JP5817372B2 - Heavy metal analyzer and heavy metal analysis method - Google Patents
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本発明は、測定試料の洗浄、測定試料からの重金属の抽出、重金属の分析測定を連続的に行うことが可能な、重金属分析装置及び重金属の分析方法に関するものである。 The present invention relates to a heavy metal analyzer and a heavy metal analysis method capable of continuously performing washing of a measurement sample, extraction of heavy metal from the measurement sample, and analysis and measurement of heavy metal.
近年、環境問題への関心が高く、土壌分析の需要が高まっている。通常、土壌汚染対策法（以下、「公定法」という。）に基づいて行われる土壌試料の前処理工程では、粉砕、ふるい、洗浄及び抽出が行われた後に測定が行われる。しかし、土壌分析を困難にしている要因として、妨害物質の混在や反応容器の洗浄、廃液の処理が面倒である点がある。また、ほぼ全ての作業を手作業で行う「公定法」に基づく操作は、熟練と時間を要し、煩雑な操作によって生じる夾雑物質の混入や試料量のロス、測定者間の誤差などに繋がる。そこで、前処理から測定までの自動化が期待されている。 In recent years, interest in environmental issues is high, and demand for soil analysis is increasing. Usually, in the pretreatment process of a soil sample performed based on the soil contamination countermeasure method (hereinafter referred to as “official method”), measurement is performed after pulverization, sieving, washing and extraction. However, as a factor that makes soil analysis difficult, it is troublesome to mix interfering substances, clean reaction vessels, and treat waste liquid. In addition, operations based on the “official method”, in which almost all operations are performed manually, require skill and time, leading to contamination by contaminants, loss of sample amount, errors between measurers, etc. caused by complicated operations. . Therefore, automation from pretreatment to measurement is expected.
土壌分析として、以下のような技術が開発されている。 The following technologies have been developed for soil analysis.
先ず、土壌中のアンモニア態窒素濃度を測定する土壌分析システムであって、データベースと演算処理部を有し、単位面積あたりの窒素系肥料施肥量に対応した経時的アンモニア態窒素の減少度合い情報が蓄積され、アンモニア態窒素濃度の測定値と窒素系肥料の施肥量を出力する土壌分析システムが開示されている（例えば、特許文献１参照。）。しかし、上記特許文献１に示される土壌分析システムは、金属類を分析対象にしたものでない。 First, a soil analysis system for measuring ammonia nitrogen concentration in soil, which has a database and an arithmetic processing unit, and information on the degree of decrease in ammonia nitrogen over time corresponding to the amount of nitrogen fertilizer applied per unit area. A soil analysis system that accumulates and outputs a measured value of ammonia nitrogen concentration and a fertilizer amount of nitrogenous fertilizer is disclosed (for example, refer to Patent Document 1). However, the soil analysis system disclosed in Patent Document 1 does not use metals as analysis targets.
次いで、植生可能な土壌に改良するための土壌分析システムであって、以下に示す土壌の分析項目について適正範囲値が設定され、解析を行って、適正値になるように肥料や土壌改良材の種類、施肥量を設定し、更に、適正な土壌改良方法や植生工法を設定する土壌分析システムが開示されている（例えば、特許文献２参照。）。分析項目：１．ｐＨ（水）、２．腐植含有率、３．りん酸吸収係数、４．塩基置換容量、５．有効態りん酸、６．置換性石灰、７．置換性苦土、８．置換性カリ、９．塩基飽和度、１０．石灰飽和度、１１．石灰・苦土比、１２．苦土・カリ比、１３．有効窒素、１４．土性、１５．土壌硬度
しかし、上記特許文献２に示される土壌分析システムは、分析項目に示される通り、土壌中の重金属を対象に分析するものではない。
Next, it is a soil analysis system for improving vegetable soil, the appropriate range values are set for the following soil analysis items, analysis is performed, and fertilizers and soil improvement materials are adjusted so that they become appropriate values. A soil analysis system that sets the type and amount of fertilization and further sets an appropriate soil improvement method and vegetation method is disclosed (for example, see Patent Document 2). Analysis items: pH (water), 2. 2. Humus content, 3. Phosphoric acid absorption coefficient, 4. Base replacement capacity, Effective phosphoric acid, 6. 6. Replaceable lime, Replaceable bitter soil, 8. 8. replaceable potash, Base saturation, 10. Lime saturation, 11. Lime / magnesia ratio, 12. Bitter / potassium ratio, 13. Effective nitrogen, 14. Earthiness, 15. However, the soil analysis system disclosed in Patent Document 2 does not analyze heavy metals in the soil as shown in the analysis items.
次に、土壌に光を照射し、その土壌が反射する反射光から得られた土壌スペクトルから該土壌の特性を分析する土壌分析方法であって、複数の土壌から得られた土壌スペクトルの波形の集合体から該波形の近似した複数の波形群を生成し、該各波形群における特徴スペクトルを求め、土壌の検出スペクトルと特徴スペクトルを比較して該検出スペクトルがどの波形群に属するかを特定するか、該検出スペクトルが属する波形群のキャリブレーション式を使って解析することにより、土壌の光スペクトルから土壌の特性及び成分、土性、タイプ等を高い精度で予測又は推定する土壌分析方法が開示されている（例えば、特許文献３参照。）。しかし、上記特許文献３に示される土壌分析方法は、土壌の光スペクトルを基に、土壌の特性等を予測、推定する方法であり、実際に重金属の含有量及び溶出量を測定するものではない。 Next, there is a soil analysis method for analyzing the characteristics of the soil from the soil spectrum obtained from the reflected light reflected from the soil by irradiating the soil with light, and the waveform of the soil spectra obtained from a plurality of soils is analyzed. Generate a plurality of waveform groups approximating the waveform from the aggregate, obtain a feature spectrum in each waveform group, compare the detected spectrum of the soil with the feature spectrum, and identify which waveform group the detected spectrum belongs to Or, a soil analysis method for predicting or estimating soil properties and components, soil properties, types, etc. from the light spectrum of the soil with high accuracy by analyzing using a calibration equation of the waveform group to which the detection spectrum belongs is disclosed. (For example, see Patent Document 3). However, the soil analysis method disclosed in Patent Document 3 is a method for predicting and estimating soil characteristics and the like based on the light spectrum of soil, and does not actually measure heavy metal content and elution amount. .
次に、農作物栽培に使用する土壌の状態を農業生産者または消費者がインターネット網を利用して確認できる土壌診断方法が開示されている（例えば、特許文献４参照。）。しかし、上記特許文献４に示す土壌診断方法は、分析機関に土壌サンプルを送付して分析してもらい、その分析結果がインターネット網を利用して閲覧することができるが、その分析手法は既知の手法を用いたものである。 Next, a soil diagnosis method is disclosed in which an agricultural producer or a consumer can check the state of soil used for crop cultivation using the Internet network (see, for example, Patent Document 4). However, in the soil diagnosis method shown in Patent Document 4, the soil sample is sent to the analysis organization for analysis, and the analysis result can be browsed using the Internet network, but the analysis method is known. The method is used.
次に、特定場所から採取した土壌を粉砕・攪拌して後その一部を取り出しプレスして円盤形状のペレット状試料とし、エネルギー分散型蛍光Ｘ線分析装置を用いて入射Ｘ線の照射スポットをその円盤面の異なる領域に移動させつつ検出データを蓄積し、統計的な処理を加えて分析することを特徴とする重金属等の含有量を測定する土壌分析方法が開示されている（例えば、特許文献５参照。）。しかし、上記特許文献５に示される土壌分析方法は、土壌の重金属の化学形態を測定する方法ではない。 Next, the soil collected from a specific place is pulverized and stirred, and then a part thereof is taken out and pressed to form a disk-shaped pellet sample, and an irradiation spot of incident X-rays is obtained using an energy dispersive X-ray fluorescence analyzer. A soil analysis method for measuring the content of heavy metals and the like, characterized by accumulating detection data while moving to different regions of the disk surface and analyzing by adding statistical processing (for example, patents) Reference 5). However, the soil analysis method disclosed in Patent Document 5 is not a method for measuring the chemical form of heavy metals in soil.
次に、土壌に含まれる分析対象成分を溶液に抽出する抽出部と、前記抽出部で得られた試料溶液に含まれる成分をコロナ放電によりイオン化するイオン化部と、前記イオン化部で生成されたイオンを質量分析する質量分析部とを備える土壌分析装置が開示されている（例えば、特許文献６参照。）。しかし、上記特許文献６に示される土壌分析装置ではダイオキシンを測定対象としており、土壌中の重金属を対象に分析するものではない。 Next, an extraction unit that extracts a component to be analyzed contained in soil into a solution, an ionization unit that ionizes components contained in the sample solution obtained by the extraction unit by corona discharge, and ions generated by the ionization unit Is disclosed (for example, see Patent Document 6). However, the soil analyzer shown in Patent Document 6 uses dioxin as a measurement target, and does not analyze heavy metals in soil.
次に、試料容器をある角度に傾ける手段と、測定容器を供給した試料ごと重量測定する手段と、試薬の比重に合わせた容積を測定・供給する手段と、これらの容積測定を行う制御機構を備えた土壌分析前処理装置において、必要な試料を供給する機構と、直接重量測定した試料に対し、試薬の比重にあわせた適量を測定・供給する機能を有していることを特徴とする土壌分析前処理装置が開示されている（例えば、特許文献７参照。）。しかし、上記特許文献７に示される土壌分析前処理装置は、重金属の選択回収及び測定装置までのラインを具備したものではない。 Next, there are means for tilting the sample container at a certain angle, means for measuring the weight of each sample supplied with the measurement container, means for measuring and supplying a volume in accordance with the specific gravity of the reagent, and a control mechanism for measuring these volumes. Soil analysis pretreatment equipment equipped with a mechanism for supplying the necessary sample and a function for measuring and supplying an appropriate amount according to the specific gravity of the reagent for the sample directly weighed An analysis pretreatment device is disclosed (for example, see Patent Document 7). However, the soil analysis pretreatment apparatus disclosed in Patent Document 7 does not include a line for selective recovery and measurement of heavy metals.
次に、土壌や地下水の汚染状況の分析において、測定データ及び複数の対象成分に関連する多系統の基礎データから特定の対象成分の分析値を算出する方法に関し、当該特定成分に関連した複数の基礎データの相関に限定した演算を繰り返し行う土壌分析装置が開示されている（例えば、特許文献８参照。）。しかし、上記特許文献８に示される土壌分析装置では、演算により特定の対象成分の分析値を算出する方法であり、測定データを得るための測定手法は既知の手法を用いたものである。 Next, in the analysis of soil and groundwater contamination, a method for calculating the analysis value of a specific target component from measurement data and multi-system basic data related to a plurality of target components, A soil analyzer that repeatedly performs calculations limited to correlation of basic data is disclosed (for example, see Patent Document 8). However, the soil analysis apparatus disclosed in Patent Document 8 is a method of calculating an analysis value of a specific target component by calculation, and a measurement method for obtaining measurement data uses a known method.
