Application of ion chromatography to the determination of water-soluble inorganic and organic ions in atmospheric aerosols

A simple, sensitive and convenient ion chromatography(IC) method was established for the simultaneous determination of twelve water-soluble inorganic anions(F -, Cl -, NO - 2, NO - 3, SO 2- 3, SO 2- 4, PO 3- 4), and fifteen water-soluble organic ions(formate, acetate, MSA, oxalate, malonate, succinate, phthalates, etc.) in atmospheric aerosols. The linear concentrations ranged from 0.005 μg/m 3 to 500 μg/m 3(r = 0.999—0.9999). The relative standard deviation(RSD) were 0.43%—2.00% and the detection limits were from 2.7 ng/m 3 to 88 ng/m 3. The proposed method was successfully applied to the simultaneous determination of those inorganic ions and organic ions in PM 2.5 of Beijing.

Deposition of water-soluble inorganic ions in PM_(2.5) in a typical forestry system in Beijing,China

Background: Rapid economic development in China has resulted in an increase in severe air pollution in city groups such as the Beijing-Tianjin-Hebei Metropolitan Region. PM2.5(fine particles with an aerodynamic equivalent diameter of 2.5 μm or less) is one of the most important pollutants. The deposition process is an important way of removing particles from the air. To evaluate the effect of an urban forest on atmospheric particle removal, a concentration gradient method was used to measure the deposition velocities of water-soluble inorganics in PM2.5 in two national forest parks in Beijing, China. The following eight water-soluble inorganic ions in PM2.5 were investigated: sodium, ammonium, potassium, magnesium, calcium, chloride, nitrate, and sulfate.Methods: Samples were taken from two sites in Beijing from the 7 th to the 15 th May, 2013. The concentrations of water-soluble inorganic ions were analyzed with ion chromatography. We used the concentration gradient technique to estimate the deposition flux and velocity. To determine the relationships between leaf traits and particle accumulation, typical leaf samples from each selected species were studied using scanning electron microscopy.Results: The total deposition flux and total deposition velocity during the daytime were higher than those at night.Sulfate showed the biggest deposition flux and velocity at both study sites, whereas the other ions showed different trends at each site. Result from higher proportion of coniferous to broadleaved trees, the total deposition flux of the eight ions measured in Jiufeng National Forest Park was greater than that in Olympic Forest Park.Conclusions: The deposition velocity was affected by meteorological conditions such as wind speed, temperature,and humidity. The deposition velocity was also influenced by tree species. The surface of plants is an important factor influencing particle deposition. The results of this study may help in assessing the effects of forestry systems on particle removal and provide evidence for urban air pollution control and afforestation of urban areas.

On-line Measurement of Water-Soluble Ions in Ambient Particles

Combining the system of rapid collection of ambient particles and ion chromatography, the system of rapid collection of fine particles and ion chromatography （RCFP-IC） was established to automatically analyze on-line the concentrations of water-soluble ions in ambient particles. Here, the general scheme of RCFP-IC is described and its basic performance is tested. The detection limit of RCFP-IC for SO4^2-, NO3^-, NO2^-, Cl^- and F- is below 0.3μg m^-3. The collection efficiency of RCFP-IC increases rapidly with increasing sized particles. For particles larger than 300 nm, the collection efficiency approaches 100%. The precision of RCFP-IC is more than 90% over 28 repetitions. The response of RCFP-IC is very sensitive and no obvious cross-pollution is found during measurement. A comparison of RCFP-IC with an integrated filter measurement indicates that the measurement of RCFP-IC is comparable in both laboratory experiments and field observations. The results of the field experiment prove that RCFP-IC is an effective on-line monitoring system and is helpful in source apportionment and pollution episode monitoring.

