We found inconsistencies in the commonly used data for chlorophyll analysis in 80% acetone. Recently developed extinction coefficients for chlorophyll b in NN-dimethylformamide (DMF) based on values from 80% acetone are low as a result of these inconsistencies. We determined extinction coefficients of chlorophyll a (Chl a) and chlorophyll b (Chi b) in DMF for wavelengths of 618 to 665 nanometers. The (2) and soybeans (3).The extinction coefficients necessary for the quantification of Chl a, Chl b, and total Chl in DMF were determined by Moran (5). The extinction coefficient for Chl b was determined using the coefficient for Chl b in 80% actone determined by MacKinney (4). This coefficient is not consistent with the results of Vernon (10) which suggest that if the equations developed by Moran (5) are used, then the calculations for Chl b content may be off by more than 10%. An error also would be introduced into the calculation of total Chl. One objective of this study was to determine which extinction coefficients were most consistent for Chl a and b in 80% acetone and DMF.

The chemical speciation of inorganic mercury (Hg) is to a great extent controlling biologically mediated processes, such as mercury methylation, in soils, sediments, and surface waters. Of utmost importance are complexation reactions with functional groups of natural organic matter (NOM), indirectly determining concentrations of bioavailable, inorganic Hg species. Two previous extended X-ray absorption fine structure (EXAFS) spectroscopic studies have revealed that reduced organic sulfur (S) and oxygen/ nitrogen (O/N) groups are involved in the complexation of Hg(II) to humic substances extracted from organic soils. In this work, covering intact organic soils and extending to much lower concentrations of Hg than before, we show that Hg is complexed by two reduced organic S groups (likely thiols) at a distance of 2.33 A in a linear configuration. Furthermore, a third reduced S (likely an organic sulfide) was indicated to contribute with a weaker second shell attraction at a distance of 2.92-3.08 A. When all high-affinity S sites, corresponding to 20-30% of total reduced organic S, were saturated, a structure involving one carbonyl-O or amino-N at 2.07 A and one carboxyl-O at 2.84 A in the first shell, and two second shell C atoms at an average distance of 3.14 A, gave the best fit to data. Similar results were obtained for humic acid extracted from an organic wetland soil. We conclude that models that are in current use to describe the biogeochemistry of mercury and to calculate thermodynamic processes need to include a two-coordinated complexation of Hg(II) to reduced organic sulfur groups in NOM in soils and waters.

Sulfur K‐edge x‐ray absorption near‐edge structure spectroscopy (XANES) was used to identify multiple organic S oxidation states in aquatic and soil humic substances. The XANES results suggest that S in humic substances exists in four major oxidation groups similar to sulfate ester, sulfonate, sulfoxide, and thiol‐sulfide. Thiol S cannot be separated from sulfide S and must be considered as a single thiol‐sulfide peak. The second derivative spectra suggest the existence of thiophene and sulfone S. The relative quantities of each major S form in our humic samples were estimated based on the integrated cross section of each s → p transition peak corresponding to different S oxidation states in the S K‐edge XANES spectra. The XANES results of the four humic samples used in this study appear to reflect the environmental settings where the humic substances originally formed. The percentage of the most reduced organic S (thiol‐sulfide and possibly thiophene) in humic substances follows the sequence: aquatic samples > organic soil sample > mineral soil sample. The percentage of most oxidized S (sulfate group) was the greatest in the humic substance from a mineral soil and the lowest in the aquatic humic substances.