Using hourly measurements to explore the role of secondary inorganic aerosol in PM2.5 during haze and fog in Hangzhou,China

This paper explores the role of the secondary inorganic aerosol （SIA） species ammonium,NH4＋,nitrate,NO3-,and sulfate,SO24-,during haze and fog events using hourly mass concentrations of PM2.5 measured at a suburban site in Hangzhou,China.A total of 546 samples were collected between 1 April and 8 May 2012.The samples were analyzed and classified as clear,haze or fog depending on visibility and relative humidity （RH）.The contribution of SIA species to PM2.5 mass increased to ～50％ during haze and fog.The mass contribution of nitrate to PM2.5 increased from 11％ during clear to 20％ during haze episodes.Nitrate mass exceeded sulfate mass during haze,while near equal concentrations were observed during fog episodes.The role of RH on the correlation between concentrations of SIA and visibility was examined,with optimal correlation at 60％-70％ RH.The total acidity during clear,haze and fog periods was 42.38,48.38 and 45.51 nmol m-3,respectively,indicating that sulfate,nitrate and chloride were not neutralized by ammonium during any period.The nitrate to sulfate molar ratio,as a function of the ammonium to sulfate molar ratio,indicated that nitrate formation during fog started at a higher ammonium to sulfate molar ratio compared to clear and haze periods.During haze and fog,the nitrate oxidation ratio increased by a factor of 1.6-1.7,while the sulfur oxidation ratio increased by a factor of 1.2-1.5,indicating that both gaseous NO2 and SO2 were involved in the reduced visibility.     

北京春季沙尘和霾期间气溶胶的对比模拟研究

利用气象模式WRF驱动区域空气质量模式RAQMS,模拟研究了2014年北京地区春季颗粒物及气溶胶化学组分的时空变化,对比分析了沙尘期（3月17日、29日）和霾期（3月25～27日）的天气形势、气象要素和气溶胶化学组分特征,比较了沙尘和人为气溶胶表面非均相化学反应对大气化学成分的影响及相对贡献。结果显示,模式对于气象要素、PM2.5、PM10及其化学组分具有较好的模拟能力,考虑了气溶胶表面非均相化学反应后明显提高了模式对PM2.5及气溶胶化学组分模拟的准确性。沙尘期间,沙尘对PM10质量浓度贡献占主导地位（50.7%）,对PM2.5的贡献与有机气溶胶（OM）和人为排放的一次颗粒物（PPM）相当;霾期间,硝酸盐NO₃?（25.6%）和OM（23.6%）对PM2.5的贡献最大,在PM10中NO₃?、PPM和OM的贡献相当。沙尘期,粗粒子明显增加,在PM10中所占比例与细粒子相当,为45.5%;霾期,细粒子占主导地位,占PM10质量浓度的85.6%。非均相化学反应使沙尘期间硫酸盐（SO₄2–）和NO₃–浓度分别增加16.9%和83.8%,使霾期间的SO₄2?和NO₃–浓度分别增加14.5%和45.0%。2014年3月,非均相化学反应使北京月均SO₂、NO₂、O₃、SO₄2?、NH₄+和NO₃?的浓度分别变化了?2.5%、?5.7%、?3.4%、11.7%、18.6%和58.5%,本文结果表明非均相化学反应对二次无机气溶胶的生成有重要贡献。     

北京雾、霾天细粒子质量浓度垂直梯度变化的观测

近年来北京城市区域雾霾天气显著增加,不仅严重影响工农业生产和交通运输,还严重影响人体健康.2007年夏秋季节,北京325 m气象塔8、80和240m平台梯度观测结果表明,雾、霾、晴三种典型天气状况大气细粒子质量浓度垂直分布各有特点,雾天(11月5～6日)低层浓度明显偏高,6日从低到高3层PM2.5(空气动力学直径小于等于2.5μ的大气气溶胶)浓度日均值分别为352.6±79.3、224.7±69.0、214.8±32.8 μg·m~(-3);霾天(8月19～20日)细粒子上下混合均匀,19日从低到高3层PM2.5浓度分别为89.8±29.3、88.9±29.8、90.0±31.7 μg·m~(-3);晴天(8月22～23日)细粒子昼夜变化明显,夜间在80 m高度出现明显分层,23日80 m以下平均值为32.6±13.1μg·m~(-3),240 m平均值为27.4±13.5μg·m~(-3).雾天细粒子主要来源于局地,霾天细粒子污染表现为时空分布十分均匀的城市群区域污染特征且污染物积累;连续晴天细粒子明显被清除.     