Diurnal variations of water-soluble ions in PM_(2.5)in Shanghai

Thirty-six daily time interval PM2.5 samples were collected in different seasonal dates in urban Shanghai, and the concentrations of four anions （Cl- , NO3-, SO4^2-, C2O4^2-） and five cations （NH＋, Na＋, K＋, Ca2＋, Mg2＋） were analyzed with ion chromatography. Sulfate, nitrate and ammonium were found to be the dominant species, accounting for about 80% of the total ions. The daily nitrate to sulfate mass ratio ranged from 0.31 to 0.82, indicating that coal combustion was still the main pollution source in Shanghai. The equivalent ratio of ammonium to stun of nitrate and sulfate showed fixed diurnal variation pattern in all the sampling days with higher values in the nighttime, suggesting that fine particles in the night were more neutralized. The oxalate to sulfate ratio was lower in the winter sampling days than that in hotter summer and autumn sampling days. Oxalate was significantly correlated with sulfate in winter sampling days, but not in the summer and autumn, suggesting that the formation mechanism of oxalate and sulfate was similar in winter, however different in hot days.

Study on changes of plasmalemma permeability and some primary inorganic ions of Antarctic ice microalgae (Chlamydomonas sp. ICE-L) in the low-temperature stress

The changes of plasmalemma permeability and some primary inorganic ions of Antarctic ice microalgae （ Chlamydomonas sp. ICE-L） in the low-temperature stress were examined. The plasmalemma of 1CE-L could maintain the stability at the freezing condition of -6 ℃. That signifies that it could maintain the proper function of plasmalemma and stability of the intracellular environment during sea ice formation. The function of inorganic ions on low-temperature adaptation of ICE-L was investigated by using the X-ray microanalysis method. Low temperature （0 - -6 ℃ ） induces Ca^2 ＋ concentration increment of cytoplasm, but after 24 h the content decrease quickly to normal value. As a matter of fact, Ca^2 ＋ plays an important role as the second messenger in the low temperature adaptation of ICE-L. In addition, low temperature also influences on the other primary inorganic ions transfer and the cell maintains activity by keeping ratio balance among different ions. Above all, it is necessary for Antarctic ice microalgae to survive and breed by maintaining the stability of K^ ＋ content and the balance of Na^ ＋/Cl^ -.

Separation of Inorganic Anions Using Methacrylate-Based Monolithic Column Modified with Trimethylamine in Ion Chromatography Capillary System

Methacrylate-based monolithic column was prepared in fused-silica capillary (80 ′ 0.32 mm i.d.) by in situ polymerizetion reaction using glycidyl methacrylate as monomer;ethylene dimethacrylate as crosslinker;1-propanol, 1,4-butanediol, and water as porogenic solvents. The monolith matrix was modified with trimethylamine to create strong anion exchanger via ring opening reaction of epoxy groups. The morphology of the monolithic column was studied by using Scanning Electron Microscope (SEM). This column had good mechanical stability and permeability. The effects of various mobile phases for separation of inorganic anions were investigated. Iodate, bromate, nitrite, bromide, and nitrate were separated within 11 min using100 mMpotassium chloride as mobile phase and detected at 210 nm. This method showed good precision of retention time, acceptable linearity and good sensitivity. Under the optimum condition, the RSD of the retention time was in the range of 1.09%-1.75% (n = 6). The calibration curve showed linear relationships between the peak area and the concentration. The limits of detection (LOD) and the limits of quantitation (LOQ) were between 0.08-0.18 mM and 0.26-0.61 mM, respectively. This method was applied to the determination of inorganic anions in tap water and ground water samples.

Concentrations,sources,and influential factors of water-soluble ions of atmospheric particles in Dunhuang Mogao Grottoes,a world heritage site in China

