飞行时间二次离子质谱法在一次污染过程中PM2.5表面组分分析中的应用

团簇离子源的发明和使用,使飞行时间二次离子质谱（TOF-SIMS）法成为材料表面化学分析越来越重要的手段,TOF-SIMS法的主要测试功能包括表层质谱、化学成像及深度剖析3种。采用TOF-SIMS法对一次污染过程中的大气细颗粒物（PM_2.5）的表层进行检测,得到了PM_2.5表面成分的质谱及成像信息。结果表明：PM_2.5表层存在多种金属离子,通过扫描电子显微镜能谱仪的形貌与飞行时间二次离子质谱仪的成像亮度分析可知,K⁺、Na⁺、Mg²⁺响应强度相对较强,含量较高;通过原子吸收光谱仪进行金属离子定量可知,2018年11月4日和12月24日的K⁺、Na⁺、Mg²⁺的平均质量分别为1.809 5、0.443 8、1.526 2 mg;从形态分布上看,PM_2.5表面烟尘集合体含量较多,其次为燃煤飞灰、矿物颗粒和超细未知颗粒;PM_2.5表层的有机物离子C_xH_y片段也较多,经过m/z的测试数据进一步确定,表明颗粒物表层含有大量的脂肪烃和芳香烃;除此之外,还存在含N、O、S等的有机物和无机物。     

The evaluation of the association constant between R-SN and Hg2+

The effective determination of heavy metals from environmental media is among the most important issues for many industrialized countries. The interaction between RS-N, as novel heavy metal probe, and metal ions was studied. RS-N shows selective color change from colorless to pink in the presence of Hg²⁺ in methanol/water solvent and the UV–Vis study shows peak at 560 nm. Fluorescence data revealed that the fluorescence enhance of RS-N by Hg²⁺ dramatically was the result of the formation of [Hg²⁺]RS-N complex. The effective association constants (K _a ) were 3.97?×?10⁵ and 0.204?×?10⁵ M^?1 for Hg²⁺ and Cu²⁺ to RS-N, respectively. The thermodynamic parameters, enthalpy change (ΔH ⁰) and entropy change (ΔS ⁰), were calculated to be ?6.431?±?0.226 kJ/mol and ?0.129?±?0.008 J/K/mol, respectively, according to van’t Hoff equation on the basis of Gibbs free energy (ΔG ⁰) ranged from ?33.8326 to ?28.5389 kJ/mol.     

Biosorption kinetics of heavy metals by leaf biomass of Jatropha curcas in single and multi-metal system

Biosorption of Cu²⁺, Zn²⁺, and Cr⁶⁺ from aqueous solutions by leaf biomass of Jatropha curcas was investigated as a function of biomass concentration, initial metal ion concentration, contact time, and pH of the solution systematically. The aim of this study was to optimize biosorption process and find out a suitable kinetic model for the metal removal in single and multi-metal system. The experimental data were analyzed using two sorption kinetic models, viz., pseudo-first- and pseudo-second-order equations, to determine the best fit equation for the biosorption of metal ions Cu²⁺, Zn²⁺, and Cr⁶⁺ onto the leaf biomass of J. curcas in different metal systems. The experimental data fitted well the pseudo-second-order equation and provided the best correlation for the biosorption process. The findings of the present investigation revealed that J. curcas leaf biomass was an eco-friendly and cost-effective biosorbent for the removal of heavy metal ions from wastewater.     

Five-year monitoring study of chemical characteristics of Wet atmospheric precipitation in the southern region of Jordan

