Environ Monit Assess (2012) 184:45174538 DOI 10.

1007/s10661-011-2282-5

Assessment of sampling and analytical uncertainty of trace element contents in arable field soils
Uwe Buczko & Rolf O. Kuchenbuch & Walter belhr & Ludwig Ntscher

Received: 16 December 2010 / Accepted: 27 July 2011 / Published online: 11 August 2011 # Springer Science+Business Media B.V. 2011

Abstract Assessment of trace element contents in soils is required in Germany (and other countries) before sewage sludge application on arable soils. The reliability of measured element contents is affected by measurement uncertainty, which consists of components due to (1) sampling, (2) laboratory repeatability (intra-lab) and (3) reproducibility (between-lab). A complete characterization of average trace element contents in field soils should encompass the uncertainty of all these components. The objectives of this study were to elucidate the magnitude and relative proportions of uncertainty components for the metals As, B, Cd, Co, Cr, Mo, Ni, Pb, Tl and Zn in three arable fields of different field-scale heterogeneity, based on a
U. Buczko (*) : R. O. Kuchenbuch Institute for Land UseApplied Plant Nutrition, University of Rostock, Justus-von-Liebig-Weg 6, 18059 Rostock, Germany e-mail: uwe.buczko@uni-rostock.de W. belhr Landwirtschaftliches Technologiezentrum Augustenberg, Nelerstrae 23-31, 76227 Karlsruhe, Germany L. Ntscher Bioanalytik im Zentralinstitut fr Ernhrungs- und Lebensmittelforschung der TU Mnchen, Alte Akademie 1, 85350 Freising-Weihenstephan, Germany

collaborative trial (CT) (standardized procedure) and two sampling proficiency tests (PT) (individual sampling procedure). To obtain reference values and estimates of field-scale heterogeneity, a detailed reference sampling was conducted. Components of uncertainty (sampling person, sampling repetition, laboratory) were estimated by variance component analysis, whereas reproducibility uncertainty was estimated using results from numerous laboratory proficiency tests. Sampling uncertainty in general increased with field-scale heterogeneity; however, total uncertainty was mostly dominated by (total) laboratory uncertainty. Reproducibility analytical uncertainty was on average by a factor of about 3 higher than repeatability uncertainty. Therefore, analysis within one single laboratory and, for heterogeneous fields, a reduction of sampling uncertainty (for instance by larger numbers of sample increments and/or a denser coverage of the field area) would be most effective to reduce total uncertainty. On the other hand, when only intra-laboratory analytical uncertainty was considered, total sampling uncertainty on average prevailed over analytical uncertainty by a factor of 2. Both sampling and laboratory repeatability uncertainty were highly variable depending not only on the analyte but also on the field and the sampling trial. Comparison of PT with CT sampling suggests that standardization of sampling protocols reduces sampling uncertainty, especially for fields of low heterogeneity.

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Keywords Soil sampling . Sampling uncertainty . Trace elements . Heterogeneity . Sewage sludge application . Heavy metals

Introduction Soil sampling is the first step when measuring trace element contents of soils, among other reasons for assessing the toxic heavy metal content (i.e. Cd, Cr, Cu, Hg, Ni, Pb, Zn) of arable soils before application of sewage sludge, which is required by the German Federal Soil Protection and Contaminated Sites Ordinance (BBodSchV 1999; see also Lewandowski et al. 1997; Nestler 2007) and similarly also in many other countries (e.g. Nagajyoti et al. 2010). However, both chemical analysis and soil sampling are fraught with uncertainty, which can seriously impair the quality of measurement results and the conclusions drawn from the measurements. Thus, in order to make a judgement about the reliability of measurements of element contents in soils, it is necessary to assess the total uncertainty of measurement and its contributions arising from sampling, sample preparation, and chemical analysis. Moreover, it is often desirable to reduce total measurement uncertainty, and in order to direct the corresponding efforts most efficiently, knowledge about the relative proportions of uncertainty is necessary (Ramsey and Thompson 2007). The accuracy of field sampling has been of concern worldwide for decades, for instance in soil tests for plant-available nutrient contents (e.g. Cline 1944; Cameron et al. 1971; Kerschberger and Richter 1992; Mallarino et al. 2006), for contaminated sites (Lam and Defize 1993; Correll 2001), for geochemical exploration of ore deposits (Garrett 1969; Ramsey et al. 1992), or in the context of sewage sludge applications (Lewandowski et al. 1997; Nestler 2007). For agricultural fields, simplified schemes to obtain representative composite samples for sub-plots of typically 35 ha are often applied, for instance, consisting of 2030 auger cores (increments) which are extracted from 0 to 20 cm soil depth, using patterns such as a double diagonal or zigzag lines (N or W pattern) (Lewandowski et al. 1997; ISO 2002). Similar simple sampling schemes are often used for determination of heavy metal contents at artificially contaminated sites (e.g. Argyraki et al. 1995), although the larger heterogeneity and spot-like nature of the

contaminations often requires more sophisticated sampling schemes (e.g. Taylor et al. 2005). Even though sampling schemes such as stratified random sampling (Brus et al. 1999) or grid sampling (Lauzon et al. 2005) may reduce sampling error, simplified sampling schemes are still often being used, since in many situations the increased effort of more elaborated sampling schemes is not commensurate with the purpose of the sampling (i.e. fitness for purpose, Ramsey and Thompson 2007). The term uncertainty encompasses both precision and bias (trueness), and it is commonly quantified by means of standard deviations (ISO 2005; Ramsey and Ellison 2007). Whereas precision refers to the variability and repeatability of sampling results (i.e. random effects), bias refers to the trueness of the results, i.e. systematic effects. Sampling uncertainty in soils can be determined by a modelling, bottom-up approach, in which the separate components of uncertainty are summed up (in form of the respective variances) to obtain the overall uncertainty, or by an empirical, top-down method, in which uncertainty is estimated based on sampling results from different sampling trials and/or samplers (i.e. sampling participants or persons; the term sampler is used in this sense throughout this paper), often by collaborative trials (CT), i.e. several samplers using identical sampling protocols (Ramsey and Argyraki 1997; Ramsey and Thompson 2007), or by sampling proficiency tests (PT), i.e. several samplers using different sampling protocols (Argyraki et al. 1995; Lischer et al. 2001; ISO 2005; de Zorzi et al. 2008; Ramsey and Ellison 2007; Ramsey et al. 2011). It has been claimed that soil sampling in the field is in most cases the main source of uncertainty and dominates sampling preparation and other laboratory sources (Ramsey 1998). This has been demonstrated for trace metals (Taylor et al. 2005; van der Perk et al. 2008; Rawlins et al. 2009), for organic contaminants (Lam and Defize 1993) and for nutrient elements on arable soils (Jacob and Klute 1956; Kerschberger and Richter 1992) and grassland (Cameron et al. 1994). However, there are also examples of analytical uncertainty prevailing over sampling uncertainty (e.g. Lischer et al. 2001). Consequently, one cannot a priori assume that sampling uncertainty always dominates over laboratory uncertainty. Total laboratory (analytical) uncertainty consists of repeatability (within one laboratory) and reproducibil-

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ity (between different laboratories) uncertainty components. The uncertainty arising from sample preparation mostly cannot be determined unambiguously. Whereas sample preparation steps involving the primary sample (i.e. mixing of composite samples, comminution, splitting) pertain to sampling uncertainty, sample preparation steps occurring in the laboratory (i.e. drying, sieving, milling, splitting, homogenization) contribute to analytical uncertainty (Lam and Defize 1993; Gerlach et al. 2002; Ramsey and Ellison 2007). Consequently, both sampling and analytical uncertainty contain some variable but largely unknown proportion of uncertainty due to sample preparation. The objective of this study is to evaluate the magnitude and relative proportions of sampling uncertainty and intra- and between-laboratory uncertainty when applying simple sampling schemes to obtain representative average trace metal contents of agricultural fields. Whereas this topic has been in general investigated in previous studies (as cited in the introductory section above), the present study contains several aspects the combination of which is novel in comparison with previous studies: 1. Both intra-laboratory and between-laboratory uncertainty components are evaluated; intralaboratory uncertainty is evaluated exhaustively by duplicate analyses of all samples 2. Several different simple sampling paths are evaluated here by incorporation of a large number (18) of samplers 3. Comparison of the effect of sampling person and sampling repetition by applying two repetitions of a sampling proficiency test 4. Evaluation of the effect of standardizing the sampling protocol by comparing proficiency tests and collaborative trials 5. Inclusion of several analytes differing in their geological origin and environmental impact

