JP4956037B2 - Simple test method for leaching amount of harmful substances in soil - Google Patents
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Description
本発明は、土壌中に含有されている重金属などの有害物質の溶出量の簡易で迅速な試験方法に係り、さらに詳しくは、簡便かつ速やかに調製した溶出試験用検液を分析した値から公定法による土壌中有害物質の溶出量を推計する簡易試験方法、さらにはこのような方法に用いる土壌中有害物質の簡易試験キット並びに演算プログラム付き分析装置に関するものである。
The present invention relates to a simple and rapid test method for the amount of elution of toxic substances such as heavy metals contained in soil, and more specifically, from a value obtained by analyzing a test solution for dissolution test prepared easily and quickly. The present invention relates to a simple test method for estimating the amount of soil toxic substances eluted by the method, and further to a simple test kit for soil toxic substances used in such a method and an analyzer with a calculation program.
土壌中に存在するＰｂ（鉛）やＣｄ（カドミウム）、Ｃｒ６＋（六価クロム）、Ａｓ（砒素）、Ｆ（フッ素）、Ｂ（ホウ素）等の有害物質は、土壌からの溶出による地下水汚染、あるいは直接摂取によって健康被害を引き起こす恐れがあることから、土壌汚染対策法等により、適用範囲、試験方法及び分析方法について基準が定められている。
しかし、土壌汚染対策法等で指定されている試験・分析方法、例えば環境庁告示第４６号（以下、「公定溶出量試験」と称する）では、試料の乾燥、検液を得るための前処理（検液調製）において、乾燥に３日以上、前処理操作に１日以上を要する。また、０．４５μｍのろ紙によりろ過する際に、大型ろ紙を使用するか、あるいは事前に遠心分離しないと、目詰まりによって迅速なろ過が困難となることが多い。さらに、分析においても、高度な技術が必要であると共に、高価な分析機器を用いることが必要となるという問題がある。
Hazardous substances such as Pb (lead), Cd (cadmium), Cr 6+ (hexavalent chromium), As (arsenic), F (fluorine), and B (boron) present in soil are contaminated with groundwater by elution from the soil. In addition, since there is a risk of causing health damage by direct ingestion, standards for the scope of application, test method and analysis method are set by the Soil Contamination Countermeasures Law.
However, in the test and analysis methods specified in the Soil Contamination Countermeasures Law, for example, Environment Agency Notification No. 46 (hereinafter referred to as “official elution amount test”), sample pretreatment and pretreatment for obtaining a test solution In (Sample preparation), it takes 3 days or more for drying and 1 day or more for pretreatment. Further, when filtering with 0.45 μm filter paper, if a large filter paper is used or if it is not centrifuged in advance, rapid filtration is often difficult due to clogging. Furthermore, in the analysis, there is a problem that it is necessary to use advanced techniques and to use expensive analytical instruments.
一方、土壌汚染調査の契機としては、土壌汚染対策法や地方自治体の条例で指定されている特定有害物質を取り扱っていた工場等を廃止する場合、都道府県知事等が健康被害の恐れがあると認めた場合、大規模な土地改変をする場合の他、現在操業中の事業所で汚染の疑いが生じた場合や定期調査、宅地売買等に絡む汚染有無を把握したい場合など、法律に定められた範囲外の測定機会も多数存在する。 On the other hand, as an opportunity for soil contamination investigations, prefectural governors, etc., may have a health hazard when abolishing factories that handle specified hazardous substances specified in the Soil Contamination Countermeasures Law or local government regulations. If approved, in addition to making large-scale land changes, or when there is a suspicion of contamination at a business site that is currently in operation, or when it is necessary to grasp the presence or absence of contamination related to periodic surveys, residential land sales, etc. There are also many measurement opportunities outside the range.
また、法律や条令で調査が定められた範囲では、公定法に則って汚染状況を把握する必要があるが、法律の枠外での調査や法律で指定された範囲を補足する目的においては、時間がかかり、分析にも技術や資金が必要となる公定試験分析法が必ずしも適当であるとは言えない。
例えば、汚染の可能性が発生した工事現場などでは、極力迅速な判断が求められる。また、操業中の工場敷地内や宅地売買における自主調査では、簡易かつ安価な測定方法が望まれている。
In addition, it is necessary to grasp the pollution status in accordance with the official law within the scope specified by the laws and regulations, but for the purpose of investigating outside the legal framework and supplementing the scope specified by the law, Therefore, the official test analysis method that requires technology and funding for analysis is not necessarily appropriate.
For example, at a construction site where there is a possibility of contamination, determination as quickly as possible is required. In addition, a simple and inexpensive measurement method is desired in the self-investigation in the factory premises and the residential land trading in operation.
さらに、法律の範囲で汚染調査を行う場合においても、その調査を効率的に行うためには、現場で汚染実態の概略を把握し、公定試験分析法の実施地点を定めることなど、簡易・迅速な試験方法が望まれている。
そのため、これまでにも多くの分析前処理（試験）方法や分析方法が提案されている。
Furthermore, even when conducting a pollution survey within the scope of the law, in order to conduct the survey efficiently, it is easy and quick to grasp the outline of the actual pollution situation at the site and determine the implementation point of the official test analysis method. Test methods are desired.
Therefore, many analysis pretreatment (test) methods and analysis methods have been proposed so far.
土壌試験における溶出過程を促進した方法として、酸抽出溶出促進金属測定法が提案されている。この方法は、通常純水で行う溶出操作を塩酸溶液で行い、土壌中の重金属を短時間で抽出して分析する簡易迅速分析法であって、公定法を補完する方法として用いることができるとされている（非特許文献１参照）。 As a method for accelerating the elution process in soil tests, an acid extraction elution accelerating metal measurement method has been proposed. This method is a simple rapid analysis method in which elution operation usually performed with pure water is performed with hydrochloric acid solution and heavy metals in the soil are extracted and analyzed in a short time, and can be used as a method to complement the official method. (See Non-Patent Document 1).
