現(xiàn)代離子色譜分析技術(shù)及進(jìn)展

1、丁丁 明玉明玉清華大學(xué)化學(xué)系清華大學(xué)化學(xué)系現(xiàn)代離子色譜分析技術(shù)及進(jìn)展二、實(shí)驗(yàn)技術(shù)與應(yīng)用二、實(shí)驗(yàn)技術(shù)與應(yīng)用 離子色譜實(shí)驗(yàn)技術(shù)離子色譜實(shí)驗(yàn)技術(shù) 樣品導(dǎo)入部分樣品導(dǎo)入部分：在線樣品預(yù)處理技術(shù)(in-line，英藍(lán))、自動(dòng)進(jìn)樣、在線預(yù)濃縮 分離部分分離部分：固定相制備技術(shù)、梯度洗脫技術(shù)、陰陽離子同時(shí)分析技術(shù)、柱切換技術(shù)（多維色譜） 檢測部分檢測部分：抑制技術(shù)、衍生化技術(shù)、間接檢測 數(shù)據(jù)處理數(shù)據(jù)處理：自動(dòng)控制、遠(yuǎn)程控制、智能色譜離子色譜固定相離子色譜固定相分離的核心 不同分離模式所采用的固定相不同；不同分離模式所采用的固定相不同； 最常用固定相是離子交換劑（樹酯）；最常用固定相是離子交換劑（樹酯）； 離

2、子交換樹酯與離子交換劑的區(qū)別；離子交換樹酯與離子交換劑的區(qū)別； 陰離子交換劑與陽離子交換劑；陰離子交換劑與陽離子交換劑； 載體（基質(zhì)）與功能基團(tuán)；載體（基質(zhì)）與功能基團(tuán)； 固定離子與可交換離子。固定離子與可交換離子。陰、陽離子交換劑陰、陽離子交換劑陰離子交換劑陰離子交換劑 強(qiáng)堿型：強(qiáng)堿型： 季胺基（季胺基（-N-N+ +(CH(CH3 3) )3 3OHOH- -） 弱堿型：弱堿型： 伯、仲、叔胺基伯、仲、叔胺基 陽離子交換劑陽離子交換劑 強(qiáng)酸型：強(qiáng)酸型： 磺酸基（磺酸基（-SO-SO3 3H H） 中強(qiáng)酸型：中強(qiáng)酸型： -PO(OH)-PO(OH)2 2 弱酸型：弱酸型： -COOH-COO

3、H其它類型固定相其它類型固定相 兩性離子交換劑兩性離子交換劑 螯合樹酯螯合樹酯 氧化還原樹酯氧化還原樹酯固定相制備技術(shù)固定相制備技術(shù) 球形、均勻的基質(zhì)顆粒；球形、均勻的基質(zhì)顆粒； 分析填料：分析填料：3 37um7um；制備填料：；制備填料：202040um40um 功能修飾：鍵合與包覆（附聚）功能修飾：鍵合與包覆（附聚） 柱尺寸：微柱柱尺寸：微柱(1mm(1mm）、半微柱）、半微柱(1-3mm)(1-3mm) 新技術(shù)：整體柱新技術(shù)：整體柱 柱填充技術(shù)：高壓、勻降柱填充技術(shù)：高壓、勻降 m 抑制型電導(dǎo)檢測陰離子交換色譜常用流動(dòng)相抑制型電導(dǎo)檢測陰離子交換色譜常用流動(dòng)相淋洗劑淋洗劑Na2B4O7N

4、aOHNaHCO3NaHCO3 + Na2CO3H2NCH(R)COOH + NaOHRNHCH(R )SO3H + NaOHNa2CO3抑制產(chǎn)物抑制產(chǎn)物H3BO3H2OCO2 + H2OCO2 + H2OH3N+CH(R)COORNH2+CH(R )SO3CO2 + H2O 淋洗強(qiáng)度淋洗強(qiáng)度很弱很弱弱弱弱弱中等強(qiáng)度中等強(qiáng)度中等強(qiáng)度中等強(qiáng)度中等強(qiáng)度中等強(qiáng)度強(qiáng)強(qiáng) 淋洗劑淋洗劑淋洗劑淋洗劑非抑制型電導(dǎo)檢測陰離子交換色譜常用流動(dòng)相非抑制型電導(dǎo)檢測陰離子交換色譜常用流動(dòng)相 羧羧 酸酸煙煙 酸酸苯甲酸苯甲酸丁二酸丁二酸檸檬酸檸檬酸富馬酸富馬酸水楊酸水楊酸 pK14.874.194.163.143.032

