The biomonitoring of atmospheric mercury (Hg) is an important topic in the recent scientific literature given the cost-benefit advantage of obtaining indirect measurements of gaseous Hg using biological tissues. Lichens, mosses, and trees are the most commonly used organisms, with many standardized methods for some of them used across European countries by scientists and pollution regulators. Most of the species used the uptake of gaseous Hg (plant leaves), or a mixture of gaseous and particulate Hg (mosses and lichens), but no method is capable of differentiating between main atmospheric Hg phases (particulate and gaseous), essential in a risk assessment. The purpose of this work was to evaluate different uptake patterns of biological tissues in terms of atmospheric Hg compounds. To accomplish this, the feasibility of two plant tissues from a tree commonly found in urban environments has been evaluated for the biomonitoring of gaseous Hg species in a Hg mining environment. Sampling included leaves and barks from Platanus hispanica and particulate matter from the atmosphere of the urban area around Almadén (south-central Spain), while analytical determinations included data for total Hg concentrations in biological and geological samples, Hg speciation data and total gaseous Hg (TGM). The results allowed us to identify the main Hg compounds in leaves and bark tissues and in atmospheric particulate matter, finding that leaves bioaccumulated only gaseous Hg (Hg0 and Hg2+), preferably during daylight hours, whereas the barks accumulated a combination of TGM and particulate bound Hg (PBM) during the day and at night. Subsequent merging of the atmospheric Hg speciation data obtained from leaves and barks allowed indicative maps of the main sources of TGM and PBM emissions to be obtained, thereby perfectly delimiting the main TGM and PBM sources in the urban area around Almadén. This method complements TGM biomonitoring systems already tested with other urban trees, adding the detection of PBM emission sources and, therefore, biomonitoring all Hg species present in the atmosphere. Scenarios other than mining sites should be evaluated to determine the utility of this method for Hg biospeciation in the atmosphere.