一方、「土壌汚染域の確定方法」として、土壌試料をマイクロ波あるいは超音波を利用した分解装置により処理し、含有されている重金属を加速溶出させ、ＩＣＰ質量分析装置により分析する方法が開示されている（特許文献１参照）。
また、「重金属抽出方法及び重金属溶出量の測定方法」として、汚染土壌や廃棄物など重金属を高濃度に含有する試料に対して、液固比１以下となるよう水を混合した後、遠心ろ過してろ液中の重金属濃度を分析する重金属溶出量の測定方法が知られている（特許文献２参照）。
On the other hand, as a “determination method of soil contaminated area”, a method is disclosed in which a soil sample is processed by a decomposition apparatus using microwaves or ultrasonic waves, and the contained heavy metals are accelerated and eluted and analyzed by an ICP mass spectrometer. (See Patent Document 1).
In addition, as a “heavy metal extraction method and heavy metal elution measurement method”, water is mixed to a sample containing heavy metals such as contaminated soil and waste at a high concentration so that the liquid-solid ratio is 1 or less, and then centrifugal filtration is performed. And the measuring method of the heavy metal elution amount which analyzes the heavy metal density | concentration in a filtrate is known (refer patent document 2).
さらに、秤量した土壌試料に硝酸とフッ化水素酸及び過酸化水素水を加えて密閉し、マイクロ波による加圧酸分解により分解し、これに蒸留水を加えて重量調整をした後、多元素同時分析装置により重金属濃度を分析し、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土壌含有重金属の測定方法が開示されている（特許文献３参照）。
また、「土壌含有金属の溶出方法」として、秤量した土壌試料に蒸留水又は希塩酸等を加え、３０〜４０ＫＨｚの超音波を照射して、乾燥試料１ｇあたり５〜１５ｃｍ２の範囲に浮遊分散させた土壌試料から重金属を溶出させ、これをろ過して得た試料液を多元素同時分析装置で分析し、土壌中の有害重金属量を求める方法が開示されている（特許文献４参照）。
Furthermore, nitric acid, hydrofluoric acid and hydrogen peroxide water were added to the weighed soil sample, sealed, decomposed by pressure acid decomposition using microwaves, and distilled water was added thereto to adjust the weight. There is disclosed a method for measuring soil-containing heavy metals by analyzing the concentration of heavy metals with a simultaneous analyzer and determining the amount of harmful heavy metals in a soil sample based on the measured value of the sample (see Patent Document 3).
In addition, as a “soil-containing metal elution method”, distilled water or dilute hydrochloric acid or the like was added to a weighed soil sample, and ultrasonic waves of 30 to 40 KHz were irradiated to float and disperse in a range of 5 to 15 cm 2 per 1 g of the dried sample. A method is disclosed in which a heavy metal is eluted from a soil sample and a sample solution obtained by filtering the heavy metal is analyzed with a multi-element simultaneous analyzer to determine the amount of harmful heavy metal in the soil (see Patent Document 4).
さらに、土壌中金属等の新しい分析方法を示したものとして、特許文献５には、「土壌に含まれる重金属類の溶出量分析方法及び分析装置、並びにこれに用いる試料」として、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、その検液をろ過し、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に吸着された対象物質濃度を定量し、この結果から検液中の測定対象物質の溶出量に換算する手順について記載されている。 Furthermore, as a new analysis method for metals in soil and the like, Patent Document 5 describes a method for analyzing the amount of elution of heavy metals contained in soil and an analysis apparatus, and a sample used therefor. A procedure for adding a chelating agent at a predetermined ratio to the test solution, and adsorbing the measurement target substance in the test solution to this chelating agent, a procedure for filtering the test solution and collecting the chelating agent adsorbing the measurement target substance, A procedure is described in which the concentration of the target substance adsorbed on the collected chelating agent is quantified by an X-ray fluorescence analyzer, and this result is converted into the elution amount of the target substance in the test solution.
また、土壌中金属等の試験分析方法に関するものとしては、特許文献６に、「土壌分析方法とそれに用いる蛍光Ｘ線土壌分析装置」として、土壌を粉砕・撹拌した後、その一部をプレスして円盤状のペレット試料を作成し、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状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ようにした重金属等の含有量測定方法が開示されている。 In addition, as for a test analysis method for metals and the like in soil, Patent Document 6 describes as “Soil analysis method and fluorescent X-ray soil analysis device used therefor”, after crushing and stirring the soil, a part thereof is pressed. Disk-shaped pellet sample, and using an energy dispersive X-ray fluorescence spectrometer, the detection data is accumulated while moving the incident X-ray irradiation spot to a different disk-shaped area, and statistical processing is added. A method for measuring the content of heavy metals and the like, which is analyzed in this manner, is disclosed.
そして、土壌汚染の試験方法に関する特許文献７には、凝集剤を添加することによって、土壌と抽出液の混合液からの被抽出液の分離を促進することが開示され、重金属等の土壌溶出簡易試験方法に関する特許文献８には、未風乾土壌に有機溶媒を加えて１分間の手振とう後、３０分静置し、遠心分離ののち、０．４５μｍのメンブレンフィルターにより減圧ろ過して得られたろ液をＩＣＰ発光分析装置等により分析する方法が開示されている。
しかしながら、上記非特許文献１、特許文献１、特許文献２、特許文献３及び特許文献４に記載の方法では、土壌中の金属等の含有量を相対的に把握することが可能であるが、公定法との相関が得られていないため、結果から何らかの判断を行うことが困難であり、実用範囲はかなり制限されることになる。
また、上記特許文献５に記載の方法は、キレート剤での選択的吸着が可能な成分については有効であるものと考えられるが、対象物質以外の多種多様な金属等を含有する土壌について適用することが困難で、広い対象物質に適用できるものではない。
However, in the methods described in
The method described in Patent Document 5 is considered to be effective for components that can be selectively adsorbed by a chelating agent, but is applied to soil containing various metals other than the target substance. It is difficult to apply to a wide range of target substances.
さらに、上記特許文献６に記載の方法は、簡易で、多くの金属種についてスクリーニングが可能であるが、原理的に土壌中に存在する金属等の一部しか溶出してこない公定法試験よりも数倍高い濃度を示すことがあり、相対比較や明らかに汚染がないことの判定にのみしか使用できないと考えられる。 Furthermore, although the method described in Patent Document 6 is simple and can be screened for many metal species, in principle, it is more than an official method test in which only a part of metals and the like existing in soil are eluted. Concentrations may be several times higher and can only be used for relative comparisons and for determining that there is clearly no contamination.
