Abstract
Tracing agricultural products’ origin via 87Sr/86Sr is critical for food quality. This study identifies optimal proxy samples for baseline maps by analyzing Sr isotopes in three vegetation life-forms (perennial herbs, shrubs, trees) and their soils under diverse parent materials. The results indicate significant differences in Sr-isotopic composition between roots and soils, likely due to the heterogeneous geological origin of eolian soils. Trees and shrubs grown on residual parent materials exhibit homogeneous isotopic signatures across organs, with 87Sr/86Sr ratios strongly correlated (R 2 > 0.85) with mixed surface vegetation samples. Thus, this study demonstrates that 87Sr/86Sr isoscapes constructed from multispecies vegetation sampling overcome methodological constraints arising from seasonal variations in agricultural traceability. These findings establish a theoretical foundation for a cross-plant-type origin-tracing framework capable of harmonizing divergent crop data sets and have implications for refining the methodology of botanical Sr sourcing.
Keywords: Sr isotopes, geographical authentication, elements, food origin

1. Introduction
With the growing demand for high-quality food, the approach of assessing food quality by tracing its origin has gained popularity. Food traceability technology is critical for establishing origin product protection, promptly tracing the source of contamination, carrying out effective recalls, minimizing economic losses, and preserving consumer health. Strontium isotope ratios have demonstrated significant potential in constructing robust traceability frameworks for various agricultural products due to their advantages, such as low radioactivity, fast analysis speed, high precision, and good accuracy. Recent 87Sr/86Sr applications in food authenticity studies include successful geographical verification of wine, grapes, coffee and olive oil. Additionally, it has played an extremely important role in site-specific differentiation of traditional Chinese medicine production areas, archeological provenance studies, − forensic geolocation and ecological habitat identification. ,
Sr has four naturally occurring isotopes: 88Sr, 87Sr, 86Sr, and 84Sr. 87Sr evolves over geological time due to the decay of87 Rb, which produces radiogenic 87Sr. As a result, the total 87Sr concentration in a rock or mineral is the sum of its initial 87Sr component and the radiogenic 87Sr accumulated since its formation. This enrichment process causes the total 87Sr abundance to vary as a function of the host rock’s age and its initial87 Rb and 87Sr concentrations. The strontium comes from the weathering of local bedrock, sediments, and atmospheric deposition (precipitation, dust, sea spray, and other aerosols). Strontium is released as Sr2+ into soil pore water, surface water, and groundwater during the weathering process. As a result of weathering processes (influenced by temperature, humidity, and bedrock composition) and atmospheric deposition, strontium isotopes become bioaccessible and are incorporated into the local food chain via plant roots. , Because of the modest mass differences between isotopes, Sr has only minor isotopic fractionation, and its mass bias can be adjusted using mathematical methods. The adjusted plant 87Sr/86Sr ratio is strongly related to the bioavailable components in the soil and varies by region exhibiting regional indicative characteristics. This association demonstrates a direct relationship between plants and their growth environment, allowing the origin of plants to be traced through their 87Sr/86Sr ratios.
Using 87Sr/86Sr ratios to determine the provenance of biological materials requires a map of bioavailable 87Sr/86Sr so that sample results can be compared. Water, soil, plants, snail shells, animals, and other archives are being widely used to create bioavailable strontium isotope maps. − The selection of archives is contingent upon two factors: the nature of the traceability object and the availability of strontium archives. Some studies focus on measuring strontium isotope ratios of specific research objects (e.g., single plant organs or species) in regions to establish strontium isotopic baselines. These maps have been used to trace samples from unknown production areas by direct comparison. Nevertheless, while this single-object approach provides targeted insights, its broader applicability may be constrained when extended to traceability studies involving disparate plant types or complex pedogenic environments.
The construction of strontium isotope maps for the traceability of different plant samples requires clarifying two issues. The first issue pertains to 87Sr/86Sr variations among diverse plant organs. Second, the analysis of the 87Sr/86Sr ratio relationship between the traceability object and its growing environment is required, as well as the identification of surrogate indicators that can represent the strontium ratios of various plant samples. Research has been conducted on foodstuffs such as grapes, cereals, and apples , and found that strontium ratios varied less in different organs of the same type of plant and at various times of harvesting. Meanwhile, plants are generally considered a good material for estimating bioavailable 87Sr/86Sr, and mixed plant samples are regarded as representative of bioavailable plant resources. , Although numerous studies have explored the relationships between strontium isotope ratios among various organs of different plant species and bioavailable strontium in the environment, research on the correspondence between mixed plant samples within a sampling site and bioavailable strontium in different organs across diverse plant species remains limited.
