Z-2000
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Introduction for HITACHI Z-2000 SERIES Polarized Zeeman Atomic Absorption Spectrophotometer About HITACHI Polarized Zeeman AAS Year 1973 1976 1980 1983 1987 1987 1988 1991 1996 2004 Model 501 (Flame) 170-70 (Furnace) 180-60 (Flame) 180-70 (Furnace) 180-80 (Tandem) Z-6000 (Flame) Z-7000 (Furnace) Z-8000 (Tandem) Z-9000 (Furnace) Z-6100 (Flame) Z-8100 (Tandem) Z-8200 (Tandem) Z-5000 series Z-2000 series Units 46 291 103 211 488 356 134 531 346 1,365 566 1,054 1,610 >450 Tandem alignment Multi-elements analysis PC control 3-D optics 三次元光学系 Dual detector system 二検知器 Hitachi introduced world’s first polarized Zeeman AAS Model 501 in 1973, and have delivered a variety of units to about 7,000 customers in 25 countries around the world. New Model / Z-2000 Series Product configuration (1) Tandem Type (2) Flame Type (3) Graphite Furnace Type Z-2300 Z-2000 Model Z-2000 Model Z-2300 Model Z-2700 Z-2700 High Quality 1. Direct-current Zeeman background correction (both Flame method and Graphite Furnace method) 直流ゼーマンバックグラウンド補正、フレームとファーネスの両方 2. Dual detector 二検知器 Photomultiplier for Sample サンプル用光電子増倍管 Photomultiplier for reference レファレンス用光電子増倍管 Z-2000 series Optics Dual detector system enables simultaneous signal capture of both Sample and Reference. 二検知器システムにより、サンプル光とレファレンス光の同時取り込みが可能になりました。 Timing Chart of Signal Processing 20 ms 20 ms Exact simultaneous measurement of sample signal and reference signal with the dual detector system realizes low noise and highly accurate analysis. New optics with dual detection system achieves better sensitivity. Comparison data among Z-8200/Z-5000/Z-2000 Model Z-8200 Model Model Z-5000 Z-5000 Detection Limit 0.4 ug/L Z-2000 0.15 ug/L Model Z-2000 Element : As (193.7nm) Graphite furnace method, As Standard Solution (1ug/L) 40uL injection Stable baseline Flame DC Zeeman correction and dual detector system achieved very stable baseline for long time. After the warm-up time of about 5 min., baseline can be stabilized over one hour. Baseline change (Flame method) : Cu lamp Zeeman background correction in Hydride Formation method Lamp Flame Optics Detector Magnet Heating Absorption Cell HFS-3 Heating Absorption Cell Burner Head Z-5000 Z-2000 Magnet descend mechanism Magnet is exposed to Flame Background correction impossible Shield Plate Background correction possible Zeeman background correction becomes possible, since heating absorption cell can be set between magnet. Zeeman background correction in Hydride Formation method As Standard Solution 0 5 10 15 ug/L As Standard Solution 0 5 10 15 ug/L River Water Z-5000 Z-2000 Measurement of As (HFS-3, Heating Absorption cell) Know-how for a better AAS expert 更なる原子吸光スペシャリストへの測定のコツ Hitachi High-Technologies FLAME The Determination of Cadmium, Copper and Lead in Nickel Plating Bath Solution. Analysis of high-calorie food 高カロリー食品の分析 Requirements for analysis 分析に対する要求項目 Rapid analysis （use of autosampler） 迅速分析 Concentration difference in elements(different dilution factors） 元素により濃度差 Continuous measurement (multi-elements sequential analysis) 連続測定 Problem 問題点 1. Different dilutions, different viscosities cause different delay times 希釈倍率による粘度差で試料の到達時間に差が出る 2. Large number of samples多数検体 3. Long-term stability required 長時間安定性が必要 4. Clogging of burner バーナーの詰り 5. Corrosion by highly acidic solution 高酸性溶液による腐食 Analysis of high-calorie food Solution １．Different dilutions, different viscosities cause different delay times 希釈倍率による粘度差で試料の到達時間に差が出る → Different delay time can be set for each element 元素毎に測定開始までの時間設定が可能 Delay time Analysis of high-calorie food 2.Large number of samples 多量検体 → Multiple autosampler racks can be used. オートサンプラのラックが複数使えます。 