and van Swinderen, 1993). The soil contains hardly any visible pedogenesis. 2.1.2. Sampling site near Moergestel This site is also situated in a forested area of aeolian periglacial deposits. The forest consists predominantly of Scots pine, silver birch and oak (Groot and van Swinderen, 1993). The low cover consists of grasses (a.o. Molinea caerulea), mosses and ferns (o.a. Osmunda regalis) (Groot and van Swinderen, 1993). The site is located in an inltration area where high and low groundwater levels are typically ~ 80 cm and ~160 cm below ground level respectively. Samples are again taken from undisturbed soils and situated within the forest at two distances from the highway A58: 10 m and 75 m (Appendix 1). The soil at 10 m from the highway is a humic podzolic soil with hydromorphic characteristics (suborder xeropodzol soil), consisting of slightly loamy ne sand with a low pH (pH-H2O 4.4; Groot and van Swinderen, 1993). The soil at 75 m from the highway is a humic podzolic soil with hydromorphic characteristics (suborder hydropodzol soils), consisting of loamy ne sand with a low pH (pH-H2O 3.8; Groot and van Swinderen, 1993). 3. Materials and methods

Most of the sediments found close to the surface of The Netherlands were deposited during the Quaternary period, and are of Pleistocene or Holocene age. They consist of uviatile, marine and glacigenic sediments, as well as sediments with a more local genesis, such as aeolian deposits and peat. Soil formation in The Netherlands essentially started after the last glacial period (Weichselien) when temperature rose and vegetation started to stabilize the unconsolidated sediments. For greater detail see Van der Veer (2006) and Walraven et al. (2013a). 2.1. Sampling site description In 1991 ve roadside locations in The Netherlands were sampled to study trafc-related soil pollution (Groot and van Swinderen, 1993). In 2003 two of these locations were revisited and sampled to study changes in anthropogenic Pb isotope composition and content over a period of 12 years. The selected sites are located along highway A28 near Nunspeet and highway A58 near Moergestel. The sample locations, highway opening dates, sampling dates and trafc densities are shown in Fig. 1. At both locations samples of forest litter, soil and groundwater were taken. 2.1.1. Sampling site near Nunspeet This site is situated in a forested area of aeolian periglacial deposits. In the forest, Scots pine (Pinus sylvestris), silver birch (Betula pendula), oak (Quercus sp.) and black cherry (Prunus serotina) are the most dominant species (Groot and van Swinderen, 1993). The low cover consists of grasses (a.o. Molinea caerulea), mosses, lichens (o.a. Cladonia

3.1. Sample collection In October and November 1991, forest litter, soil and groundwater samples were collected near highway A28 (Nunspeet) and A58 (Moergestel) (Groot and van Swinderen, 1993). Soil and forest litter were sampled every 50 cm along 80 m transects perpendicular to the highway. This sampling strategy resulted in 160 forest litter samples and 160 soil samples for each sampling distance from the highway. Every forty samples were put into a sample container, resulting in 8 containers for each sampling distance. The sample containers were brought to the laboratory for further analysis. Groundwater was sampled (in monitoring wells) every 4 m along 100 m transects perpendicular to the highway at two distances from the highway. Contamination of groundwater with lead from the topsoil was prevented by removing the litter and topsoil layer (~20 cm) before drilling the well with a hand auger. To prevent vertical movement of water, the groundwater well was sealed using granular bentonite. After placement of the monitoring well (casing), possible contaminated groundwater was removed from the well by pumping. Groundwater samples were taken a week after drilling the monitoring well. Before sampling, the monitoring well was thoroughly pumped and samples were taken when the water reached a constant temperature and electrical conductivity. A total of 24 groundwater samples were taken for each sample distance. The groundwater samples for the analysis of the heavy metals were ltered (0.45 micron pore size) and acidied with HNO3 (pro analysis) in the eld. In the laboratory

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Sample site Highway

Highway

Traffic
#1

Sampling

brought into use density

(year) Nunspeet A28 1962

(cars/day) 50282

(year) 1991, 2003

Moergestel A58

1963

63182

1991, 2003

Fig. 1. Map showing the locations and general information (sampling date, highway construction date, trafc density) of the two studied roadside soils. Nunspeet (N) is located 2 km of highway A28 and Moergestel (M) is located 1.5 km of the highway A58. #1 Rijkswaterstaat (2012).

the 24 groundwater samples were combined to a total of six samples before analysis. In May and June 2003 the sample sites near Nunspeet and Moergestel were revisited and sampled. The remnants of the groundwater well from 1991 were still present so it was possible to resample within 1 m of the 1991 sample sites. The 1991 procedure of Groot and van Swinderen (1993) for soil sampling was repeated. In 1991 a distinct litter layer was present at 8 m from the highway A28 near Nunspeet. However, in 2003 this litter layer had partly disappeared (most likely broken down). For consistency sufcient litter was collected to perform the planned analyses. In addition to the sampling procedure followed in 1991, in 2003 samples from the depth interval 45 55 cm and 90 100 cm were taken with an Edelman hand auger and soil proles were sampled by digging a pit with a depth of 60 cm. The soil pro les were sampled at 8 and 10 m from the A28 and A58 respectively. High-

resolution sampling was performed from the bottom to the top of pit walls. The procedure of groundwater sampling of Groot and van Swinderen (1993) was repeated. However, instead of 24 groundwater wells, 4 groundwater wells were placed at each distance from the highway. The distance between each well was about 40 m. Again special care was taken to prevent contamination of the groundwater with lead from the topsoil.