Atmospheric particle pollution is one of the major factors leading to degradation of ancient wall paintings,particularly heritage sites in arid and semi-arid regions.However,current systematic research on the changes,sources,and influential factors of atmospheric particulate matter and its water-soluble ion concentrations is not sufficient.Thus,the major water-soluble ion concentrations,sources,and influential factors of atmospheric particles PM_(2.5) and PM_(10)(particulate matter with an aerodynamic equivalent diameter≤2.5 and 10.0μm,respectively,in ambient air)were collected from Cave 16 and its ambient exterior environment in the Dunhuang Mogao Grottoes,China,between April 2015 and March 2016.Results showed that the concentrations of PM_(2.5) and PM_(10) inside and outside the cave were the highest in March 2016 and the lowest in December 2015.The higher particle concentration from March to May was related to the frequent occurrence of sand and dust events,and the lower particle concentration from June to September was associated with good diffusion conditions,increased precipitation,and an established cave shelterbelt.The concentration of particulate matter inside the cave was affected by the concentration of particles in the air outside the cave.Ca2+,NH+4,Na+,Cl-,and SO2-4were the main components of the total ions of PM_(2.5) and PM_(10) both inside and outside the cave.The total ions inside the cave were frequently affected by the disturbance of tourists'activities during the peak tourist season from May to August.Under the influence of dust,the total concentrations of Cl-,SO2-4,Na+,NH+4,and Ca2+in particles of different sizes inside and outside the cave increased,and the concentrations of Cl-,SO2-4,Na+,and Ca2+decreased during precipitation period.Backward air mass trajectory analysis suggested that the pollutants were mainly from Xinjiang,China.The pollutant sources of air particulates are straw burning,secondary pollution sources,soil dust,dry spring rivers,and tourist activities.

Organic acids and inorganic anions in Bayer liquors by ion chromatography after solid-phase extraction

A method for the simultaneous separation and determination of organic acids and inorganic anions in Bayer liquors was developed by gradient ion chromatography with suppressed conductivity detection. Formate, acetate, propionate, oxalate, succinate, glutarate, fluoride, chloride and sulfate were separated and determined in 33 min. The samples were pretreated with solid-phase extraction, which has high selectivity for removing a large number of metallic ions in the Bayer liquors, and filtered with a 0.45 μm filter membrane before being injected into the ion chromatographic system. The separation of six organic acids and three inorganic anions was achieved on an IonPac AS11-HC column with KOH as the eluent, and the detection was performed by a conductivity detection mode. No interference is found in the presence of fluorate, chlorate and sulphate when organic acids are determined. The calibration graphs of peak area for all the analytes are linear over a wide range. The relative standard derivation of the peak area of analytes is less than 2.14%. Under optimum conditions the detection ranges from 0.2 to 100.0 mg/L. The average recoveries of the added standards are between 94.3% and 102.8%.

Determination of inorganic anions in ethyl acetate by in-line hollow fiber membrane extraction with ion chromatography

在这个工作，一个新奇空纤维膜抽出者被设置用 deionized 水从乙醇醋酸盐提取无机的阴离子。在稍微可溶的器官的溶剂的无机的阴离子能被结合的同轴的空纤维膜抽出者决定离子层析起初时间。象磁性的激动人心的速度，抽取流动率和抽取时间那样的抽取过程的不同方面被优化完成高抽取效率和好分离结果。令人满意的线性范围，察觉的限制和好重覆性被获得。过程被使用在二件商业乙醇醋酸盐样品分析无机的阴离子。

The spatial and temporal distribution and characteristics of inorganic ion concentrations of TSP in the Tarim Basin

Based on Total Suspended Particulates （TSP） observations of Tazhong, Tikanli, Kashi and Minfeng in 2009, combined wa- ter-soluble inorganic ion analyses, this paper studied the spatial and temporal distribution of TSP in the Tarim Basin and analyzed concentration characteristics. The results are as follows： （1） monthly average TSP concentrations shows a similar trend in Tazhong, Tikanli, Kashi and Minfeng with peak values in April-May and low values in November-December. As for the quarter average mass concentration trends, spring has the highest value, followed by summer and autumn, and winter is the lowest; （2） total annual concentration trend of water-soluble inorganic ions in TSP is as follows： Tazhong 〉 Tikanli 〉 Minfeng 〉 Kashi. SO4^2- concentra- tions are 58%, 50%, 54% and 51% of total ion concentration; Ca^2＋ concentrations are 13%, 16%, 16% and 11%; Na^＋ concentra- tions are 12%, 13%, 10% and 12% and Cl^- concentrations are 12%, 16%, 11% and 22%, respectively. Therefore, sulfate, calcium, sodium and chloride ions are the main inorganic components of TSP in the Tarim Basin; （3） the correlation coefficients of anions and cations in Tikanli, Minfeng, Kashi and Tazhong are 0.99, 0.99, 0.25 and 0.91, respectively; the average anion concentrations are 2.57, 2.12, 2.15 and 3.02 times the average cation concentrations, indicating that ions were unbalanced; （4） SO4^2-/NO3^- ratio is much larger than the ratio of coal-fired emissions SO4^2-/NO3^-, thus the impact of fixed emission sources in the four regions on the atmosphere is far greater than that of mobile emission sources.

