Rept for th Jaa of Votune 27,08 6 Not De 1988, Cope © 15H ASA. CSSA, SSSA 177 Sot ep Ra Matson, W1SS717 USA. Comparison of Four USEPA estion Methods for Trace Metal Analysi Using Certified and Florida Soils Ming Chen and Lena Q. Ma* ABSTRACT 1s ercal to compare existing sample digestion methods for evaluating sol contamination and remediation. USEPA. Methods ‘3050, 351, 3a, and 3082 were used to digest standard reference ‘materials and epresenlative Moria surface sol Fifteen trace metals (Ag, As, Ba, Be, Cd, Ce, Cu, Hg, Ma, Mo, Ni, Pb, Sb Se, and Za), and six macro elements (AL, Ca, Fe, K, Mi, and P) were analyzed. ‘Preise analysis was achieved for all lements except for C8, Mo, Se, ‘and Sb in NIST SRMs 2704 and 2009 by USEPA Methods 30 and ‘3051, and for all elements except for AS, Mo, Sb, and Se ln NIST 'SRM 2711 by USEPA Method 3052. No sigaficant differences were ‘observed forthe three NIST SRMs between the microwave-austed USEPA Methods 051 and Sia and the conventional USEPA Method 3080 except for Hg, Sb, and Se. USEPA Method 51a pro- vided comparable valves for NIST SRMs certiged axing USEPA "Method 3058. However, for method correlation coefficients and ele- mental recoveries in 40 Florida surface sols, USEPA Method 305In tras an overall better alternative for Method MSO than wat Method $351, Among the four digestion methods, the microwave-assted [USEPA Method 3052 achieved satisfactory recoveries forall elements except As and Mg using NIST SRM 2711 This coval-foal digestion ‘method provided greater recoveries for 12 elements Ag, Be, Cr, Fe, K, Ma, Mo, Ni, Pb, 9b, Se, and Za, but lower recoveries for Mg in ‘Florida soils than did the cova-recoverable digestion methods (350, 351, and 30518). Se federal and state regulations lit A, As, Ba Be, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, and Za as potentially toxic metals (FDEP, 1996; USEPA 41995a). The USEPA has identified consumption of gar- den fruits and vegetables as a potential exposure path- way (soil-plant-human pathway) for metals in residen- tial sols. To properly assess metal health hazard in sols, the USEPA has evaluated several sample preparation methods to calculate soil screening levels for the soi plant-human pathway (USEPA, 1996). These sample preparation techniques for total metal analysis can re- quire several hours, or even several days, to complete. ‘They use acid digestion and thermal decomposition steps, which can result in analyte losses, incomplete recoveries, and/or sample contamination (Smith, 1994; ‘Smith and Arsenault, 1996). These limitations are well known to the analytical community and to end users of these methods (Binstock et al., 1991). As a result, total- recoverable (rather than totally decomposing) methods 1M. Chen, Commission for Integrated Survey of Natural Resources, Chinese Academy of Sciences, Building 917, P.O. Box 9717, Bling 100101, Peoples Republic of Chinas and ILO. Ma, Soll and Water Science Dep. Univ-of Florida, Gainesville, FL 32611-0290, Contribu- tions from the Sol and Water Science Dep, Univ. of Florida and the Florida Agri: Exp. St, Journal Series no. 806187. Reesived 24 Nov 1997, *Corresponting author (qmapny issued) ‘Published in J. Environ. Qual. 27:1284-1300 (1988, have become a common method for sample pre} Total recoverable methods have been used in many environmental studies, including monitoring the mobil- ity of heavy metals and approximating total elemental concentrations for site assessment (Kane, 1995). The USEPA has adopted several sample preparation tech- niques (Binstock et al, 1990; USEPA, 1995b, 1996; Lor- entzen and Kingston, 1996) to serve the needs of differ- cent users. Currently, four USEPA digestion methods are available: USEPA Methods 3050 (hot-plate, HNO.