3.2. Preparation and chemical analyses of the litter and soil samples Forest litter and soil samples from 1991 were stored in glass containers at 4 C in the sample depot at RIVM. Only two of the four soil samples from every distance and depth from the highway were present. The samples from 1991 were analysed in 1996 and the samples

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from 2003 were analysed in 2003. Due to this time difference, some analytical procedures differ slightly. 3.2.1. Sample pre-treatment After determination of bulk density (based on 25 cm3 sample), all soil samples were dried at 105 C. The soil samples were disintegrated and sieved over a 2 mm sieve to remove the gravel fraction. Soil and forest litter samples were ground with an automated tungsten carbide swing-mill (Herzog HSM-HTP) to a grain size b 20 m, homogenised for 5 min in a Turbula T2C and stored in glass containers. 3.2.2. X-ray uorescence (XRF) Aluminium (Al) and iron (Fe) have been measured by X-ray uorescence spectroscopy (XRF) with a precision (1 RSD) of 0.51.0% based on replicate analysis. For details see Spijker (2005) and Walraven et al. (2013a). One reference sample (ISE 921) was added to each batch of 20 samples to determine accuracy. The certied Al and Fe content of ISE 921 was 5.7 wt.% and 3.2 wt.% respectively. The accuracy for Al and Fe was 46% relative bias. 3.2.3. Thermo gravimetric analyses (organic matter and carbonate) Organic matter (OM) and carbonate (CO2carb) contents were analysed with a LECO TGA 601. Temperatures were varied from 105 C to 550 C for organic matter content determination, 550 C to 800 C for carbonate content (mainly CaCO3) and from 800 C to 1000 C for clay bound water content. The relative precision (2 RSD) for OM and CO2carb based on sample duplicates is 3.8% and 4.5% respectively. One reference soil sample (ISE 921) was added to each batch of 20 samples to determine accuracy. The accuracy for OM and CO2carb determined on ISE 921 was 0.2% and 13% respectively (relative bias). 3.2.4. Inductively coupled plasma-mass spectroscopy (ICP-MS) Lead and Pb isotopes were analysed after HF-based sample destruction. Details of the methodology of the Pb content analysis for the 1991 and 2003 samples can be found in Walraven et al. (1997) and Van der Veer (2006) respectively. The relative precision (2 RSD) for Pb based on sample duplicates is 3.6%. The accuracy for Pb as determined by soil standard ISE 921 (Pb = 167 mg/kg) was 0.7% (relative bias). The methodology of the Pb isotope analysis is described in detail in Walraven et al. (2013a,b). All 206Pb/207Pb ratios of the 1991 samples were determined with a precision of 2RSD b 1%. The 206Pb/207Pb ratios of the soil and groundwater samples collected in 2003 were determined with a precision of 2RSD b 0.3% and 2RSD b 0.8% respectively. The average measured value and absolute precision (2 SD) of ISE 921 sample was 1.167 0.008 for 206Pb/207Pb. Average, precision and accuracy are based on the entire analytical procedure starting with the sample splits. Blanks indicate that reagents contain negligible amounts of Pb (b 20 ng/kg). 3.3. Preparation and chemical analyses of groundwater samples The Pb content of the groundwater sampled in 1991 was determined by means of AAS (details in Groot and van Swinderen, 1993). The groundwater samples from 2003 were analysed by ICP-MS (Agilent 7500i) for 66 elements (including Pb) according to NEN 6427. Lead isotope analysis was performed according to the method described in Section 3.2, with the difference that groundwater samples were not diluted prior to introduction into the mass spectrometer. 4. Results and discussion 4.1. Natural and anthropogenic lead in roadside soils The Pb content of polluted soil samples consists of natural Pb and anthropogenic Pb. Lead inherited from the underlying sediment lithology and added in the form of dust, that is the natural fallout from regional

geological processes, will be referred to as natural Pb. Lead inherited from anthropogenic activity, in the case of The Netherlands, predominantly from the combustion of leaded gasoline (Walraven et al., 2013a,b, submitted for publication) is referred to as anthropogenic Pb (see discussion below). If the natural Pb content is known, the anthropogenic Pb content can be calculated. The natural Pb content (Pbn) in sediments and soils can be calculated based on the common relationship between Pb and Al in unpolluted soils and sediments (o.a. Huisman, 1998; Van der Veer, 2006; Walraven et al., 2013a,b,submitted for publication). Because roadside soils are seldom polluted with Al, and the studied roadside soils are not located close to industrial sites, the measured Al content is used as a lithogenic proxy for Pbn. Walraven et al. (submitted for publication) established the following relationship for unpolluted sedimentary soils in The Netherlands: Pbn 3:69 Al 1:75 where: Pbn = calculated natural Pb content (mg/kg). Al = measured Al content in wt.%. (n = 303; R2 = 0.89; Standard error of estimate is 2.6 mg/kg) Based on Eq. (1), it is possible to calculate the anthropogenic Pb content in polluted soil samples according to Eq. (2): Pba Pbt Pbn where: Pbn = calculated natural Pb content (mg/kg). Pbt = measured total Pb content (mg/kg). Pba = calculated anthropogenic Pb content (mg/kg). The calculated natural Pb content in the roadside soils from Nunspeet and Moergestel varies from 3.1 to 10.3 mg/kg with an average of 6.3 mg/kg (Appendix 2 to 4). The calculated natural Pb content agrees well with the total Pb content of the soil samples from the depthintervals of 4555 cm-g.l. and 90100 cm-g.l. (4.5 to 7.0 mg/kg with an average of 5.8 mg/kg; Appendix 34). This implies that these deeper soil samples do not contain excess Pb. In Fig. 2 the Al contents of the soil and litter samples, gathered in 2003, are plotted versus the total Pb content. The Pb contents of unpolluted Dutch soils are also presented in this gure (Walraven et al., 2013a,b). All litter samples are strongly enriched in Pb with the samples from Moergestel having the highest content. The enrichment factors, dened as Pbt/Pbn, are as high as 35 for Nunspeet and 115 for Moergestel. The anthropogenic Pb content in the roadside litter and topsoils is higher than the average anthropogenic Pb content in rural sandy topsoils in Dutch forests (12 mg/kg (n = 55); Walraven et al., 2013b). The highest anthropogenic Pb contents in the roadside soils from Moergestel and Nunspeet are 645 mg/kg and 191 mg/kg respectively. The Pb contents in the Dutch roadside soils are comparable to roadside soils reported from Vancouver and Auckland (Pb contents up to 1500 mg/kg; Schmitt et al., 1979; Ward et al., 1977). Extremely high Pb levels of over 6000 mg/kg have been recorded in individual roadside soil samples from Venezuela (Garcia-Miragaya et al., 1981) and United Kingdom (Harrison et al., 1981). The Pb content of the soils from Nunspeet is considerably lower than the soils from Moergestel (Fig. 2). The extent of Pb pollution in roadside soils is often strongly (linearly) correlated with trafc density (e.g. Kloke and Riebartsch, 1964; Ward et al., 1977; Ho and Tai, 1988; Fakayode and Olu-Owolabi, 2003). However, the trafc density near Moergestel is only 20% higher than near Nunspeet (based on gures from 2000 to 2003: no data available earlier than 2000), while the Pb content in the litter samples from Moergestel is 2 to 4 times higher. The difference between the two studied sites cannot be explained by 2 1