Temporal variations in geochemistry of hydraulic fracturing fluid and flowback water in a tight oil reservoir

Hydraulic fracturing facilitates the development and exploitation of unconventional reservoirs.In this study,the injected hydraulic fracturing fluid(HFF)and flowback and produced water(FPW)in tight oil reservoirs of the Lucaogou Formation in the Junggar Basin are temporally sampled from day 1 to day 64.Freshwater is used for fracturing,and HFF is obtained.The chemical and isotopic parameters(including the water type,total salinity,total dissolved solids(TDS),pH,concentrations of Na^(+),Cl^(-),Ba^(+),K^(+),Fe^(2+)+Fe^(3+),and CO_(3)^(2-),dD,and δ^(18)O)are experimentally obtained,and their variations with time are systematically analyzed based on the flowback water.The results show that the water type,Na/Cl ratio,total salinity,and TDS of the FPW change periodically primarily due to the HFF mixing with formation water,thus causing δD and δ^(18)O to deviate from the meteoric water line of Xinjiang.Because of watererock interaction(WRI),the concentrations of Fe^(2+)+Fe^(3+)and CO_(3)^(2-)of the FPW increase over time,with the solution pH becoming more alkaline.Furthermore,based on the significant changes observed in the geochemistry of the FPW,three separate time intervals of flowback time are identified:Stage Ⅰ(<10 days),where the FPW is dominated by the HFF and the changes in ions and isotopes are mainly caused by the WRI;Stage Ⅱ(10-37 days),where the FPW is dominated by the addition of formation water to the HFF and the WRI is weakened;and finally,Stage Ⅲ(>37 days),where the FPW is dominated by the chemistry of the formation water.The methodology implemented in this study can provide critical support for the source identification of formation water.

The effect of inorganic salt precipitation on oil recovery during CO2 flooding:A case study of Chang 8 block in Changqing oilfield,NW China

Static experiments and dynamic displacement experiments were conducted to quantitatively determine the amount of precipitate generated by the CO_(2)-formation water reaction at different temperatures,pressures,and scaling ion concentrations during CO_(2) flooding in the Chang 8 block of Changqing Oilfield,the influence of precipitate on the physical properties of reservoirs was investigated,and the corresponding mathematical characterization model was established.The mathematical characterization equation was used to correct the numerical simulation model of E300 module in Eclipse software.The distribution pattern of inorganic salt precipitates during continuous CO_(2) flooding in Chang 8 block was simulated,and the influence of inorganic salt precipitates on oil recovery was predicted.The inorganic salt precipitate generated during CO_(2)-formation water reaction was mainly CaCO_(3),and the pressure difference and scaling ion concentration were proportional to the amount of precipitate generated,while the temperature was inversely proportional to the amount of precipitate.The rate of core porosity change before and after CO_(2) flooding was positively correlated with temperature and flooding pressure difference.The core porosity increase in the CO_(2)-formation water-core reaction experiment was always lower than that of CO_(2)-distilled water-core reaction experiment because of precipitation.The area around the production wells had the most precipitates generated with the injection of CO_(2).The oil field became poor in development because of the widely distributed precipitate and the recovery decreased to 33.45% from 37.64% after 20-year-CO_(2) flooding when considering of precipitation.

Comparative study on water-soluble inorganic ions in PM2.5 from two distinct climate regions and air quality