(5112 N, 855 E). The geological underground is composed of a lower Triassic sandstone-shale sequence and upper Permian dolomites and salt clays. The fields are located approximately 400 m above sea level. The soil texture of the fields is loamy sand (F1), sandy loam (F2) and clay loam (F3). The outline of the fields along with schematics of the reference sampling, the CT sampling and the PT samplings is depicted in Fig. 1. Normal background ranges and threshold values (according to BBodSchV 1999) of the analytes are summarized in Table 2. Since the parent material of F1 consists of a large variety of bedrocks from Permian limestone and dolomites to Triassic sandstones and shales and because soil texture exhibits the largest variety on this field, it was assumed before the sampling trial that the F1 field is the most heterogeneous among the three fields. Based on similar criteria, F2 was considered to be the most homogeneous of the fields. Whereas F1 and F2 were managed during the last few years using reduced tillage practices (cultivator), F3 was tilled in a conventional manner by mouldboard ploughing. The crop rotations during the preceding years show a great variety among fields and years. At the time of sampling, F2 and F3 were prepared for maize cultivation, and at F1 was a standing grass crop intended for seed production. Climatic conditions in the area (station Kassel, 231 m above msl) are characterized by an average annual temperature of 8.9C and mean annual precipitation of 686 mm (average over the years 19712000). Soil sampling Prior to the main sampling trials, a reference sampling was performed, in order to obtain reference average analyte contents and an estimate of the spatial heterogeneity of the fields. The plots were subdivided into seven (F1) and nine (F2 and F3) sub-plots of approximately equal area. From each sub-plot, 20 sample increments were taken by auger cores (diameter of 14 mm) from 0 to 20 cm soil depth. The locations of core extraction were equally distributed along the perimeter of a circle located centrally within the sub-plot (Fig. 1). The perimeter of this circle was approximately equal to the diagonal of the respective sub-plot (MLUV 2009). This circle sampling pattern has the advantage that an area can be covered equally without much effort, and no spatial direction is

Material and methods Study sites Sampling trials were performed on three fields (F1, F2, F3) located in Vhl near Korbach, about 40 km southwest of Kassel (Federal state Hesse, Germany)

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Sampling reference

F1

F2

F3

1
1

sampling
5

2 3 6

3 2
4

(RS)
6 7

5 4 7

9 8 7

8 9

collaborative trial (CT)

sampling proficiency test (PT)

Fig. 1 Schematic of the three investigated fields; upper row reference sampling numbers within the fields denote sub-plots; middle row sampling pattern of CT sampling; bottom row

examples of frequently used sampling patterns of the sampling proficiency test. The double-headed arrow scale bar is 100 m

favoured. Since the sub-plots of each field were of approximately equal area, the circles used for collecting the increments of the reference samples were also of approximately equal size for each field (Fig. 1). The increments of each sub-plot were combined into a composite sample for the respective sub-plot. The analysis of these samples resulted in element concentrations for each sub-plot, which were (arithmetically) averaged to yield reference values for the whole field. For estimating sampling uncertainty using the top-

down (or empirical) approach, a collaborative trial in sampling (i.e. multiple samplers using a single protocol) and a sampling proficiency test (i.e. multiple samplers using multiple protocols) were applied. In both the collaborative sampling trial and sampling proficiency test, 18 professional soil samplers from institutions of ten German Federal states participated. Each of the three fields was sampled three times by each of the 18 participants. Two sampling repetitions were performed by the partic-

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ipants procedure of choice (sampling proficiency test, PT samples; the two repetitions are termed PT1 and PT2 in the following), and one sampling repetition was a standardized procedure (sampling CT). The aim of all sampling was to obtain a representative average element concentration of the whole field. For the standardized procedure (CT), the sample increments were taken from 0 to 20 cm depth. Twenty cores were extracted using an X-shaped (double diagonal) sampling pattern (Fig. 1) with augers of 14 mm diameter. For the PT sampling, various sampling patterns were used by the participants. The fields were covered using W and N (zigzag) shapes, double diagonals (X), circles and simple lines for sample collection (Fig. 1). The number of sample increments varied between 15 and 40, but the majority (more than 50%) of the participants took 20 cores. The diameter of the auger varied between 12 and 18 mm, with 50% of the participants using 14 mm diameter augers. Fifty percent of the participants chose the same sampling depth as in the collaborative trial (20 cm), whereas six sampled 025 cm and three sampled 030 cm. As a consequence, the resulting total masses of the composite samples varied widely between 266 and 1,177 g, with a mean of 590 g (total dry mass before sieving). All samples of the collaborative trial and the sampling proficiency test were taken on April 17, 2007. Prior to this date, there had been no precipitation for 2 weeks. At the sampling day, the weather conditions were dry with temperatures of 12C in the morning and 20C in the afternoon. Sample preparation and analysis The composite samples were filled, after mixing and homogenization, into plastic bags, immediately transported to the laboratory and oven-dried at 50C overnight. The following day, after drying and breaking up agglomerates by a jaw crushing machine, the samples were weighed and passed through a 2mm sieve (mechanical sieving machine). Particles with diameters >2 mm were discarded. From the fraction <2 mm, about 65 g was extracted manually with a spatula (grab sampling) to form laboratory samples for further analyses. All chemical analyses were done in duplicate, and all sample preparation steps and chemical analyses were performed in the

same reference laboratory (LUFA Rostock) by the same person, such that systematic effects between laboratories were avoided and the analytical uncertainty derived from the duplicate analyses encompassed only within-laboratory repeatability uncertainty. Total contents of the metals As (arsenic), B (boron), Cd (cadmium), Co (cobalt), Cr (chromium), Mo (molybdenum), Ni (nickel), Pb (lead), Tl (thallium) and Zn (zinc) were determined after aqua regia extraction and analysis with ICP spectrometry (Hoffmann 1991). All laboratory samples were analysed in duplicate in order to estimate uncertainty due to analytical repeatability. For quality control and quality assurance of the analytical procedure, the following points are important: (1) inspection of trueness: Because all samples were analysed in the same laboratory, a constant analytical bias would have no effect on data variation due to sampling. Although such an analytical bias could be accounted for by use of certified reference materials, for estimating uncertainty due to sampling, this is not strictly required. On the other hand, the effects of a possible analytical bias were accounted for in this study by evaluating numerous interlaboratory proficiency tests (see below); (2) longterm stability control: During the course of the analytical session of a few weeks, laboratory-owned control materials were constantly run, to ensure quality control and assurance of the analytical procedures. If necessary, data correction of day-today effects was carried out, using a correction factor evaluated from the results of the control material. Data analysis Reference sampling Arithmetic averages of the sub-plot analyte contents obtained by the reference sampling were taken as reference values (cref) for comparison with analyte contents determined by the sampling trials (cpt, cct). Coefficients of variation (sref =[standard deviation/ mean]100%) were calculated for each field and analyte and used as an index for the field-scale heterogeneity. Note that the increments constituting the sub-plot samples were not analysed separately, and therefore, the overall number of samples was not sufficiently large for geostatistical analyses. The

