Recent Development on Determination of Low-Level ⁹⁰Sr in Environmental and Biological Samples: A Review

Abstract

In the context of the rapid development of the world’s nuclear power industry, it is vital to establish reliable and efficient radioanalytical methods to support sound environment and food radioactivity monitoring programs and a cost-effective waste management strategy. As one of the most import fission products generated during human nuclear activities, ⁹⁰Sr has been widely determined based on different analytical techniques for routine radioactivity monitoring, emergency preparedness and radioactive waste management. Herein, we summarize and critically review analytical methods developed over the last few decades for the determination of ⁹⁰Sr in environmental and biological samples. Approaches applied in different steps of the analysis including sample preparation, chemical separation and detection are systematically discussed. The recent development of modern materials for ⁹⁰Sr concentration and advanced instruments for rapid ⁹⁰Sr measurement are also addressed.

1. Introduction

⁹⁰Sr (T½ = 28.79 y) is one of the most important hazardous radionuclides with respect to radiological safety to human and the environment due to its long half-life and high fission yield [1,2,3]. ⁹⁰Sr is a fission product of ²³⁵U and ²³⁹Pu; its decay chain is shown in Figure 1 [4]. ⁹⁰Sr emits beta particles with a maximum energy of 546 keV and decays to short-lived ⁹⁰Y (t½ = 64 h). ⁹⁰Y decays to a stable nuclide ⁹⁰Zr by emitting beta particles with a maximum energy of 2280 keV [5]. There are three main sources of ⁹⁰Sr in the environment: (1) Global fallout from the atmospheric nuclear weapons testing during the 1950s–1980s [6,7,8,9], with a total ⁹⁰Sr inventory of 804 PBq [10,11,12]. (2) Nuclear accidents including the former Soviet Union Chernobyl nuclear power plant (SUCNPP) accident in 1986 and the Fukushima Daiichi nuclear power plant (FDNPP) accident in 2011 in Japan. The Chernobyl NPP accident had released up to 10 PBq of ⁹⁰Sr into the surrounding environment, especially in the Black Sea [13,14,15,16], while the Fukushima accident was reported to release 1 PBq of ⁹⁰Sr mostly into the Pacific Ocean [17,18,19,20,21]. (3) Regulated releases from the operation of nuclear facilities such as nuclear power plants and nuclear reprocessing plants [22].

Strontium is easily dissolved in water; thus, it is very mobile in the environment [23,24]. ⁹⁰Sr can be transported by different pathways from the environment into the food chain and finally enter into human bodies [25]. Sr and Ca are both elements of group IIA, their chemical properties are similar. Therefore, the biological process of ⁹⁰Sr in the human body is also very similar to that of Ca, which belongs to the typical bone-seeking nuclides. Once ⁹⁰Sr enters the body, it will follow the uptake of Ca and be quickly accumulated on the surface layer of bone salt as Sr₃(PO₄)₂ [26]. With time, ⁹⁰Sr participates in the formation of bone salt and enters the crystals of bone inorganic salt; thus, it becomes immobilized in the bone with the physiological osteogenesis process. The release of high-energy beta particles from ⁹⁰Y imposes severe damage to the human bone and bone marrow hematopoietic tissues, leading to bone cancer or leukemia [27,28].

With the rapid development of the global nuclear power industry and the widespread application of nuclear technology, it sets high demands in radiation protection and radiological risk assessment during routine operation and nuclear emergency situations. Therefore, it is of great significance to establish efficient analytical methods to be applied for the determination of radiological toxic radionuclides including ⁹⁰Sr. In the past few decades, substantial efforts have been devoted to method development for ⁹⁰Sr determination in various samples. Several researchers have made good reviews about the analytical methodologies of ⁹⁰Sr, some focusing on the development of radiochemical separation procedures for ⁹⁰Sr based on the use of radiometric measurement techniques [29], and some focusing on methods for ⁹⁰Sr routine environmental monitoring [1,29] or determination in milk [30]. In the present work, we aim to summarize the analytical methods developed in the past few decades for low-level (e.g., in the range of 1–1000 mBq/L in water or 1–1000 mBq/kg in solid samples) ⁹⁰Sr analysis in environmental and biological samples and critically review the pros and cons of different analytical approaches. Here, we focus on presenting the recent progresses in technical development for low-level ⁹⁰Sr analysis, specifically on the development and application of advanced materials for Sr isolation/purification and modern instruments for Sr measurement.

In our literature search, keywords ‘strontium-90′, ‘determination’, ‘analysis’, ‘separation’, ‘environmental’, and ‘biological’ were used.

Table 1. Overview of analytical methods developed for determining ⁹⁰Sr in environmental and biological samples since 2000.