また、上記特許文献７に記載の方法は、試験方法のごく一部を迅速化したものに過ぎなく、試験方法全体からみた場合には、簡易化、迅速化にはほど遠いものといわざるを得ない。
そして、特許文献８に記載の方法は、比較的迅速ではあるものの、有機溶媒を使用する点、模擬的に調製した土壌でのデータが主であるため、実用上の測定精度が不明確である点、拡散溶出及び固液分離を目的とした静置時間が長い点、さらに試験サイズが大きくて廃液が多くなり、また多地点の現場調査を行う際に手間がかかる点に問題がある。
Further, the method described in Patent Document 7 is only a part of the test method that has been accelerated, and when viewed from the whole test method, it can be said that the method is far from being simplified and quicker. Absent.
And although the method of patent document 8 is comparatively quick, since the data in the point which uses an organic solvent and the soil prepared by simulation are mainly, the practical measurement precision is unclear. However, there are problems in that the standing time for the purpose of diffusion elution and solid-liquid separation is long, the test size is large and the waste liquid is increased, and it takes time to conduct a multi-site field survey.
本発明は、従来の土壌中有害物質の分析、測定方法における上記題に着目してなされたものであって、その目的とするところは、有機溶媒を使用することなく、多数の検体について、公定試験方法と比較して十分に短い時間で、簡易に公定試験方法に相当する濃度を推計することができ、土壌汚染調査のスクリーニングとして、汚染の有無の一次確認や高濃度汚染地点の探索などに利用することができる土壌中有害物質の溶出量の簡易試験方法を提供することにある。
The present invention has been made by paying attention to the above-mentioned problems in conventional methods for analyzing and measuring harmful substances in soil, and the object of the present invention is the official determination of a large number of specimens without using an organic solvent. Concentration equivalent to the official test method can be estimated easily in a sufficiently short time compared to the test method, and as a soil contamination survey screening, such as primary confirmation of the presence of contamination and search for high-concentration contamination points The object is to provide a simple test method for the amount of toxic substances in soil that can be used.
本発明者らは、上記目的を達成すべく鋭意検討を重ねた結果、公定試験方法に較べて十分に短い時間でも相当量の有害物質が水や酸水溶液などの溶媒中に溶出することから、各有害物質の溶出挙動を把握することによって、試験サイズを縮小し、検液の調製時間を短縮したとしても、公定試験方法による測定値を推算することができ、上記目的が達成されることを見出し、本発明を完成するに到った。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a considerable amount of harmful substances are eluted in a solvent such as water or an acid aqueous solution even in a sufficiently short time compared to the official test method. By knowing the elution behavior of each harmful substance, even if the test size is reduced and the preparation time of the test solution is shortened, the measured value by the official test method can be estimated, and the above objective can be achieved. The headline and the present invention have been completed.
すなわち、本発明は上記知見に基づくものであって、本発明の土壌中有害物質の簡易溶出量試験方法においては、５０ｇ未満の質量の土壌を採取し、これに採取した土壌質量の５倍以上の水を加え、公定溶出量試験で定められた公定時間未満の時間振とうさせた後、ろ過して検液を得、得られた検液の分析値から、公定溶出量試験濃度を推計するようにしており、振とう時間と、その時間における物質の溶出濃度を公定時間振とう後の溶出濃度を「１」とする比で表した溶出率との関係を振とう時間を変数とする指数関数として求めておき、当該指数関数に基づいて公定時間未満の上記振とう時間に対応する溶出率を求め、該溶出率で上記振とう時間後の分析値を除すことによって公定溶出量試験の推計値を算出することを特徴とする。
That is, the present invention is based on the above knowledge, and in the simple method for testing the amount of toxic substances in soil of the present invention, soil having a mass of less than 50 g is sampled and at least five times the mass of soil sampled therein. Of water, shake for less than the official time specified in the official dissolution test , filter to obtain a test solution, and estimate the official dissolution rate test concentration from the analytical value of the obtained test solution An index with the shaking time as a variable, the relationship between the shaking time and the dissolution rate of the substance at that time, expressed as a ratio with the dissolution concentration after the official time shaking as the ratio “1”. It is obtained as a function, and the dissolution rate corresponding to the shaking time less than the official time is obtained based on the exponential function, and the analysis value after the shaking time is divided by the dissolution rate to obtain the official dissolution rate test. An estimated value is calculated .
このとき、上記簡易溶出量試験方法におけるろ過操作においては、孔径０．４５μｍのろ紙の上に、孔径１μｍ以上のろ紙を重ねて成る複層ろ紙によりろ過することが望ましい。
At this time, in the filtration operation in the simple elution amount test method, it is desirable to filter with a multilayer filter paper in which a filter paper having a pore diameter of 1 μm or more is stacked on a filter paper having a pore diameter of 0.45 μm.
そして、本発明の土壌中有害物質の簡易試験キットは、上記した土壌中有害物質の簡易試験方法に好適に用いられるものであって、少なくとも、土壌試料を溶媒と共に振とうする蓋付容器と、孔径０．４５μｍのろ紙の上に、孔径１μｍ以上のろ紙を重ねて成り、上記蓋付容器内の上澄み液をろ過するための複層ろ紙と、上記複層ろ紙によるろ液を収納する検液容器を備えたことを特徴としている。
さらに、本発明の分析装置は、上記方法において得られる溶出量試験用検液の分析値から、公定試験濃度を推計する演算処理プログラムを備えたことを特徴とする。
And the simple test kit for harmful substances in soil of the present invention is preferably used in the above-described simple test method for harmful substances in soil, and at least a container with a lid for shaking a soil sample with a solvent, A filter paper having a pore diameter of 0.45 μm overlaid with a filter paper having a pore diameter of 1 μm or more, a multi-layer filter paper for filtering the supernatant liquid in the lidded container, and a test solution for storing the filtrate from the multi-layer filter paper It is characterized by having a container.
Furthermore, the analyzer of the present invention is characterized by comprising an arithmetic processing program for estimating the official test concentration from the analysis value of the elution amount test solution obtained by the above method.