In this study, five plant species representing four functional typesperennial herbs (Astragalus membranaceus var. mongholicus (Bunge) P. K. Hsiao), deciduous shrubs (Chaenomeles speciosa(Sweet) Nakai, Paeonia ostiiT. Hong & J. X. Zhang), broadleaved trees (Citrus reticulataBlanco), and conifers (Pinus hwangshanensisW. Y. Hsia)were selected. The strontium ratio relationships within the various plant types and between them and their growing environments were tested in terms of root depth, plant height, and plant organs which enables traceability for complex traditional medicines (multiorgan formulations) and agricultural products with diversified sourcing. This approach elucidated the corresponding relationship between plants and bioavailable strontium in soil and then identified the optimal surrogate sample type for constructing strontium ratio baseline maps, which could facilitate traceability in diverse plant production areas. These findings establish a geographical authentication framework for agrifood traceability, particularly addressing challenges in seasonal product verification.
2. Materials and Methods
2.1. Reagents
Hydrochloric acid (GR, Tianjin Fengchuan Chemical Reagent Co., Ltd.) was purified by two sub-boiling distillations for use in resin column rinsing. Nitric acid (Trace metal analysis, Fisher) was used directly for sample digestion and Sr elution solution acidification. Hydrofluoric acid (Trace metal analysis, Fisher) enabled complete digestion of silicate samples, with residual HF removed by evaporation to prevent instrument corrosion. Perchloric acid (MOS grade, Tianjin Fengchuan Chemical Reagent Co., Ltd.) oxidized organic matter and dissolved SrF2 precipitates to enhance Sr recovery. All experiments utilized freshly prepared Milli-Q water (18.2 MΩ) to eliminate metal ion interference.
2.2. Sampling Sites
The study was conducted across six geographical sites in Shanxi and Anhui provinces (China), encompassing seven pedological profiles, and the distribution and details of the sample sites are shown in Figure and Table Species selection prioritizes functional diversity to capture variability in strontium uptake across different root depths and organ types, while ensuring coverage of representative soil parent materials and considering regional agricultural economic significance. The sampling sites in this paper cover two different types of soil parent material and the sampling strategy prioritized GCM-certified regions.
1.
Seven sampling point locations. (The shaded area is the extent of the Loess Plateau and the Geological map modified after Ma et al., 2002.)
1. Sampling Site Information.
| NO. | Species | Life-form | Site name | Latitude (°N) | Longitude (°E) | Altitude (m) | Bedrock Type |
|---|---|---|---|---|---|---|---|
| 1 | A. membranaceusvar. mongholicus | Perennial herbaceous plant | Shanxi Province, Hunyuan | 39.54 | 113.69 | 1891.03 | Gray Gneiss, Charnockite |
| 2 | A. membranaceusvar. mongholicus | Perennial herbaceous plant | Shanxi Province, Hunyuan | 39.54 | 113.69 | 1891.03 | Gray Gneiss, Charnockite |
| 3 | Ch. speciosa | Deciduous shrub | Anhui Province, Xuanzhou | 30.71 | 118.73 | 176.73 | Fine sandstone, Bituminous limestone, Chert-bearing limestone, Dolomite, Siliceous rock |
| 4 | C. reticulata | Evergreen tree | Anhui Province Qimen | 29.95 | 117.28 | 391.69 | Phyllitic sandstone, Sandy phyllite |
| 5 | P. hwangshanensis | Evergreen tree | Anhui province Yuexi | 31.15 | 116.34 | 401.35 | Granodiorite gneiss |
| 6 | P. hwangshanensis | Evergreen tree | Anhui Province, Yuexi | 31.08 | 116.36 | 785.76 | Monzonitic gneiss |
| 7 | Pa. ostii | Deciduous shrub | Anhui Province, Nanling | 30.82 | 118.01 | 77.04 | Quartz conglomerate, Quartz sandstone, Limestone, Dolomite, Coal-bearing shale |
Hunyuan, Shanxi is the traditional production area of the high-quality conventional Chinese medicine Astragali Radix; the soils is wind-deposited loess, and the bedrock type is Gray Gneiss, Charnockite, here two perennial herbs A. membranaceus var. mongholicus was selected as a study of the relationship between perennial herb strontium ratio under wind-deposited soil. Except for A. membranaceus var. mongholicus sampling sites, which exhibited transported parent materials, all soil parent materials originated from rock weathering. The deciduous shrub Ch. speciosa is the botanical source of the traditional Chinese medicine "Xuanmugua", and Xuancheng, Anhui Province, is its high-quality production area. The local soil-forming parent material at the sampling site was sandy shale with saline crystalline deposits derived from weathering. The deciduous shrub Pa. ostii (PO), a characteristic plant of Tongling City in Anhui Province, grows in sampling sites where the soil consists of sandstone-shale and light-colored crystalline salt weathering products. The evergreen tree C. reticulata (CR), sampled from high-yielding̀ and premium-quality orchards in Qimen County, Anhui Province, thrives in areas where the soil predominantly comprises sandstone-shale weathering products with partial contributions from limestone weathering products. P. hwangshanensis (PH) is a distinct, endemic Chinese species shaped by the Huangshan region’s unique geological and climatic conditions. It was represented by two evergreen experimental trees collected from Huangshan with contrasting bedrock types. The first P. hwangshanensis (PH-1) was established on soils derived from granodiorite gneiss, while Specimen Tree 2 (PH-2) occurred on soils developed from monzonitic gneiss.