- HCI, total-recoverable), 3051 (microwave, HNO, total- recoverable), 3051a (microwave, HNO;-HCi, total- recoverable), and 3052 (microwave, HNO;-HCI-HF, total-total). USEPA Method 3050 is satisfactory for all elements regulated by the USEPA except for Ag, Ba, and Sb from soil of sludge samples (Kimbrough and Waka- kuwa, 1991). This method has become widely accepted since it allows adaptation to newer technological imple- mentations, such as microwave digestion (Lorentzen and Kingston, 1996). However, variations in hot plate temperatures, refluxing times and acid additions using Method 3050 directly affect elemental recoveries. The observed relative standard deviations (RSD) of 10 to 30% for this method are considerably greater than the expected instrumental error (<5%) for an ICP (Kane, 1995). USEPA Method 3051 is commonly regarded as a regulatory alternative to Method 3050 (USEPA, 1995b; Hewitt and Reynolds, 1990; Kokot et al., 1992; Lorent” zen and Kingston, 1996). This technique provides rapid, safe, and efficient digestion and is not susceptible to losses of volatile metals (Hewitt and Reynolds, 1990). Several papers reported that metal concentrations of several NIST SRMs using Method 3051 compared well to Method 3050 (Binstock et al., 1991, Kane, 1995), However, only limited work has been performed to com- pare Methods 3051 and 3050 using research samples. USEPA Methods 3050 and 3051 are comparable for NIST SRM 2704 but, for nine sediment samples, no trend between those two methods was found for ‘Cd, Cu, Pb, Ni,and Zn, A bias as high as 217% was measured between the two methods (Wei et al., 1997). USEPA Method 3051a is a modification of Method 3051 to mimic Method 3080 by adding HCI to improve recovery for Ag, Al, Fe, and Sb (USEPA, 1997). How- “Abbreviations: CVAAS, cold vapor atomic absorption spectzopho- tometer, GFAAS, graphite furnace atomic absorption spectrophotom. ther, ICPMS, inductively couple plasma-mass spectrometer, ICP, Inductively coupled plasma spectrometer, MDL, method detection ti(CHEN & MA: COMPARISON OF FOUR USEPA DIGESTION METHODS 1295 ever, litte information is available on this new method regarding its performance using SRMs or actual soil samples. Itis also recognized that these total-recoverable diges- tion procedures (3050, 3051, and 30512) do not recover all metals in the samples (Sawhney and Stilwell, 1994) Modifications of these methods led to a more vigorous HNO,-HCI-HF digestion method (USEPA Method 3052), which has proven to be more satisfactory (Am. mons et al., 1995; USEPA, 1995b; Kokot et al., 1992; Paudyn and Smith, 1992; Smith, 1994). This method uses microwave-assisted acid digestion for foral sample ‘decomposition and is applicable to 26 elements includ- ing Ag, Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Ma, Mo, Na, Ni, Pb, Sb, Se, Ti, V, and Zn (USEPA, 1995b), It is thus critical to evaluate and compare these four USEPA digestion methods using soil samples that may be relevant to soil cleanup standards and to regulation cof land application of nonhazardous materials. Unfortu- nately, no such comparisons have been made to date. ‘The objective of this study was to compare the four USEPA digestion methods for determining concentra tions of 15 trace metals (Ag, As, Ba, Be, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, and Zn), and six macro elements (Al, Ca, Fe, K, Mg, and P) using three NIST SRMs 2704, 2709, and 2711 and 40 representative Flor- ida surface soils. EXPERIMENTAL SECTION ‘Three NIST SRMs (2704, 2709, and 2711), representing sediment, sandy soil, and contaminated soil samples, were ‘sed in this study (NIST, 1995). In addition, 40 representative Surface soil samples (genetic horizon A. Al, or Ap) from Uee soll orders (Spodosos, Entisols, and Ultisols) were used Detaled information on these samples can be found in Ma tal (1997) Physical and chemical properties of these soils were previously determined (Sodek etal, 1950). The 40 soil Samples were ground to pass a 6O-mesh sieve, whereas the NIST SRMs were digested as received (particle size: 100 mesh for SRM 2704, 200 mesh for SRMs 2709 and 2711, and unit size: 50). Standard stock solutions of 1000 mg L~* Ca, Me, KP, Al Fe, Hg, Sb, As, Ba, Be, Cd, Cr, Cu, Pb, Mr, Mo, Ni, Se, Ag, and Zn wete obtained from Fisher Scientific (Far Lawn, N}). Nitric acid, HCl and HIF of trace-metals grade were also oblained trom Fisher Scientific. Instrument calibration stan dards were obtained from Spex Industries (Edison, NJ). Method precision and accuracy (elemental spike recoveries) for 21 elements were determined by digesting three NIST SRMs and 40 Florida surface soils using USEPA Methods 3050, 3051, 30813, and 3082 (USEPA. 199%b, 197). Precision ‘vas defined as RSD, which was calculated using standard {eviation divided by the mean for replicated samples calculated using percent relative difference between du determinations. The accuracy was judged by comparing the fnalytical result with the certified value for NIST SRM or concentration ofthe spike and was expressed as the pereentage recovery %R) (Smith, 1994), Satisfactory precision and act racy were required to be within 220% and between 80 and 12046. respectively Aluminum, Ca, Fe, K, Mg, and P in the digestates were analyzed on # multichannel Jarrel-Ash ICP OL-E unit by +A, quay asurance: QC, quay contol USEPA SW 846 method 6010 and, in a few cases, by USEPA ‘SW 846 method 200.7 (Keith, 1996). Concentrations of Ag, Ba, Be, Cr, Cu, Ma, Mo, Ni, Sb, Se, and Zn were determined on 1 Perkin-Elmer ELAN 6000 inductively couple plasma-mase spectrometer (ICP-MS) unit using USEPA SW 846 method 6020. Concentrations of As, Cd, and Pb were determined on 1 Perkin-Fimer SIMAA 6000 graphite furnace atomic absorp- tion spectrophotometer (GFAAS) unit using USEPA SW 846 ‘methods 700A, 7191, and 7421, respectively (Smith, 1994). ‘A Perkin-Elmer Model 2380 AAS, equipped with a Perkin Elmer MHS-10 mercury/hydride system (CVAAS), was used for Hg determination using USEPA SW 846 method 7061 (USEPA, 1995b; Keith, 1996). ‘Al calibration curves for trace metals had a correlation ‘coefficient of R* = 0,995, Quality assurance samples (a blank, ‘8 duplicate, a spike, and a SRM) were analyzed every 20 samples. Al the target elements had matrix spike recoveries within =10% R and precision of 10% PRD except for Ni, which was 125% (Table 1). All statistical analyses were performed using a PC-version SAS program. Analysis of variance was used to assess signi ‘cant differences between the different methods. The confi dence level for the Student test was calculated at « = 0.05. RESULTS AND DISCUSSION Comparison of USEPA Methods 3050, 3051, ‘and 3051a using NIST SRM 2704 Data quality objectives for both accuracy and preci- sion for a laboratory test represent a statistically derived 95% confidence level (Smith, 1994). In the current study, precise analysis was achieved for all elements using NIST SRM 2704 by USEPA Methods 3051 and 3050 except for Sb-and Sé, which were out of the target precision range of +20% (Table 2). NIST certified val- ues of Ag, Be, and Mo in SRM 2704 were unavailable; they, were thus not considered. The precision of repl cate analyses of NIST SRM 2704 for Methods 3050 and 3051 was calculated from eight independent measure- ‘ments. The RSDs for all elements except Mo, Sb, Se, and K by Method 3050 and Pb, Sb, Se, and K by Method1296 | ENVIRON. QUAL, VOL. 7, NOVEMBER-DECEMBER 1998 ‘Table 2. Concentrations of 21 elements in NIST SRM 2704 Method 350 (W = #) ested by USEPA Methods 350, 3051, and 30Sta, ‘Method M81 WV = 8) Method asta (W = 0) Element Concentration _Accaracy Predhion Concentration Aes Ae NAS ev) a "s as Be Ey ae ca o as cr o 30 He is a Me i as x = a Ea 1 a7 & B 2 3051 were close to the expected