更に、土壌中の複数の成分をイオン交換反応により置換抽出する塩基化合物として他のイオンと化合させることにより析出除去することが可能な塩を使用し、塩の水溶液に土壌を加えて振とうし土壌中の複数の成分を抽出する抽出工程と、振とう・抽出後の液を濾過して抽出液を取り出す抽出液取出し工程と、抽出液に他のイオンを生成する物質を加えて塩を析出させ、析出物を除去する析出・除去工程と、分析計により析出物除去後の抽出液から土壌中の複数の成分を測定する分析工程とを有する土壌分析方法が開示されている（例えば、特許文献９参照。）。しかし、上記特許文献９に示される土壌分析方法では、重金属の選択回収及び測定装置までのオンラインでの測定を可能にしたものではない。 Furthermore, a salt that can be precipitated and removed by combining with other ions is used as a base compound that substitutes and extracts a plurality of components in the soil by an ion exchange reaction. Extraction process to extract multiple components in the soil, extraction process to extract the extraction liquid by filtering the liquid after shaking and extraction, and adding substances that generate other ions to the extraction liquid to precipitate the salt A soil analysis method having a precipitation / removal step for removing precipitates and an analysis step for measuring a plurality of components in the soil from the extract after removal of the precipitates by an analyzer (for example, patents) Reference 9). However, the soil analysis method disclosed in Patent Document 9 does not enable on-line measurement up to the selective collection and measurement device for heavy metals.
また、土壌中の重金属分析として、以下のような技術が開発されている。 In addition, the following techniques have been developed for analyzing heavy metals in soil.
先ず、採取した土壌試料に水または塩酸を混合して遠心分離することにより得られた土壌抽出液を不溶化濃縮する工程と、濃縮された土壌抽出液を蛍光Ｘ線分析して含有多元素成分を同時分析する工程とからなる重金属等多元素成分同時分析方法が開示されている（例えば、特許文献１０参照。）。しかし、上記特許文献１０に示される土壌中における重金属等多元素成分同時分析方法は、重金属の土壌成分の溶出試験を具備しているものではない。 First, insolubilizing and concentrating the soil extract obtained by mixing water or hydrochloric acid with the collected soil sample and centrifuging, and fluorescent X-ray analysis of the concentrated soil extract, A method for simultaneous analysis of multi-element components such as heavy metals comprising the step of simultaneous analysis is disclosed (for example, see Patent Document 10). However, the method for simultaneous analysis of multi-element components such as heavy metals in soil shown in Patent Document 10 does not include an elution test for soil components of heavy metals.
次いで、搬送されてくる汚染土壌中に含まれる重金属濃度を蛍光Ｘ線分析装置で測定する方法であって、汚染土壌と蛍光Ｘ線分析装置の測定窓との間に樹脂フィルムを供給すると共に、汚染土壌と樹脂フィルムを停止させた状態で蛍光Ｘ線分析装置を下降させ、樹脂フィルムを挟んで蛍光Ｘ線分析装置の測定窓と汚染土壌を近接させて測定した後、蛍光Ｘ線分析装置を上昇させて汚染土壌と樹脂フィルムを搬送する汚染土壌の重金属濃度測定方法が開示されている（例えば、特許文献１１参照。）。しかし、上記特許文献１１に示される汚染土壌の重金属濃度測定方法では、重金属の土壌成分の溶出試験を具備しているものではない。 Next, it is a method of measuring the heavy metal concentration contained in the contaminated soil being conveyed with a fluorescent X-ray analyzer, and supplying a resin film between the contaminated soil and the measurement window of the fluorescent X-ray analyzer, The X-ray fluorescence analyzer is lowered while the contaminated soil and the resin film are stopped, the measurement window of the X-ray fluorescence analyzer is brought close to the contaminated soil with the resin film interposed therebetween, and then the X-ray fluorescence analyzer is A method for measuring the concentration of heavy metals in contaminated soil that raises and transports contaminated soil and resin film is disclosed (see, for example, Patent Document 11). However, the heavy metal concentration measurement method for contaminated soil disclosed in Patent Document 11 does not include an elution test for heavy metal soil components.
次に、土壌から溶出される重金属等の有害物質を蛍光Ｘ線分析により定量的に分析する土壌中有害物質含有量分析方法であって、採取された土壌を試料として蛍光Ｘ線分析により有害物質の含有量を分析する前分析工程と、試料とされた土壌から有害物質を溶出するように土壌に水系溶媒を加えて混合した後に固液分離する溶出工程と、溶出工程において固液分離されたうちの固体成分を試料として蛍光Ｘ線分析法により有害物質の含有量を分析する後分析工程と、前分析工程で分析された有害物質の含有量から後分析工程で分析された有害物質の含有量を減算し、溶出された有害物質の含有量を算出する溶出量算出工程と、を備える土壌中有害物質含有量分析方法が開示されている（例えば、特許文献１２参照。）。しかし、上記特許文献１２に示される土壌中有害物質含有量分析方法では、固体成分中の重金属含有量を測定するが、環境影響に直接かかわる溶出液中の重金属を直接測定できない。 Next, there is a method for analyzing the content of hazardous substances in soil by quantitatively analyzing the harmful substances such as heavy metals eluted from the soil by fluorescent X-ray analysis, and using the collected soil as a sample, the harmful substances are analyzed by fluorescent X-ray analysis. In the pre-analysis process for analyzing the content of sucrose, an elution process in which water-based solvent is added to the soil and mixed so as to elute harmful substances from the sampled soil, and the solid-liquid separation in the elution process A post-analysis process that analyzes the content of harmful substances by X-ray fluorescence analysis using a solid component as a sample, and a content of hazardous substances analyzed in the post-analysis process from the content of harmful substances analyzed in the pre-analysis process An elution amount calculation step of subtracting the amount and calculating the content of the eluted harmful substance is disclosed (for example, see Patent Document 12). However, in the method for analyzing toxic substance content in soil shown in Patent Document 12, the heavy metal content in the solid component is measured, but the heavy metal in the effluent directly related to the environmental influence cannot be measured directly.
次に、土壌に含まれる重金属類の溶出量分析方法において、土壌から作成した検液に所定の割合でキレート剤を加え、このキレート剤に検液中の測定対象物質を吸着させる手順と、検液をろ過し、測定対象物質を吸着したキレート剤を回収する手順と、蛍光Ｘ線分析装置により、回収したキレート剤が吸着した測定対象物質を定量分析し、この分析結果を検液中の測定対象物質の溶出量に換算する手順とを有する溶出量分析方法が開示されている（例えば、特許文献１３参照。）。しかし、上記特許文献１３に示される溶出量分析方法では、測定までの操作工程が複数存在する。 Next, in the method for analyzing the amount of elution of heavy metals contained in soil, a chelating agent is added to the test solution prepared from the soil at a predetermined ratio, and the measurement target substance in the test solution is adsorbed to the chelating agent. The solution is filtered and the chelating agent that has adsorbed the measurement target substance is recovered and the measurement target substance adsorbed by the recovered chelating agent is quantitatively analyzed using a fluorescent X-ray analyzer. An elution amount analysis method having a procedure for converting into an elution amount of a target substance is disclosed (for example, see Patent Document 13). However, the elution amount analysis method disclosed in Patent Document 13 includes a plurality of operation steps up to measurement.
次に、土壌、底質、灰、排水などを試料として採取し、この採取された試料を所定のｐＨに調整された液体に溶解して被検液とし、この被検液を機能性フィルタを用いて濾過し、この機能性フィルタに捕集された微量特定物質をＸ線分析装置によって分析する環境における微量特定物質の簡易定量分析方法が開示されている（例えば、特許文献１４参照。）。しかし、上記特許文献１４に示される環境における微量特定物質の簡易定量分析方法では、試料を機能性フィルターに導入するための、土壌からの重金属抽出工程は含まれていない。 Next, soil, sediment, ash, drainage, etc. are collected as samples, and the collected samples are dissolved in a liquid adjusted to a predetermined pH to obtain a test solution. This test solution is filtered with a functional filter. A simple quantitative analysis method of trace specific substances in an environment in which the trace specific substances collected by the functional filter and collected by the functional filter are analyzed by an X-ray analyzer is disclosed (for example, see Patent Document 14). However, the simple quantitative analysis method for trace specific substances in the environment shown in Patent Document 14 does not include a heavy metal extraction step from soil for introducing a sample into a functional filter.
次に、秤量した土壌試料に蒸留水または希塩酸等の鉱酸を加え、超音波照射して土壌試料から重金属を溶出させ、これを濾過して得た試料液を多元素同時分析装置に導入して試料から溶出した有害重金属濃度を測定し、試料の秤量値に基づいて有害重金属量を求める分析方法において、超音波の周波数を３０〜４０ＫＨｚとし、超音波照射時に土壌試料を乾燥試料１ｇあたり５〜１５平方ｃｍの範囲に浮遊分散させる土壌含有重金属の溶出方法が開示されている（例えば、特許文献１５参照。）。しかし、上記特許文献１５に示される土壌含有重金属の溶出方法では、土壌試料に含まれるマトリックスの影響を考慮していない。 Next, a mineral acid such as distilled water or dilute hydrochloric acid is added to the weighed soil sample, ultrasonic irradiation is performed to elute heavy metals from the soil sample, and the sample solution obtained by filtering this is introduced into the multi-element simultaneous analyzer. In an analysis method for measuring the concentration of harmful heavy metals eluted from a sample and determining the amount of harmful heavy metals based on the measured value of the sample, the ultrasonic frequency is set to 30 to 40 KHz, and the soil sample is 5 per gram of dry sample at the time of ultrasonic irradiation. A method for eluting soil-containing heavy metals that are suspended and dispersed in a range of ˜15 square cm is disclosed (see, for example, Patent Document 15). However, the soil-containing heavy metal elution method disclosed in Patent Document 15 does not consider the influence of the matrix contained in the soil sample.