本発明によれば、５０ｇ未満の比較的少量の土壌に、その５倍以上の質量の水を加えて公定時間未満の任意の時間振とうさせた後、ろ過するようにしているので、比較的短時間で、容易に土壌中有害物質の溶出量の試験用検液を調製することができる。このような検液の任意の振とう時間での溶出量分析値を指数関数から求めた任意振とう時間での溶出率で割り算することにより、公定試験方法による溶出量を推計するようにしていることから、公定試験方法よりも短時間で、簡易に公定試験方法に相当する土壌中有害物質の濃度をかなりの精度で把握することができる。
また、ろ過操作において、孔径０．４５μmのろ紙の上に孔径１μm以上のろ紙を重ねてなる複層ろ紙によりろ過を行うことで、さらに迅速、簡易に試験することを可能とした。
According to the present invention, a relatively small amount of soil of less than 50 g is added with 5 times more mass of water and shaken for an arbitrary time less than the official time , and then filtered. short time, Ru can be easily prepared, the quantity eluted of the test sample solution of harmful substances in the soil. The elution amount by the official test method is estimated by dividing the elution amount analysis value at the arbitrary shaking time of such a test solution by the elution rate at the arbitrary shaking time obtained from the exponential function . For this reason, the concentration of harmful substances in the soil corresponding to the official test method can be easily grasped with considerable accuracy in a shorter time than the official test method.
Moreover, in the filtration operation, it was possible to test more quickly and easily by performing filtration with a multilayer filter paper in which a filter paper having a pore diameter of 1 μm or more is superimposed on a filter paper having a pore diameter of 0.45 μm.
以下、本発明について、その実施形態などと共に、さらに詳細に説明する。なお、本明細書において、「％」は特記しない限り質量百分率を表すものとする。 Hereinafter, the present invention will be described in more detail together with embodiments thereof. In the present specification, “%” represents mass percentage unless otherwise specified.
本発明の土壌中有害物質の簡易溶出量試験方法において、試験用検液を調製するには、まず、調査対象である土壌試料を秤量し、５０ｇ未満の質量を採取し、これにその５倍以上の質量の水を加え、公定時間である３６０分未満の任意の時間振とうさせ、土壌中物質を溶媒（この場合は水）中に溶出させる。
このとき、土壌試料の採取量としては、少な過ぎれば測定精度が悪化し、多すぎると後述するように水の量も多くなることから、振とう容器の大型化、重量増に繋がり、採取現場における手操作による振とう作業が困難になることから、３〜１０ｇ程度とすることが望ましい。
In the simple dissolution amount test method for harmful substances in soil of the present invention, in order to prepare a test solution, first, a soil sample to be investigated is weighed, a mass of less than 50 g is collected, and this is five times as much. Water with the above mass is added and shaken for an arbitrary time of less than 360 minutes, which is the official time, to elute the substance in the soil into the solvent (in this case, water).
At this time, if the amount of the soil sample collected is too small, the measurement accuracy will deteriorate, and if it is too large, the amount of water will increase as will be described later, leading to an increase in the size and weight of the shaking container. Since it is difficult to perform a shaking operation by manual operation, it is desirable that the amount be about 3 to 10 g.
土壌中物質を溶出させる溶媒としての水については、通常脱イオン水や蒸留水を用いるが、調査対象である被検出成分の分析値に影響を及ぼすものが含有されていなければ、特に限定されない。 About water as a solvent which elutes the substance in soil, deionized water or distilled water is usually used, but it is not particularly limited as long as it does not contain anything that affects the analysis value of the component to be detected.
このときの水の添加量については、採取した土壌試料に対して余りに多過ぎると検出感度が低下し、少な過ぎると土壌中物質が十分に溶出せず、また、固液分離（ろ過）が困難となることから、採取した土壌試料の８〜１５倍の質量とすることが望ましい。
なお、溶出量の単位はｍｇ／Ｌで表わされ、公定試験分析法では、採取土壌の１０倍の液固比としているため、このような液固比に換算することが必要となる。したがって、本発明の簡易試験方法においても、採取した土壌試料の１０倍の水を加えるようにすることがより望ましく、換算の手間を省くことができる。
If the amount of water added is too much for the collected soil sample, the detection sensitivity will decrease, and if it is too small, substances in the soil will not be sufficiently eluted, and solid-liquid separation (filtration) will be difficult. Therefore, the mass is preferably 8 to 15 times that of the collected soil sample.
In addition, since the unit of the elution amount is expressed in mg / L and the official test analysis method has a liquid-
土壌試料を含む水の振とう時間、すなわち土壌中物質の溶出時間については、余りに短いと土壌中物質が溶媒中に十分溶出しない反面、長すぎると簡便法としてのメリットがなくなる。また、簡便法として、現地での検液調製を考えれば、手操作による振とう作業を続けるには限界がある。
このような観点から、振とう時間としては、３０分以内、例えば１分程度とすることができる。なお、本発明は、動力を用いた機械的振とうを排除するものではなく、状況に応じて機械による振とうを採用し、溶出時間をさらに延長することによって、検出精度が向上する可能性もある。
As for the shaking time of water containing the soil sample, that is, the elution time of the substance in the soil, if it is too short, the substance in the soil will not be sufficiently eluted in the solvent, but if it is too long, there will be no merit as a simple method. As a simple method, considering the preparation of the test solution at the site, there is a limit in continuing the manual shaking operation.
From such a viewpoint, the shaking time can be within 30 minutes, for example, about 1 minute. It should be noted that the present invention does not exclude mechanical shaking using power, and the possibility of improving detection accuracy by adopting mechanical shaking according to the situation and further extending the elution time. is there.
このようして得られた土壌試料と水との懸濁液は、ろ過され、これによって溶出量試験用検液が得られる。なお、ろ過には、孔径０．４５μｍのろ紙の上に、孔径１μｍ以上のろ紙を重ねて成る複層ろ紙を用いることが望ましい。 The suspension of the soil sample and water thus obtained is filtered, thereby obtaining a test solution for the elution amount test. For filtration, it is desirable to use a multilayer filter paper in which a filter paper having a pore diameter of 1 μm or more is stacked on a filter paper having a pore diameter of 0.45 μm.
