北京夏季大气主要含氮无机化合物的变化规律与相互作用

利用SJAC-MOBIC/FIA在2006年8月16日—9月9日在线测量了北京城市大气细颗粒物中主要水溶性含氮离子组分(NO₃^-和 NH₄⁺),与重要含氮气态污染物(HNO₃、HNO₂和 NH₃),以追踪细颗粒物中含氮二次无机组分和含氮气态污染物的变化规律及其相互作用。观测期间,NO₃^- 和 NH₄⁺的平均浓度分别为13.08和11.93 μg/m³,它们与SO₄^2-浓度之和在细颗粒物(PM_2.5)中的平均比例为55%,明显高于其他季节;污染过程中,积聚模态颗粒物体积浓度及其与爱根核模态颗粒物体积浓度比值逐渐增加,说明二次转化是北京夏季细颗粒物的重要来源。白天HONO迅速光解产生OH自由基,而OH自由基是生成HNO₃的重要物种,因此HONO和HNO₃具有相反的日变化规律。在温度较高的白天,大气环境不利于NH₄NO₃的生成与存在;夜间低温高湿的条件下硝酸铵理论平衡系数Ke与气态氨和硝酸的乘积Km相当或低于后者,较有利于NH₄NO₃的生成。北京夏季大气具有足量气态NH₃以中和硫酸盐;但在NO₃^-与阳离子的电荷平衡中,金属阳离子也非常重要。     

南京大气细颗粒物中水溶性组分的污染特征

为了解南京城区大气细颗粒物中水溶性组分的污染特征,在国控点草场门进行了连续一年的PM_2.5采样与分析。6种离子日均浓度为5.29~67.6 μg/m³,其中SO₄^2-、NH₄⁺、NO₃^-是PM_2.5的主要组成成分,6 种离子约占PM_2.5总质量的31%,SO₄^2-、NO₃^-和NH₄⁺相关性较好,NH₄⁺是PM_2.5中硫酸盐和硝酸盐中居于主导地位的离子。     

天津市PM2.5中水溶性离子组分特征

2006年8—12月连续采集PM_2.5样品,分析其中水溶性无机离子浓度特征。结果表明,采样期间,天津市PM_2.5日均浓度均不同程度超过美国EPA日均浓度标准(35 μg/m³);SO₄^2-、NO₃^-、NH₄⁺和Cl^-为无机离子的主要成分,占全部无机离子的88.6%;各离子均表现出不同季节变化特征。对NH₄⁺和NO₃^-、SO₄^2-进行相关性分析发现,NH₄⁺和NO₃^-相关性最好,相关系数为0.795。SOR和NOR的平均值分别为0.16和0.23,均为8月最高,表明前体物二次转化夏季最明显。     

1997—2010年北京市大气降水离子特征变化趋势研究

依据北京市环境保护监测中心1997—2010年降水监测资料,分析北京地区降水中离子特征及变化趋势,阐明北京市降水污染现状及变化特征。结合北京市特有的气象条件、地形地貌和工业分布情况,分析污染物来源及污染变化趋势。研究表明:年度降水电导率呈现波动变化,降水污染严重程度依次为南部郊区>市区>北部背景点。北京地区大气降水中的主要阳离子成分是Ca²⁺和NH₄⁺,主要阴离子成分是SO₄^2-和NO₃^-。近年来[SO₄^2-]/[NO₃^-]比值逐步下降,污染类型由典型硫酸型发展为硫酸+硝酸混合型。阳离子[Ca²⁺]/[NH₄⁺]比值下降,碱性离子缓冲能力降低。9种离子各季节浓度变化趋势基本一致,由高到低依次是春季>秋季>冬季>夏季,这种季节变化特征与气象因素密切相关。相关性及聚类分析表明:NO₃^-与SO₄^2-存在很强相关性,说明其前体物SO₂和NO_X在大气中经常一同排放且进入降水途径相同;H⁺浓度不是由某个离子决定,是所有致酸离子和中和离子相互作用的结果,而NH₄⁺来源不同于其它离子,北京地区的氨存在其单独排放源。     

