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Air quality is a worldwide problem. Thousands of chemicals appear in the atmosphere from various sources and numerous atmospheric reactions. Unfortunately, only few organic compounds are monitored regularly. Therefore, an important task involves discovering the most important pollutants for particular regions. Direct measurements of atmospheric contaminants are not always efficient as air represents an extremely dynamic medium. Alternative analysis of precipitations becomes more popular. The present work represents comprehensive analysis of the rainwater contaminants in Valparaiso, Chile. Rainwater samples collected at the same location every June during 2002-2012 were analyzed using GC×GC-HRMS to detect and identify as many as possible organic pollutants to select the most relevant emerging pollutants and estimate the quantitative changes in pollutants levels over 10 years.