Improving Carbonate Equilibria-Based Estimation of pCO2 in Anthropogenically Impacted River Systems

Estimating riverine carbon dioxide (CO2) emissions has been constrained by lacking field measurements of the partial pressure of CO2 (pCO2) and inaccuracies in calculating pCO2 using carbonate equilibria-based models such as CO2SYS. To evaluate potential errors in applying the carbonate equilibria-based pCO2 calculation to river systems affected by monsoon rainfall and water pollution, we compared pCO2 values calculated using CO2SYS and those measured by headspace equilibration in five Asian rivers (Ganges, Mekong, Yangtze, Yellow, and Han rivers) undergoing various water pollution stages. Across the five rivers, calculated and measured pCO2 values exhibited larger discrepancies during the monsoon season, particularly in the low pH range, while in the Han River mismatches were also noticeable during the dry season. In the Han River, pH was negatively correlated with dissolved organic carbon (DOC) during the monsoon, indicating organic acids flushed from soils during rainfalls as a key factor for overestimated pCO2 at sites with low pH and alkalinity, whereas dry-season overestimation of pCO2 may be ascribed to non-carbonate alkalinity including organic acids and inorganic anions delivered by wastewater effluents or sporadic rainfalls. The four large rivers exhibited a positive correlation between pH and DOC in tributaries during the monsoon season, indicating that DOC flushed from soils may be diluted by monsoonal floods to such a degree as to exert little influence on pH and hence pCO2. Therefore, the monsoonal overestimation of pCO2 at sites with low pH and alkalinity warrants further investigation of other factors than non-carbonate alkalinity to explain the increased sensitivity of pCO2 to subtle changes in acidity and buffering. These results illustrate the importance of direct measurements of pCO2 in highly polluted rivers, especially during the monsoon season. For river systems lacking pCO2 measurements, we suggest that carbonate equilibria-based models be complemented with corrective measures: 1) presenting pCO2 values calculated from low pH values (pH < 6.5 for monsoon and pH < 6.3 for dry season) together with the pH range to warn potential overestimation; 2) using pre-established regressions between measured pCO2 and environmental variables to correct pCO2 values, particularly during wet periods when large changes in pH and acid buffering are expected.

Chemical Composition and Metal Speciation in Porewaters from the Upper Qu’Appelle River Basin, Saskatchewan

Porewater samples from the upper Qu’Appelle River basin in Saskatchewan, Canada, were analyzed to obtain metal, inorganic ligand and amino add profiles. These data were used to compute the aqueous speciation of the metals in each porewater using the computer program GEOCHEM-PC. The porewaters were classified as slightly to moderately saline. Metal concentrations reflected both the geology of the drainage basin and the impact of anthropogenic activities. Whereas K and Na were present almost entirely as the free aquo ions, carbonate equilibria dominated the speciation of Ca. Mg and Mn (the predominant metal ligand species were of the type MCO3 (s). MCO30. and MHCO3+). Trace metal concentrations were generally within the ranges reported for non-polluted freshwater systems. Whereas the speciation of the trace metals Cr(III) and Co(II) was dominated by carbonate equilibria, Hg(II)-, Zn(II)- and Fe(II)-speciation was dominated by hydroxy-metal complexes of the type M(OH)+ and M(OH)2°. The speciation of Fe(III) was dominated by Fe(OH)3 (s). In porewaters with high chloride concentrations (> 2 mM), however, significant amounts of Hg(II) were bound as HgCl20 and HgClOH0. The aqueous speciation of Al was dominated by Al(OH)4− and Al2Si2O4(OH)6 (s). Total concentrations of dissolved free amino acids varied from 15.21 to 25.17 umole L−1. The most important metal scavenging amino acids were histidine (due to high stability constants for the metal-histidine complexes) and tryptophan (due to its relatively high concentration in the porewaters. i.e., 5.96 to 7.73 umole L−1). Secondary concentrations of various trace metal-amino add complexes were computed for all the porewaters, but metal-amino acid complexes dominated the speciation of Cu(II) in all the porewaters and Ni(II) in two of the porewaters.