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Mandrile 2020 - organotin migration from PVC food packaging by SERS

Mandrile and colleagues evaluated surface-enhanced Raman scattering (SERS) for detecting dibutyltin maleate (DTM) and tributyltin chloride (TBT) migrating from intentionally spiked PVC cling film into 3% acetic-acid food simulant. The study is useful food-contact leachate context, but it is not a market-occurrence survey because the PVC films were experimentally additivated. Organotin values are reported as compound-specific DTM/TBT or as tin equivalents and should not be collapsed into total tin or inorganic tin.

Key numbers

  • Source identity: Talanta 220 (2020) article 121408; DOI 10.1016/j.talanta.2020.121408; local readable PDF has 20 pages.
  • Food-contact matrix: an industrial food-grade PVC cling film described as 10 mm thickness in the extracted text was dissolved and re-cast after spiking with TBT, DTM, or both compounds.
  • Regulatory context stated by the authors: for organotin compounds, the specific migration limit was 0.05 mg of tin per kg of food; the paper gives corresponding legal limits of 0.15 mg/l for DTM and 0.14 mg/l for TBT.
  • Migration test setup: 5 cm2 film portions, 8.33 ml of 3% acetic-acid food simulant, proportional relationship 1 dm3 simulant per 6 dm2 packaging, 10 days at 40 ºC.
  • SERS calibration: DTM dynamic range 0-1 mg/l with reduced χ2 = 0.8; TBT dynamic range 0.5-5 mg/l with reduced χ2 =0.2.
  • SERS detection limits as described in different parts of the paper: abstract says DTM and TBT were detected down to 0.01 mg/l and 0.08 mg/l; the Results section reports TBT LOD 0.10 mg/l and LOQ 1.53 mg/l; the conclusion says TBT down to 0.1 mg/l.
  • ICP-MS calibration in 3% acetic acid: DTM R2 0.99, LOD 0.005 mg/l, LOQ 0.007 mg/l; TBT R2 = 0.99, LOD 0.027 mg/l, LOQ 0.092 mg/l.
  • UV-Vis DTM calibration: linear dynamic range 0.1 to 2.0 mg/l, reduced χ2 = 1.4, LOD 0.08 mg/l, and LOQ 0.13 mg/l.
  • Authors’ overall comparison: the organotin migration limit was exceeded for all tested spiked-PVC cases except PVC spiked with low-concentration DTM.

Spiked PVC-film loadings

Table 1 reports the following added organotin and corresponding tin loadings; the paper states uncertainty for all values is 0.1 mg/g.

PVC samplemg OTCs/g (PVC)mg Sn/g (PVC)
PVC + TBT l.c.0.70.3
PVC + TBT h.c.74.127.0
PVC + DTM l.c.0.60.2
PVC + DTM h.c.70.423.9
PVC + OTCs l.c. (DTM and TBT 50:50)0.70.3
PVC + OTCs h.c. (DTM and TBT 50:50)75.026.1

Migration results as compound concentrations

The Results prose reports SERS and UV-Vis compound concentrations in mg/l food simulant:

Sample and methodDTMTBT
PVC + DTM h.c., SERS0.41 ± 0.04 mg/lnot applicable
PVC + TBT h.c., SERSnot applicable10.72 ± 1.11 mg/l
PVC + OTCs h.c., SERS0.12 ± 0.01 mg/l4.16 ± 0.11 mg/l
PVC + DTM h.c., UV-Vis0.40 ± 0.27 mg/lnot applicable
PVC + OTCs h.c., UV-Vis0.61 ± 0.41 mg/lnot applicable

Table 2 migration results as tin equivalents

Table 2 reports mg(Sn)/kg (simulant) by method:

