Sludge-based candidate reference materials for enhanced quality control of particulate processes in total organic carbon analysis for wastewater1.

Accurate analyses of total organic carbon (TOC) encompassing particulate organic carbon in wastewater are key for evaluating the behavior of particulate organic contaminants and maintaining the carbon mass balance throughout the wastewater treatment process. This study was conducted to develop candidate reference materials of environmental origin from excess sludge collected from wastewater treatment facilities, primarily receiving industrial wastewater and livestock manure as the main sources. Homogeneity and stability assessments for total carbon (TC) and TOC were conducted in the particle samples following the standardized procedures of ISO Guide 35 and ISO 13258. The results showed that high inorganic carbon (IC) content in particles, such as YJ(500) (IC: 29%), rendered them unsuitable for TOC quality control (QC), as they increased uncertainty in both homogeneity and stability assessments. Additionally, a13C NMR analysis revealed that samples with a high (O-alkyl)/(C-H-alkyl) ratio in their carbon structures exhibited relatively low stability. Through the homogeneity and stability assessments, a particle sample, YJ(100), was selected as the reference material (RM); the assigned values were as follows: 30.78% for TC and 27.94% for TOC, with uncertainties of 0.01% and 1.1%, respectively. Furthermore, considering sample transportation conditions, the safe storage period for the RM particles was determined to be 2 weeks under harsh conditions (at 40 °C). In our inter-laboratory test (n = 8) using the particle samples, we confirmed that the particle samples can effectively enhance particle processing QC and validate a proposed suspended solids pretreatment method. This study showcases valuable environmental particle sample production and evaluation, offering potential advancements in the QC of TOC analysis for wastewater samples.

Identification of the cause of the difference among TOC quantitative methods according to the water sample characteristics.

Total organic carbon (TOC) analysis with accurate determination of particulate organic carbon (POC) content in suspended solids (SS) containing water is critical for evaluating the environmental impact of particulate organic pollutants in water and calculating the carbon cycle mass balance. TOC analysis is divided into the non-purgeable organic carbon (NPOC) and differential (known as TC-TIC) methods; although the selection of method is greatly affected by the sample matrix characteristics of SS, no studies have investigated this. This study quantitatively evaluates the effect of SS containing inorganic carbon (IC) and purgeable organic carbon (PuOC), as well as that of sample pretreatment, on the accuracy and precision of TOC measurement in both methods for various environmental water sample types (12 wastewater influents and effluents and 12 types of stream water). For influent and stream water with high SS, the TC-TIC method expressed 110-200 % higher TOC recovery than that for the NPOC method due to POC component losses in SS owing to its conversion into PuOC during sample pretreatment (using ultrasonic) and subsequent loss in the NPOC purging process. Correlation analysis confirmed that particulated organic matter (POM, mg/L) content in SS directly affected this difference (r > 0.74, p < 0.01, n = 24); for POC water samples (those containing >10 mg/L of POM) featuring purgeable dissolved organic matter, TC-TIC was appropriate in securing TOC measurement accuracy. In constrast, in effluent and stream water with low SS (i.e., < ∼5 mg/L) and high IC (> 70 %) contents, the TOC measurement ratios (TC-TIC/NPOC) of both methods were similar, between 0.96 and 1.08, suggesting that NPOC is appropriate for improving precision. Our results provide useful basic data to establish the most reliable TOC analysis method considering SS contents and its properties along with the matrix characteristics of the sample.