Recently, air quality has significantly improved in developed country, but that issue is of concern in emerging megacity in developing country.In this study, aerosols and their precursor gas were collected by NILU filter pack at two distinct urban sites during the winter and summer in Osaka, Japan and dry and rainy seasons in Ho Chi Minh City(HCMC),Vietnam.The aims are to investigate the contribution of water-soluble inorganic ions(WSIIs) to PM2.5, thermodynamic characterization and possible formation pathway of secondary inorganic aerosol(SIA).The PM2.5 concentration in Osaka(15.8 μg/m^3) is lower than that in HCMC(23.0 μg/m^3), but the concentration of WSIIs in Osaka(9.0 μg/m^3) is two times higher than that in HCMC(4.1 μg/m^3).Moreover, SIA including NH4^+, NO3^-and SO4^2-are major components in WSIIs accounting for 90% and 76%(in molar) in Osaka and HCMC,respectively.Thermodynamic models were used to understand the thermodynamic characterization of urban aerosols.Overall, statistical analysis results indicate that very good agreement(R2> 0.8) was found for all species, except for nitrate aerosol in HCMC.We found that when the crustal species present at high amount, those compositions should be included in model calculation(i.e.in the HCMC situation).Finally, we analyzed the characteristics of NH4^+– NO3^-– SO4^2-system.A possible pathway to produce fine nitrate aerosol in Osaka is via the homogeneous reaction between NH3 and HNO3, while nonvolatile nitrate aerosols can be formed by the heterogeneous reactions in HCMC.

Characteristics of Aerosol Pollution Under Different Visibility Conditions in Winter in a Coastal Mega-City in China

To investigate chemical profiles and formation mechanisms of aerosol particles in winter haze events,comprehensive measurements including hourly concentrations of PM2.5 and water-soluble inorganic ions and related gasphase precursors were conducted via an online monitoring system from January to March of 2016 in Shenzhen,a coastal mega-city in south China.In this study,high concentrations of PM2.5,NO2 and lower levels of O3 were observed during haze periods in comparison with clear days(Visibility>15 km).The major secondary ionic species were NH+4、NO-3 and SO2-4,which varied significantly on haze and clear days.The ratio of NO-3/SO2-4 in haze days was greater than that on clear days and tended to be larger when air pollution became more serious.At the same time,compared with previous studies,it has been found that the ratio has been increasing gradually in Shenzhen,indicating that the motor vehicle exhaust emissions have a more and more important impact on air quality in Shenzhen.Sulfur oxidation rate(SOR)and nitrogen oxidation rate(NOR)was higher during the haze period than that in clean days,indicating efficient gas to particle conversion.Further analysis shows that high concentrations of sulfate might be explained by aqueous oxidation,but gas-phase reactions might dominate nitrate formation.This study also highlights that wintertime nitrate formation can be an important contributor to aerosol particles,especially during haze periods.

Evaluation of trans-ferulic acid degradation by dielectric barrier discharge plasma combined with ozone in wastewater with different water quality conditions

In this study, dielectric barrier discharge plasma and ozone(O_3) were combined to synergistically degrade trans-ferulic acid(FA), and the effect of water quality on FA degradation was studied. The results showed that 96.9% of FA was degraded after 40 min treatment by the plasma/O_3 process. FA degradation efficiency increased with the p H values. The presence of suspended solid and humic acid inhibited FA degradation. FA degradation efficiency increased as the water temperature increased to 30 °C. However, the further increase in water temperature was adverse for FA degradation. Effects of common inorganic ions on FA degradation were also investigated. The addition of Cl^- inhibited the FA degradation, whileCO_3^(2-) had both negative and positive influences on FA degradation.NO_3^- andSO_4^(2-) did not have significant effect on FA degradation. Fe^(3+)and Cu^(2+)benefited FA degradation through the Fenton-like and catalytic ozonation reactions.

Determination of sulfur anions by ion chromatography-postcolumn derivation and UV detection

A novel method for determination of formaldehyde sulfoxylate, sulfite, thiocyanate, and thiosulfate in foodstuffs by ion chromatography separation with postcolumn derivation and UV detection has been developed. All species are separated at Dionex IonPac AG22A and AS22A with mobile phase of a mixture of 4.5 mmol/L sodium carbonate and 0.8 mmol/L sodium bicarbonate at a flow-rate of 1.0 mL/min. The postcolunm derivation solution was 0.24% iodine in 0.2% phosphate acid and the detection wavelength was set at 288 nm. The detection limits （LOD, signal-to-noise ratio of 3） of formaldehyde sulfoxylate, sulfite, thiocyanate, and thiosulfate were 0.004, 0.006, 0.006, and 0.007 mg/L, respectively. Within-day relative standard deviations （RSD, n = 10） of formaldehyde sulfoxylate, sulflte, thiocyanate, and thiosulfate were 3.24%, 3.76%, 2.68%, and 2.07%, respectively. The recoveries of the four anions were in the range of 67.2-116.5%.