Chemical Composition of Summertime PM2.5 and Its Relationship to Aerosol Optical Properties in Guangzhou, China

Urban aerosols have a large effect on the deterioration of air quality and the degradation of atmospheric visibility.Characterization of the chemical composition of PM 2.5 and in situ measurements of the optical properties of aerosols were conducted in July 2008 at an urban site in Guangzhou,Southern China.The mean PM 2.5 concentration for the entire period was 53.7±23.2 μg m 3.The mean PM 2.5 concentration (82.7±25.4 μg m 3) on hazy days was roughly two times higher than that on clear days (38.8±8.7 μg m 3).The total water-soluble ion species and the total average carbon accounted for 47.9%±4.3% and 35.2%±4.5%,respectively,of the major components of PM 2.5.The increase of secondary and carbonaceous aerosols,in particular ammonium sulfate,played an important role in the formation of haze pollution.The mean absorption and scattering coefficients and the single scattering albedo over the whole period were 53±20 M m 1,226±111 M m 1,and 0.80±0.04,respectively.PM 2.5 had a high linear correlation with the aerosol extinction coefficient,elemental carbon (EC) was correlated with aerosol absorption,and organic carbon (OC) and SO 4 2 were tightly linked to aerosol scattering.     

北京冬季雾霾事件的气象特征分析

利用观测的气象要素和细颗粒物(即PM2.5)浓度资料,并结合中尺度数值天气模式WRF(Weather Research and Forecasting Model),对2013年1月北京地区雾霾污染期间天气条件和边界层气象特征进行了分析。模拟与观测对比表明,WRF模式可以较好地反映北京—天津—河北地区地面和高空主要气象要素的时空分布。对1月10~14日、27~31日两次重雾霾天气的分析表明,雾霾的形成是高浓度的大气颗粒物和特殊的气象条件共同作用的结果。小风或静风、稳定的大气层结,使大气扩散能力减弱,造成污染物堆积,偏南气流将周边污染物和水汽输送到北京,不仅增加了污染物浓度,而且有利于气溶胶吸湿增长,消光增强,使能见度下降,进而形成雾霾。     

广州地区旱季一次典型灰霾过程的特征及成因分析

通过研究2009年11月广州市气溶胶颗粒物质量浓度(PM10、PM2.5、PM1)、黑碳浓度、散射系数(Scatter)等大气成分要素,以及微波辐射计、激光雷达及风廓线雷达所探测的风、温、湿等边界层结构,统计分析广州旱季一次典型灰霾过程(2009年11月23—29日)中气溶胶颗粒物及其光学特性的时空变化特征,并配合天气形势背景、边界层结构对其形成原因进行详细分析。在典型灰霾过程中,黑碳浓度高达58.7μg/m3,散射系数高达1 902.7 Mm-1,PM10浓度高达423.5μg/m3,PM2.5浓度高达355.7μg/m3,PM1浓度高达286.5μg/m3。通过对同期的气象条件分析表明在广州地区旱季,区域性污染过程,特别是灰霾天气的形成具有以下三种气象条件:大气边界层高度较低;高压变性出海的天气形势与之密切相关;在偏东和偏南气流带来的高湿度环境下,气溶胶吸湿增长效应显著,导致出现严重灰霾天气。     