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Fig. 2. Al content (wt.%) of the litter and soil samples from Nunspeet and Moergestel, sampled in 2003, are plotted vs. Pb content (mg/kg). The line indicates the average relationship between the Al and Pb content of unpolluted Dutch sedimentary soils, based on 303 samples (). The dashed lines are the 95% condence intervals of the relationship between Al and Pb.

trafc density, however, prevailing wind direction in The Netherlands is southwest. Moergestel is situated downwind of the highway and Nunspeet to windward of the highway. In addition, Moergestel is located 3040 km from several Zn smelters. This might explain the higher Pb content in the soils from Moergestel compared to Nunspeet (see Section 4.2). 4.2. Sources of Pb The measured Pb isotope ratios of the litter and soil samples represent a mixture of natural and anthropogenic Pb in which the natural Pb content in the studied soils varies only slightly (310 mg/kg; Appendix 24). The individual 206Pb/207Pb ratios of a mixture of two Pb sources can be determined with a hyperbolic mixing equation under the condition that the 206Pb/207Pb ratios of the two Pb sources differ substantially (Faure, 1986). The equation for a two component mixture is given in Eqs. (3a), (3b) and (4): 
206

Pb=

207

Pb


m

h     i 206 207 206 207 =Pbt Pba Pb= Pb Pbn Pb= Pb

a n

3a hence 
206

Pb=

207

Pb


m

206

h Pbn

Pb=

207

Pb h

 Pb=
207

a 206

  i 206 207 Pb Pb= Pb =Pbt

n a

3b where: Pbn = calculated natural Pb content (mg/kg). Pbt = measured total Pb content (mg/kg). Pba = calculated anthropogenic Pb content (mg/kg). (206Pb/207Pb)m = measured isotope ratio. (206Pb/207Pb)a = isotope ratio of anthropogenic Pb. (206Pb/207Pb)n = isotope ratio of natural Pb. This is the equation of a hyperbola in co-ordinates of (206Pb/207Pb)m and Pbt: 
206

The mixing hyperbola can be transformed into a straight line by plotting (206Pb/207Pb)m versus the reciprocal of Pbt. The intercept (b) represents the 206Pb/207Pb ratio of anthropogenic Pb (end-member). In Fig. 3 Pbt and 1/Pbt are plotted against (206Pb/207Pb)m. The 1991 and 2003 data for both Nunspeet and Moergestel show mixing hyperbolae for two Pb sources. No difference is observed between the 1991 and 2003 data indicating that the 206Pb/207Pb ratios of the two Pb sources were constant in time. The average 206Pb/207Pb ratios of natural Pb (end-member) for Nunspeet and Moergestel are well dened at 1.21 and 1.20, respectively (average 206Pb/207Pb values of the soil samples from the depth interval of 45 to 55 and 90 to 100 cm-g.l., sampled in 2003). These values are in accordance with the Pb isotope composition of unpolluted soils in The Netherlands (206Pb/207Pb = 1.181.22, Walraven et al., 2013a). The mixing relationships record signicant scatter in the 206Pb/207Pb ratios making the anthropogenic Pb source for Nunspeet and Moergestel less well dened, with 1.122 and 1.139 respectively (Fig. 3). These values resemble the values for gasoline Pb observed in Belgium (206Pb/207Pb = 1.121.14, Petit et al., 1984) and Germany (206Pb/207Pb = 1.101.11, Krause et al., 1993). According to Petit et al. (1984), Pb added in gasoline in Belgium and neighbouring countries comes mainly from Canadian and Australian Pb ores of preCambrian origin having characteristic low 206Pb/207Pb ratios of 1.04 1.07 (Table 1). Fig. 3(D) shows that 206Pb/207Pb ratios versus the reciprocal of Pb content of the samples from Moergestel do not t a straight line, in contrast to samples from Nunspeet. The Moergestel 206Pb/207Pb ratios are slightly more radiogenic (1.139 vs. 1.122). This may point to an additional anthropogenic Pb source with a 206Pb/207Pb ratio N 1.12. The Moergestel sample site lies 30 to 40 km downwind of Belgian Zn smelters in Balen, Lommel, Neerpelt and Overpelt (the Zn smelters in Budel, Balen and Overpelt are still in operation). The processed Zn ores mainly originate from the former Belgium Congo (now Democratic Republic of Congo). The average Pb isotope composition of these ores is 1.135, 2.400 and 0.473 for 206Pb/207Pb, 208Pb/207Pb and 206Pb/208Pb respectively (Doe and Rohrbough, 1977; Sonke et al., 2002). The smelters could represent the extra Pb source in Moergestel. This is supported by the higher Zn contents in the litter layer in Moergestel (67190 mg/kg with a median of 82 mg/kg) than in Nunspeet (2878 mg/kg with a median of 48 mg/kg). Accordingly, the Moergestel sample site might also have been inuenced by atmospheric deposition from Belgian Zn smelters. Besides gasoline Pb and smelter Pb, other atmospherically derived anthropogenic Pb sources could potentially be present in the roadside soils (e.g. y ash and coal ashes). Atmospheric deposition also took place before construction of the highways. However both roadside sample locations are located in rural forested areas and the input of other anthropogenic Pb sources is expected to be negligible. The average anthropogenic Pb content in rural sandy topsoils in forests in The Netherlands is 12 mg/kg (n = 55; Walraven et al., 2013b) This is negligible compared to the input measured in the roadside soils of Nunspeet and Moergestel. Walraven et al. (2013b) also showed that even in these rural forested topsoils (far away from highways) gasoline Pb is the major anthropogenic Pb source. In addition, a clear relationship between the anthropogenic Pb content and distance to the highways is observed in this study (see Section 4.3.1). The Pb content in the litter and topsoils close to the highways (proximal sites) is substantially higher (factor 24) than further away (distal sites). We therefore conclude that Pb in the roadside soils near Moergestel and Nunspeet is predominantly a mixture of two sources: natural Pb and anthropogenic Pb, the latter mainly derived from gasoline. 4.3. Behaviour of Pb 4.3.1. Lead content in relation to distance from road It is generally considered that Pb content decreases rapidly and exponentially with distance from the road (a.o. Page and Ganje, 1970;

Pb=

207

 Pb a=Pbt b
m

where: a = Pb n [( 206 Pb/ 207 Pb) n ( 206 Pb/ 207 Pb) a ] and b = (206Pb/207Pb)a.

