The abatement of acid rain in Guizhou province, southwestern China: Implication from sulfur and oxygen isotopes

The high frequency of acid rain in southern China has captured public and official concern since 1980s. Subsequently, gas emission reduction measures have been implemented to improve the air quality. Variations in SO₂ emission intensities can influence the sulfur and oxygen isotopic compositions of sulfate in rainwater, since atmospheric sulfate is mainly formed via the oxidation of sulfur gases from natural and anthropogenic sources. To evaluate the impacts of emission reduction measures on atmospheric sulfate, the seasonal and long-term trends in stable isotopic compositions of sulfate in rainwater in Guizhou province, southwestern China have been investigated based on rainwater samples collected from June 2016 to June 2018 and literature investigation (2000–2010).The results reveal that coal combustion remains a major contributor to sulfate in rainwater, although its SO₂ emission has significantly decreased over the past two decades. The δ³⁴Sₛᵤₗfₐₜₑ and δ¹⁸Oₛᵤₗfₐₜₑ values in rainwater are negatively correlated and have significant seasonal changes. The seasonality in δ³⁴Sₛᵤₗfₐₜₑ has been interpreted as due to the changes in contributions of dimethyl sulfide and coal combustion, while the seasonal pattern of δ¹⁸Oₛᵤₗfₐₜₑ is consistent with that of δ¹⁸Owₐₜₑᵣ values, indicating sulfate in rainwater is mainly formed by heterogeneous oxidation of SO₂. Combined with the data from previous studies (Xiao and Liu, 2002; Liu, 2007; Xiao et al., 2009; Xiao et al., 2014), we found that the volume weighted mean δ³⁴S values of sulfate in rainwater in Guizhou province show a marked increase between 2001 and 2018, indicating that the ³⁴S-depleted SO₂ emission from coal combustion has declined during this period. Furthermore, the synchronous changes in δ³⁴S values, sulfate concentration and pH values of rainwater suggest that the frequency of acid rain in Guizhou province has dropped over the past two decades, which is likely to result from the emission reduction measures taken in Guizhou province.