Multi-element analysis of unfiltered samples in river water monitoring-digestion and single-run analyses of 67 elements.

Routine analysis of inorganic analytes in whole water samples from rivers (unfiltered river water) is rarely reported in scientific publications. However, this sample type is valuable and often used in long-term monitoring, regulation, and catchment element budgets, as it includes the dissolved, colloidal, and particulate fraction in one sample type. Preservation measures are not needed and solid-liquid partitioning can be disregarded, which simplifies automated sampling and storage procedures. In this study, we provide several digestion protocols for whole water samples from rivers and the subsequent multi-element analysis of 67 major, minor, and trace elements: Li, Be, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ru, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Ir, Pt, Au, Hg, Tl, Pb, Bi, Th, U. In the absence of whole water reference materials for inorganic analytes, we introduce simulated whole water samples by suspending sediment reference materials as quality control measures. The applicability for improved routine water quality monitoring was successfully tested on samples from different rivers revealing variations of the element fingerprints over time.