Reprinted from the Journal qf Environmental Quality Volume 28, no. 4, July-Aug. 1999. Copyright © 1999, ASA, CSSA, SSSA 677 South Segoe Rd., Madison, WI 53711 USA Baseline Concentrations of 15 Trace Elements in Florida Surface Soils Ming Chen, Lena Q. Ma,* and Willie G. Harris ABSTRACT The objective of this study was to establish baseline concentrations for 15 potentially toxic elements (Ag, As, Ba, Be, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, and Zn) based on 448 representative Florida surface soils using microwave assisted HNOrHCI-HF digestion. Baseline concentrations of those elements were (mg kg-I): Ag 0.072.50, As 0.02-7.01, Ba 1.67-112, Be 0.04-4.15, Cd 6-0.33, Cr 0.89-80.7, Cu 0.22-21.9, Hg 0.00075--0.0396, Mo 0.13-6.76, Ni 1.70-48.5, Pb 0.6942.0, Sb 0.06-0.79, Se 0.01-1.11, and Zn 0.89-29.6, respectively. Upper baseline values for most elements corresponded with these reported in literature, except Ba, Hg, Mn, Sb, and Zn, which were 3 to 23 times lower. Soil properties, including pH, organic carbon (OC), particle size, cation-exchange capacity (CEC), available water, extractable base, extractable acidity, total Ca, Mg, P, K, Fe, and AI concentrations, were related to metal concentrations using factorial analysis. Eight factors were identified (total Fe and AI, CEC, pH, clay, OC, total Ni and Mo, total Sb and Pb, and total Hg) and accounted for 87% of the total variance, suggesting that metal concentrations were primarily controUed by soil compositions. Multiple regression of elemental concentrations against total Fe, total AI, clay, OC, CEC, and pH was significant for aU elements. Partial correlation coefficients indicated that total Fe and/or AI explained most of the variance for Mn, Ni, Ba, Be, Hg, As, Cd, Cr, Cu, Mo, Pb, and Zn concentrations. Most of the variance in Se was related to clay, whereas those of Ag and Sb related to clay and total AI. T HE PRESENCE of potentially toxic metals in landapplied waste materials is of public concern. Federal and state regulations list Ag, As, Ba, Be, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, and Zn as potentially toxic elements (Florida Department of Environmental Protection, 1995; U.S. Environmental Protection Agency, 1996). The U.S. Environmental Protection Agency (1996) has established risk-based soil screening levels as a reference for site-specific cleanup for trace metals. However, no federal regulation specifies the maximum metal concentrations in non-hazardous wastes for land Soil and Water Sciences Dep., Univ. of Florida, Gainesville, FL 326110290. Approved for publication as the Florida Agricultural Experiment Station Journal Series No. R-06229. Received 19 Mar. 1998. *Corresponding author (Qma@gnv.ifas.ufl.edu). Published in J. Environ. Qual. 28:1173-1181 (1999). application, except in the case of sewage sludge (U.S. Environmental Pt;otection Agency, 1995). Natural background concentrations of trace elements in soils where these materials are to be applied can be used as a reference (Kabata-Pendias and Pendias, 1992). Unless a reliable database on concentrations of trace metals in soils is available, inaccurate or unrealistically low mandatory guideline levels may be set by regulators (Davies, 1992; McGrath, 1986; Pierce et aI., 1982). Thus, it is important to establish background concentrations of trace metals for soils occurring within a region, and to document systematic variation in concentrations according to soil classes and properties. Background measurement represents natural elemental concentrations in soils without human influence (Kabata-Pendias et aI., 1992; Gough, 1993). This measurement depicts an idealized situation. Due to longrange transport of contaminants, truly pristine ecosystems may no longer exist, making establishing background concentrations a difficult task. For example, background levels for Pb are commonly elevated due to long-term usage of Pb-based gasoline and paint. Thus, it is almost impossible to find a surface soil sample completely free of Pb contamination (Fergusson, 1990). The term geochemical baseline concentration is often used to express an expected range of element concentrations around a mean in a normal sample medium. It is not generally a true background concentration and is defined as 95% of the expected range of background concentration (Kabata-Pendias et aI., 1992; Dudka, 1993; Gough, 1993). Based on log- normal distribution theory, the expected range can be expressed as the average of logarithms ::!:: 2 standard deviations (Dudka et aI., 1995). Since it is becoming more and more difficult to determine background levels of certain elements, the baseline values have been recognized as the only means to establish reliable worldwide elemental concentraAbbreviations: AM, arithmetic mean; ASD, arithmetic standard deviation; CEC, cation exchange capacity; FCSSP, the Florida Cooperative Soil Survey Program; GM, geometric mean; GSD, geometric standard deviation; OC, organic carbon. 