2.3. Sampling
In July 2023, two plants of the perennial herb A. membranaceus var. mongholicus (AM-1; AM-2) were collected in Hunyuan County, Shanxi Province. Samples of the above-ground part of the plant were collected at 30, 60, and 90 cm above ground. Samples of the root system of the plant were collected at depths of 0, 5, 20, 40, 60, and 80 cm below ground, while 50 g soil samples were collected at corresponding depths. Root samples from AM-1 at 20, 40, and 60 cm depths and from AM-2 at 40, 60, 80, and 100 cm depths were anatomically dissected into phloem and xylem tissues based on histological structures.
In November 2023, the study focused on C. reticulata in Xin’an Town, Qimen County, Anhui Province, where leaf, seed, and pericarp samples were systematically collected at 1 m intervals from 1 to 4 m aboveground. Belowground sampling involved collecting root system specimens and corresponding soil samples at 15 cm depth increments from 0 to 105 cm.
Two specimen trees of P. hwangshanensis (PH-1; PH-2) were collected from Huangwei Town and Toutuo Town in Yuexi County, Anhui Province, respectively. PH-1 (height: 4 m; rooting depth: 90 cm) was systematically sampled with the following protocol: (1) Aboveground (1–4 m): whole trunk segments and needles were collected at 1-m intervals. These trunk specimens were dissected into outer bark and xylem subsamples at each height. (2) Belowground (0–90 cm): root system specimens with corresponding soil matrices were obtained at 15 cm depth intervals. Three root samples from 0–30 cm depth were specifically processed into periderm and xylem fractions. (3) Multilayer xylem partitioning: Larger-diameter specimens from aboveground trunks (2 m, 1 m, 0 m) and belowground roots (0 cm, 15 cm) underwent radial division, yielding distinct xylem subsamples (Xylem-1: outer zone; Xylem-2: inner zone).
PH-2 (height: 2.5 m; rooting depth: 105 cm) was sampled through a stratified protocol comprising aboveground and belowground components. Aboveground sampling at 1–2.5 m height involved collecting trunk segments and needles at 0.5 m vertical intervals. Belowground operations encompassed three-tiered sampling: root system specimens with corresponding soil matrices were systematically obtained at 30 cm depth increments from 0–90 cm, supplemented by the targeted collection of root apex samples at the maximum rooting depth (105 cm). In the meantime, synchronous soil sampling was conducted across all investigated rhizospheric horizons.
The deciduous shrub Ch. speciosa was sampled in Xuanzhou District, Anhui Province. Aboveground sampling involved collecting coheight leaf, fruit, and seed specimens at 1 m, 1.5 m, 2 m, and the apical point (2.3 m). Belowground operations comprised root system sampling at 20 cm intervals from 0–60 cm depth, with corresponding soil matrices collected at each sampled horizon, supplemented by additional soil collections at 80 and 100 cm depths. Selected roots from 15 and 30 cm depths were anatomically dissected into periderm, Xylem-1 (outer vascular zone), and Xylem-2 (inner vascular core). Roots from 45 cm depth were partitioned into periderm and xylem fractions.
During November 2023, three vegetation categories were systematically collected within a 1 m radius of each plant profile sampling site: monocotyledonous plant assemblages (P1), aboveground portions of dicotyledonous plants (P2), and a mixed sample of monocotyledons and dicotyledons (P3), using random sampling within each sampling locus.
In May 2024, a specimen plant of the perennial deciduous shrub Pa. ostii was collected in Nanling County, Anhui Province. A stratified sampling protocol was implemented for its root system: soil matrices were collected at 20 cm intervals from 0–100 cm depth, while hierarchical root sampling targeted different root orders across corresponding horizons. This investigation systematically analyzed the Pa. ostii root system architecture, including targeting main roots (R1), primary lateral roots (R2), and secondary lateral roots (R3). Concurrently, three vegetation categories were systematically acquired within a 1 m radius of the sampling locus: monocotyledonous plant assemblages (P1), aboveground portions of dicotyledonous plants (P2), and a mixed sample of monocotyledons and dicotyledons (P3).