5、.97 離解度離解度(%)(%)1111222225255858626263 63 淋洗強(qiáng)度淋洗強(qiáng)度弱弱強(qiáng)強(qiáng)弱弱弱弱弱弱強(qiáng)強(qiáng) 混合淋洗劑混合淋洗劑 淋洗液中添加有機(jī)溶劑淋洗液中添加有機(jī)溶劑（疏水性離子的吸附、分配）（疏水性離子的吸附、分配） 強(qiáng)淋洗劑弱淋洗劑強(qiáng)淋洗劑弱淋洗劑（淋洗強(qiáng)度的準(zhǔn)確調(diào)節(jié)）（淋洗強(qiáng)度的準(zhǔn)確調(diào)節(jié)） 淋洗劑中有目的地添加特殊試劑淋洗劑中有目的地添加特殊試劑（如：酒石酸冠（如：酒石酸冠醚，用于鉀鈉分離）醚，用于鉀鈉分離）調(diào)節(jié)淋洗液強(qiáng)度和極性調(diào)節(jié)淋洗液強(qiáng)度和極性梯度洗脫梯度洗脫 為什么要進(jìn)行梯度洗脫為什么要進(jìn)行梯度洗脫 常用流動(dòng)相強(qiáng)度（組成）梯度常用流動(dòng)相強(qiáng)度（組成）梯度 高壓梯

6、度與低壓梯度高壓梯度與低壓梯度 線性梯度、階梯梯度線性梯度、階梯梯度 常規(guī)分析中不必采用梯度洗脫常規(guī)分析中不必采用梯度洗脫抑制技術(shù)抑制技術(shù) 目的目的（提高靈敏度） 效果效果（靈敏度提高12個(gè)數(shù)量級(jí)） 原理原理（后述）（后述） 抑制器類型抑制器類型（柱抑制器、微膜抑制器） 抑制劑抑制劑（再生液）再生液）的提供的提供（外加、在線電解）廢液廢液背景電導(dǎo)背景電導(dǎo)： ： Na2CO3 / NaHCO3(700S)NaF ,NaCl, NaNO3Na2HPO4, Na2SO4ConductivityNaFNaClNaNO3Na2HPO4Na2SO4背景背景電導(dǎo)電導(dǎo)： ： Na2CO3 / NaHCO3(7

7、00S)ConductivityHFHClHNO3H3PO4H2SO4Retention time背景電導(dǎo)背景電導(dǎo)： H2CO3 (15S)Conductivityw溶質(zhì)電導(dǎo)增強(qiáng)（溶質(zhì)電導(dǎo)增強(qiáng)（H H的電導(dǎo)率最大）的電導(dǎo)率最大）Na+, Cl- H+, Cl-w降低流動(dòng)相背景電導(dǎo)降低流動(dòng)相背景電導(dǎo)Na+, HCO3- H2CO3Na+,OH-H2O Cation Anion Total conductivity （ （ ） ） （ （ ） ） （unit：S/m equivalent）離子交換膜離子交換膜離子交換膜離子交換膜流流動(dòng)動(dòng)相屏相屏再生液屏再生液屏再生液屏再生液屏柱流出物柱流出物至檢測

8、池至檢測池廢液廢液 再生液再生液: :Anion in the sampleAnion in the sample: :Cation in the sampleCation in the sampleH2CO3H2O: :Anion in the sampleAnion in the sample: :Cation in the sampleCation in the sample微膜抑制器的優(yōu)缺點(diǎn)微膜抑制器的優(yōu)缺點(diǎn)優(yōu)點(diǎn)：優(yōu)點(diǎn)： 可以連續(xù)再生可以連續(xù)再生 交換容量高交換容量高 死體積小（死體積?。?050 L L以下）以下） 缺點(diǎn)：缺點(diǎn)： 基體物質(zhì)和溶劑對膜可能帶來損害基體物質(zhì)和溶劑對膜可能帶