Sample Type	Quantity	Analytical Protocol			Analytical Performance			Reference
		Pretreatment	Purification	Measurement	Chemical Yield, %	Turnover Time or Sample Throughput	Detection Limit
Soil, water, vegetation	Ash 10 g 100 mL of water	Acid digestion with conc. HNO3	Liquid–liquid extraction with tributyl phosphate (TBP)	LSC via 90Y	75–90	/	0.03 Bq/kg	[31]
Soil	50 or 1000 g	Acid digestion with conc. HNO3 + conc. HCl	Method 1. Sr resin Method 2: No purification	Method 1: ICP-MS Method 2: CRC-ICP-MS/MS, O2 as reaction gas	Method 1: 67–80 Method 2: /	/	Method 1: 0.04 ng/kg Mehotd 2: /	[32]
Soil	1 g	Microwave digestion with 10 v/v% HNO3	Sr resin in an automated lab-on-valve system	On-line DRC-ICP-MS, O2 as reaction gas	/	14.6 min (from injection to MS detection)	3.9 Bq/kg	[33]
Soil	0.5 g	Alkaline fusion with LiBO2-LiBr	Sr resin in an automated flow system	On-line ICP-MS	>80	2.4 h (10 samples in 24 h)	0.37 ng/kg	[34]
Soil	1 g	Microwave digestion with conc. HF + conc. HClO4 and aqua regia	Sr resin with a vacuum box	DRC-ICP-MS	/	2 d	1 Bq/g (0.2 pg/g)	[35]
Soil	10–500 g	For 10 g samples: acid digestion with conc. HF + conc. HClO4 + conc. HNO3 For 50–500 g samples: acid digestion with conc. HCl + conc. HNO3	Sr resin	CRC-ICP-MS/MS, O2 as reaction gas	67–80%	2 d	0.1 pg/g	[36]
Soil, plant	Soil: 50 g Plant: 10 g of ash	Acid digestion with conc. HCl followed by oxalate co-precipitation (SrC2O4 and Y2(C2O4)3)	Chromatography by HDEHP-kel-F	Low-level gas flow alpha-beta counter via 90Y	/	/	Soil: 0.16 Bq/kg Plant: 0.39 Bq/kg	[7]
River water, aquatic plant and sediment	Water: 1 L Plant/sediment: 2–3 g	Water: pre-concentration with cation exchange resin Plant: microwave digestion with 8 M HNO3 Sediment: microwave digestion with 8 M HNO3 + H2O2	Sr resin (two time)	DRC-ICP-MS, O2 as reaction gas Cerenkov counting	Water: 84–98 Plant: 62–82 Sediment: 68–98	Water: 36 samples in 24 h Plant/sediment: 24 samples in 24 h	Water: 5 Bq/L (3 pg/L) Plant: 0.2 Bq/g (0.04 pg/g) Sediment: 0.5 Bq/g (0.1 pg/g)	[37]
Water	20 mL	Acidification to 8 M HNO3 with conc. HNO3	Sr resin	Cherenkov and LSC	86.2 ± 2.2	/	140 mBq for 20 mL water samples	[38]
Water	20 mL	No pretreatment	Liquid–liquid extraction with 10% di-2-ethylhexylphosphoric acid (HDEHP)	Cherenkov counting	~90%	/	2.4 Bq/L	[39]
Ground water	10 mL	Evaporation	No purification	ICP-SFMS with medium mass resolution under cold plasma conditions	82%	/	11 fg/mL	[40]
Water, reactor coolant	4 mL–1 L	Cation exchange resin in an automated multisyringe flow-injection analysis lab-on-valve (MSFIA-LOV) system	Sr resin in an MSFIA-LOV system	DRC-ICP-MS, CH4 as reaction gas	53–101	16 min to 6 h depending on sample size	14.5 Bq/L for 1 L sample	[41]
Seawater	1–10 L	Ca3PO4 +Fe(OH)3 co-precipitation	Sr and DGA resin	Gas flow proportional counter	>80%		1–10 mBq/L (MDA)	[42]
Water and soil	Water: 10 mL Soil: 0.3 g	Water: filtration and dilution with 0.1 M ammonium acetate Soil: microwave assisted acid digestion with conc. HNO3-cocn. HCL-cocn. HF	InertSep ME-1 resin in an automated separation system	DRC-ICP-MS	/	/	0.6 ng/L	[43]
Milk	40 mL	Fat/protein removal with HCl, trichloroacetic acid, centrifugation	Co-precipitation + Sr resin	LSC	70 ± 4	5 h	2.8 ± 0.3 Bq/L	[44]
Milk	5 mL	HNO3 + H2O2, microwave digestion	No purification	Cherenkov counting	/	Sample preparation: ca. 1 h Counting time varied from 0.5 h to 10 h	5.13–6.76 Bq/L (10 h measurement)	[45]
Milk	20 mL	No pretreatment	No purification	Cherenkov counting	/	/	1.7 Bq/L	[46]
Milk	500 mL	Cation exchange chromatography	Sr resin	LSC	80–95	7 h	0.1 Bq/L	[47]
Milk	500 mL	Cation exchange chromatography	Sr resin	Low background proportional counter	62	10 h	0.09 Bq/L for 500 mL milk	[30]
Milk and dairy products	Milk: 100 mL Dairy products: 50 g	Fat and proteins isolation using tri-chloroacetic acid (TCA)	Sr resin	LSC	90	7–8 h	0.8 Bq/L	[48]
Milk and dairy products	Milk: 100 mL Dairy products: 50 mL	Fat and proteins isolation using tri-chloroacetic acid (TCA) and anion exchange chromatography	Sr resin	LSC	70–80	20 h	0.2 Bq/L for milk 0.4 Bq/L for dairy products	[49]
Vegetation	40–500 g	Acid digestion with HCl or HNO, followed by Fe(OH)3	DGA resin	Cherenkov counting via 90Y	82–107	<3 d	14 mBq/kg	[50]
Vegetation	10 g of ash	Acid digestion with conc. NO3 + H2O2	Extraction chromatography (crown ether on teflon powder)	LSC	78	10 h	1.28 Bq/kg	[51]
Bone	7–10 g of ash	Total dissolution with conc. HNO3	Sr resin (AnaLigr®Sr-01)	Cherenkov counting via 90Y	85–96	/	2.6 Bq/kg	[52]
Bone	5 g of ash	Acid digestion with conc. NO3 + H2O2	Sr(NO3)2 precipitation with fuming acid + Sr resin	LSC	71–83	/	10 Bq/kg	[53]
Urine	50 mL	Acidification with conc. HClO4 to 4M HClO4	Sr resin in a HPLC system	Cherenkov countering	About 85	<8 h	2 Bq/L	[54]
Urine	5–20 mL	Acidification with methanesulfonic acid and pretreatment with activated charcoal	Diphonix + Sr resin	/	>98	<1 h	/	[55]
Urine	/	Ca3PO4 co-precipitation	Sr resin	ICP-SFMS	82–86	/	0.4 pg/L	[56]
Urine	25–500 mL	Acidification with conc. HNO3 to 2 M HNO3	Sr resin (AnaLigr®Sr-01)	Cherenkov counting	60.2–100	Separation: 2.5–3.0 h Counting: 2 weeks	0.12 Bq/L	[57]
Urine	5–20 mL	Acidification with methanesulfonic acid and decolorization with charcoal, and treatment with Diphonix® resin	Sr resin	/	99	<1 h	/	[55]
Urine	1–2 L	Phosphate precipitation	Pre-filter + TRU + Sr resin	ICP-MS/MS, O2 as collision gas	67–84 (77 on average)	10 h	1 Bq/sample	[58]