2.4. Specimen Preprocessing Procedures
Soil samples were oven-dried at 65 °C, sieved through a 75-mesh sieve (aperture: 0.2 mm), and manually depurated of all plant tissues. Plant specimens underwent sequential ultrasonication in Milli-Q water to remove superficial particulates and sedimentary residues, followed by desiccation at 65 °C for 48 h. The dehydrated plant sample was then pulverized and homogenized through a 200-mesh sieve (aperture: 0.075 mm), awaiting subsequent fractionation and purification processes.
2.5. Sample Digestion
Botanical specimens were processed: precisely 150 mg of homogenized plant powder was weighed into polytetrafluoroethylene (PTFE) digestion vessels. Initial digestion involved 3 mL concentrated HNO3 overnight immersion followed by evaporation to dryness. Subsequently, aqua regia and hydrofluoric acid (HF) were introduced for sealed hot plate digestion at 70–80 °C over 12 h. Vigorous effervescence necessitated protocol repetition after redrying. For residual particulates, supplemental HClO4 was added for intensified digestion at 150 °C (12 h). Upon achieving optical clarity, solutions were evaporated and reconstituted with concentrated HNO3 for matrix conversion. Final dissolution employed 1 mL 3.5 M HNO3 with 1 h thermal equilibration (60 °C) to ensure complete solubilization, with aliquots reserved for subsequent analysis. Strontium quantification was performed via ICP-MS (Analytik Jena AG) following EPA Method 6020B, with measured concentrations determining optimal column loading volumes for chromatographic separation.
Soil samples were processed as follows: Precisely 1.0 g aliquots were weighed into 50 mL centrifuge tubes, mixed with 10 mL 1 M ammonium oxalate ((NH4)2C2O4) solution, and vortex-mixed. After 6 h incubation with periodic agitation, centrifugation (4000 × g, 15 min) separated the exchangeable fraction (L1) supernatant. This extract was filtered through 0.45 μm membranes, evaporated to dryness, and subjected to triplicate acid digestion with 0.1 mL concentrated HNO3. The residue was reconstituted in 1 mL 3.5 M HNO3 for Sr quantification via ICP-MS prior to chromatographic column loading.
2.6. Sr/Matrix Separation
Strontium isotope separation was conducted using Sr-specific resin columns (Triskem International, 100–150 μm particle size, 0.5 mL column bed volume). The protocol involved sequential elution steps: matrix and rare earth elements (REEs) were removed with 3.5 M HNO3, followed by Milli-Q water rinsing to elute the Sr fraction. Purified Sr eluate was evaporated to dryness, reconstituted in 1 mL 2% HNO3, and prepared for ICP-MS analysis.
2.7. ICP-MS and MC-ICP-MS Measurements
All Sr isotopic measurements were conducted in static mode. Instrumental mass bias correction was applied using the exponential law with the reference ratio 88Sr/86Sr = 8.375209. Program blank samples are analyzed alongside each batch of samples. NBS-987 is used as a standard sample to monitor instrument status and testing processes. The test value for NBS-987 in this instance was 0.710247 ± 0.000013 (2σ). Analytical precision is expressed as 2σ values, which are calculated from 60 replicate measurements per sample. Full-process quality control (QC) samples were analyzed with every sample batch, and procedural blanks were run with every sample batch. One randomly selected sample was reanalyzed every ten samples to monitor analytical stability. Prior to sample analysis, the MC-ICP-MS (Neptune Plus, Thermo Fisher Scientific) system was optimized with a Sr standard solution (200 μg/L) to maximize sensitivity by adjusting plasma interface parameters (torch positioning, carrier gas flow rate) and ion lens voltages.
2.8. Statistical Analysis
Statistical analyses were conducted to evaluate the significance of differences in 87Sr/86Sr ratios across distinct specimen categories (soil, root systems, foliage, and fruits from identical sampling loci). Parametric approaches were employed to detect intergroup variations in 87Sr/86Sr ratios, with distribution patterns further characterized through supplemental descriptive statistics and visualization methods. Strontium isotopic analyses were performed on 133 botanical specimens (encompassing root, foliage, fruit, pericarp, seed, and mixed plant composites) and 43 soil matrices collected from seven pedological profiles spanning six sampling sites. All results are presented in Table S1.
