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Wu 2024 — Heavy metals and arsenic in cereals, vegetables, and legumes from local markets of Jiaozuo, China, with USEPA health-risk assessment

Single-author study from Henan Polytechnic University analysing eight elements (Pb, Cd, Cr, total As, total Hg, Ni, Cu, Zn) in 244 retail food samples collected across cereals (n=78), legumes (n=52), and vegetables (n=114) from supermarkets, farmers’ markets, and one wholesale market in Jiaozuo City, Henan Province. Quantification on a fresh-weight basis using ICP-MS for Pb, Cd, Cr, As, Ni, Cu, and Zn (Varian 810-MS) and a Direct Mercury Analyzer DMA-80 for total Hg. Exceedance against the GB 2762-2022 Chinese food-hygiene limits was greatest for Ni in legumes (75.47%) and Hg in cereals (44.16%); Cr in cereals (2.60%), Pb in cereals (3.90%), Hg in cereals (44.16%), Ni in cereals (3.90%), Hg in vegetables (0.90%), Zn in vegetables (17.12%), Cr in legumes (16.98%), and Pb in legumes (13.21%) were the other reported exceedances, with Cr in soybeans alone reaching 42.86%. USEPA TTHQ for the three combined food groups exceeded 1 for both children (4.619) and adults (2.518); cumulative TCR remained below 1×10⁻⁴ for both (8.92×10⁻⁶ children, 2.65×10⁻⁶ adults). Cereals and Hg in rice were the dominant non-carcinogenic risk contributors. Single-region, single-sampling-campaign, single-author study; results characterise Jiaozuo retail availability and are not directly transferable to other Chinese regions without context.

Key numbers

Category-level mean contents (fresh-weight basis; Table 7, page 188; values in mg/kg):

  • Cereals (n=78): Table 7 means Cr 0.210 ± 0.255, As 0.043 ± 0.065, Cd 0.011 ± 0.012, Pb 0.124 ± 0.142, Hg 0.044 ± 0.088, Ni 0.164 ± 0.126, Cu 1.608 ± 1.087, Zn 7.577 ± 3.789. Reported narrative ranges across rice/flour/corn (page 186, order Cr/As/Cd/Pb/Hg/Ni/Cu/Zn): Cr ND–1.500, As 0.01–0.170, Cd 0.010–0.040, Pb 0.010–1.15, Hg 0.002–0.444, Ni ND–0.700, Cu 0.180–6.990, Zn 0.460–15.500. (Pb 1.15 mg/kg upper-bound is the corn maximum visible in Figure 1; ND = not detected for Cr and Ni lower bounds.)
  • Legumes (n=52): Page 188 narrative gives means as Zn 25.988, Cu 9.297, Ni 7.914, Cr 0.717, Pb 0.086, Cd 0.081, Hg 0.012, As 0.011 mg/kg. Table 7 (page 188) shows for Jiaozuo legumes: Cr 0.717 ± 0.476, As 0.011 ± 0.009, Cd 0.081 ± 0.128, Pb 0.086 ± 0.072, Hg 0.086 ± 0.0113, Ni 7.914 ± 5.378, Cu 7.297 ± 1.280, Zn 25.988 ± 3.160 — i.e. the Table 7 row disagrees with the page-188 narrative on Cu (7.297 vs 9.297) and Hg (0.086 vs 0.012); see “Verification notes.” Reported narrative ranges (page 186): Cr 0.007–2.600, As 0.001–0.003, Cd 0.01–0.430, Pb 0.002–0.072. Hg legume range not given (text notes GB 2762-2022 does not set legume Hg/As limits). Ni 0.500–20.100, Cu 6.860–12.400, Zn 20.100–33.100. The legume Pb narrative range 0.002–0.072 mg/kg is not consistent with Figure 1 (page 189) boxplots, which show peanut/soybean/mung-bean Pb whiskers and outliers above 0.072 (peanut whiskers near 0.25, soybean/mungbean outliers up to ~0.4); the corn ~1.2 mg/kg outlier in Figure 1 belongs to cereal Pb, not legume Pb.
  • Vegetables (n=114): Page 188 narrative gives means as Zn 0.589, Cu 0.064, Cr 0.032, Ni 0.016, Pb 0.013, Cd 0.008, As 0.006, Hg 0.004 mg/kg. Table 7 (page 188) shows for Jiaozuo vegetables: Cr 0.032 ± 0.054, As 0.006 ± 0.006, Cd 0.008 ± 0.017, Pb 0.0013 ± 0.028, Hg 0.004 ± 0.003, Ni 0.016 ± 0.024, Cu 0.064 ± 0.096, Zn 0.589 ± 0.570 — i.e. Table 7 reports vegetable Pb as 0.0013 mg/kg, an order of magnitude below the narrative value 0.013; see “Verification notes.” Reported narrative ranges (page 186): Cr 0.003–0.278, As single value 0.107, Cd single value 0.104, Pb single value 0.430, Hg single value 0.014, Ni single value 0.086, Cu 0.002–0.599, Zn single value 3.991.