Wet atmospheric samples were collected from different locations in the southern region of Jordan during a 5-year period (October 2006 to May 2011). All samples were analyzed for pH, EC, major ions (Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?), and trace metals (Fe²⁺, Al³⁺,Cu²⁺, Pb²⁺, and Zn²⁺). The highest ion concentrations were observed during the beginning of the rainfall events because large amounts of dust accumulated in the atmosphere during dry periods and were scavenged by rain. The rainwater in the study area is characterized by low salinity and neutral pH. The major ions found in rainwater followed the order of HCO₃?>?Cl^??>?SO₄ ^2? and Ca²⁺?>?Na⁺ > Mg²⁺ > NH₄ ⁺ > K⁺. Trace metals were identified to be of anthropogenic origin resulting from cement and phosphate mining activities located within the investigated area and from heating activities during the cold period of the year (January to April). The wet precipitation chemistry was analyzed using factor component analysis for possible sources of the measured species. Factor analysis (principal component analysis) was used to assess the relationships between the concentrations of the studied ions and their sources. Factor 1 represents the contribution of ions from local anthropogenic activities, factor 2 represents the contribution of ions from natural sources, and factor 3 suggests biomass burning and anthropogenic source. Overall, the results revealed that rainwater chemistry is strongly influenced by local anthropogenic sources rather than natural and marine sources, which is in a good agreement with the results obtained by other studies conducted in similar sites around the world.     

大同市大气颗粒物浓度与水溶性离子季度分布特征

为研究大同市大气颗粒物质量浓度与水溶性离子组成特征,于2013年2、7、9、12月,分别对大同市及其对照点庞泉沟国家大气背景点进行了PM2.5及PM10的采样,通过超声萃取-IC法测定了样品中的9种水溶性离子,结果表明,大同市大气颗粒物污染1、4季度重于2、3季度,PM2.5季度均值全年均未超标,PM10仅第1季度超标1.4倍,污染状况总体良好,PM2.5与PM10相关系数R为0.75,说明大同市颗粒物污染有较为相近的来源,且不同季节均以粗颗粒物为主;大同市PM2.5中水溶性离子浓度分布为SO2-4、NO-3、NH+4Cl-、Ca2+K+、Na+F-、Mg2+,PM10中Ca2+浓度仅次于SO2-4、NO-3,控制扬尘将有效降低PM10的浓度;PM2.5及PM10中的9种水溶性离子在不同季度的浓度与颗粒物浓度分布规律类似,1、4季度较高,2、3季度较低;由阴阳离子平衡计算结果可知,相关性方程的斜率K为1.045,表明大同市大气颗粒物中阳离子相对亏损,大气细粒子组分偏酸性。NO-3与SO2-4浓度比值均小于1,大同市以硫酸型污染为主,大气中的SO2-4主要来源于人类活动排放。     

Toxicity assessment of textile effluents treated by advanced oxidative process (UV/TiO2 and UV/TiO2/H2O2) in the species Artemia salina L.

Textile industry wastes raise a great concern due to their strong coloration and toxicity. The objective of the present work was to characterize the degradation and mineralization of textile effluents by advanced oxidative processes using either TiO₂ or TiO₂/H₂O₂ and to monitor the toxicity of the products formed during 6-h irradiation in relation to that of the in natura effluent. The results demonstrated that the TiO₂/H₂O₂ association was more efficient in the mineralization of textile effluents than TiO₂, with high mineralized ion concentrations (NH ₄ ⁺ , NO ₃ ^? , and SO ₄ ^2? ) and significantly decreased organic matter ratios (represented by the chemical oxygen demand and total organic carbon). The toxicity of the degradation products after 4-h irradiation to Artemia salina L. was not significant (below 10 %). However, the TiO₂/H₂O₂ association produced more toxicity under irradiation than the TiO₂ system, which was attributed to the increased presence of oxidants in the first group. Comparatively, the photogenerated products of both TiO₂ and the TiO₂/H₂O₂ association were less toxic than the in natura effluent.     

