Determination of molecular weight parameters of native and, in particular, technical lignins are based on size exclusion chromatography (SEC) approaches. However, no matter which approach is used, either conventional SEC with a refractive index detector and calibration with standards or multi‐angle light scattering (MALS) detection at 488 nm, 633 nm, 658 nm, or 690 nm, all variants can be severely erroneous. The lack of calibration standards with high structural similarity to lignin impairs the quality of the molar masses determined by conventional SEC, and the typical fluorescence of (technical) lignins renders the corresponding MALS data rather questionable. Application of MALS detection at 785 nm by using an infrared laser largely overcomes those problems and allows for a reliable and reproducible determination of the molar mass distributions of all types of lignins, which has been demonstrated in this study for various and structurally different analytes, such as kraft lignins, milled‐wood lignin, lignosulfonates, and biorefinery lignins. The topics of calibration, lignin fluorescence, and lignin UV absorption in connection with MALS detection are critically discussed in detail, and a reliable protocol is presented. Correction factors based on MALS measurements have been determined for commercially available calibration standards, such as pullulan and polystyrene sulfonate, so that now more reliable mass data can be obtained also if no MALS system is available and these conventional calibration standards have to be resorted to.

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31 P nuclear magnetic resonance (NMR) based on the derivatization reagent 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane is a common approach for the hydroxyl group determination of lignins, but the results are sometimes less reproducible compared to other methods. In the present work, common pitfalls in 31 P NMR analysis of kraft lignin (KL) and lignosulfonates (LS) are addressed and the results are compared to those obtained by 1 H NMR spectroscopy. Several experimental parameters are revisited in terms of the reliability of the obtained data, such as the choice of relaxation delay, internal standards, and the best solution technique for the 31 P NMR analysis of LS. For the first time, 31 P NMR data of LS are presented based on a new dissolution protocol. The analytical data of a set of lignins consisting of three KLs, one LS, and one milled wood lignin are presented based on the optimized 31 P NMR approach.Keywords: 1 H NMR of lignin, 31 P NMR of lignin, Indulin AT kraft lignin, internal standard for NMR, lignosulfonate, milled wood lignin (MWL), quantification of hydroxyl groups

Technical lignins (waste products obtained from wood pulping or biorefinery processes) have so far required lengthy analysis procedures and different eluents for molar-mass analysis by gel permeation chromatography (GPC). This challenge has become more pressing recently since attempts to utilize lignins have increased, leading to skyrocketing numbers of samples to be analyzed. A new approach, which uses the eluent DMSO/LiBr (0.5 % w/v) and converts lignosulfonate salts into their acidic form before analysis, overcomes these limitations by enabling measurement of all kinds of lignins (kraft, organosolv, soda, lignosulfonates) in the same size-exclusion chromatography (SEC) system without the necessity of prior time-consuming derivatization steps. In combination with ultra-performance liquid chromatography (UPLC), analysis times are shortened to one tenth of classical lignin GPC. The new approach is presented, along with a comparison of GPC and UPLC methods and a critical discussion of the analytical parameters.

In this study, a novel approach for isolation and purification of lignosulfonates from spent sulfite liquor was established.