3. Results and Discussion
3.1. Difference in Sr Isotopic Ratios for All Sampling Points
The data range for all sampling points is between 0.718514 and 0.708792. The results show significant differences in 87Sr/86Sr among the six sampling sites (Table ). For the PO sampling site in Wuhu City, Anhui Province, the 87Sr/86Sr of all samples range from 708514 to 0.708617 (n = 9) which is the lowest ratio align with dominant carbonate rocks (limestone, dolomite) with low Rb and radiogenic Sr. Quartz sandstone and coalbearing shale have minimal influence, resulting in an overall low value. For the PH-1 in Anqing City, Anhui Province, the 87Sr/86Sr is 0.708837–0.709553 (n = 43), slightly higher than Wuhu (PO), consistent with felsic granodiorite gneiss. The lower-than-expected value may result from high alteration or young formation age reducing Rb. The 87Sr/86Sr ratio of PH-2 is 0.710626–0.711102 (n = 19), significantly higher than PH-1, reflecting higher Rb in monzonitic gneiss, showing geological differentiation’s control on Sr isotopes. For the CS profile samples collected in Xuancheng City, Anhui Province, the 87Sr/86Sr ratios of all samples range from 0.710422 to 0.711954 (n = 26) due to mixed sandy shale (medium Rb) and salt crystals (low Rb). A slightly higher upper limit relates to local feldspar-rich shale. For the CR profile samples in Huangshan City, Anhui Province, the 87Sr/86Sr ratios range from 0.716424 to 0.717039 (n = 36). It may result from dominant metamorphic sandy shale (higher Rb from felsic minerals) or hidden granite inputs. For the two AM sampling sites in Datong City, Shanxi Province, the 87Sr/86Sr ratios of the samples range from 0.71312 to 0.718368 (n = 20) and 0.713387–0.717955 (n = 24), respectively. It reflects the influence of the dissolution of overlying loess and eolian evaporites, as well as silicate/carbonate weathering. ,
It was shown that 87Sr/86Sr ratios for intrasite specimens across seven sampling loci (Figure ) revealed relatively constrained isotopic ranges in all but two AM sampling sites. Although strontium isotope ratios (87Sr/86Sr) exhibit overlapping ranges among some sampling sites, statistical analyses revealed statistically significant differences in isotopic composition across all sites. Comparative evaluation of outlier demonstrated that only the AM-1 profile exhibited anomalous values, with an outlier proportion of 17.86% (n = 28). These findings substantiate the geospatial specificity of strontium isotopic signatures in soil-plant systems, validating the applicability of 87Sr/86Sr ratios as robust provenance tracers for agricultural products across distinct cultivation regions.
2.
Boxplot of 87Sr/86Sr ratios of all samples within the sampling point.
While the observed 87Sr/86Sr ratios in plants strongly correlate with local lithology, it is important to acknowledge that 87Sr/86Sr signatures are not geographically unique. Comparative analysis of 87Sr/86Sr ratios revealed partial isotopic overlap between CR from Huangshan City, Anhui Province, AM-2 specimens from Datong City, Shanxi Province, PH-2 from Huangshan City, Anhui Province, and CS from Xuancheng City, Anhui Province. Such overlaps highlight that Sr-isotopic data, while a powerful tracer of geological provenance, should be interpreted in conjunction with complementary lines of evidence (e.g., multielemental signatures, regional geological maps, or spatial distribution patterns of isotopic variability) to strengthen locality-specific inferences.
3.2. 87Sr/86Sr Signatures between Perennial Herbaceous Plants and Win-Blown Soil
The two perennial herbaceous A. membranaceus var. mongholicus specimens were collected from Hunyuan County, Shanxi Province, situated within the Loess Plateau – a geo-authentic production region for this medicinal species. The Loess Plateau, representing the world’s largest contiguous loess deposits, exhibits friable textures and poor erosion resistance, rendering it a global hotspot for intense soil erosion (Figure ). Some studies demonstrate that the plateau’s soils predominantly originate from sediments in the Yinchuan-Hetao Basin, which were initially transported by the Yellow River from the Tibetan Plateau and subsequently reworked by winter monsoon winds to their current depositional setting. , Comparative analysis of plant specimens from different anatomical compartments of two colocated perennial herbaceous A. membranaceus var. mongholicus individuals and their corresponding depth-specific soil matrices revealed significant disparities in 87Sr/86Sr ratios between root tissues and ambient soils (Figure a,b). Additionally, variation in 87Sr/86Sr signatures was detected between the two A. membranaceus var. mongholicus specimens within the identical sampling site. Profile soils of AM-1 exhibited pronounced heterogeneity in 87Sr/86Sr ratios across 0–100 cm depth, while the AM-2 profile soils demonstrated constrained interhorizon 87Sr/86Sr variability. These findings substantiate the pedogenic complexity of local soil matrices, where significant microscale isotopic variance in 87Sr/86Sr ratios was detected even within identical depth intervals at a single geolocation.
3.