このとき、所定時間の振とうを終えた懸濁液を数分間静置した後、例えばシリンジなどを用いて採取した上澄み液を上記複層ろ紙に通すことによってろ過することができ、上記のような複層ろ紙を用いることによって、土壌中の比較的粗粒の粒子が上層側の粗い孔径のろ紙によって捕捉されることから、ろ過操作の大幅な迅速化と小型化を図ることができる。
なお、複層ろ紙については、孔径の異なる複数のろ紙を成形したものも市販されており、このような市販品の中から、上記孔径に一致するものを選択して使用することもできる。
At this time, after the suspension after shaking for a predetermined time is allowed to stand for several minutes, the supernatant collected using, for example, a syringe can be filtered by passing through the multilayer filter paper, as described above. By using such a multilayer filter paper, relatively coarse particles in the soil are captured by the filter paper having a coarse pore diameter on the upper layer side, so that the filtration operation can be greatly speeded up and downsized.
In addition, about the multilayer filter paper, what shape | molded the several filter paper from which a hole diameter differs is marketed, The thing which corresponds to the said hole diameter from such a commercial item can also be selected and used.
上記したように、本発明においては、土壌のサンプリング量や溶媒量を少なくしたり、振とう時間を短くしたりすることによって、検液の調製に要する時間を大幅に短縮できると共に、手作業による振とうも可能になることから、土壌のサンプリング現場において、溶出量試験用の検液を調製することができ、検液調製の迅速化、簡便化が可能になり、土壌汚染調査全体の迅速化、簡易化に繋がる。
As described above, in the present invention, it is possible to significantly reduce the time required for preparing the test solution by reducing the sampling amount of the soil and the amount of the solvent, or shortening the shaking time, and by manual work. Since shaking is also possible, it is possible to prepare a test solution for the elution amount test at the site of soil sampling, making it quicker and easier to prepare the test solution, and accelerating the entire soil contamination survey. , Leading to simplification.
本発明の土壌中有害物質の簡易溶出量試験方法においては、それぞれ上記調製方法によって得られた溶出量試験検液の分析値から、公定溶出量試験濃度を推計することができる。
In the simple dissolution amount test method for harmful substances in soil according to the present invention, the official dissolution rate test concentration can be estimated from the analysis value of the dissolution amount test solution obtained by the above preparation method.
すなわち、本発明者らは、上記のように試験サイズを小さくした簡易試験方法における振とう時間と土壌中有害物質の溶媒への溶出濃度との関係を求めたところ、表１に示すように、振とう時間、すなわち溶出時間さえ公定試験方法と一致させれば（３６０分）、試験サイズを小さくした場合でも公定試験方法による溶出濃度とほぼ一致することが確認された。
That is, the present inventors determined the relationship between the shaking time in the simple test method with a reduced test size as described above and the elution concentration of harmful substances in soil to the solvent, as shown in Table 1, It was confirmed that even if the shaking time, that is, the elution time, was matched with the official test method (360 minutes), even if the test size was reduced, it almost coincided with the elution concentration obtained by the official test method.
また、溶出濃度を公定試験方法に規定された振とう時間（溶出時間）における溶出濃度を「１」とする溶出率で表した場合、土壌の種類や有害物質の含有量に拘らず、一部の例外を除いて、概ね同様の溶出挙動を示し、各物質の溶出率は、時間を変数とする１つの指数関数でそれぞれ表わされることを見出した。 In addition, when the elution concentration is expressed as an elution rate with an elution concentration of 1 at the shaking time (elution time) specified in the official test method, regardless of the type of soil and the content of harmful substances, some It was found that the dissolution behavior of each substance was expressed by one exponential function with time as a variable.
この知見を利用することによって、各有害物質の溶出率曲線（時間を対数で表示すれば直線となる）に基づいて、振とう時間に対応する溶出率を求め、得られた分析値を当該溶出率で除することによって、公定試験方法に相当する溶出濃度を推計することが可能となる。
この場合、土壌と汚染金属等の種類によって、関数のパラメーターが多少異なることが想定されるが、現実の汚染土壌での最小溶出率を用いることで安全側の判定を行うことが可能となる。
By using this knowledge, the elution rate corresponding to the shaking time is obtained based on the elution rate curve of each toxic substance (it becomes a straight line if the time is displayed in logarithm), and the obtained analytical value is used as the elution rate. By dividing by the rate, the elution concentration corresponding to the official test method can be estimated.
In this case, although it is assumed that the parameters of the function are slightly different depending on the types of soil and contaminated metals, it is possible to make a determination on the safe side by using the minimum elution rate in the actual contaminated soil.
一方、公定試験分析法においては、風乾土壌を５０ｇ以上採取するよう規定されているが、採取した土壌を風乾するには、少なくとも３日を要し、試料を採取した現場での検液調製が不可能となって、簡易法としての迅速性が著しく損なわれることになる。
表２は、現場で採取したままの湿潤土壌と、これに４日間の風乾処理を施して成る風乾土壌を用いて、溶出量試験を実施し、溶媒中への溶出濃度に及ぼす土壌の乾燥状態の影響を調査した結果を示すものである。なお、表中の溶出濃度は、それぞれの含水率に基づいて、乾燥土壌５０ｇ当たりの溶出濃度に換算してある。
On the other hand, the official test analysis method stipulates that 50 g or more of air-dried soil should be collected. However, it takes at least 3 days to air-dry the collected soil, and preparation of the test solution at the site where the sample was collected is required. It becomes impossible, and the quickness as a simple method is remarkably impaired.
Table 2 shows the results of the elution test using moist soil as collected at the site and air-dried soil that was air-dried for 4 days. It shows the result of investigating the influence of In addition, the elution density | concentration in a table | surface is converted into the elution density | concentration per 50g of dry soil based on each moisture content.
この表から明らかなように、風乾土壌を用いた場合も、現場で採取したままの湿潤土壌を用いた場合も、乾燥土壌の質量当たりに換算すれば、溶出濃度は概ね同一とみなすことができる。
このことから、本発明においては、数日間かけて風乾処理を行う必要は必ずしもなく、検液調製用の土壌試料を採取するに際して、含水量測定用の試料を同時にサンプリングさえしておけば、現場で採取した湿潤土壌を用いて、その場で溶出量試験用の検液を調製したとしても、同時にサンプリングされた試料の含水率に基づいた測定値の補正を最終的に行なう限り、何ら問題なく、含有物質の分析に供することができる。また、多少精度は低下するものの、目視等により土壌の含水率を定めて試験を行うことも可能である。
As is apparent from this table, the elution concentration can be regarded as almost the same when converted to the mass of dry soil, whether air-dried soil or wet soil collected on site is used. .