北京市典型重污染过程中PM2.5载带水溶性无机离子污染特征分析

为研究北京地区冬季PM_(2.5)载带的水溶性无机离子组分污染特征,2013年1月在中国环境科学研究院内采用在线离子色谱(URG-9000B,AIM-IC)对PM_(2.5)中水溶性无机离子(SO_4~(2-)、NO_3~-、Cl~-、NH_4~+、Na~+、K~+、Mg~(2+)、Ca~(2+))进行监测与分析。结果表明,采样期间总水溶性无机离子(TWSI)浓度为61.0μg/m~3,其中二次无机离子SO_4~(2-)、NO_3~-、NH_4~+(SNA)占比达72.3%,在PM_(2.5)中占比为40.29%,表明北京市PM_(2.5)二次污染严重。重污染天[NO_3~-]/[SO_4~(2-)]表明,固定源污染较移动源更为显著。三元相图表明,在空气质量为优的情况下,NH_4~+(在SNA中占比为30.3%~65.5%,下同)主要以NH_4NO_3的形式存在,较少比例以(NH_4)_2SO_4存在;严重污染时,NH_4~+(47.3%~77.9%)主要以(NH_4)_2SO_4形式存在,其次以NH_4NO_3的形式存在,其余的NH_4~+以NH_4Cl的形式存在。[NO_3~-]/[SO_4~(2-)]日变化表明,早、晚机动车高峰影响北京重污染发生。     

Groundwater quality and its suitability for drinking and agricultural use in the Yanqi Basin of Xinjiang Province, Northwest China

The Yanqi Basin in Xinjiang Province is an important agricultural area with a high population density. The extensive agricultural activities in the Yanqi Basin started in the 1950s with flood irrigation techniques. Since then, the groundwater table was raised because of the absence of an efficient drainage system. This obstacle is a crucial factor that restricts sustainable socioeconomic development. Hydrochemical investigations were conducted in the Yanqi Basin, Northwestern China, to determine the chemical composition of groundwater. Sixty groundwater samples were collected from different wells to monitor the water chemistry of various ions. The results of the chemical analysis indicate that the groundwater in the area is generally neutral to slightly alkaline and predominantly contains Na⁺ and Ca²⁺ cations as well as HCO₃ ^? and SO₄ ²⁺ anions. High positive correlations between HCO₃ ^?–Mg²⁺ + Ca²⁺, SO ₄ ^2?–Mg²⁺, SO₄ ^2?–Na⁺ + K⁺, and Cl^?–Na⁺ + K⁺ were obtained. The total dissolved solids (TDS) mainly depend on the concentration of major ions such as HCO₃ ^?, SO₄ ^2?, Cl^?, Ca²⁺, Mg²⁺, and Na⁺ + K⁺. The dominant hydrochemical facies for groundwater are Ca²⁺–Mg²⁺–HCO₃ ^?, Mg²⁺–Ca²⁺–SO₄ ^2?–Cl^?, Na⁺–K⁺–Cl^?–SO₄ ^2?, and Na⁺–K⁺–Mg²⁺–Cl^?–HCO₃ ^? types. The hydrochemical processes are the main factors that determine the water quality of the groundwater system. These processes include silicate mineral weathering, dissolution, ion exchange, and, to a lesser extent, evaporation, which seem to be more pronounced downgradient of the flow system. The saturation index (SI), which is calculated according to the ionic ratio plot, indicates that the gypsum–halite dissolution reactions occur during a certain degree of rock weathering. SI also indicates that evaporation is the dominant factor that determines the major ionic composition in the study area. The assessment results of the water samples using various methods indicate that the groundwater in the study area is generally hard, fresh to brackish, high to very high saline, and low alkaline in nature. The high total hardness and TDS of the groundwater in several places indicate the unsuitability of the groundwater for drinking and irrigation. These areas require particular attention, particularly in the construction of adequate drainage as well as in the introduction of an alternative salt tolerance cropping.     

重庆市黔江区降水地球化学特征

为了解生态旅游城市重庆市黔江区大气污染状况,2015年采集了91个降水样品,分析了降水中离子组分分布特征,运用富集因子法、海盐示踪法、相关性分析、主成分分析、聚类分析和HYSPLIT模型分析了降水化学组分来源。研究结果表明:黔江区域降水p H为5.66~6.96,加权平均值为6.34,降水离子组分浓度大小次序为SO_4~(2-)Ca~(2+)NH_4~+Mg~(2+)NO_3~-Cl~-Na~+K~+F~-,SO_4~(2-)、Ca~(2+)之和占总离子的63.95%;除Mg~(2+)和K+外,其余组分离子浓度与总离子浓度随季节变化(冬季春季秋季夏季)呈同样的变化特征。Ca~(2+)、Mg~(2+)和K+大部分均来源于陆源贡献,Na~+可能受到了海洋源的影响,SO_4~(2-)和NO_3~-主要来源于人为输入源的贡献,Cl~-是受土壤物质和海洋的双重影响。轨迹水汽运输结果表明:黔江区域的降水主要受到西北气团、西南季风、西风环流和极地气候共同作用输入。降水中各个离子组分均表现出显著性或极显著性关系,主成分分析结果表明,第一主成分上研究的降水离子组分中都具有相对较大正载荷,第二组分pH、降水量和气温为一类。     