1174 J. ENVIRON. QUAL., VOL. 28, JULY-AUGUST 1999 tions in natural materials (Gough et aI., 1988; KabataPendias and Pendias, 1992). Baseline concentrations of many elements can be obtained for soils of the USA (Shacklette and Boerngen, 1984; Gough et aI., 1988, 1994; Ames and Prych, 1995), China (Wei et aI., 1990), Great Britain (McGrath, 1986), and other European countries (Dudka, 1993). Researchers pointed out that baseline concentrations were a better measure of the variation in trace element concentrations than the observed ranges (i.e., ranges of background concentrations) since the distorting effects of a few high values were minimized by log-transformation of the data (Dudka et aI., 1995). They recommended the use of baseline concentrations as alternative criteria for assessing possible trace element contamination in soils (Gough et aI., 1994), or the use of the upper limit of the baseline concentration range to assess the background concentration with an acceptable degree of confidence (Dudka et aI., 1995). Unfortunately, existing data on baseline concentrations of trace elements in Florida soils are inadequate for determining the issue of how clean is clean for cleaning up contaminated soils and how dirty is dirty for land application of waste materials. Since only 40 soil samples were used in a previous study (Ma et aI., 1997), a larger soil sample pool and more systematic sampling strategy is necessary to establish a comprehensive database for baseline concentrations of potentially toxic elements in Florida soils. The present investigation was conducted to (i) establish baseline concentrations of the 15 potentially toxic trace elements in 448 representative Florida surface soil horizons; and (ii) investigate relationship among elements and between soil properties and elemental concentrations. Results of this research can be used as a reference in assessing anthropogenic vs. natural levels of trace elements in Florida soils. MATERIAL AND MEmODS Sample Selection and Characterization Soils used in this study were sampled and characterized as part of the Florida Cooperative Soil Survey Program (FCSSP) conducted jointly by the University of Florida Soil and Water Science Department and the USDA Natural Resources Conservation Service. Soil horizons were delineated and sampled using USDA soil survey conventions and procedures (Soil Survey Division Staff, 1993) as guidelines. Based on the mean coefficient of variations from a previous study (Ma et aI., 1997), a minimum of 214 soil samples are required to establish a statistically valid database for Florida soils (with 95% confidence level and 20% accepted error). In the present study, a total of 448 archived soil samples were selected to assure both taxonomic and geographic representation. The overall taxonomic representation was achieved by weighting the number of samples for each soil order by their estimated areal occurrences in Florida. The total mapped area is 11 265 532 ha and covers as much as 80% of the total land area of Florida. Most of the mapped areas in Florida are represented in the current study. Seven soil orders were identified from 51 counties in Florida and their approximate coverages are: Spodosols (28%), Entisols (22%), Ultisols (19%), Alfisols (14%), Histosols (10%), Mollisols (4%), and Inceptisols (3%). Based on the areal occurrence of each soil order, the samples included surface horizons from 122 Spadosols, 107 Entisols, 90 Ultisols, 60 Alfisols, 39 Histosols, 17 Mollisols, and 13 Inceptisols. Physical, chemical, and mineralogical analyses were previously determined through the FCSSP, include taxonomic class, morphological information and mineralogy (Sadek et aI., 1990). A statistical summary of selected properties for the 448 soils samples used in this study is presented in Table 1. Sample Preparation and Trace Element Analysis All soil samples were air dried, ground, and passed through a 6O-mesh sieve. The screened samples were stored in polyethylene containers before analysis. Approximately 1 g of soil sample was weighed into a 120-mL teflon pressure digestion vessel; 9 mL of concentrated HN03, 4 mL of concentrated HF, and 1 mL of concentrated HCI were then added. Samples and reagents were well mixed, sealed, and digested in a CEM MDS-2000 digestion microwave oven (CEM, Matthews, NC) for 20 min at 120 psi. After cooling, 2 g of boric acid were added to the digested solution to neutralize excess HF. For Histosols rich in organic matter, only 0.5 g of sample was used and 1.0 mL of HzO z was added prior to digestion. The fmal volume of the digested solution was 100 mL after filtration Table 1. Statistical summary of selected properties for the 448 soil samples used in this study. Sand Silt Clay Organic C Cation exchange capacity pH-H2O pH-KO (emol kg-I) 0.28--375 21.9 51.0 10.2 3.35 2.70-8.10 5.04 0.97 4.94 1.21 2.08--8.30 4.24 :!: 1.11 4.11 1.28 Total AI Total Fe Range AM ASDt GM GSD:j: - - - - - - - - - - gkg- I - - - - - - - - - 12.0-999 0-734 0-820 0.80-559 41.7 :!: 83.3 893=164 64.4 102 51.0 111 36.2 :!: 3.05 84S:!: 1.62 19.9 3.12 3.34 17.1 Range AM ASDt GM:!: GSD:j: - - - - - - - - - - - - - - - - - g kg- I - - - - - - - - - - - - - - - - 0.01-383 0-14.9 0-5.57 0-2.87 0.13--26.5 0.09-34.2 8.30 :!: 45.2 0.40 1.50 0.40 0.80 0.20 0.40 2.20 3.00 2.30 4.SO 0.308 :!: 6.76 4.98 3.33 0.045 0.185 3.87 0.088 1.41 2.41 1.01 3.24 Range AM ASDt GM GSD:j: - - - - - - - - - - - - - cmol kg-I - - - - - - - - - - - - 0-271 0-10.2 0.01-254 0-221 0-84.3 2.48 :!: 18.0 1.01 :!: 6.43 0.84 2.18 :!: 8.07 0.22 13.8 26.8 0.08:!: 6.18 19.9:!: 3.12 4.42 0.06 5.56 0.29 3.13 6.32 = = = Total Ca = = = Extr-Na = = t Arithmetic mean :j: Geometric mean Total Mg Extr-K = = =standard deviation. =geometric standard deviation. = Total K = = Extr-Ca = = Total P = = Extr·Mg = = = = = = = = = Total acid Avail-H2O (em em-I) 0.02--0.72 0.16 0.12 0.82 1.96 = = = = = 1175 CHEN ET AL.: BASELINE CONCENTRATIONS OF TRACE ELEMENTS IN FLORIDA SOILS based on the loading of the variables. Each factor contains all variables but only variable with loadings above 0.50 was considered to be important for interpreting a factor (Dudka, 1992). In addition, multiple regression analysis was used to regress the concentrations of trace elements against clay, OC, pH, CEC, and total concentrations of Al and Fe of the soils based on the factorial analysis. If regression against the six independent variables was significant, partial correlation coefficients were calculated to show the contribution of individual variable to the total explained variance. Because concentration of trace elements showed a log-normal distribution (data not shown), the data were log transformed before analysis to meet the assumption of normality required for the regression model. (Whatman 42) and was stored in precleaned polyethylene bottles in a refrigerator before analysis. Concentrations of Ag, Ba, Be, Cr, Cu, Mn, Mo, Ni, Sb, and Zn were analyzed on a Perkin-Elmer ELAN 6000 ICP-MS unit (Norwalk, Cf), whereas those of As, Se, Pb, and Cd were analyzed on a Perkin-Elmer SIMAA 6000 atomic absorption spectrophotometer. Mercury was analyzed on Perkin-Elmer 2380 atomic absorption spectrophotometer equipped with a Perkin-Elmer MHS-lO mercury-hydride system. Data Analysis All element concentrations are presented on a dry matter basis. Both arithmetic and geometric means were used to describe the central tendency and variation of the data. The arithmetic mean (AM) and arithmetic standard deviation (ASD) are best used as estimates of geochemical abundance of an element. The geometric mean (GM) and geometric standard deviation (GSD), however, are better maximum likelihood estimators for most geochemical data (Gough et aI., 1988). Baseline concentrations of 15 trace elements were calculated using GM/GSD2 and GM X GSD2 of the samples, which include 95% of sample population (Dudka et aI., 1995). All statistical analyses were performed using SAS (SAS Institute, 1987). Analysis of variance was used to assess significant differences between different parameters. The confidence interval for the Student (-test was calculated at <X = 0.05. Simple correlation analysis was used to relate element concentrations to soil properties and among elements themselves. R-mode factorial analysis was employed to associate elemental concentrations with soil properties using 34 variables (Davis, 1986). The 34 variables include the total concentrations of 15 trace elements (Ag, As, Ba, Be, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, and Zn) and 19 quantitative soil properties (Table 1). These properties include pH measured in water and KCl; organic carbon (OC); particle size distribution (clay, silt, sand); cation-exchange capacity (CEC); N~OAC-extractablebases (K, Na, Ca, Mg); available water, BaCIz-triethanolamineextractable acidity (total acid); total Ca, Mg, P, K, Fe, and AI. A factor was interpreted as a physical or chemical process RESULTS AND DISCUSSION Baseline Concentrations of 15 Trace Elements in 448 Florida Surface Soils Florida soils formed primarily from well-weathered sandy marine sediment (Brown et aI., 1990), thus they are very sandy with a mean sand concentration of 89.3% (Table 1) and contain little weatherable primary minerals. The small amount of resistant secondary minerals present in Florida soils occurs mainly as sand-grain coatings. The coatings are dominated by minerals such as kaolinite, hydroxy-interlayered vermiculite, gibbsite, and quartz, as cemented by lesser amounts of metal oxides (Harris et aI., 1995). These minerals have relatively low CEC compared with other secondary soil minerals such as smectite (Brady and Weil, 1990). The dominance of quartz sand in Florida soils along with the low activity and small amount of clay, contributed to their extremely low elemental concentrations. Concentrations of most elements in Florida soils were significantly lower than those reported for other regions (Table 2). Concentrations of Cd, Cu, Ni, and Pb in the Table 2. Concentration of trace elements in Florida surface soils (mg kg-I except for "g, which is p.g kg-I) with comparison data from different sources. Florida soils in this study Elements Ag As Ba Be Cd Cr Co Hg Mn Mo Ni Pb Sb Se Zn No. of samplest 448 445 444 417 439 444 444 443 436 442 444 439 353 445 448 Range Median 0.16-6.00 0.01-SO.6 1.0-1990 0.01-5.92 0.004-2.80 0.02-447 0.1-318 0.62-430 1.40-1642 0.04-14.1 0.04-375 0.18-290 0.02-3.2 0.01-4.62 0.90-169 0.42 0.35 11.3 0.46 0.004 8.40 L90 4.31 18.8 1.00 8.55 4.89 0.15 0.082 4.60 Comparison chlta AM ± ASO:j: 0.50 ± 1.34 ± 30.7 ± 0.67 ± 0.07 ± 15.9 ± 6.10 ± U.6 ± 48.8 ± 1.52 ± 13.0 ± 11.2 ± 0.28 ± 0.25 ± 8.35 ± 0.38 3.77 108 0.76 0.23 30.6 22.1 34.4 123 1.81 23.0 26.3 0.30 0.50 13.8 GM ± GSO§ 0.42 0.42 13.7 0.40 0.01 8.45 2.21 5.45 20.3 0.95 9.08 5.38 0.22 0.10 5.U ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 2.44 4.10 2.86 3.24 5.26 3.09 3.15 2.70 3.41 2.67 2.31 2.79 0.19 3.32 2.40 Florichl soilsl California soW NAn 0.41 2.8 1.1 NA NA 0.21 3.9 3.7 4.2 25 NA 6.5 4.1 NA NA U 468 1.14 0.26 76 24.0 200 592 0.90 36 21.7 0.50 0.028 145 U.s. soiIstt NA 5.2 440 0.63 NA 37 17 58 330 0.59 13 16 0.48 0.26 48 t Number of samples above the detection limits. :j: Arithmetic mean ± arithmetic standard deviation. § Geometric mean ± geometric standard deviation. 