Therefore, in the present invention, it is not always necessary to perform the air drying treatment over several days. When collecting a soil sample for preparing a test solution, if the sample for measuring the water content is sampled at the same time, Even if a sample solution for dissolution test is prepared on the spot using the wet soil collected in step 3, there is no problem as long as the measurement value is corrected based on the moisture content of the sample sampled at the same time. It can be used for analysis of contained substances. In addition, although the accuracy is somewhat lowered, it is possible to determine the moisture content of the soil by visual inspection or the like and perform the test.
なお、状況が許す限り、風乾土壌や、現地に持ち込んだ適当な乾燥装置によって乾燥した土壌の試料を用いて検液を調製することが可能であることは言うまでもない。 Needless to say, the test solution can be prepared using air-dried soil or a soil sample dried by an appropriate drying apparatus brought to the site as long as the situation permits.
このように、本発明の土壌中有害物質の簡易溶出量試験方法は、簡便法であって、極めて迅速かつ容易に有害物質の溶出量レベルを把握することができることから、土壌汚染調査のスクリーニングに利用することができる。すなわち、適宜公定試験方法と組み合わせながら、明らかに汚染されていないことの確認や、高濃度地点の探索、公定法による調査の実施が必要な地点の絞り込み、明らかな汚染地域の把握、大まかな汚染レベルの把握などに広く適用することができる。
なお、土壌中有害物質の分析には、これら有害物質の種類に応じて、例えば吸光光度法、イオン電極法、ＩＣＰ発光分析法、イオンクロマトグラフ法などを適用することができる。
As described above, the simple method for testing the amount of toxic substances in soil according to the present invention is a simple method, and the level of toxic substances eluted can be grasped extremely quickly and easily. Can be used. In other words, by combining with official test methods as appropriate, it is confirmed that there is no obvious contamination, search for high concentration points, narrow down the points that need to be investigated by official methods, grasp of clear contaminated areas, rough contamination It can be widely applied to grasp the level.
For the analysis of harmful substances in soil, for example, an absorptiometric method, an ion electrode method, an ICP emission analysis method, an ion chromatographic method, or the like can be applied depending on the type of these harmful substances.
本発明によって、振とう・濾過作業時間の大幅な短縮及び振とう試料の少量化が実現されるので、汚染土壌現場での手作業による振とう作業が可能となり、現場に持ち運んで簡易測定ができる簡易キットが実現可能となった。本発明の具体例としての簡易測定キットは、土壌試料を溶媒と共に振とうする蓋付容器、孔径０．４５μｍのろ紙の上に、孔径１μｍ以上のろ紙を重ねて成り、上記蓋付容器内の上澄み液をろ過するための複層ろ紙、上記複層ろ紙によるろ液を収納する検液容器を備え、例えばこれらをバッグなどの可搬容器に収納しておけば、調査現場で速やかに土壌中有害物質の溶出量試験用の検液を調製することができる。
さらに、当該試験キットには、振とう後の土壌と溶媒との懸濁液の上澄み液を採取するためのシリンジや、これに接続されるろ紙ホルダーや、溶媒、すなわち溶出量試験用の水などを組み込むようにすることができる。
According to the present invention, the shaking / filtering operation time is greatly shortened and the amount of the shaking sample is reduced, so that the shaking work can be performed manually on the contaminated soil site, and it can be carried to the site for simple measurement. A simple kit became feasible. A simple measurement kit as a specific example of the present invention is a container with a lid for shaking a soil sample together with a solvent, and a filter paper with a pore diameter of 1 μm or more is stacked on a filter paper with a pore diameter of 0.45 μm. A multi-layer filter paper for filtering the supernatant liquid and a test container for storing the filtrate from the multi-layer filter paper are provided. For example, if these are stored in a portable container such as a bag, they can be quickly put into the soil at the investigation site. It is possible to prepare a test solution for a toxic substance elution test.
In addition, the test kit includes a syringe for collecting the supernatant of the suspension of the soil and solvent after shaking, a filter paper holder connected to this, water for solvent, ie, elution amount test, etc. Can be incorporated.
そして、本発明の土壌中有害物質の分析装置には、当該装置によって得られた分析値から、公定試験濃度を推計するための演算処理プログラム、例えば上記のようにして得られた各成分ごとに求められた、振とう時間と溶出率の関係式による演算プログラムを搭載しておくことが望ましく、これによって本発明の簡易法によって求めた分析値から、公定試験法による分析値へ換算した値が極めて容易に得られるようになる。 And in the analytical apparatus for harmful substances in soil of the present invention, an arithmetic processing program for estimating the official test concentration from the analytical value obtained by the apparatus, for example, for each component obtained as described above It is desirable to have a calculation program based on the relationship between the obtained shaking time and dissolution rate, so that the value converted from the analytical value obtained by the simplified method of the present invention into the analytical value by the official test method is obtained. It can be obtained very easily.
以下、本発明を実施例により更に詳述するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（１）予備試験（溶出時間と各成分の溶出率の関係把握）
（１）−１ Ａｓの溶出量試験
黒ボク土や関東ローム土などから成る各種汚染土壌のうち、サンプルＢの風乾土壌を５ｇ採取して、１００ｍＬのポリエチレン容器に入れ、これに５０ｍＬの脱イオン水を加え、卓上振とう器によって１分〜３６０分の各時間それぞれ振とうした。
(1) Preliminary test (Understanding the relationship between dissolution time and dissolution rate of each component)
(1) -1 As elution amount test Among various contaminated soils such as black soil and Kanto loam soil, sample 5g of sample B air-dried soil, put it in a 100mL polyethylene container, and add 50mL of deionized water to it. Water was added, and each time was shaken for 1 minute to 360 minutes using a tabletop shaker.