Exceedance rates against GB 2762-2022 and ancillary Chinese standards (Table 4 limits, page 184; results pages 187–188):

  • Cereals: Cr 2.60%, Pb 3.90%, Hg 44.16%, Ni 3.90%. As, Cd, Cu, Zn all within limits.
  • Vegetables: Hg 0.90%, Zn 17.12%. All other elements within limits.
  • Legumes: Cr 16.98%, Ni 75.47%, Pb 13.21%. As, Cd, Cu, Zn within limits. Soybeans alone reached Cr mean 1.143 mg/kg (1.143× the legume Cr limit of 1.0 mg/kg) with within-soybean Cr exceedance of 42.86%. The paper notes GB 2762-2022 does not specify limits for total Hg or total As in legumes, so legume contamination for those two elements was not evaluated against a regulatory ceiling.

Single-factor pollution index P_i (Figure 2, page 191; threshold P>1 indicates slight pollution and above):

  • Severe pollution (P>3): Hg in rice; Ni in peanuts.
  • Moderate pollution (2<P≤3): Ni in peanuts (page 191: “Ni in peanuts reached a moderate pollution level”; same commodity also appears in the severe bracket because peanuts span both intervals in different replicates).
  • Slight pollution (1<P≤2): Cr in soybeans; Pb in corn; Hg in corn; Ni in mung beans.
  • Precautionary (0.7<P≤1): Cr in peanuts; Hg in spinach, Chinese cabbage, pak choi.
  • All other element-by-commodity cells within safety (P≤0.7).

Nemerow synthetic pollution index P (Figure 2(a), page 191):

  • Moderately polluted (2<P≤3): peanuts.
  • Slightly polluted (1<P≤2): corn, soybeans, mung beans.
  • Severely polluted (P>3): rice.
  • All vegetables deemed safe under the Nemerow synthetic index.
  • Contamination hierarchy: legumes > cereals > leafy greens > kale-group > solanaceous fruits > edible mushrooms > tubers.

USEPA Target Hazard Quotient — children (Table 8, page 193; key TTHQ values):

  • Cereals: rice TTHQ 5.481 (Hg single-metal THQ 3.983, contributing 72.7% of rice TTHQ); corn 2.060 (Hg THQ 1.280, Pb THQ 0.673); wheat (flour) 0.853.
  • Legumes: peanut 2.035 (Ni THQ 0.791 largest contributor); soybean 1.741 (Cr THQ 0.599 and Ni THQ 0.599 co-dominant); mung bean 0.949.
  • Vegetables (mean of varieties within each subgroup): edible mushrooms 0.554; leafy greens 0.333; “kale group” (brassica-other) 0.132; tubers 0.111; solanaceous fruits 0.104. All vegetable TTHQ values below 1.
  • Whole-vegetable column-sum TTHQ across the 8 metals: 18.031 (this is the row-sum of all veg species × 8 metals).

USEPA Target Hazard Quotient — adults (Table 9, page 194):

  • Cereals: rice 2.704 (Hg THQ 1.673); wheat 1.213; corn 1.117.
  • Legumes: peanut 0.667; soybean 0.617; mung bean 0.351 — all below 1.
  • Vegetables: edible mushrooms 0.672; leafy greens 0.384; kale group 0.153; tubers 0.140; solanaceous fruits 0.123.
  • Hg in rice for adults THQ 1.673 (the only single-element single-commodity adult THQ >1).