9、來損害 工作曲線線性范圍受離子交換膜的影響工作曲線線性范圍受離子交換膜的影響 柱抑制器柱抑制器 填充了帶相反電荷離子交換劑的柱管狀抑制器 柱抑制器的優(yōu)點(diǎn)：交換容量高、制備容易 早期柱抑制器的缺點(diǎn)： 不能連續(xù)再生 死體積大（色譜峰展寬） 新型連續(xù)自動(dòng)再生柱抑制器克服了上述缺點(diǎn)新型連續(xù)自動(dòng)再生柱抑制器新型連續(xù)自動(dòng)再生柱抑制器 三根高容量、長壽命和易操作的微填充抑制柱。 一根在流路工作 一根用硫酸再生 一根用水沖洗Na+ H+H2SO4 H2O 工作工作再生再生待用（待用（清洗）清洗）新型連續(xù)自動(dòng)再生柱抑制器新型連續(xù)自動(dòng)再生柱抑制器洗脫液洗脫液 泵柱廢液廢液外加水電解產(chǎn)生抑制劑的抑制器外加水電解產(chǎn)生

10、抑制劑的抑制器純水電源加加壓壓 進(jìn)樣閥進(jìn)樣閥 抑制器抑制器 檢測池反壓管洗脫液洗脫液泵柱廢液廢液 再生液外加化學(xué)抑制劑連續(xù)再生模式流程圖外加化學(xué)抑制劑連續(xù)再生模式流程圖 加壓進(jìn)樣閥 抑制器抑制器 檢測池洗脫液洗脫液泵柱廢液廢液 再生液進(jìn)樣閥 抑制器 檢測池蠕動(dòng)泵 高純水 淋洗液 泵 進(jìn)樣閥 柱 抑制器 檢測池廢液 反壓管 電源流出物循環(huán)在線流出物循環(huán)在線再生模式流程圖再生模式流程圖衍生化 將被測物轉(zhuǎn)變?yōu)橐子跈z測的形式 柱前衍生、柱后衍生 紫外衍生、熒光衍生、光度衍生衍生化是不得已而為之含柱后衍生裝置的分析系統(tǒng)含柱后衍生裝置的分析系統(tǒng)輸輸液液分離分離檢測檢測 進(jìn)樣進(jìn)樣泵泵進(jìn)樣閥色譜柱色譜柱流動(dòng)相

11、流動(dòng)相衍生衍生試劑試劑反應(yīng)環(huán)廢廢液液加加壓壓UV/VIS檢測器記錄記錄陰陽離子同時(shí)分離技術(shù)陰陽離子同時(shí)分離技術(shù) 采用雙流路系統(tǒng) 陽離子轉(zhuǎn)變成配陰離子后與無機(jī)陰離子一起分析 采用兩性離子交換劑做固定相 采用陰陽離子混合床固定相 采用含陰陽離子基團(tuán)的有機(jī)分子包覆固定相 柱切換技術(shù)（陰陽離子交換柱并聯(lián)） 陰陽離子交換柱串聯(lián)1. 環(huán)境領(lǐng)域2. 食品領(lǐng)域3. 其他領(lǐng)域離子色譜的應(yīng)用離子色譜的應(yīng)用ICIC在環(huán)境領(lǐng)域的應(yīng)用在環(huán)境領(lǐng)域的應(yīng)用主要物質(zhì)：主要物質(zhì)：無機(jī)陰陽離子、小分子羧酸主要分離模式：主要分離模式：離子交換、離子排斥主要樣品：主要樣品： 水樣（江、河、湖泊、飲用水、地下水、 廢水、雨水、電廠循環(huán)水

12、） 大氣、大氣顆粒物 土壤、植物 電子制造環(huán)境飲用水和廢水分析標(biāo)準(zhǔn)飲用水和廢水分析標(biāo)準(zhǔn) EPAEPA方法方法EPA 218.6EPA 218.6 CrCr6 6的測定EPA 300.0EPA 300.0 Method A: 標(biāo)準(zhǔn)陰離子 (F-, Cl-, NO2-, Br-, NO3-, HPO42- or PO43-, SO42-) Method B: 陰離子副產(chǎn)物或鹵素氧化物(ClO2-, BrO3-, ClO3-)飲用水和廢水分析標(biāo)準(zhǔn)EPA 300.1Method A: 常見陰離子測定 (F-, Cl-, NO2-, Br-, NO3-, HPO42- or PO43-, SO42-)M

13、ethod B: 消毒副產(chǎn)物測定 (Br-, ClO2-, BrO3-, ClO3-)EPA 314ppb級(jí)ClO4-測定 （致癌、損傷甲狀腺功能）無機(jī)陰離子分析：EPA Method 300.0 A無機(jī)陰離子分析： EPA Method 300.1 A0123456789 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 min13141516171819uS/cmCondfluoride 0.522chloride 1.070nitrite 2.190bromide 1.910DCA 1.860nitrate 1.990phosph

