氮、硫输入对河口湿地土壤有机碳矿化的实验研究

通过室内培养实验,研究了氮、硫输入对闽江河口湿地土壤有机碳矿化和土壤理化性质的影响.结果表明:NH_4Cl(N1)、NH_4NO_3(N3)、K_2SO_4(S)和NH_4Cl+K_2SO_4(NS1)处理显著促进了湿地土壤有机碳矿化速率(p0.05),较对照分别提高了76.57%、60.09%、83.20%和52.59%,并且不同处理下土壤有机碳矿化速率均表现为随培养时间的增加而递减.氮、硫输入在不同时间对湿地土壤有机碳矿化的影响不尽一致,在前6 d各处理的促进作用最明显.湿地土壤有机碳累积矿化量在不同处理下均表现为随培养时间逐渐增加,其增长速率在培养初始阶段较快,而后逐渐减慢;不同培养时间有机碳累积矿化量在N1、N3、S和NS1处理下与对照处理间均存在显著差异(p0.05).短期培养结束后,N3、NS1处理显著增加了湿地土壤DOC含量(p0.05);N1、N3、NS1和NH_4NO_3+K_2SO_4(NS3)处理均显著增加了土壤NH_4~+-N含量(p0.05);KNO_3(N2)、N3、NS2和NS3处理均显著增加了土壤NO_3~--N含量(p0.05);S、NS1、NS2和NS3处理均显著增加了土壤SO_4~(2-)含量(p0.05).不同处理下湿地土壤Cl-、pH、EC具有微弱的波动变化特征,但在不同处理组间均不存在显著差异(p0.05).多元回归分析显示,DOC、NH_4~+-N和SO_4~(2-)是氮、硫输入处理下影响闽江河口湿地土壤有机碳矿化速率的主要控制因素.     

Interactions of aerosols (ammonium sulfate,ammonium nitrate and ammonium chloride) and of gases (HCl,HNO3) with fogwater

The concentrations of aerosols (NH₄NO₃, (NH₄)₂SO₄ and NH₄Cl) and of gases (HCl_(g), HNO_3(g), NH_3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl_(g) and HNO_3(g) are observed. NH₄Cl and NH₄NO₃ aerosols represent a major fraction of the Cl⁻ and NO₃⁻ aerosols (<2.4 μm)collected by denuders. During a fog event, very high concentrations of SO₄²⁻ were found in small aerosols, which are attributed to the aqueous phase oxidation of SO₂ under the influence of high pH due to the presence of NH₃. Differences in SO₄²⁻ concentrations measured in aerosols (<2.4 μm) and in fog droplets were probably due to mass-transport limitations of the SO₂ oxidation. Ammonium sulfate aerosols represent in some cases a significant fraction of the total S present (SO_2(g) + SO₄²⁻. Soluble aerosols and gases contribute to the composition of fogwater and are released again after fog dissipation.     

A comparison of major chemical species seasonal concentration and accumulation at the South Pole and summit,Greenland

High-resolution snow chemistry records have been recovered from a site close to the South Pole, covering the period 1955–1989, and from Summit, Greenland, for the periods 1979–1987 and 1259–1989. The seasonal variation of the major ions relative to δ¹⁸O and their average yearly fluxes are compared for the two sites. Comparisons are also made to limited available aerosol data. Gaseous species and some species with gaseous precursors (NO₃, NH₄ and excess Cl) have similar timings in South Pole and pre-1900 Summit snow. Timing of non-sea-salt (nss) SO₄ and species that are generated as marine and crustal aerosols (Na, nss Mg and nss Ca) differ between the two sites. The timing of nss SO₄ and NO₃ is complicated in recent precipitation at Summit, Greenland, by the impact of anthropogenic emissions. Fluxes of sea-salt species, nss SO₄ and NO₃ (pre-11900 values for Summit) are less than a factor of 2 higher at Summit. Species with a continental source: nss K, nss Mg, nss Ca and NH₄ are more than five-fold higher at Summit.     