Strontium isotope ratios (87Sr/86Sr) in A. membranaceus var. mongholicus and P. hwangshanensis sample sites with dashed lines indicating the mean 87Sr/86Sr values of intraprofile botanical specimens (excluding composite samples). (a) AM-1; (b) AM-2; (c) Sampling schematic of A. membranaceus var. mongholicus; (d) PH-1; (e) PH-2; (f) Sampling schematic of P. hwangshanensis. (P1: monocotyledonous plant assemblages; P2: aboveground portions of dicotyledonous plants; P3: mixed sample of monocotyledons and dicotyledons.)
In the AM-1 profile, the surface soil (0 depth) exhibited a 87Sr/86Sr ratio of 0.71642 ± 0.000005. This ratio peaked at 0.717868 ± 0.000008 at a depth of 20 cm, followed by a significant isotopic decline to 0.71612 ± 0.000007 at 40 cm. A subsequent stabilization occurred at 60 cm, with a ratio of 0.71638 ± 0.000004, which approximated the values found at the surface level. The root systems exhibited minimal intraplant variation (σ2 = 0.00005) between 20 and 40 cm, consistent with efficient xylem Sr translocation mechanisms. Pronounced root-soil divergence (Δ87Sr/86Sr = +0.00075) was observed at 20 cm. Subsoil roots displayed transient isotopic elevation (0.71789 ± 0.000006) at 60 cm, with progressive attenuation to 0.71641 ± 0.000003 at 80 cm, achieving convergence (|Δ| < 0.00002) with corresponding soil (0.71639 ± 0.000005), indicative of groundwater-mediated Sr equilibrium in saturated zones.
The AM-2 soil profile exhibited complex vertical 87Sr/86Sr dynamics: soil 87Sr/86Sr ratios declined from 0.713387 ± 0.000004 (0 depth) to 0.713418 ± 0.000005 at 40 cm, rebounded to 0.713846 ± 0.000003 at 60 cm, and attenuated to 0.713215 ± 0.000004 at 80 cm. Below 80 cm, ratios ascended, converging with surface values at 110 cm (0.713402 ± 0.000002). Roots exhibited divergent trends: from 20 cm (0.71721 ± 0.000005) to 60 cm (0.71543 ± 0.000006), a decrease of Δ87Sr/86Sr = −0.00178, with maximum root-soil divergence (Δ = +0.00212) at 20 cm and transient convergence (Δ = +0.00047) at 40 cm. Below 60 cm, ascending root ratios (0.71801 ± 0.000005 at 110 cm) amplified disparities (Δ = +0.00381) relative to the soil.
Soil erosion and eolian deposition processes have resulted in soil genesis complexity across the Loess Plateau, manifesting as stratigraphic heterogeneity in 87Sr/86Sr ratios among distinct soil horizons. Given that plant-acquired strontium predominantly originates from bioavailable soil fractions, this vertical isotopic zonation directly induces corresponding 87Sr/86Sr disparities in root systems along depth gradients, which also is the primary reason for the significant differences in strontium levels between Astragalus and its growing environment. Plant strontium is conventionally recognized to originate from dual provenance: petrogenic weathering of lithospheric substrates and atmospheric deposition inputs. − In oligotrophic soil systems, compromised Sr bioavailability frequently obscures accurate quantification of pedogenic contributions to plant uptake, resulting in detectable root-soil isotopic decoupling at identical sampling loci. Our findings observed biogeochemical incongruence between soil matrices and root systems substantiates this mechanistic framework.
Researchers encounter significant challenges when using strontium isotope source analysis on agricultural products in regions with complex geology, such as areas with heterogeneous bedrock composition, alluvial parent material or severe soil erosion. In geologically intricate areas, the optimization of sampling strategies for strontium isotope mapping can be achieved by either focusing on particular plant taxa or choosing plant sample types that accurately represent the 87Sr/86Sr ratios of specific soil layers, such as deep-rooted or shallow-rooted species to denote different soil horizons. This method utilizes the vertical connection between bioavailable strontium in plants and soil, which may improve spatial resolution in heterogeneous landscapes.
3.3. Correlation of Sr Isotopic Ratios in Plants and Soils
Residual parent materials, formed through weathering processes including mechanical disintegration, chemical dissolution, and humification of bedrock, exhibit elevated moisture retention capacity and nutrient density, demonstrating critical agronomic utility through enhanced phytoavailability of essential elements. This study analyzes the 87Sr/86Sr signatures in arboreal species, deciduous shrubs, and herbaceous taxa grown on residual parent material substrates, revealing pedogenic Sr fractionation dynamics across plant functional types.