CRC: reaction/collision cell; DRC: dynamic reaction cell; MDA: minimum detectable activity of the method; /: no available data.

summarizes the analytical methods reported for ⁹⁰Sr determination in environmental and biological samples since the 21st century. Generally, analytical procedures for ⁹⁰Sr determination are divided into three stages including sample pretreatment, chemical purification and measurement as illustrated in Figure 2 and detailed in this review. It is noteworthy that the quantification of ⁹⁰Sr can be performed by directly measuring ⁹⁰Sr using a radiometric or mass spectrometric method or by an indirect measurement through its daughter ⁹⁰Y using a radiometric method. In both cases, the isolation of ⁹⁰Sr or ⁹⁰Y from the sample matrix and interfering elements is necessary due to the relatively low penetrating abilities and continuous energy spectrum of beta particles. Thereby, the development of sample pretreatment and chemical purification protocol is always served for the measurement technique selected for ⁹⁰Sr quantification.

2. Sample Pretreatment

The purpose of sample pretreatment is to obtain a homogeneous sample, pre-concentrate the analyte and remove the majority of sample matrix such as organic matter and stable elements. The selection of sample pretreatment methods depends on the sample type.

2.1. Pretreatment of Environmental Samples

For environmental solid samples including soil, sediment, sludge, etc., the commonly used pretreatment method is acid digestion and, in some cases, the acid digestion is assisted with microwave [7,8,59,60,61,62,63,64]. Prior to the acid digestion, the sample needs to be dried and combusted to decompose organic matter. Acid digestion using mineral acids such as HNO₃, HF, HCl, HClO₄ or mixed acids (e.g., mixture of HF, HClO₄ and HNO₃, mixture of HF, HNO₃ and HCl) has been widely used to extract ⁹⁰Sr from solid samples [32,35,65,66,67]. The advantage of the acid digestion method is its easy operation and capacity of processing large sample amounts (e.g., up to 200 g); however, it requires a large amount of aggressive acids and long operation time [68].

With the use of microwave-assisted acid digestion, the sample processing time can be significantly reduced [4,33,35,69]. For instance, Feuerstein et al. [35] took only 25 min to digest a sample with HF and HClO₄ in a microwave oven. Compared with traditional acid digestion operated in open vessels, microwave-assisted digestion is much faster. However, the sample size is usually limited to a few grams [37] as restricted by the volume of microwave ovens and digestion vessels. Therefore, the microwave-assisted acid digestion is not suitable to process low-level environmental samples, where tens or hundreds of grams of sample would be needed for ⁹⁰Sr determination.

Another pretreatment method for solid environmental samples is alkaline fusion, in which fusion flux such as Na₂CO₃ and Na₂O₂, NaOH or LiBO₃ is mixed with the solid sample and melted at a high temperature, e.g., 300–1000 °C [70,71,72,73,74,75]. Jurecic et al. [72] compared conventional acid digestion using a mixture of HNO₃, HClO₄ and HF, microwave-assisted digestion using HNO₃ and HF, and alkali fusion with Na₂CO₃ and Na₂O₂. The complete decomposition of soil samples could only be achieved by alkaline fusion. The disadvantage of alkaline fusion is the high temperature and aggressive reaction required, which concerns the safety of the analysts. As restricted by the operating condition, alkaline fusion is mostly applicable to smaller sized samples, e.g., up to 5–10 g.

For environmental water samples including seawater, groundwater, lake water and river water, evaporation or co-precipitation is the commonly used pretreatment method for ⁹⁰Sr determination [76]. For large volume of environmental samples, evaporation is seldom used due to its time-consuming feature. ⁹⁰Sr in environmental water samples is usually co-precipitated with oxalates or carbonates, e.g., ⁹⁰Sr in natural waters can be co-precipitated with calcium oxalate under lower pH (pH = 4–5) which is thereafter decomposed into carbonate [2] or co-precipitated directly with calcium carbonate under higher pH (pH > 10).

2.2. Pretreatment of Biological Samples

A number of biological samples including bones, teeth, blood, urine, plants, milk, etc., are often analyzed for ⁹⁰Sr in radioactivity monitoring and radiological risk assessment. For biological samples, similar sample pretreatment approaches as for environmental samples can be applied [7,61,62,77,78,79] but with a focus on tackling challenges introduced by the complex biological matrices. For example, bones and teeth usually contain substantial amount of calcium. Milk contains large amount of fat and protein as well as antiseptic additives, e.g., formaldehyde or sodium azide [48,80]. Urine contains a large amount of organic compounds and inorganic salts [54,55,81,82]. Blood has a high concentration of iron and even more complex matrix composition.