14、ate 5.000sulphate 6.700消毒副產(chǎn)物：EPA Method 300.0 B消毒副產(chǎn)物：EPA Method 300.1 B012345678910 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28min1314151617uS/cmCondchloritebromatechloridebromidechlorateDCA(1 ppm)0.004.008.0012.0016.00Retention Time (min.)0.0050.00100.00150.00200.00Signal (m V)ClO4ClO4的測定

15、：EPA Method 314.025 g/L in Reagent WaterCr+6的測定：EPA 218.60123min50100150200250300350mVch11.89Instrument: Metrohm Modular IC with753 Suppressor Module for Post Column DeliveryBischoff Lambda 1010 UV/Vis DetectorEluent: 250mM Ammonium Sulfate 100mM Ammonium HydroxidePump Flow: 1.5 mL/minColumn: Cetac

16、ICSep AN1 Column with Guard-Disc TechnologyPCR: 2mM DPC*, 10% Methanol, 1 N Sulfuric Acid * (DPC 1,5 Diphenylcarbazide)Cr+61.89 ppb1Column:Column:IonPacIonPac AG14, AS14AG14, AS14EluentEluent: :3.53.5 mM mM Sodium carbonate Sodium carbonate1.01.0 mM mM Sodium bicarbonate Sodium bicarbonateFlow Rate:

17、Flow Rate:1.21.2 mL mL/min/minInjInj. Volume:. Volume: 10 10 L LDetection:Detection:Suppressed conductivity, ASRSSuppressed conductivity, ASRS , ,AutoSuppressionAutoSuppression recycle mode recycle modeSample:Sample:Drinking water from Milpitas, CADrinking water from Milpitas, CAPeaks:Peaks:1. 1. Fl

18、uorideFluoride0.030.03 mg/Lmg/L2. 2. BicarbonateBicarbonate 3. 3. ChlorideChloride3.123.124. 4. NitrateNitrate0.150.155. 5. PhosphatePhosphate0.040.046. 6. SulfateSulfate4.454.45Analysis of Municipal Drinking WaterAnalysis of Municipal Drinking Water3 3-1 -1 S S3 31 1 2 24 45 56 60.50.50 02 24 46 68

19、 8101012121414 S SMinutesMinutes-0.5-0.51 1 2 24 45 53 36 61CationsCations in Tap Water in Tap WaterEluentEluent: :30mM 30mM Methanesulfonic Methanesulfonic acidacidFlow Rate:Flow Rate:1.0 mL/min1.0 mL/minTemperature:Temperature:40 40 C CInj. Volume:Inj. Volume:25 25 L LDetection:Detection:Suppresse

20、d conductivity,Suppressed conductivity,CSRSCSRS -ULTRA 4-mm,-ULTRA 4-mm,AutoSuppressionAutoSuppression recycle mode recycle mode Calculated CalculatedPeaks:Peaks:1. Lithium1. Lithium0.002 mg/L (ppm)0.002 mg/L (ppm)2. Sodium 19.7302. Sodium 19.7303. Ammonium3. Ammonium0.0650.0654. Potassium4. Potassi

21、um0.9870.9875. Magnesium5. Magnesium7.2107.2106. Calcium 18.5446. Calcium 18.5440 05 510101515202025250.100.101.001.001 13 34 4 S S2 25 56 6Minutes1EPA Method 300.0 (A): Anions in Wastewater0 02 24 46 68 8101012121414MinutesMinutes0 02020 S S1 12 23 35 54 46 6Column:Column:IonPacIonPac AG14, AS14AG1

22、4, AS14EluentEluent: :3.53.5 mM mM Sodium carbonate/ Sodium carbonate/1.01.0 mM mM Sodium bicarbonate Sodium bicarbonateFlow rate:Flow rate:1.21.2 mL mL/min/minInjInj. volume:. volume:50 50 L LDetection:Detection:Suppressed conductivity,Suppressed conductivity,ASRS-ULTRAASRS-ULTRA AutoSuppressionAut

