X-ray absorption fine structure evidence for amorphous zinc sulfide as a major zinc species in suspended matter from the Seine River downstream of Paris, Ile-de-France, France.

Zinc is one of the most widespread trace metals (TMs) in Earth surface environments and is the most concentrated TM in the downstream section of the Seine River (France) due to significant anthropogenic input from the Paris conurbation. In order to better identify the sources and cycling processes of Zn in this River basin, we investigated seasonal and spatial variations of Zn speciation in suspended particulate matter (SPM) in the oxic water column of the Seine River from upstream to downstream of Paris using synchrotron-based extend X-ray absorption fine structure (EXAFS) spectroscopy at the Zn K-edge. First-neighbor contributions to the EXAFS were analyzed in SPM samples, dried and stored under a dry nitrogen atmosphere or under an ambient oxygenated atmosphere. We found a sulfur first coordination environment around Zn (in the form of amorphous zinc sulfide) in the raw SPM samples stored under dry nitrogen vs an oxygen first coordination environment around Zn in the samples stored in an oxygenated atmosphere. These findings are supported by scanning electron microscopy and energy dispersive X-ray spectrometry observations. Linear combination fitting of the EXAFS data for SPM samples, using a large set of EXAFS spectra of Zn model compounds, indicates dramatic changes in the Zn speciation from upstream to downstream of Paris, with amorphous ZnS particles becoming dominant dowstream. In contrast, Zn species associated with calcite (either adsorbed or incorporated in the structure) are dominant upstream. Other Zn species representing about half of the Zn pool in the SPM consist of Zn-sorbed on iron oxyhydroxides (ferrihydrite and goethite) and, to a lesser extent, Zn-Al layered double hydroxides, Zn incorporated in dioctahedral layers of clay minerals and Zn sorbed to amorphous silica. Our results highlight the importance of preserving the oxidation state in TM speciation studies when sampling suspended matter, even in an oxic water column.

Validation of IMERG precipitation in Africa.

Our understanding of hydroclimatic processes in Africa has been hindered by the lack of in-situ precipitation measurements. Satellite-based observations, in particular, the TRMM Multi-Satellite Precipitation Analysis (TMPA) have been pivotal to filling this void. The recently-released Integrated Multi-satellitE Retrievals for GPM (IMERG) project aims to continue the legacy of its predecessor, TMPA, and provide higher resolution data. Here, we validate IMERG-V04A precipitation data using in-situ observations from the Trans-African Hydro-Meteorological Observatory (TAHMO) project. Various evaluation measures are examined over a select number of stations in West and East Africa. In addition, continent-wide comparisons are made between IMERG and TMPA. The results show that the performance of the satellite-based products varies by season, region and the evaluation statistics. Precipitation diurnal cycle is relatively better captured by IMERG than TMPA. Both products exhibit a better agreement with gauge data in East Africa and humid West Africa than in the Southern Sahel. However, a clear advantage for IMERG is not apparent in detecting the annual cycle. Although all gridded products used here reasonably capture the annual cycle, some differences are evident during the short rains in East Africa. Direct comparison between IMERG and TMPA over the entire continent reveals that the similarity between the two products is also regionally heterogeneous. Except for Zimbabwe and Madagascar, where both satellite-based observations present a good agreement, the two products generally have their largest differences over mountainous regions. IMERG seems to have achieved a reduction in the positive bias evident in TMPA over Lake Victoria.