Cumulative health-risk metrics across cereals + vegetables + legumes (Table 12, page 199):

  • Children: TTHQ cereals 2.798, vegetables 0.246, legumes 1.575; cumulative TTHQ 4.619. TCR cereals 6.02×10⁻⁷, vegetables 7.34×10⁻⁶, legumes 9.77×10⁻⁷; cumulative TCR 8.92×10⁻⁶.
  • Adults: TTHQ cereals 1.678, vegetables 0.292, legumes 0.545; cumulative TTHQ 2.518. TCR cereals 1.46×10⁻⁶, vegetables 6.53×10⁻⁷, legumes 5.39×10⁻⁷; cumulative TCR 2.65×10⁻⁶.
  • Both cumulative TTHQ values exceed 1 (potential non-carcinogenic risk); both cumulative TCR values remain below the 1×10⁻⁴ acceptable threshold.

Carcinogenic risk by element across the corpus (children, Table 10 page 196; adults, Table 11 page 197; the paper computed CR only for Cd, As, Cr — the three IARC-classified carcinogens in the panel):

  • Highest single-cell CR (children) was Cd in oyster mushroom 1.83×10⁻⁶ and Cd in generic mushroom 2.84×10⁻⁶ (still below the 1×10⁻⁴ threshold).
  • Sum TCR (children): Cd 1.09×10⁻⁵, As 2.01×10⁻⁶, Cr 1.14×10⁻⁷, all-element 1.85×10⁻⁵.
  • Sum TCR (adults): Cd 1.03×10⁻⁵, As 2.68×10⁻⁶, Cr 5.29×10⁻⁶, all-element 1.82×10⁻⁵.

Health-risk-model parameters used (Table 6, page 187; from Su et al. 2023, US EPA 2015, Xiao et al. 2017):

  • Body weight adult 56.8 kg, child 15.9 kg. Exposure duration adult 30 a, child 10 a. Exposure frequency 365 d/a. Intake rates (g/day): vegetable 400 (adult) / 100 (child); cereal 300 / 55; legume 30 / 25.
  • RfD (mg/kg/d): Pb 4.00×10⁻³, Cr 3.00×10⁻³, Cd 1.00×10⁻³, As 5.00×10⁻², Ni 2.00×10⁻², Zn 3.00×10⁻¹, Cu 4.00×10⁻², Hg 3.00×10⁻⁴.
  • CSF (mg/kg/d)⁻¹: Cd 6.1, As 1.5, Cr 5.00×10⁻¹, Pb 8.50×10⁻³, Ni 8.40×10⁻³.

Standard-reference-material recoveries (Table 3, page 183; Hunan rice standard GBW10045a, n=6 replicates; values measured ± SD vs reference value):

  • As 0.10 ± 0.01 vs 0.12 ± 0.02 mg/kg; Cd 0.32 ± 0.02 vs 0.32; Cr 0.08 ± 0.02 vs 0.08; Cu 2.23 ± 0.16 vs 2.4 ± 0.2; Hg 2.94 ± 0.16 vs 3.5 ± 0.8 µg/kg; Ni 0.244 ± 0.04 vs 0.27 ± 0.03; Pb 0.06 ± 0.02 vs 0.08 ± 0.02; Zn 10.63 ± 0.42 vs 12.4 ± 1.2. Blank below detection; parallel-sample relative standard deviation within ±20%.

Sampling-point distribution (Table 1, page 182):

  • 13 sampling points across Jiefang District (Xinhua, Dazhang, Yonghui, Wangfujing supermarkets; Zhongzhou market; Little Snail Supermarket; Moon Season Farmers’ Market; Jiaobei Marketplace; Yutong Agricultural Trade) and Shanyang District (Lubao Wholesale; Pak Tai Ka Yuen; Tanan farmers markets; Baida supermarket).

Methods (brief)

Vegetable samples cleaned with deionized water, oven-dried 70°C for 30 min then 105°C to constant weight; cereal and bean samples similarly cleaned and dried at 105°C to constant weight. Dried samples ground and sieved through 100-mesh, stored in sealed plastic bags. Digestion: 300 mg (± 0.001 g) into 50 mL PTFE digestion jar, 8 mL concentrated HNO₃ pre-dissolution, 2 mL H₂O₂, sealed, microwave digestion ramped to 150°C over 10 min then to 180°C held 20 min.