PVC sampleICP-MS (mg/kg)SERS (mg/kg)UV-Vis (mg/kg)
PVC + DTM l.c.0.004 ± 0.001> LOD; < LOQ> LOD; < LOQ
PVC + TBT l.c.0.049 ± 0.021> LOD; < LOQ-
PVC + OTCs l.c.-not reported in table cell> LOD; < LOQ
PVC + DTM h.c.0.273 ± 0.0540.14 ± 0.020.14 ± 0.09
PVC + TBT h.c.5.70 ± 2.523,91 ± 0.78-
PVC + OTCs h.c.-DTM 0.04 ± 0.01; TBT 1.52 ± 0.04DTM 0.21 ± 0.14; TBT -

Methods (brief)

The authors prepared spiked PVC films from dissolved PVC cling film and TBT/DTM stock solutions, then performed migration tests into 3% acetic acid under EU food-contact-material simulant conditions. Simulants were analyzed by direct-in-liquid SERS using 30 nm silver nanoparticles, by ICP-MS for tin, and by UV-Vis for DTM. ICP-MS used five tin isotopes (116Sn, 117Sn, 118Sn, 119Sn, 120Sn) with gallium isotopes as internal standards; high-concentration migration samples were diluted at 1:40.

Implications

Certification (HMTc): This paper should be used as food-contact organotin leachate context only. The measurements come from intentionally spiked PVC films and should not be pooled as representative market packaging occurrence, and the TBT/DTM values should remain organotin-specific rather than being converted into total or inorganic tin evidence.

Courses: The source is useful for showing how migration-test design, speciation, and method selectivity interact: SERS can distinguish TBT from DTM, while ICP-MS quantifies tin but cannot by itself distinguish which organotin species produced the signal.

App: If flexible food-packaging organotin context is surfaced, this source can support a method-context warning that PVC food-contact films can release organotin stabilizers under acidic simulant conditions, with the caveat that the tested films were deliberately spiked.

Wiki pages this source may touch

Verification notes

  • The readable sibling PDF was extracted with pdftotext -layout to /tmp/ingest_alt.txt; abstract, introduction, Materials and method, Table 1, Results, Table 2, Discussion, and Conclusions were checked against this page.
  • Identity checks before creation: DOI 10.1016/j.talanta.2020.121408, exact title phrase, author surname Mandrile, raw SHA-256 cbe37097d9dfadf1d101bec9c7f1368a5889a8f65b7da78774eeb54ec019c1b8, raw handle MFK_migration-study-of-organotin-compounds-from-food-p, and cite key mandrile2020-organotin-food-packaging-sers were searched in wiki/sources/ and evidence files; only intake/tracker CSV rows were found.
  • A corrupt sibling file, raw/Manual Fetch Kimi /June 8/Kimi_Agent_Download Corruption Issue/_extracted_may31_cat23_food_contact/cat23_food_contact/Migration Study of Organotin Compounds from Food Packaging.pdf, has SHA-256 932618e8a420c4204fc21ac9e6c058bc255f1b382c361995b6c1a0a3c9f2fd0a; pdftotext and pdfinfo fail with invalid xref/page-tree errors. The readable _2 PDF is used as the canonical raw file for this source.
  • Units are preserved as printed: mg/l, mg/kg, mg(Sn)/kg (simulant), mg/g, cm2, ml, dm3, dm2, and ºC. No conversion to ppb or µg/kg was performed.
  • Speciation check: the source measures organotin species DTM and TBT and tin-equivalent Sn by ICP-MS. This page does not treat organotins as total tin or inorganic tin.
  • The 3,91 ± 0.78 SERS value for PVC + TBT h.c. is copied with the source table’s comma decimal mark.
  • The page records the source’s regulatory migration-limit comparison as context only and does not propose any HMTc threshold.
  • Closed-vocabulary check: product routing uses the broad flexible food-packaging films row. No PVC-cling-film product or organotin ingredient slug was invented.

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
4039d202026-06-10scope: broaden ingest to the full upstream+downstream literature (marine, atmospheric, attribution, exposure, toxicology) — inclusion is the default