Assessment of Treatment Alternatives for Laboratory COD Wastewater: a Practical Comparison with Emphasis on Cost and Performance

This study focused on investigation of treatment alternativesfor COD wastewater from academic laboratories, using a number oftechnologies including chemical reduction/precipitation, ion exchange and adsorption by chitosan. Results showed that highconcentrations of 375 mg l^-1 chromium, 1,740 mg l^-1mercury and 993 mg l^-1 silver in COD wastewater can be reduced to 2.34 mg l^-1, 3.65 mg l^-1 and 1.89 mg l^-1 respectively, by the chemical reduction/precipitationprocess. Results from ion exchange at a flowrate of 20 ml min^-1 showed breakthrough effluent concentrations obtainedat 0.59 mg l^-1 chromium, 3.92 g l^-1 mercury and 0.65 mg l^-1 silver corresponding to 75.6 l at 63 hr, 40.8 l at 34 hr and 33.6 l at 28 hr respectively. Kinetic and isotherm studies revealed that chitosan can adsorb Cr⁶⁺, Hg²⁺ and Ag⁺ ions most effectively at a flowrate of 20 ml min^-1 and the optimum pH for feed solution is 4. Chitosan column experiments indicated that average effluent concentrations at breakthrough point for chromium, mercury andsilver are 0.76 mg l^-1, 6.04 mg l^-1 and 0.51 mg l^-1 respectively with throughput volumes and retention times of 120 l at 100 hr, 60 l at 50 hr and 48 l at 40 hr. Results of solidification experiments for chemical sludge and residual chitosan based on compressive strength and metal leachabilitytests showed, that the acceptable ranges of the solidificationparameters were: sludge/cement = 0.1–1.0 (weight/weight), water/cement = 0.5–0.6 (weight/weight) and sand/cement = 0.5–3.0 (weight/weight). Operating cost per litre of COD wastewater treated, based on the current prices in Thailand wasfound to be Baht 19.95 for the chemical reduction/precipitationprocess, Baht 96.35 for ion exchange treatment and Baht 18.29 forchitosan adsorption.     

Factor analysis and linear regression model (LRM) of metal speciation and physico-chemical characters of groundwater samples

An approach is described for viewing the interrelationship between different variables and also tracing the sources of pollution of groundwater of north Chennai (India). The data set of 43 variables which include major ions, minor ions and trace metal speciation (Cu, Pb, Cd and Zn) collected during the pre-monsoon and post-monsoon seasons of the year 2000–2001, was subjected to R-mode factor analysis to comprehend the distribution pattern of the said variables. It was found that first factor measures salinity and hardness which explained 19.12% of the total variance (comprised of variables EC, TDS, Na⁺, K⁺, Ca²⁺, Mg²⁺, total hardness, Cl⁻ and SO₄ ²⁻) during pre-monsoon, while it was 25.08% during post-monsoon. The second and third factors were attributed to speciation of zinc and copper ions during both pre-monsoon and post-monsoon. Although there were two more factors, loaded with speciation parameters of lead and cadmium, the variance of them were less than 10%. From this study it is seen that sea water intrusion, municipal solid waste disposal are the identified sources of component of pollution. The importance of metal ions is taking a secondary role and the anthropogenic origin-industrial activity, is the reason in the evaluation of pollution status as they come in the second, third, fourth and fifth factors. As the trace metal speciation was grouped in separate factors, linear regression model (LRM) with correlation analysis was applied to check its validity for prediction of speciation and to apply LRM for rapid monitoring of water pollution.     