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Environ Monit Assess (2012) 184:45174538 Fig. 2 Sketch (similar as in Ramsey and Thompson 2007) of the sampling design and data used for estimating uncertainty components with VCA. Note that only the uppermost branch is depicted completely. Consecutive branches below have an analogous structure and are not shown due to space constraints. The compilation beneath the graph shows equivalences and conversion equations of variables for (1) effect on separate data (Eq. 1), (2) corresponding variances (absolute values), (3) variance components (percent) and (4) standard uncertainty values (percent). Sampling targets (i.e. fields) and analytes are analysed only separately; consequently, refers to a given analyte and field

coefficient of variation has been used in many studies of field-scale variability as an indicator for heterogeneity (e.g. Cameron et al. 1971; Lauzon et al. 2005; Taylor et al. 2005; Mallarino et al. 2006). However, in most cases, measured data based on point-like support (i.e. area or volume that is represented by a single sample or measurement) were used. In this study, the support of separate data (i.e. composite samples) was an appreciable percentage of the field area. This should result in lower standard deviations compared with data based on point measurements. Components of variance The proportions of total measurement variance of the sampling trials contributed by the sampler, the sampling repetition and laboratory analysis were estimated with variance component analysis (VCA) (Cox and Solomon 2002). It was assumed that the effects of sampler, sampling repetitions of the proficiency test and analytical repeatability errors (chemical analyses in duplicate) are random. The effects of different fields and the sampling of the collaborative trial cannot be viewed as random and therefore were not included in the VCA. Since the design of the sampling trials is structured in a hierarchical way (each of 18 samplers took two PT samples, each of which was analysed in duplicate, Fig. 2), the following statistical model was used: Yijk m ai bj ai "ijk 1

with the dependent variable Yijk representing one individual result of one chemical analysis of a given analyte on a given field (of i-th sampler, j-th sampling repetition, k-th chemical duplicate analysis), is the overall mean value (for a given analyte and sampling target, i.e. field), i is the effect of the i-th sampler (i =1 18) and j(i) the effect of the j-th sampling repetition of i-th sampler (j =1, 2) and ijk is the residual effect (corresponding to the analytical repeatability error, the index k denotes the analytical repetition, k =1, 2). It is assumed that the mean values of the variables i, j(i) and ijk are zero and that they have corresponding variances sp2, sr2, ak2, respectively. Further, it is assumed that both the random variables i, j(i) and ijk and the corresponding variances are distributed normally, in accordance with assumptions

generally made in chemical analyses (e.g. Thompson and Howarth 1976). Tests for normal distribution using the KolmogorovSmirnov test revealed that the variables were not significantly different from a normal distribution. The VCA was conducted using the restricted maximum likelihood (REML) method (Corbeil and Searle 1976), in which negative variance components are set to zero. Estimates of variance components using ANOVA are often biased and can be negative (variances, by definition, must be either zero or positive). Maximum likelihood estimation methods of variance components such as REML provide less biased estimates of variance components, since fixed effects are filtered out so that the variance component estimates do not depend on them. This reduces bias in the variance estimates (e.g. Webster et al. 2006). The equivalences and interconversion of variables are summarized in Fig. 2. The analytical (laboratory) uncertainty resulting from different laboratories could not be analysed here with VCA because all chemical analyses were conducted in the same laboratory. Therefore, the residual component ijk contains only the random error of one laboratory and thus corresponds to the intra-laboratory (repeatability) uncertainty uak. The statistical calculations were performed using the software SAS 9.1. Laboratory uncertainty Total analytical uncertainty (uat) consists of repeatability uncertainty within one laboratory (uak) and reproducibility uncertainty between different laboratories (uab) (Thompson and Lowthian 1995; Lischer et al. 2001; Munzert et al. 2007; Nestler 2007). uak was estimated from duplicate determinations of all sam-

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sample PT1

analytical repetition 1 analytical repetition 2

sampler 1 sampling target fields F1 F3, ...analytes

sample PT2 sample CT

sampler i

sampler 18 field F sampler F.i (i : 1...18)

sample F.i.j (j : PT1, PT2, CT)
chemical analysis result F.j.j.k (k : 1,2)

effect for single result (eq. 1),mean ,actual value Yijk corresponding variances 2 2 (total variance: t = sp +

b et w een -s am p l er (sampling person) i

between sample repetition j (i )

between analytical repetitions ij k

sp 2

sr 2

ak 2

sr 2 + ak 2)

Variance components (%)

sp 2 vcsp = 2 100 t
usp 100 100 vcsp = 2
2

vcsr =

sr 2 100 t 2
2

vcak =

ak 2 100 2 t
2

u sr 100 100 vcsr = 2

u ak 100 100 vcak = 2

Standard uncertainty (%), total uncertainty:

ut =

sp u sp = 100
2
2

sr 2 u sr = 100
100

ak 2 u ak = 100
u ak = vcak t 100 100
2

usp + usr + uak + uab

2 2 2

vcsp t u sp =

total analytical uncertainty:

100

uat = uak + uab

2

u sr =

vcsr t 100 100

2

sampling uncertainty:

us = usp + usr
2

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Environ Monit Assess (2012) 184:45174538

ples, using the root-mean-square (RMS) precision estimator (Hyslop and White 2009): v u n p ! u 1 X ci;1 ci;2 = 2 2 t uak 100 2 n i1 ci with ci,1 and ci,2 the measured concentration (of the i-th sample) of the first and second analytical replication, respectively, and ci the mean concentration of both analytical repetitions. Compared with other estimators of analytical precision (for instance, mean absolute value or percentile spread), the RMS precision estimator is somewhat sensitive to extreme values and tends to yield larger precision uncertainty estimates (Hyslop and White 2009). Thus, this estimator provides a larger safety margin, which seems advantageous when estimating overall sampling uncertainty of toxic metals. Values of uak calculated with Eq. 2 proved to be nearly identical with uak values obtained by the VCA (for the PT samplings); uak values were calculated for each analyte, field, and sampling trial. The between-laboratory (reproducibility) analytical uncertainty uab was not captured by the data of the present study (because analyses were conducted within a single laboratory). It was estimated instead (for Cd, Cr, Pb, Zn) using linear regression equations which are based on analytical proficiency tests conducted in several laboratories throughout Germany (Table 1). The calculation procedure of these regressions and the results for macro- and micronutrient elements are given in Munzert et al. (2007). In a similar manner, for total contents of the heavy metals Cd, Cr, Ni, Pb and Zn from the same type of data, linear regression equations were developed for estimation of the betweenlaboratory uncertainty uab a b c=c 100,

with c the mean concentration of one out of n laboratory proficiency tests and a and b the intercept and slope parameters, respectively). Regression parameters and characteristics of the regression are compiled in Table 1. Because the regressions are based on mean values for each laboratory, we assumed that the uncertainty derived from these regressions comprises only inter-laboratory uncertainty, but not uncertainty within one specific laboratory. For As, data of laboratory proficiency tests from 27 laboratories given in Nestler (2007) were used. From both repeatability and reproducibility analytical uncertainty components, total analytical uncertainty uat is calculated as (addition of variances): q 2 uat u2 3 ak uab Sampling uncertainty For the PT sampling, sampling uncertainty us is calculated from VCA, the components due to the sampling person usp and that due to the sampling repetition usr: q 2 4 us u2 sp usr The us values obtained from VCA are similar to us values estimated from reproducibility standard deviation (rsd; i.e. standard deviation of results among different samplers) and uak using r u2 us rsd 2 ak 2

Table 1 Values of regression parameters and characteristics of the regression (all analyte concentrations are in milligrams per kilogram) for estimation of uab values based on laboratory proficiency tests Analyte Cd Cr Ni Pb Zn Number of data 20 22 22 20 21 a 0.01 0.791 0.24 0.8 1.5 b 0.188 0.076 0.074 0.057 0.042 r2 0.50 0.65 0.87 0.79 0.66 n 20 22 22 20 21 cmin 0.12 14.5 7.6 12.2 29.9 cavrg 0.25 37.9 25.8 26.8 69.7 cmax 0.35 58.6 42.1 59.3 122.9

For the regression equation uab a b c=c 100, with c the mean concentration of one specific of the n datasets and a and b the intercept and slope parameters; cmin and cmax denote the minimum and maximum concentration values on which the regression is based, whereas cavrg is the overall mean concentration of all n datasets (i.e. proficiency tests)

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Therefore, for the CT samples, us was estimated using Eq. 5. Total measurement uncertainty ut comprises us and uat and is calculated by addition of variances as q 2 6 ut u2 at us

Results and discussion Reference sampling Mean values of cref and sref of the three fields obtained by the reference sampling are summarized in Table 3. The mean contents of most analytes are within the normal background range and indicate no contamination (Table 2). However, thallium contents are extraordinarily high on all fields, but especially on F1 and F3. Since F2 is located between F1 and F3 and no contamination sources of Tl are known in this region, the elevated Tl contents are presumably connected with the upper Permian parent material of F1 and F3. Elevated Tl contents are known to occur in
Table 2 Natural background and threshold concentrations of the analytes Analyte Background concentrationa Threshold concentrationb As B Co Mo Tl Cd Cr Ni Pb Zn
a b