合肥市不同天气条件下大气气溶胶粒子理化特征分析

为探讨合肥市霾天气大气气溶胶粒子的组成及来源,在2012-2013年代表性月份用安德森分级采样器在合肥市区进行大气气溶胶粒子采样,并分析各样本中水溶性无机离子成分(NH4+、Mg2+、Ca2+、Na+、 K+、NO2-、NO3-、Cl-、SO42-)。根据同期气象资料把采样背景天气分为晴空、雾、霾、轻雾等4类,详细分析了这4种天气下大气细粒子(指PM2.1)和粗粒子(粒径大于2.1 μm部分)的浓度、组成以及主要离子组分的异同。结果表明:(1)观测期间晴空天多对应空气质量优良,雾、霾天对应轻度到重度污染,从晴空天到雾、霾天,PM2.1浓度大幅度上升,且其占总悬浮颗粒物(TSP)的比例显著上升。(2)从晴空天到雾、霾天,水溶性无机离子质量占PM2.1质量浓度的比例上升,分别为46%(晴空)、67%(霾)、61%(雾)、80%(轻雾)。PM2.1中水溶性无机离子浓度居前3位的雾、霾天是SO42-、NO3-和NH4+,晴空天为SO42-、Ca2+、NO3-。(3)与晴空天相比,霾天PM2.1中水溶性无机离子浓度变化倍数最大的是NO3-(为晴空的6.1倍,下同)、其次是NH4+(3.6倍)和SO42-(3.0倍);雾和轻雾天PM2.1中水溶性无机离子浓度变化最大的是NO3-(>10倍)、其次是NH4+(>5倍)和Cl-(>4.0倍)。(4)4种天气下,与人为污染有关的离子(SO42-、NO3-、Cl-、NH4+)尺度谱存在显著差异,呈双峰型、单峰型、三峰型等;而Ca2+的尺度谱无明显变化,基本上都呈双峰型。(5)在粒径3.3 μm以下,阳、阴离子平衡较好,随着尺度增大变差,且晴空天比雾、霾天差。主要阴离子浓度间、Cl-和Na+间的比值和相关性,在晴空天和雾、霾天差异较大。      

一次大雾天气下PM2.5二次无机粒子的数值模拟

利用多尺度空气质量模式系统（Models-3/CMAQ）对2002年12月1—3日北京及周边地区发生的一次大雾天气进行数值模拟,分析了大雾天气下PM2.5二次无机粒子的演变及其影响。结果表明,白天相对湿度降低,雾滴蒸发脱水后PM2.5二次无机粒子会悬浮在大气中;夜间在水汽凝结成雾滴的过程中,大量的PM2.5二次无机粒子提供了充足的凝结核,促进大雾天气的进一步发展。午后PM2.5二次无机粒子积聚及较高的相对湿度是造成北京及周边地区低能见度的重要原因,并推断该区域很可能是霾天气。     

Seasonal Variability of the Ion Composition,Phase State,and Mass Concentration of Aerosol in the Rural and Urban Atmosphere over Belgium (2001–2003)

Field data on the ion composition and mass concentration of aerosol in the rural (Wingene) and urban (Antwerp) regions of Belgium and the results of their thermodynamic analysis are presented. Ammonium nitrate and ammonium sulfate are found to be the major water-soluble components of aerosol particles. The seasonal variability of mass concentration, phase state, and ion composition of aerosol particles is largely determined by variations in temperature and relative humidity. It is shown that the content of ammonium nitrate and ammonium sulfate in PM2.5 is close to their thermodynamic equilibrium concentrations.     

秸秆燃烧对北京秋季气溶胶浓度和短波辐射影响的模拟研究

利用地面细颗粒物（PM2.5）浓度和气象常规观测资料、地基 AERONET观测资料、GFED生物质燃烧排放清单和大气化学—天气耦合模式WRF-Chem,模拟研究了华北地区2014年10月气象要素和大气污染物的时空演变,重点关注北京10月7～11日的一次重霾事件及其天气形势、边界层气象特征、输送路径、PM2.5及其化学成分浓度变化等特征,以及秸秆燃烧对华北和北京地区细颗粒物浓度和地面短波辐射的影响。与观测资料的对比结果显示,模式可以很好地模拟北京地区地面气象要素和PM2.5质量浓度,考虑秸秆燃烧排放源可以明显改进北京PM2.5浓度模拟的准确性,但在重度污染情况下,模式总体上低估气溶胶光学厚度和高估地面短波辐射。10月7～11日北京地区重霾事件主要是不利气象条件下人为污染物累积和区域输送造成,也受到华北地区南部秸秆燃烧的影响。河南北部、河北南部和山东西部大面积秸秆燃烧释放的气态污染物和颗粒物在南风的作用下输送至北京,秸秆燃烧对北京地区地面PM2.5、有机碳（OC）、硝酸盐、铵盐、硫酸盐和黑碳（BC）的平均贡献率分别为24.6%、36.8%、23.2%、22.6%、7.1%和19.8%,秸秆燃烧产生的气溶胶可以导致北京地面平均短波辐射最大减小超过20 W m－2,约占总气溶胶导致地表短波辐射变化的24%。     