Therefore, Gasa et al. [77] used a combination of HF, HNO₃, HCl, and H₃BO₃ to digest mammalian skulls. Fuming nitric acid is also commonly used to digest biological samples (such as teeth and bones) enrich in calcium [19]. With the addition of oxidizing reagents such as H₂O₂, the acid digestion process for bones using mineral acids can be accelerated [53].

The typical protocol for the pretreatment of fresh milk includes drying, ashing and then acid digestion of the ashed sample. To ensure the complete decomposition of organic substance in milk, the ashing usually last for 3–5 days, which is somewhat time-consuming. The microwave-assisted acid digestion has been demonstrated successfully to increase the efficiency for organic matter decomposition by a factor of 2–5 [45] and has become popular for biological sample pretreatment [83]. Microwave-assisted enzymatic digestion has also been proven to substantially reduce digestion times to 20 min for proteins [84], which might also have the potential to be applied in milk pretreatment for ⁹⁰Sr analysis. After digestion, co-precipitation is generally used to isolate Sr from the milk samples [49].

Similar to milk, urine samples are usually digested by concentrated acids and pre-concentrated by co-precipitation [58,85]. In recent years, adsorption and chromatographic methods have been applied directly in biological sample pretreatment to remove the matrix. For example, Hawkins et al. [55] developed a rapid method for detecting ⁹⁰Sr in human urine, wherein the organic matrix was removed by activated carbon. Sadi et al. [54] applied Sr resin in an HPLC system to remove the urine matrix, while some other researchers used cation exchange resin [54,55]. It is noteworthy that direct pretreatment with adsorption and chromatographic methods are mostly applicable to small-size samples (e.g., up to 250 mL). For large volumes (e.g., >1 L) of biological samples, the co-precipitation approach is more practical for the sample pre-concentration.

3. Chemical Purification

Chemical purification is a method by precipitation, calcination, acid and alkali treatment, leaching and so on. The main purpose of chemical purification is to concentrate the target radionuclide and to remove interferences, thus obtaining a purified fraction. Interferences for ⁹⁰Sr or ⁹⁰Y measurement with radiometric methods include all other beta emitters which will directly affect the detection of ⁹⁰Sr and any alpha/gamma emitters which will increase the background. When using mass spectrometric methods for ⁹⁰Sr measurement, focus should be given to remove isobaric and polyatomic interferences formed by stable isotopes, such as ⁹⁰Zr and ⁸⁹Y¹H. In any case, ⁹⁰Sr or ⁹⁰Y must be isolated in the chemical purification step, wherein different techniques have been applied including precipitation, liquid–liquid extraction, ion exchange chromatography, extraction chromatography, electrosorption and adsorption.

3.1. Precipitation

The nitrate precipitation using fuming nitric acid is a classical method and widely applied for ⁹⁰Sr purification [1,29,60,64,86]. The method is based on the low solubility of Sr(NO₃)₂ in high concentration (>14 M) of nitric acid to achieve the selective isolation of Sr. The method using fuming nitric acid treatment is recommended by the International Atomic Energy Agency (IAEA, ISO 18589-5: 2019 [87], ISO 13160: 2012 [88]), the United States Department of Energy and other agencies (e.g., HJ815-2016 GB [89], GB 14883.3-2016 [90]). In many cases, nitrate precipitation is combined with other precipitation approaches including chromates, hydroxides, carbonates, etc. to achieve a complete removal of interferences and concentration of Sr as reviewed by Shao et al. [1]. The precipitation method is robust and provides reliable results. However, it is very tedious and labor intensive, as it often requires repeated precipitation for 3–5 times. In addition, the method involves the use of offensive fuming nitric acid, which could potentially impose health risks to the operator.

3.2. Liquid–Liquid Extraction

Liquid–liquid extraction is a separation process based on the different solubility of a solute in two partially miscible liquid solvents. In ⁹⁰Sr purification, Sr is typically extracted from an aqueous phase into an organic solvent containing hydrophobic ligand (so-called extractant) which forms a stable electrically neutral complex with Sr. Traditional extractants such as di- (2-ethylhexyl) phosphoric acid (HDEHP), tributyl phosphate (TBP), trioctylphosphine oxide (TOPO), and thiopheneyl trifluoroacetone (TTA) have been used to separate ⁹⁰Sr and ⁹⁰Y. For example, HDEHP is a phosphorous extractant and maintains a good extraction rate of high-valent metal ions when the aqueous phase has high acidity. Borcherding et al. firstly adopted HDEHP as an extractant for ⁹⁰Sr purification in 1968 [91]. Reddy et al. [39] studied the effect of HDEHP concentration and pH on the extraction efficiency and observed that about 90% of ⁹⁰Sr can be extracted into the organic phase with a 10% (v/v) mixture of HDEHP and toluene at pH 4–4.5. In 1969, Pedersen proposed that crown ethers can form stable coordination compounds with alkaline earth metals [92]. The crown ether molecules modified with hydrophobic groups, such as benzo crown ether and dibenzo crown ether, make the crown ether complex easily enter the organic phase and improve the extraction rate of metal ions. Cyclohexyl and substituted cyclohexyl-modified crown ethers, such as dicyclohexyl-18-crown-6 (DCH₁₈C₆), di-tert-butyl dicyclohexyl-18-crown-6 (DtBuCH₁₈C₆), etc., have high extraction efficiency on Sr [93]. Tormos et al. [94] used the DCH₁₈C₆-Cl₂CHCHCl₂ system as a rapid separation method for ⁹⁰Sr in soil and plant samples. The chemical yield of strontium was 70–85%. The advantage of liquid–liquid extraction is its simplicity and high efficiency. However, organic solvents are usually volatile and toxic. Therefore, liquid–liquid extraction for ⁹⁰Sr analysis is gradually fading out in radioanalytical laboratories for human and environmental safety reasons.