3.3.1. 87Sr/86Sr Ratios of Trees and Soil
According to recent study, the 87Sr/86Sr ratios of perennial deep-rooted deciduous trees exhibit excellent intratree homogeneity and do not significantly differ among their various organs (stem axis, leaves, apple skin, and meat). Empirical data from the evergreen tree C. reticulata also corroborated these findings. Figure a delineates the 87Sr/86Sr signatures across different compartments (foliage, seeds, fruits, periderm, xylem, and root systems), pedogenic horizons, and phyllosphere-associated herbaceous plants within the citrus profile. Organs from identical canopy strata (e.g., leaf, pericarp, seed) exhibited statistically indistinguishable isotopic signatures (p > 0.05). Furthermore, the exceptionally low intraplant variance (σ2 = 2.73 × 10–8) among CR specimens substantiates remarkable 87Sr/86Sr homogeneity within individual trees.
The evergreen gymnosperm P. hwangshanensis demonstrates dual pedo-acidification mechanisms: litterfall-induced soil acidification coupled with base cation depletion via root uptake. To investigate the biogeochemical coupling between deep-rooted arboreal species and bioavailable Sr ratios in specific edaphic contexts, two P. hwangshanensis were collected from Huangwei Town and Toutuo Town in Yuexi County, Anhui Province. Both pines exhibited exceptionally low intraplant 87Sr/86Sr variance (σ2 PH1 = 2.49 × 10–8; σ2 PH2= 1.85 × 10–8). This suggests that deep-rooted trees living in acidic soil have constant 87Sr/86Sr ratios across their many organs.
Analytical results from C. reticulata and P. hwangshanensis specimens revealed no statistically significant divergence in 87Sr/86Sr compositions between monocotyledonous and dicotyledonous herbaceous plants within identical geographical units (p > 0.05; R > 0.90). On the other hand, the 87Sr/86Sr in the local strontium isotope range is found in the mixed sample of surface vegetation in the exact location (Figures d,e and a). Therefore, the 87Sr/86Sr baseline isoscape constructed using plant composite samples (mixed-specimen assemblages) can be effectively applied for provenance tracing of organ-specific samples from deep-rooted arboreal species developed on residual parent materials.
4.
Strontium isotope ratios (87Sr/86Sr) in different sample sites with dashed lines indicating the mean 87Sr/86Sr values of intraprofile botanical specimens (excluding composite samples). (a) CR; (b)CS; (c) PO; (d) sampling schematic of C. reticulata; (e) sampling schematic of Ch. speciosa; (f) sampling schematic of Pa. ostii. (P1: monocotyledonous plant assemblages; P2: aboveground portions of dicotyledonous plants; P3: mixed sample of monocotyledons and dicotyledons;R1: main root; R2: primary lateral roots; R3: secondary lateral roots. S0-4 denotes soil at different depths: S0 for 0 cm (surface soil), S1 for 20 cm underground, S2 for 40 cm underground, S3 for 60 cm underground, and S4 for 100 cm underground.)
3.3.2. 87Sr/86Sr Ratios of Deciduous Shrubs and Soil
This study employs Ch. speciosa, a deciduous shrub of the Rosaceae family and the source plant of the geo-authentic Chinese medicine “XuanMugua” in Xuancheng City, as a model system to investigate intraplant 87Sr/86Sr relationships within woody perennials inhabiting lithogenic weathering substrates. Experimental results demonstrated that CR specimens exhibited minimal isotopic divergence in 87Sr/86Sr ratios across vertical strata and organ types (fruits, seeds, foliage; σ2 = 5.98 × 10–8). Furthermore, three kinds of composite plant samples from the sampling locus were fully constrained within the locally established bioavailable Sr isotopic range (Figure b).
Previous studies posit that differential root proliferation patterns in soil matrices may induce distinct 87Sr/86Sr signatures among root architectures, with reported isotopic divergence between lateral and taproots in species exhibiting extensive root systems. Contrary to these reports, our findings demonstrated no significant isotopic variance (σ2 < 1 × 10–7) across root orders and branching hierarchies. This investigation systematically analyzed the P. ostii root system architecture, including targeting main roots, primary lateral roots, and secondary lateral roots. The experimental results indicated that the 87Sr/86Sr ratios in different root segments exhibited minimal variation (σ2 = 4.96 × 10–10), demonstrating internal homogeneity within the root system (Figure e). This uniformity may be associated with the consistent 87Sr/86Sr composition observed in soil profiles at different depths (σ2 = 1.63 × 10–9), suggesting potential interactions between root system homogeneity and soil isotopic stability across vertical soil layers. Analytical results revealed no statistically significant divergence (p > 0.05) yet strong positive correlations (R > 0.90) between ground vegetation composite samples and Paeonia root systems in 87Sr/86Sr ratios within the sampling locus. These findings collectively validate the biogeochemical fidelity of 87Sr/86Sr baseline isoscapes for provenance tracing different samples in perennial shallow-rooted shrubs, indicating negligible fractionation during Sr allocation within root system architectures. The plant isotope ratios fluctuate following the soil isotope ratios and tend to approach the soil isotopes within a comparatively short time frame, which aligns with the findings from earlier research on various soil and plant kinds.
