Determination of carbonate-C in biochars

Abstract

Although carbonate-carbon (C), an integral part of biochar-C, contributes to the liming properties of that material, it also interferes with the estimation of the stable organic C fraction in biochars. In this study, four methods were compared in order to quantify the carbonate-C in biochars: two direct (a titrimetric procedure and thermogravimetric analysis, TGA), and two indirect (acid treatment with separation by filtration and acid fumigation). The titrimetric method showed a high recovery of added carbonate-C (average 98.8%, range 1.5–38 mg), and the standard deviations of carbonate-C for all biochars tested were <0.1% when 1 g of sample was used. The acid treatment with a filtration step overestimated the carbonate-C content (on average by a 4-fold increment) due to the loss of dissolved or fine particulate organic C during filtration. The acid fumigation method was suitable for biochars containing high amount of carbonate-C (>0.3% wt) and when the isotopic signature of organic C in biochars is to be determined. The TGA method (either in N2 or a dry air atmosphere) was reliable when calcite was the main carbonate form in biochars, but was inadequate for samples containing a considerable amount of whewellite and certain carbonate-bearing minerals (e.g. magnesite) that decompose at <600°C. Because more than half of the biochar samples investigated in the literature and in this study (58% of the 117 samples) contained <0.4% carbonate-C (and 38% of these contained no detectable carbonate-C), low-cost screening methods were developed to identify the biochars needed for carbonate-C analysis. For this purpose, two methods were proposed: (i) a manometric test; and (ii) a ratio between predicted fixed C : total C (FC/TC) and measured FC/TC, where predicted FC/TC was estimated using the following relationship: (FC/TC) = –0.1081(H/C)2 – 0.1794(H/C) + 1.0097, as derived from values obtained in the literature. A decision tree, including two steps (a screening step and a titrimetric procedure) could be used to determine accurately the carbonate-C in biochars.