Pesticide concentrations in water and sediment and associated invertebrate toxicity in Del Puerto and Orestimba Creeks, California, 2007�C2008

The California??s San Joaquin River and its tributaries including Orestimba (ORC) and Del Puerto (DPC) Creeks are listed on the 2006 US EPA Clean Water Act §303(d) list for pesticide impairment. From December 2007 through June 2008, water and sediment samples were collected from both creeks in Stanislaus County to determine concentrations of organophosphorus (OP) and pyrethroid insecticides and to identify toxicity to Ceriodaphnia dubia and Hyalella azteca. OPs were detected in almost half (10 of 21) of the water samples, at concentrations from 0.005 to 0.912 ??g L^???1. Diazinon was the most frequently detected OP, followed by chlorpyrifos and dimethoate. Two water samples were toxic to C. dubia; based on median lethal concentrations (LC₅₀), chlorpyrifos was likely the cause of this toxicity. Pyrethroids were detected more frequently in sediment samples (18 detections) than in water samples (three detections). Pyrethroid concentrations in water samples ranged from 0.005 to 0.021 ??g L^???1. These concentrations were well below reported C. dubia LC₅₀s, and toxicity was not observed in laboratory bioassays. Cyfluthrin, bifenthrin, esfenvalerate, and ??-cyhalothrin were detected in sediment samples at concentrations ranging from 1.0 to 74.4 ng g^???1, dry weight. At DPC, all but one sediment sample caused 100% toxicity to H. azteca. Based on estimated toxicity units (TUs), bifenthrin was likely responsible for this toxicity and ??-cyhalothrin also contributed. At ORC, survival of H. azteca was significantly reduced in four of the 11 sediment samples. However, pyrethroids were detected in only two of these samples. Based on TUs, bifenthrin and ??-cyhalothrin likely contributed to the toxicity.     

Prediction of the solubility of zinc, copper, nickel, cadmium, and lead in metal-contaminated soils

Risk assessment of metal-contaminated soil depends on how precisely one can predict the solubility of metals in soils. Responses of plants and soil organisms to metal toxicity are explained by the variation in free metal ion activity in soil pore water. This study was undertaken to predict the free ion activity of Zn, Cu, Ni, Cd, and Pb in metal-contaminated soil as a function of pH, soil organic carbon, and extractable metal content. For this purpose, 21 surface soil samples (0–15 cm) were collected from agricultural lands of various locations receiving sewage sludge and industrial effluents for a long period. One soil sample was also collected from agricultural land which has been under intensive cropping and receiving irrigation through tube well water. Soil samples were varied widely in respect of physicochemical properties including metal content. Total Zn, Cu, Ni, Cd, and Pb in experimental soils were 2,015?±?3,373, 236?±?286, 103?±?192, 29.8?±?6.04, and 141?±?270 mg kg^?1, respectively. Free metal ion activity, viz., pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺, as estimated by the Baker soil test was 9.37?±?1.89, 13.1?±?1.96, 12.8?±?1.89, 11.9?±?2.00, and 11.6?±?1.52, respectively. Free metal ion activity was predicted by pH-dependent Freundlich equation (solubility model) as a function of pH, organic carbon, and extractable metal. Results indicate that solubility model as a function of pH, Walkley–Black carbon (WBC), and ethylenediaminetetraacetic acid (EDTA)-extractable metals could explain the variation in pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺ to the extent of 59, 56, 46, 52, and 51 %, respectively. Predictability of the solubility model based on pH, KMnO₄-oxidizable carbon, and diethylenetriaminepentaacetic acid-extractable or CaCl₂-extractable metal was inferior compared to that based on EDTA-extractable metals and WBC.     