广州冬季大气消光系数的贡献因子研究

2008年1月1～31日和2月6～24日在广州城区每天采集一个PM2.5样品,对样品进行有机碳、元素碳及水溶性离子分析,利用美国IMPROVE能见度方程计算得到广州冬季大气消光系数.结果发现:冬季PM2.5 日均值质量浓度为89.0±53.4/μg·m~(-3),OC(Organics Carban)质量浓度为16.9±11.9μg·m~(-3),EC(Element Carbon)质量浓度为5.9±3.4 μg·m～(-3),水溶性离子总浓度为43.9±23.5μg·m~(-3).冬季大气消光系数均值为342±185 Mm~(-1).广州冬季大气消光系数主要贡献者为(NH_4)_2SO_4、NH_4NO_3、POM(Par-ticular organic matter)、EC和NO_2,对消光系数的贡献率分别为36.3%、14.5%、26.6%、17.4%和5.2%.     

天津冬季大气能见度与空气污染的相互关系

为探求天津冬季大气能见度特征与空气污染的相互关系,于2008年12月至2009年1月连续观测大气能见度和空气污染物浓度(PM10、PM2.5质量浓度,O_3、NO_2和SO_2体积浓度),并结合相对湿度进行相关分析。结果表明:天津冬季大气能见度平均值为11.59 km,日变化呈明显的单峰特征,其变化特征受到空气污染物,尤其是气溶胶质量浓度及相对湿度变化共同影响;观测期内霾的发生频率接近50%;采用非线性回归方程拟合能见度与气溶胶质量浓度相互关系显示,PM2.5质量浓度对水平能见度的贡献大于PM10质量浓度,并且高湿情况下,能见度与气溶胶质量浓度相关性更好。     

Chemical characteristics of haze during summer and winter in Guangzhou

Airborne particles were collected with a 10-stage MOUDI and a PM₁₀ sampler in Guangzhou, China, during both haze and normal days in the summer of 2002 and 2003, and winter 2002. The characteristics of PAHs, organic carbon, elemental carbon and water-soluble inorganic ions were studied under four periods (summer normal, summer haze, winter normal and winter haze). In this study, secondary pollutants (OC, SO₄²⁻, NO₃⁻ and NH₄⁺) were the major chemical components and appeared to show a remarkably rapid increase from normal to haze days. The particle mass size distributions were bimodal and dominated by fine particles in haze days. A significantly higher OC/EC ratio was found in haze days (3.2–4.7) compared to normal days (1.8–2.8), indicating secondary organic aerosol formation might be significant during haze days. Correlation analysis between visibility and chemical species showed that the major scattering species were TC (total carbon) and sulfate in normal days and nitrate and TC in haze days, respectively. Simultaneously, correlation analysis between visibility and meteorological factors demonstrated that visibility increased with both temperature and wind speed, while it decreased with relative humidity. Furthermore, the relatively higher value of IcdP/(BghiP + IcdP) and the low value of Cmax, CPI, and BghiP/BeP in winter haze could be due to the growth of motor vehicle usage and energy consumption in winter.     

南京市大气细颗粒物化学成分分析

为了解南京大气细粒子的污染水平和污染特征,在南京市中心鼓楼和北郊南京信息工程大学校内进行了连续1a、每季度5d的大气气溶胶同步采样。用称重法、离子色谱法和电感耦合等离子质谱法分别测得细颗粒物的质量浓度、水溶性离子和元素组成。结果表明,南京地区PM2.1污染比较严重,水溶性离子是细粒子的重要组分,所测6种离子质量浓度总和分别占市区和北郊PM2.1的46.99％、42.32％。PM2.1中的各离子最高浓度都出现在冬季。NH^＋4与SO^2-4的相关性好,可能主要以（NH4）2SO4形式存在。温度对SOR和NOR的影响显著,温度升高时SOR值增大而NOR显著减小。通过计算NO^-3与SO^2-4的质量比发现,南京市SO2和NOx主要来自于固定源（如煤的燃烧）。分析细颗粒物中元素含量和富集因子结果表明,Pb、As、Zn、Hg、Cu、Cr、Ni元素的人为污染较明显,且北郊的污染重于市区。比较PM2.1和PM3.3中的离子成分发现,SO^2-4、NH^＋4在PM2.1中占据绝对优势,F^-、Cl^-、NO^-2、NO^-3等不在细粒子中占明显优势。从元素组成来看,Pb、Zn在PM2.1细粒子中含量显著,而Ca、Mg、Na等在粗粒子中富集。     