邯郸市PM_(2.5)中水溶性无机离子污染特征及来源解析

本研究通过对邯郸市环境空气中PM2.5样本进行采集和成分检测,分析了该地区PM2.5中水溶性无机离子的污染特征,并结合气象要素(风速、温度)、气态污染物(O3、NO2、SO2、CO)、SOR(硫氧化率)、NOR(氮氧化率)对其主要来源进行了解析.研究结果表明:总水溶性无机离子(TWSII)浓度季节变化特征明显,秋、冬季高于春、夏季.SO2-4、NO-3、NH+4是PM2.5中主要的水溶性无机离子,在TWSII中所占的比例为夏(93.2%)冬(85.6%)秋(85.5%)春(84.0%).春、夏、秋三季PM2.5呈酸性,冬季显碱性.此外还分析得到,SO2-4在四季中均以(NH4)2SO4的形式存在.NO-3在冬季以NH4NO3的形式存在,其余季节中以NH4NO3、HNO3等共存.绝大部分Cl-在冬季以NH4Cl的形式存在,其它季节中以NH4Cl、KCl等的形式存在.均相反应是SO2-4的主要生成途径,夏、冬季也伴随有非均相反应.NO-3的生成以均相反应为主(春、夏、秋),在冬季均相反应与非均相反应同时存在.应用因子分析法解析出4个主因子,其中,工业、燃煤、交通、生物质燃烧等综合源是PM2.5中水溶性无机离子的主要来源.     

应用扩散管测量霾污染期间大气氮硫化合物浓度的方法

活性氮和硫化合物在大气颗粒物形成过程中扮演重要角色,但对它们气相/颗粒相的同步观测结果比较缺乏.本研究尝试基于扩散管的DELTA系统测量氮和硫化合物短时累积浓度,以期捕捉它们在霾污染期间的演变规律.结果表明,DELTA系统收集气态污染物的扩散管中以及颗粒物滤膜上NH_4~+和NO-3空白干扰较小,适用于研究NH_3、HNO_3、NH_4~+和NO-3的日均浓度,可以作为城市环境空气质量监测参数的有效补充;但采样系统中SO_2-4背景含量较高,仅适合监测48 h以上时间尺度的SO_2浓度和周~月尺度SO_2-4浓度,用于大气硫沉降观测.北京2016年5月9日~6月7日观测期间,大气NH_3、HNO_3、NH_4~+和NO-3浓度具有明显的逐日演变规律,呈现出随着风向转变而发生周期性波动的典型特征;这些含氮污染物与PM_(2.5)、CO、SO_2和NO_2浓度的变化规律一致,其来源可能与化石燃料燃烧源有关.污染天NH_3、HNO_3、NH_4~+和NO-3浓度约为清洁天的2倍,但还原性氮和氧化性氮的相态分布在清洁天和污染天无明显差异;整个观测期间,HNO_3/NO-3约为1.2,NH_3/NH_4~+为4.5,春夏之交较高的温度有利于活性氮在气粒平衡过程中偏向于气态形式存在.     

The spatial distribution and particle size of some inorganic nitrogen,sulphur and chlorine species over the North Sea

The use of filter packs and a cascade impactor during a series of research cruises in the southern area of the North Sea has yielded detailed spatial distribution patterns of aerosol concentrations, Cl⁻, NO₃⁻, SO₄²⁻¹ and NH₄⁺ and gaseous concentrations, HCl, HNO₃ and NH₃. The overall distribution of the atmospheric concentrations closely parallels published modelled results for metallic species. The chemical transformations of these aerosols and gases are investigated together with their interactions with the seasalt aerosol. Aerosol chloride loss is greatest in the more polluted areas, whilst concentrations products of NH₃ with HNO₃ and HCl appear insufficient to sustain the existence of NH₄NO₃ and NH₄Cl. Nitrate is associated predominantly with larger particles and appears to be present substantially as a surface coating on marine aerosol. The total dry deposition input for nitrogen species is calculated for the southern sector with extrapolation to the whole of the North Sea, using particle size weighted deposition velocities of 0.63 and 0.21 cm s⁻¹ for NO₃⁻¹ and NH₄⁺, respectively, and literature-derived values for the gaseous constituents. Finally the use of air-mass back trajectories illustrates the role of source regions in influencing the chemical composition of the North Sea atmosphere.     

Kinetics of evaporation of ammonium chloride and ammonium nitrate aerosols

The evaporation rates of ammonium chloride and ammonium nitrate were measured by continuously and rapidly removing gaseous NH₃ and HNO₃ or HCl from aerosols in an annular denuder. The experiments gave the evaporation rates in terms of mass loss of chloride or nitrate which can be expressed conveniently as the rates of reduction of aerosol radius with time. Both dry aerosols (humidity 30–60% r.h.) and aqueous aerosols (humidity ca 97% r.h.) were studied. Dry aerosols evaporate at rates of −1.05 Å s⁻¹ for NH₄Cl and −0.45Å s⁻¹ for NH₄NO₃, while the evaporation rates of aqueous aerosols expressed as for equivalent dry particles are −4.52 Å s⁻¹ for NH₄Cl and −0.49 Å s⁻¹ for NH₄NO₃. The experimentally measured rates are independent of particle radius and remarkably low compared with those predicted from existing theories of aerosol evaporation, thus implying that there is an unknown kinetic constraint to the achievement of equilibrium at atmospheric temperature and pressures.     