徐州市不同类型颗粒物重污染过程特征及组分差异性分析

经过多年的大气污染防治,我国空气质量有了大幅改善,但重污染过程仍有发生。对2018—2021年徐州市3种不同类型颗粒物重污染过程的污染特征、演变趋势、PM_2.5组分特征和相关性及污染成因分析结果表明:在不同类型的重污染过程中,二次无机离子NO₃^-、SO₄^2-、NH₄⁺在PM_2.5中的占比均是最高。在累积型重污染期间,NO₃^-、SO₄^2-、NH₄⁺分别增长144%、142%、183%,二次无机离子对PM_2.5的增长贡献较大。结合相关性分析及SOR、NOR值发现,硝酸盐和硫酸盐的二次生成作用显著。在沙尘型重污染期间,结合雷达监测结果及后向轨迹图可以看出,沙尘沉降至高空与近地面污染物叠加造成颗粒物高值。化学组分中Ca²⁺、Mg²⁺浓度对PM_2.5浓度的影响最大,二次生成和转化对其影响较小。在烟花燃放型重污染期间,和烟花爆竹有关的K⁺、Mg²⁺、Cl^-离子较污染前分别上升1 112%、2 058%、和239%,对污染过程影响显著。     

小体系连续快速批量测定淡水亚硝酸盐氮分光光度法

亚硝酸盐氮(NO^-₂-N)是水体中的含氮有机物被氧化转变为硝酸盐反应过程中的中间产物,水环境中存在的NO^-₂-N具有毒性与致癌性,因此,NO^-₂-N含量的准确快速测定具有非常重要的意义。用酶标仪代替传统的紫外分光光度计,以2 mL离心管为反应容器进行NO^-₂-N含量的测定,优化小体系测定NO^-₂-N含量的关键影响因素,即反应体系的体积、显色时间、显色剂用量,研究结果表明:小体系反应总体积1 mL、显色剂用量20 μL、显色时间20 min、pH范围7~9,NO^-₂-N质量浓度为0~0.6 mg/L标准曲线的线性良好(r＞0.999)。根据小体系与国标体系测定的结果进行线性拟合和正交验证,结合2种方法的差异显著性分析,证明了小体系测定NO^-₂-N含量新方法的准确性与可靠性。     

基于DPeRS模型的渭河典型断面汇水区面源污染评估及污染成因分析

近年来甘肃渭河桦林断面月度水质不稳定达标的问题引起了管理部门的广泛关注,掌握桦林断面汇水范围面源污染现状,对控制流域面源污染和促进水质稳定达标具有重要意义。采用遥感分布式污染估算（DPeRS）面源污染评估模型,对2018年黄河流域甘肃桦林断面汇水区面源污染空间分布特征进行分析,开展多类型污染量产排特征解析。结果表明：农业面源污染量方面,2018年甘肃桦林断面汇水区总氮（TN）、总磷（TP）、氨氮（NH⁺₄-N）、重铬酸盐指数（COD_Cr）面源污染排放量分别为11 591,2 697,7 141和1 458 t,入河量分别为2 184,512,1347,263 t;空间分布上,氮型（TN和NH⁺₄-N）排放负荷高值区主要分布在陇西县、武山县县段和岷县县段;武山县县段TP排放负荷较为突出;COD_Cr型面源污染高负荷区主要分布在陇西县、渭源县县段和武山县县段。农业面源污染物入河排放负荷空间分布差异明显,氮磷型（TN、NH⁺₄-N和TP）入河高负荷区主要分布在武山县县段、陇西县、临洮县县段;COD_Cr型面源污染入河高负荷区呈分散分布。漳县西部地区水土流失量较高,漳县西部、陇西县和渭源县县段北部局部地区泥沙负荷量较高。枯水期污染治理仍是保障水质稳定达标的关键期,农田径流是渭河桦林断面所在汇水区氮磷型面源污染的首要污染类型,畜禽养殖是COD_Cr型面源污染的首要污染类型。     