11 Geometric mean reported by Ma et aI., 1997; N = 40. # Geometric mean reported by Bradford et aI., 1996; N = SO. tt Geometric mean reported by Shacklette and Boemgen, 1984; N = U18. :j::j: Geometric mean reported by Wei et aI., 1990; N = 4095. §§ Geometric mean reported by Berrow and Reaves, 1984, and arithmetic mean reported by Fergusson, 1990 (in bracket). 111 NA; Data not available. China soilsH 0.105 9.2 450 1.82 0.074 53.9 20.0 40 482 1.2 23.4 23.6 1.06 0.22 67.7 World soiIs§§ NA (11.3) NA 6 0.4 (0.62) SO U 60 (98) 450 1.5 25 15 (29.2) «0.9) (0.4) 40 1176 J. ENVIRON. QUAL., VOL. 28, JULY-AUGUST 1999 current study were lower than these trace elements in Florida agricultural soils reported by Holmgren et aI. (1993). This is possible because many of the soils used in this study were collected through the FCSSP from uncultivated, or minimally cultivated sites (Sodek et aI., 1990). Concentrations of 15 trace elements in this study agreed with previously published values for 11 metals in 40 Florida soils (Ma et aI., 1997). Concentrations of Zn, As, and Cd, however, were much lower and those of Cr were much greater in the current study than those of Ma et aI. (1997). Discrepancies may relate to the greater variety of soils analyzed in the current study. Soil contamination may be considered when concentrations of an element in soils were two- to three times greater than the mean background levels (Logan and Miller, 1983). In the current study, the observed concentration ranges of 15 trace elements (Table 2) were significantly greater than their upper baseline concentration limits (Table 3), which may suggest either contamination in these soils (Dudka, 1993), or influence from pedogenic factors (Ma et aI., 1997). The fact that the GMs were much closer to the medians than were AMs for all elements in Florida surface soils confirms that the data were strongly positively skewed (Table 2). The calculated baseline concentrations of trace elements in Table 3, therefore, better represent their natural concentrations in the soils because the distorting effects of a few high concentrations are minimized (Dudka, 1993). The upper baseline concentration limits of Cd, Co, Cr, Cu,- Fe, Mn, Ni, S, and Zn were used by Dudka et aI. (1995) to assess possible metal contamination in Ontario soils. McGrath (1986) reported that the upper baseline concentration range for Pb concentrations in topsoils from England and Wales fell well within most soil protection guidelines. In the current study, upper baseline ranges for 10 elements (Ag, As, Be, Cd, Cr, Cu, Mo, Ni, Pb, Se) corresponded well with ,~he upper baseline values reported in literature (Table 3). In instances where significant differences were found (i.e., Ba, Hg, Mn, Sb, and Zn), Florida soils generally showed lower baseline concentrations (Table 3). Correlation Analysis for Concentrations of 15 Trace Elements in 448 Florida Surface Soils Correlation analysis is a useful tool for analyzing similarities between paired data and is widely used in trace metal data analyses (Bradford et aI., 1996; Dudka et aI., 1995; Lee et aI., 1997). In the current study, correlation analysis between elemental concentrations and soil properties (total Fe, total AI, pH, clay, OC, and CEC) of 448 surface soils and among trace elements was conducted (Tables 4 and 5). Correlation between Trace Element Concentrations and Soil Properties Soil pH significantly correlated with concentrations of As, Cd, Cr, Cu, Mn, Se, and Zn (Table 4). This is consistent with the fact that their concentrations were the lowest in Spodosols (Ma et aI., 1997), which had the lowest pH among the seven soil orders. No such correlation, however, was reported by Ma et aI. (1997), possibly due to the limited sample numbers in that study. Clay content is highly correlated with concentrations of all trace elements except for Ba, Hg, and Ni (Table 4). This is consistent with previously published data by Ma et aI. (1997). They reported that concentrations of AI, As, Cr, Cu, Fe, Hg, Ni, Pb, and Zn were strongly correlated with clay content in 40 Florida surface soils. Correlations between clay content and concentrations of Zn and Ni in Oklahoma soils (Lee et at, 1997), and between clay content and concentrations of As, Cd, Cr, Cu, Mo, Ni, Pb, Sb, and Zn in Canada soils (Mermut et aI., 1996) were reported. Soon and Abboud (1990) Table 3. Calculated baseline concentrations of trace elements in Florida surface soils (mg kg-I except for "g, which is fLg kg-I) compared with published baseline concentrations in soils. This study Element Ag As Ba Be Cd Cr Cu Hg Mn Mo Ni Pb Sb Se Zn Soil from other studies Florida Floridat 0.07-2.50 0.02--7.01 1.67-112 0.04-4.15 NAn 0.03-37 NA NA ~.33 0.11~.41 0.89-80.7 0.22--21.9 0.75-39.6 1.74-236 0.13-6.76 1.76-48.5 0.69--42.0 0.06--0.79 0.01-1.11 0.89--29.6 0.88-17.2 0.84-16.3 0.62--28.4 3.2--196 NA 4.5-9.4 0.93-18.1 NA NA 7.1-20.0 Bull Island§ Alaska'll California# USAtt ChinaH NA NA NA 1.2&-35.8 213-1659 0.6S-3.33 NA 12.5-200 7.33-78.6 NA 76-3718 0.14-5.29 5.1-113 0.06--2.86 0.63-12.3 197-1110 0.36--3.65 0.05-1.34 14.8-392 7.41-77.8 44.5-899 263-1332 0.181-4.48 6.25-207 9.64-48.8 0.154-1.62 O.OOH.23 NA NA 1.05-25.9 96.1-2015 0.11-3.57 NA 6.59--208 2.86--101 9.1-368 43-2532 0.08-4.37 2.44-69.4 4.62-55.4 0.093-2.47 0.043-1.57 12.