instrumental error of 5% (Table 2). Poor precision has been reported for Se in SRM 2704 when using Method 3051, and has been attributed to alow Se concentration in the sample (Bins- tock et al, 1991). Low precision for Ni in SRM 2704 ‘when using Methods 3050 and 3051 has also been re- ported by Wei et al. (1997), ‘The observed elemental recoveries for As, Cd, Cr, Cu, Pb, Mn, Ni, Zn, Ca, Mg, P, Fe, and Hin NISTSRM 2704 by all three total-recoverable digestion methods (USEPA Methods 3050, 3051, and 3051a) were >60%, ‘whereas those for Ba, K,and Al were =25%. The recov. eries of Sb and Se from SRM 2704 were <8% by Method 3051 and increased to =52% by Method 3050, However, ‘most elemental recoveries were in the same ranges a3 those reported by Binstock et al. (1991) and Hewitt and Reynolds (1990), and slightly lower than those of Wei etal. (1997). Te biases between USEPA Methods 3050 or 3051, and USEPA Method 305ia for most elements were negligible (< * 20%) except for Sb and Se, which can be partially contributed to poor precision (34-245% RSD, Table 2). Except for Hg, which was slightly higher by Method 30851 than by Method 3050, observed elemental recov- eries for many elements (As, Cd, Cr, Cu, Mo, Sb, Se, ‘Ca, Mg, K, and Fe) from SRM 2704 when using Method 3051 were slightly lower than when using Method 3050. Biases for Al, As, Ba, Be, Co, Pb, Sr, Mg, Fe, and V for SRM 2704 and other certified materials by the two ‘methods have been reported (Binstock et al, 1990). ‘Observed elemental recoveries for most elements by Method 3051a, except for Cr and Pb, were slightly higher than those by Method 3050, This was especially truc for Sb, Se, Ag, and Hg, which gave high positive biases (Table’2). Similar results for Cu, Mn, Pb, and Zn have been reported when using conventional and microwave aqua regia (HNO,/HCI = 1:3) sample digestion (Nieu. Bias}__Concentation Accurney Blast mee “RO% 9 Om NA 9 ms ° 7 NA ‘ @ 4 a” ‘ » 3 NA ‘ = 2 181s a 2 ‘ Comparison of USEPA Methods 3050, 3051, ‘1a, and 3052 using NIST SRMs 2709 and 2711 Relative standard deviation values of 10 to 30% by Method 3050 and 6 to 10% by Method 3051 have been reported (Binstock et al, 1991; Kane, 1995). In the cur- rent study, satisfactory precision was achieved for SRM. 2709 for all elements except Mo (24%) and Se (25%) by Method 3050, and except Sb (245%), Cd (38%), and Se (89%) by Method 3051 (Table 3). Poor precision for Sb, Cd, Mo, and Se analyses can be attributed to the extremely low metal concentrations in SRM 2709 (Ta- ble 3), The biases between Methods 3051_and 3050 using ‘SRM 2709 for Sb, Cd, Mo, Se, and Zn were >20%, whereas for As, Ba, Be, Cr, Cu, Pb, Mn, Ni, Se, Ag, Ca, Mg, K, P, Al, and Fe biases were all within +20%. Poor precision of either or both methods may have resulted in the biases for Sb, Cd, Mo, and Se. ‘The majority of observed elemental recoveries when using Method 3051 were in the same range, or slightly lower, than the certified values when using Method 3050, except for Sb, As, Cd, Mo, Se, and Hg (Table 3), which have no certified values available (Kane, 1995) Observed recoveries of As, Cd, Ca, Cr, Cu, Fe, Mg, Mo, Ni, P, Sb, and Zn in SRM 2709 when using Method 3051 were 10 to 89% lower than when using Method 3050 (with negative biases as shown in Table 3). Low values obtained by Method 3051 could be caused by either more accurately controlled, but relatively lower temperatures during digestion (Lorentzen and Kings- ton, 1996), or by contributions of HCl and H;0; used in Method 3050 (Binstock et al, 1991; Hewitt and Reyn- olds, 1990; Kane, 1995), ‘The precision and accuracy for 21 elements in SRM 2711 by Method 3051a and Method 3052 are presented eeCHEN & MA: COMPARISON OF FOUR USEPA DIGESTION METHODS 1297 ‘Table 3. Concentrations of 21 elements in NIST SRM 2709 digested by USEPA Methods 3050 and 3051. Method 