120 580 515 0.25 0.020.4 0.10.6 5100 350 260 1080

25 0.4c, 1.0d, 1.5e 30c, 60d, 100e 15c, 50d, 70e 40c, 70d, 100e 60c, 150d, 200e

Natural background concentration range (cf. Nagajyoti et al. 2010)

Threshold values given here are precautionary threshold values (depending on soil texture) according to the German sewage sludge and Federal Soil Protection Ordinance (BbodSchV 1999); the precautionary nature of these values entails that they are lower than threshold values reported elsewhere and in other countries (cf. Nagajyoti et al. 2010)
c d e

upper Perminan sediments (e.g. Wedepohl 1964) and also in PbZn mineralizations, which have been mined in the area (Kulick 1997). Highly elevated soil Tl contents have been reported from other areas of the European Variscan Orogeny, for instance in France (Tremel et al. 1997). Averaged for all analytes of a specific field, sref values were the highest for F1 (average of ten analytes 27.5%) and the lowest for F2 (12.7%) (Table 3). This was expected before the sampling trials, since before the sampling, F1 was considered to be the most heterogeneous and F2 the most homogeneous of the three fields. Overall, compared with CV values reported in other studies, these values are rather low (see general discussion). However, sref values varied considerably among the analytes (Table 3), whereas for six of the ten analytes, the highest sref values were observed for F1; for Co and Ni, F2 exhibited the highest sref values of the three fields and for B and Cr, the highest sref values were observed on F3. Averaged over the three fields, the highest sref values were observed for Cd (34.6%) and Tl (28.7%) and the lowest for Cr (9.7%), while average sref values for the other analytes range between 13% and 21%. The mean concentrations cpt1, cpt2 and cct of the composite samples of the PT1, PT2 and CT sampling repetitions, respectively, indicate that bias values (i.e. the mean sampling errors of the 18 samplers, related to cref values) are on F1 distinctly negative for most analytes and sampling repetitions. In contrast, absolute bias values are generally lower on F2 and F3 (Table 3). This is probably caused by the relatively irregular shape and the nutrient distribution within the F1 field, combined with the sampling patterns preferred by the participants: In the two sub-plots 4 and 5, in the western part of the field (Fig. 1), distinctly different analyte concentrations compared with the other sub-plots of this field were observed (connected with different parent materials in these sub-plots). On the other hand, sub-plots 4 and 5 were avoided by most of the participants, among other reasons because the soil in these sub-plots was relatively hard and therefore difficult to sample. Sampling trials: analytical uncertainty The results of the sampling trials show distinct differences between analytes and sampling trials as regards the relative variation between samplers,

For loamy sand (F1) For sandy loam (F2) For clay loam (F3)

4526 Table 3 Summary of results: mean (cref) and sref values of the reference sampling and mean (cpt1, cpt2, cct) and bias values from the PT and CT sampling trials for the three fields F1F3; units of cref, cpt1, cpt2 and cct are milligrams per kilogram Field Analyte Reference sampling crefb F1 As B Co Mo Tl Cd Cr Ni Pb Zn Meana F2 As B Co Mo Tl Cd Cr Ni Pb Zn Meana F3 As B Co Mo
a

Environ Monit Assess (2012) 184:45174538 PT sampling cpt1b 9.1 10.2 6.2 0.3 3.9 0.2 21.6 17.0 21.2 56.9 7.5 7.9 7.0 0.4 0.9 0.2 26.3 12.6 17.2 39.7 17.0 15.9 10.8 0.6 3.0 0.5 24.3 24.2 29.7 112.8 Bias 7.6 2.9 4.6 12.3 15.6 53.6 8.5 11.5 11.6 13.5 14.2 12.8 16.6 11.7 22.7 51.2 24.8 12.2 9.6 5.7 3.0 1.8 4.7 6.8 1.2 31.8 30.0 1.7 11.4 18.8 24.2 20.0 4.5 17.8 16.4 10.8 0.5 3.0 0.5 24.9 22.0 32.2 108.0 7.1 8.0 6.8 0.4 1.6 0.2 26.3 13.0 17.6 41.9 cpt2b 9.6 10.9 6.5 0.3 3.1 0.2 23.2 13.6 18.1 45.9 Bias 2.9 3.6 0.0 13.8 32.6 35.3 2.0 29.2 24.3 30.1 16.7 8.1 17.6 8.6 27.2 16.5 22.3 12.2 6.8 3.8 2.2 2.6 0.2 9.9 1.7 6.5 30.7 1.9 14.1 26.0 17.9 23.5 6.4 17.6 16.9 11.1 0.5 3.2 0.5 24.8 22.4 33.7 110.8 7.0 8.5 7.2 0.4 1.7 0.2 26.6 13.6 16.9 41.5 CT sampling cctb 10.4 11.3 6.7 0.4 2.7 0.3 22.5 13.2 17.6 40.9 Bias 4.7 7.8 3.3 3.8 41.1 29.9 5.0 31.2 26.6 37.8 15.9 5.4 25.7 14.7 47.0 11.7 3.3 13.3 2.2 7.4 1.3 8.3 0.9 13.1 4.1 0.2 26.9 4.5 13.6 25.0 14.1 21.5 5.3

sref 23.6 19.5 14.1 16.8 44.1 49.6 7.5 17.1 24.7 27.6 27.5 9.6 12.7 15.5 8.4 8.2 16.8 10.0 19.1 8.2 12.9 12.7 19.2 21.4 12.1 14.3 21.2 29.0 11.3 15.0 14.0 20.3 18.5

9.9 10.5 6.5 0.37 4.7 0.4 23.6 19.2 23.9 65.7 6.6 6.8 6.3 0.3 1.9 0.24 23.5 13.9 18.3 41.0 17.8 14.9 10.7 0.5 4.3 0.4 21.8 29.8 39.2 141.1

All means of standard deviation are calculated by averaging the corresponding variances because variances rather than standard deviation are additive

Tl Cd Cr Ni Pb Zn Meana

Units of cref, cpt1, cpt2 and cct are milligrams per kilogram

sampling trials or analytical repetitions. This is depicted exemplarily in Fig. 3 for all 18 samplers separately (left side) and as boxplots (right side): Co on F2 is an example for high variability between samplers, Pb on F1 shows high variability between sampling repetitions and Mo on F3 shows high variability between analytical repetitions. Among the fields and the sampling trials, uak values varied considerably (Table 4), especially for Cd, Ni, Tl and Pb. Mean uak values (averaged over

the three fields and the PT and CT samplings), for the analytes, are for As 4.0%, B 3.2%, Co 4.0%, Mo
Fig. 3 Results of the sampling trials for all 18 samplers separately (left side) and as boxplots (right side), exemplarily for Co on F2 (top, high variability between samplers), for Pb on F1 (centre, high variability between sampling repetitions) and for Mo on F3 (bottom, high variability between analytical repetitions). The dashed horizontal lines in the left side graphs and in the boxplots indicate mean values of the reference sampling (RS)

Environ Monit Assess (2012) 184:45174538

8.5

4527
PT1 PT2 CT
8.5

F2 Co

8.0

8.0

Co conc. (mg / kg)

7.5

7.5

7.0

7.0

6.5

6.5

6.0

6.0

5.5 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
PT1 PT2 CT RS

5.5

sampler

25

F1 Pb

23

PT1 PT2 CT

24

22

Pb conc. (mg / kg)

21
20

19
18

17
16

15
14

13 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
PT1 PT2 CT RS

sampler

0.9 0.85 0.8 Mo conc. (mg / kg) 0.75 0.7 0.65 0.6 0.55 0.5 0.45 0.4 0 1 2 3 4 5 6 7

F3 Mo

0.9

PT1 PT2 CT

0.8

0.7

0.6

0.5

0.4

10 11 12 13 14 15 16 17 18

PT1

PT2

CT

RS

sampler

4528 Table 4 Repeatability and reproducibility analytical uncertainty for all fields, analytes and sampling trials Field Analyte uak PT1 F1 As B Co Mo Tl Cd Cr Ni Pb Zn F2 As B Co Mo Tl Cd Cr Ni Pb Zn F3 As B Co Mo Tl Cd Cr Ni Pb Zn All fields As B Co Mo All uncertainty (u) values are as percentage values (i.e. relative to the concentration of the analyte)
a