Chemistry of fogs at Agra, India: Influence of soil particulates and atmospheric gases

Fog water samples were collected in the months of December and January during 1998–2000 at Agra, India. The samples were analyzed for pH, major anions (F⁻, Cl⁻, SO₄ ²⁻, NO₃ ⁻, HCOO⁻ and CH₃COO⁻), major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺) and NH₄ ⁺ using ion chromatography, ICP-AES and spectrophotometer methods, respectively. pH of fog water samples ranged between 7.0 and 7.6 with a volume weighted mean of 7.2, indicating its alkaline characteristic. NH₄ ⁺ contributed 40%, SO₄ ²⁻ and NO₃ ⁻ accounted for 28%, while Ca²⁺, Mg²⁺, Na⁺ and K⁺ accounted for 16% of the total ionic concentration. The ratios of Mg²⁺/Ca²⁺ and Na⁺/Ca²⁺ in fog water indicates that 50–75% of fog water samples correspond to the respective ratios in local soil. Significant correlation between Ca²⁺, Mg²⁺, Na⁺ and K⁺ suggests their soil origin. The order of neutralization, NH₄ ⁺ (1.4) > Ca²⁺ (0.28) > Mg²⁺ (0.12), indicates that NH₄ ⁺ is the major neutralizing species. Fog water and atmospheric alkalinity were also computed and were found to be 873 and 903 neqm⁻³, respectively. Both of these values are higher than values reported from temperate sites and thus indicate that at the present level of pollutants, there is no risk of acid fog problem. The study also shows that the alkaline nature of fog water is due to dissolution of ammonia gas and partly due to interaction of fog water with soil derived aerosols.     

Heavy metals regulate physiological and behavioral events by modulating ion channels in neuronal membranes of molluscs

The interaction of heavy metals (HgCl₂, CdCl₂, CuCl₂, PbCl₂ and ZnCl₂) and neurotransmitters (ACh, 5HT and DA) was studied on the excitable membrane of identified neurons of Lymnaea stagnalis and Helix pomatia. It was shown that,

1. The excitability and chemosensitivity of molluscan neurons were modified under the influence of the heavy metals Hg²⁺, Cd²⁺, Cu²⁺, Pb²⁺ and Zn²⁺.
2. Change in excitability to transmitters occurred as a potentiation or depression of the evoked response both in duration of membrane polarization and in frequency of spike activity.
3. The chemosensitivity changes in various ways, namely:
4. excitatory effect was totally eliminated;
5. one component of the effect was depressed.
Different neurons may show different reactions to the same heavy metal.
6. There were differences in the effects of various heavy metals. Hg²⁺ has a more generalized effect than Cd²⁺; Cu²⁺, Pb²⁺ and Zn²⁺ were less effective in a number of neurons. The heavy metal effect was dose dependent, too.
7. Both inward and outward currents, which were evoked by neurotransmitters or voltage induced, were modified in most of the tested neurons. Both an increase and decrease of the membrane permeability occurred in different neurons in response to the same or different heavy metals.
8. The changes can be interpreted as a result of
9. direct effect on specific ionic channels;
10. modification of receptors binding ACh, 5HT, or DA;
11. modification of intracellular processes responsible for the regulation of membrane permeability.

     

Occurrence of Acid Rain over Delhi

Precipitation samples were collected as wet-fall only andprimarily on event basis in Delhi during the monsoon period of1995. Concentrations of major anions (SO₄ ^2-,NO₃ ^- and Cl^-) andcations (Ca²⁺, Mg²⁺,Na⁺ and K⁺) were determined. The pH of the rain waterwas found to be more than 5.6, showing alkalinity during theearly phase of monsoon, but during the late phase of monsoon pHtendency was towards acidity due to lack of proper neutralizationof acidic ions. Neutralization is not only due to the localprocess but also due to the pre-monsoon Andhi which bringsSuspended Particulate Matter (SPM) containing Ca²⁺,Mg²⁺, Na⁺ and K⁺ as well as the local emission ofNH₃. In the late monsoon the concentration of cations getsreduced because of heavy rainfall and relatively unfavourablecondition for their transport from the adjoining areas, whereasthe anion concentrations remain unchanged owing to theircontinuous emission.     