23、oSuppression, , R Recycle Modeecycle ModePeaks:Peaks:1. 1. FluorideFluoride 0.34 0.34 mg/Lmg/L ( (ppmppm) )2. 2. ChlorideChloride70.470.43. 3. BromideBromide 0.13 0.134. 4. NitrateNitrate 0.31 0.315. 5. PhosphatePhosphate24.024.06. 6. SulfateSulfate154.1154.11Anions in High Chloride Wastewater:Condu

24、ctivity Detection0 05 51010151520202525MinutesMinutes8 80 0 S S3 37 76 65 54 42 21 13 3Column:Column:IonPacIonPac AG9-HC, AS9-HC AG9-HC, AS9-HCEluentEluent: :9.09.0 mM mM Sodium carbonate Sodium carbonateFlow rate:Flow rate:1.01.0 mL mL/min/minInjInj. volume:. volume:25 25 L LDetection:Detection:Sup

25、pressed conductivity,Suppressed conductivity,ASRS-ULTRA, ASRS-ULTRA, Recycle ModeRecycle ModePeaks:Peaks:1. 1. FluorideFluoride 1.14 1.14 mg/L (mg/L (ppmppm) )2. 2. Acetate Acetate 3. 3. Chloride Chloride 4. 4. NitriteNitrite0.140.145. 5. BromideBromide0.820.826. 6. NitrateNitrate1.471.477. 7. Phosp

26、hatePhosphate21.121.18. 8. SulfateSulfate30.330.3Sample:Sample:Synthetic waste waterSynthetic waste watercontaining 2 g/L chloridecontaining 2 g/L chloride1Anions in High Chloride Wastewater:UV Detection0 05 51010151520202525MinutesMinutes0 04.04.0 x10 x10-2 -2AUAU3 32 21 1Column:Column:IonPacIonPac

27、 AG9-HC, AS9-HC AG9-HC, AS9-HCEluentEluent: :9.09.0 mM mM Sodium carbonate Sodium carbonateFlow rate:Flow rate:1.01.0 mL mL/min/minInjInj. volume:. volume:25 25 L LDetection:Detection:UV at 214 nmUV at 214 nmPeaks:Peaks:1. 1. NitriteNitrite0.180.18 mg/L (mg/L (ppmppm) )2. 2. BromideBromide0.79 0.79

28、3. 3. NitrateNitrate1.581.58Sample:Sample: Synthetic waste waterSynthetic waste watercontaining 2 g/L chloridecontaining 2 g/L chloride1Column:Column:IonPacIonPac AS7 AS7EluentEluent: :0.5 M 0.5 M NaOAcNaOAc0.1 0.1 NaOHNaOH0.5% (v/v) EDA0.5% (v/v) EDAFlow Rate:Flow Rate:1.0 1.0 mLmL/min/minDetection

29、:Detection: dc dc AmperometryAmperometry, ,Working Electrode: AgWorking Electrode: Ag0.00 V vs. Ag/0.00 V vs. Ag/AgClAgClCyanide in Waste WaterCyanide in Waste Water6 68 80 02 22 24 40 0MinutesMinutes4 46 68 8S S2- 2- 1000 ppb 1000 ppbCNCN- - 100 ppb 100 ppbCNCN- - 125 ppb 125 ppbS S2- 2- 25 ppb25 p

30、pbWaste WaterWaste WaterIncludingIncluding1M 1M NaOHNaOHMinutesMinutes1Anions in Lake WaterColumn:IonPac AG11, AS11Eluent:KOH (EG-40使用) 2mmol/L (05分), 230 mmol/L (5.1 26分)Flow Rate:1.0 mL/minSuppressor:ASRS-ULTRAInj.Volume:20 LDetection:Conductivity A A B B1. F1. F1.91.90.8 mg/L0.8 mg/L2. ClO2. ClO2

31、 22.92.9- -3. BrO3. BrO3 35.1 5.1 - - 4. 4. ClCl5.45.430.030.05. NO5. NO2 24.94.9- -6. Br6. Br10.210.2- -7. NO7. NO3 311.411.4- -8. ClO8. ClO3 310.110.12.22.29. 9. SeOSeO3 32 210.710.7- -10. SO10. SO3 32 215.715.7- -11. SO11. SO4 42 224.324.334.034.012. 12. SeOSeO4 42 220.020.0- -13. I13. I20.920.9-

32、 -14. PO14. PO4 43 352.752.7- -A) STDA) STD0 01010B) Lake WaterB) Lake Water2020151510105 50 00 010101 14 48 81111141413131212111110109 98 86 67 75 54 43 32 21 1 S/cmS/cm S/cmS/cmTime (min)1SampleSampleAbsorbantAbsorbantDiffusion scrubberGas sample collectionGas sample collectionImpingerSamplePumpAb

