Friday, 28 August 2015

The first chemical analysis concerning the legend of spinach's iron-richness

[Update: While the chemical analyses of Richardson (1848) may well be the first scientific research touching the iron-content of spinach, the folklore of the medical use of spinach is much older (see here).]

[For an introduction to the whole problem of the spinach-iron myth and its many ramifications read the last 7 posts of this blog (chronology: oldest post deals with oldest literature) and follow the links given in them. Beware, this myth is a mess concocted in over 160 years. What has never been discovered is the first source for spreading the opinion, during the second half of the 19th century, that spinach was a good source for dietary iron.]

As you can see from my comments under this earlier blog entry, the data of Thomas Richardson (1848. Beiträge zur chemischen Kenntnis der Vegetabilien. Annalen der Chemie und Pharmacie LXVII Bd. 3.)* may well be this first chemical research that has fed into the widespread opinion that spinach is a good source of iron.

*[This publication hangs in a digital limbo, because it has been concatenated to the end of the preceding article by C. List (1848. Ueber das sogenannte Terpentinölhydrat. Justus Liebigs Annalen der Chemie 67(3): 362-376. That is, you currently must download List (1848) in order to get Richardson (1848) at the end of that download. I've informed Wiley Online about the glitch, so you better check whether a separate publication by Richardson (1848) occurs after List (1848) before downloading List (1848).]

Educational publications from shortly after 1848 spread the belief that spinach was rich in iron and good for anemic people. For example, an encyclopaedia published by Brockhaus (1852. Die Gegenwart. Eine encyklopädische Darstellung der neuesten Zeitgeschichte für alle Stände. Siebenter Band. Leipzig: F. A. Brockhaus) stated at page 172: "Weiße Rüben enthalten nur eine geringe Menge von Eisen, Spinat dagegen viel." [White turnips contain only a little iron, spinach however a lot.] One year later, Aaron Bernstein published a popularisation of scientific findings in a work called "Aus dem Reiche der Naturwissenschaft: ein Buch für Jedermann aus dem Volke" (Berlin: Franz Duncker, 1853). At pages 157-158, Bernstein praised spinach as an iron rich and organic alternative to medicine for pale children. The patriarchic Hermann Klencke (1867. Chemisches Koch- und Wirtschaftsbuch oder die Naturwissenschaft im weiblichen Berufe. Leipzig: Eduard Kummer. p. 49) lists spinach among the food that is good for the breath and hematosis.

Richardson gave the values of various chemical compounds of various vegetables as percent values in relation to the raw ash and as percent values in relation to the pure ash (raw ash minus carbonic acid, charcoal and sand). The iron content, in particular, was given as the percent values of "Phosphorsaures Eisenoxyd," which literally translates as phosphor-acidic iron oxide but chemically means iron(III) phosphate (FePO4). Richardson's data sheet also provides the percent values of the ashes in relation to the fresh matter.

As I have argued elsewhere, it is false to calculate the portion of, say, the iron compound in the fresh matter by simply multiplying the portion of the iron compound in relation to the ash with the portion of ash in relation to the fresh matter. This leads to false values, because the ashes gain mass during combustion. Gaseous oxygen binds to the burning matter, and some products of combustion end up gaseous themselves (e.g. carbon dioxide), while others end up as solid ash (e.g. magnesium oxide). That is, the ashes gain matter through combustion that is not part of the fresh matter.

It is not anachronistic to call the above mentioned calculation a mistake in relation to Richardson's time, because Phlogiston theory had been questioned in the second half of the 18th century already, and experiments had  shown that metals gain mass during combustion. Hence Richardson's contemporaries and followers should have known that simply multiplying the portion of iron compound in ash times the portion of ash in fresh matter would yield false values for the portion of iron compound in the fresh matter.

Nevertheless, Bunge (1892) failed to correct the ash values accordingly in manipulating data from Wolff (1871) as shown here. Therefore, it seems likely that others have also simply multiplied the percent values of Richardson's data and drawn false conclusions. Or, anyway, it is interesting to reconstruct what conclusions might have been drawn from such a data manipulation.

As you can see from the table below, spinach comes out second after radish herbage. Assuming that the herbage of radish was usually not eaten, however, spinach would be the edible item with the highest iron content in Richardson's data set. Hence Richardson (1848) may well be the first source from which the widespread opinion sprang that spinach was a good source for dietary iron in turn.

Item portion of iron phosphate in raw ash times portion of ash in fresh matter portion of iron phosphate in pure ash times portion of ash in fresh mater
Ananas, ganze Frucht   

ditto Schopf   

Spargel                               1,25E-04 1,60E-05
Lauch, Zwiebel                        5,52E-04 6,11E-04
ditto Stengel                         6,76E-04 8,91E-04
Feige, ganze Frucht   

Walnuts, Kern   

ditto Schale

Gurke                                 1,19E-04 1,30E-04
Brocoli (Kohl), Herz                  2,02E-04 2,14E-04
ditto Blätter                        9,86E-04 1,06E-03
Blumenkohl, Herz                      2,80E-04 2,61E-04
Rettig, Wurzel                       1,20E-03 1,41E-03
ditto Kraut                          3,20E-03 4,54E-03
Kastanie, ganze Frucht                1,77E-04 1,93E-04
Erdbeere, ganze Frucht                3,69E-04 4,56E-04
Orange ditto   

Rhabarber, Stengel                    1,66E-04 1,91E-04
ditto Blätter                         2,62E-04 2,87E-04
Spinat                               1,28E-03 1,76E-03
(Kidney Beans) Bohnen                 3,09E-04 3,56E-04
Erbsen, Hülsen                        6,90E-05 8,00E-05
Pflaumen (greengages), ganze Frucht   1,80E-04 2,42E-04
Orleans-Pflaumen, Haut der Frucht     5,39E-04 6,63E-04
Orleans-Pflaumen, Fleisch derselben   9,50E-05 1,49E-04
Orleans-Pflaumen, Kern                5,76E-04 6,28E-04
ditto Samenschale                     9,40E-05 1,05E-04
Kirschen, ganze Frucht                1,47E-04 1,61E-04
ditto Stiel derselben                 4,74E-04 5,57E-04
Birne, ganze Frucht                   6,60E-05 8,00E-05
Apfel, ditto                          5,90E-05 7,20E-05
Artischoke                            4,86E-04 5,55E-04
Lattich                               Spur Spur
Endivie                               6,72E-04 8,71E-04
Stachelbeere                          2,94E-04 3,37E-04
Sellerie                              2,56E-04 2,85E-04
Möhre                                 2,46E-04 2,39E-04
Pastinak                              4,63E-04 5,53E-04
Values in scientific notation: 1,76E-03 means 1.76*10-3 or 0.00176. This portion would be equal to 176 milligram in 100 gram fresh matter.

P.S: The Genealogical World of Phylogenetic Networks has a new post with a phylonetwork illustrating the whole dataset of Richardson (1848).