STUDY ON THE VISIBILITY REDUCTION CAUSED BY ATMOSPHERIC HAZE IN GUANGZHOU AREA

In recent years the pollution of aerosol is getting worse and worse in Guangzhou area. The haze weather mainly occurs from October to April of the following year, resulting in visibility deterioration. From the beginning of the 1980's the visibility dramatically deteriorated, obviously increasing haze weather, in which there are three big fluctuations, respectively showing the periods of pollution of dust, sulphate and dust, fine particle from photochemical process and sulphate and dust accompanying the development of economy. The long-term tendency of visibility caused by fog and light fog does not have the tendency due to human activity or economical development and the variation mainly show the inner interannual and interdecadal variation of climate. The deterioration of visibility has close relation to the fine particles in Guangzhou area, with half of PM10 surpassing the limits set by national second graded standard, meanwhile, all values of PM2.5 rise above the day-mean limits of American national standard, indicating very high fine particle concentration. The ratio of PM2.5 to PM10 is also very high, reaching 62% - 69%, especially higher in dry seasons than in rainy seasons.     

基于卫星遥感AOD的华北地区2003—2014年PM2.5浓度时空分布特征

华北及周边地区PM_2.5造成的污染, 近十年来引起了社会的广泛关注, 也是科学研究的重要领域。利用2003—2014年的卫星遥感MODIS AOD数据和2014—2015年的地面观测PM_2.5浓度数据, 采用聚类分析、混合效应模型、EOF分解等统计分析方法, 反演了2003—2014年华北及周边地区PM_2.5浓度, 分析其时空分布特征。主要结论如下:(1)卫星遥感MODIS AOD与地面观测PM_2.5值有较高的相关系数, 可利用MODIS卫星遥感AOD对地面观测的PM_2.5浓度进行反演; (2)华北地区PM_2.5浓度呈现出明显的空间分布特征:太行山脉是污染强弱明确的分界线, 山脉东南部的污染显著高于西部, 且在地势变化的地方出现明显的突变; 河北南部、河南北部和山东西北部分区域是污染最严重的地区; (3)2004年、2009年以及2013年后都是污染浓度比较低的年份。      

基于经验模态分解的西安市空气质量预报订正方法

为提高城市空气质量预报的准确率,研制了针对数值预报模式CAPPS2的订正方法,对2001—2007年西安市逐日PM10、SO_2、NO_2浓度均值和相应的降水、风速作经验模态分解(EMD)分析,用最大熵谱方法检验各本征模态函数(IMF)周期,计算其方差贡献率,制定订正方法并进行数值试验。结果表明:PM10浓度波动以周尺度为主,有明显周末效应,与主要清除过程匹配较好;SO_2、NO_2浓度波动与主要清除过程不同步;基于周末效应的订正规则对PM10、SO_2订正效果较理想,对NO_2订正效果不确定。     

Evolution of aerosol vertical distribution during particulate pollution events in Shanghai

A set of micro pulse lidar(MPL)systems operating at 532 nm was used for ground-based observation of aerosols in Shanghai in 2011.Three typical particulate pollution events(e.g.,haze)were examined to determine the evolution of aerosol vertical distribution and the planetary boundary layer(PBL)during these pollution episodes.The aerosol vertical extinction coefficient(VEC)at any given measured altitude was prominently larger during haze periods than that before or after the associated event.Aerosols originating from various source regions exerted forcing to some extent on aerosol loading and vertical layering,leading to different aerosol vertical distribution structures.Aerosol VECs were always maximized near the surface owing to the potential influence of local pollutant emissions.Several peaks in aerosol VECs were found at altitudes above 1 km during the dust-and bioburning-influenced haze events.Aerosol VECs decreased with increasing altitude during the local-polluted haze event,with a single maximum in the surface atmosphere.PM2.5 increased slowly while PBL and visibility decreased gradually in the early stages of haze events;subsequently,PM2.5 accumulated and was exacerbated until serious pollution bursts occurred in the middle and later stages.The results reveal that aerosols from different sources impact aerosol vertical distributions in the atmosphere and that the relationship between PBL and pollutant loadings may play an important role in the formation of pollution.     