PVDF-Based Micro Inorganic Fillers-Containing Polymer Electrolyte Membranes

Polymer electrolyte membranes based on poly （vinylidene fluoride-co-hexafluoropropylene） （PVDFHFP） with and without different types of micro inorganic fillers were prepared by phase-inversion process. Morphologies, porosities and electrochemical properties ＇of the as-prepared membranes were investigated by means of scanning electronic microscopy （SEM）, PC （propylene carbonate） uptake and alternating current （AC） impedance technique. Compared with other membranes, the membrane with micro SiO2 filler shows a dense morphology so that its PC uptake is the highest, namely, 339 %. The membrane filled with micro TiO2 exhibits good electrochemical performances： the ion conductivity is as high as 1.1 × 10^-3 S/cm at 18 ℃, which can meet the demand of lithium ion batteries. Moreover, its initial charge-discharge efficiency exceeds 89 %. The composite membranes with micro SiO2, TiO2 and Al2O3 are more suitable for the utilization in lithium ion batteries due to better cycle.ability, whereas the battery assembled with the blank membrane containing no inorganic fillers encounters a short circuit after the 5th cycle.

Effects of Fe3+ and Ca2+ on sorption of phenanthrene by Humin in karst soil,Southwest China

Humin(HM) is the main organic matter component to af fect the migration and transformation of polycyclic aromatic hydrocarbons(PAHs) in soil. The study on infl uence of the morphology change of inorganic ions on the adsorption of PAHs in soil and its organic matter is still rare at microscopic scale. In this paper, yellow soil humin(YS-HM) and lime soil humin(LS-HM) were chosen as samples, then Fe^(3+) and Ca^(2+) were added into samples to facilitate the precipitation by changing the existing conditions of ions, and the mechanism by which inorganic precipitation changed adsorption capacity of karst soil was analyzed from the microscopic scale. The results showed that the adsorption capacity of HM reduced with the inorganic precipitation increasing. The precipitation of Ca^(2+)and Fe^(3+) both reduced the adsorption capacity of YS-HM and LS-HM by 61.71% and 71.83% on average, respectively. The results of scanning electron microscope-energy dispersive spectrometry(SEM-EDS) and pore analysis showed that the HM porosity decreased after formation of Ca^(2+) and Fe^(3+) precipitation. According to the value of Freundlich parameter n, it may be because the precipitation or colloid of Ca^(2+) and Fe^(3+) fi lled micropores and covers high-energy adsorption sites of the HM. This research provides theoretical support for studying the PAHs migration and bioavailability of Calcium-rich in karst soil.

Impact of Winter Transit Air Masses on the Sources and Composition Characteristics of Atmospheric Pollution in Hengyang

Through the integration and analysis platform of particulate matter components,a preliminary comparison was conducted on the pollution contribution of the three winter transit air masses in December to environmental quality,and the changes and related relationships of water-soluble ions and particulate matter elements were analyzed.The results showed that winter transit air masses had a significant impact on the air quality in Hengyang.In the quantitative comparison of the primary pollutant contribution during the transit period of air masses,local sources and transit sources each accounted for half,and the impact of transit source on ambient air quality was much greater than that of seasonal base increase.Fine particulate matter was closely related to secondary ions,and particulate matter was closely related to primary ions.The transit of air masses promoted the improvement of secondary ion conversion rate,and the unit increment of fine particulate matter was greater than that of particulate matter.During the transit period,the mass concentrations of most water-soluble ions and most particulate matter elements maintained synchronous growth,with a superimposed effect.The composition ratio of organic carbon and nitrate ions increased,while the composition ratio of ammonia and sulfate ions decreased.Both disposable ions and secondary conversions in the composition of PM_(2.5)had increases and decreases.The high conversion rate of nitrate and the high composition ratio of ammonia radical in Hengyang indicated that transportation source factors had a significant impact on the local environmental quality of Hengyang.