Environ Monit Assess (2012) 184:45174538 uab PT2 2.6 3.6 3.9 6.7 2.7 10.0 4.4 2.3 3.8 6.9 3.8 3.1 4.2 7.0 6.3 12.7 3.1 2.8 1.7 7.1 3.9 3.3 3.1 13.3 3.3 4.3 5.7 2.2 1.8 1.8 3.5 3.3 3.7 9.5 4.4 9.7 4.5 2.4 2.6 5.8 CT 4.6 4.6 3.6 9.0 2.5 4.8 3.6 6.5 3.8 7.0 2.9 3.2 5.4 8.4 6.1 4.6 3.3 9.6 1.6 2.7 5.3 3.0 3.6 9.6 3.4 3.2 4.2 8.0 6.5 3.0 4.4 3.7 4.3 9.0 4.3 4.3 3.7 8.1 4.4 4.7 Meana 3.3 3.7 3.8 8.1 2.9 15.5 4.0 5.2 3.5 5.9 3.5 2.8 4.9 7.2 7.9 8.5 3.5 5.9 1.8 4.9 5.1 3.0 3.1 10.3 3.1 5.1 4.5 5.2 4.1 2.7 4.0 3.2 4.0 8.6 5.2 10.6 4.0 5.5 3.3 4.7 23.3 10.9 8.8 9.5 6.8 22.7 10.8 8.9 9.6 7.0 22.2 10.8 8.9 9.7 7.1 22.8 10.9 8.9 9.6 7.0 21.0 10.9 8.4 8.4 5.5 16.2 21.0 10.8 8.4 8.2 5.6 16.2 21.0 10.8 8.4 8.1 5.5 16.0 21.0 10.8 8.4 8.3 5.5 16.1 24.4 10.6 9.2 10.4 8.0 12.5 24.1 10.6 9.2 10.3 7.8 12.5 23.1 10.6 9.1 10.5 7.8 12.5 23.9 10.6 9.2 10.4 7.8 12.5 24.4 11.3 8.8 9.5 6.8 18.0 22.9 11.0 9.1 10.2 7.4 18.0 22.5 11.1 9.2 10.3 7.8 18.0 23.3 11.1 9.0 10.0 7.4 18.0 PT1 17.5 PT2 17.5 CT 17.0 Mean 17.3

2.2 2.8 3.8 8.4 3.4 24.5 4.0 5.9 3.0 3.0 3.7 1.9 5.0 5.9 10.6 5.7 4.1 1.8 2.1 3.9 5.8 2.7 2.4 7.0 2.6 6.9 3.2 3.7 2.2 3.2 4.2 2.5 3.9 7.2 6.6 15.1 3.8 4.2 2.5 3.4

Tl Cd Cr Ni Pb Zn

All means of standard deviation are calculated by averaging the corresponding variances

8.6%, Tl 5.2%, Cd 10.6%, Cr 4.0%, Ni 5.0%, Pb 3.3% and Zn 4.7%. Although one would expect that

uak is more or less constant for a given analyte (and concentration), the results show that uak values are

Environ Monit Assess (2012) 184:45174538

4529

highly variable between fields and sampling trials (Table 4). This finding may be explained by the fact that both analytical and sampling uncertainty contain to a variable and mostly unknown degree uncertainty components arising from mixing and homogenization of the composite samples (which incurs inevitable segregation effects, Lam and Defize 1993), sample preparation (drying, sieving, grinding) and sample splitting (Gerlach et al. 2002; Lyn et al. 2003; Kurfrst et al. 2004). These factors contributing to uak might vary in an unpredictable manner for a given analyte between samplings and fields, thus giving rise to the observed variability of uak values. In the top-down approach used here, these components could not be separated from the pure analytical uncertainty. Values for uak seem rather high for Mo and Cd. Concerning the other analytes, several studies reported similar uak values to the ones found here, e.g. van der Perk et al. (2008) reported 24% for As, Cr and Zn and Kurfrst et al. (2004) reported ua,i values of 13% for Cd, 5.8% for Cu, 8.3% for Pb and 4.5% for Zn. Consequently, uak values found in this study seem to be more or less within the normal range. On the other hand, between-laboratory uncertainty (uab) values estimated from the laboratory proficiency tests are for a given analyte for the different fields and sampling trials similar and mostly larger than the corresponding uak values (Table 4), with an average uab/uak ratio of about 3 (but highly variable depending on the analyte). Consequently, uat is in general dominated by uab. Values of uab are exceptionally high for Cd and As. For the other analytes, uab values are within a range of about 511%. Sampling trials: sampling uncertainty Both rsd and us values are highly variable depending on the analyte, field and sampling (Table 5); however, rsd and us values are similar and highly correlated (r = 0.98); on average, us values are 12.3% lower than rsd values. Sampling uncertainty is different among the fields: Averaged for all ten analytes on a given field, us is the highest for F1 (12%) and the lowest for F3 (7.5%), whereas on the most homogeneous F2, average us was 11.5%. However, this relatively high average us value for F2 is dominated by the unusually high value for Tl in the PT1 sampling (44.6%); without this outlier, the average us value for F2 would be 8.1%. Thus, for average us values of the fields, there is no strict ranking in relation to average sref values (i.e.

heterogeneity). However, for specific analytesfields samplings, sampling uncertainty exhibits an overall positive (weak though statistically significant) correlation with spatial heterogeneity (i.e. sref), when data for all fields, analytes and samplings are pooled (r =0.4, not shown here in detail). Consequently, sampling uncertainty increases in general with field-scale spatial heterogeneity, although this relation in particular depends strongly on the considered analyte. Increasing sampling uncertainty with increasing field-scale heterogeneity has been described in previous studies by other authors, for instance by Jacob and Klute (1956), Cameron et al. (1971), Kerschberger and Richter (1992) and Mallarino et al. (2006) for nutrient elements on arable fields and by Kurfrst et al. (2004), Taylor et al. (2005) and van der Perk et al. (2008) for trace metals. Although us values depend not only on the analyte but also on the field and sampling, averaged us values show clear differences among the analytes: Averaged over the three fields and the PT and CT samplings, mean us values for the analytes are for As 7.1%, B 9.0%, Co 5.2%, Mo 11.7%, Tl 20.3%, Cd 12.1%, Cr 6.0%, Ni 11.1%, Pb 6.4% and Zn 7.4%. A comparison of the two approaches to conduct the sampling trials (PT vs CT) shows that overall, average us values are lower for the CT (7.4%) sampling compared with the PT (11.8%) sampling repetitions (Table 5), especially for the most homogeneous field F2. This is as one would expect because of the lower number of degrees of freedom in the CT sampling (due to the prescribed sampling protocol) compared with the PT sampling. There are only few cases for specific analytes with higher us values for the CT than for the PT sampling (As, B on F1; Cd on F3). The relative difference (of analyte-averaged us values between PT and CT samplings) is larger for F2 (13.5% vs 5.5%) than for the other fields. This implies that standardization of the sampling protocol in the CT sampling (sampling trajectory according to a double diagonal, X) has the strongest effect on the field of low heterogeneity F2, but a lower effect on the fields of higher heterogeneity. Relation between sampling and laboratory uncertainty When total analytical uncertainty is considered, the total uncertainty of measurement, ut, is dominated by laboratory uncertainty, with an overall averaged (for

4530 Table 5 Repeatability standard deviation (rsd) and sampling uncertainty (us), for all fields, analytes and sampling trials (PT1, PT2, CT) Field F1 Analyte As B Co Mo Tl Cd Cr Ni Pb Zn Mean F2 As B Co Mo Tl Cd Cr Ni Pb Zn Mean F3 As B Co Mo Tl Cd Cr Ni All uncertainty (u) values are as percentage values (i.e. relative to the concentration of the analyte) Pb Zn Mean rsd(PT1) 5.8 5.1 6.2 15.0 14.5 21.3 5.3 7.5 5.3 7.5 10.7 5.6 3.1 6.9 21.3 45.2 7.4 5.7 17.6 3.1 4.9 17.4 8.8 12.7 5.0 9.8 5.7 8.7 5.5 7.1 5.2 6.8 7.9 rsd(PT2) 6.8 9.8 5.9 14.1 34.2 19.9 11.8 18.8 13.7 16.5 17.0 5.2 5.0 8.5 9.7 10.1 19.9 6.4 11.1 3.0 7.9 9.7 10.8 12.0 5.0 11.0 5.4 9.2 6.9 12.2 5.1 7.4 8.9