&-183 0.OH.41 2.5-33.6 266-761 0.85-3.9 1~380 NA NA 6.8-29 0.35-5~2 NA 45-500 NA 0.96-4.6 5.7-15 NA NA 2.8-12 3.~36.3 NA NA 2&-188 t Based on 95% confidence intervals (GMlGSDt to GM X GSDt); N = 448. t Calculation based on data reported by Ma et aI., 1997; N = 40. § Calculation based on data reported by Gough et aI., 1994; N = 16. 'II Calculation based on data reported by Gough et al., 1988; N = 437. # Calculation based on data reported by Bradford et al., 1996; N = 50. tt Calculation based on data reported by Shaddette and Boemgen, 1984; N = 1218. H Calculation based on data reported by Wei et al., 1990; N = 4095. §§ Data reported by Dudka, 1992, 1993; N = 127. I'll NA; Data not available. PoJand§§ NA 0~.1 19.3-154) 7.3-55 5.9--270 1343--1740 0.15-9.8 7.73-70.9 9.95-56.0 0.38-3.0 125-409 NA 0.1-1.7 3.7-75.3 2.6-18.0 NA 83-1122 NA 2.6-27.0 NA 2.6-27.0 0.047~.99 0.07~.30 28.5-161 10.5-154 0.0~.33 1177 CHEN ET AL.: BASELINE CONCENTRATIONS OF TRACE ELEMENTS IN FLORIDA SOILS Table 4. Correlation coefficient (r) of element concentrations with soil properties in 448 Florida surface soils. Element Clay NCt pH 0 0 0 0 0 1 1 1 1 1 1 2 2 3 4 0.14** 0.10§ 0.27'11 0.10§ 0.221 -0.03 NS:j: 0.10§ 0.271 -8.07 NS 0.03 NS -0.01 NS 0.03 NS 0.00 NS -0.01 NS 0.00 NS As Cd Cu Se Zn All Cr Mn Me Pb Sb Ba Hil Be Ni 0.331 0.12§ 0.14** 0.28'1[ 0.461 0.401 0.3411 0.3411 0.441 0.131 0.20*** 0.05 NS 0.02 NS 0.58'11 0.04 NS OC CEC Total Fe Total AI 0.581 0.13** 0.15** '-0.551 0.191 0.631 0.06 NS 0.06 NS 8.571 8.16*** 0.581 0.191 0.331 -0.02 NS 0.02 NS 8.391 0.13** 0.11§ 0.451 0.231 8.511 8.13** 8.13** 0.661 0.421 8.571 0.431 0.741 8.511 0.671 0.751 0.421 0.571 0.2S1 0.611 8.38'1 0.471 0.271 0.601 0.391 0.511 0.421 0.621 0.571 0.581 0.571 0.451 0.541 0.301 0.591 0.281 0.451 0.231 tt.6lIt 0.17*** 0.391 0.13** 0.241 0.07 NS -0.01 NS **,*** Significantly different at levels of a = 0.01 and 0.001, respectively. t NC, number of correlation that are not significant among trace elements and soil properties. :j: NS, not significant. § Significantly different at levels of a = 0.10. 1 Significant different at levels of a = 0.0001. found that Cr, Pb, and Cu were correlated with clay content. Strong correlations between concentrations of As, Cr, Cu, Mn, and Ni and the amounts of particles <0.02 mm in surface soils of Poland also were reported by Dudka (1993). They suggested that clay content was important in controlling the level and distribution of trace metal concentrations in soils (Soon and Abboud, 1990; Dudka, 1993). Mermut et ai. (1996) indicated that Pb was likely adsorbed on the 2:1 silicate clay minerals, and therefore Pb concentrations would be expected to increase with increasing clay content. High correlation coefficients (P < 0.001) between background values of trace elements (As, Ba, Cr, Mn, Sb, and Zn) and clay content in Dutch topsoils were attributed to the phenomenon that soils in the Netherlands had been developed from sediments (Edelman and de Bruin, 1986). As such, elemental concentrations were used with clay and OC contents to establish guideline values for contaminant levels in Dutch soils (Forstner, 1995). In contrast to previously published data (Ma et aI., 1997), OC showed significant correlation with trace element concentrations except for Be, Cr, Mn, and Ni (Table 4). This may be due to the fact that no organic soil was included in the former study. Ames and Prych (1995) reported that concentrations of most transition metals (Co, Cu, Hg, Mn, Ni, and Zn) in soils of Washington showed significant correlation with Oc. This finding was attributed to the strong absorption of transition metals by soil organic matter (Stevenson, 1982). Significant correlation (P < 0.05) was also found between certain metal concentrations and OC contents in Dutch topsoils (Edelman and de Bruin, 1986) and agricultural soils of northwestern Alberta (Soon and Abboud, 1990). In Florida, surface oxidation of OC in the aerobic layers of Histosols may concentrate Cd in the surface of these soils (Holmgren et aI., 1993). Furthermore, humic substances in organic soils can serve as strong reducing and complexing agents and influence the processes controlling mobilization of many toxic metals including Hg (Gough et aI., 1996). A recent study on the sawgrass (Cladium jamaicense Crantz) prairie wetlands in south Florida demonstrated that nonessential trace elements (such as Cr, Co, Pb, and Hg) were generally not being cycled but were concentrated in the organic-rich sediments (U.S. Geological Survey, 1996). CEC showed significant positive correlation with most trace elements except Be and Ni (Table 4). This result agrees well with Holmgren et ai. (1993), who Table 5. Correlation coefficients (r) among elemental concentrations in 448 Florida surface soils. Ag As Mo Zn Se Sb Mn Cu Cr Cd Pb Ba Be Hg Ni NCt Ag As 0 1 1 1 1 2 2 2 3 3 3 3 4 6 10 1 0.18 0.67 0.39 0.49 0.75 0.16 0.25 0.17 0.17 0.15 0.41 0.18 0.56 0.09 *** 1 0.23 0.21 