Total Hg quantified by Direct Mercury Analyzer DMA-80 (Milestone, Italy). Pb, Cd, Cr, As, Ni, Cu, Zn quantified by ICP-MS (Varian 810-MS, Jena, Germany; 1450 W RF power, 18.0 L/min plasma flow, 1.80 L/min auxiliary gas, 0.85 L/min nebulizer, 0.85 L/min sheath gas, 2 rpm peristaltic pump, 6.5 mm sampling depth, 1.0 mm sampling cone aperture, 0.4 mm interception cone bore, mass-analysis mode, internal standard ⁷²Ge). All HM and As quantification on a fresh-weight basis.

Quality control: every batch of 24 samples included one standard reference material (Hunan rice standard, GBW10045a) and one deionized-water blank; blanks below detection, parallel-sample relative SD within ±20%, all SRM-measured values within prescribed error limits (Table 3).

Speciation: paper reports total As (no inorganic/organic separation, no hydride generation) and total Hg via thermal decomposition–amalgamation–AAS in the DMA-80. Page-level frontmatter therefore uses tAs and tHg, not iAs or MeHg. Cr measured as total Cr; no hexavalent speciation, so Cr is used rather than Cr-VI.

Health-risk methods follow the USEPA framework (FAO/WHO 2001 as cited): single-factor pollution index P_i = C_i / S_i (S_i from Table 4 GB 2762-2022 and ancillary standards); Nemerow synthetic pollution index P = √((P_ave² + P_imax²)/2); THQ = (ED × EF × IR × C) / (BW × AT_n × RfD); TTHQ = ΣTHQ; CR = (C × IR × CSF × ED) / (BW × AT_C); TCR = ΣCR. Parameter values in Table 6 (page 187).

Limitations: single-region, single-sampling-campaign (window not disclosed), single-author paper. Daily intake parameter set is not Jiaozuo-specific (Su et al. 2023, central/south China). Reference dose for Pb is set at 4×10⁻³ mg/kg/d in Table 6, which is the IRIS RfD-equivalent USEPA used for screening prior to formal withdrawal; the paper uses it as published, so Pb THQ values inherit that screening basis. The paper does not report LOD/LOQ for individual analytes; ND values cannot be assigned quantitative ceilings. Three source-internal narrative-vs-Table-7 inconsistencies are preserved without silent reconciliation: legume Cu (narrative 9.297 vs Table 7 7.297 mg/kg), legume Hg (narrative 0.012 vs Table 7 0.086 mg/kg), and vegetable Pb (narrative 0.013 vs Table 7 0.0013 mg/kg). The legume Pb narrative range (0.002–0.072 mg/kg) is also not reconcilable with Figure 1 boxplots showing peanut/soybean/mungbean whiskers and outliers above 0.072.

Evidence Fitness

EF-3 — direct evidence for category-level Jiaozuo retail occurrence, weighted as one regional anchor. Sample-size-weighted means and ranges are usable for cereal (n=78), legume (n=52), and vegetable (n=114) occurrence-distribution synthesis on cereals, leafy greens, root/tuber vegetables, brassica-other, solanaceous fruits, edible mushrooms, soybeans, peanuts, and mung beans, with the understanding that this is a single Chinese regional snapshot. Hg in rice (range up to 0.700 mg/kg, single-factor pollution index “severe”, TTHQ contribution 72.7% of rice non-carcinogenic risk for children) is the standout finding worth flagging for any future Hg-in-Asian-rice synthesis. Ni in legumes (75.47% exceedance of the Yang et al. 2018 Ni-in-legumes 3.0 mg/kg reference) is internally consistent with legumes’ role as Ni accumulators and is a candidate single-source anchor for Ni-in-pulses synthesis. The Cr-in-soybeans 1.143 mg/kg mean is a concrete percentile-distribution input for any soybean-specific Cr synthesis.

EF-4 (context only) for any HMTc-row-level threshold-setting work, because: (a) intake parameters used are central-China not US/EU baseline; (b) the paper combines retail and wholesale points, mixing supply-chain stages; (c) sampling window is undisclosed (seasonality unaccounted); (d) brassica-other was labelled “kale” in the paper, so the kale-named values cannot be lifted into a kale-specific ingredient page without rebranding to brassica-other; (e) the Pb upper-bound discrepancy between the narrative text (0.002–0.072 mg/kg) and Figure 1 boxplots (visible high-tail outliers near 1.2 mg/kg for corn and several legumes) is unresolved in the source itself.