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Fig. 3. A: Hyperbolic mixing curve dened by 206Pb/207Pb and Pb content (mg/kg) of litter and soil samples from roadside soils near Nunspeet. B: Plot of 206Pb/207Pb and reciprocal Pb content of litter and soil samples from roadside soils near Nunspeet which t on a straight line (R2 = 0.97). C: Hyperbolic mixing curve dened by 206Pb/207Pb and Pb content (mg/kg) of litter and soil samples from roadside soils near Moergestel. D: Plot of 206Pb/207Pb and reciprocal Pb content of litter and soil samples from roadside soils near Moergestel which t on a straight line (R2 = 0.96). E: Hyperbolic mixing curve dened by 206Pb/207Pb and Pb concentrations (g/l) of groundwater samples collected near two highways (A58 near Moergestel and A28 near Nunspeet). F: Plot of 206Pb/207Pb and reciprocal Pb concentrations of groundwater samples collected near two highways (A58 near Moergestel and A28 near Nunspeet). 1 = Petit et al. (1984); 2 = Krause et al. (1993); 3 = this study.

Impens et al., 1973; Fakayode and Olu-Owolabi, 2003). In Nunspeet and Moergestel, the soil Pb content also decreases rapidly with distance from the highway (Fig. 4). However, since samples were only taken at two distances from the highway (approximately 8 m and 75 m), it was impossible to determine the exact spatial control on the decrease. Anthropogenic Pb in the forest litter, sampled in 1991, decreases with distance from the highway by 74% and 46% for Nunspeet and Moergestel respectively. The decrease in litter Pb content with distance from the highway in 2003 is comparable, 69% for Nunspeet and 41%

for Moergestel. The same pattern is observed for the Pb content in the topsoil (010 cm). 4.3.2. Depth proles Pb contents in soils close to the highways (810 m) decrease with depth (Fig. 5). There is no resolvable enrichment of Pb at depths greater than ~15 cm below soil surface. Fig. 5 demonstrates that high organic matter content is associated with high Pb content. According to Nriagu (1978) signicant elevation of Pb above the background level is not common below 10 cm from the soil surface. Evidence for deeper

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Table 1 Pb isotope composition (206Pb/207Pb) of some major worldwide Pb ore deposits and the Pb isotope composition (206Pb/207Pb) of leaded gasoline used in The Netherlands and neighbouring countries. Location Broken Hill Australia Canada Mexico United States, Mississippi Valley United States, Idaho The Netherlands Belgium Germany United Kingdom Great Britain France Sample type Pb ore (galena) Pb ore (galena) Pb ore (galena) Pb ore (galena) Pb ore (galena) Leaded gasoline Automobile exhaust Leaded gasoline Leaded gasoline Leaded gasoline Leaded gasoline
206

Pb/207Pb

Reference Facchetti (1989) Hurst et al. (1996) Hurst et al. (1996) Hurst et al. (1996) Hurst et al. (1996) Hopper et al. (1991) Petit et al. (1984) Krause et al. (1993) Krause et al. (1993) Monna et al. (1997) Monna et al. (1997)

(80120 mg/l) are signicantly higher than distal soils (1530 mg/l). Since chloride ions can participate directly in anodic dissolution reactions of heavy metals (a.o. Pb and Zn), they are expected to enhance downward transport of Pb in polluted soils (a.o. Vandenabeele and Wood, 1972; Norrstrm and Jacks, 1998 and Lu, 2005). 4.3.3. Lead concentrations and Pb isotope composition of groundwater By determining Pb isotope composition and concentration of the groundwater it is possible to verify if anthropogenic Pb reached the groundwater. Lead concentrations in groundwater at the studied sites vary from 0.22 to 15 g/l (Table 2). The background concentration of Pb in shallow groundwater (b 5 m g.l.) in The Netherlands is 6.2 g/l (Fraters et al., 2001). With the exception of three samples (M2, M3 and N5), Pb concentrations in groundwater from the studied sites are lower than the Dutch background concentration for Pb (Fig. 3). However, based on the 206Pb/207Pb ratios of the groundwater samples analysed in this study it can be concluded that Pb in all groundwater samples in this study has an anthropogenic origin. The 206Pb/207Pb ratios of the groundwater samples (206Pb/207Pb = 1.1351.176) are signicantly lower than the 206Pb/207Pb composition of unpolluted soils in the study area (average ( 206 Pb/ 207 Pb) n values of the soil samples from the depth interval of 45 to 55 and 90 to 100 cm-g.l., sampled in 2003 are 206 Pb/207 Pb = 1.20 1.21). Table 2 demonstrates that there is no clear trend between the distance from the highway and the Pb isotope composition and concentration of the groundwater. In Fig. 3 the Pb concentrations and the reciprocal of the Pb concentrations are plotted versus the 206Pb/207Pb ratios of the groundwater samples. These data show that in general the 206Pb/207Pb ratios become more radiogenic with decreasing Pb concentrations. In addition, a clear mixing hyperbola between two sources (natural Pb and anthropogenic Pb) is observed. In Fig. 3 the y-axis intercept is 1.149 suggesting that gasoline Pb is an important anthropogenic Pb source in groundwater (Fig. 3). However, 206Pb/207Pb ratios of groundwater vary between 1.135 and 1.176 suggesting that natural Pb is also mobilized. Mol et al. (2003) showed that in acidic sandy soils, such as at Moergestel and Nunspeet, feldspars tend to dissolve and release Pb to groundwater. These data can be used to determine the contribution of anthropogenic Pb to the total groundwater Pb. The average 206Pb/207Pb ratio of background Pb for Nunspeet and Moergestel is 1.21 and 1.20 respectively (Section 4.2). The average 206Pb/207Pb ratio of anthropogenic Pb in soils from Nunspeet and Moergestel is 1.122 and 1.139 respectively (Fig. 3) indicating that 3070% and 40100% of groundwater Pb in Nunspeet and Moergestel respectively, originates from anthropogenic Pb. 4.3.4. Changes in soil Pb between 1991 and 2003 Variation in Pb content and 206Pb/207Pb ratios of the roadside soils between 1991 and 2003 are visualized in Fig. 6. The average Pb content