3.3. Ion Exchange Chromatography

Ion exchange chromatography is based on the different affinities of ions and polar molecules onto ion exchangers to separate the target analyte from interfering elements. Ion exchange resins commonly used for ⁹⁰Sr (or ⁹⁰Y) purification include Dowex-50, Amberlite IR-120, Zeokarb 225, AG 1-X8 and AG 50W-X8 [47,49,59,93]. Castrillejo et al. [95] combined anion (AG1-X8) and cation (AG50W-X8) exchange chromatography to purify ⁹⁰Y, and 63–93% of chemical yield was achieved. The Ministry of Environmental Protection of China has recommended a national standard method for ⁹⁰Sr determination in water and biological samples, where Sr is separated based on the selective adsorption of EDTA-Sr complexes on a cation exchanger [89]. Nguyen et al. [96] used cation exchange resin to analyze radioactive strontium in water and the result was compared with current methods from the U.S. Environmental Protection Agency (EPA) and Food Emergency Response Network (FERN). The comparison indicated that the method using cation exchange resin to separate radiostrontium was more environmentally friendly and easier to perform. In short, the advantages of ion exchange chromatography include that it can handle large volumes of samples and is highly applicable to different sample matrixes. However, the selectivity of ion exchangers is not very high; thus, repeated chromatographic separation is usually needed, making the analytical processes tedious and less effective.

3.4. Extraction Chromatography

Extraction chromatography is also called solid phase extraction, which employs the same basic principle as liquid–liquid extraction, but the extractant is immobilized on the surface of an inert solid support material. HDEHP and Crown ether have been widely used in extraction chromatographic separation for ⁹⁰Sr. Horwitz et al. [97] developed the Sr resin consisting of DtBuCH₁₈C₆-n-butanol system on an inert support [51], based on the research of crown ether liquid–liquid extraction. Nowadays, the Sr resin has been widely used in many international, e.g., ISO18589-5: 2019 and national standards, e.g., the American Society for Testing and Materials (US-ASTM), the French Association for Standardization (AFNOR), and the British Standards Institute (GB-BSI). Chu et al. [86] compared the performance of strontium nitrate precipitation, ion exchange chromatography, and extraction chromatography for the determination of ⁹⁰Sr in tea, brown rice, milk powder and soil samples. The results showed that the extraction chromatographic method is more effective and can reduce the analytical time to 2 h. Compared with ion exchange chromatography, extraction chromatography has a higher selectivity. However, Grahek et al. [98] noticed that the separation efficiency on the Sr resin decreased with the increase in Sr, Ca and Na concentrations in the sample. By pre-separating matrix elements (e.g., Na and Ca) on an anion exchange column, and further isolating Sr from Ca on a Sr resin column, the Sr chemical yield can be improved from 50% to 75%. Therefore, it is a good strategy to combine ion exchange chromatography with extraction chromatography to achieve high selectivity for ⁹⁰Sr and meanwhile ensure high-capacity sample processing. For example, Taylor et al. [37] directly loaded 1 L of water onto a 50 mL cation exchange column followed by purification of ⁹⁰Sr using a Sr resin, and they achieved satisfactory results with 84–98% of chemical yields.

3.5. Adsorption

Adsorption is a process of uptaking target analytes from aqueous phase onto the surface of an adsorbent. The adsorption method has the advantages of cost-effective, high capacity and flexibility in operation and no generation of secondary pollutants [99,100]. Thus, adsorption is considered to be the most effective method for removing environmental pollutants [101]. Various adsorbents, including metal sulfides, metal–organic frameworks (MOFs) and graphene oxide (GO), have been developed to remove strontium through different mechanisms. Soft S²⁻ ligands in their frameworks have an innate strong affinity for soft metal ions (Sr²⁺) rather than coexisting hard ions (H⁺, Na⁺, K⁺) [102]; thus, they can effectively remove Sr from wastewater. Zhang et al. [103] synthesized a metal sulfide (NaTS), which can reach adsorption equilibrium within 5 min for Sr²⁺, and a maximum adsorption capacity of 80 mg/g. However, when multiple ions coexist in the system, the strongly bound ions dominate the surface since adsorption depends on the binding strength of the ions onto the adsorbent surface [104]. Thus, the selectivity enhancement of adsorbents to target nuclides remains a great challenge. To address the challenges, an ion imprinting technique has been developed to effectively improve the selectivity of materials by which a functional monomer and a crosslinker were polymerized in the presence of a template ion [105,106]. It can create specific cavities containing a ligand for the template ion that possesses the right size and charge [107,108,109]. Yin et al. [110] employed biogene-derived aerogels for the selective adsorption of strontium (II) by the imprinting method from a high-salt environment.

3.6. Electrosorption

Electrosorption, integrating adsorption and electrochemistry, is a separation technique through a non-Faradic process independent of electron gain and loss [111]. Electrosorption such as the half-wave rectified alternating current electrochemical (HW-ACE) method [112] and asymmetrical alternating or direct (DC)/alternating current (AC) electrochemical method [104] have been extensively developed for the removal of heavy metal ions from aqueous solutions. Different from the traditional adsorption method, which is intrinsically constrained by the limited utilization of the surface adsorption sites, electric field-induced ion migration fully utilizes the active sites on the adsorbent surface. Xiang et al. [113] achieved a significant enhancement of the Sr²⁺ adsorption capacity by using the modified porous carbon material as a capacitive deionization electrode. Furthermore, the ions are released from the electrical double layers (EDL) through reverse potential or power cut, and then, the electrode material is regenerated without generating waste liquid, avoiding the secondary pollution [111]. Wang et al. [114] grafted 4′-aminobenzene-18-crown-6 ether onto the surface of carbon felt to obtain a composite (CE@CF), which was used as an electrode to extract Sr²⁺ from aqueous solutions and simulated seawater by an asymmetric pulsed current-assisted electrochemical (APCE) method. The Sr²⁺ ions adsorbed on the surface of the CE@CF electrode could be desorbed by applying a positive voltage without an eluent, and the CE@CF electrode displayed good recyclability. Currently, electrochemical adsorption is a rapidly developing method for the removal of Sr²⁺ from industrial wastes.