利用SPAMS研究石家庄市冬季连续灰霾天气的污染特征及成因

2014年11月18~26日石家庄市发生了连续的灰霾天气.利用位于石家庄市大气自动监测站(20 m)的单颗粒气溶胶质谱仪(SPAMS)分析了细颗粒物的化学组成,根据石家庄市大气污染物排放源谱库对主要成分进行了来源解析,并结合颗粒物质量浓度和气象条件研究了该地区冬季灰霾天气成因.结果表明,石家庄市大气细颗粒物来源分为7类,各源示踪离子:燃煤源为Al,工业源为OC、Fe、Pb,机动车尾气源为EC,扬尘源为Al、Ca、Si,生物质燃烧源为K和左旋葡聚糖,纯二次无机源为SO-4、NO-2和NO-3,餐饮源为HOC.灰霾期间大气中主要含有OC、HOC、EC、HEC、ECOC、富钾颗粒、矿物质和重金属等8类颗粒,其中OC和ECOC颗粒最多,分别占到总数的50%和20%以上,OC颗粒主要来自燃煤和工业工艺,ECOC颗粒主要来自燃煤和机动车尾气排放.灰霾发生时含有NH+4、SO-4、NO-2和NO-3等二次离子的颗粒物占比升高,其中含NH+4颗粒增幅最大;EC、OC与NO-3、SO-4、NH+4在灰霾天气下的混合程度均比干净天气高,其中与NH+4的混合程度加剧最为明显.冬季采暖期煤炭的大量燃烧、医化行业工艺过程及机动车尾气等污染源排放的一次气态污染物(SO2、NOx、NH3、VOCs)和一次颗粒物在静稳天气中难以扩散而迅速累积,气态污染物发生二次转化形成硝酸铵、硫酸铵,而颗粒物之间通过碰撞形成二次颗粒物并发生不同程度的混合,从而导致大气能见度下降,以上是石家庄市冬季灰霾形成的主要原因.     

Elements in the precipitation of S. Paulo City (Brazil)

Rainwater samples in S. Paulo city were collected on an event basis from October 1983 to October 1985 covering two dry and two rainy periods. Bulk samples only were obtained. At the same site and period, fine, coarse and inhalable particles were also collected. Na⁺, Ca²⁺, K⁺, Mg²⁺, NO₃⁻, SO₄²⁻ and NH₄⁺ contents were determined in rainwater samples, while Na, Ca, K, Cl and S concentrations were measured in aerosol samples. Rainwater is slightly acid (mean pH = 5.0), and contains high concentrations of Ca²⁺, NO₃⁻, SO₄²⁻ and NH₄⁺. Dry and wet fluxes and washout ratios were determined for some elements. Results obtained suggest that the atmospheric composition in this city is strongly influenced by anthropogenic sources.     

Ambient concentrations,scavenging ratios,and source regions of acid related compounds and trace metals during winter in northern michigan

Daily measurements the atmospheric cocnentrations of HNO₃, NO₃^-, NO₂, SO₂, SO₄²⁻, NH₄⁺, and several trace metals were made at the University of Michigan Biological Station over a 124-day period during the 1984–1985 winter. The composition of the daily precipitation was also determined. The relative contributions of scavenged NO₃⁻ and HNO₃ to the precipitation was estimated by assuming that the NO₃⁻ scavenging ratio was the same as that of trace metals with a similar particle size. Similarly, the SO₄²⁻ and SO₂ contributions were based on the scavenging ratios of NH₄⁺ and trace metals. On this basis, it was determined that the event median NO₃⁻ and HNO₃ scavenging ratios were 500 and 3500, respectively. HNO₃ scavenging accounted for 83% of the total scavenged NO₃⁻. Scavenging of SO₄²⁻ accounted for all the snow SO₄²⁻ in 67% of the events. In the remaining events, some SO₂ was scavenged, with a median scavenging ratio of 219. Overall, 67% of the snowfall acidity appeared to be due to HNO₃ scavenging. Backward air-mass trajectories that were calculated for each event were used to determine the general source regions of the acidic species. Snow associated with air masses from the south and west accounted for 81 and 75% of the deposited NO₃⁻ and SO₄²⁻, respectively.     