0.28 0.18 0.35 0.15 0.17 0.32 0.45 0.09 0.13 0.13 0.01 Mo 'II 'II 1 0.30 0.52 0.53 0.10 0.37 0.50 0.13 0.07 0.16 0.13 0.20 0.31 Zn 'II 'II 'II 1 0.25 0.22 0.53 0.70 0.31 0.37 0.20 0.20 0.46 0.12 0.07 Se Sb Mn 'II t 'II ** *** 'II 'II § 11 1 0.60 0.12 0.63 0.16 0.24 0.10 0.22 0.03 0.38 0.08 'II 'II 1 0.12 0.15 0.15 0.17 0.15 0.35 -0.01 0.65 0.05 § 11 Cu Cr Cd Pb 1 ** 11 *** *** *** *** 11 .. ** ** § NS I § ** ** § NS § § ** 1 0.39 0.25 0.24 0.15 0.12 0.45 0.01 0.08 1 0.23 0.44 0.12 0.13 0.21 0.07 0.05 'I 'II 1 *** ** *** 'II I 'I 'I 1 0.13 0.05 0.07 0.36 0.07 0.56 ** 1 0.34 0.07 0.17 0.08 0.01 **,*** Significantly different at levels of a = 0.01 and 0.001, respectively. t NC, number of correlation that are not significant among trace elements with the maximum being 14. :j: NS, Not significant. § Significantly different at levels of a = 0.10. 'II Significant different at levels of a = 0.0001. 'I 'I '1\ 1 0.10 0.08 0.09 -0.04 BA Be Hg Ni 1 § *** NS *** *** ** 'I ** 'I § § NS:j: 1 I NS NS 'I 'I *** § § 1 -0.04 0.07 NS NS NS NS § ** NS 1 0.01 1 § ** NS NS § 1 0.08 0.11 -0.01 ,, , 'I § NS NS NS , NS NS NS II(S NS 1 1178 J. ENVIRON. QUAL., VOL. 28, JULY-AUGUST 1999 reported that trace elements show good correlation with both CEC and Oc. This is understandable since CEC is simply correlated with clay containing trace elements and shows significant positive correlation with OC and pH (Stevenson, 1982). All 15 trace elements were highly correlated to both total Fe and Al concentrations in Florida surface soils (Table 4). These correlation coefficients were the strongest among all six variables tested in Table 4. A similar but a slightly weaker correlation was reported by Ma et aI. (1997). Dudka (1993) found good correlation between concentrations of As, Co, Cr, Cu, Ga, Mn, Ni, and Se and concentrations of Al and Fe in surface soils of Poland. He concluded that levels of most elements were mainly controlled by minerals present in those soils (Dudka, 1992). Total Fe and Al concentrations (2300 and 2200 mg kg-I) in Florida soil are 16 to 32 times lower than the average concentrations reported for other soils (38000 and 71 000 mg kg-I; Lindsay, 1979). Apparently, total Fe and total AI, even at such low concentrations, are significant in controlling metal concentrations in Florida soils. The capacity of Fe and/ or Al oxides in sorbing and/or co-precipitating trace elements has been widely studied (Zachara et aI., 1993; Karthikeyan, 1997). We hypothesize that trace elements may have co-precipitated with Fe-AI oxides during their formation in soils, existing as structural components of Fe-AI oxides instead as exchangeable ions on Fe-AI oxide surface. This is supported by the fact that trace element concentrations correlated better with total Fe and total Al than with CEC (Table 4). (1997). They reported that concentrations of AI, As, Cr, Cu, Fe, Mn, Pb, and Zn in 40 Florida soils positively correlated with each other. Among the 15 trace elements tested in the present study, Ag was correlated with all other elements, whereas Ni correlated only with Ag, Cr, Mo, and Se. Good correlation between concentrations of Ni and Cr has been reported, however, for surface soils of California (r = 0.95, P <0.01; Bradford et aI., 1996) and Minnesota (r = 0.90, P < 0.01; Pierce et aI., 1982). Correlation between concentrations of Ni and Cr and concentrations of Ti and Al in Washington soils was reported by Prych et aI. (1995). They suggested that Cr and Ni were associated mostly with the mineral phase in the soils. Lead and Ba displayed significant correlation with most elements, excluding Mo, Ni, Cr, and Cd; beryllium displayed significant positive correlation with most elements, excluding Ni, Se, and Sb; and Hg showed significant correlation with most elements except for Be, Cd, Cr, Cu, Mn, and Ni (Table 5). High correlation among trace elements in Florida soils suggests that similar processes control element associations in parent materials (Bradford et aI., 1996). To separate natural from anthropogenic factors influencing trace element concentrations in soils, however, normalization of the data based on weather- or leach- resistant reference elements, such as AI, Ti, and Zr, is needed. Correlation among Trace Elements Factorial Analysis Significant correlation was found among most trace elements, especially Ag, As, Cd, Cr, Cu, Mn, Mo, Sb, Se, and Zn (Table 5). This may occur because they have similar ionic radii, with the exception of Ag (KabataPendias and Pendias, 1992; Dean, 1992). This result is consistent with previously published data by Ma et aI. Factorial analysis is an extension of correlation analysis. It can divide variables into groups that are consistent with anthropogenic or pedogenic processes (Davies and Wixson, 1987; Dudka, 1992). In the present study, eight factors satisfactorily described distributions of trace element concentrations in Florida surface soils. These fac- Factorial Analysis and Multiple Regression of Trace Element Concentrations and Soil Properties Table 6. Results of R-mode factorial analysis for Florida surface soils showing relative loading from element concentrations and soil properties on eight factors derived by varimax rotation. Factor number Factor loading Factor I 28.9t Factor II 14.8t Factor III 10.3t Factor IV 8.1t Factor