This paper reports the development of an innovative sample preparation method for the determination of the chemical oxygen demand (COD) in heterogeneous solid or semisolid samples, with high suspended solids and COD concentrations, using an optimized closed reflux colorimetric method. The novel method, named solid dilution (SD), is based on a different technique of sample preparation, diluting the sample with magnesium sulfate (MgSO(4)) previous to COD determination. With this, it is possible to obtain a solid homogeneous mixture much more easily analyzable. Besides, a modification of concentration and ratio of reagents was optimized to make the closed reflux colorimetric method suitable for complex substrates with COD levels ranging from 5 to 2500 g O(2) kg(-1) TS. The optimized method has been tested with potassium hydrogen phthalate (KHP) as primary solid standard and using different solid or semiliquid substrates like pig slaughterhouse waste and sewage sludge, among others. Finally, the optimized method (SD/SM-CRC) was intensively tested in comparison to the standard titrimetric method (SM-ORT) using different certified reference materials (CRM). The developed method was found to give higher accuracy, 1.4% relative standard deviation (RSD) vs 10.4%, and bias of 2.8% vs 8.0%, in comparison to the standard open reflux titrimetric method.

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A b s t r a c tThe performance parameters of volatile fatty acids (VFAs) measurements were assessed for the first time by a multi-laboratory validation study among 13 laboratories. Two chromatographic techniques (GC and HPLC) and two quantification methods such as external and internal standard (ESTD/ISTD) were combined in three different methodologies GC/ESTD, HPLC/ESTD and GC/ISTD. Linearity evaluation of the calibration functions in a wide concentration range (10-1000 mg/L) was carried out using different statistical parameters for the goodness of fit.Both chromatographic techniques were considered similarly accurate. The use of GC/ISTD, despite showing similar analytical performance to the other methodologies, can be considered useful for the harmonization of VFAs analytical methodology taking into account the normalization of slope values used for the calculation of VFAs concentrations. Acceptance criteria for VFAs performance parameters of the multi-laboratory validation study should be established as follows: (1) instrument precision (RSDINST≤ 1.5%); (2) linearity (R 2 ≥ 0.998; RSDSENSITIVITY≤ 4%; REMAX≤ 8%; REAVER≤3%); (3) precision (RSD ≤ 1.5%); (4) trueness (recovery of 97-103%);(5) LOD (≤3 mg/L); and (6) LOQ (10 mg/L).