次に、土壌試料を秤量し、硝酸とフッ化水素酸および過酸化水素水を容器に入れて密封し、マイクロ波による加圧酸分解を進めた後に、容器内の試料溶液に蒸留水を加えて重量調整して一定容量にし、これを多元素同時分析装置に導入して試料中の有害重金属濃度を測定し、試料の秤量値に基づいて土壌試料中の有害重金属量を求めることを特徴とする土壌含有重金属の分析方法が開示されている（例えば、特許文献１６参照。）。上記特許文献１６に示される土壌含有重金属の分析方法では、従来の公定法に比較して試料調製から元素分析にいたる所要時間が極めて短くなっているが、高濃度の塩を除去し、様々な測定機器に対応できる分析方法とはなっていない。 Next, weigh the soil sample, put nitric acid, hydrofluoric acid, and hydrogen peroxide in a container, seal it, proceed with pressurized acid decomposition using microwaves, and then add distilled water to the sample solution in the container. It is characterized by adjusting the weight to a constant volume, introducing this into a multi-element simultaneous analyzer, measuring the concentration of harmful heavy metals in the sample, and determining the amount of harmful heavy metals in the soil sample based on the measured value of the sample A method for analyzing soil-containing heavy metals is disclosed (for example, see Patent Document 16). In the method for analyzing soil-containing heavy metals shown in Patent Document 16 above, the time required from sample preparation to elemental analysis is extremely short compared to the conventional official method. It is not an analytical method that can be used with measuring instruments.
次に、対象液中の重金属物を分析する装置であって、重金属物を吸着保持するキレート体と、キレート体に対象液を流通させる対象液供給手段と、キレート体にレーザ光またはＸ線を照射する照射手段と、レーザ光またはＸ線の照射に伴うキレート体からの発光の強度に基づいて対象液中の重金属物の量を求める重金属物量測定手段とを備えていることを特徴とする重金属物分析装置が開示されている（例えば、特許文献１７参照。）。しかし、上記特許文献１７に示される重金属物分析装置では、あらかじめ土壌から重金属を溶出する必要があり、妨害物の存在（ケイ素、鉄、アルミニウム等）の除去技術についても触れられていない。 Next, an apparatus for analyzing heavy metal in the target liquid, which is a chelate body that adsorbs and holds the heavy metal object, target liquid supply means for circulating the target liquid in the chelate body, and laser light or X-rays on the chelate body Irradiation means for irradiating, and heavy metal substance amount measuring means for determining the amount of heavy metal substance in the target liquid based on the intensity of light emitted from the chelate body associated with laser light or X-ray irradiation An object analyzer is disclosed (for example, see Patent Document 17). However, in the heavy metal substance analyzer shown in the above-mentioned Patent Document 17, it is necessary to elute heavy metals from the soil in advance, and there is no mention of a technique for removing the presence of obstacles (silicon, iron, aluminum, etc.).
次に、土壌の試料にレーザ光を照射し、レーザ光の照射に伴う試料からの発光の強度を測定して、発光強度に基づいて、試料中の重金属系有害物質の量を求める土壌中の重金属系有害物質分析方法において、試料の少なくともレーザ光の照射表面を乾燥させるようにした土壌中の重金属系有害物質分析方法が開示されている（例えば、特許文献１８参照。）。しかし、上記特許文献１８に示される土壌中の重金属系有害物質分析方法では、重金属の土壌成分の溶出試験を具備しているものではない。 Next, irradiate the soil sample with laser light, measure the intensity of light emission from the sample accompanying the laser light irradiation, and determine the amount of heavy metal-based harmful substances in the sample based on the light emission intensity. In the method for analyzing heavy metal-based harmful substances, a method for analyzing heavy metal-based harmful substances in soil in which at least the surface irradiated with laser light is dried is disclosed (for example, see Patent Document 18). However, the method for analyzing heavy metal-based hazardous substances in soil disclosed in Patent Document 18 does not include an elution test for heavy metal soil components.
次に、土壌中の水分量および土壌の粒径を測定する一方、レーザ光を土壌に照射して、レーザ光の照射に伴う土壌からの発光の強度を測定し、水分量および粒径に基づいて発光強度を補正し、補正した発光強度に基づいて、土壌中の重金属系有害物質の量を求める土壌中の重金属系有害物質分析方法が開示されている（例えば、特許文献１９参照。）。しかし、上記特許文献１９に示される土壌中の重金属系有害物質分析方法では、重金属の土壌成分の溶出試験を具備しているものではない。 Next, while measuring the amount of water in the soil and the particle size of the soil, the soil is irradiated with laser light, and the intensity of light emitted from the soil accompanying the laser light irradiation is measured. Thus, there is disclosed a method for analyzing heavy metal harmful substances in soil, in which the amount of heavy metal harmful substances in the soil is determined based on the corrected emission intensity (see, for example, Patent Document 19). However, the heavy metal-based hazardous substance analysis method in soil disclosed in Patent Document 19 does not include an elution test for heavy metal soil components.
更に、被測定土壌試料をその内部にセットするための測定ベッセルと、測定ベッセル内に保持された被測定土壌試料に対してレーザを照射するためのレーザ照射手段と、レーザ照射によって被測定土壌試料から放射された励起光を測定ベッセル外へ導波する光搬送手段と、光搬送手段によって運ばれてきた励起光のスペクトルから存在する汚染物質である金属元素の種類と濃度を検出するスペクトル分析手段と、測定ベッセル内を真空状態にすると共に、レーザ照射によって加熱された被測定土壌試料から生じた気体を測定ベッセル外へ吸引搬送する真空吸引手段と、真空吸引手段によって運ばれてきた気体から存在する汚染物質である有機物の種類と濃度を検出する質量分析手段との組み合わせからなる土壌の汚染物質測定装置が開示されている（例えば、特許文献２０参照。）。特許文献２０によれば、共通の被測定土壌試料を用い、短時間で同時的に重金属とハロゲン化炭化水素の測定ができ、２つの異なる種類の測定を１つの装置で行うことで装置の集約小型化と可搬性を可能とし、現場と分析場所との近接化によるメリットを得ることができる土壌の汚染物質測定装置の提供を課題とするものである。しかし、上記特許文献２０に示される土壌の汚染物質測定装置では、土壌中の重金属の含有量と溶出量の測定を両方可能にする構成とはなっていない。 Furthermore, a measurement vessel for setting the soil sample to be measured therein, a laser irradiation means for irradiating a laser to the soil sample to be measured held in the measurement vessel, and a soil sample to be measured by laser irradiation Carrier means for guiding the excitation light radiated from the measurement vessel, and spectrum analysis means for detecting the type and concentration of the metallic element that is a contaminant from the spectrum of the excitation light carried by the light carrier means And vacuum suction means for sucking and transporting the gas generated from the soil sample to be measured heated by laser irradiation to the outside of the measurement vessel, and the gas carried by the vacuum suction means. Disclosed is a soil pollutant measuring device comprising a combination of a mass spectrometric means for detecting the type and concentration of organic substances that are pollutants. Are (e.g., see Patent Document 20.). According to Patent Document 20, it is possible to measure heavy metals and halogenated hydrocarbons simultaneously in a short time using a common soil sample to be measured, and to consolidate the apparatus by performing two different types of measurements with one apparatus. An object of the present invention is to provide a soil pollutant measuring device that can be miniaturized and portable, and that can obtain the merit of proximity between the site and the analysis site. However, the soil pollutant measuring device disclosed in Patent Document 20 does not have a configuration that enables measurement of both heavy metal content and elution amount in soil.
また、畜産や食品の重金属分析として、以下のような技術が開発されている。 In addition, the following technologies have been developed for the analysis of heavy metals in livestock and food.
蛍光Ｘ線分析装置による毛髪・皮膚・爪・歯・骨など生体内固形物中の元素検査、血液・尿・涙・汗・唾液などの生体液中の元素検査、穀類・豆類・いも及びでん粉類・キノコ類・果実類・野菜類など農作物中の元素検査、藻類・魚介類など海産物中の元素検査、食肉・卵類・乳類など畜産物中の元素検査、菓子類、調味料及び香辛料、調理加工食品類中の元素検査方法が開示されている（例えば、特許文献２１参照。）。しかし、上記特許文献２１に示す検査方法は、元素分析が目的であり、抽出液別での重金属の溶出、化学形態を判断できる方法にはなっていない。 Elemental inspection of living body solid matter such as hair, skin, nails, teeth and bones by X-ray fluorescence analyzer, elemental inspection in biological fluids such as blood, urine, tears, sweat, saliva, cereals, beans, potatoes and starches Elemental inspection in agricultural products such as seafood, mushrooms, fruits and vegetables, elemental inspection in marine products such as algae and seafood, elemental inspection in livestock products such as meat, eggs and milk, confectionery, seasonings and spices An element inspection method in cooked processed foods is disclosed (for example, see Patent Document 21). However, the inspection method shown in Patent Document 21 is intended for elemental analysis, and is not a method that can determine the elution and chemical form of heavy metals for each extract.
前述した通り、土壌から焼却灰、畜産廃棄物まで、多種多様な固体試料を迅速に測定するためには、土壌試料からの重金属の抽出のみにとどまらず、目的の重金属を回収し、高濃度の塩（Ｎａ，Ｋ，Ｍｇ）の除去することによって、炎光分析、原子吸光分析、ＩＣＰ発光分析などの測定装置に直接分析できる方法が必要となっている。 As described above, in order to quickly measure a wide variety of solid samples from soil to incineration ash and livestock waste, not only the extraction of heavy metals from soil samples but also the recovery of target heavy metals and high concentration By removing salts (Na, K, Mg), there is a need for a method that can be directly analyzed by a measuring device such as flame analysis, atomic absorption analysis, and ICP emission analysis.
従来の技術において、前処理から分析までを一つのラインとして行う土壌分析が困難であった主な理由として、第１に土壌の粒度が不均一であるため、同じ抽出操作を行っても実験結果にバラつきが生じること、第２に土壌には鉄、シリカ等のマトリックスが多く含まれるため、これらを除去する溶媒のｐＨやキレート剤投入等、複数のマスキングが必要であること、第３に様々な酸や有機化合物を用いるため、反応容器の洗浄、廃液の処理が面倒であること、第４に工場跡地や重金属汚染土壌地域に浄化技術を導入するための分析において迅速な対応が要請されていること、などが挙げられる。上記第４の理由で「迅速な対応」としたが、これは非常に重要なキーワードであり、土壌分析そのものが時間を要し、例えば農地や宅地の依頼分析を行うと約１ヶ月程度を要し、他の依頼分析よりも時間がかかるのは常識となっている。ライン化すると早くなるので、問題ないとも考えられるが、実際には測定項目が多く、土壌の前処理を測定者自身が手作業で行うので、遅速に係わらず測定値のばらつきが大きい。そして、セシウムやカドミウムのように「流動性の高い」元素の測定は、測定時間の経過が長いほど誤差が大きくなるためである。 In the prior art, the main reason for the difficulty in soil analysis from pretreatment to analysis as a single line is that the soil size is not uniform. Second, the soil contains a lot of matrix such as iron, silica, etc. Therefore, multiple masking is necessary, such as pH of the solvent to remove these and addition of chelating agent, The use of simple acids and organic compounds makes it difficult to clean the reaction vessel and dispose of the waste liquid. Fourth, there is a demand for prompt responses in analysis to introduce purification technologies in factory sites and heavy metal contaminated soil areas. And so on. Although “rapid response” was selected for the fourth reason, this is a very important keyword. Soil analysis itself takes time. For example, when request analysis of farmland or residential land is performed, it takes about one month. However, it is common sense that it takes longer than other request analysis. It is considered that there is no problem because it becomes faster when the line is made, but in reality there are many measurement items, and the measurement person himself performs manual pretreatment of the soil, so the variation in measured values is large regardless of the slow speed. This is because the measurement of elements with high fluidity such as cesium and cadmium has a larger error as the measurement time elapses.