Analysis of high-calorie food 3. Long-term Stability Element Conc.(mg/１００ｍL) RSD（％） 長時間安定性 Na 82 K 173 Ca 51 Mg 20 Fe 520 Zn 521 Mn 126 Cu 116 0.7 0.7 1.8 0.6 1.6 1.4 1.8 2.3 Analysis of high-calorie food 4. Clogging of burnerバーナーの詰り → Clean by setting the delay time (pre-spray) 予備噴霧時間の設定により洗浄 1～30min Cleaning of nebulizer ネブライザｰの洗浄 OK NG insert from this side Inlet 吸入口 Nebulizer tip 先端 Cleaning wire A cleaning wire has to be inserted from inlet. クリーニングワイヤーは吸入口から入れる。 Cleaning of burner head The burner head is cleaned by thick paper. バーナースロットは厚紙でクリーニング。 Overhaul cleaning is required once a week. 分解清掃は週1回程度は必ず行う。 Analysis of high-calorie food 5. Corrosion by highly acidic solution 高酸性溶液による腐食 Engineering plastic (chemical resistant) エンジニアプラスチック (耐薬品性） Chemical Resistance of Flame Burner Chamber Name of Chemical Concentration Temperature Hydrochloric acid Concentrated Normal temp. Hydrofluoric acid Concentrated Normal temp. Nitric acid 10% or less Normal temp. Sulfuric acid 10% or less Normal temp. Aqua regia 3-fold dilution or lower Normal temp. NaCl solution Saturated 80 C or less Tetrahydrofuran Normal temp. Tri-n-octylamine Normal temp. Xylene Normal temp. 1-methyl-2-pyrolidone Normal temp. Heptane Normal temp. Acetonitrile Normal temp. Acetone Normal temp. Propanol Normal temp. N, N-dimethylacetoamide Normal temp. Ethylene glycol Normal temp. Cyclohexane Normal temp. 2-ethoxyethyl acetate Normal temp. Butyl acetate Normal temp. 4-methyl-2-pentanone (MIBK) Normal temp. Concentration range can be changed by analytical line selection. 分析線を変えることにより測定濃度範囲を変えられます Sensitivity for 1mg/L Na Use of oxydizing flame and reduction flame 酸化炎と還元炎の使い分け Flame condition Oxydizing flame (fuel lean) Reduction flame (fuel rich) フレームの状態 酸化炎 還元炎 Applicable elements Cd, Pb, Mn, Fe... Sn, Cr, Mo... Difference of linearity in working curves フレーム状態による検量線の違い Oxydizing flame 酸化炎 Example of Fe 0.2 Reduction flame 還元炎 Absorbance Absorbance 0.2 0 Conc. 0 Conc. Oxydizing flame may be changed to reduction flame by introduction of real sample. Also, the flame condition may be changed acetone come from C2H2 cylinder when residual pressure < 0.5MPa 実試料の導入によって酸化炎→還元炎に変わる場合がある。アセチレンガスの残圧が0.5MPa以下の場合、ボンベ からのアセトンの混入も、炎の状態を変化させる。 Contamination Laboratory environment: use of indoor shoes 室内環境 :上履き使用 Contamination Laboratory environment: use of local ventilation 室内環境 :局所排気 Desktop local hood Contamination from environment Zn signal Aspirate DW Flame on tobacco smoke Zn signal in flame AAS DW left for 3days Contamination from environment ABS 0.100 0.095 0.090 0.085 0.080 0.075 0.070 0.065 0.060 0.055 0.050 0.045 0.040 0.035 0.030 0.025 0.020 0.015 0.010 0.005 0.000 -0.005 -0.010 -0.015 -0.020 REF 0.20 0.15 0.10 0.05 0.00 Na signal Aspirate DW DW left for 3days Tobacco smoke Flame on 0 100 200 時間(s) Na signal in flame AAS 300 Open the drain valve of the compressor after measurement 測定後は必ずドレインを開けてください Drain valve Otherwise, oil and water vapor may be introduced into the AAS, resulting in data imprecision and malfunction of the instrument. ドレイン抜きをしないとオイルを含んだ水分が装置に入り、データ不良､故障の原因になります。 Graphite Furnace Determination of Pb in tap water（bad example） 水道水中の鉛の定量(悪い例) Determination of Pb in tap water in Hitachi Lab. 装置条件 温度プログラム Component of a typical borosilicate glass 代表的なホウケイ酸ガラスの組成 Component (%) SiO2 80.90 B 2 O3 12.70 Al2O3 2.30 Na2O 4.00 K 2O 0.04 Fe2O3 0.03 other 0.03 Si, B, Al, Na, K, Fe are contained in % level. Others are contained in 0.03%. Contamination form containers 容器からの汚染 (1) Grass wares should be avoided for inorganic analysis of ppb (ug/L) or lower level. μg/L以下の無機分析で.