Effects of Cu2+, Pb2+ and Zn2+ on voltage-activated currents in Helix pomatia L. Neurons

Effects of Cu²⁺, Pb²⁺ and Zn²⁺ were studied on voltage-activated Na-, Ca-, and K-currents in snail neurons. It was found that: 1. In normal physiological saline Cu²⁺, Pb²⁺ and Zn²⁺ ions exerted complex changes on the total ionic currents; 2. All three metal ion have depressed the inward Na-currents but with different K _D , moreover Pb ²⁺ increased Na-current at low concentrations (5 M); 3. The inward Ca-current was also reduced. The sequence of the blocking effect of metals was different: Pb>Cu>Zn, however the steady-state inactivation was influenced only by Cu²⁺; 4. Outward currents were decreased in all neurons by Cu²⁺, but the effects of Pb²⁺ and Zn²⁺ were either depression or enhancement in different indentified neurons; 5. The possibility of binding heavy metals to wide variety of membrane proteins and the observed effects on different ionic channels suggest that the metal effect is complex and cannot be taken as a specific one to a single channel type or site of location.     

上海青浦地区大气降水的化学特征

利用上海青浦地区2003—2014年观测的大气降水监测资料,分析该区域12 a以来大气降水的酸化程度、化学组成特征,探讨降水中化学成分的不同来源及相对贡献。结果表明:降水pH年均值为4.43~6.33,酸雨频率为2.6%~86.8%,降水酸化程度大致经历了明显恶化和波动变化2个阶段。降水电导率年均值为1.77~4.01 m S/m,呈下降趋势。降水中各离子雨量加权平均当量浓度顺序为SO_4~(2-)NH_4~+Ca~(2+)NO_3~-Cl~-Na~+Mg~(2+)F-K~+,SO_4~(2-)、NH+4、Ca~(2+)和NO_3~-是降水中的主要离子,占离子总量的83.0%;降水类型由硫酸型向硫酸和硝酸混合型转变。降水离子中的二次组分SO_4~(2-)、NO_3~-和NH_4~+绝大部分来源于人为源,Ca~(2+)、Mg~(2+)和K+主要来自于土壤源和人为源的贡献,Cl~-主要来自海洋源,同时人为源的影响也不可忽视。     

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。     

Monitoring of Fogwater Chemistry in the Gulf Coast Urban Industrial Corridor: Baton Rouge (Louisiana)

Seventeen fog events were sampled in Baton Rouge, Louisiana during 2002–2004 as part of characterizing wet deposition by fogwater in the heavily industrialized corridor along the Louisiana Gulf Coast in the United States. These samples were analyzed for chemical characteristics such as pH, conductivity, total organic and inorganic carbon, total metals and the principal ion concentrations. The dominant ionic species in all samples were NH₄⁺, NO₃⁻, Cl⁻ and SO₄²⁻. The pH of the fogwater sampled had a mean value of 6.7 with two cases of acidic pH of 4.7. Rainwater and fogwater pH were similar in this region. The acidity of fogwater was a result of NO₃⁻ but partly offset by high NH₄⁺. The measured gaseous SO₂ accounted for a small percentage of the observed sulfate concentration, indicating additional gas-to-particle conversion of SO₂ to sulfate in fogwater. The gaseous NO_x accounted for most of the dissolved nitrate and nitrite concentration in fogwater. The high chloride concentration was attributable to the degradation of chlorinated organics in the atmosphere. The metal composition was traced directly to soil-derived aerosol precursors in the air. The major metals observed in fogwater were Na, K, Ca, Fe, Al, Mg and Zn. Of these Na, K, Ca and Mg were predominant with mean concentrations > 100 μM. Al, Fe and Zn were present in the samples, at mean concentrations < 100 μM. Small concentrations of Mn (7.8 μM), Cu (2 μM), Pb (0.07 μM) and As (0.32 μM) were also observed in the fogwaters, and these were shown to result from particulates (PM_2.5) in the atmosphere. The contribution to both ions and metals from the marine sources in the Louisiana Gulf Coast was minimal. The concentrations of all principal ionic species and metals in fogwater were 1–2 orders of magnitude larger than in rainwater. Several linear alkane organic compounds were observed in the fogwater, representing the contributions from petroleum products at concentrations far exceeding their aqueous solubility. A pesticide (atrazine) was also observed in fogwater, representing the contribution from the agricultural activities nearby.