3.4. Assessment of Strontium Distribution among Plants
The parent rock in the soil–vegetation–atmosphere system contributes strontium, which is further enhanced by dust and precipitation deposition. Primary and secondary minerals, soil solution, cation exchange sites, and plants (including leaves, wood, roots, and decomposing matter) all contain strontium. Through biological disturbance, cation exchange and leaching, mineral weathering, and root absorption, strontium is redistributed throughout the soil–plants system. The primary sources of strontium in terrestrial plants are influenced by atmospheric deposition and rock weathering. The efficiency of strontium absorption is governed by an integrated set of factors, including species-specific physiological traits (e.g., ion transporter activity), root architectural features (morphology and exudate profiles), soil properties (type, pH, and fertility), and climatic conditions. Notably, rhizosphere processes at the soil–root interface further modulate strontium bioavailability, particularly through organic acid exudation and microbial interactions.
This study examined the distribution patterns of Sr in different regions of plants and hypothesized Sr migration mechanisms in distinct plant kinds. The study involved segmenting and analyzing pine and citrus trees, and the overall findings revealed that the 87Sr/86Sr ratio in the xylem was higher than that in the phloem. This is consistent with the process by which Sr is absorbed in the root tips and transported to various plant organs via xylem sap. , The overall trend of 87Sr/86Sr in citrus is root > leaf ≈ seed, and the 87Sr/86Sr levels decrease with height, comparable to the strontium enrichment mechanism in cannabis. In PH-1, the 87Sr/86Sr ratio reveals a pattern of leaves > stems > roots, whereas in PH-2, the 87Sr/86Sr ratio displays the opposite enrichment outcome as in PH-1. This pattern has also been observed in rapeseed research, suggesting that strontium is concentrated in different areas of pine trees at different phases of growth. The total 87Sr/86Sr ratio of Ch. speciosa demonstrates that samples from the aboveground sections are higher than those from the subsurface. As a result, it may be concluded that the distribution patterns of strontium in various organs of plants differ. However, due to the extremely minor changes in 87Sr/86Sr inside the plants, more individual Sr investigations are required to corroborate this viewpoint.
This study primarily focuses on analyzing different types of plant samples (leaves, stems, fruits, seeds, etc.) from various plant species under different types of diagenetic parent materials, as well as soil and surface vegetation at different depths, to investigate the relationship between the accumulation of strontium stable isotopes in different plant parts and the environment. This will help infer which type of sample can best represent the bioavailable strontium in the local area for provenance studies. The results demonstrate the predominant role of soil parent materials in governing 87Sr/86Sr variability. This study confirms isotopic congruence between phyto-compartment-specific samples (varying heights/organ types) and ground vegetation composites across plant functional types within residual parent material environments. Importantly, our findings demonstrate that strontium isotopes in ground vegetation composites serve as more reliable and spatially applicable proxies than conventional Sr isotopic baselines in the studied pedogenic system. While preliminary data suggest possible physiological fractionation pathways, confirmation requires extended, species-level verification, which is currently underway.
The derived phytocomposite-based 87Sr/86Sr isoscapes provide a robust framework for provenance determination of diverse plant types within the sampling domain, offering particular significance for tracing food products with seasonal availability or ambiguous edible portions. However, the intraplant 87Sr/86Sr characteristics of deep-rooted species in transported parent material environments (excluding eolian deposits) remain a critical knowledge gap requiring systematic investigation to advance Sr isotopic provenance methodology. Although the design of soil sampling depths in this study is based on the root system characteristics of the species, there are still limitations: the interval precision at different sites may introduce subtle differences. Future studies can be further optimized to a “stratified uniform interval”, which enhances method standardization while retaining ecological relevance and improves the comparability of cross-regional data.
Supplementary Material
The original data presented in the study are included in the Supporting Information.
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jafc.5c05277.
87Sr/86Sr of analyzed sample from different locations (Table S1), Selected cross-sectional views in the experiment (Figure S2), and sample diagrams of Paeonia ostii (Figure S3) (PDF)
This work was supported by the National Key Research and Development Program of China (2022YFC3500904, 2022YFC3500903), the CACMS Innovation Fund (CI2023E002, CI2024E001), the Innovation Team and Talents Cultivation Program of National Administration of Traditional Chinese Medicine (ZYYCXTD-C-202409), and the Major Increase and Reduction Project at the Central Level (2060302).
This article does not contain any studies with human or animal subjects.
The authors declare no competing financial interest.
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Supplementary Materials
Data Availability Statement
The original data presented in the study are included in the Supporting Information.