杭州秋冬季PM2.5污染特征分析

为研究杭州PM_2.5污染来源特征,利用2013—2019年杭州市PM_2.5监测数据和气象观测数据,分析了杭州市2013—2019年PM_2.5浓度变化,选取本地积累型和输入型2种PM_2.5污染过程,结合单颗粒气溶胶飞行时间质谱仪（SPAMS）和在线离子色谱数据,探讨杭州市PM_2.5化学组分和污染来源。结果表明：每年秋冬季（11月至次年3月）杭州以东北风、西北风及偏南风为主,风速低于4 m/s时,大气扩散条件差,受本地污染物积累影响,PM_2.5浓度容易出现超标;风速较大且为东北风和西北风时,受上游污染输入影响,易出现PM_2.5重度污染。本地积累型和输入型案例中,PM_2.5化学组分中占比最大的为NO₃^-、SO₄^2-和NH₄⁺;PM_2.5浓度上升过程中,二次NO₃^-和SO₄^2-转换率明显上升,其中NO₃^-上升更为显著,二次气溶胶污染严重。2次案例中,PM_2.5来源贡献占比前3位均为机动车尾气源、燃煤源和工业工艺源,其中本地积累型PM_2.5浓度上升阶段,机动车尾气源占比会明显上升;输入型案例中,输入阶段机动车尾气源占比显著上升,燃煤源贡献也小幅上升。     

北京城区降水对PM2.5和PM10清除作用分析

基于北京市PM_2.5和PM₁₀质量浓度、组分浓度以及降水数据,利用数理统计、相关性分析等方法分别从降水总量、降水时长和降水前颗粒物浓度3个角度研究降水对PM_2.5、PM₁₀的清除作用,同时以一次典型降水过程为例,具体分析降水对颗粒物的影响。结果表明：降水总量的增加有助于促进PM_2.5、PM₁₀的清除,随着降水总量增加,PM_2.5、PM₁₀的平均清除率提高,有效清除的比例增加;连续降水可增强对大气颗粒物的湿清除作用,连续降水达3d可有效降低PM_2.5、PM₁₀浓度;降水对PM_2.5、PM₁₀浓度的清除率和大气颗粒物前一日的平均浓度有较好的正相关性。降水对大气颗粒物的清除可分为清除、回升和平稳3个阶段,各个阶段大气颗粒物的变化趋势不同。降水对于大气气溶胶化学组分和酸碱性的改变具有明显作用,对于大气颗粒物各种组分的清除效果不完全相同。对于大气中OC、NO₃^-、SO₄^2-和NH₄⁺去除率较高,且这4种组分主要以颗粒态形式被冲刷进入降水中,加剧了北京市降水酸化程度。     

香溪河库湾氮的时空分布及影响因子分析

为研究解决香溪河库湾水体富营养化问题，需探明库湾水体氮的时空分布及影响因子。2010年12月—2011年11月对香溪河与水库干流交界处至香溪河库湾尾部共12个采样点进行连续监测，分析香溪河库湾氮的时空分布，结果表明，香溪河库湾氮存在明显的时空分布规律。空间上，回水末端处TN和NO₃^--N浓度低，河口处浓度高，随着与回水末端距离的增加，浓度逐渐升高。在时间上，香溪河库湾TN和NO₃^--N浓度的变异系数随着与河口距离的增加总体上逐渐增大，研究时间内的变化程度逐渐变大；且香溪河库湾TN和NO₃^--N浓度在三峡水库不同运行阶段的时间变化规律不同。     

汾河河津段主要污染物时间序列分析

基于Mann-Kendall趋势检验法和小波分析法,研究了汾河河津段2004—2013年高锰酸盐指数、氨氮、溶解氧含量时间序列的变化趋势和突变特性。结果表明:高锰酸盐指数和氨氮含量有显著下降趋势,溶解氧含量有显著上升趋势。高锰酸盐指数和氨氮含量在1、2月较大,8、9月较小;溶解氧含量在1、2月较大,6、7月较小。高锰酸盐指数含量在2004—2009年差异较大;氨氮含量在2004—2013年差异均较大;溶解氧含量在2010—2013年差异较大。     