所定の振とう時間を終えた各容器を５分間静置したのち、各容器の上澄み液をシリンジによってそれぞれ２０ｍＬ程度採取し、これを直径４７ｍｍの孔径０．４５μｍのろ紙の上に、孔径２．７μｍのろ紙を重ねた複層ろ紙とろ紙ホルダーを用いてろ過することによって、振とう時間の異なる溶出量試験用検液を得た。 After leaving each container for a predetermined shaking time for 5 minutes, about 20 mL of the supernatant of each container was collected with a syringe, and this was placed on a filter paper having a diameter of 47 mm and a hole diameter of 0.45 μm. Elution amount test solutions with different shaking times were obtained by filtering using a multilayer filter paper on which 7 μm filter paper was stacked and a filter paper holder.
得られた検液を適宜希釈し、水素化物発生ＩＣＰ発光分析装置を用いてそれぞれ分析し、振とう時間に対するＡｓの溶出濃度を測定した。
その結果、振とう時間を３６０分とした時の溶出濃度が６．９ｍｇ／Ｌとなり、公定試験分析法による値とほぼ等しくなることが確認された。
The obtained test solution was appropriately diluted and analyzed with a hydride generation ICP emission spectrometer, and the elution concentration of As with respect to the shaking time was measured.
As a result, it was confirmed that the elution concentration when the shaking time was 360 minutes was 6.9 mg / L, which was almost equal to the value obtained by the official test analysis method.
また、時間ごとの溶出濃度を３６０分における上記溶出濃度６．９ｍｇ／Ｌを「１」とする溶出率に換算し、時間軸に対してプロットした結果、図１に示す溶出曲線が得られた。
そして、これの両軸を対数表示にすると、図２に示すように、良好な直線関係が得られ、Ａｓの溶出率ｙが次式で表わされることが判った。
ｙ＝０．４５５ｘ０．１３６（式中のｘは振とう時間（分））
Moreover, as a result of converting the elution concentration per time to an elution rate with the above elution concentration of 6.9 mg / L at 360 minutes being “1” and plotting it against the time axis, the elution curve shown in FIG. 1 was obtained. .
Then, when both axes are logarithmically expressed, as shown in FIG. 2, it was found that a good linear relationship was obtained, and the As elution rate y was expressed by the following equation.
y = 0.455x 0.136 (where x is the shaking time (minutes))
（１）−２ Ｃｄの溶出量試験
各種汚染土壌のうち、サンプルＡの風乾土壌を用い、Ｃｄの分析にＩＣＰ発光分析装置を用いたこと以外は、上記同様の操作を繰り返すことによって、図３に示すようなＣｄの溶出直線を得た。
図に示すように、Ｃｄの場合には、溶出速度が速く、１分程度の振とう時間でも３６０分経過後でも、溶出濃度に相違がなく、ほとんど公定試験法による値に一致することから、試験サイズを縮小した簡易法による分析値をそのまま利用しても差し支えないことが確認された。ただし、汚染の有無を判断する際などに基準値に近い値が分析された場合には、現実の汚染土壌での最小溶出率を用いることで安全側の推計値を得ることも可能である。
(1) -2 Cd elution amount test By using the air-dried soil of sample A among various contaminated soils and using the ICP emission analysis apparatus for the analysis of Cd, the same operation as described above was repeated, so that FIG. A Cd elution line as shown in FIG.
As shown in the figure, in the case of Cd, the elution rate is fast, and there is no difference in the elution concentration even after a shaking time of about 1 minute or after 360 minutes, and it almost matches the value by the official test method. It was confirmed that the analysis value obtained by the simplified method with a reduced test size can be used as it is. However, when a value close to the reference value is analyzed when determining the presence or absence of contamination, it is possible to obtain an estimated value on the safe side by using the minimum elution rate in the actual contaminated soil.
（１）−３ Ｂの溶出量試験
各種汚染土壌のうち、サンプルＦの風乾土壌を用いたこと以外は、上記同様の操作を繰り返すことによって、図４に示すように、Ｂの溶出直線を得た。
その結果、振とう時間を３６０分とした時のＢの溶出濃度は２０．２ｍｇ／Ｌとなり、公定試験分析法による値とほぼ等しくなると共に、Ｂの溶出率ｙが次式によって表わされることが判明した。
ｙ＝０．５２４ｘ０．１０８（式中のｘは振とう時間（分））
(1) -3 Elution amount test of B As shown in FIG. 4, an elution line of B is obtained by repeating the same operation except that the air-dried soil of sample F is used among various contaminated soils. It was.
As a result, when the shaking time is 360 minutes, the elution concentration of B is 20.2 mg / L, which is almost equal to the value obtained by the official test analysis method, and the elution rate y of B can be expressed by the following equation. found.
y = 0.524x 0.108 (where x is the shaking time (minutes))
（１）−４ Ｃｒ６＋の溶出量試験
各種汚染土壌のうち、サンプルＤの風乾土壌を用いると共に、分析に吸光光度計を用いたこと以外は、上記同様の操作を繰り返すことによって、図５に示すように、Ｃｒ６＋の溶出直線を得た。
その結果、振とう時間を３６０分とした時のＣｒ６＋の溶出濃度が１３．４ｍｇ／Ｌとなり、公定試験分析法による値とほぼ等しくなると共に、Ｃｒ６＋の溶出率ｙが次式によって表わされることが判明した。
ｙ＝０．６４７ｘ０．０７６（式中のｘは振とう時間（分））
(1) -4 Cr 6+ elution amount test Among the various contaminated soils, while using the air-dried soil of sample D and using an absorptiometer for the analysis, the same operation as described above was repeated to obtain FIG. As shown, an elution line of Cr 6+ was obtained.
As a result, when the shaking time is 360 minutes, the elution concentration of Cr 6+ is 13.4 mg / L, which is almost equal to the value obtained by the official test analysis method, and the elution rate y of Cr 6+ is expressed by the following equation. It has been found.
y = 0.647x 0.076 (where x is the shaking time (minutes))
（１）−５ Ｆの溶出量試験
各種汚染土壌のうち、サンプルＥの風乾土壌を用いると共に、分析装置としてイオンクロマトグラフを用いたこと以外は、上記同様の操作を繰り返すことによって、図６に示すようなＦの溶出直線が得られた。
その結果、振とう時間を３６０分とした時のＦの溶出濃度は１３４ｍｇ／Ｌとなり、公定試験分析法による値とほぼ等しくなると共に、Ｆの溶出率ｙが次式によって表わされることが確認された。
ｙ＝０．６７７ｘ０．０６９（式中のｘは振とう時間（分））
(1) -5 F elution amount test By using the air-dried soil of sample E among various contaminated soils and repeating the same operation as above except that an ion chromatograph was used as an analyzer, FIG. An elution line of F as shown was obtained.