3050 (W = 8) Method 3051 W = 8) F ment Preciion _Accracy NIST cerca} Concentration Presson Accuracy ma ke soRSD oe ok me he “Rs *R as a 40 ni sea. 3 S Be a7 a NAN NA 3s 33 ca 4 as mm 20%, due to the greater recovery with method 3051a, No certified values were available for Sb, Mo, Se, and Hg, Comparison of USEPA Methods 3050, 3051 30S1a, and 3052 using 40 Florida Surface Soils Florida soils form primarily from sandy sediments (Brown et al., 1990). Those soils are especially prone to leaching and have lower trace metal concentrations than U.S. averages for soils (Ma ct al., 1997). Generally, total concentrations of Al, As, Cd, Cr, Cu, Fe, Hg, Mn ‘Table 4, Concentrations of 21 clements in NIST SRM 2711 digested by USEPA Methods 3052 and 30Sta, Method 3052 (Y= 8) Method s05ta (W Toncentration —__Prechion Accuracy Concentra ‘Accuney NIST eeriiedt Blast me he “RSD oR me he oe =e % ro an a2 m2 an om 6 “o a 27 a "3 sas o s te a sto “i a rs 26 = “9 Be 23 36 NAL 106 NA NA NA a aa 6 ch sae 33 MS e us a 3S 2a & 3 o co ms. 03 2 a > os a ie 366 S ot es 16 BA NA Me or uM By swe ” 7 Ms Mo i a aa 10 e =MDLL NA x ur 16 i 160" m ” Bt » 1039 03 2 ona o s ° & 18. ar oe "a % MDL. NA Ss nas 0 = 0 is “a NA Pa 20 ey a a2 * = 0 G 236 a3 a1 a0 2 B w Me 748 ri m 0 > % 33 x 2506 a m2 S300 2 is = e 0 2 33 0 = 100 an a 2s % a 19180 x * “a “detection tit. overy (oR) valves asing USEPA Method 3050 (Kane, 1995) ‘Method 0s0 (2) ~ (chemental concentrations, ~ NIST cevtifed clement conceatationa)/NIST cerifed elemental1298 Table 5. Comparison of USEPA Methods 3050, Concentration Element Element Method Method a a0 Mn ae ie ost Besta Siete es us ae so Mo 200 ast est esta Seste es Pt Be so N 2es0 est mast Siete ‘Besta us ma Be so * 050 ‘ast mast iste ‘esta er aa ca 3050 * wo mast as ‘esi ile best we c 3050 se a0 et ast sie asia ws Py oo so za 0 et st asta ase ms aa { Means ftiowed by the same eter are no signal ierent (a NAT dnote o 08. Pb, Ni, and Zn in Florida soils decreased in the order Untisols > Entisols = Spodosols (Ma et al., 1997), In the current study, 21 elements in 40 Florida surface soils were determined after digesting using four different methods (USEPA Methods 3050, 3051, 3051a, and 3052). Total-Recoverable Methods Total-Total Method As expected, most elements in the 40 Florida surface soils showed significantly greater concentrations using the total decomposition method (Method 3052) than when using total recoverable digestion methods (3050, 3051, and 3051a). This was especially true for Ag, Be, Cr, Fe, K, Mn, Mo, Ni, Pb, Sb, Se, and Zn (Table 5). ‘There were no significant differences for Ca, P, and Al between Methods 3051 and 3052, and for As, Ba, Cu, Ca, P, Al, and Hg between Methods 3050, 3051a, and 3052 (Table 5). This agrees with our results using NIST SRMs, except for Al, Ba, and Zn (Table 4). The dis- agreement with some metals can be explained by varia- tion in the amount of metal liberated from a nonaqueous environmental sample (Nagourney et al., 1997). Metals such as Cd (Krishnamurti et al., 1994) and Zn are effi- ciently recovered from SRMs and soils by total recover able methods, whereas metals such as Ba, Cr, and Ni that are contained in aluminosilicate lattices éan only be efficiently recovered via HNO:-HF total digestion (Hewitt et al, 1990; Sawhney and Stilwell, 1994). Highly efficient recoveries of Co, Ni, Cr, Cd, Pb, Cu, Zn, Mn, Fe, K, Na, Ca, and Mg from sewage sludge samples using conventional HNOs digestion has been reported cee eo eee en oey ye es Jeen Teporie’ |LENVIRON. QUAL VOL. 27, NOVEMBER-DECEMBER 1998 30Sta, and 3082 using 40 Florida surtace soils Concentration Element Method Concentration me ke"! mb oo 2 we (020 be Mg. a Fe Hy C4, Cu, Fe, Mn, Pb, and Zn from sewage sludge samples using tmicrowave-assisted HNO, digestion have also been reported (Morales et al., 1989). In a