Environ Monit Assess (2012) 184:45174538 rsd(CT) 12.5 13.5 5.6 10.4 13.1 7.6 7.1 8.9 10.0 5.5 9.8 3.3 3.2 5.6 13.8 8.8 4.9 3.4 9.0 3.0 2.4 6.7 5.7 11.1 3.5 8.2 3.5 16.9 4.2 6.5 4.4 6.2 8.1 us(PT1) 5.6 4.7 5.6 13.8 14.3 12.3 4.5 6.2 4.8 7.2 8.7 4.9 2.8 5.9 20.9 44.6 6.2 4.9 17.6 2.7 4.1 17.0 7.8 12.6 4.7 8.4 5.4 7.1 5.0 6.6 5.0 6.4 7.3 us(PT2) 6.5 9.5 5.2 13.3 34.1 18.6 11.4 18.7 13.4 15.8 16.6 4.4 4.5 8.0 8.3 9.0 17.7 6.0 10.9 2.8 6.1 8.8 10.4 11.8 4.5 5.8 4.9 8.7 5.5 12.1 4.9 7.3 8.1 5.9 7.5 us(CT) 12.1 13.1 5.0 8.3 13.0 6.8 6.6 7.6 9.6 2.4 9.1 2.6 2.3 4.1 12.5 7.7 3.7 2.5 5.9 2.8 1.5 5.5 4.3 10.9 2.5 4.7 2.5 16.8 3.0 3.2 us(avrg) 8.6 9.7 5.2 12.0 22.6 13.4 8.0 12.2 10.0 10.1 12.0 4.1 3.3 6.2 14.9 26.6 11.0 4.7 12.4 2.8 4.3 11.5 7.9 11.8 4.0 6.5 4.4 11.7 4.7 8.2 4.0 6.5 7.5

all ten analytes, three fields and samplings) us/uat ratio of 0.62 (Table 6). This average ratio value is the lowest for the homogeneous F2 (0.46) and the highest for the heterogeneous F1 (0.74). Moreover, it is on average lower for the CT than for the PT samplings (Table 6). This difference between CT and PT samplings is more pronounced on the homogeneous F2 than on the heterogeneous F1. However, for particular fields and analytes, these ratios varied widely, between 0.14 for As on F2 with CT sampling and 1.99 for Ni on F1 with PT2 sampling.

When only intra-laboratory analytical uncertainty is considered, us/uak ratios are by a factor of 3.4 higher on average than the corresponding us/uat ratios, and sampling uncertainty in general prevailed over analytical uncertainty. However, also for the case when only uak is considered, the ranking of the ratio values among fields (F1 > F3 > F2) and sampling trials (PT > CT) is the same as for the case of us/uat ratios. Also here, large variations among analytes are observed. However, in contrast to the case when total analytical uncertainty is considered, total uncertainty

Environ Monit Assess (2012) 184:45174538 Table 6 us/uak and us/uat ratios for all fields, analytes and sampling trials Field Analyte us/uak PT1 F1 As B Co Mo Tl Cd Cr Ni Pb Zn Mean F2 As B Co Mo Tl Cd Cr Ni Pb Zn Mean F3 As B Co Mo Tl Cd All uncertainty (u) values are as percentage values (i.e. relative to the concentration of the analyte)
a

4531 us/uat PT2 2.56 2.66 1.34 1.98 12.46 1.86 2.60 7.99 3.58 2.30 3.93 2.87 1.33 1.43 1.19 3.56 4.22 1.09 1.20 9.67 1.29 1.04 2.60 1.34 4.63 1.96 1.19 2.05 1.03 1.59 1.76 2.29 2.01 1.99 1.17 1.45 1.90 1.19 1.43 1.39 1.91 3.95 1.63 0.86 1.69 2.15 2.65 3.56 1.47 0.44 1.49 2.02 0.97 5.61 2.69 3.95 2.48 2.23 1.64 1.54 2.05a 2.13
b

CT 2.62 2.86 1.37 0.92 5.24 1.42 1.86 1.18 2.53 0.34 2.03 0.90 0.74 0.76 1.48 1.25 0.80 0.75 0.61 1.74 0.54 0.96 0.82 3.63 0.68 0.49 0.74 5.28 0.71 0.40 1.96 1.75
a

PT1 0.32

PT2 0.37

CT 0.69

2.51 1.65 1.47 1.65 4.16 0.50 1.12 1.04 1.60 2.42 1.81

0.36 0.38 0.58 0.48 0.96 0.51 2.59a 0.27

0.74 0.96 1.99 1.24 1.56 1.14 0.83 0.24

0.30 0.57 0.68 0.88 0.22 0.55 0.14 0.74a

0.25 0.43 1.88 0.25 0.46 0.59 0.57

0.65 0.54 1.14 0.27 0.58 0.57 0.58 0.79

0.16 0.22 0.44 0.26 0.18 0.23 0.32 0.46a

0.32 0.45 0.72 0.57 1.00 0.60

0.41 0.45 1.39 0.58 1.24 0.81 0.71 0.71

0.79 0.26 0.28 0.93 0.52 0.43 0.65a 0.62b

Cr Ni Pb Zn Mean All fields Mean

Averaged for ten analytes and three sampling trials

Averaged for ten analytes, three sampling trials and three fields

2.42

is dominated by sampling uncertainty for most analytefieldsampling combinations. Thus, in terms of the relative proportions of uncertainty components which constitute the total measurement uncertainty, it makes a large difference whether samples are ana-

lysed in a single laboratory or in several different laboratories. Summarizing, comparison of the us/ua ratios suggests that (1) sampling uncertainty plays a smaller role on more homogeneous fields (F2) compared with

4532

Environ Monit Assess (2012) 184:45174538

more heterogeneous fields (F1) and (2) the proportion of sampling uncertainty is lower when sampling patterns are prescribed or standardized (CT sampling), compared with the case of free (individual) sampling patterns (PT samplings). This difference in the mean us/uat ratio between CT and PT is especially pronounced at the homogeneous field F2. This is according to the theoretical considerations: Since the sampling procedure was standardized among the samplers in the CT sampling, it was expected that sampling uncertainty would be smaller compared with the PT samplings and correspondingly also the us/uat ratios. Variance components The proportion of components of the total variance based on the hierarchical statistical model (Eq. 1) for the results of the PT sampling trials is compiled in Table 7. The components vcsp and vcsr combined correspond to the proportion of sampling uncertainty, and the residual component vcak represents the analytical repeatability (within-laboratory) uncertainTable 7 Variance components (percent) based on the hierarchical variance model (Eq. 1) for proficiency test samples Analyte F1 vcsp vcsr As B Co Mo Tl Cd Cr Ni Pb Zn Mean F2 vcak vcsp vcsr F3 vcak vcsp vcsr vcak

3.2 84.9 11.9 15.2 49.4 35.4 14.4 54.6 31.0 0.0 86.3 13.7 43.3 32.5 24.2 5.2 93.3 1.4 8.2 59.0 32.9 31.8 61.8 0.0 83.8 16.2 0.0 93.8 6.2 6.3 0.0 66.8 33.2 48.6 20.6 30.9 3.2 66.4 30.4 0.0 49.7 50.3 7.2 67.0 25.8 8.9 40.8 50.3 0.0 90.4 9.6 0.0 89.1 10.9 0.0 84.9 15.1 8.7 64.5 26.8

0.0 63.0 37.0 29.2 37.3 33.5 21.2 40.1 38.7 8.3 73.4 18.3 42.9 23.7 33.3 0.0 89.5 10.5 47.7 45.7 0.0 92.3 0.0 90.7 6.7 7.7 42.6 26.1 31.3 9.3 14.2 31.2 54.6