4. Measurement

As mentioned earlier, the measurement of ⁹⁰Sr can be performed via directly measuring the isolated ⁹⁰Sr or by an indirect measurement through its daughter ⁹⁰Y. The techniques for ⁹⁰Sr measurement include radiometric method to detect the beta decay of ⁹⁰Sr using a beta counter or liquid scintillation counting (LSC) and mass spectrometry to detect ⁹⁰Sr ions. The measurement of ⁹⁰Y is typically performed by detecting the higher energy (2280 Kev) beta emission of ⁹⁰Y by LSC/beta counter or Cerenkov counting.

4.1. Beta Counter

Beta counters commonly used for ⁹⁰Sr measurement include proportional counters and Geiger–Müller counter (GM counters). The proportional counter has a satisfactorily high efficiency (about 50%) and a relatively low background, which can be used as a sensitive detection tool for ⁹⁰Sr. The GM counter can also be used to detect relatively high-energy beta radiation. However, none of them can distinguish between ⁸⁹Sr, ⁹⁰Sr, and ⁹⁰Y. In such case, the sample is repeatedly counted for the in-growth of ⁹⁰Y; thereby, the activity of ⁹⁰Sr can be calculated. Sato et al. [115] have developed a technique to visualize the locations of ⁹⁰Sr source in 3D by combining a directional GM counters with Structure from Motion (SfM) and a method to estimate the radioactivity of the visualized source. Additionally, by combining a beta-ray detector with a Compton camera, they demonstrated that ⁹⁰Sr and ¹³⁷Cs can be visualized separately.

4.2. Electrosorption Liquid Scintillation Counting

Liquid scintillation technology is widely used to measure the activity of radionuclides, especially low energy β emitters. LSC is favored for ⁹⁰Sr determination because of the high resolution which can distinguish ⁸⁹Sr, ⁹⁰Sr and ⁹⁰Y [116] and very high counting efficiencies (close to 100%) for ⁸⁹Sr, ⁹⁰Sr and ⁹⁰Y. The samples prepared for LSC generally have high transparency and low self-absorption, but they could have a quenching effect [117,118]. LSC has the advantages of high detection efficiency and fast measurement, which is suitable for the rapid analysis of ⁹⁰Sr in emergency situations. The samples can be measured immediately after ⁹⁰Sr is separated, without waiting for ⁹⁰Sr–⁹⁰Y equilibrium or ⁹⁰Y separation. The measurement can also wait until the activities of ⁹⁰Sr and ⁹⁰Y reach equilibrium. In the latter case, the analytical turnover time is longer but with high precision and high counting efficiency.

4.3. Cherenkov Counting

Cherenkov radiation is a bluish light that occurs when an electrically charged particle travels faster than the local speed of light in an optical medium. As long as the beta particle energy is greater than 0.26 MeV, Cherenkov radiation can be generated in the water, and this radiation can be detected by a low background LSC. The energy (0.546 MeV) of β particles of ⁹⁰Sr is relatively low, which is not suitable for direct measurement by Cherenkov counting. Both ⁸⁹Sr (β energy is 1.46 MeV) and ⁹⁰Y (β energy is 2.29 MeV) have high Cherenkov counting efficiencies (>40%); therefore, ⁹⁰Y needs to be separated from ⁸⁹Sr before measuring by Cherenkov counting. Cherenkov counting can also be combined with LSC to obtain a fast quantification for ⁹⁰Sr. After the chemical separation of Sr, Cherenkov counting can be performed immediately (ignoring the in-growth of ⁹⁰Y). The sample is measured again by LSC after mixing with cocktail. Cherenkov counting provides a count rate of ⁸⁹Sr, and the LSC measurement provides the sum of ⁹⁰Sr and ⁸⁹Sr; thereby, the ⁹⁰Sr count rate can be calculated. Compared with LSC, the Cherenkov counting has the advantages of simple sample preparation, no addition of organic scintillator and thus no chemical quenching, and a recyclable sample for other uses. However, it also has disadvantages such as lower counting efficiency and severe color quenching effect compared with LSC. Other studies [69] showed that when ⁹⁰Sr and ¹³⁷Cs coexist, the beta rays emitted by ¹³⁷Cs could affect the Cherenkov measurement of ⁹⁰Sr. The contribution of ¹³⁷Cs could be mathematically corrected by multiple linear regression calibration to avoid the chemical separation step.

Grahek et al. [98] observed that the ⁹⁰Sr measured on the proportional counter by counting ⁹⁰Sr–⁹⁰Y in the radioactive equilibrium can significantly reduce the detection limit compared to the measurement on the low-level scintillation counter by Cherenkov counting. Rondahl et al. [119] compared three measurement strategies for ⁸⁹Sr and ⁹⁰Sr, wherein Method A was based on a two-stage chemical separation and measures ⁸⁹Sr and ⁹⁰Sr (via ⁹⁰Y) sequentially; B was a spectral subtraction method, and C was a spectral convolution method (Figure 3). The results indicate that Method A is suitable for the determination of ⁹⁰Sr over the entire range of the ⁸⁹Sr/⁹⁰Sr ratio. The simultaneous determination of ⁸⁹Sr and ⁹⁰Sr in Methods B and C has great uncertainty, especially for ⁹⁰Sr. In an emergency, the most appropriate method is to measure ⁸⁹Sr after the first chemical separation and then measure ⁹⁰Sr and ⁹⁰Y after the second chemical separation.