ガラス容器の使用は避ける。 (2) Plastic wares such as polypropylene (PP), polyethylene(PE) are suitable. But blank level should be checked before use because metal oxides may be added as a plasticizer. PP, PE等の樹脂製の容器が適する。 ただし、可塑剤に金属酸 化物が使われている場合があるので、ブランク値の確認をする。 (3) An ultrapure grade or EL-grade acid is preferable to analytical grade or AAS grade. 特級、原子吸光用よりもUltrapureやELグレードの酸が望ましい。 Use of matrix modifier 0.15 Absorbance As 10μg/L + Pd 100mg/L 0.10 0.05 As 10μg/L 0 500 1000 1500 Ashing temp.灰化温度 Effect of matrix modifier on arsenic absorbance Asの吸光度に対するマトリックス修飾剤の効果 Use of matrix modifier Modifier：Mg(NO3)2 without modifier with modifier Atomization signal of Al in soil extract. 土壌溶出液中Alの原子吸光信号 Use of matrix modifier 元素 As 灰化 差 温度 Pb 灰化 差 温度 400 600 none Pd・Mg 1,400 1,000 1,400 1,400 1,000 1,200 Ｎｉ 1,300 900 1,200 Mg Se 灰化 差 温度 Sb 灰化 差 温度 400 600 800 600 200 1,000 600 1,400 1,000 1,400 600 1,600 1,200 1,200 Cd 灰化 差 温度 400 400 1,000 800 1,000 600 400 600 600 0 Modifier concentration Ｐｄ・Mg：500 ppm Ｎｉ： 1,000 ppm Ｍｇ： 1,000 ppm The matrix modifiers for AAS are provided from Kanto Chemicals and Merck. Use of 1000ppm AAS Standard Solution as a matrix modifier is not recommended because they are contaminated with some trace elements. Determination of Pb in tapwater Sample preparation 試料の調製 1)Use acid-washed plastic 25mL volumetric flasks. 酸洗浄した樹脂製のフラスコ25ｍLを用意する。 2)Dispense 0.2mL of ultra-pure nitric acid into each flask. 高純度硝酸0.2mLを各フラスコに入れる。 3)Dispense 0, 25, 75, 125, 250uL of 1.0mg/L Pb into each flask, and fill with DW. Use these solution as working standards. Pbの標準液1.0mg/Lをマイクロピペッターにて0，25，75 ，125, 250μLを入れ、純水で全量を25ｍLとし、こ れを検量線用試料とする。 4)Use a mixture of Pd and Mg(NO3)2 as matrix modifier (1000mg/L each as Pd and Mg). マトリックス修飾剤は Pd＋Mg(NO３)２混合液(Pd、Mgそれぞれ1000mg/L)を用意する。 Analysis of data imprecision データ不良の解析 Injection hole 試料注入口 Graphite tube 試料注入口 Light 光源 Electrode電極 Construction of electrothermal atomizer 電気加熱原子化部の構造 Factors for imprecision 再現性不良の原因 Sampling error サンプリング不良 Contamination from environment 周囲環境からの汚染 Contamination of rinse port 洗浄ポートの汚染 Wrong temperature program (sample boiling) 温度条件不適(突沸) Contamination of electrode ring 電極リングの汚染 Factors for imprecision 再現性不良の原因 Sampling error サンプリング不良 Factors for imprecision 再現性不良の原因 Adjusting nozzle position ノズル位置の調整 Caution on nozzle height ノズル高さに注意 OK NG Set the nozzle height very close to injection hole Nozzle tip 上下位置はキュベット穴に対し ぎりぎりにセットする 0～0.5mm Better for low volume low viscosity Nozzle height can be set without Graphite Tube Camera グラファイト炉カメラなしでノズル高さが合 わせられます。 The same distance Caution on sample volume 注入試料に注意 up to１００μL Simple Aqueous solution 単純な水溶液 up to ３０μL Organic solvent 有機溶媒 Factors for imprecision 再現性不良の原因 Wrong temperature program (sample boiling) 温度条件不適(突沸) DC Zeeman method can monitor all stages in heat program 直流ゼーマン法は全加熱ステージをモニターできます。 Analysis of Juice sample Hitachi DC Zeeman method enables monitoring for all stages (Drying, Ashing, Atomization), and this helps operator to set up optimal analysis condition. AC Zeeman method can monitor only Atomization stage. Optimum temperature can be set without monitoring inside of the graphite tube by camera グラファイトチューブ内をカメラでモニターしなくても、最適な温度が設定できます。 