33、sorbant1Analysis of Analysis of GasGasMinutesMinutes0 01 12 23 34 45 56 67 78 89 910100.00.00.80.8 S S1 1Sep. Column : Sep. Column : IonPacIonPac CS12A CS12AConc. Column : TCC-LP1Conc. Column : TCC-LP1Eluent Eluent : 20mM : 20mM 酸酸Flow Rate : 1 Flow Rate : 1 mLmL/min/minSampling Sampling : :Absorban

34、t Absorbant D.I.Water 20mLD.I.Water 20mL 10min. Pumping as 1L/min. 10min. Pumping as 1L/min. 5 5mLmL injection to IC injection to ICDetection :Suppressed ConductivityDetection :Suppressed Conductivity (CSRS-ULTRA) (CSRS-ULTRA)1. NH1. NH3 3+ + 11 11 nLnL/L/LBasicsubstances1Analysis of Analysis of Gas

35、Gas0 01 1 S S1010MinutesMinutes0 01 12 23 34 45 56 67 78 89 91 1Sep. Column :Sep. Column : IonPac IonPac AS4A-SC AS4A-SCConc. Column: TAC-LP1Conc. Column: TAC-LP1Eluent Eluent : 1.8: 1.8mM mM NaNa2 2COCO3 3 1.7mM NaHCO 1.7mM NaHCO3 3Flow Rate : 1 Flow Rate : 1 mLmL/min/minInjInj. Volume : 5 . Volume

36、 : 5 mLmLDetection :Suppressed ConductivityDetection :Suppressed Conductivity (ASRS-ULTRA) (ASRS-ULTRA)1. SO1. SO4 42-2- (10 (10 nLnL/L as SO/L as SO2 2) )AcidicSubstance離子色譜在食品領(lǐng)域的應(yīng)用主要物質(zhì)主要物質(zhì) 無機(jī)陰、陽離子 有機(jī)酸、氨基酸、糖、有機(jī)胺 食品添加劑主要分離模式：主要分離模式：離子交換、離子排斥、反相主要樣品主要樣品 飲料、糧食、酒、水果、蔬菜、生鮮食品牛奶中陰離子0.004.008.0012.0016.00R

37、 etention T im e (m in.)0.0020.0040.0060.0080.00D etector Signal (m V)C l -H PO42-SO42-IonnConc. Measured(mg/L)RSD(%)Recovery(%)Cl-39230.28106HPO42-317580.28100SO42-31560.539010246uSGreen Tea12345Brown Tea0246uS1234502468101214MinutesCoffee0246uS123451. F- 2. Cl- 3. NO2- 4. SO42- 5. N3- spiked NaN3

38、8mg in each 1mL beverageColumn : Column : IonPacIonPac AG15, AS15AG15, AS15EluentEluent: 42: 42mMmM KOH KOHTemp. : 30Temp. : 30Flow : 1.2 Flow : 1.2 mLmL/min/minInjInj. Vol.: 25 . Vol.: 25 L LPrep.: dilute Prep.: dilute 200 x200 xfilteredfiltered 1Column:Column:IonPacIonPac AS9-SC, AG9-SCAS9-SC, AG9

39、-SCEluentEluent: :1.71.7 mM mM Sodium bicarbonate Sodium bicarbonate 1.81.8 mM mM Sodium carbonate Sodium carbonateFlow Rate:Flow Rate:1.51.5 mL mL/min/minInjInj. Volume:. Volume: 25 25 L LDetection: Detection: Suppressed conductivitySuppressed conductivityPeaks:Peaks:A: SampleA: Sample 2. Nitrate2.