preliminary study, the dissolved solids for Florida soil samples after digesting by Method 3051 remained low (only 3.4- 16.1%), indicating that most solids remained intact dur- ing, the total-recoverable digestion. Significantly lower amounts of Mg were found by Method 3052 than by Methods 3050 and 3051a (Table 5). This agrees with the low recoverable Mg value of 71% by Method 3052 (compared with 79% by Method 3051a) for SRM 2711 (Table 4). Incomplete dissolution ‘of sandy soil (sand content > 45%) by aqua regia and HEF also has been reported (Ammons et al., 1995). The extremely high sand contents of the soil samples used inthis study, which ranged from 79.8 to 99.7% with one exception (Sodek et al., 1990), probably contributed to the low Mg recovery. Large positive correlation coefficients for P were ob- served between Methods 3050, 3051, 3051a, and 3052 (Table 6). This suggests that the three total-recoverable methods may be equivalent to total-total digestion for determining P in Florida soils. No other significant and positive correlation coefficients were found between Method 3050 and the thee total recoverable methods, except for As, Ba, Cr, Cu, Al, Fe, Pb, and Zn in some cases (Table 6). Thus, the total-recoverable and total- total methods are not interchangeable for evaluating total metal contents in Florida soils for most elements. USEPA Methods 3051 vs. 3050 Several studies have shown that Method 3051 was(CHEN & MA: COMPARISON OF FOUR USEPA DIGESTION METHODS 1299 ‘Table 6. Correlation coeficients (-value) between USEPA Methods 3050, 3051, 35a, and 352 for 21 elements in 40 Florida surface sols. hme 950 951 NSO Tn RSL esta x 8 SS x32 Slax A aoe st a03ns ~ea6N a “taser pd ae a ton te tee Hf sor sans tase & oer Sens tens & Feta teens oS £ oa san tates ie Nex tens bread i ‘ie cere See A tans -tarNs airs " teen cme ra fg tans 3 138 g “tagns i wer é tee tats “ sean f Soon tu tine ft tee is INA = eto arte Seinen Sino SRMs (Binstock et al., 1990, 1991; Kane, 1995). How- ever, mixed observations have been reported using sedi- ment samples (Wei et al., 1997). In our study, signifi- cantly lower concentrations of As, Ba, Cr, Cu, Pb, Mn, ‘Ag, and Zn in 40 Florida soils were found by Method 30851 than by Method 3050. Biases for those elements ‘were unacceptably large for direct method comparisons. ‘There were no significant differences in mean concen- trations of Al, Be, Ca, Cd, Fe, K, Mg, Mo, Ni, P, Se, and Sb in 40 Florida soils between Methods 3051 and 3050 (Table 5). Among these 12 elements, significant positive coefficients existed only for Ba, Be, Ca, Mg, P, Al, and Fe (0.76-1.00) (Table 6). This suggests that Methods 3051 and 3050 may be equivalent only for two trace metals (Ba and Be) and five macro elements (Ca, Me, P, Al, and Fe) for Florida surface soils. Such discrep” ancies were possibly due to the low total metal concen- trations in Florida surface soils (Ma et al., 1997) and the low elemental recovery for some metais (Tables 2 and 3). It was thus difficult to obtain precise determina- tions for those metals, especially using total-recoverable ‘methods such as Methods 3050 and 3051. Another possi- ble reason was that soils from three differing soil orders (Entisols, Spodosols, and Ultisols) were used in this study. Morphological, chemical, and mineralogical dif- ferences in these soils influence the contents and distri- butions of trace metals (Ma et al., 1997). Differences in acid types and concentrations (Binstock et al., 1991), temperatures, and pressures during digestion, and in matrices for the digestate and total dissolved solid after digestion could also have caused bias (Wei etal, 1997), USEPA Methods 30518 vs. 3050 In general, no significant differences were observed between Methods 3051a and 3050 for all 21 elements in 40 Florida soils. It is unclear why