使用RCFP-IC对南京市不同污染状况下PM_(2.5)中水溶性离子的观测分析

本文使用大气细颗粒物快速捕集系统及化学成分在线分析系统(RCFP-IC)和美国热电污染气体分析系统(EMS系统)对2013年11月16日—12月10日南京地区PM2.5中主要水溶性离子和污染气体进行了观测分析,并结合气象要素数据分析了灰霾天PM2.5中主要水溶性离子的污染特征.结果表明:不同污染条件下PM2.5中水溶性离子分布差异较大,清洁天浓度最大的6种离子排序为SO2-4NO-3NH+4Cl-NO-2K+,霾天(11月20—24日)和雾-霾天(12月1—8日)前6种离子排序分别是SO2-4NH+4NO-3NO-2Cl-K+和NO-3SO2-4NH+4Cl-NO-2K+.受污染源和化学反应的日变化影响,不同离子的日变化特征不同.污染天NO-3、SO2-4和NH+4的浓度是干净天的2.8~5.0倍.不同水溶性离子对能见度的影响不同.     

The chemical composition of intercepted cloudwater in the Sierra Nevada

The chemical composition of cloudwater in the Sierra Nevada is dominated by NO₃⁻, SO₄²⁻, and NH₄⁺. Cloudwater pH is determined largely by the balance between the concentrations of these three species, although inputs of formic and acetic acid also are believed to be important, particularly when anthropogenic inputs are small. Cloudwater samples collected in Sequoia National Park (SNP) exhibited pH values ranging from 3.9 to 6.5; Yosemite National Park (YNP) cloudwater samples had pH values ranging from 3.8 to 5.2. Samples collected at YNP were more acidic than those collected at SNP. The difference in pH between the two regions appears to be due to relatively small differences in inputs of NO₃⁻, SO₄²⁻, and NH₄⁺. In the absence of inputs of NH₃, cloudwater pH values in the Sierra may fall below 3.Over 250 h of cloud interception were observed during a 12 month period at a cloud monitoring site at 1856 m elevaton in SNP. Estimates of cloudwater deposition of NO₃⁻, SO₄²⁻, and NH₄⁺ indicate that cloud interception contributes significantly to regional acid deposition for closed forest canopies. Cloud interception may be the dominant deposition mechanism for isolated conifers and ridgetop canopies, where wind speeds are higher and cloudy air parcels can impact directly on foliar surfaces.     

Cloud chemistry at Mt Rigi,Switzerland: Dependence on drop size and relationship to precipitation chemistry

The chemical composition of winter and spring cloud water sampled at 1620 masl elevation on Mt Rigi in central Switzerland was dominated by NO₃⁻, SO₄²⁻, NH₄⁺ and H⁺. A wide range of concentration levels was observed, with maxima of 3700, 1800 and 4600 micronormal for NO₃⁻, SO₄²⁻ and NH₄⁺, respectively. Concentrations at a lower elevation (1030 masl) site on the mountain were higher due to lower cloud liquid water contents and higher pollutant levels at that site. The lowest pH observed was 2.95; large concentrations of NH₃ in the region prevented pH values from falling even lower. A comparison of simultaneously sampled cloud water and precipitation revealed much higher concentrations for most species in the cloud water, except in one case of extreme precipitation riming when the concentrations in the two phases converged. An exception to the pattern was H⁺; at times the precipitation was more acidic than the cloud water. The chemical composition of the cloud drops varied with drop size. Drops smaller than 10 μm diameter were enriched in NO₃⁻, SO₄²⁻ and NH₄⁺ relative to larger drops. Since the larger drops are the ones most effeciently captured by snow crystals, knowledge of their composition is essential to understanding the chemical implications of accretional growth of precipitation.     

