Interlaboratory validation of the Mehlich 3 method as a universal extractant for plant nutrients.

The Mehlich 3 (M3) method is widely used to extract plant-available phosphorus from soil over a wide range of pH values. The method is also used by many laboratories to determine multiple plant-available nutrients simultaneously. However, except for P, this method has not been statistically validated within and among laboratories. The objective of this study was to determine the repeatability (within-laboratory performance) and reproducibility (among-laboratories performance) of the M3 method for several different nutrients by using a wide variety of soils. An in-house homogeneity test was conducted for 11 soils. Three replicates of each of the 11 soils were sent to 23 domestic and international laboratories for analyses primarily for K, Ca, Mg, Zn, Mn, Fe, and Cu. Samples were scooped, weighed, or both scooped and weighed for extraction. The various nutrients in the extracts were quantified by the participating laboratories by using inductively coupled plasma-atomic emission spectrometry. Ranges (in parentheses) of the repeatability relative standard deviation (RSDr) values for the scooped samples were K (3.88-6.14%), Ca (2.19-10.6%), Mg (2.27-5.73%), Zn (4.11-42.7%), Mn (3.15-8.53%), Fe (2.32-7.74%), and Cu (3.65-11.2%). For the weighed samples, the ranges (in parentheses) of the RSDr values were K (1.65-4.65%), Ca (1.43-16.9%), Mg (1.37-9.83%), Zn (2.60-33.0%), Mn (1.61-4.90%), Fe (1.56-4.47%), and Cu (2.95-17.9%). Ranges (in parentheses) of the reproducibility relative standard deviation (RSDR) values for the scooped samples were K (7.44-20.0%), Ca (7.10-33.5%), Mg (7.63-26.4%), Zn (11.6-48.7%), Mn (10.5-19.7%), Fe (12.4-22.0%), and Cu (8.86-45.3%). Ranges (in parentheses) of the RSDR values for the weighed samples were K (3.47-12.7%), Ca (7.61-34.6%), Mg (7.53-29.0%), Zn (10.6-49.2%), Mn (6.54-20.7%), Fe (11.0-21.5%), and Cu (9.73-43.0%). The Horwitz ratios (HorRat) were also used to evaluate the repeatability, HorRatr, and the reproducibility, HorRatR. Overall, the M3 method appears to be both repeatable and reproducible across the two categories for K, Mg, Zn, Mn, and Cu, and the vast majority of the HorRat values for both repeatability and reproducibility were within the acceptable range. However, a large number of soils in both the weighed and scooped categories displayed unacceptable HorRat values for the reproducibility of Ca and Fe, indicating that the M3 is not suitable for the extraction and quantitation of Ca and Fe in soils. The results of this study indicate that the M3 method for the determination of K, Mg, Zn, Mn, and Cu in soils is both accurate and precise when standardized procedures are used. The method has been proven to be suitable for use as a reference method for testing soil materials for extractable P, K, Mg, Zn, Mn, and Cu. Further study may be needed to confirm the suitability of the M3 method for Ca and Fe.

Interlaboratory validation of the Mehlich 3 method for extraction of plant-available phosphorus.

The Mehlich 3 (M3) method is widely used for extraction of plant-available phosphorus (P) from soil over a wide range of pH values. The method is also used by many laboratories to determine multiple plant-available nutrients simultaneously. However, this method has not been statistically validated within and among laboratories. The objective of this study was to determine the repeatability (within-laboratory performance) and reproducibility (among-laboratories performance) of the M3 method by using a wide variety of soils. An in-house homogeneity test was conducted for 10 soils. Three replicates of each of the 10 soils were sent to 26 domestic and international laboratories primarily for P analysis. Samples were scooped, weighed, or both scooped and weighed for extraction. The P in extracts was quantified by the participating laboratories by using inductively coupled plasma-atomic emission spectrometry (ICP-AES) or colorimetrically. For the scooped samples analyzed colorimetrically, the repeatability relative standard deviation (RSDr) ranged from 2.07 to 12.1%; the RSDr ranged from 2.2 to 21.4% for the scooped samples analyzed by ICP-AES. For the weighed samples analyzed colormetrically, the RSDr values were 1.09-9.34%, and for the weighed samples analyzed by ICP-AES, they were 1.70-5.76%. For the reproducibility data, the RSDR values ranged from 6.85 to 50.8% for the scooped-colorimetry category, from 6.95 to 73.9% for the scooped-ICP-AES category, from 7.19 to 42.6% for the weighed-colorimetry category, and from 5.29 to 35.9% for the weighed-ICP-AES category. The greatest RSD values were associated with the Susitna soil, which had the smallest concentration of extractable P. Because of the relatively small concentration of P in this soil, the laboratories were attempting to measure solution concentrations that were close to the detection limits. The Horwitz ratios (HorRat) were also used to evaluate the repeatability, HorRat(r), and reproducibility, HorRat(R). Overall, the M3 P method appears to be both repeatable and reproducible across the 4 categories, and the vast majority of the HorRat values for both repeatability and reproducibility were within the acceptable range. The results of this study indicate that the M3 P method for the determination of plant-available P in soil is both accurate and precise when standardized procedures are used. The method has been shown to be suitable for use as a reference method for testing soil materials for extractable P.

Evaluating the contribution of soil properties to modifying lead phytoavailability and phytotoxicity.

Soil properties affect Pb bioavailability to human and ecological receptors and should be considered during ecological risk assessment of contaminated soil. We used path analysis (PA) to determine the relative contribution of soil properties (pH, organic C [OC], amorphous Fe and Al oxides [FEAL], and cation-exchange capacity [CEC]) in modifying Pb bioavailability. The response of biological endpoints (bioaccumulation and dry matter growth [DMG]) of lettuce (Lactuca sativa) grown on 21 Pb-spiked (2,000 mg/kg) soils were determined. Lettuce tissue Pb ranged from 3.22 to 233 mg/kg, and relative DMG ranged from 2.5 to 88.5% of their respective controls. Simple correlation showed strong relationships between CEC and OC (p < 0.01) and weaker relationships between pH and FEAL (p < 0.05) and Pb bioaccumulation. Results of PA suggest that soil pH increased the negative surface charge of organic matter and clay, thereby increasing CEC and decreasing Pb bioaccumulation. Also, the direct effect of OC on tissue Pb can be attributed to formation of surface Pb complexes by organic matter functional group ligands. Increased OC and/or CEC reduced Pb solubility and bioavailability in the 21 soils in the present study. The relative importance of soil properties likely will vary between studies employing different soils. Soil properties should be considered during the ecological risk assessment of metal in contaminated soils. Path analysis is useful for ecological studies involving soils with a wide range of physicochemical properties and can assist in site risk assessment of metals and remediation decisions on contaminated sites.