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Heterogeneous uptake of ammonia and dimethylamine into sulfuric and oxalic acid particles

机译:氨和二甲胺的异质吸收成硫酸和草酸颗粒

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Heterogeneous uptake is one of the major mechanisms governing the amounts of short-chain alkylamines and ammonia (NH3) in atmospheric particles. Molar ratios of aminium to ammonium ions detected in ambient aerosols often exceed typical gas phase ratios. The present study investigated the simultaneous uptake of dimethylamine (DMA) and NH3 into sulfuric and oxalic acid particles at gaseous DMA?∕?NH3 molar ratios of 0.1 and 0.5 at 10, 50 and 70?% relative humidity (RH). Single-gas uptake and co-uptake were conducted under identical conditions and compared. Results show that the particulate dimethyl-aminium/ammonium molar ratios (DMAH?∕?NH4) changed substantially during the uptake process, which was severely influenced by the extent of neutralisation and the particle phase state. In general, DMA uptake and NH3 uptake into concentrated H2SO4 droplets were initially similarly efficient, yielding DMAH?∕?NH4 ratios that were similar to DMA?∕?NH3 ratios. As the co-uptake continued, the DMAH?∕?NH4 gradually dropped due to a preferential uptake of NH3 into partially neutralised acidic droplets. At 50?%?RH, once the sulfate droplets were neutralised, the stronger base DMA displaced some of the ammonium absorbed earlier, leading to DMAH?∕?NH4 ratios up to four times higher than the corresponding gas phase ratios. However, at 10?%?RH, crystallisation of partially neutralised sulfate particles prevented further DMA uptake, while NH3 uptake continued and displaced DMAH+, forming almost pure ammonium sulfate. Displacement of DMAH+ by NH3 has also been observed in neutralised, solid oxalate particles. The results can explain why DMAH?∕?NH4 ratios in ambient liquid aerosols can be larger than DMA?∕?NH3, despite an excess of NH3 in the gas phase. An uptake of DMA to aerosols consisting of crystalline ammonium salts, however, is unlikely, even at comparable DMA and NH3 gas phase concentrations.
机译:异质吸收是在大气颗粒中有关短链烷基胺和氨(NH3)的主要机制之一。在环境气溶胶中检测到的氨基铵的摩尔比通常超过典型的气相比。本研究研究了在10,50和70〜50℃下为0.1和0.5的气态DMAα/α的同时吸收二甲胺(DMA)和NH 3含量为硫酸和草酸颗粒。在相同的条件下进行单气吸收和共同吸收。结果表明,在摄取过程中,颗粒二甲基 - 氨基 - 氨基/摩尔比(DMAHα/βnH4)变化,其受中和程度和颗粒相位态的严重影响。通常,DMA吸收和NH3吸收成浓缩H2SO4液滴最初是类似的有效的,得到DMAH?/□与DMA相似的NH4比率?/□NH3比率。随着共吸收的继续,DMAH?/□NH 4由于优先吸收NH 3进入部分中和的酸性液滴而逐渐滴落。在50℃下,一旦硫酸盐液滴被中和,较强的基础DMA就移位了一些前面吸收的铵,导致DMAH?/□比相应的气相比高出4倍。然而,在10?%αrH下,部分中和硫酸盐颗粒的结晶可预防DMA摄取,而NH3摄取继续并移位DMAH +,形成几乎纯硫酸铵。在中和的固体草酸盐颗粒中也已经观察到DMAH +对NH 3的位移。结果可以解释为什么DMAH?/?环境液体气溶胶中的NH4比率可以大于DMAα/Δnh3,尽管气相中有过量的NH 3。然而,即使在相当的DMA和NH 3气相浓度下,也不太可能对由结晶铵盐组成的DMA的吸收。

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