富营养化湖泊叶绿素a时空变化特征及其影响因素分析

基于内蒙古乌梁素湖区20个监测点5、7、9、11月的监测数据,分析水体中叶绿素a浓度时空变化情况。同时,分析水体中总氮、总磷、氨氮、硝酸盐氮、COD、p H、总有机碳与叶绿素a的相关性。结果显示,叶绿素a浓度呈现由西北向东南逐渐减少的趋势,而浓度峰值出现在7月下旬,低值出现在11月下旬。相关因素与叶绿素a的相关性呈复杂性,线性拟合结果显示,与COD没有明显相关性;与总有机碳呈弱负相关性,与p H呈负相关性;而与总磷、总氮、氨氮、硝酸盐氮呈正相关性。期望该研究为干旱区湖泊水体富营养化控制和水资源管理提供科学依据。     

三峡水库干流氮和磷含量的季节变化

三峡水库成库后对6个水平断面、4个垂直断面采样分析,对水体水质参数、不同化学形态N以及不同物理形态P的水平分布和垂直分布进行了研究。研究结果表明,成库后TP、NH3-N、NO2--N、NO3--N、IN含量范围分别在0.06～0.34、0.01～0.72、0.002～0.100、0.76～2.09、0.855～2.52 mg/L。TP分布为丰水期>平水期>枯水期,受悬浮物沉降的影响,TP在水库区域含量低于上游区。枯水期、平水期水体中TP以可溶解态为主,丰水期以颗粒态为主。NO2--N、NO3--N、IN含量均为平水期>枯水期>丰水期。水体中IN以NO3--N为主,占IN70%～90%。NO2--N比例最低,占IN3.5%以下。表明水体虽受成库影响流速减缓,但水体依然有较强的自净能力。垂直分布上,TP、IN在3个层次变化不显著,未出现分层现象。各采样站点TP、NO3--N、IN通量和流量有显著相关。     

Temporal and Spatial Variation of Nutrient Levels in the Nemunas River (Lithuania and Belarus)

There are discordant results on trends in nutrient river water quality from the economical transition countries in Europe. The present study assessed the impact of these economical changes on the load and concentration at 17 monitoring stations along the Nemunas River and its major tributaries (Lithuania and Belarus). Three time periods were evaluated: the Soviet rule command system period 1986–1991, the transfer to market economy period 1992–1996 and the post reform period 1997–2002. The most surprising result in this study, was the increased area-specific load of NO₃-N from the first to the third period at almost all the sampling sites. The increase was particularly large (43–78%) at the sites in the Lithuanian part of the river. The corresponding load increase in the Belarussian part of the river was only 1–15%. The statistical analyses of concentration data confirm the strong upward NO₃-N trend at the Nemunas mouth and at 5 of the 6 tributaries in the lower part of Nemunas. Temporal and spatial analysis of nitrates transport in the Nemunas River and its main tributaries revealed that nitrates mainly originate from agricultural areas. The upward trends were most likely an effect of ploughing of pastures and unbalanced crop fertilisation in combination with large storage and accumulation of soil-nitrogen during the Soviet period.On contrary to nitrate-N, the area-specific load of PO₄-P decreased significantly from the first to the third period at all sites along the Nemunas River (31–86%). Seasonal (SMK) and Partial (PMK) Mann-Kendall tests on PO₄-P concentrations also showed significant downward trend at 14 of 16 investigated sites. The decrease of PO₄-P levels was attributed to the reduction of municipal and industrial point source emissions and to the decreased livestock numbers.The NH₄-N load showed the same pattern as PO₄-P. At the river mouth the load was 90 kg km⁻² yr⁻¹ during the first period compared to only 20–30 kg km⁻² yr⁻¹ in the third period. The trend test on NH₄-N concentrations detected significant downward trends at 5 out of 16 sites. The declines were explained by decreased emissions from cities and large animal breeding farms.This study showed that trend analysis at multiple sites in a river basin is crucial for the understanding of the variability in time and space. Such analysis is also important for our interpretation of underlying sources and fluxes in a drainage basin over time. This is particularly important for compounds that have different source origin.     