本発明の目的は、測定試料の洗浄、測定試料からの重金属の抽出及び重金属の分析測定を連続的に行うことが可能な、重金属分析装置及び重金属の分析方法を提供することにある。 An object of the present invention is to provide a heavy metal analyzer and a heavy metal analysis method capable of continuously performing measurement sample washing, heavy metal extraction from the measurement sample, and heavy metal analysis measurement.
本発明の別の目的は、従来の測定まで時間の短縮を図ることができ、かつ測定値のばらつきを抑制し得る、重金属分析装置及び重金属の分析方法を提供することにある。 Another object of the present invention is to provide a heavy metal analyzing apparatus and a heavy metal analyzing method capable of reducing the time required for conventional measurement and suppressing variations in measured values.
本発明者らは、土壌中の重金属による生態系への影響に関する研究を実施するに当たり、前処理から測定までの工程を自動で行うことが可能な重金属分析装置の開発について鋭意検討した結果、測定試料を洗浄するとともに、重金属を抽出する循環型の重金属抽出部、目的の重金属のみを選択的に吸着する重金属吸着部及び吸着させた重金属を溶離させる溶離部を具備し、これらを流路により相互に接続する構成を見出し、本発明を完成した。 As a result of intensive investigations on the development of a heavy metal analyzer capable of automatically performing the processes from pretreatment to measurement in conducting research on the effects of heavy metals in the soil on the ecosystem, It is equipped with a circulation type heavy metal extraction unit for washing the sample and extracting heavy metal, a heavy metal adsorption unit for selectively adsorbing only the target heavy metal, and an elution unit for eluting the adsorbed heavy metal. As a result, the present invention has been completed.
本発明の第１の観点は、図１に示すように、一定量の抽出液１７ａを循環させることにより重金属を含む測定試料１６ａを充填したカラム１６に上記抽出液１７ａを通過させて測定試料１６ａを洗浄するとともに抽出液１７ａに重金属を抽出する重金属抽出部１１と、重金属抽出部１１で重金属を抽出した抽出液１７ａから測定対象の重金属を選択的に吸着する重金属吸着部１２と、溶離液１８ａにより重金属吸着部１２で吸着した重金属を溶離する溶離部１３とを備え、重金属抽出部１１と重金属吸着部１２とが第１流路１９により相互に接続され、溶離部１３と重金属吸着部１２とが第２流路２１により相互に接続され、重金属吸着部１２が第３流路２２により溶離液１８ａに含まれる溶離した重金属を測定する測定部１４に接続されることを特徴とする重金属分析装置である。 As shown in FIG. 1, the first aspect of the present invention is that the extract 17a is passed through a column 16 filled with a measurement sample 16a containing heavy metal by circulating a certain amount of the extract 17a. A heavy metal extraction unit 11 that extracts heavy metal into the extract 17a, a heavy metal adsorption unit 12 that selectively adsorbs a heavy metal to be measured from the extract 17a from which the heavy metal is extracted by the heavy metal extractor 11, and an eluent 18a And an elution part 13 for eluting the heavy metal adsorbed by the heavy metal adsorption part 12, the heavy metal extraction part 11 and the heavy metal adsorption part 12 are connected to each other by the first flow path 19, and the elution part 13 and the heavy metal adsorption part 12 Are connected to each other by the second flow path 21, and the heavy metal adsorbing section 12 is connected to the measuring section 14 for measuring the eluted heavy metal contained in the eluent 18a by the third flow path 22. DOO is a heavy metal analysis apparatus according to claim.
本発明の第２の観点は、第１の観点に基づく発明であって、更に図２〜図４に示すように、重金属抽出部１１が、抽出液１７ａを貯える第１容器１７と、脱イオン化水２４ａを貯える第２容器２４と、重金属を含む測定試料１６ａを充填可能なカラム１６と、カラム１６に抽出液１７ａ又は脱イオン化水２４ａを導入するための導入流路２６と、カラム１６を通過した抽出液１７ａが循環するための導入流路２６を含む循環流路２７と、第１流路１９に接続され循環した抽出液１７ａを脱イオン化水２４ａとともに送出するための送出流路２８と、第１容器１７から抽出液１７ａをカラム１６に導入するように又は第２容器２４から脱イオン化水２４ａをカラム１６に導入するように切換える第１切換弁２９と、第１切換位置と第２切換位置を有する第２切換弁３１と、カラム１６と第２切換弁３１の間の流路に設けられた第１ポンプ３２とを備え、第２切換弁３１が第１切換位置に切換えられたときに、第１ポンプ３２が導入流路２６を介して抽出液１７ａ又は脱イオン化水２４ａをカラム１６に導入しかつ抽出液１７ａを脱イオン化水２４ａとともに送出流路２８に送出し、第２切換弁３１が第２切換位置に切換られたときに、第１ポンプ３２が循環流路２７を介して抽出液１７ａを循環させるように構成されたことを特徴とする。 2nd viewpoint of this invention is invention based on 1st viewpoint, Comprising: As further shown in FIGS. 2-4, the heavy metal extraction part 11 is the 1st container 17 which stores the extract liquid 17a, and deionization. A second container 24 for storing water 24a, a column 16 that can be filled with a measurement sample 16a containing heavy metal, an introduction channel 26 for introducing the extract 17a or deionized water 24a into the column 16, and the column 16 A circulation flow path 27 including an introduction flow path 26 for circulating the extracted liquid 17a, a delivery flow path 28 for sending the extracted liquid 17a connected to the first flow path 19 together with the deionized water 24a, A first switching valve 29 for switching to introduce the extract 17a from the first container 17 into the column 16 or to introduce the deionized water 24a from the second container 24 into the column 16, and a first switching position and a second switching. position A second switching valve 31 having a first pump 32 provided in a flow path between the column 16 and the second switching valve 31, and when the second switching valve 31 is switched to the first switching position, The first pump 32 introduces the extract 17a or deionized water 24a into the column 16 through the introduction channel 26, and sends the extract 17a together with the deionized water 24a to the delivery channel 28. The second switching valve 31 When switched to the second switching position, the first pump 32 is configured to circulate the extract 17a through the circulation channel 27.
本発明の第３の観点は、第１の観点に基づく発明であって、更に図５に示すように、重金属吸着部１２が、対極電極３４、参照電極３６及び高温焼結炭素繊維カラムからなる作用電極３７を備えた電着セルであり、作用電極３７と第１流路１９で送られてきた抽出液１７ａとの間に測定対象の重金属に応じた電着電位を印加することにより、重金属抽出部１１で抽出された抽出液１７ａに含まれる測定対象の重金属のみを選択的に作用電極３７に吸着するように構成されたことを特徴とする。 A third aspect of the present invention is an invention based on the first aspect, and further, as shown in FIG. 5, the heavy metal adsorbing portion 12 includes a counter electrode 34, a reference electrode 36, and a high-temperature sintered carbon fiber column. This is an electrodeposition cell having a working electrode 37, and by applying an electrodeposition potential corresponding to the heavy metal to be measured between the working electrode 37 and the extract 17 a sent through the first flow path 19, the heavy metal Only the heavy metal to be measured contained in the extract 17 a extracted by the extraction unit 11 is selectively adsorbed to the working electrode 37.
本発明の第４の観点は、第１の観点に基づく発明であって、更に図１に示すように、溶離部１３が、溶離液１８ａを貯える第３容器１８と、溶離液１８ａを第２流路２１、重金属吸着部１２及び第３流路２２を経て測定部１４に移送する第２ポンプ３９とを有することを特徴とする。 The fourth aspect of the present invention is an invention based on the first aspect, and as shown in FIG. 1, the elution part 13 stores a third container 18 for storing an eluent 18a and an eluent 18a as a second. It has the 2nd pump 39 transferred to the measurement part 14 through the flow path 21, the heavy metal adsorption | suction part 12, and the 3rd flow path 22, It is characterized by the above-mentioned.
本発明の第５の観点は、第１の観点に基づく発明であって、更に測定試料が、０．０１ｍｍ〜０．１ｍｍの粒度を有する、土壌、畜産廃棄物、農産廃棄物、海産廃棄物、焼却灰、食品又は植物を少なくとも１種含むことを特徴とする。 A fifth aspect of the present invention is an invention based on the first aspect, wherein the measurement sample has a particle size of 0.01 mm to 0.1 mm, soil, livestock waste, agricultural waste, marine waste It contains at least one kind of incinerated ash, food or plant.
本発明の第６の観点は、重金属を含む測定試料を充填したカラムに導入流路を介して一定量の抽出液を導入する工程Ａと、導入した抽出液を導入流路を含む循環流路を介してカラムに一定時間循環させて抽出液に重金属を抽出する工程Ｂと、カラムを循環する抽出液の循環を停止した後、抽出液を脱イオン化水とともに送出流路を介して重金属吸着部に送る工程Ｃと、送られてきた抽出液から測定対象の重金属を選択的に重金属吸着部に吸着する工程Ｄと、溶離液により重金属吸着部に吸着した重金属を溶離する工程Ｅと、溶離液に含まれる溶離した重金属を測定する工程Ｆとを含む重金属の分析方法である。 According to a sixth aspect of the present invention, there is provided a step A for introducing a fixed amount of an extraction liquid into a column filled with a measurement sample containing heavy metal via an introduction flow path, and a circulation flow path including the introduced extraction liquid including the introduction flow path. Circulates through the column for a certain period of time to extract heavy metal into the extract, and after stopping the circulation of the extract through the column, the extract is combined with deionized water through the delivery channel and the heavy metal adsorption unit Step C, step D for selectively adsorbing the heavy metal to be measured to the heavy metal adsorption portion from the sent extract, step E for eluting the heavy metal adsorbed on the heavy metal adsorption portion by the eluent, and eluent And step F for measuring the eluted heavy metal contained in the heavy metal.
本発明の第７の観点は、第６の観点に基づく発明であって、更に測定試料が、０．０１ｍｍ〜０．１ｍｍの粒度を有する、土壌、畜産廃棄物、農産廃棄物、海産廃棄物、焼却灰、食品又は植物を少なくとも１種含むことを特徴とする。 A seventh aspect of the present invention is an invention based on the sixth aspect, wherein the measurement sample has a particle size of 0.01 mm to 0.1 mm, soil, livestock waste, agricultural waste, marine waste It contains at least one kind of incinerated ash, food or plant.
