The what, how, why, and when of dendrochemistry: (paleo)environmental information from the chemical analysis of tree rings.

The chemical analysis of tree rings has attracted the interest of researchers in the past five decades in view of the possibility of exploiting this biological indicator as a widely available, high-resolution environmental archive. Information regarding the surrounding environment can be derived either by directly measuring environmental variables (nutrient availability, presence of pollutants, etc.) or by exploiting proxies (e.g. paleoclimatic and paleoenvironmental reconstructions). This review systematically covers the topic and provides a critical view on the reliability of dendrochemical information. First, we introduce the determinable chemical species, such as major elements, trace metals, isotopic ratios, and organic compounds, together with a brief description of their uptake mechanisms and functions in trees. Subsequently, we present the possibilities offered by analytical techniques in the field of tree ring analysis, focusing on direct methods and recent developments. The latter strongly improved the details of the accessible information, enabling the investigation of complex phenomena associated with plant life and encouraging the direct analysis of new analytes, particularly minor organic compounds. With regard to their applications, dendrochemical proxies have been used to trace several processes, such as environmental contamination, paleoclimate reconstruction, global environmental changes, tree physiology, extreme events, ecological trends, and dendroprovenance. Several case studies are discussed for each proposed application, with special emphasis on the reliability of tracing each process. Starting from the reviewed literature data, the second part of the paper is devoted to the critical assessment of the reliability of tree ring proxies. We provide an overview of the current knowledge, discuss the limitations of the inferences that may be drawn from the dendrochemical data, and provide recommendations for the best practices to be used for their validation. Finally, we present the future perspectives related to the advancements in analytical instrumentation and further extension of application fields.