夏季厄尔尼诺-Modoki和东部型ENSO海表温度异常分布型特征及其与海洋性大陆区域气候异常的联系

2007年,Ashok等揭示了赤道太平洋区域存在一种三极型分布海表温度异常并称之为厄尔尼诺-Modoki,同时定义了相应的海表温度异常指数EMI（记为I_EM）。在此基础上,利用英国哈得来中心逐月海表温度资料、美国NCEP/NCAR月平均再分析数据集、美国国家海洋和大气管理局（NOAA）逐月降水资料（CMAP）,通过在太平洋海表温度异常中扣除厄尔尼诺-Modoki信号后,在Nino1+2区域上定义了东太平洋型海表温度异常指数EPNI（I_EPN）。据此,由I_EPN和I_EM可构成描述热带太平洋海表温度异常变化的一对指数。分析了两个指数相应的海气状态及对海洋性大陆区域气候异常的影响。结果表明,厄尔尼诺-Modoki和东太平洋型海表温度异常及其影响存在显著差异。在北半球夏季,当I_EM处于正位相时,热带太平洋海表温度异常呈现“负-正-负”的结构,海洋性大陆大部分区域海表温度异常为负,此时对流层低层太平洋地区辐合,海洋性大陆地区辐散,对流层高层太平洋地区辐散,海洋性大陆地区辐合。对应于辐合辐散中心,存在着自赤道中太平洋分别向赤道东太平洋和海洋性大陆中东部地区的异常垂直环流圈,同时也存在自海洋性大陆西部向印度洋西部的垂直环流。大气在海洋性大陆区域北部加热,南部冷却;在太平洋地区西部加热而东部冷却;在海洋性大陆区域10°N以南降水偏少,而10°N以北降水偏多。当I_EPN处于正位相时,热带太平洋海表温度异常呈现“西负东正”分布型,海洋性大陆区域海表温度异常呈现“西正东负”分布,对流层低层海洋性大陆地区辐散中心范围偏大、位置偏东、强度偏强,太平洋地区辐合中心范围偏小、位置偏东,热带环流异常在垂直方向上呈斜压结构,海洋性大陆区域北部大气加热而南部冷却,太平洋地区大气均呈加热正异常,海洋性大陆大部分区域降水均偏少,赤道太平洋降水偏多。以上这些结果有利于深刻理解热带太平洋海表温度异常的特征及其对海洋性大陆区域气候的影响。     

Acidity of Aerosols during Winter Heavy Haze Events in Beijing and Gucheng,China

We investigated the acidity and concentrations of water-soluble ions in PM_2.5 aerosol samples collected from an urban site in Beijing and a rural site in Gucheng, Hebei Province from November 2016 to January 2017 to gain an insight into the formation of secondary inorganic species. The average SO₄^2–, NO₃^–, and NH₄⁺ concentrations were 8.3, 12.5, and 14.1 μg m^–3, respectively, at the urban site and 14.0, 14.2, and 24.2 μg m^–3, respectively, at the rural site. The nitrogen and sulfur oxidation ratios in urban Beijing were correlated with relative humidity (with correlation coefficient r = 0.79 and 0.67, respectively) and the aerosol loadings. Based on a parameterization model, we found that the rate constant of the heterogeneous reactions for SO₂ on polluted days was about 10 times higher than that on clear days, suggesting that the heterogeneous reactions in the aerosol water played an essential role in haze events. The ISORROPIA II model was used to predict the aerosol pH, which had a mean (range) of 5.0 (4.9–5.2) and 5.3 (4.6–6.3) at the urban and rural site, respectively. Under the conditions with this predicted pH value, oxidation by dissolved NO₂ and the hydrolysis of N₂O₅ may be the major heterogeneous reactions forming SO₄^2– and NO₃^– in haze. We also analyzed the sensitivity of the aerosol pH to changes in the concentrations of SO₄^2–, NO₃^–, and NH₄⁺ under haze conditions. The aerosol pH was more sensitive to the SO₄^2– and NH₄⁺ concentrations with opposing trends, than to the NO₃^– concentrations. The sensitivity of the pH was relatively weak overall, which was attributed to the buffering effect of NH₃ partitioning.