significantly lower Cr contents were obtained by Method 305la than by Method 3050 (Table 5); while low, but comparable re- ccoveries (60%) of Cr had been obtained for SRM 2704 by both methods (Table 2). Analytical difficulty and low recoveries of Cr both from SRMs and organicwastes by microwave-based aqua regia digestion have been reported (de Abreu et al.. 1996; Nieuwenhuize et al., 1991). Morales etal. (1996) obtained greater values for Cr, Co, and Cu by Method 3051 than by the dry ashing, method for sewage sludge samples. Further investiga- tion with respect to Cr analysis is needed. Significant positive correlation coefficients between ‘Methods 3051 and 3050 were found in Florida surface soils for all elements except for Mo, Ni, Se, and Ag (Table 6). High coefficients existed between the two methods not only for macro elements such as Ca, Mg, P, K, Al, and Fe (0.94-0,97), but also for heavy metals such as As, Ba, Be, Cd, Cu, Pb, Mn, and Zn (0.77-1.00). In addition, Method 3051a showed significant positive correlation with Method 3050 for Cr, Hg, and Sb. Silver and Sb were difficult to reproduce precisely using Method 3050, and were not certified for Method 3050, (Kimbrough and Wakakuwa, 1991). Poor correlation coefficients between Methods 30S1a and 3050 for Cr, Hg, Mo, Ni, and Sb could be explained either by the extremely low total metals levels in Florida soils, or by the low elemental recoveries for these metals both by Methods 3051a and 3050 (Tables 2, 3, and 4). For Florida soils with extremely low trace metals lev- els, greater recovery should be sought during method selection, Based on overall better elemental recoveries and significant correlation coefficients, Method 3051a seemed to be a better alternative to Method 3050 than Method 3051 in Florida soils for 15 trace metals (Ag, As, Ba, Be, Cd, Cr, Cu, Hg, Pb, Mn, Mo, Ni, Sb, Se, land Zn) and six macro elements (Ca, Mg, K, P, Al, and Fe). SUMMARY Precise analyses were achieved for all elements except Sb and Se from SRMs 2704 and 2709 by Methods 30511300 JL ENVIRON. QUAL, VOL. 27, NOVEMBER-DECEMBER 1998 and 3050, Observed recoveries for As, Cr, Cu, Ca, Mg K, and Fe by Method 3051 were slighily lower than by Method 3050 for SRMs 2704 and 2709. However, biases for most elements between the two digestion methods were negligible. Observed recoveries for all elements except Cr and Pb from SRM 2704 by Method 305ta were slightly greater than by Method 3050, especially for Hg. Nearly all metals determined for SRM 2711 by Method 30Sla agreed well with the NIST-certified values for Method 3050. No significant bias between the two methods was observed except for Zn, which showed better recovery by Method 3051. Satisfactory recoveries (80-117%) were obtained from SRM 271 by Method 3052 forall elements except ‘As and Mg. Moreover, all elements except Pb and Mg, showed significantly higher concentrations by this total ecomposition method than by the three total-recover- able digestion methods (USEPA Methods 3050, 3051, and 3051a) for analyzing 40 Florida surface soil. The microwave-assisted Method 305la was a better alternative method for the hot-plate Method 3050 than Method 3051, with respect to Florida surface soils. In the analysis of both macro elements (Ca, Mg, K, P, Aland Fe) and trace metals (Sb, As, Ba, Be, Cd, Cr, Cu, Pb, Ma, Mo, Ni, Se, Ag, and Zn). Method 30514 yielded overall comparable elemental recoveries and Significant positive correlation coefficients with values, from Method 3050. ACKNOWLEDGMENTS. ‘This research was sponsored in part by the Florida Cente for Solid and Hazardous Waste Management (Contract no. 96011017). The authors thank the Chemistry Laboratory of the Florida Department of Environmental Protection, espe- cially Mr. Timothy W. Fitzpatrick and Dr. Julio 1. 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