1.04 1.06 1.19 1.31 1.06 1.062 0.019 1.121.14 1.101.11 1.061.07 1.0591.079 1.0691.094

penetration of gasoline Pb have been encountered in soils where the combined effect of low temperature and the presence of sodium chloride diminish the ability of the topmost layer to retain Pb (Vandenabeele and Wood, 1972). However, a low Pb content at greater depths (depth below 1015 cm) does not necessarily mean that Pb is completely retained in the topsoil. If the soil pH and binding capacity of the soil at greater depths are extremely low, dissolved Pb simply migrates to the groundwater without being absorbed. The binding capacity of a soil is predominantly determined by the amount of clay, calcium carbonate (CaCO3), organic matter (OM) and reactive iron (Fereact). The content of Fereact was calculated according to Fereact(wt.%) = (Fe2O3(wt.%) (Al2O3(wt.%)/4) 1.4297 (Huisman and Kiden, 1997). The soils deeper than 15 cm contain minimal amounts of these reactive phases (Fig. 5). In Nunspeet, CaCO3, OM and Fereact content below 15 cm are 0.1 wt.%, 0.6 wt.% and not present (n.p.) respectively. Comparable values are found in Moergestel, CaCO3, OM and Fereact 0.3 wt.%, 2.7 wt.% and n.p. respectively. Although the clay content was not determined specically, the low Al values and eld observations suggest that clay contents are negligible (Appendix 1). In Dutch soils, Al content shows a positive correlation with clay content (Huisman, 1998). However, in general soils with Al contents below 2.0 wt.% do not contain clay minerals and Al is most often present in feldspars (Huisman, 1998 and Mol et al., 2003). A low soil pH in combination with a low binding capacity of the soil could result in percolation of anthropogenic Pb towards the groundwater. In addition, the soils close to the highway receive large amounts of sodium chloride, which is used to de-ice the highways during winter. Groot and van Swinderen (1993) showed that the chloride concentrations in groundwater close to the highways

Fig. 4. Sampling distance from the highway vs. Pb content (mg/kg) of the litter and topsoils (010 cm) sampled in 1991 and 2003.

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Fig. 5. A: Pb content (mg/kg), 206Pb/207Pb ratio and content of OM (wt.%), Fereact (wt.%), and CaCO3 (wt.%) for the litter and soil samples, collected from the soilpit 8 m from the highway near Nunspeet, are plotted vs. sampling depth (cm-g.l.). The error bars indicate the depth interval at which the samples are taken. B: Pb content (mg/kg), 206Pb/207Pb ratio and content of OM (wt.%), Fereact (wt.%), and CaCO3 (wt.%) for the litter and soil samples, collected from the soilpit 10 m from the highway near Moergestel, are plotted vs. sampling depth (cm-g.l.). The error bars indicate the depth interval at which the samples are taken.

in roadside litter and soil near Nunspeet were higher in 2003 than in 1991. In contrast, the average Pb content in roadside litter and soil near Moergestel were lower in 2003 than in 1991. However, these

Table 2 Acidity (pH), Pb content and Pb isotope composition (206Pb/207Pb) of roadside groundwater samples (#1 Average relative error 1RSD: 206Pb/207Pb = 0.28 0.13%. This error is higher than observed with the Pb isotope measurements of the soil samples, because Pb concentrations of the groundwater samples were lower than 50 g/l (increased mass fractionation). Location N1 N2 N3 N4 N5 N6 N7 N8 M1 M2 M3 M4 M5 M6 M7 M8 Distance from highway (m) 8 8 8 8 80 80 80 80 8 8 8 8 80 80 80 80 Groundwater depth (cm-g.l.) 282 302 323 323 367 304 294 293 258 275 288 269 220 227 250 221 pH 4.56 4.53 4.42 4.45 4.76 4.56 4.51 4.57 4.52 4.08 3.97 5.26 3.86 5.26 4.35 5.29 Pb (g/l) 0.65 0.30 0.87 0.75 10 0.76 0.22 0.49 1.23 8.58 15 0.93 2.10 0.23 1.62 1.14
206

Pb/207Pb#1

1.158 1.167 1.156 1.168 1.148 1.161 1.185 1.174 1.160 1.135 1.143 1.155 1.176 1.172 1.153 1.145

differences in Pb content are not signicant because of variability. In both locations there are, however, signicant changes in the average Pb isotope compositions in most roadside litter and soil samples between 1991 and 2003. These data imply that there is transport of anthropogenic Pb in the studied soils (Fig. 6). The only exception is the Nunspeet litter sampled 8 m from the highway, which shows no signicant change in the 206Pb/207Pb ratios between 1991 and 2003. The 206Pb/207Pb ratios of roadside litter from Moergestel increased signicantly between 1991 and 2003, whereas the 206Pb/207Pb ratios of litter 75 m from the highway decreased. The average 206Pb/207Pb ratios of the topsoils from Moergestel in 1991 and 2003 are within analytical error. The changes in 206Pb/207Pb ratios between 1991 and 2003 appear to be caused by a temporal change in the isotopic composition of anthropogenic Pb. If the atmospheric Pb ux between 1991 and 2003 and its Pb isotope composition are known, it is possible to calculate 1) the downward Pb ux from the litter layer into the topsoil (010 cm) and 2) the Pb isotope composition of the mobile Pb fraction. 4.4. Fluxes of Pb The downward Pb ux can be calculated from the changes in Pb inventories using the following mass-balance equation:

Fdown LT Fatmos CL2003 2003 z2003 10CL1991 1991 z1991 10=t

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Fig. 6. Sampling date (1991 and 2003) vs. Pb content (mg/kg) and 206Pb/207Pb ratios of the litter and topsoils (010 cm). Error bars indicate the variation in Pb content and 206Pb/207Pb ratios of the replicates. A and B = Nunspeet; C and D = Moergestel; 1 = Petit et al. (1984); 2 = Krause et al. (1993); 3 = this study.

