Evaluation of a rapid physical-chemical method for the determination of extant soluble COD

Characterization of total chemical oxygen demand (COD) in wastewater is critical for accurate modeling of constituent biotransformation steps. We evaluated the accuracy and precision of a commonly used soluble COD determination technique (coagulation using ZnSO4 at pH 10.5) in relation to three other physical-chemical separation techniques: destabilization with a non-hydrolyzing trivalent cation (LaCl3), sequential filtration, and ultracentrifugation. Samples of deionized water and domestic wastewater were spiked with aliquots of synthetic soluble COD and recoveries using the different separation methods were compared. Although mechanisms of coagulation using LaCl3 and ZnSO4 are different, the mean COD recoveries using these methods were in close agreement. Further, sorption of soluble COD onto zinc hydroxide precipitate flocs appeared to be negligible. The two coagulation methods yielded statistically different (p = 0.05) soluble COD values when applied to nine independent wastewater samples (obtained on nine different days). but the difference was less than 10%. The COD quantified by the coagulation techniques corresponded most closely with the < 1,000 Da molecular weight fraction defined as "truly soluble COD". Centrifugation of wastewater samples amended with mercuric chloride (HgCl2) at 10 mg/L overestimated the soluble COD concentration. Our results confirm that coagulation using either ZnSO4 or LaCI3 is appropriate for the rapid determination of soluble COD fraction in wastewater matrices.