4.4. Mass Spectrometry

Mass spectrometric techniques are highly sensitive for the measurement of radionuclides, especially for the long-lived radionuclides. Compared with radiometric methods, ⁹⁰Sr measurement with mass spectrometric methods may not be advantageous in terms of detection limit due to the relatively short half-life of ⁹⁰Sr (28.79 y), but it provides high analytical throughput and multi-isotope capability. In recent years, efforts were increasing devoted to develop modern mass spectrometric setups to push the detection limit for ⁹⁰Sr to a lower end.

4.4.1. Inductively Coupled Plasma Mass Spectrometry (ICP-MS)

For the measurement of radionuclides, inductively coupled plasma mass spectrometry (ICP-MS) is the most widely used mass spectrometry technique due to its relatively low cost, easy operation, and high sensitivity. Therefore, ICP-MS has been adopted for the rapid determination of radionuclides in environmental samples since the 1990s [32,36,37,82,120]. For ⁹⁰Sr measurement, a variety of ICP-MS setups including single-quadrupole ICP-MS (ICP-QMS), triple-quadrupole ICP-MS (ICP-MS/MS), sector filed ICP-MS (SF-ICP-MS), dynamic reaction cell ICP-MS (DRC-ICP-MS), and electrothermal vaporization ICP-MS (ETV-ICP-MS) have been applied [4,33,35,40,71,74,121,122]. Among different mass spectrometric methods, ICP-MS is the mainstream in the measurement of ⁹⁰Sr.

Nevertheless, ⁹⁰Sr measurement by ICP-MS is challenged by spectroscopic and non-spectroscopic interferences, matrix and carry-over effects.

Table 2. Interferences affecting the determination of ⁹⁰Sr by mass spectrometry.

Interference	Abundance (%)
90Zr+	90Zr 51.5
89Y1H+	89Y 100
78Kr12C+	78Kr 23.3
74Ge16O+	74Ge 36.5
50Cr40Ar+	50Cr 4.29
50Ti40Ar+	50Ti 5.34

shows the interferences affecting ⁹⁰Sr in the mass spectrometric measurement, including both isobaric/polyatomic interfaces, primarily ⁹⁰Zr due to its high content in sample matrix and chemical reagents, and peak tailing of ⁸⁸Sr. Therefore, besides the thorough chemical purification of ⁹⁰Sr prior to the detection, sufficient suppression of the signals from interferences during the ICP-MS measurement is important to ensure the analytical accuracy.

In an ICP-QMS with a reaction cell, the reaction gas reacts with the interfering substance, e.g., ⁹⁰Zr thus suppresses the ⁹⁰Zr signal but still keeps high sensitivity for ⁹⁰Sr. The reaction gas can be selected based on thermodynamic and kinetic data [1,3,4,33,71,74,123,124]. The most commonly used reaction gas for the suppression of ⁹⁰Zr from ⁹⁰Sr is Q₂ [125]. An ultrasonic nebulizer (USN) can be adopted to enhance the sensitivity of ICP-MS for the determination of ⁹⁰Sr, e.g., 22-fold sensitivity enrichment was reported by Takagai et al. [33]. Al-Meer et al. [36] established a new method for the determination of ⁹⁰Sr in soil samples by ICP-MS/MS, introducing oxygen into the reaction cell to suppress the interference of ⁹⁰Zr. The detection limit was found to be 0.1 pg/g, using a microflow nebulizer.

4.4.2. Resonance Ionization Mass Spectrometry (RIMS)

The Resonance Ionization Mass Spectrometry (RIMS) can avoid some isobaric interference and improve the selectivity of traditional mass spectrometry toward isotopes of interest. The system is mainly composed of three parts: an ion source sample loading system, atomic ionization continuous wave laser system and mass spectrometer [126]. In RIMS, a laser beam is used to selectively/resonantly excite and ionize analyte atoms, thereby eliminating the isobaric interference caused by other elements. In a recent work, Cheon et al. [127] developed an interference filtered external cavity diode laser system, which significantly improved the selectivity of ⁹⁰Sr. In the study of Bushaw et.al [128], a diode laser-based scheme for the isotopically selective excitation and ionization of strontium was presented. With the use of graphite crucible atomization, the detection limit was demonstrated as low as 0.8 fg, and the overall ⁹⁰Sr selectivity was >10¹⁰ against stable Sr. Due to the limited accessibility, the application of RIMS in ⁹⁰Sr measurement for environmental and biological samples is still scarce.

4.4.3. Thermal Ionization Mass Spectrometry (TIMS)

The thermal ionization mass spectrometry (TIMS) is equipped with a sample changer, a sector magnetic field mass analyzer, and a Faraday cup detector [4,25,70,124,129]. By setting the magnetic field, TIMS works in a peak-hopping mode, in which the specified ion beam is directed to the detector in sequence, and voltage data are acquired in a digital format as a measure of peak intensity and used to calculate the isotope ratio. TIMS is suitable for measuring the Sr isotope ratio, such as ⁹⁰Sr/⁸⁶Sr, and then calculating the concentration of ⁹⁰Sr by multiplying the concentration of ⁸⁶Sr. Compared to ICP-MS, TIMS has higher precision and a lower detection limit for ⁹⁰Sr measurement [129]. In addition, TIMS measurement is not affected by isobaric interferences and any carry-over effect. However, the target preparation for TIMS is very time-consuming; therefore, TIMS has not gained as high popularity as ICP-MS for ⁹⁰Sr detection.

