Tag: trace elements

  • 98.5% Hydroxyapatite. The Other 1.5% Came From the Shell.

    98.5% Hydroxyapatite. The Other 1.5% Came From the Shell.

    Indonesia produced 67,201,200 kg of eggshell waste as the world’s eighth-largest egg-producing nation in 2017. Most of it goes to landfill, where it decomposes into ammonia, hydrogen sulfide and amines, and attracts what that attracts. Converting that stream into a biomaterial is a genuinely good idea, and it is the idea this entire industry rests on.

    It also means the feedstock is an agricultural product, with an agricultural product’s variability. So the useful question is not whether eggshell makes good hydroxyapatite. It is what else comes along.

    What a shell is made of

    El Milla, Hartami, Priyanto and Adrian, working at Universitas Brawijaya in Malang, published exactly that measurement in the Malaysian Journal of Medicine and Health Sciences in April 2023.

    They start with the shell itself. Calcium carbonate makes up 94–97% of an eggshell’s chemical components, with 3–4.5% organic content. Alongside it sit small quantities of other things: MgO at 0.83%, SO₃ at 0.66%, SrO at 0.43%, plus P₂O₅, Al₂O₃, K₂O, SiO₂ and Cl₂O₃.

    Their material was made by the hydrothermal route from Golden Comet chicken eggshells collected in Serang, Banten — milled to 100 mesh, calcined at 1000 °C for five hours to convert the carbonate to calcium oxide, then reacted with diammonium hydrogen phosphate at a Ca/P mole ratio of 1.67 and held at 230 °C for 48 hours. Particle size analysis put the average grain size at 243.4 ± 5 nm.

    98.5, and the remainder

    The X-ray diffraction result is a good one. The synthesised material came out at 98.5% hydroxyapatite.

    The remaining 1.5% was silica — and the paper does not leave its origin ambiguous. The impurity, it says, “came from the egg shell which was used as the starting material for the synthesis.”

    That is the sentence worth keeping. The contaminant was not introduced by poor handling or a dirty vessel. It was in the feedstock, it survived 1000 °C and 48 hours of hydrothermal synthesis, and it arrived in the product. There were also peaks in the diffractogram the authors could not assign — “not compounds of the elements Ca, Si, O, H, and P” — which they marked and reported rather than quietly smoothing away.

    Their own conclusion notes the material is a good candidate “but other strategy needed to eliminate the impurities especially for tissue regeneration material.”

    Why the trace table exists

    Set this beside ISO 13779-1, which caps arsenic at 3 mg/kg, cadmium at 5, mercury at 5 and lead at 30, with a total ceiling of 50 mg/kg for metals with adverse biological reactions.

    Those limits can look like bureaucratic furniture until you have read a paper that traces a product impurity directly back to the raw material it was made from. A biogenic feedstock inherits its source’s composition — the beneficial trace elements everyone advertises, and the ones nobody puts on a label, by the same mechanism. Magnesium and strontium are sold as advantages. Silica arrived by exactly the same route and is sold as nothing at all.

    None of which argues against eggshell as a source. It argues against treating “naturally derived” as though it settled the purity question, when it is the reason the question has to be asked.

    Chickens are fed differently in different places, and their shells reflect it. Which makes the composition of the feedstock a supplier variable like any other — one that a serious producer measures per lot, and an unserious one describes in a marketing sentence.

    Sources

    El Milla L, Hartami E, Priyanto R, Adrian AGW. “Synthesis and Characterization of Eggshell Based Hydroxyapatite Nanoparticles: X-ray Diffraction and Spectroscopy Analysis.” Malaysian Journal of Medicine and Health Sciences, 19(SUPP5):15–18, April 2023 (open access) — medic.upm.edu.my. Trace-element limits from ISO 13779-1:2008(E), Table 1 — iso.org/standard/43826.html.

  • “Meets ISO 13779.” The Standard Says It Does Not Apply to Powder.

    “Meets ISO 13779.” The Standard Says It Does Not Apply to Powder.