本発明の第１の観点では、測定試料を洗浄するとともに、重金属を抽出する循環型の重金属抽出部、目的の重金属のみを選択的に吸着する重金属吸着部及び吸着させた重金属を溶離させる溶離部を具備し、これらを第１流路及び第２流路により相互に接続する構成とし、かつ重金属吸着部を第３流路により溶離液に含まれる溶離した重金属を測定する測定部に接続する構成としたので、測定試料の洗浄、測定試料からの重金属の抽出及び重金属の分析測定を連続的に行うことができる。 In the first aspect of the present invention, a measurement type sample is washed and a circulation type heavy metal extraction unit that extracts heavy metals, a heavy metal adsorption unit that selectively adsorbs only the target heavy metal, and an elution unit that elutes the adsorbed heavy metal And a configuration in which these are connected to each other by the first flow path and the second flow path, and the heavy metal adsorbing section is connected to the measurement section for measuring the eluted heavy metal contained in the eluent by the third flow path. Therefore, washing of the measurement sample, extraction of heavy metal from the measurement sample, and analysis and measurement of heavy metal can be performed continuously.
次に本発明を実施するための形態を図面に基づいて説明する。 Next, an embodiment for carrying out the present invention will be described with reference to the drawings.
図１に示すように、本発明の重金属分析装置１０は、重金属抽出部１１と重金属吸着部１２と溶離部１３とを備える。重金属抽出部１１では一定量の抽出液１７ａを循環させることにより重金属を含む測定試料１６ａを充填したカラム１６に上記抽出液１７ａを通過させて測定試料１６ａを洗浄するとともに抽出液１７ａに重金属を抽出する。重金属吸着部１２では重金属抽出部１１で重金属を抽出した抽出液１７ａから測定対象の重金属を選択的に吸着する。溶離部１３では溶離液１８ａにより重金属吸着部１２で吸着した重金属を溶離する。 As shown in FIG. 1, the heavy metal analyzer 10 of the present invention includes a heavy metal extraction unit 11, a heavy metal adsorption unit 12, and an elution unit 13. The heavy metal extraction unit 11 circulates a certain amount of the extraction liquid 17a to pass the extraction liquid 17a through the column 16 filled with the measurement sample 16a containing heavy metal to wash the measurement sample 16a and extract the heavy metal into the extraction liquid 17a. To do. The heavy metal adsorption unit 12 selectively adsorbs the heavy metal to be measured from the extract 17 a from which the heavy metal is extracted by the heavy metal extraction unit 11. In the elution part 13, the heavy metal adsorbed by the heavy metal adsorption part 12 is eluted by the eluent 18a.
そして、重金属抽出部１１と重金属吸着部１２とが第１流路１９により相互に接続され、溶離部１３と重金属吸着部１２とが第２流路２１により相互に接続され、重金属吸着部１２が第３流路２２により溶離液１８ａに含まれる溶離した重金属を測定する測定部１４に接続される。 Then, the heavy metal extraction unit 11 and the heavy metal adsorption unit 12 are connected to each other by the first flow channel 19, the elution unit 13 and the heavy metal adsorption unit 12 are connected to each other by the second flow channel 21, and the heavy metal adsorption unit 12 is The third flow path 22 is connected to the measurement unit 14 that measures the eluted heavy metal contained in the eluent 18a.
なお、図１では、第１流路１９と第２流路２１とが第３切換弁２３で合流し、第３切換弁２３から重金属吸着部１２までの流路を共有させ、第３切換弁２３を切り換えることにより、第１流路１９で重金属抽出部１１と重金属吸着部１２とが相互に接続され、第２流路２１で溶離部１３と重金属吸着部１２とが相互に接続された構成としている。 In FIG. 1, the first flow path 19 and the second flow path 21 merge at the third switching valve 23, share the flow path from the third switching valve 23 to the heavy metal adsorption unit 12, and the third switching valve. 23, the heavy metal extraction unit 11 and the heavy metal adsorption unit 12 are connected to each other in the first flow path 19, and the elution unit 13 and the heavy metal adsorption unit 12 are connected to each other in the second flow path 21. It is said.
重金属抽出部１１は、図２〜図４に示されるように、抽出液１７ａを貯える第１容器１７と、脱イオン化水２４ａを貯える第２容器２４と、重金属を含む測定試料１６ａを充填可能なカラム１６と、カラム１６に抽出液１７ａ又は脱イオン化水２４ａを導入するための導入流路２６と、カラム１６を通過した抽出液１７ａが循環するための導入流路２６を含む循環流路２７と、第１流路１９に接続され循環した抽出液１７ａを脱イオン化水２４ａとともに送出するための送出流路２８と、第１容器１７から抽出液１７ａをカラム１６に導入するように又は第２容器２４から脱イオン化水２４ａをカラム１６に導入するように切換える第１切換弁２９と、第１切換位置と第２切換位置を有する第２切換弁３１と、カラム１６と第２切換弁３１の間の流路に設けられた第１ポンプ３２とを備える。 As shown in FIGS. 2 to 4, the heavy metal extraction unit 11 can be filled with a first container 17 for storing the extract 17a, a second container 24 for storing deionized water 24a, and a measurement sample 16a containing heavy metal. A column 16, a circulation channel 27 including an introduction channel 26 for introducing the extract 17 a or deionized water 24 a into the column 16, and an introduction channel 26 for circulating the extract 17 a that has passed through the column 16; A delivery channel 28 for delivering the circulated extract 17a connected to the first channel 19 together with the deionized water 24a, and the second vessel so that the extract 17a is introduced from the first vessel 17 into the column 16; 24, a first switching valve 29 for switching to introduce deionized water 24a into the column 16, a second switching valve 31 having a first switching position and a second switching position, a column 16 and a second switching valve 31 And a first pump 32 provided on the flow path.
そして、第２切換弁３１が第１切換位置に切換えられたときに、第１ポンプ３２が導入流路２６を介して抽出液１７ａ又は脱イオン化水２４ａをカラム１６に導入しかつ抽出液１７ａを脱イオン化水２４ａとともに送出流路２８に送出し、第２切換弁３１が第２切換位置に切換られたときに、第１ポンプ３２が循環流路２７を介して抽出液１７ａを循環させるように構成される。なお、図２〜図４では、導入流路２６から分岐するように形成され、第２切換弁３１を経て送出流路２８へと合流する、循環を補助するための補助流路３３が設けられ、この補助流路３３にも第１ポンプ３２’が設けられる。 When the second switching valve 31 is switched to the first switching position, the first pump 32 introduces the extract 17a or deionized water 24a into the column 16 through the introduction flow path 26, and supplies the extract 17a. When the second switching valve 31 is switched to the second switching position together with the deionized water 24a and the second switching valve 31 is switched to the second switching position, the first pump 32 circulates the extract 17a via the circulation channel 27. Composed. 2 to 4, an auxiliary flow path 33 that is formed so as to branch from the introduction flow path 26 and joins the delivery flow path 28 via the second switching valve 31 is provided to assist circulation. The auxiliary flow path 33 is also provided with a first pump 32 ′.
重金属吸着部１２は、図５に示すように、対極電極３４、参照電極３６及び高温焼結炭素繊維カラムからなる作用電極３７を備えた電着セルである。作用電極３７は、炭素棒３７ａ、高温焼結炭素繊維３７ｂ及び多孔質パイコールガラス管３７ｃから構成される。 As shown in FIG. 5, the heavy metal adsorption unit 12 is an electrodeposition cell including a counter electrode 34, a reference electrode 36, and a working electrode 37 including a high-temperature sintered carbon fiber column. The working electrode 37 includes a carbon rod 37a, a high-temperature sintered carbon fiber 37b, and a porous Pycor glass tube 37c.
そして、作用電極３７と第１流路１９で送られてきた抽出液との間に測定対象の重金属に応じた電着電位を印加することにより、重金属抽出部１１で抽出された抽出液に含まれる測定対象の重金属のみを選択的に作用電極３７に吸着するように構成される。また、図１に示すように、対極電極３４、参照電極３６は、電圧を一定にすることが可能なポテンショスタット３８に接続されている。 Then, by applying an electrodeposition potential corresponding to the heavy metal to be measured between the working electrode 37 and the extract sent through the first flow path 19, it is included in the extract extracted by the heavy metal extraction unit 11. Only the heavy metal to be measured is selectively adsorbed to the working electrode 37. As shown in FIG. 1, the counter electrode 34 and the reference electrode 36 are connected to a potentiostat 38 that can maintain a constant voltage.
溶離部１３は、図１に示すように、溶離液１８ａを貯える第３容器１８と、溶離液１８ａを第２流路２１、重金属吸着部１２及び第３流路２２を経て測定部１４に移送する第２ポンプ３９とを有する。なお、測定部１４は、その測定対象の分析に適した装置を自由に選択することが可能であり、例えば、炎光分析、原子吸光分析、ＩＣＰ（高周波誘導結合プラズマ）発光分析を用いた装置などが挙げられる。 As shown in FIG. 1, the elution unit 13 transfers the eluent 18 a to the measurement unit 14 via the second channel 21, the heavy metal adsorption unit 12, and the third channel 22, and the third container 18 that stores the eluent 18 a. Second pump 39. Note that the measurement unit 14 can freely select a device suitable for the analysis of the measurement target. For example, a device using flame light analysis, atomic absorption analysis, or ICP (high frequency inductively coupled plasma) emission analysis. Etc.
このように構成された重金属分析装置を用いた本発明の重金属の分析方法について説明する。 The heavy metal analysis method of the present invention using the thus configured heavy metal analyzer will be described.
測定対象の重金属を含む測定試料は、０．０１ｍｍ〜０．１ｍｍの粒度を有する、土壌、畜産廃棄物、農産廃棄物、海産廃棄物、焼却灰、食品又は植物を少なくとも１種含む固体試料である。測定試料の粒度を上記範囲内に揃えることで、様々な種類の固体試料に含まれる重金属の抽出、回収、測定に対応することができ、測定値のばらつきを抑制することができる。なお、下限値未満の粒度では、細かすぎて取り扱い難く、また抽出の際に、カラムに充填した試料が流路内に流れ出てしまうなどの不具合が生じるおそれがあり、上限値を越える粒度では、抽出が不十分になる、抽出時間がかかるなどの不具合が生じるおそれがあるためである。また、測定試料を上記範囲内の粒度だけでなく、上記範囲外の粒度を含むことにすると、同様の抽出操作を行っても実験結果にばらつきが生じてしまう。なお、本発明の分析方法で分析対象とする重金属としては、銅、亜鉛、鉛、カドミウム、ヒ素、セレン、水銀などが挙げられる。またストロンチウムやセシウムのようなイオン半径の大きな陽イオンの濃度測定なども可能である。 The measurement sample containing the heavy metal to be measured is a solid sample having a particle size of 0.01 mm to 0.1 mm and containing at least one kind of soil, livestock waste, agricultural waste, marine waste, incinerated ash, food or plant. is there. By aligning the particle size of the measurement sample within the above range, it is possible to cope with extraction, recovery, and measurement of heavy metals contained in various types of solid samples, and to suppress variations in measurement values. In addition, if the particle size is less than the lower limit value, it is too fine to handle, and there may be a problem that the sample packed in the column flows out into the flow path during extraction. This is because problems such as insufficient extraction and extraction time may occur. In addition, if the measurement sample includes not only the particle size within the above range but also the particle size outside the above range, even if the same extraction operation is performed, the experimental results vary. In addition, copper, zinc, lead, cadmium, arsenic, selenium, mercury etc. are mentioned as a heavy metal made into the analysis object by the analysis method of this invention. It is also possible to measure the concentration of cations with a large ion radius such as strontium and cesium.