4.4.4. Accelerator Mass Spectrometry (AMS)

Accelerator mass spectrometry (AMS) can also measure trace amounts of ⁹⁰Sr, which has the characteristics of high sensitivity for radionuclides with long half-lives [123,130]. Environmental ⁹⁰Sr/Sr atomic ratios are estimated to be 10⁻⁷–10⁻¹⁴; therefore, AMS may extend capability in research into environmental ⁹⁰Sr owing to superior abundance sensitivity of 10⁻¹⁵ [131]. However, ⁹⁰Sr-AMS is affected by two major difficulties, which are related to the Sr beam current and interference by ⁹⁰Zr. Removal of the interference by using a chemical process would drastically improve the AMS detection limit. Satou et al. have developed a simple chemical procedure for rapid AMS-based ⁹⁰Sr-level determination and confirmed the validity of the chemical procedure [132]. Very recently, Ion-Laser Interaction Mass Spectrometry (ILIAMS), a novel technique for the efficient suppression of a stable isobaric background, has been developed and achieved isobar suppression factors of >10⁵ for the fission products including ⁹⁰Sr [133]. This new approach has already been validated for ⁹⁰Sr in selected reference materials (e.g., IAEA-A-12) and is ready for application in environmental studies. In addition, the high cost and high technical demands in AMS instrument maintenance and operation still restrict the application of AMS in the measurement of ⁹⁰Sr.

5. Automation in ⁹⁰Sr Analytical Methods

In recent years, the application of automation techniques in ⁹⁰Sr analytical methods has become popular. Flow-based techniques such as flow injection, sequential injection, and lab-on-valve were the main approaches reported for the automated chemical separation of ⁹⁰Sr [41]. These developed flow systems were mostly designed and assembled in-house of research laboratories with the use of commercial available components (such as pumps, valves, fittings, etc.); some of them were directly hyphatened to ICP-MS instruments for the rapid on-line detection of ⁹⁰Sr. Takagai et al. [33] integrated Sr resin (50 mg) into a lab-on-valve platform which was coupled with an DRC-ICP-MS for the on-line separation and detection of ⁹⁰Sr from microwave digested soil samples. ⁹⁰Sr can be detected at levels of femtograms per gram of soil. The analytical turnover time for on-line separation and detection was only 14.6 min. Habibi et al. [34] developed a protocol for the rapid determination of actinides and ⁹⁰Sr in soil samples (0.5 g/sample), wherein automated chemical separation and on-line ICP-MS measurement were performed after alkaline fusion for the sample pretreatment. The protocol provided satisfactory chemical yields (>80%) and sample throughput (10 samples in 24 h).

6. Quality Control

Quality control is important to ensure the reliability of the obtained analytical methods. This includes laboratory background control, the calibration of instruments, evaluation of trueness of the method, and uncertainty calculations. For each batch of samples, a procedure blank should be analyzed following the sample procedure for the samples. Under normal circumstances, the number of blank samples should not be less than 5% of the total number of samples analyzed.

In order to evaluate the impact of various operational processes on data quality, IAEA [134] conducted an inter-comparison exercise for ⁹⁰Sr determination in ore samples. It was found that the main sources of deviations were from ineffective purification procedures, high background values and lack of statistical control over background values. The main source of bias that led to the underestimation was the overestimated chemical yield due to failure to correct for stable strontium in the sample and quenching correction in LSC. Cheng’s report [135] analyzed the uncertainty composition of the ⁹⁰Sr measurement results of environmental soil samples. For environmental soil samples, the relative uncertainty was 22% (k = 1). The results show that the factors that contribute greatly to the uncertainty of the measurement results are the uncertainties in β radioactivity measurement (counting statistics), instrument detection efficiency, chemical yield, and sample mass. The relative uncertainties are 22%, 4.4%, 1.1%, 0.83% and 0.69% (k = 1), respectively. In Jiang’s report [136], the fishbone diagram method was used to analyze the uncertainty of ⁹⁰Sr measurement for water samples. The uncertainty caused by the chemical yield was the largest, which was 6.65%, because the sample preparation of the method was complicated.

7. Conclusions and Perspectives

We herein review the analytical methods of ⁹⁰Sr in environmental and biological samples, discuss in detail the advantages and disadvantages of different pretreatments, chemical purification methods and measurement techniques developed for ⁹⁰Sr. At present, the most widely used pretreatment method is acid digestion. Crown ether extraction chromatography is gradually replacing the precipitation method because of its superior separation efficiency. Among the different measurement methods of ⁹⁰Sr, LSC is widely accepted as the most practical analytical technique for quantifying radioactive strontium isotopes. Cerenkov counter can also quickly measure ⁹⁰Sr by ⁹⁰Y. In terms of detection limit and instrument cost, radiometric measurement methods are superior to mass spectrometry.

Traditional methods often take two weeks or more, and the standard processes established by most countries still continue the routine procedure developed in the last century. To improve this, it is necessary to increase the efficiency of pretreatment, chemical separation and detection methods. In terms of pretreatment, the rapid processing of large volume samples still needs to be explored. In terms of chemical separation, crown ether extraction chromatography has become a new trend, but synthesis of new modern materials (such as nanomaterials) and technologies (such as electrosorption) with high absorption capacity, high selectivity toward ⁹⁰Sr and low cost is still desired. In terms of detection methods, the advantages of mass spectrometry are obvious and attractive. The promises of modern ICP-MS/MS and AMS setups for low-level ⁹⁰Sr environmental and biological assay are foreseen yet requiring dedicated efforts in instrumental development and optimization. In addition, rapid analytical methods based on automated techniques for ⁹⁰Sr still need further exploration, especially in the direct hyphenation with mass spectrometry for online measurement.