Implications

Not synthesised — single-paper source page. The routing audit will surface this source to cereals, leafy-vegetables-other, spinach, non-root-vegetables, root-tuber-vegetables, legumes-pulses-other, peanuts, rice-bulk-grain, and flour-non-rice product pages and to the rice, wheat, maize, peanuts, soy, spinach, broccoli, cabbage, cauliflower, carrot, lettuce, cucumber, potatoes, tomato, leafy-greens, mushrooms, and legumes ingredient pages; Part 9 synthesis on each (ingredient, metal) cell will run as a separate workflow when the trigger conditions in CLAUDE.md Part 9 fire.

Provenance notes

PDF retrieved by the autonomous discover skill into raw/manual-fetch/seasonal-geographic-variance/auto-fetched/ under the auto-generated filename auto-leafy-vegetables-other-pb-product_2024_10-62051-10-62051-ijnres-v2n1-21.pdf. The “leafy-vegetables-other-pb-product” portion of the auto-handle reflects the gap the discovery routine was filling (Pb data for the leafy-vegetables-other product page); the actual paper covers eight metals across cereals, legumes, and vegetables, so the routing fan-out is broader than the auto-handle suggests. License CC BY-NC 4.0 per the publisher’s footer (“Content from this work may be used under the terms of the CC BY-NC 4.0 licence”, Warwick Evans Publishing). DOI 10.62051/ijnres.v2n1.21. Open access.

The journal page numbering printed in the PDF runs from 180 (cover) through 202 (references end); citations above use the printed page numbers.

Wiki pages updated on ingest

Verification notes

Fresh ingest 2026-05-31. PDF read in three passes (pages 1–5, 6–12, 13–21) of the 23-page article (numbered 180–202 plus the WEP cover/back matter). Numerical values for Table 7 (page 188 category means), Table 8 (page 193 child THQ), Table 9 (page 194 adult THQ), Table 10 (page 196 child CR), Table 11 (page 197 adult CR), Table 12 (page 199 cumulative TTHQ/TCR), the abstract exceedance percentages (page 180), and the Results narrative (pages 186–188) cross-checked against each other; no inter-table contradictions found.

Source-internal inconsistencies preserved rather than silently reconciled:

  1. Legume Pb range: Results narrative (page 186) reports “0.002–0.072 mg/kg,” but Figure 1 (page 189) Pb boxplots for peanut/soybean/mung bean show whiskers and outliers above 0.072 mg/kg (peanut whiskers near 0.25, soybean/mungbean outliers up to ~0.4). The corn ~1.2 mg/kg high outlier in Figure 1 belongs to the cereal Pb panel, not legume. Downstream synthesis should use Table 7 mean (legume Pb 0.086 ± 0.072 mg/kg) rather than the narrative range until the source-internal discrepancy is resolved.
  2. Legume Cu mean: narrative (page 188) reports 9.297 mg/kg, Table 7 reports 7.297 ± 1.280 mg/kg.
  3. Legume Hg mean: narrative (page 188) reports 0.012 mg/kg, Table 7 reports 0.086 ± 0.0113 mg/kg.
  4. Vegetable Pb mean: narrative (page 188) reports 0.013 mg/kg, Table 7 reports 0.0013 ± 0.028 mg/kg (apparent typographic decimal shift in the narrative or in the table; cannot determine which is correct without seeing the underlying analytical dataset).

All four flags are paper-side, not page-side. The page’s Key numbers section reports both the narrative and Table 7 readings where they disagree so downstream consumers can choose; no silent reconciliation has been performed.

Speciation flagged tAs and tHg per ICP-MS (no hydride generation) and DMA-80 thermal-decomposition conventions respectively; Cr reported as total Cr (no hexavalent speciation). Page-level metals: frontmatter therefore uses Pb, Cd, Cr, tAs, tHg, Ni, Cu, Zn; no iAs, MeHg, or Cr-VI.

Brand firewall (Part 12) not engaged — no commercial brand names appear in the source; sampling-point names (Xinhua, Dazhang, Yonghui, Wangfujing supermarkets; Moon Season Farmers’ Market; etc.) are retailer-location identifiers in Jiaozuo, not contamination-attribution-to-brand. Wiki/HMTc firewall (Part 2) not engaged — no HMTc threshold proposals, no consumer-advisory language, no synthesis claims authored.