V 7.5t Factor VI 6.7t Factor VII 6.4t Factor VIII 3.8t Percent variance explained (%)86.6:1: 100 1.00 Extr-Mg, Extr-Na, CEC 90 80 0.90 Fe,AI Extr-Ca OC Total-acid pH-KCI 70 Ni 0.80 K, Mn, Ba Extr-K pH-H,O, Ca Silt, Clay Hg Mo 0.70 Avail-H,O Zn,P,Be Cr 60 50 Sb 40 0.60 Pb, As Mg Cr, Co Co Pb,Ag 30 0.50 0.40 t Percentage of tbe total variance explained by a factor. t Percentage of the total variance explained by all factors. Se, Avail-H,O Ag Cd,As Mg 20 1179 CHEN ET AL.: BASELINE CONCENTRATIONS OF TRACE ELEMENTS IN FLORIDA SOILS tors explained 87 % of the variance using the 34 variables in the analysis (Table 6). The resulting varimax factors were not correlated and different variables generally had different loadings on different factors. Apparently some of the elements (As, Ag, Cr, Cu, and Pb) were controlled by more than one factor. Factor 1 (total Fe and AI) explained 29% of the total variance and was the most important factor, which was consistent with correlation data in Table 4. It had large loadings from total concentrations of Fe and Al and moderate loadings from total concentrations of K and P in the soils. This factor may represent Fe and Al oxides, perhaps combining with K and P minerals as well as some resistant metals. Four trace elements Mn, Ba, Zn, Be showed strong associations with Factor 1. Relatively low loadings from Cr, Cu, Pb, and As on the total Fe and Al factor suggest that other factors influence these elements in Florida soils. It was reported that in acidic soils, the main forms of As were Al and Fe arsenates (AIAs0 4and FeAs04), whereas in alkaline and calcareous soils the main form was Ca3(As04)2 (Fergusson, 1990). Factors 2, 3, 4, and 5 were related to major soil properties; namely CEC (Factor 2), pH (Factor 3), clay (Factor 4), and OC (Factor 5), which together explained 41 % of the total variations. The large loadings from the extractable bases on Factor 2 (soil CEC factor) means that these extractants were highly correlated with CEC. Factor 3 (soil pH factor) had a large loading from pH. Total concentrations of Ca and Mg had moderate loadings on Factor 3, implying that total concentrations of both base elements contributed to the soil pH factor. Total concentrations of Cu had some loading on the soil pH factor, confirming the significant associations between Cu and soil pH (Table 4). Factor 4 (soil clay factor) was primarily due to particle-size distribution (positively associated with silt and clay, negatively associated with sand), and to a lesser extent, with available moisture content of the soils. The loading of Se on Factor 4 was consistent with the significant correlation coefficients between concentrations of Se with soil clay content (Table 4). Factor 5 (soil OC) is clearly due to OC and total acid, and to a lesser extent, available moisture content of the soils. The lack of significant loading of any trace metals on Factor 2 and Factor 5 implies that both OC and CEC did not have major influence on occurrences of these trace elements in Florida surface soils. Factor 6 (Ni and Mo factor) explains 7% of the total variances. It had large loadings from Ni and Mo and to a lesser extent of Cr and Ag. This is consistent with the relationships between concentrations of Ni with Mo, Cr and Ag (Table 5). Chromium and Mo are transition elements that locate at Group 6b of the Periodic Table and have strong lithophile tendencies. Though they have variable oxidation states, they are preferably hexavalent in their oxygen compounds (Kabata-Pendias and Pendias, 1992). Nickel and Cr in soils are mostly from pedogenic sources (Kabata-Pendias et aI., 1992). During magnetic fractionation, Cr is closely associated with Ni and accumulates in ultrabasic rocks (Davies and Wixson, 1987). Factors 7 and 8 were of minor importance; together they explained ~ 10% of the total variations. They may be regarded as anthropogenic factors based on information described previously. These factors included Sb, Pb, Ag, Cd, As (Factor 7), and Hg (Factor 8). Factor 7 (Sb and Pb) confirmed significant associations among total concentrations of these elements (Table 5). Accumulations of Cd in organic soils were attributed to application of phosphate fertilizers containing Cd (Holmgren et aI., 1993). The composition of Factor 8 (Hg) indicates an obvious relationship of total concentration of Mg with Hg in the soils. It was reported atmospheric deposition was more important for Pb, As, and Hg, whereas phosphate fertilizer is marginally more important for Cd Table 7. Multiple and partial correlation coefficients for regression of concentrations of trace metals in florida surface soils against key soil properties. I l Trace elementt Number of variable Mn Ni Ba Be Hg Ag Sb Se As Cd Cr Cu Pb Zn Mo Number of elements 3 2 2 2 2 2 2 1 1 1 1 1 1 1 1 Multiple correlation coefficient Partial correlation coefficients (r) Total Fet Total Alt 0.597 0.125 0.240 0.234 0.187 NS NS NS 0.252 0.139 0.407 0.169 0.203 0.358 0.116 12 NS:j: NS 0.119 0.270 -0.128 0.196 0.130 NS NS NS NS NS NS NS NS 5 *** Significantly different at levels of a = 0.0001. t Concentration after log-transformation. :j: NS, not significant at levels of a = 0.05 using the student '-test. Clay -0.134 NS NS NS NS 0.130 0.199 0.245 NS NS NS NS NS NS NS 4 OC CEC pH-HzO R' F-test ~0.157 NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS 0 NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS 0 0.65 0.09 0.33 0.44 0.10 0.29 0.10 0.25 0.42 0.23 0.46 0.33 0.30 0.52 0.13 *** *** *** *** *** *** *** *** *** *** *** *** *** *** *** -0.126 NS NS NS NS NS NS NS NS NS NS NS NS NS 2 1180 J. ENVIRON. QUAL., VOL. 28, JULY-AUGUST 1999 contamination in soils (Fergusson, 1990). Very recent studies suggest that Hg deposition in South Florida is generally driven by large-scale regional or hemispheric processes as opposed to local emission/deposition processes (Gough et aI., 1996). Multiple Regression Analysis Multiple regression of concentrations of trace elements against clay, OC, pH, CEC, and total concentrations of Al and Fe supported the relationships of trace elements with important soil properties (Table 4) and the results of factorial analysis (Table 6). Regressions of log-transformed concentrations of the 15 trace elements against six soil variables were all significant, explaining between 9 to 65% of the total variance (Table 7). Partial correlation coefficients between individual element and soil property provided the relative importance of each soil property on elemental distributions. The number of variables and magnitude of partial correlation coefficients (r) confirmed that total Fe and total Al were the two major variables controlling concentrations and distributions of most trace elements in Florida surface soils as demonstrated previously using simple correlation analysis (Table 4) and factorial analysis (Table 6). Total Fe concentrations are important for all 15 trace elements except for Ag, Sb, and Se, which were apparently related to clay content, whereas total Al concentrations were important for elements Ba, Be, Hg, Ag, and Sb. Though CEC and pH are critical soil properties, their importance on the distribution of trace elements was not significant because they depend highly on soil components (i.e., clay, OC, Fe, and Al oxides), which also had significant positive correlation with concentrations of most trace elements (Tables 4 and 6). Our results demonstrated the importance of Fe and/or Al oxides and clay in controlling trace element concentrations in Florida soils (Table 7). Among the 15 trace elements, partial correlation coefficients of Fe with Mn (r = 0.60), Cr (r = 0.41), and Zn (r = 0.36) were the highest (Table 7). Iron and Mn have similar redox chemistry and geochemical behavior, which explain their high covariance in soils. Actually, hydrous oxides of Fe and Mn in soils were reportedly the most important compounds in sorption of trace metallic pollutants, and they exhibit diverse affinities to NiH, CuH , ZnH , CdH , Pb4+, and Ag+, which have approximately the same physical dimensions as Mn and Fe ions (Fergusson, 1990). In addition, oxidation of As, Cr, and Hg by Mn oxides is likely to control the redox behavior of these three elements in soils (Kabata-Pendias and Pendias, 1992). In general, Cr closely resembles Fe and Al in ionic size and in geochemical properties. The association between Cr and Fe may reflect the fact that most of the Cr in soils is present as chromite (FeCrz04) or in other spinel structures, substituting for Fe. However, under conditions induced by fluctuating water tables, Fe is depleted and Al is rendered less crystalline and more prone to organo-complexation. Aluminum hydroxides can thus adsorb a variety of trace elements and be more important than that of Fe oxides in remaining certain trace elements like Ag, Be, and Sb (Table 7). CONCLUSIONS The GM concentration levels of 15 potentially toxic trace elements in Florida surface soils were lower than the average of USA and world soils. The upper limit of baseline concentrations for most trace elements (Ag, As, Be, Cd, Cr, Cu, Mo, Ni, Pb, Se), however, corresponded well with those reported in the literature. Baseline concentrations of 15 trace elements in 448 representative Florida soil samples were proposed as reference concentrations in Florida. Due to possible influence from anthropogenic factors on concentrations of Sb, Pb, Ag, Cd, As, and Hg (Table 6), however, baseline concentrations estimated for Ba, Be, Cu, Mn, Mo, Ni, Cr, Se, and Zn are probably a better measure of the natural levels of these elements in Florida surface soils. Total Fe and Al showed the strongest relationship with concentrations of most trace elements, based on simple correlation analysis, factorial analysis and multiple regression (Tables 4, 6, and 7). Other important variables include clay and Oc. The importance of CEC and pH on the distribution of trace elements was diluted by these component variables. Significant correlation coefficients were also found among Ag, As, Cd, Cr, Cu, Mn, Mo, Sb, Se, and Zn (Table 5). ACKNOWLEDGMENTS This research was sponsored in part by the Florida Center for Solid and Hazardous Waste Management (Contract no. 96011017). The authors would like to thank the Chemistry Laboratory of the Florida Department of Environmental Protection for determining concentrations of 10 trace elements. We are also indebted to those who participated in the Florida Cooperative Soil Survey. Their collection and characterization of a large number of Florida soil samples made this study possible. 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