6.0 77.3 16.7 24.9 47.1 28.1

ty. Note that the percentage values in Table 7 refer to the proportion of total measurement variance (=100%) captured by the PT sampling trial (i.e. without uab), whereas percentage values of uak and us refer to the mean analyte content (cf. Fig. 2). Overall, averaged for the analytes, vcak is the lowest for F1 (16.7%) and the highest for F2 (28.1%), i.e. the proportion of sampling error is the highest for the most heterogeneous F1 (83.3%) and the lowest for the most homogeneous F2 (71.9%). On all fields, the influence of sampling repetition (vcsr) is in general higher than that of the samplers (vcsp). This implies a low degree of specificity of the applied sampling patterns (and a low influence of sampling-related parameters), especially for the most heterogeneous field F1, and a relatively high influence of spatial variability (because the variability between the samplers may be caused, besides soil heterogeneity, by the different sampling patterns and other sampling parameters, whereas in the sampling repetitions, identical sampling patterns and parameters are compared and variability can be caused solely by soil heterogeneity). However, for separate analytes, vc values vary over a wide range for a given field, similarly as us and uak values. In summary, results of the VCA reflect the different field-scale heterogeneity as determined by the reference sampling, in that the proportion of sampling uncertainty increases with field-scale heterogeneity, whereas on the most heterogeneous field F1, more than 80% of total uncertainty are due to sampling; on the most homogeneous F2, only about 70% and on the intermediate F3, about 73% can be attributed to sampling uncertainty. These results are largely in accordance with estimated ratios of sampling and analytical uncertainty (Table 6). Moreover, the low proportions of the sampling person (vcsp) compared with that of sampling repetition (vcsr) indicate that heterogeneity has a larger influence on sampling uncertainty than sampling parameters. Total uncertainty and probability of exceeding threshold values In the context of the German Federal Soil Protection and Contaminated Sites Ordinance (BBodSchV 1999), it is of interest whether measured soil element contents exceed a prescribed maximum permissible

Note that no variance components for the differences between the fields are calculated because the fields cannot be viewed as random repetitions; note also that the values of vc(sp), vc(sr) and vc(sr) do not add up exactly to 100% in all cases due to rounding errors vcsp between samplers (i.e. sampling persons, n =18) within field, vcsr between duplicate samples within fields and samplers, vcak residual component, corresponding to analytical variance (within samples, samplers, fields)

Environ Monit Assess (2012) 184:45174538

4533

threshold value. Even if the measured average value is below the threshold, it is possible that there exists an appreciable probability that the true element content nevertheless exceeds the threshold. This is demonstrated exemplarily for the data of this study in Table 8. The uncertainty of measured contents is characterized by the total expanded measurement uncertainty Ut (i.e. the simple uncertainty multiplied by a coverage factor, in this case 2), which encompasses total laboratory uncertainty and sampling uncertainty and defines the 95% probability range of measured values. From the measured contents and Ut, the probability that the true value exceeds the threshold can be calculated, assuming here a normal distribution. It can be seen from Table 8 that in most cases (40 out of 53), the measured contents are safely below the threshold value and the exceedance probability is zero. Only in some cases where the measured content is only little below the threshold there is an appreciable probability that the true value is above the threshold. But there are also examples where the measured value seems to be safely below the threshold, but due to the large total expanded uncertainty there is a non-negligible probability that the true value exceeds the threshold. Consider for instance Zn on F1 in the PT2 sampling with a measured content of 45.9 which seems to be safely below the threshold of 60. However, Ut is 38% and consequently there is an appreciable probability of 5.2% that the true Zn concentration is above the threshold. General discussion The results of this study show that both the absolute values and the importance of us relative to total analytical uncertainty, i.e. us/uat ratios, increase in general with field-scale heterogeneity (Table 5 and 6). Although this is largely in agreement with many previous studies (e.g. Jacob and Klute 1956; Kerschberger and Richter 1992; Kurfrst et al. 2004; van der Perk et al. 2008), us/uat ratios estimated here are lower than most values reported in earlier studies. It is often claimed that sampling uncertainty dominates over analytical uncertainty, and sampling uncertainties have been reported which were by a factor of up to 30 larger than analytical uncertainty (e.g. Taylor et al. 2005; Rawlins et al. 2009). Other studies reported more moderate us/ua ratios but still higher than found here. For instance, van der Perk

et al. (2008) reported mean us/ua ratios of 3.4 and Kurfrst et al. (2004) mean us/ua ratios of 1.54. However, most studies also yielded highly variable us values and us/ua ratios depending on the type of analyte and the magnitude of field-scale heterogeneity. The results of the present study show in general no predominance of sampling uncertainty over total analytical uncertainty, and total laboratory uncertainty overall prevails over sampling uncertainty. However, this preponderance of laboratory uncertainty compared with sampling uncertainty is clearly connected with the inclusion of uab into uat. When only uak is considered as laboratory uncertainty (and uab ignored), sampling uncertainty in general prevails over analytical uncertainty with us/uak ratios on average of about 2. However, even in that case, the proportion of sampling uncertainty on total uncertainty is lower than in several other studies. This can be explained by (1) low spatial heterogeneity, (2) low concentration levels and (3) large number of increments constituting the composite samples. Overall, the spatial heterogeneity of element contents found in this study is relatively low, when compared with other studies, whereas here average sref values (mean of ten analytes for each of the three fields) of 1328% were found (Table 3), for instance Taylor et al. (2005) reported for a Pb contaminated site CV values >50%. On the other hand, variation of trace metals on uncontaminated sites is mostly lower and comparable to values found in the present study: for instance van der Perk et al. (2008) reported for an agricultural site CV values of 9.3% (As), 67% (Cr) and 11% (Zn). Kurfrst et al. (2004) reported for an arable plot CV values of 54% (Cd), 13.2% (Cu), 12.9% (Pb) and 18.3% (Zn). Contrary to other studies, in the present study, the support of samples used to calculate the relative standard deviations of the reference samplings encompassed an appreciable percentage of the total field area, and therefore, the resulting standard deviations are presumably lower than standard deviations calculated from point-like data. On the other hand, point-samples are often actually composite samples consisting of several samples taken within a radius of a few meters (e.g. Lauzon et al. 2005). Another explanation for the low proportion of sampling uncertainty on total uncertainty found here may be the general low level of element contents (cf. Table 8), representing largely background concentra-

4534

Environ Monit Assess (2012) 184:45174538

Table 8 Trace metals considered in German Federal Soil Protection Ordinance (BBodSchV 1999) Field Analyte Sampling trial PT1 PT2 CT F1 Cd PT1 PT2 CT F1 Cr PT1 PT2 CT F1 Ni PT1 PT2 CT F1 Pb PT1 PT2 CT F1 Zn PT1 PT2 CT F2 As PT1 PT2 CT F2 Cd PT1 PT2 CT F2 Cr PT1 PT2 CT F2 Ni PT1 PT2 CT F2 Pb PT1 PT2 CT F2 Zn PT1 PT2 CT F3 As PT1 PT2 CT F3 Cd PT1 PT2 CT F3 Cr PT1 PT2 Mean (mg/kg) 9.1 9.6 10.4 0.17 0.25 0.27 21.6 23.2 22.5 17.0 13.6 13.2 21.2 18.1 17.6 56.9 45.9 40.9 7.5 7.1 7.0 0.18 0.19 0.23 26.3 26.3 26.6 12.6 13.0 13.6 17.2 17.6 16.9 39.7 41.9 41.5 17.0 17.8 17.6 0.46 0.46 0.47 24.3 24.9 Thresholda

Ut % 2 ut

Probability that true value exceeds threshold 0.0 0.0 0.0 0.0 2.4 2.1 0.1 3.6 0.6 83.0 30.8 15.7 0.0 0.0 0.0 29.7 5.2 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.8 0.2 0.0 0.0 0.0 0.0 0.0

F1

As

25 25 25 0.4 0.4 0.4 30 30 30 15 15 15 40 40 40 60 60 60 25 25 25 1 1 1 60 60 60 50 50 50 70 70 70 150 150 150 25 25 25 1.5 1.5 1.5 100 100

37 38 43 73 62 48 26 33 27 25 42 27 22 35 29 21 38 22 38 38 37 52 65 48 25 25 23 40 29 29 22 22 22 20 24 17 32 33 29 47 46 54 25 27