大连市中心城区地下水“三氮”污染分析

依据《地下水质量标准》(GB/T 14848-1993),对大连市中心城区2006-2010年地下水"三氮"监测资料进行分析。结果表明,"三氮"的检出率(最高为100%)和超标率(最高为58.8%)都较高,其中亚硝酸盐氮超标显著。氨氮浓度各年均值均超标,呈波动变化;亚硝酸盐氮浓度各年均值均超标,并呈上升趋势;硝酸盐氮各年均值波动变化,总体呈上升趋势。除2009年以外,其他4年中丰水期的硝酸盐氮浓度都比枯水期高;除2007年外,其他4年中的丰水期氨氮浓度都比枯水期低。"三氮"最高浓度值主要出现在中心城区周边区域。     

Sulphate, Nitrogen and Base Cation Budgets at 21 Forested Catchments in Canada, the United States and Europe

To assess the concern over declining base cation levels in forest soils caused by acid deposition, input-output budgets (1990s average) for sulphate (SO₄), inorganic nitrogen (NO₃-N; NH₄-N), calcium (Ca), magnesium (Mg) and potassium (K) were synthesised for 21 forested catchments from 17 regions in Canada, the United States and Europe. Trend analysis was conducted on monthly ion concentrations in deposition and runoff when more than 9 years of data were available (14 regions, 17 sites). Annual average SO₄ deposition during the 1990s ranged between 7.3 and 28.4 kg ha⁻¹ per year, and inorganic nitrogen (N) deposition was between 2.8 and 13.8 kg ha⁻¹ per year, of which 41–67% was nitrate (NO₃-N). Over the period of record, SO₄ concentration in deposition decreased in 13/14 (13 out of 14 total) regions and SO₄ in runoff decreased at 14/17 catchments. In contrast, NO₃-N concentrations in deposition decreased in only 1/14 regions, while NH₄-N concentration patterns varied; increasing at 3/14 regions and decreasing at 2/14 regions. Nitrate concentrations in runoff decreased at 4/17 catchments and increased at only 1 site, whereas runoff levels of NH₄-N increased at 5/17 catchments. Decreasing trends in deposition were also recorded for Ca, Mg, and K at many of the catchments and on an equivalent basis, accounted for up to 131% (median 22%) of the decrease in acid anion deposition. Base cation concentrations in streams generally declined over time, with significant decreases in Ca, Mg and K occurring at 8, 9 and 7 of 17 sites respectively, which accounted for up to 133% (median 48%) of the decrease in acid anion concentration. Sulphate export exceeded input at 18/21 catchments, likely due to dry deposition and/or internal sources. The majority of N in deposition (31–100%; median 94%) was retained in the catchments, although there was a tendency for greater NO₃-N leaching at sites receiving higher (<7 kg ha^-1 per year) bulk inorganic N deposition. Mass balance calculations show that export of Ca and Mg in runoff exceeds input at all 21 catchments, but K export only exceeds input at 16/21 sites. Estimates of base cation weathering were available for 18 sites. When included in the mass balance calculation, Ca, Mg and K exports exceeded inputs at 14, 10 and 2 sites respectively. Annual Ca and Mg losses represent appreciable proportions of the current exchangeable soil Ca and Mg pools, although losses at some of the sites likely occur from weathering reactions beneath the rooting zone and there is considerable uncertainty associated with mineral weathering estimates. Critical loads for sulphur (S) and N, using a critical base cation to aluminium ratio of 10 in soil solution, are currently exceeded at 7 of the 18 sites with base cation weathering estimates. Despite reductions in SO₄ and H⁺ deposition, mass balance estimates indicate that acid deposition continues to acidify soils in many regions with losses of Ca and Mg of primary concern. The U.S. Government's right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged. The Canadian Crown reserves the right to retain a non-exclusive, royalty free licence in and to any copyright.     

Spatial and seasonal distribution of nitrogen in marsh soils of a typical floodplain wetland in Northeast China