Dry Nozzle injection Ash Atomize Sharp peaks cased by sample sputtering Atomization peak Effects of Drying Temperature (too high) on Performance. Sharp peaks caused by sputtering can be recognized in the beginning of the drying stage. Factors for imprecision 再現性不良の原因 Contamination from environment 周囲環境からの汚染 Contamination from environment can be reduced by the standard equipped clean cover 標準装備のクリーンカバーにより環境からの汚染を低減できます Exhaust duct 排気ダクト Graphite furnace 電気加熱炉 Autosampler オートサンプラ Flame atomizer ﾌﾚｰﾑ部 Clean cover クリ－ンカバー Contamination from environment can be reduced by the standard equipped clean cover 標準装備のクリーンカバーにより環境からの汚染を低減できます Determination of aluminum アルミニウムの定量 Contamination 汚染の混入 Clean cover open Clean cover closed クリーンカバー開放 クリーンカバー閉じる Factors for imprecision 再現性不良の原因 Contamination of rinse port 洗浄ポートの汚染 time interval 洗浄ポート Rinse port Factors for imprecision 再現性不良の原因 Contamination of rinse port 洗浄ポートの汚染 Contamination of rinse port 洗浄ポートの汚染 1.Clean with cotton swab 綿棒で清掃 2. Add 100uL of conc.HCl and leave for 2-3 min. 塩酸１００μLを入れ２～３分待つ 3. Rinse with DW 純水で洗浄 Factors for imprecision 再現性不良の原因 Contamination of electrode ring 電極リングの汚染 Absorption signal does not appear at the beginning of the atomization, but increases at the end of atomization and cleaning. Electrode ring 電極リング 最大加熱をかけた場合、初期にはピークが出ず後半に 出現する Exchange of electrode ring 電極リングの交換 Ar gas Water in/out O-ring Be aware the o-rings not to be sandwiched between electrode and base. The o-rings should be attached to the base side. O-リングを電極とベースの間に挟まないように注意｡O-リングはベース側につけておく。 Another factors for imprecision 再現性不良の他の原因 Quartz window 石英窓 突沸や過剰冷却により窓が曇りノイズが増え再現性が悪くなります。 Condensation by overcooling of the quartz window 過冷却による石英窓の結露 Cooling circulator 循環冷却機 Normal Overcooled 正常 過冷却 Set around room temperature 室温±5℃程度に設定 Sample volume in the Sample Cup サンプルカップの液量 Half cup of sample is enough. Too mach sample may cause carryover. カップ半分で十分。多すぎるとキャリーオーバーの原因になります｡ Contamination with matrix modifier マトリックス修飾剤による汚れ High conc. of matrix modifier (eg. Pd/Mg 1000ppm) piles up at the ends of the cuvette. 高濃度のマトリックス修飾剤を使用すると、 キュベットの末端に修飾剤が付着してきま す｡ Clean the end of cuvette with a cotton swab each 100 measurements. 約100測定毎に、綿棒などで 清掃します｡ Contamination with matrix modifier マトリックス修飾剤による汚れ Matrix modifier piles up also at the electrode rings. Clean the ring by passing a paper like Kimwipe. 電極リングにもマトリックス修飾剤が付着し てきます｡ キムワイプなどをリングに通して 清掃します｡ Another factors for imprecision 再現性不良の他の原因 Bubbling in syringe pumps 気泡の発生 Loosening of screw 接続部の緩み Deterioration of packing パッキンの劣化 Autosampler syringe pump オートサンプラーシリンジポンプ Analysis of semiconductor reagent (organic Si) 半導体試薬(有機Si)の分析 1-Ca 422.7 nm ABS 0.25 REF 0.10 BKG 0.05 0.20 0.00 Sample＋Ca5ng/ｍL 0.15 Sample＋Ca2.5ng/mL Sample×５Dilution 0.10 Xylene 0.05 0.00 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 時間(s) Avoid contamination from environment and containers. The sample is diluted with Xylene. Add hydrofluoric acid (HF) to remove Si. Add tetrahydrofuran (THF) to improve HF and organic Si. →Matrix modifier : HF/THF (1:1) Only GFAAS can analyze the sample. Z-2000 series New Platform Cuvette EPA method compatible Cumbersome insert operation is eliminated by built-in platform. 面倒な挿入作業が不要 Long life. 長寿命 Sensitivity is enhanced for some elements (1.5 times for Cu and Cr). いくつかの元素では感度向上 0.2 O m ega type Insert Abs orba nce surface deteriorated C onventional 0.1 Conventional type baseline unstable 0 0 200 400 600 800 1000 1200 1400 1600 1800 2000 Firings Repeated measurement for Cr standard solution. Note: The lifetime of the cuvette will be variable according to samples and heat conditions. The data shown above is only rough reference for simple aqueous solution and is not certified value. New Omega type キュベットの寿命は単純な標準液での目安であり、保証値ではありません。 Know-how for a better AAS expert 更なる原子吸光スペシャリストへの測定のコツ Thank you !
