Investigation of pollution history in XKS mining area in China using dendrochronology and LA-ICP-MS

Highlights: • Elemental peaks reveal Sb and Zn pollution is noticeable during 1986–1990. • Antimony levels are elevated in trees near the north mine and mine tailing pond. • Average tree core Sb levels ranged from 18.8 to 4.8 mg/kg near mine sites. • LA-ICP-MS is an elegant analytical method for elemental dendrochronology. Past pollution episodes and the intensity of mining activity in a contaminated region can be unraveled, using archived elemental information in tree rings. Elemental dendrochronology can be utilized with laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to make a timeline of metal(loid)s uptake in trees. In this study, six tree core samples from five tree species were collected around the XKS antimony mine region in Hunan, China, which is impacted by metal pollution: NM1 shuitong (Camptotheca acuminate L.), M1 shuitong (Camptotheca acuminate L.), G1 xiangchun (Toona sinensis L.), J2 wutong (Firmiana platanifolia L.), BSN kulian (Melia azedarach L.), and MT1 zhang (Cinnamomum camphora L.). Tree cores were dated by counting annual rings, and concentrations of As, Ca, Pb, Sb, and Zn were determined using LA-ICP-MS. Results demonstrate that the highest concentrations of Sb are present in the areas closer to mining activity: NM1 - north mine (shuitong), MT1 - mine tailing site (zhang), and BSN - between south and north mine (kulian) tree cores have average Sb concentrations of 18.8 mg/kg, 13 mg/kg, and 4.8 mg/kg, respectively. In comparison, at the village sites located farther away from the mining areas, G1 xiangchun, J2 wutong, and M1 shuitong have average Sb concentrations of 0.69 mg/kg, 0.57 mg/kg, and 0.66 mg/kg, respectively. NM1 shuitong, G1 xiangchun, and MT1 zhang all have large Sb and Zn peaks around 1986, while BSN kulian has larger Sb peaks slightly later around 1988–1990. J2 wutong has Sb peaks somewhat earlier, at 1977 and 1980. Unlike the others trees, M1 shuitong has greater Sb concentrations in more recent years (2009, 2015–2016) demonstrating Sb pollution.