Horizontal and profile distributions of nitrogen in marsh soils in different seasons were studied in a typical site within the Erbaifangzi wetland in Northeast China. Results showed that there was higher spatial heterogeneity for nitrate nitrogen (NO₃^--_{3}^{-}-N) and ammonium nitrogen (NH₄⁺_{4}^{+}–N), as well as available nitrogen (AN), in surface soils in July compared to that in September. Relative to July, the mean nitrogen contents in surface soils were slightly higher in September; however, in November, soils contained significantly lower NO₃^--_{3}^{-}-N and NH₄⁺_{4}^{+}–N, higher AN, organic nitrogen (Org-N), and total nitrogen (TN). Except for mineral nitrogen, no significant differences were observed between Org-N and TN contents in September and November. Nitrogen contents generally declined exponentially with depth along soil profiles in three sampling dates (July, September, and November), except for a significant accumulation peak of NO₃^--_{3}^{-}-N at the 20–30 cm depth in September. However, NH₄⁺_{4}^{+}–N contents showed a vertical alternation of “increasing and decreasing” in both July and September, while nearly kept constant with depth in November. The depth ranking of nitrogen showed the shallowest distribution for AN, followed by Org-N and TN, while deeper distributions for NO₃^--_{3}^{-}-N and NH₄⁺_{4}^{+}–N. TN, Org-N, and AN were significantly correlated with soil organic matter and total phosphorus. Soil pH values were significantly correlated with TN and AN contents in surface soils. Clay contents showed significant correlations with nitrogen contents except for NO₃^--_{3}^{-}-N in surface soils and NH₄⁺_{4}^{+}–N in profile soils. However, soil moisture was not significantly correlated with nitrogen contents among all soil samples.     

Odour emission characteristics of 22 recreational rivers in Nanjing

The odour emission characteristics of 22 recreational rivers in Nanjing were investigated and analysed. Eight odorous compounds (ammonia (NH₃), hydrogen sulphide (H₂S), sulphur dioxide (SO₂), carbon disulphide (CS₂), nitrobenzene (C₆H₅NO₂), aniline (C₆H₅NH₂), dimethylamine (C₂H₇N), and formaldehyde (HCHO)) were measured in odour emission samples collected using a custom-made emission flux hood chamber. The results showed that all odorants were detected in all monitoring rivers. NH₃ was the main odorant, with emission rates ranging from 4.86 to 15.13 μg/min m². The total odour emission rate of the Nan River, at 1 427.07 OU/s, was the highest of the all investigated rivers. H₂S, NH₃ and nitrobenzene were three key odour emission contributors according to their contributions to the total odour emission. A correlation analysis of the pollutants showed there was a significant positive correlation between the emission rate of NH₃ and the concentration of ammonia nitrogen (NH₄ ⁺-N) and total nitrogen (TN). The H₂S and SO₂ emission rates had a significant positive correlation with sulphides (S^2?) and available sulphur (AS) in the water and sediment. The content of TN, NH₄ ⁺-N, S^2? and AS in the water and sediment affected the concentration of H₂S, SO₂ and NH₃ in the emission gases. NH₄ ⁺-N, S^2? and AS are suggested as the key odour control indexes for reducing odours emitted from these recreational rivers. The study provides useful information for effective pollution control, especially for odour emission control for the recreational rivers of the city. It also provides a demonstrate example to show how to monitor and assess a contaminated river when odour emission and its control need to be focused on.     

Assessing the Impact of Leather Industry to Water Quality in the Aojing Watershed in Zhejiang Province, China

The development of the leather industry in the Aojiang watershed of Zhejiang province increased the release of waste water. In the waste water, ammonium nitrogen (NH⁺ ₄-N) and germanium (Ge) are the main pollutants. In recent years, literature has documented that the intake of high concentrations of NH⁺ ₄-N and Ge harms human health and biological species. This paper focuses on assessing the trends of NH⁺ ₄-N and Ge concentrations in the released waste water in Aojiang watershed and on understanding their relationships with the released waste water using regression and correlation statistics. The paper also utilizes the integrated pollution index to evaluate the water quality in the watershed. Preliminary results show that, from 1992 to 1998, the concentrations of NH⁺ ₄-N and total Ge increased 13 and 14 times, respectively, and they decreased somewhat after 1998. The concentrations of NH⁺ ₄-N and total Ge are positively correlated to the amount of released waste water. These concentrations of NH⁺ ₄-N and Ge, respectively, exceed 12 and 3 times, of the water standards. The water quality in the watershed degraded from Type III in 1992 to over Type V in 2003 when they were compared with the national water quality standards. It appeared that the pollution had positive correlation with leather industry production. The degraded water has no doubt affected human health and the ecosystem health. These results can provide scientific information for the local government to reasonably adjust the industry structure and reduce the pollution to protect the environment.