Where: CL = Pb content (mg/kg) of the litter layer in 1991 and 2003. = bulk density (g/cm3) of the litter in 1991 and 2003. z = thickness (cm) of the litter layer in 1991 and 2003. Fatmos = average atmospheric Pb ux (mg m 2 y 1) between 1991 and 2003. Fdown L T = average downward Pb ux (mg m 2 y 1) from the litter layer towards the topsoil (010 cm) between 1991 and 2003. Eq. (5) is based on the assumption that water movement through the soil prole was largely vertical and bulk density and layer thickness are assumed constant (1991 = 2003; z1991 = z2003). The latter assumptions had to be made since there are no data regarding the density and exact thickness of the litter layer and topsoil sampled in 1991. If Fdown L T is known, it is also possible to calculate the downward Pb ux from the topsoil (010 cm) to the subsoil (N 10 cm), expressed as Fdown T S, by replacing Fatmos with Fdown L T in Eq. (5) and using the Pb content, bulk density and thickness of the topsoil in place of the litter layer. The results of the downward Pb uxes can be validated by calculating the 206Pb/207Pb ratios of the mobile Pb fraction according to Eq. (6). If the

calculated 206Pb/207Pb ratios of the mobile Pb fractions agree with the measured 206Pb/207Pb ratios of the soils and groundwater samples (206Pb/207Pb =1.111.21) this means that the calculated Pb uxes are of the correct order of magnitude.

206

Pb=

207

 Pb

Fdown LT

  206 207 Fatmos Pb= Pb Cl2003   206 207 6 CL2003 2003 z2003 10 Pb= Pb
Fatmos Cl1991

  206 207 Pb= Pb

CL1991 1991 z1991 10=t= Fdown LT

Where: (206Pb/207Pb)Cl = 206Pb/207Pb ratio of the litter layer in 1991 and 2003. (206Pb/207Pb)Fatmos = average 206Pb/207Pb ratio of atmospheric Pb between 1991 and 2003. (206Pb/207Pb)Fdown L T = average 206Pb/207Pb ratio of Pb moving from the litter layer towards the topsoil (010 cm) between 1991 and 2003. The Pb isotope composition of the mobile fraction in the topsoil was calculated in an analogous way. The calculated downward Pb uxes are somewhat uncertain, since atmospheric Pb deposition, Pb content,

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thickness and density of the litter and topsoil layers are subject to temporal and spatial variation. Estimations of the uncertainties were calculated using the Gaussian law for propagation of error, taking all errors (as 1 SD) of the quantied variables in Eqs. (5) and (6) into account.

4.4.1. Atmospheric Pb deposition and its Pb isotope composition (19912003) Downward Pb transport can only be calculated if atmospheric Pb deposition between 1991 and 2003 is known (Eq. (5)). Data on atmospheric Pb deposition in The Netherlands and its isotopic composition are summarised in Table 3 and include lake deposits, snail shells and aerosols as proxies of atmospheric Pb deposition (Walraven et al., submitted for publication; Notten et al., 2008; Rosman et al., 1998). Clearly some of these data will include input from natural Pb derived from the underlying sediments. Walraven et al. (submitted for publication) reported atmospheric deposition based on the chemical composition of lake sediments from Lake Vechten, which is located only 75 m from a national highway (A12). Atmospheric Pb deposition in the roadside soils near Nunspeet and Moergestel is assumed to be similar to that deposited in Lake Vechten. The atmospheric Pb deposition between 1991 and 2002 in Lake Vechten varies from 121 to 173 mg m 2 y 1 with an average of 142 mg m 2 y 1. These values are in the same order of magnitude as determined by others in peat and lake sediments (Table 3). However, atmospheric Pb deposition in The Netherlands is higher than in most other western European countries (250 mg m 2 y 1), except for Lake Geneva (Table 3). The Netherlands is a more densely populated country compared to the other countries and the studied lake sediments in The Netherlands are from an urban area (city of Utrecht) and hence Pb deposition is predicted to be among the highest recorded in Europe.

The 206Pb/207Pb ratios of anthropogenic Pb, deposited between 1991 and 2003 in Lake Vechten, vary from 1.162 to 1.169 with an average of 1.166 (Table 3). These values are in agreement with the data from Notten et al. (2008) (206Pb/207Pb = 1.1511.172), but deviate from the values of Rosman et al. (1998)(206Pb/207Pb = 1.1331.137). The values of Walraven et al. (submitted for publication) and Notten et al. (2008) also deviate from the Pb isotope composition of aerosols from North Western Europe (206Pb/207Pb = 1.145 0.003) as determined by Deboudt et al. (1999). However, the database reported by Deboudt et al. (1999) includes no data from Belgium and The Netherlands. Significant spatial and temporal variations in the Pb isotope composition of aerosols are observed in Europe (Table 3). In France and Switzerland, for example, the 206Pb/207Pb ratios varied from 1.110 to 1.162 and 1.114 to 1.155 respectively over the last 10 years (Table 3). These differences are a.o. caused by seasonal variations in the origin of aerosols and local factors, such as the presence of Pb working industries and the origin of the Pb that is being processed. In this study the atmospheric Pb ux and 206Pb/207Pb ratios of atmospheric Pb deposition based on the lake sediments from Lake Vechten are used to calculate Pb uxes from Dutch topsoil. 4.4.2. Pb uxes in the roadside soils The calculated values for Fdown L T, (206Pb/207Pb)Fdown L T, Fdown 206 Pb/207Pb)Fdown T S and uncertainties (2) for Nunspeet T S and ( and Moergestel are presented in Table 4. 4.4.2.1. Pb ux from litter to topsoil to subsoil. The downward ux of Pb from the litter layer to the topsoil (Fdown L T) varies from 117 70 to 261 211 mg m 2 y 1. The downward ux of Pb from the topsoil to the subsoil (Fdown T S) consisting of ne sand with a negligible amount of reactive phases varies from 72 95 to