Chemical characterization of acid precipitation in Albany,New York

Chemical composition of precipitation in Albany, NY from July 1986 to December 1988 has been studied. Mean volume-weighted concentrations (μeq^ℓ−1) were: acidity, 104.0; alkalinity, −63.7; SO₄²⁻, 52.8; NO₃⁻, 29.8; Cl⁻, 5.6; F⁻, 0.50; NH₄⁺, 19.3; Ca²⁺, 6.5; Mg²⁺, 2.8; Na⁺, 3.5; and K⁺, 1.4. Mean pH was 4.2 . Seasonal patterns were pronounced for most species. Concentrations of H⁺, SO₄²⁻, NO₃⁻, NH₄⁺ and Ca²⁺ peaked in the summer and spring. Deposition was related to rainfall amount by a power law relationship in which the exponent of the equation was ∮.6. Wet SO₄²⁻ deposition was 2.35 keq ha⁻¹ over a 30-month period. The SO₄²⁻ and NO₃⁻ deposition rates observed at Albany indicate that transport from midwestern sources have a major influence at this site. On the average, free H⁺ ion concentrations determined from pH measurements accounted for 51% of the measured total acidity. There were unknown species, most likely organic acids, that could contribute to the acidity. Correlation and regression analyses indicated that major anions, SO₄²⁻ and NO₃⁻, were closely associated with H⁺ and NH₄⁺ ions. Factor analysis revealed four common factors which are related to fossil-fuel combustion, sea spray, cement factory and biomass burning.     

Spatial variability of urban precipitation chemistry and deposition: Statistical associations between constituents and potential removal processes of precursor species

The precipitation chemistry of Greater Manchester, a Metropolitan County in the northwest of England, has been examined for small scale spatial variability using a network of 18 bulk precipitation collectors. Significant spatial variability was found for concentrations of non-marine SO₄²⁻, NO₃⁻, NH₄⁺, Ca²⁺ and H⁺ ions. The statistical associations between the data were investigated using correlation, partial correlation and principal components analyses. It was found that zero-order correlation coefficients were inadequate for the interpretation of the data and that the computation of first, and higher order partial correlation coefficients was necessary in order to explain the interrelationships between the data and their spatial variability. The statistical associations between the data suggest relationships between Ca²⁺ and non-marine SO₄²⁻, and NO₃⁺ in precipitation which are discussed in terms of their possible precursor species. Potential source effects were examined in conjunction with atmospheric removal processes. The dry deposition of SO₄ particles, rather than the dry deposition of SO₂, may explain the spatial variability of non-marine SO₄²⁻. The erosion of CaSO₄ formed from the reaction of SO₂ with CaCO₃ on urban surfaces with subsequent resuspension is thought to be the basis of the relationship between Ca²⁺ and non-marine SO₄²⁻ concentrations in precipitation. The wet and dry deposition of CaCO₃ particles from local sources may be partially responsible for the spatial variability of H⁺, and dry deposition and scavenging of NH₃, in conjunction with the predominant wind direction may explain the spatial variability of NO₃⁻ and NH₄⁺ ions. Ammonia is thought to originate from sources both outside the study area and within it.     

西安市大气降水污染和沉降特征及其来源解析

基于东亚酸沉降监测网(Acid Deposition Monitoring Network in East Asia,EANET)的湿沉降观测数据,分析了2000～2017年西安市大气降水化学特征、沉降特征以及潜在来源.结果表明,2000～2017年西安市降水pH和电导率的变化分别呈上升和下降趋势;大气降水中离子平均浓度大小依次为SO₄^2-> Ca²⁺> NH₄⁺> NO₃^-> Na+> Cl-> Mg²⁺> K+,其中SO₄^2-浓度占总离子的比值由2000年的38. 6%降低到2017年的27. 9%.近年来的SO₄^2-和NO₃^-的比值表明,西安市大气污染物排放类型有由燃煤型向混合型转变的趋势.近十几年来SO₄     

Effect of ammonium sulfate and urea on PCDD/F formation from active carbon and possible mechanism of inhibition

The effect of ammonium sulfate （（NH4）2SO4） and urea （CO（NH2）2） on polychlorinated dibenzo-p-dioxin and dibenzofuran （PCDD/F） formation from active carbon was investigated in this study. Both additives could significantly inhibit PCDD/F formation, and PCDD/F （TEQ） generation was reduced to 98.5% （98%） or 64.5% （77.2%） after 5% （NH4）2S04 or CO（NH2）2 was added into model ash, respectively. The inhibition efficiency of PCDDs was higher than the value of PCDFs, however, the reduction of PCDD/F yield was mainly from PCDFs decreasing. In addition, the solid-phase products were reduced more than the gas-phase compounds by inhibitors. By the measurement of chlorine emission in the phase of ion （Cl[Cl^-]） and molecule gas （Cl[Cl2]）, it was observed that both Cl[Cl^-] and Cl[Cl2] were reduced after inhibitors were added into ash. Cl[Cl2] was reduced to 51.0% by urea addition, which was supposed as one possible mechanism of PCDD/F inhibition.     