As a result, it was confirmed that the elution concentration of F when the shaking time was 360 minutes was 134 mg / L, almost equal to the value obtained by the official test analysis method, and the elution rate y of F was expressed by the following equation. It was.
y = 0.677x 0.069 (where x is the shaking time (minutes))
（２）本発明による土壌中有害物質の簡易溶出量試験
各種汚染土壌のうちから、湿潤状態のサンプルＢ、Ｇ、Ｌ、Ｍ、Ｎの各土壌試料をそれぞれ乾燥重量で５ｇとなるように採取し、１００ｍＬのポリエチレン容器に入れ、この中に５０ｍＬの脱イオン水を加え、手作業によって１分間振とうした後、５分間静置し、容器内の上澄み液をシリンジによって２０ｍＬ程度採取し、これを直径４７ｍｍの孔径０．４５μｍのろ紙の上に、孔径２．７μｍのろ紙を重ねた複層ろ紙とろ紙ホルダーを用いてろ過することによって、溶出量試験検液を調製した。
(2) Simple leaching test of harmful substances in soil according to the present invention From various contaminated soils, wet samples B, G, L, M, and N are collected so that the dry weight is 5 g. Place in a 100 mL polyethylene container, add 50 mL of deionized water, shake manually for 1 minute, let stand for 5 minutes, and collect about 20 mL of supernatant in the container with a syringe. Was filtered using a multi-layer filter paper in which a filter paper with a pore size of 2.7 μm was stacked on a filter paper with a pore size of 0.45 μm having a diameter of 47 mm and a filter paper holder, to prepare a dissolution test solution.
得られた溶出量試験用検液を適宜希釈し、Ａｓについては水素化物発生ＩＣＰ発光分析装置、Ｐｂ、Ｃｄ及びＢについてはＩＣＰ発光分析装置、Ｃｒ６＋については吸光光度計、Ｆについてはイオンクロマトグラフによってそれぞれ分析し、各成分の溶媒（水）中への溶出濃度を測定した。
そして、上記予備試験によって求めた各成分の溶出式において、ｘ＝１に相当する溶出量ｙを求め、得られた溶出濃度をそれぞれの溶出率ｙで除した結果、表３に示すように、公定試験分析法による溶出濃度と概ね一致する結果となった。
The obtained test solution for dissolution test is appropriately diluted. As for hydride generation ICP emission analyzer for As, ICP emission analyzer for Pb, Cd and B, Absorptiometer for Cr 6+ , Ion chromatograph for F Each was analyzed by a graph, and the elution concentration of each component in the solvent (water) was measured.
And in the elution formula of each component calculated | required by the said preliminary test, as a result of calculating | requiring the elution amount y corresponding to x = 1 and dividing the obtained elution concentration by each elution rate y, as shown in Table 3 , The result was almost consistent with the elution concentration obtained by the official test analysis method.
なお、この実施例においては、土壌中有害物質の代表例として、Ｃｄ、Ａｓ、Ｂ、Ｃｒ６＋及びＦの分析例について説明したが、Ｐｂの溶出量やこれら以外の有害物質であるＳｅ、Ｈｇ、シアンの溶出量についても、同様の操作によって試験することができる。
さらに、推計に用いる各式については、今後さらに集積されるデータに基づいて式の係数を変更していくことによってより精度の高い推計が可能になるものと考えられる。
In addition, in this Example, although the analysis example of Cd, As, B, Cr 6+ and F was demonstrated as a representative example of a harmful substance in soil, the elution amount of Pb and other harmful substances such as Se and Hg The amount of cyan eluted can be tested by the same operation.
Furthermore, for each formula used for estimation, it is considered that estimation with higher accuracy is possible by changing the coefficient of the formula based on further accumulated data.
Claims (7)
振とう時間と、その時間における物質の溶出濃度を公定時間振とう後の溶出濃度を「１」とする比で表した溶出率との関係を振とう時間を変数とする指数関数として求めておき、
当該指数関数に基づいて公定時間未満の上記振とう時間に対応する溶出率を求め、該溶出率で上記振とう時間後の分析値を除すことによって、公定溶出量試験の推計値を算出することを特徴とする簡易溶出量試験方法。 Collect soil with a mass of less than 50 g, add water more than 5 times the mass of the collected soil, shake for less than the official time specified in the official dissolution test , filter, and extract the test solution. Obtained, from the analytical value of the obtained test solution, is a simple dissolution amount test method for harmful substances in soil to estimate the official dissolution amount test concentration ,
The relationship between the shaking time and the dissolution rate of the substance at that time, expressed as a ratio with the dissolution concentration after the official time shaking as “1”, is obtained as an exponential function with the shaking time as a variable. ,
Calculate the elution rate corresponding to the shaking time less than the official time based on the exponential function, and calculate the estimated value of the official elution amount test by dividing the analysis value after the shaking time by the elution rate. A simple dissolution test method characterized by the above.
土壌試料を溶媒と共に振とうする蓋付容器と、
孔径０．４５μｍのろ紙の上に、孔径１μｍ以上のろ紙を重ねて成り、上記蓋付容器内の上澄み液をろ過するための複層ろ紙と、
上記複層ろ紙によるろ液を収納する検液容器を備えたことを特徴とする土壌中有害物質の簡易試験キット。 A kit for use in the simple dissolution test method according to claim 1 or 2,
A container with a lid for shaking a soil sample with a solvent;
A filter paper having a pore diameter of 0.45 μm overlaid with a filter paper having a pore diameter of 1 μm or more, and a multilayer filter paper for filtering the supernatant liquid in the lidded container;
A simple test kit for toxic substances in soil, comprising a test container for storing filtrate from the multilayer filter paper.
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