Table 3 Atmospheric Pb ux (mg m 2 y1) and 206Pb/207Pb of atmospheric Pb between 1991 and 2003 in The Netherlands and other western European countries. Location The Netherlands and neighbouring countries The Netherlands (Utrecht) The Netherlands (Petrusplaat, Lelystad) The Netherlands (Groningen, Emmen) Belgium (Kempen) Germany (Mainz, Nurnberg) Germany (Constance) Germany (Pln) Other Western European countries United Kingdom, South Drumboy Hill United Kingdom, Oxford United Kingdom, Loch Lomond (Scotland) United Kingdom, Perth (Scotland) United Kingdom (Scotland) United Kingdom (Scotland) Ireland (Dublin) Switzerland (5 peat bog lakes) Switzerland (Lake Constance) SwitzerlandFrance (Lake Geneva) Chateau of Versailles, 15 km from Paris, France Sampling medium Lake sediments Aerosols Rainwater Aerosols Peat bog sediments Aerosols Aerosols Aerosols Year Pb (mg m 2 y1) (n) 121173 (10) 446563 (2) 8 (1) 650 4.537 (3) 12 (1) 25150 29 14 (1) 19 12 (1) 2.2 (1)
206 Pb/207Pb (n)

Reference

19912002 20022003 2003 1994 19911995 1994 19971998 19971998 1990 19971998 1995 1994 19901999 2000 19971998 19971998 1994 19901993 1994 N 1991 1991 1994 2002 1994 19901991 1995 19961998 19971998 1995 1995 1995

1.1621.169 (10) 1.1551.172 (3) 1.1511.152 (2) 1.1331.137 (2) 1.1301.132 (2) 1.1331.145 (3) 1.1381.148 (6) 1.1471.165 (6) 1.13 (1) 1.1181.123 (6) 1.1251.145 1.101 (1) 1.1251.163 (16) 1.1371.165 (7) 1.1121.121 (68) 1.1181.161 (30) 1.101 1.1311.153 (3) 1.114 (1) 1.131.155

Walraven et al. (submitted for publication) Notten et al. (2008) Rosman et al. (1998) Sonke et al. (2002) Rosman et al. (1998) Bollhfer and Rosman (2002) Bollhfer and Rosman (2002)

Ombotrophic peat Aerosols Lake sediments Aerosols Moss Rainwater (open gauge) Rainwater (lter gauge) Aerosols Peat Lake sediment Lake sediment Soil

MacKenzie et al. (1998) Bollhfer and Rosman (2002) Eades et al. (2002) Rosman et al. (1998) Farmer et al. (2002) Farmer et al. (2000) Rosman et al. (1998) Weiss et al. (1999) Kober et al. (1999) Monna et al. (1999) Semlali et al. (2004)

France (Montpellier, Grenoble) France (Mont Blanc) France (Lille) France (Grenoble) France (Avignon) Straits of Dover Straits of Dover Straits of Dover

Aerosols Ice Aerosols Aerosols Aerosols Aerosols from North Western Europe Aerosols from Western Europe Aerosols from Eastern Europe

1.1301.142 (3) 1.1551.162 (3) 1.158 1.1101.134 (10) 1.1241.134 (6) 1.145 + 0.003 1.1111.142 1.1451.169

Rosman et al. (1998) Rosman et al. (2000) Deboudt et al. (1999) Bollhfer and Rosman (2002) Bollhfer and Rosman (2002) Deboudt et al. (1999) Deboudt et al. (1999) Deboudt et al. (1999)

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Table 4 Pb uxes (mg m 2 y1) through the soil and 206Pb/207Pb ratios of the migrating Pb fraction. Location Distance from highway (m) Pb ux from litter to topsoil Fdown L T (mg m 2 y 1) Nunspeet Nunspeet Moergestel Moergestel 8 74 10 75 117 133 261 149 70 114 211 120 (206Pb/207Pb)Fdown L T 1.16 1.17 1.10 1.19 Pb ux from topsoil to subsoil (mg m 2 y 1) Fdown TS (mg m 2 y 1) 73 72 324 174 58 95 279 159 (206Pb/207Pb)Fdown L T 1.21 1.19 1.10 1.18

324 279 mg m 2 y 1. Fdown L T and Fdown T S near Moergestel are higher close (10 m) to the highways than further away (75 m). This is most likely caused by the larger amount of anthropogenic Pb present in the soils close to the highways (Fig. 4). In addition, the use of sodium chloride to de-ice the highways during winter will contribute to the higher downward ux close to the highways. The nature in downward Pb transport differs at Nunspeet and Moergestel in that the downward Pb movement near Nunspeet is higher from the litter layer towards the topsoil than from the topsoil to the subsoil, whereas near Moergestel the opposite relationship is observed. The reason for this variation is unknown. The calculated 206Pb/207Pb ratios of the mobile Pb fraction vary from 1.10 to 1.21. These values agree with the values measured in the soil and groundwater samples (206Pb/207Pb = 1.111.21), which establishes that the calculated Pb uxes are of the right order of magnitude. Although the 206Pb/207Pb ratio measured close to the highway near Moergestel is low (206Pb/207Pb = 1.10), the value falls within the range of Pb isotope compositions of gasoline Pb known to have been used in The Netherlands and neighbouring countries (Table 1). The calculated 206Pb/207Pb ratios indicate that both anthropogenic and natural Pb is transported downwards, which is conrmed by the 206Pb/207Pb ratios in the groundwater (Table 2). We conclude that the low pH of the soils caused Pb mobilization of both anthropogenic and natural Pb, the latter most likely released due to dissolution of feldspars (Mol et al., 2003). Due to the large errors in the ux calculations it is impossible to establish if the isotopic composition of the mobile Pb fraction close and distal to the highway is identical. 4.4.2.2. Pb transport towards groundwater. At depths N 15 cm g.l., Pb is no longer retained due to the low pH and low binding capacity of the sandy soils. This means that most Pb that migrated through the topsoil, eventually ends up in the groundwater. It is possible to estimate the total amount of anthropogenic Pb that migrated to the groundwater between 1962/1963 (construction date of the highways) and 2003, assuming that Fdown T S was constant during this time. The total amount of Pb that migrated towards the groundwater at the studied sites varies from 2.95 to 12.96 g/m2 (Table 5). By comparing the sum of migrated Pb and anthropogenic Pb still present in the soils with the total amount of anthropogenic Pb present in the lake sediment of Lake Vechten, it is possible to check if the downward Pb ux was constant over time, assuming that 1) Pb in the lake sediments is immobile and 2) anthropogenic Pb deposition in Lake Vechten was similar to that at the roadside soil locations. Since the lake is located about 75 m from a national highway, the comparison is best made with the sampling sites 75 m from

