The use of zinc (Zn) isotope ratios as a tracer of anthropogenic contamination has been assessed using an extensive collection of river water samples from the Seine River basin (France) collected between 2004 and 2007. The 66Zn/64Zn ratios (expressed as delta66Zn) of dissolved Zn have been measured by MC-ICP-MS after chemical separation of Zn using an improved technique adapted to large volumes of water. Significant isotopic variations (0.07-0.58 per thousand) occur along a transect from pristine areas of the Seine basin to the estuary and with time in Paris, and are coherent with the Zn enrichment factor. Dissolved Zn in the Seine River displays conservative behavior, making Zn isotopes a good tracer of the different sources of contamination. Dissolved Zn in the Seine River is essentially of anthropogenic origin (> 90%) compared to natural sources (< 7%). Roof leaching from Paris conurbation is a major source of Zn, characterized by low delta66Zn values that are distinct from other natural and anthropogenic sources of Zn. Our study highlights the absence of distinctive delta66Zn signatures of fertilizer, compost or rain in river waters of rural areas, and therefore suggests the strong retention of Zn in the soils of the Basin. Our study demonstrates that Zn isotope ratios will be a powerful new tool to trace pathways of anthropogenic Zn in the environment.

Abstract. The critical zone (CZ), the dynamic living skin of the Earth, extends from the top of the vegetative canopy through the soil and down to fresh bedrock and the bottom of the groundwater. All humans live in and depend on the CZ. This zone has three co-evolving surfaces: the top of the vegetative canopy, the ground surface, and a deep subsurface below which Earth's materials are unweathered. The network of nine CZ observatories supported by the US National Science Foundation has made advances in three broad areas of CZ research relating to the co-evolving surfaces. First, monitoring has revealed how natural and anthropogenic inputs at the vegetation canopy and ground surface cause subsurface responses in water, regolith structure, minerals, and biotic activity to considerable depths. This response, in turn, impacts aboveground biota and climate. Second, drilling and geophysical imaging now reveal how the deep subsurface of the CZ varies across landscapes, which in turn influences aboveground ecosystems. Third, several new mechanistic models now provide quantitative predictions of the spatial structure of the subsurface of the CZ.Many countries fund critical zone observatories (CZOs) to measure the fluxes of solutes, water, energy, gases, and sediments in the CZ and some relate these observations to the histories of those fluxes recorded in landforms, biota, soils, sediments, and rocks. Each US observatory has succeeded in (i) synthesizing research across disciplines into convergent approaches; (ii) providing long-term measurements to compare across sites; (iii) testing and developing models; (iv) collecting and measuring baseline data for comparison to catastrophic events; (v) stimulating new process-based hypotheses; (vi) catalyzing development of new techniques and instrumentation; (vii) informing the public about the CZ; (viii) mentoring students and teaching about emerging multidisciplinary CZ science; and (ix) discovering new insights about the CZ. Many of these activities can only be accomplished with observatories. Here we review the CZO enterprise in the United States and identify how such observatoriesPublished by Copernicus Publications on behalf of the European Geosciences Union. 842 S. L. Brantley et al.: Designing a network of critical zone observatories could operate in the future as a network designed to generate critical scientific insights. Specifically, we recognize the need for the network to study network-level questions, expand the environments under investigation, accommodate both hypothesis testing and monitoring, and involve more stakeholders. We propose a driving question for future CZ science and a "hubs-and-campaigns" model to address that question and target the CZ as one unit. Only with such integrative efforts will we learn to steward the life-sustaining critical zone now and into the future.