40、 Nitrate71.671.6 ppmppm 3. Unidentified3. Unidentified 4. Unidentified4. Unidentified 5. Unidentified5. Unidentified B: Sample SpikedB: Sample Spiked 1. Nitrite1. Nitrite0.50.5 ppmppm 2. Nitrate2. NitrateSampleSamplePreparation:Preparation: 1. Approximately 8 g diluted1. Approximately 8 g dilutedwit

41、h 50with 50 mL mL DI water DI water 2. Centrifuged 15 min2. Centrifuged 15 min 3. Filtered to 0.2 3. Filtered to 0.2 m mNitrite and Nitrate in BananaNitrite and Nitrate in Banana0 02 24 46 68 81010121214140 0 10 10 S S A: SampleA: Sample B: Sample Spiked with 0.5B: Sample Spiked with 0.5 ppm ppm Nit

42、rite Nitrite2 23 34 45 5MinutesMinutes0 02 24 40 0 4 4 S S1 12 20 .0 04 .0 08 .0 01 2 .0 0R e te n tio n T im e (m in .)0 .0 05 .0 01 0 .0 01 5 .0 02 0 .0 0D etector S ignal (m V )N a +K +C a 2+M g 2+IonnConc. Measured(mg/L)RSD(%)Recovery(%)Na+43900.67893K+514810.55798Ca2+59110.989104Mg2+41101.0287果

43、汁中陽離子0 .0 04 .0 08 .0 01 2 .0 0R e te n tio n T im e ( m in .)0 .0 01 0 .0 02 0 .0 03 0 .0 04 0 .0 0D e te c to r S ig n a l (m V )N a+K+C a2 +M g2 +IonnConc. Measured(mg/L)RSD(%)Recovery(%)Na+534.80.7093K+58800.7499Ca2+585.60.7295Mg2+549.40.96951Column:Column:IonPacIonPac CS12 analytical column (4

44、mm) CS12 analytical column (4 mm) CG12 guard column (4 mm)CG12 guard column (4 mm) CTC-1CTC-1 Cation Cation Trap TrapEluentEluent 1: 1:DeionizedDeionized water waterEluentEluent 2: 2:100100 mM Methanesulfonic mM Methanesulfonic acid acidFlow Rate:Flow Rate:1.01.0 mL mL/min/minInjInj. Volume:. Volume

45、:25 25 L LDetection: Detection: Suppressed conductivitySuppressed conductivityPeaks:Peaks:1. Sodium1. Sodium5.3 5.3 mg/Lmg/L 2. Ammonium2. Ammonium2.32.3 3. Potassium3. Potassium9.09.0 4. Magnesium4. Magnesium0.20.2 5. Calcium5. Calcium1.71.7Sample dilution: 1:10Sample dilution: 1:10CationsCations i

46、n a Diet Cola by IC in a Diet Cola by ICMinutesMinutes024681012010S12345Gradient:TimeE1E2E3E4 Initial8416 5.008416 5.016040 10.0060401Column:Column:CS12/CG12/CS12/CG12/CationTrapCationTrapEluentEluent 1: 1:DeionizedDeionized water waterEluentEluent 2: 2:100100 mM Methanesulfonic mM Methanesulfonic a

47、cid acidFlow Rate:Flow Rate:1.01.0 mL mL/min/minInjInj. Volume:. Volume: 25 25 L LDetection:Detection:Suppressed conductivitySuppressed conductivityPeaks:Peaks:1. Sodium1. Sodium 2. Ammonium2. Ammonium3. Potassium3. Potassium 4. Magnesium4. Magnesium5. Calcium5. CalciumCationsCations in Wine in Wine

48、MinutesMinutes0 02 24 46 68 8101012120 0 10 10 S S1 12 23 34 45 51Comparison ofComparison of Cation Cation Concentrations in Lager Beer, Concentrations in Lager Beer,Stout and Ale Using Ion ChromatographyStout and Ale Using Ion ChromatographyColumn:Column:IonPacIonPac CS12 analytical column (4 mm) C

49、S12 analytical column (4 mm)CG12 guard column (4 mm)CG12 guard column (4 mm) CTC-1CTC-1 CationTrap CationTrapEluentEluent 1: 1:DeionizedDeionized water waterEluentEluent 2: 2:100100 mM Methanesulfonic mM Methanesulfonic acid acidFlow Rate:Flow Rate:1.01.0 mL mL/min/minInjInj. Volume:. Volume:25 25 L

50、 LDetection:Detection:Suppressed conductivity Suppressed conductivity Peaks:Peaks:1. Sodium1. Sodium 2. Ammonium2. Ammonium 3. Potassium3. Potassium 4. Magnesium4. Magnesium 5. Calcium5. CalciumGradient:Gradient:TimeTimeE1E1E2E2E3E3E4E4 InitialInitial 84 841616 5.005.00 84 841616 5.015.01 60 604040