the national highway near Moergestel and Nunspeet (Fig. 4). Between 1960 and 2003, a total of 12.65 g/m2 anthropogenic Pb was deposited atmospherically in the lake (Table 5). The total amount of anthropogenic Pb (still present and migrated to groundwater) that entered the soil at a distance of 75 m from the highway near Moergestel (15.05 g/m2) is in general agreement with the amount deposited in Lake Vechten during the same time period (12.65 g/m2). However, this is not the case for Nunspeet (74 m from the highway). The total amount of Pb migrated towards the groundwater and still present in the soil near Nunspeet (4.38 g/m2) is lower than deposited in Lake Vechten. Although the trafc density is ~ a factor of 2 lower near Nunspeet (~50,000 cars/day: Fig. 1) than near Lake Vechten (~90,000 cars/day: based on data from 2000 to 2003), this difference is not sufciently large to explain the observed difference. It is most likely that the downward transport of anthropogenic Pb before 1991 was considerably higher between 1991 and 2003 due to the higher input of gasoline Pb before 1991 (Walraven et al., submitted for publication) and the higher mobility of gasoline Pb that has just (freshly) entered the soil compared to aged gasoline Pb (Laxen and Harrison, 1997; and references therein). By comparing the total amount of anthropogenic Pb still present in the roadside soils with the total amount of anthropogenic Pb deposited in Lake Vechten, it is estimated that about 90% of the deposited Pb in the studied soils near Nunspeet, ended up in the groundwater compared to 35% in Moergestel. This difference can be explained by the difference in soil thickness, organic matter content and stability of the litter layer for the two locations. The litter layer near Nunspeet is thinner and contains less organic matter than at Moergestel. In addition, a net breakdown in litter between 1991 and 2003 is observed near Nunpseet. A decrease of 4090% in the Pb burden of soils is high. Friedland et al. (1992) and Miller and Friedland (1994), for example, found a decrease of the Pb burden in forest oors at several sites in eastern North America in the order of 2040%. Zhang (2003) calculated that about 56% of the atmospherically derived Pb has migrated into the lower A horizon of agricultural soils in central Illinois in 50 years. Marsh and Siccama (1997) reported that about 65% of atmosphericallyderived Pb on long abandoned, ploughed, soils in New England had migrated into mineral soils as of 1990. This study demonstrates that anthropogenic Pb in the studied roadside soils is mobile. In addition, the work establishes that the groundwater is already polluted with anthropogenic Pb. However, it remains to be established why Pb uxes in the studied soils are so high compared to soils studied by others. Lead uxes in the studied soils might be high due to the low soil pH, negligible calcium carbonate and reactive iron content, poor soil development and thin litter thickness compared to soils in the other studies. It would be worthwhile to determine and

Table 5 Anthropogenic Pb (in g/m2) migrated towards groundwater and still present in the soil/sediment. Anthropogenic Pb (%) still present in roadside soils compared to data from Lake Vechten. Location Lake Vechten Nunspeet Nunspeet Moergestel Moergestel Distance from highway (m) 75 8 74 10 75 Pb migrated towards groundwater (g/m2) 2.99 2.95 12.96 6.96 Total anthropogenic Pb still present (g/m2) 12.65 3.55 1.43 18.43 8.09 Anthropogenic Pb still present compared to Lake Vechten (%) 100% 10% 65%

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quantify the factors that determine uxes of anthropogenic Pb in soils in more detail. 5. Conclusions Sandy roadside soils near Nunspeet and Moergestel (NL) are polluted with Pb. The highest Pb content (up to 652 mg/kg) has been measured in the litter layer. The Pb isotope composition of the polluted top soils (206Pb/207Pb = 1.121.14) differs from the deeper soils (206Pb/207Pb = 1.201.21). Based on the characteristic 206 Pb/207Pb ratios of the polluted soils it was concluded that gasoline Pb was the dominant anthropogenic source responsible for the elevated Pb content in the roadside soils. Since the Pb isotope composition of the anthropogenic component differs from natural background Pb, the behaviour and fate of the anthropogenic Pb in the sandy roadside soils could be calculated. The main ndings were: 1. Only the litter layer and the topsoil retain anthropogenic Pb. Anthropogenic Pb is strongly associated with organic matter in the topsoil. The reason for the absence of anthropogenic Pb at depths N 15 cm is the low soil pH (pH-H20 = 4.35.0) and the lack of reactive phases (e.g. organic matter, clay, reactive iron and calcium carbonate), to which anthropogenic Pb can bind. 2. Pb isotope measurements of the groundwater (206Pb/207Pb = 1.135 1.176) prove the presence of anthropogenic Pb. Due to the absence of reactive phases in the deeper soils and the low soil pH, anthropogenic Pb migrated rapidly towards the groundwater. The contribution of anthropogenic Pb to groundwater Pb concentrations varies between ~30 and 100%. 3. Downward Pb transport was calculated to vary from 72 95 to 324 279 mg m 2 y 1, depending on distance from the highway and type of soil horizon. 4. Based on estimates of total atmospheric Pb deposition from 1962/ 1963 to 2003, it was calculated that 3590% of the atmospherically derived Pb migrated to the groundwater. 5. This study supports the recent ndings of others that anthropogenic Pb can be highly mobile, resulting in groundwater pollution. Supplementary data to this article can be found online at http:// dx.doi.org/10.1016/j.scitotenv.2013.11.110. Conict of interests All authors hereby state that there are no actual or potential conicts of interest including any nancial, personal or other relationships with other people or organizations (within three years of beginning the submitted work) that could inappropriately inuence, or be perceived to inuence, their work. Acknowledgements This work was supported nancially by TNO and Deltares. We thank Jaap Willemse and Hans Reinders of the Dutch National Institute of Public Health and the Environment (RIVM) for collaborating in this research (providing the roadside samples from 1991). Erik van Vilsteren and Rob van Galen are acknowledged for performing the chemical and isotopic analysis. Special thanks to Menno van der Heiden for providing the map. We thank the four anonymous reviewers for their thorough and constructive reviews of the manuscript. References
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