本発明の分析方法では、予め分析目的の重金属に併せた抽出液の選択ができ、更に土壌分析において重要な「土壌からの溶出のし易さに基づいた化学形態分析」に適用できる。具体的には、土壌中の重金属の化学形態分析を行うため、Ｔｅｓｓｉｅｒらの「土壌の化学形態分析」を適用し、溶出のし易さで下記の５段階に分けるものである（例えば、非特許文献１，２参照。）。 In the analysis method of the present invention, an extract combined with a heavy metal to be analyzed can be selected in advance, and can be applied to “chemical form analysis based on easiness of elution from soil” which is important in soil analysis. Specifically, in order to analyze the chemical form of heavy metals in soil, the “chemical form analysis of soil” by Tessier et al. (See Patent Documents 1 and 2.)
１段階：イオン交換体と結合している形態であり、中性条件でも容易に溶出する形態（塩化物等）
２段階：炭酸塩と結合している形態
３段階：Ｆｅ−Ｍｎ酸化物と結合している形態
４段階：コロイド状の有機物あるいは硫黄と結合している形態
５段階：ケイ酸塩岩石などの結晶内に存在し最も溶出しにくい形態（鉱物）
このとき用いられる抽出液は、
１段階：ＭｇＣｌ2（ｐＨ７）、
２段階：ＣＨ3ＣＯＯＨ／ＣＨ3ＣＯＯＮａ（ｐＨ５）、
３段階：ＮＨ2ＯＨ−ＨＣｌ／ＣＨ3ＣＯＯＨ（ｐＨ３）、
４段階：ＨＮＯ3−Ｈ2Ｏ2（ｐＨ１〜２）、
５段階：ＨＦ−ＨＣｌＯ4（ｐＨ＜１）
となっているが、本発明の分析方法では、機器への影響を考慮して１段階から４段階までの化学形態分析を連続的に行うことができる。これは、重金属に汚染された土壌から、どのｐＨレベルの水によって溶出するか判定するものであり、特に酸性雨の多い、火山地帯周辺地域での農地、埋め立て処分場、工場跡地などの土壌分析診断に迅速な対応が可能である。なお、上記化学形態分析の５段階目においては、熱を加えなければ土壌を溶かすことできず、加熱によって危険なフッ素や塩素ガスが発生するため、本発明の適用外とした。また、４段階目は１段階目〜３段階目に比べて抽出効率が悪いため、抽出効率を上げるためには、５段階目と同様に熱を加えることが考えられるが、４段階においては、１段階目〜３段階目に比べて流速を半分程度に減少させ、循環（抽出）時間も倍程度に延ばすことで、室温でも重金属を抽出することができる。
1st stage: Form bound to the ion exchanger and easily eluted even under neutral conditions (chlorides, etc.)
2 stage: Form bonded to carbonate 3 stage: Form bonded to Fe-Mn oxide 4 stage: Form bonded to colloidal organic substance or sulfur 5 stage: Crystal such as silicate rock Forms (minerals) that exist in the body and are most difficult to elute
The extract used at this time is
One stage: MgCl 2 (pH 7),
Two stages: CH 3 COOH / CH 3 COONa (pH 5),
Three steps: NH 2 OH-HCl / CH 3 COOH (pH3),
Four stages: HNO 3 —H 2 O 2 (pH 1-2),
Five stages: HF-HClO 4 (pH <1)
However, in the analysis method of the present invention, chemical form analysis from the first stage to the fourth stage can be continuously performed in consideration of the influence on the equipment. This is to determine which pH level of water is eluted from soil contaminated with heavy metals. Especially, soil analysis of agricultural land, landfill site, factory site, etc. in the area around volcanic area where there is a lot of acid rain. A quick response to diagnosis is possible. In the fifth stage of the chemical form analysis, the soil cannot be dissolved unless heat is applied, and dangerous fluorine and chlorine gas are generated by heating. In addition, since the extraction efficiency in the 4th stage is lower than that in the 1st to 3rd stages, in order to increase the extraction efficiency, it is conceivable to apply heat as in the 5th stage, but in the 4th stage, The heavy metal can be extracted even at room temperature by reducing the flow rate to about half of that in the first to third stages and extending the circulation (extraction) time to about twice.
先ず、本発明の分析方法では、重金属抽出部１１において、重金属を含む測定試料１６ａを充填したカラム１６に導入流路２６を介して一定量の抽出液１７ａを導入する（工程Ａ）。この工程Ａでは、図２に示すように、測定試料１６ａの入ったカラム１６を重金属抽出部１１の第２切換弁３１と第１ポンプ３２との間に接続し、第１切換弁２９を抽出液導入側に切換え、第２切換弁３１を第１切換位置に切換えて、第１ポンプ３２，３２’を駆動することにより、第１容器１７内の抽出液１７ａを導入流路２６を介してカラム１６内に一定量導入する。 First, in the analysis method of the present invention, a certain amount of the extract 17a is introduced into the column 16 filled with the measurement sample 16a containing heavy metal through the introduction channel 26 in the heavy metal extraction unit 11 (step A). In this step A, as shown in FIG. 2, the column 16 containing the measurement sample 16a is connected between the second switching valve 31 and the first pump 32 of the heavy metal extraction unit 11, and the first switching valve 29 is extracted. By switching to the liquid introduction side, switching the second switching valve 31 to the first switching position, and driving the first pumps 32 and 32 ′, the extract 17 a in the first container 17 is passed through the introduction flow path 26. A fixed amount is introduced into the column 16.
なお、図２において、抽出液１７ａは、第１切換弁２９及び循環流路２６を通って第２切換弁３１の６番目の弁に入り、第２切換弁３１の５番目の弁から出て、第１ポンプ３２を介してカラム１６に導入される。なお、カラム１６から溢れた余剰の抽出液１７ａは循環流路２７を通って第２切換弁３１の８番目の弁に入り、第２切換弁３１の７番目の弁から出て、送出流路２８へと至る。また、抽出液１７ａは、第１切換弁２９、循環流路２６及び補助流路３３を通って第２切換弁３１の２番目の弁に入り、第２切換弁３１の１番目の弁から出て、第１ポンプ３２’を介して第２切換弁３１の４番目の弁に入り、第２切換弁３１の３番目の弁から出て、送出流路２８へと至る。 In FIG. 2, the extract 17 a passes through the first switching valve 29 and the circulation flow path 26 and enters the sixth valve of the second switching valve 31 and exits from the fifth valve of the second switching valve 31. And introduced into the column 16 via the first pump 32. The excess extract 17a overflowing from the column 16 enters the eighth valve of the second switching valve 31 through the circulation flow path 27, exits from the seventh valve of the second switching valve 31, and is sent out. To 28. The extract 17 a passes through the first switching valve 29, the circulation channel 26 and the auxiliary channel 33, enters the second valve of the second switching valve 31, and exits from the first valve of the second switching valve 31. Then, the valve enters the fourth valve of the second switching valve 31 via the first pump 32 ′, exits from the third valve of the second switching valve 31, and reaches the delivery flow path 28.
次いで、導入した抽出液１７ａを導入流路２６を含む循環流路２７を介してカラム１６に一定時間循環させて抽出液１７ａに重金属を抽出する（工程Ｂ）。この工程Ｂでは、図３に示すように、第２切換弁３１を第２切換位置に切換えて、第１ポンプ３２，３２’を駆動することにより、導入した抽出液１７ａを導入流路２６を含む循環流路２７を介してカラム１６に一定時間循環させる。 Next, the introduced extract 17a is circulated through the column 16 for a certain period of time through the circulation channel 27 including the introduction channel 26 to extract heavy metals in the extract 17a (step B). In this process B, as shown in FIG. 3, the second switching valve 31 is switched to the second switching position and the first pumps 32 and 32 ′ are driven, whereby the introduced extract 17a is introduced into the introduction flow path 26. It is made to circulate through the column 16 through the circulation path 27 containing it for a fixed time.
なお、図３において、第２切換弁３１を第２切換位置に切換えた状態では、カラム１６及び循環流路２７を通って第２切換弁３１の７番目の弁に入り、第２切換弁３１の８番目の弁から出て、補助流路３３を通って第１ポンプ３２’を介して第２切換弁３１の３番目の弁に入り、第２切換弁３１の４番目の弁から出て、第１ポンプ３２を介してカラム１６へと至る閉鎖系の環状流路が形成されている。 In FIG. 3, when the second switching valve 31 is switched to the second switching position, the second switching valve 31 enters the seventh valve of the second switching valve 31 through the column 16 and the circulation passage 27. The third valve of the second switching valve 31 enters the third valve of the second switching valve 31 via the first pump 32 ′ through the auxiliary flow path 33 and exits from the fourth valve of the second switching valve 31. A closed annular channel that reaches the column 16 via the first pump 32 is formed.
重金属の種類及びその化学形態によっても多少前後するが、１時間〜３時間の循環時間で測定試料から重金属を抽出でき、従来の公定法に定められた方法と比較して、測定時間の大幅な時間短縮が見込める。 Depending on the kind of heavy metal and its chemical form, it can be extracted from the measurement sample in a circulation time of 1 hour to 3 hours, and the measurement time is significantly longer than the method defined in the conventional official method. Time reduction is expected.
次に、カラムを循環する抽出液の循環を停止した後、抽出液を脱イオン化水とともに送出流路２８を介して重金属吸着部１２に送る（工程Ｃ）。この工程Ｃでは、図４に示すように、第１切換弁２９を脱イオン化水導入側に切換え、第２切換弁３１を第１切換位置に切換えて、第１ポンプ３２，３２’を駆動することにより、第２容器２４内の脱イオン化水２４ａを導入流路２６を介してカラム１６内に導入する。脱イオン化水２４ａを送りこむことで、循環して重金属を抽出した抽出液１７ａを脱イオン化水２４ａとともに送出流路２８から送出する。 Next, after the circulation of the extraction liquid circulating through the column is stopped, the extraction liquid is sent together with deionized water to the heavy metal adsorption unit 12 through the delivery flow path 28 (step C). In step C, as shown in FIG. 4, the first switching valve 29 is switched to the deionized water introduction side, the second switching valve 31 is switched to the first switching position, and the first pumps 32 and 32 ′ are driven. As a result, the deionized water 24 a in the second container 24 is introduced into the column 16 through the introduction flow path 26. By feeding the deionized water 24a, the extract 17a, which has been circulated and extracted heavy metals, is sent from the delivery channel 28 together with the deionized water 24a.
