Low-level summertime isoprene observed at a forested mountaintop site in southern China: implications for strong regional atmospheric oxidative capacity

Abstract

<p><strong>Abstract.</strong> To investigate the atmospheric oxidative capacity (AOC) in forested high mountain areas adjacent to the photochemistry-active Pearl River Delta (PRD) region in southern China, one-month online observations of isoprene and its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were conducted at a national background station in Nanling Mountains in summer 2016. The results showed that the observed daytime isoprene levels (<span class="inline-formula">377±46</span><span class="thinspace"></span>pptv) were significantly lower in comparison with other forest sites within and outside China, although the sampling site was surrounded with subtropical evergreen broad-leaved trees which are strong isoprene emitters. Also, high daytime (MVK<span class="thinspace"></span><span class="inline-formula">+</span><span class="thinspace"></span>MACR)<span class="thinspace"></span><span class="inline-formula">∕</span><span class="thinspace"></span>isoprene ratios (<span class="inline-formula">1.9±0.5</span>) were observed. Based on the observations, we hypothesized that the lower isoprene levels in the study forest might be attributable to a strong AOC in relation to the elevated regional complex air pollution. In further data analyses, high site-level concentrations of daytime OH (<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M5" display="inline" overflow="scroll" dspmath="mathml"><mrow><mn mathvariant="normal">7.3</mn><mo>±</mo><mn mathvariant="normal">0.5</mn><mo>×</mo><msup><mn mathvariant="normal">10</mn><mn mathvariant="normal">6</mn></msup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="72pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="4ab567b4f0685721a8163971485d3ef9"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-18-14417-2018-ie00001.svg" width="72pt" height="14pt" src="acp-18-14417-2018-ie00001.png"/></svg:svg></span></span><span class="thinspace"></span>molecules<span class="thinspace"></span>cm<span class="inline-formula">⁻³)</span> and nighttime <span class="inline-formula">NO₃</span> radicals (<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M8" display="inline" overflow="scroll" dspmath="mathml"><mrow><mn mathvariant="normal">6.0</mn><mo>±</mo><mn mathvariant="normal">0.5</mn><mo>×</mo><msup><mn mathvariant="normal">10</mn><mn mathvariant="normal">8</mn></msup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="72pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="84e4f19f6ef9fb8a310e5d91b89a673b"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-18-14417-2018-ie00002.svg" width="72pt" height="14pt" src="acp-18-14417-2018-ie00002.png"/></svg:svg></span></span><span class="thinspace"></span>molecules<span class="thinspace"></span>cm<span class="inline-formula">⁻³)</span> were estimated by using a photochemical box model incorporating the master chemical mechanism (PBM-MCM), and high regional mixing ratios of OH (<span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M10" display="inline" overflow="scroll" dspmath="mathml"><mrow><mn mathvariant="normal">19.7</mn><mo>±</mo><mn mathvariant="normal">2.3</mn><mo>×</mo><msup><mn mathvariant="normal">10</mn><mn mathvariant="normal">6</mn></msup></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="78pt" height="14pt" class="svg-formula" dspmath="mathimg" md5hash="df4d6b2943fd48a62a518aec8017dbf2"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-18-14417-2018-ie00003.svg" width="78pt" height="14pt" src="acp-18-14417-2018-ie00003.png"/></svg:svg></span></span><span class="thinspace"></span>molecules<span class="thinspace"></span>cm<span class="inline-formula">⁻³)</span> during 09:00–15:00<span class="thinspace"></span>LT were also obtained by applying a parameterization method with measured aromatic hydrocarbons. And besides, high initial mixing ratios (<span class="inline-formula">1213±108</span><span class="thinspace"></span>pptv) and short atmospheric reaction time (0.27<span class="thinspace"></span>h) of isoprene during the day were derived by a sequential reaction approach. All these indicate that isoprene was rapidly and highly oxidized in this forest, which supports our hypothesis. The study suggests that the complex air pollution in the PRD may have significantly elevated the background AOC of the adjacent forests, and probably affects the regional air quality and ecological environment in the long term. The feedback of forest ecosystems to the increasing AOC in southern China warrants further studies.</p>