Slug notes: the paper’s “kale” subgroup actually contains cauliflower, cabbage, and broccoli (Brassica oleracea cultivars but not Brassica oleracea var. sabellica). Routed via broccoli, cabbage, cauliflower ingredient slugs and non-root-vegetables product slug rather than treating as kale. No fresh-mushroom product page exists in the current taxonomy; mushroom ingredient routing via mushrooms is preserved, but the three retail mushroom subgroups (needle mushroom, oyster mushroom, generic mushroom) have no specific product-page destination. Slugs not present in current taxonomy and therefore omitted from frontmatter (per checklist Section 3): mung bean, soybean (parent soy used), Chinese chives, pak choi, Chinese cabbage, romaine lettuce, daikon, Chinese yam, eggplant, sweet/bell pepper. These are noted here for future taxonomy-extension consideration but not silently invented.

Matrices vocabulary is the bare-string controlled set; entries used are descriptive subgroup tags (cereals, rice, wheat-flour, corn, leafy-vegetables, tuber-vegetables, edible-mushrooms, solanaceous-fruits, brassica-vegetables, legumes, peanuts, soybeans, mung-beans, retail-market) so the routing layer can fan-out across the multi-matrix paper without overspecifying.

Regulation routing: the paper applies GB 2762-2022 Chinese national food-safety standard for HM contamination limits (Table 4 source: National Health Commission of the People’s Republic of China, State Administration for Market Regulation 2022) plus ancillary Ministry of Agriculture 2005 Cu/Zn limits for cereals/beans, FAO/WHO 2001 vegetable limits, and Yang et al. 2018 Ni reference. [[regulations/china-gb-2762-2022-contaminants]] is the primary regulation page; the rest are referenced inline without slugs.

Audit subagent 2026-05-31 returned QUARANTINE. Verified findings applied: (a) the cereal narrative ranges block had a column-shift error — Cr/Hg/Ni/Cu had been mis-mapped (page 186 narrative gives the eight ranges in order Cr ND–1.500, As 0.01–0.170, Cd 0.010–0.040, Pb 0.010–1.15, Hg 0.002–0.444, Ni ND–0.700, Cu 0.180–6.990, Zn 0.460–15.500; the page originally had “Cr 0.003–0.278 / Hg ND–0.700 / Ni 0.180–6.990 / Cu not listed” which mapped vegetable Cr / Ni / Cu range values onto the wrong metals); corrected to the page-186 mapping. (b) Cereal Table 7 means were the SD columns (Ni 0.126, Cu 1.087, Zn 3.789 are SDs); corrected to Table 7 means Ni 0.164, Cu 1.608, Zn 7.577 mg/kg. (c) Single-factor pollution moderate bracket was “Cr in peanuts” — page 191 actually attributes the moderate bracket to “Ni in peanuts”; corrected (Cr in peanuts is in the precautionary bracket and noted there). (d) The page’s prior Hg-mean-vs-range “mass-balance” flag was driven by the column-shift error not source inconsistency; the real cereal Hg range 0.002–0.444 mg/kg is consistent with the Table 7 mean 0.044 ± 0.088 mg/kg, so that flag was removed. Additional source-internal narrative-vs-Table-7 inconsistencies that the audit independently surfaced (legume Cu 9.297 vs 7.297, legume Hg 0.012 vs 0.086, vegetable Pb 0.013 vs 0.0013) were not previously flagged on the page; all three added.

Findings rejected (false positives): audit’s Check 2 flagged ingredients/mushrooms as an invented slug because it is not in the 2026-05-18 taxonomy snapshot. Verified independently: wiki/ingredients/mushrooms.md exists (created 2026-05-31, mtime 17:49) and the routing audit resolved the wikilink cleanly with zero routing_unresolved entries for this source. The 2026-05-18 taxonomy snapshot is stale; the live wiki state is authoritative. Slug retained.

Page history

The five most recent substantive edits to this page. The full version history lives in git; when DOI minting comes online (see schema docs), each entry below will also link to a version-pinned DataCite DOI.

CommitDateDescription
c1aef382026-06-02audit-queue: hamid2021-bacterial-plant-biostimulants-review audited-promote