Chemical and optical properties of aerosols and their interrelationship in winter in the megacity Shanghai of China

A field campaign on air quality was carried out in Shanghai in winter of 2012. The concentrations of NO, NO₂, NO_x, SO₂, CO, and PM_2.5 increased during haze formation. The average masses of SO₄^2-, NO₃^- and NH₄⁺ were 10.3, 11.7 and 6.7 μg/m³ during the haze episodes, which exceeded the average (9.2, 7.9, and 3.4 μg/m³) of these components in the non-haze days. The mean values for the aerosol scattering coefficient (b_sp), aerosol absorption coefficient (b_ap) and single scattering albedo (SSA) were 288.7, 27.7 and 0.91 Mm^-1, respectively. A bi-peak distribution was observed for the mass concentrations of CO, NO, NO₂, and NO_x. More sulfate was produced during daytime than that in the evening due to photochemical reactions. The mass concentration of NH₄⁺ achieved a small peak at noontime. NO₃^- showed lower concentrations in the afternoon and higher concentrations in the early morning. There were obvious bi-peak diurnal patterns for bsp and bap as well as SSA. bsp and bap showed a positive correlation with PM_2.5 mass concentration. (NH₄)₂SO₄, NH₄NO₃, organic mass, elemental carbon and coarse mass accounted for 21.7%, 19.3%, 31.0%, 9.3% and 12.3% of the total extinction coefficient during non-haze days, and 25.6%, 24.3%, 30.1%, 8.1% and 8.2% during hazy days. Organic matter was the largest contributor to light extinction. The contribution proportions of ammonium sulfate and ammonium nitrate to light extinction were significantly higher during the hazy time than during the non-haze days.     

A numerical simulation of kinetic constraints upon achievement of the ammonium nitrate dissociation equilibrium in the troposphere

Various mechanisms and associated rate expressions for the reversible evaporation of volatile ammonium salts are presented, and experimental evidence for them discussed. The literature concerned with the existence of stable NH₄⁺ salt monomers in the gas phase in highlighted. Four kinetic mechanisms are presented: monomer formation; adsorption of one precursor species on the particle surface; biomolecular surface reaction; and transport-limited particle growth. No mechanism emerges as the rate-limiting process for all experimental studies. Rate constant ratios for the first two mechanisms are calculated from the literature and shown to differ greatly from the thermodynamic equilibrium constant.A simple box model is developed to determine the importance of kinetic constraints on aerosol growth and evaporation in the tropospheric boundary layer. No attempt is made to model actual tropospheric processes other than the daytime oxidation of NO₂ and the kinetics of aerosol growth itself, so that model output is representative rather than definitive.Substantial departures from equilibrium are seen, giving gas concentration products ranging from −200 to 5000% of the theoretical value, Ke. At low temperatures and high relative humidities (r.h.) a large proportion of the potential condensable NO₃⁻ remains in the gas phase. The behaviour is general over a range of initial aerosol loadings, temperatures, r.h. and model formulations. Both pure NH₄NO₃ aerosol and a hypothetical equimolar mixture with (NH₄)₂SO₄, conform to the general case.     

Changing sources of impurities to the Greenland ice sheet over the last 250 years

Because the composition of precipitation reflects the composition of the atmosphere, polar ice cores provide a useful way of investigating past and present atmospheres. We have measured concentrations of major ions in nine sections of a central Greenland ice core and we found that concentrations of both SO₄²⁻ and NO₃⁻ have increased dramatically over the last 250 years, up to three to four times the 18th century levels. Large changes have also occurred in the average concentrations of several other chemical species, such as NH₄⁺, excess Cl, and Ca²⁺. We used a principal-component analysis to characterize variations of the season of maximum deposition rate of HNO₃ and H₂SO₄ to the snow. We found that source fluctuations of H₂SO₄ are faithfully recorded in the Greenland snow and appear to switch their preferential time of deposition in the snow from summer to winter early in the 20th century. On the other hand, HNO₃ is deposited preferentially during summer throughout the core, emphasizing the role of photochemistry in understanding nitrogen cycling in the Arctic. Anthropogenic inputs have clearly modified the behavior of several chemical compounds in the atmosphere.