51、10.0010.00 60 604040 0.002.004.006.008.0010.00 -1 10 uS0.002.004.006.008.0010.00 -1 10 uSMinutesMinutes0.002.004.006.008.0010.0012.00 -1 10 uS1010 S S0 01 12 23 34 45 51010 S S0 01 13 34 45 51010 S S0 01 12 23 34 45 5BritishBritishAleAleBritishBritishStoutStoutAmericanAmericanLagerLager2 20 02 24 46

52、 68 81010121211 10 0 S S15153 3Organic Acids in Grape JuiceOrganic Acids in Grape JuiceGrape Juice, 1:100 DilutionGrape Juice, 1:100 Dilution4 48 85 52 20 05 5101015152020Column:Column:IonPacIonPac ICE-AS6 ICE-AS6EluentEluent: :0.40.4 mM Heptafluorobutyric mM Heptafluorobutyric acid acidFlow Rate:Fl

53、ow Rate:1.01.0 mL mL/min/minInjInj. Volume:. Volume:50 50 L LDetection:Detection:Suppressed conductivitySuppressed conductivity AMMS-ICEAMMS-ICEPeaks:Peaks:1. 1.InorganicsInorganics 2. 2.TartaricTartaric 3. 3.GalacturonicGalacturonic 4. 4.CitricCitric 5. 5.MalicMalic 6. 6.FormicFormic 7. 7.AceticAce

54、tic 8. 8.UnknownUnknownMinutesMinutes6 67 71Organic Acids in Tomato ProductsOrganic Acids in Tomato ProductsTomato Juice, 1:100 DilutionTomato Juice, 1:100 DilutionKetchup, 1:100 DilutionKetchup, 1:100 Dilution1 14 46 60 0MinutesMinutes S S15153 35 52 2 S S0 00 010101010202025255 57 77 74 43 31 1Col

55、umn:Column:IonPacIonPac ICE-AS6 ICE-AS6EluentEluent: :0.40.4 mM Heptafluorobutyric mM Heptafluorobutyric acid acidFlow Rate:Flow Rate:1.01.0 mL mL/min/minInjInj. Volume:. Volume:50 50 L LDetection:Detection:Suppressed conductivitySuppressed conductivity AMMS-ICEAMMS-ICEPeaks:Peaks:1. 1.InorganicsIno

56、rganics2. 2.MalonicMalonic3. 3.CitricCitric4. 4.MalicMalic5. 5.FormicFormic6. 6.AceticAcetic7. 7.UnknownUnknown10.005.0010.0015.00 -0 5 uSGradient Separation of Organic Acids in Orange Juice(1:100 dilution)Minutes5S012345678910111213141516 18051015Peaks:1. Quinate1.0mg/L2. Lactate0.43. Acetate0.14.

57、Glycolate0.15. Formate0.256. d-Galacturonate0.37. Chloride0.68. Nitrate0.259. Glutarate1.010. Succinate0.211. Malate10.012. Sulfate0.813. Oxalate2.014. Phosphate2.015. Citrate8.016. Isocitrate1.517. cis-Aconitate0.518. trans-Aconitate0.5Column:IonPac AS11Eluent 1:D.I. WaterEluent 2:1.0 mM Sodium hyd

58、roxideEluent 3:100 mM Sodium hydroxideEluent 4:100% MethanolFlow Rate:2.0 mL/min.Detection:Suppressed conductivity,Chemical suppression modeTime (min.)%E1%E2%E3%E4 07020010 57020010 150354520171Organic Acid Profiles of Different Fruit JuicesColumn:Column:IonPacIonPac AS11 AS11EluentEluent: :Hydroxid

59、e/Methanol GradientHydroxide/Methanol GradientPeaks:Peaks:1. 1. Quinate Quinate2. Lactate2. Lactate 3. Acetate3. Acetate 4. 4. Glycolate Glycolate 5. 5. FormateFormate 6. 6. d-Galacturonate d-Galacturonate 7. Chloride7. Chloride 8. Nitrate8. Nitrate 9. 9. Glutarate Glutarate 10.10. Succinate Succina

60、te 11.11. Malate Malate 12.12. Malonate Malonate 13.13. Tartrate Tartrate 14. Sulfate14. Sulfate 15. Oxalate15. Oxalate 16. Phosphate16. Phosphate 17. Citrate17. Citrate 18.18. Isocitrate Isocitrate 19.19. cis-Aconitate cis-Aconitate 20.20. trans-Aconitate trans-Aconitate 5 S 0051015Apple Juice12345