Caffeine Determination in Various Types of Coffee Brews and Studying the Effect of QuEChERS Method on Its Extraction Compare to Conventional Approach

Coffee is the most important and popular beverage in the world. The main differences between coffee and other beverages like tea is the variety of applied brewing techniques. Coffee is a complex chemical mixture of compounds including, caffeine, as a natural alkaloid. Besides its beneficial effect including enhancement in mental activity and alertness as well as improving the cognitive functioning, caffeine indicated adverse effects such as headache and anxiety when it is consumed in higher quantity. In terms of chemical extraction, it can be also considered as an interference when analyzing other pollutants, therefore, its removal from extract is of great interest. Therefore, the present study was designated to investigate the caffeine content of 18 various coffee-related products. Furthermore, the effect of two extraction techniques (QuEChERS and conventional) on caffeine removal from coffee extract was investigated.
 
Coffee brews including classical (boiled, French, moka and filtered coffees) and commercial brews (various types of espresso as well as instant and iced coffees) were prepared using Robusta, Arabica coffee or commercial powders. In conventional extraction approach, a 2.5 mL of coffee sample was treated with 0.1 mL each of Carrez solutions I and II to clarify the sample. The total volume was brought to 50 mL by the addition of 10% methanol (v/v). After centrifugation, the supernatant was filtered and analyzed using high-performance liquid chromatography coupled with a diode array detector (HPLC-DAD) at 273 nm. In QuECHERS approach, the effect of extraction solvent (acetonitrile and ethyl acetate) and sorbents (primary and secondary amines and, octadecyl silane) on caffeine removal was investigated and was compared to conventional approach as reference method. The extraction and clean-up were accomplished by two types of solvents and sorbents in the presence of sodium chloride and magnesium sulfate. Finally, caffeine was determined using HPLC-DAD at 273 nm.
 
According to the results, the two coffee varieties (Arabica and Robusta) were clearly separated by their caffeine contents as Robusta presented higher values in all classical brews. Among the classical brewing techniques, the coffee with the highest content of caffeine was moka brewed from roasted Robusta coffee, with a mean value of 1044 ± 26 mg/L. The caffeine content was also determined per serving (cup size) to determine the actual content received by consumers. Accordingly, among traditional brews the most caffeine-rich coffee was espresso type pod coffee, with a mean value of 1371 ± 16 mg/L, equivalent to 56 ± 0.6 mg/40 mL of serving size. The lowest mean caffeine content (13.4 mg / 240 mL) was found in iced coffee. With regards to caffeine extraction, with recovery of 101%, the conventional method was the most efficient approach for caffeine determination. Caffeine significantly reduced (around 20% compare to conventional approach) when QuEChERS was used as extraction technique which could be valuable for analysis of pesticides, which are usually present in small quantities in food samples like coffee. In general, the use of acetonitrile as well as the simultaneous application of PSA and C18 resulted in a significant decrease in caffeine content of Robusta coffee extract.
Here, different coffee brews were assessed and compared for their caffeine content (mg/mL and mg/serving). Technical differences like coffee varieties, coffee/water ratio or method of brewing (pressurized, fusion, filtering, etc) led to coffee brews with different caffeine profiles. Interestingly, despite the high concentration of caffeine in espresso types brews, they provided moderate coffee in terms of caffeine content per cup. On the other hand, classical methods in particular boiled, French and filtered Robusta coffee were rich in terms of caffeine per cup. When studying caffeine extraction, the efficiency of conventional method was significantly superior to QuEChERS approach as caffeine significantly reduced when QuEChERS was used as extraction method.