    The certificate of analysis runs to a single page. Assay, appearance, loss on drying, heavy metals, a Ca/P figure — and then, near the bottom, the line that ends most procurement conversations before they start: conforms to ISO 13779.

    It is a reassuring line. ISO 13779 is the international standard for hydroxyapatite in surgical implants, and a supplier willing to name it is a supplier submitting to an external rule. So the sensible next step is the one almost nobody takes: open the standard and read the first clause.

    Clause 1

    ISO 13779-1:2008, Implants for surgery — Hydroxyapatite — Part 1: Ceramic hydroxyapatite, opens its scope like this: “This part of ISO 13779 applies to hydroxyapatite blocks.”

    Then it says what it does not apply to: “hydroxyapatite coatings, hydroxyapatite powder or nanoparticle-type and calcium phosphate ceramics which are not mainly composed of crystalline hydroxyapatite.” In case the point is missed, a separate sentence repeats it: “This part of ISO 13779 does not apply to nanoparticle-type materials.”

    Powder is excluded by name. Nanoparticles are excluded twice.

    None of which makes the supplier dishonest. Part 2 of the standard covers thermally sprayed coatings, Part 3 covers the chemical analysis and characterisation methods, Part 4 covers coating adhesion. A powder house may well run its material against the Part 3 methods and get good numbers. But “conforms to ISO 13779” on a powder certificate is a claim against a document whose own scope clause excludes the product it is printed on.

    What the standard actually demands

    Here is the part that reframes the whole exercise. Suppose the standard did apply. What would passing it prove?

    Clause 4.3 sets the crystalline phase composition: “hydroxyapatite shall be 50 % mass fraction or greater”, while α-tricalcium phosphate, β-tricalcium phosphate, tetracalcium phosphate and calcium oxide “shall each be equal to or less than 5 % mass fraction.” The definition backs this up — “ceramic hydroxyapatite” is defined in the standard as material containing “more than 50 % mass fraction of crystalline hydroxyapatite.”

    Fifty per cent. A material can be half something else and still be ceramic hydroxyapatite under ISO 13779-1.

    The remaining requirements are tighter and more useful. The calcium-to-phosphorus atomic ratio must fall between 1.65 and 1.82. The hydroxyapatite phase must show a crystallinity value not less than 95 % of the fully crystalline reference. And Table 1 sets hard trace-element ceilings in mg/kg: arsenic 3, cadmium 5, mercury 5, lead 30 — with a further rule that “the maximum allowable limit for metals having adverse biological reactions shall be a total of 50 mg/kg.”

    Those are the numbers worth having on a certificate. They are also the numbers most powder certificates summarise into two words: heavy metals, followed by a single pooled figure that tells you nothing about which metal.

    The question that replaces the line

    So the reassuring line turns out to be the least informative thing on the page — a standard cited for its authority rather than its content, against a product it excludes, with a purity floor of 50 % that no one intends you to notice.

    The replacement is not a longer certificate. It is four specific asks: the four trace elements reported individually against those ceilings, the Ca/P ratio as a measured number, the crystallinity value, and the phase breakdown with each secondary phase named and quantified. A supplier who can produce those every lot is telling you what their process does. A supplier who answers with a standard’s name is telling you what their marketing does.

    Sources

    ISO 13779-1:2008(E), Implants for surgery — Hydroxyapatite — Part 1: Ceramic hydroxyapatite, second edition 2008-10-01, ISO/TC 150/SC 1 — scope (clause 1), definitions (3.1), and requirements (4.1–4.4, Table 1). Standard catalogue entry: iso.org/standard/43826.html. The related parts are ISO 13779-2 (thermally sprayed coatings), ISO 13779-3 (chemical analysis and characterisation of crystallinity ratio and phase purity) and ISO 13779-4 (coating adhesion strength). ASTM F1185, Standard Specification for Composition of Hydroxylapatite for Surgical Implants, is listed in the standard’s own bibliography.