なお、この工程Ｃにおける脱イオン化水２４ａの流れは、前述した工程Ａにおける抽出液１７ａの流れと同様であり、送出流路２８から送出された、重金属を抽出した抽出液１７ａ及び脱イオン化水２４ａは、第１流路１９を経て、重金属吸着部１２へと送られる。 The flow of the deionized water 24a in the process C is the same as the flow of the extract 17a in the process A described above, and the extract 17a and the deionized water 24a extracted from the heavy metal flow and sent from the delivery channel 28. Is sent to the heavy metal adsorbing portion 12 through the first flow path 19.
従来の公定法に基づく土壌試料からの重金属抽出で実施されるバッチ式では、土壌試料から重金属を溶出する際、実験操作中でのコンタミネーションが生じ易い問題があったが、本発明の重金属分析装置の重金属抽出部１１で行われる本発明の分析方法の工程Ａ〜工程Ｃでは、測定試料から重金属を循環抽出する際に閉鎖系の環状流路で行うため、系外の影響が小さく、また重金属吸着部への抽出液の移送も重金属抽出部１１と重金属吸着部１２とが第１流路１９によって相互に接続されているため、コンタミネーションの影響が大きく軽減される。また、本発明の分析方法では循環抽出を採用しているため、廃液量が軽減される。 In the batch system implemented by heavy metal extraction from soil samples based on the conventional official method, there was a problem that contamination was likely to occur during experimental operations when eluting heavy metals from soil samples. In steps A to C of the analysis method of the present invention performed in the heavy metal extraction unit 11 of the apparatus, since heavy metal is circulated and extracted from the measurement sample in a closed annular channel, the influence outside the system is small. Since the heavy metal extraction unit 11 and the heavy metal adsorption unit 12 are connected to each other by the first flow path 19 in the transfer of the extract to the heavy metal adsorption unit, the influence of contamination is greatly reduced. In addition, since the analysis method of the present invention employs circulation extraction, the amount of waste liquid is reduced.
また、重金属抽出部１１では、上記工程Ａ〜工程Ｃを連続して行うことができ、また、上記工程Ａ〜工程Ｃは、コンピューターによって重金属抽出部１１の主要な可動部である第１切換弁２９、第２切換弁３１の切替や第１ポンプ３２，３２’の駆動を連動させることにより、自動化が可能である。 Moreover, in the heavy metal extraction part 11, the said process A-process C can be performed continuously, and the said process A-process C is the 1st switching valve which is a main movable part of the heavy metal extraction part 11 with a computer. 29. Automation is possible by linking the switching of the second switching valve 31 and the driving of the first pumps 32, 32 ′.
次に、重金属抽出部１１から第１流路１９で送られてきた抽出液１７ａから測定対象の重金属を選択的に重金属吸着部１２に吸着させる（工程Ｄ）。 Next, the heavy metal to be measured is selectively adsorbed to the heavy metal adsorption unit 12 from the extract 17a sent from the heavy metal extraction unit 11 through the first flow path 19 (step D).
土壌などの試料から重金属を抽出しただけでは、抽出液中にはフミン酸のような高分子有機物等が、畜産廃棄物が混入した試料では、抽出液中にはタンパク質、脂肪及び糖等のマトリックスが存在する。また、高濃度の塩分を含む試料では、抽出液中には塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、塩化アルミニウム、炭酸ナトリウム、炭酸カリウム、炭酸マグネシウム、炭酸カルシウム、硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸カルシウムなどのマトリックスが存在する。そして、これらのマトリックスを重金属と一緒に、ＩＣＰ装置を具備した発光分析装置のような分析装置に導入すると、ＩＣＰでの干渉作用並びに試料を吸引するネブライザーの塩析による故障等の原因に繋がる。従って、従来の技術では、これらを除去するために、溶媒のｐＨやキレート剤投入等、複数のマスキングが必要であった。しかし、重金属の選択的回収に汎用されているキレート樹脂は溶離が困難であり、また土壌のような測定試料の場合、多く含まれる鉄やカルシウム等のマトリックスの妨害を受けやすい問題があった。 By simply extracting heavy metals from a sample such as soil, a matrix of proteins, fats, sugars, etc. is contained in the extract if the sample is contaminated with high-molecular organic substances such as humic acid in the extract and livestock waste. Exists. For samples containing high concentrations of salt, the extract contains sodium chloride, potassium chloride, magnesium chloride, calcium chloride, aluminum chloride, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium sulfate, potassium sulfate, sulfuric acid. There is a matrix such as magnesium or calcium sulfate. When these matrices are introduced together with heavy metals into an analyzer such as an emission analyzer equipped with an ICP device, it causes interference with ICP and failure due to salting out of the nebulizer that sucks the sample. Therefore, in the conventional technique, in order to remove these, a plurality of masks such as a solvent pH and a chelating agent are required. However, the chelating resin widely used for the selective recovery of heavy metals is difficult to elute, and in the case of a measurement sample such as soil, there is a problem that it is likely to be disturbed by a matrix such as iron or calcium contained in a large amount.
そのため、本発明の分析方法の工程Ｄでは、重金属抽出部１１で抽出した抽出液１７ａを直接測定部１４には送らず、図５に示すような、重金属を選択的に吸着することが可能な高温焼結炭素繊維カラムを作用電極３７とした電着セルからなる重金属吸着部１２に送り、ここで測定対象の重金属を選択的に吸着させ、重金属とマトリックスとを分離することで、測定部１４に導入する成分からマトリックスを除去する。重金属吸着部１２によってマトリックスを除去するため、後述する測定部１４において、得られる重金属分析結果へのマトリックスが存在することによる影響を軽減することができる。また重金属吸着部１２の作用電極３７への吸着で重金属が濃縮されることから、後述する測定部１４において、ｐｐｂオーダーの高感度重金属測定が可能となる。 Therefore, in step D of the analysis method of the present invention, it is possible to selectively adsorb heavy metals as shown in FIG. 5 without directly sending the extract 17a extracted by the heavy metal extraction unit 11 to the measurement unit 14. The high temperature sintered carbon fiber column is sent to the heavy metal adsorption unit 12 composed of an electrodeposition cell using the working electrode 37, where the heavy metal to be measured is selectively adsorbed and the heavy metal and the matrix are separated, thereby the measurement unit 14 is separated. The matrix is removed from the components introduced into the. Since the matrix is removed by the heavy metal adsorption unit 12, the influence of the presence of the matrix on the obtained heavy metal analysis result can be reduced in the measurement unit 14 described later. Moreover, since heavy metal is concentrated by adsorption to the working electrode 37 of the heavy metal adsorption part 12, the measurement part 14 mentioned later enables highly sensitive heavy metal measurement of ppb order.
具体的には重金属吸着部１２では、作用電極３７と第１流路１９で送られてきた抽出液１７ａとの間に、重金属の吸着に最適な−１〜０Ｖの範囲で電位を印加することで、作用電極３７に重金属を選択的に吸着させる。 Specifically, in the heavy metal adsorbing unit 12, a potential is applied between the working electrode 37 and the extract 17 a sent through the first flow path 19 in a range of −1 to 0 V that is optimal for heavy metal adsorption. Thus, heavy metal is selectively adsorbed to the working electrode 37.
次に、溶離液１８ａにより重金属吸着部１２の作用電極３７で吸着された重金属を溶離する（工程Ｅ）。この工程Ｅでは、溶離部１３の第２ポンプ３９を駆動することにより、溶離液１８ａを第２流路を介して重金属吸着部１２へと移送し、重金属吸着部１２の作用電極３７に選択的に吸着させた重金属を溶離液１８ａによって溶離する。そして、溶離させた重金属を含む溶離液１８ａは重金属吸着部１２から第３流路２２を経て、そのまま、測定部１４へと運び入れることができる。重金属を溶離することが可能な溶離液１８ａとしては、硝酸、塩酸、硫酸のいずれかが挙げられる。 Next, the heavy metal adsorbed by the working electrode 37 of the heavy metal adsorption unit 12 is eluted by the eluent 18a (step E). In this step E, the second pump 39 of the elution unit 13 is driven to transfer the eluent 18a to the heavy metal adsorption unit 12 via the second flow path, and is selectively applied to the working electrode 37 of the heavy metal adsorption unit 12. The heavy metal adsorbed on is eluted with the eluent 18a. Then, the eluent 18 a containing the eluted heavy metal can be carried directly from the heavy metal adsorbing unit 12 to the measuring unit 14 through the third flow path 22. Examples of the eluent 18a capable of eluting heavy metals include nitric acid, hydrochloric acid, and sulfuric acid.
最後に、測定部１４において、溶離液１８ａに含まれる溶離した重金属を測定する（工程Ｆ）。第３流路２２を経て測定部１４に送られた溶離させた重金属を含む溶離液１８ａは、重金属吸着部１２によってマトリックスが除去されているため、マトリックスが存在することによる影響を軽減した、信頼度の高い分析結果が得られる。また、重金属吸着部１２の作用電極３７への吸着で重金属が濃縮されていることから、ｐｐｂオーダーの高感度重金属測定が可能となる。 Finally, the measurement unit 14 measures the eluted heavy metal contained in the eluent 18a (step F). The eluent 18a containing the eluted heavy metal sent to the measurement unit 14 through the third flow path 22 has the matrix removed by the heavy metal adsorbing unit 12, and thus the influence of the presence of the matrix is reduced. Highly accurate analysis results can be obtained. Moreover, since heavy metals are concentrated by adsorption to the working electrode 37 of the heavy metal adsorption part 12, highly sensitive heavy metal measurement in the ppb order becomes possible.
このように、本発明の重金属分析装置で行われる本発明の分析方法では、測定試料の洗浄、測定試料からの重金属の抽出及び重金属の分析測定を連続的に行うことができる。即ち、通常土壌汚染対策法に行われる土壌試料の前処理工程のうち、粉砕とふるい以外は、連続的に行うことができる。 As described above, in the analysis method of the present invention performed by the heavy metal analyzer of the present invention, the measurement sample can be washed, the heavy metal extracted from the measurement sample, and the heavy metal analysis measurement can be performed continuously. That is, in the pretreatment process of the soil sample usually performed in the soil contamination countermeasure method, the steps other than pulverization and sieving can be performed continuously.