Environ Monit Assess (2012) 184:45174538 Table 8 (continued) Field Analyte Sampling trial CT F3 Ni PT1 PT2 CT F3 Pb PT1 PT2 CT F3 Zn PT1 PT2 CT Mean (mg/kg) 24.8 24.2 22.0 22.4 29.7 32.2 33.7 112.8 108.0 110.8 Thresholda

4535

Ut % 2 ut

Probability that true value exceeds threshold 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

100 70 70 70 100 100 100 200 200 200

24 23 30 24 20 20 18 19 17

Soil threshold values according to precautionary values, total expanded measurement uncertainty and resulting probability that true value exceeds threshold
a

Precautionary threshold value according to BBodSchV

tions. In contrast, on contaminated sites, us values and the proportion of sampling uncertainty from total uncertainty are usually higher (e.g. Taylor et al. 2005). On the other hand, similar us values as found here have been described for sites with relatively low metal concentrations (Kurfrst et al. 2004; van der Perk et al. 2008). In the present study, total analytical uncertainty encompassed both within-laboratory repeatability uncertainty uak and between-laboratory reproducibility uncertainty uab. For comparison, in many studies, only uak was considered (e.g. Taylor et al. 2005; van der Perk et al. 2008; Rawlins et al. 2009). Interlaboratory proficiency tests suggest that uab is usually by a factor of 1.53 higher than uak (Desaules and Dahinden 1994; Nestler 2007). Average uab/uak ratios found in the present study are about 3, i.e. total analytical uncertainty is mostly dominated by reproducibility uncertainty. As a consequence, for reducing total measurement uncertainty, it seems to be most efficient to analyse samples in only one selected laboratory. However, the resulting low analytical uncertainty (uak) probably underestimates the analytical bias (Desaules and Dahinden 1994; Ramsey et al. 2011). When the focus of an investigation is on uncertainty arising from soil sampling, it is reasonable to eliminate as far as possible analytical variance, i.e. to aim for the highest analytical precision in order not to mask sampling variability by analytical variability (Muntau et al. 2001). Analytical bias could be

accounted for by either certified reference materials or other independent estimation methods (for instance, as in this study, by utilizing results of interlaboratory proficiency tests, cf. Munzert et al. 2007; Nestler 2007). The variability of uak values between fields and samplings found in the present study is considerable. In most studies, constant uak values for specific analytes were used. However, it is well recognized that standard deviations between specific duplicate pairs are usually highly variable for a given analyte (Thompson and Howarth 1976; Minkkinen 1986; Hyslop and White 2009), although no clear relation of this variation with soil properties has been found. This variation is difficult to explain and seems to be erratic. In this context, it is important that uak comprises not only uncertainty due to chemical analysis per se but to a large degree also uncertainty arising from sample preparation (drying, sieving, grinding), mixing including segregation effects (Lam and Defize 1993) and splitting (De Zorzi et al. 2002; Lyn et al. 2003; Kurfrst et al. 2004). Moreover, the force applied when breaking up the aggregates could have an influence on the uncertainty estimate. However, since conditions were standardized by using a jaw crushing machine, the uncertainty contribution can be assumed as small (Kurfrst et al. 2004, 2011). The question remains whether it is justified to use preferably these variable uak values to indicate

4536

Environ Monit Assess (2012) 184:45174538

analytical uncertainty instead of averaged values for each analyte, as long as there is no good explanation for this variation. Due to the uncertainty and variability of estimated uak values (Thompson and Howarth 1976; Minkkinen 1986; Hyslop and White 2009), it is clear that uak values themselves are fraught with uncertainty. Therefore, it may be justified to indicate analytical repeatability uncertainty using averaged uak values, even when more detailed uak values have been calculated. Information about the variability of uncertainty estimates can be provided as confidence intervals of the u values (Lyn et al. 2007). The comparison of the PT with the CT sampling repetitions suggests that standardization of sampling protocols effectively reduces sampling uncertainty, especially for fields of relatively low heterogeneity. Such a standardized sampling protocol could be for instance the X pattern with 20 sample increments tested here in the CT sampling and utilized in many countries, among others, in Germany (Lewandowski et al. 1997; MLUV 2009). On the other hand, when using standardized sampling protocols (CT approach), systematic sampling bias is less likely to be detected than with many different sampling protocols (PT approach). Consequently, sampling uncertainty estimated with a CT may be artificially low (Ramsey et al. 2011).

Conclusions The relatively simple sampling patterns tested here are adequate to characterize the mean contents of trace elements in arable soils of 36 ha area and low to moderate heterogeneity, with relative standard sampling uncertainty values of about 10%, and total uncertainty mostly not dominated by the influence of sampling uncertainty. Sampling uncertainty and the ratio of sampling uncertainty to laboratory uncertainty in general increase with field-scale heterogeneity; however, total analytical uncertainty, encompassing both within- and between-laboratory components, is on average larger than sampling uncertainty, especially on fields of low and moderate heterogeneity. Laboratory repeatability uncertainty estimated from duplicate chemical analyses is highly variable, depending not only on the analyte but also on the field and the sampling trial. If duplicate analyses of all samples are available, repeatability uncertainty could

be indicated utilizing these individual laboratory values, for instance by means of ranges assigned to uncertainties. Reproducibility (between-laboratory) analytical uncertainty is on average by a factor of 2.7 higher than repeatability uncertainty. Consequently, total laboratory uncertainty is dominated by reproducibility uncertainty, and total uncertainty is dominated by total laboratory uncertainty. Reducing the sampling uncertainty has little effect in that case. Thus, when analysing samples in a single laboratory, uncertainty is effectively reduced. However, this analytical uncertainty is probably artificially low, if analytical bias is not accounted for. When only repeatability laboratory uncertainty is considered, total uncertainty is dominated by sampling uncertainty, especially on the most heterogeneous field; consequently, when samples are analysed in only one single laboratory, total uncertainty may be effectively reduced by reducing sampling uncertainty (for instance by a larger number of sample increments), at least for heterogeneous fields. Although comparison of the PT and the CT approach suggests that standardization of sampling protocols leads to reduced sampling uncertainty, sampling bias is less likely to be detected by the CT than by the PT approach (i.e. sampling uncertainty estimated with a CT may be artificially low). For all investigated uncertainty variables, large differences among the analytes are observed; these are mostly difficult to explain and seem to a large degree unpredictable. Consequently, conclusions drawn for one specific element are not necessarily transferable to other nutrient elements. Based on the VCA, the effect of sampling repetition is larger than the effect of different sampling persons. This indicates that field heterogeneity has a larger influence on uncertainty than sampling-related parameters, especially for the more heterogeneous fields. When measured element contents in fields are characterized by both mean values and total measurement uncertainty, there is in several cases an appreciable probability that prescribed maximum threshold values are exceeded even in cases when the mean value is well below the threshold. This is important when threshold element contents are of concern, for instance in the German Sewage Sludge and Federal Soil Protection Ordinance.

Environ Monit Assess (2012) 184:45174538 Acknowledgments We want to thank Monika Preis from the engineering company Schnittstelle Boden (Ober-Mrlen) for kind support in providing management and fertilization data of the study sites. The cooperation with the Association of the German Agricultural Analysis and Research Institutes (VDLUFA) is greatly acknowledged. The following professional soil samplers participated in the sampling trials: J. Balsing (Oldenburg), M. Bldner (Jena), T. Blumstengel (Rostock), O. Dillmann (Mnster), H. Geyer (Jena), Goll (Karlsruhe), L. Herold (Jena), A. Hoppe (Leipzig), G. Hrig (Leipzig), W. Klein (Speyer), C. Laue (Hameln), Maul (Kassel), Paris (Bernburg), A. Pudimat (Rostock), Dr. H. Schaaf (Kassel), S. Schnersch (Karlsruhe), D. Virkus (Bernburg) and H. Wundlechner (Mnchen). We acknowledge the support of Christian Kleimeier (Institute for Land Use, University of Rostock), Ulrich Kurfrst (University of Applied Sciences, Fulda), and Manfred Munzert (Bavarian State Research Centre for Agriculture, Freising-Weihenstephan).

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