Phthalates in Liquors

Keywords food safety spirits plasticizer phthalate acid ester PAE dinonyl-phthalate DNP 

The beverage sample used for this application was a white spirit, bought from a local liquor store. Chinese liquor typically contains 30-60vol% of ethanol. As phthalate esters are highly soluble in ethanol the extraction of phthalate esters using n-hexane as solvent is less effective (Dongliang, 2010). The removal of the major part of ethanol from the liquor before n-hexane extraction is necessary to avoid low recoveries. For optimization of the extraction procedure and recovery determination, one liquor sample was spiked with 4 mg/L concentration of a commercial phthalate standard. 

For the determination of the recoveries the standard solution was added to the sample to obtain a spiked solution at 0.80 mg/L concentration level. The results were compared with and without ethanol removal, shown in Table 4.22. After removal of ethanol before the extraction with n-hexane, good and consistent recoveries of the phthalate compounds in the range of 89-112% were obtained. 

Compound CAS Abbreviation Without ethanol removal recovery (%) With ethanol removal recovery (%) 

All measurements have been carried out using a single quadrupole GC-MS system equipped with split/splitless injector and liquid autosampler. 

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Lv, J., Liang, L. and Hubschmarm, H.-J. (2013) Determination of Phthalates in Liquor Beverages by Single Quadrupole GC-MS. Application Note AN10339, Thermo Fisher Scientific. 

Introduce 197 g. of anhydrous brucine or 215 g. of the air-dried dihydrate (4) into a warm solution of 139 g. of dZ-acc.-octyl hj drogen phthalate in 300 ml. of acetone and warm the mixture vmder reflux on a water bath until the solution is clear. Upon cooling, the brucine salt (dA, IB) separates as a crystalline solid. Filter this off on a sintered glass funnel, press it well to remove mother liquor, and wash it in the funnel with 125 ml. of acetone. Set the combined filtrate and washings (W) aside. Cover the crystals with acetone and add, slowly and with stirriug, a slight excess (to Congo red) of dilute hydrochloric acid (1 1 by volume about 60 ml.) if the solution becomes turbid before the introduction of... 

A solution of 447 g. (2 moles) of pure s-butyl hydrogen phthalate in 2 1. of warm acetone is treated with 790 g. (2.01 moles) of anhydrous brucine and the mixture is kept under reflux at about 40° for an hour. The solution is then heated to boiling and filtered hot. The solution is kept for several hours in a cold room or icebox, after which the first crop (Ai) of crude brucine d-s-butyl phthalate is filtered and washed with about 300 cc. of cold acetone. The combined filtrate and washings are concentrated to about 11., and a second crop (A2) is taken. Further concentration to about 400 cc. may yield a small third crop (A3). The final mother liquor is set atide. 

The described application follows the China regulation GB/T 21911-2008 for the determining of phthalates in food (Standardization Administration of China, 2008). The used sample preparation procedure was optimized from GB/T 21911-2008 with the ethanol removal from liquor beverages followed by an n-hexane extraction and GC-MS detection. The method is sensitive, rapid, and accurate and covers a wide linear concentration range to meet the need for trace level detection of phthalate esters in different types of beverages. 

Faolini and Divizia have succeeded in partially resolving inactive linalol into its optically active isomers hut only to the extent of optical rotations of + 1° 70 and — 1° 60 respectively. Linalol was converted into its acid phthalate, and an alcoholic solution of this compound was treated with the equivalent quantity of strychnine. By fractional crystallisation the laevo-rotatory salt, yielding dextro-rotatory linalol, separates first, leaving the more soluble dextro-rotatory strychnine salt, which yielded laevo-rotatory linalol in the mother liquor. 

Purification of the Crude Active Hydrogen Phthalates. The purpose of this step is to remove the small proportion of df-octyl hydrogen phthalate that still is present in the crude active forms. The active forms are crystallized separately from about 2 parts by weight of 90% acetic acid, in which the racemic form is much more soluble than the active forms. Two crystallizations are usually required to give products melting at 75° and having [a]o =t 48.4° (c = 5, 95% ethanol). The yield of the active forms at this point is about 70%. The crude di-form may be recovered from the acetic acid mother liquors and used in another run. 

Working in this way it is possible to obtain fairly readily about 50-55% of the calculated amount of pure brucine d-s-butyl phthalate the yield depends on how long the fractionation is continued and how the mother liquors are handled (see below). When large quantities of alcohol are to be resolved it is convenient to unite the material from several runs at this stage. 

The Worm of the alcohol can be obtained in 85-90% purity from the combined acetone and final methanol mother liquors by a rather laborious process of fractional crystallization aided by mechanical separation.137 140 Thus on long standing the acetone solution may deposit characteristic nodular aggregates of leaflets of nearly pure brucine 1-8-butyl phthalate, [a]n — 18.0° these are separated by filtration or decantation. The solution, upon concentration, may then yield more of the crude d-salt and then again the 1-salt. The method is tedious but gives rather good yields, especially when large quantities of material may be worked up in a leisurely fashion. 

Eight samples of commercially available liquor brands were analyzed using the described method. The concentrations of phthalate ester residues found are shown in Table 4.25. The samples tested showed that DEHP was found in low concentration in all samples, and DIBP, DBP, DEHP in many of the analyzed liquor samples. 

Table 4.25 The phthalate ester concentration in eight commercial liquor samples (mg/L).

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