なお、重金属抽出部１１、重金属吸着部１２及び溶離部１３は、各々手動で行ってもよいが、それぞれをコンピューターによって切換弁の切替やポンプの駆動を連動させることにより、全自動化も可能である。 The heavy metal extraction unit 11, the heavy metal adsorption unit 12, and the elution unit 13 may each be performed manually, but can be fully automated by switching the switching valve and driving the pump with a computer. .
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１＞
先ず、採取した土壌を測定試料とし、粒度は０．０１〜１ｍｍに調整した。また図１に示す重金属分析装置１０を用いた。次いで、図２に示すように、測定試料１６ａを充填したカラム１６を重金属抽出部１１に接続し、このカラム１６に導入流路２６を介して抽出液（１Ｍ塩酸）１７ａを一定量導入した。そして、図３に示すように、導入した抽出液１７ａを導入流路２６を含む循環流路２７を介してカラム１６に１時間循環させて、抽出液１７ａに測定試料に含まれる重金属（Ｃｕ、Ｚｎ、Ｐｂ）を抽出した。次に、カラム１６を循環する抽出液１７ａの循環を停止した後、図４に示すように、抽出液１７ａを脱イオン化水２４ａとともに送出流路２８を介して重金属吸着部１２に送り、図５に示すように、重金属吸着部１２の作用電極３７と抽出液１７ａとの間に−０．８Ｖの電位を印加することにより、測定対象の重金属を選択的に重金属吸着部１２に吸着させ、重金属と、鉄やアルミニウム、ナトリウム、カリウム、カルシウム、ケイ素、高分子有機物等のマトリックスとを分離した。次に、溶離液（１Ｍ硝酸）１８ａにより重金属吸着部１２に吸着した重金属を溶離させ、溶離液１８ａに含まれる溶離した重金属を原子吸光装置により測定した。その結果を次の表１にそれぞれ示す。
<Example 1>
First, the collected soil was used as a measurement sample, and the particle size was adjusted to 0.01 to 1 mm. Moreover, the heavy metal analyzer 10 shown in FIG. 1 was used. Next, as shown in FIG. 2, the column 16 filled with the measurement sample 16 a was connected to the heavy metal extraction unit 11, and a fixed amount of the extract (1M hydrochloric acid) 17 a was introduced into the column 16 through the introduction flow path 26. Then, as shown in FIG. 3, the introduced extract 17a is circulated through the column 16 through the circulation channel 27 including the introduction channel 26 for 1 hour, and the heavy metal (Cu, Zn, Pb) were extracted. Next, after the circulation of the extract 17a circulating in the column 16 is stopped, as shown in FIG. 4, the extract 17a is sent to the heavy metal adsorbing unit 12 through the delivery channel 28 together with the deionized water 24a. As shown in FIG. 2, by applying a potential of −0.8 V between the working electrode 37 of the heavy metal adsorption unit 12 and the extract 17a, the heavy metal to be measured is selectively adsorbed on the heavy metal adsorption unit 12, And a matrix of iron, aluminum, sodium, potassium, calcium, silicon, polymer organic matter, etc. were separated. Next, the heavy metal adsorbed on the heavy metal adsorbing portion 12 was eluted with the eluent (1M nitric acid) 18a, and the eluted heavy metal contained in the eluent 18a was measured with an atomic absorption device. The results are shown in Table 1 below.
＜比較例１＞
実施例１と同様の採取した土壌を測定試料とし、公定法（土壌汚染対策法）に基づく溶出試験法を用いて測定試料中に含まれる重金属を測定した。その結果を次の表１にそれぞれ示す。
<Comparative Example 1>
The collected soil as in Example 1 was used as a measurement sample, and heavy metals contained in the measurement sample were measured using an elution test method based on the official method (Soil Contamination Countermeasures Method). The results are shown in Table 1 below.
また、実施例１では測定時間は２〜３時間程度であり、比較例１（公定法）の測定時間が１０〜１５時間を要するのに対し、大幅な時間短縮となった。更に、比較例１の測定時に生じる廃液量に比べ、実施例１では測定時に生じる廃液は約１／１０迄削減することができており、本発明の重金属分析装置を用いた分析方法は、公定法と比較して、土壌のような測定試料から重金属を容易に分析することができることが確認された。 In Example 1, the measurement time was about 2 to 3 hours, and the measurement time in Comparative Example 1 (official method) required 10 to 15 hours. Furthermore, compared with the amount of waste liquid generated during the measurement in Comparative Example 1, the waste liquid generated during the measurement in Example 1 can be reduced to about 1/10, and the analysis method using the heavy metal analyzer of the present invention is officially approved. Compared with the method, it was confirmed that heavy metals can be easily analyzed from measurement samples such as soil.
本発明の重金属分析装置及び重金属の分析方法は、分析、無機、環境の化学分野、不動産、環境アセスメント、製鉄場など、土壌中の重金属分析を採用する分野、又は畜産業からの家畜糞、一般及び工業からの焼却灰、浄水場の汚泥等の常時大量の産業廃棄物が産出され、埋め立て処分や再利用開発を行う際に重金属の測定が必須項目に関わる技術分野、最近では、放射能汚染における土壌のセシウム、ストロンチウムのようなイオン半径の大きな陽イオンの濃度測定が必要な分野への利用にも適用が可能である。 The heavy metal analysis apparatus and heavy metal analysis method of the present invention include analysis, inorganic, environmental chemistry fields, real estate, environmental assessment, steelworks, etc., fields that employ heavy metal analysis in soil, or livestock manure from the livestock industry, In addition, a large amount of industrial waste such as incinerated ash from industry and sludge from water treatment plants is produced at all times, and technical fields related to the measurement of heavy metals in landfill disposal and reuse development, recently, radioactive contamination It can also be applied to fields that require measurement of cations with a large ionic radius such as cesium and strontium in soil.
１０ 重金属分析装置
１１ 重金属抽出部
１２ 重金属吸着部
１３ 溶離部
１４ 測定部
１６ カラム
１６ａ 測定試料
１７ 第１容器
１７ａ 抽出液
１８ 第３容器
１８ａ 溶離液
１９ 第１流路
２１ 第２流路
２２ 第３流路
２３ 第３切換弁
２４ 第２容器
２４ａ 脱イオン化水
２６ 導入流路
２７ 循環流路
２８ 送出流路
２９ 第１切換弁
３１ 第２切換弁
３２ 第１ポンプ
３３ 補助流路
３４ 対極電極
３６ 参照電極
３７ 作用電極
３８ ポテンショスタット
３９ 第２ポンプ
DESCRIPTION OF SYMBOLS 10 Heavy metal analyzer 11 Heavy metal extraction part 12 Heavy metal adsorption part 13 Elution part 14 Measurement part 16 Column 16a Measurement sample 17 1st container 17a Extraction liquid 18 3rd container 18a Elution liquid 19 1st flow path 21 2nd flow path 22 3rd Flow path 23 Third switching valve 24 Second container 24a Deionized water 26 Introduction flow path 27 Circulating flow path 28 Delivery flow path 29 First switching valve 31 Second switching valve 32 First pump 33 Auxiliary flow path 34 Counter electrode 36 Electrode 37 Working electrode 38 Potentiostat 39 Second pump
Claims (7)
前記重金属抽出部と前記重金属吸着部とが第１流路により相互に接続され、前記溶離部と前記重金属吸着部とが第２流路により相互に接続され、前記重金属吸着部が第３流路により前記溶離液に含まれる溶離した重金属を測定する測定部に接続されることを特徴とする重金属分析装置。 A heavy metal extraction unit that passes the extract through a column filled with a measurement sample containing heavy metal by circulating a certain amount of the extract to wash the measurement sample and extract the heavy metal into the extract, and the heavy metal extraction A heavy metal adsorption part that selectively adsorbs the heavy metal to be measured from the extract obtained by extracting the heavy metal in the part, and an elution part that elutes the heavy metal adsorbed by the heavy metal adsorption part by the eluent,
The heavy metal extraction part and the heavy metal adsorption part are connected to each other by a first flow path, the elution part and the heavy metal adsorption part are connected to each other by a second flow path, and the heavy metal adsorption part is a third flow path. The heavy metal analyzer is connected to a measuring unit for measuring the eluted heavy metal contained in the eluent.
前記第２切換弁が前記第１切換位置に切換えられたときに、前記第１ポンプが前記導入流路を介して前記抽出液又は前記脱イオン化水を前記カラムに導入しかつ前記抽出液を前記脱イオン化水とともに前記送出流路に送出し、前記第２切換弁が前記第２切換位置に切換られたときに、前記第１ポンプが前記循環流路を介して前記抽出液を循環させるように構成された請求項１記載の重金属分析装置。 A first container for storing the extract; a second container for storing deionized water; the column capable of being filled with a measurement sample containing heavy metal; and the extract or the deionized water in the column. An introduction flow path for introducing the extraction liquid; a circulation flow path including the introduction flow path for circulating the extraction liquid that has passed through the column; and the circulated extraction liquid connected to the first flow path. A delivery flow path for delivery with ionized water and a first switch for switching to introduce the extract from the first container into the column or to introduce the deionized water from the second container into the column. A valve, a second switching valve having a first switching position and a second switching position, and a first pump provided in a flow path between the column and the second switching valve,
When the second switching valve is switched to the first switching position, the first pump introduces the extraction liquid or the deionized water into the column through the introduction flow path, and the extraction liquid is supplied to the column. When the second switching valve is switched to the second switching position together with the deionized water, the first pump circulates the extract through the circulation channel. The heavy metal analyzer according to claim 1, which is configured.
前記導入した抽出液を前記導入流路を含む循環流路を介して前記カラムに一定時間循環させて前記抽出液に重金属を抽出する工程と、
前記カラムを循環する抽出液の循環を停止した後、前記抽出液を脱イオン化水とともに送出流路を介して重金属吸着部に送る工程と、
前記送られてきた抽出液から測定対象の重金属を選択的に前記重金属吸着部に吸着する工程と、
溶離液により前記重金属吸着部に吸着した重金属を溶離する工程と、
前記溶離液に含まれる溶離した重金属を測定する工程と
を含む重金属の分析方法。 Introducing a predetermined amount of the extract into the column filled with the measurement sample containing heavy metal via the introduction channel;
Circulating the introduced extract through the circulation channel including the introduction channel for a certain period of time to extract heavy metals in the extract;
After stopping circulation of the extract circulating in the column, sending the extract together with deionized water to the heavy metal adsorbing section via a delivery channel;
A step of selectively adsorbing a heavy metal to be measured from the sent extract to the heavy metal adsorption portion;
Eluting heavy metal adsorbed on the heavy metal adsorbing portion with an eluent;
And a step of measuring the eluted heavy metal contained in the eluent.
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