HOP STORAGE INDEX INDICATOR OF A BREWING QUALITY

Majda VIRANT, Duica MAJER Institute of Hop Research and Brewing alec, Cesta alskega tabora 2, 3310 alec, Slovenia e-mail:majda.virant@guest.arnes.si e-mail:dusica.majer@guest.arnes.si

ABSTRACT Hop Storage Index (HSI) could be used as an indicator of hop freshness and therefore gives the user of hop (the brewer) a more accurate insight and confirmation on appropriate handling of hops during picking, storage and processing. In our laboratory we tested an influence of late hop-picking and storage on hop freshness on four Slovenian and one foreign hop varieties. Immediately after hop picking (time of technological ripeness) we determinated the HSI by using the ASBC H-6,12 method and the - acids contents after the EBC 7.4 method. The samples of raw hops picked up at the time of the technological ripeness were than stored at temperatures 0C and +20C and the analyses were performed again after one, two, three and six months. To determine changes of - acids contents and HIS in time of physiological ripeness, 30 plants of each variety were left on the field and were picked and analysed in same time intervals (after one, two and three months), last samples were picked by the end of November. The results show that in time of physiological ripeness oxidation processes run slower when compared to storing of hops at +20C for one, two, three and six months of storaging as was demonstrated by a higher HIS in stored hops at +20C. Hops picked in time of physyological ripeness has the HSI in terms of A275/325 the quality of fresh hops. INTRODUCTION Storage stability and Hop Storage Index (HSI) are well known characteristics of hop cultivars which can be influenced by proper handling during storage, processing and production /1/. When the situation on the hop market is unfavourable and changing is has become an important issue and financial concern for the producer (hopgrower) to maintain hop quality. With storage and delayed sale, these two parameters are very important in determinating brewing value of hops /2/. The chemical composition of hops depends on hop variety, growing district, growing conditions, crop, harvesting time and on drying and storage conditions. Hops are picked when fully ripe, i.e. in the time of its 'technological ripeness'. The contents of bittering substances as

well as that of -acids depends on the ripening stage of hops. Early harvesting can mean up to 20 % lower values, late harvesting can lower them for as much as 10 % /1/. The lupulin glands of hops contain an endogenous anti-oxidant which protects the resins whilst the cones are still attached to the plant. The protection also lasts for a time after harvesting providing the glands remain unruptured, however significant proportion of the glands do become damaged during this process /3/, /4/. This is also one of the reasons why oxidation processes in time of physiological ripening run much slower on the plant when compared with stored hops. Packing into rectangular bales can cause lupulin glands crushing, depending on the weight of the bales or the pressing pressure. Hops with intact lupulin glands are consequently more stable during storage /5/. During storage in bales or pellets oxidation processes take place that cause loss of bitter substances, hop oil and polyphenols. Oxidation products significantly change beer taste, and therefore lower brewing value of hops /9/. The rate of loss depends on the storage temperature, the amount of air present and the hop variety. The lower the temperature, the less the hops deteriorate. It has been shown that the rate of loss halves for every 15C (27 degrees F) drop in temperature /6/. Oxygen is definitely bad for - acids content and are responsible for the cheesy aroma detected in old hops /7/. Oxidized - acids loss their bitterness and cannot be isomerized. Because - acids form bitter compounds when they are oxidized, some believe that this result of oxidation makes up for the loss of -acids /8/. The bittering power of old hops is not solely due to their alpha acid content and it has been found that as little as 20% of the total bitterness of beer brewed with old hops was derived from this source. The loss of alpha acid (LCV) in old hops is not paralleled by an equivalent loss in organoloptic bitterness, this is because oxidation of -acid results in the formation of bitter tasting products. For this reason the LCV of hops at harvest of most varieties remains the most reliable data for the calculation of hop additions to the cooper. Where old hops are concerned the ratio of -acid to -acid affects the perceived brewing bitterness of a hop variety. Modern high - varieties have ratio in the order of 3:1 and when oxidation occour the concentration of oxidised -acid product is insufficient to make up for the loss of -acids /4/. It has been proved that cold storage and anaerobic contition are necessary for preserving hop quality. Optimal conditions would be in a cold-storage chamber at 00C /13/. The Hop Storage Index (HSI) was formulated for assessing the brewing value of old hops and also the stability of hop varieties /4/. HSI is important for the brewer who buys and uses hop pellets to indicate hop freshness and gives an insight in hop handling until delivery (picking, drying, storage, processing and transportation). The HSI will increase with the three basic contributors: time, temperature nad hop damage /10/. Varieties of hops differ in their original ratios, but an HSI of less than 0,28 to 0,31 will normally indicate that the hops are fresh and have been handled well /9/. Aged hops can have an index of up to 0.690 and still contribute to flavor characteristics of the particular beer or ale brewed /10/. Hop grower should store hops in a cold-storage chamber at 00C to preserve HSI during longer storage time before hop delivery. During six months of storage of raw hops in bales the average decrease in -acids content (Method EBC 7.4.) in moderate storage with up to 300C was 42% relative, in good storage with up to 200C 31% relative and in cold storage with about 30C the relative loss was 8% /11/. In this time HSI increased in moderate storage to 120% relative, in good storage to 93% relative and in cold storage to 23% relative /11/.

If -acids content in hops before storage was 6,5% w/w (Method EBC 7.4), after storage in bales for six months in unsatisfactory storage it lowerd to 3,8% w/w, in good storage to 5,4% w/w and in cold storage to 5,9% w/w. Hop Storage Index before storage was 0,30, after six months in bales in unsatisfactory storage it was 0,66, in good storage 0,58 and in cold storage 0,37 /12/. The method of determinating of Hop Storage Index employs the American Society of Brewing Chemists spectrophotometric technique of hop analysis.The HSI is defined as the ratio of absorbance at 275 nm to the absorbance at 325 nm of an alkaline methanolic solution of a non-polar extract of hops. It is often written as A275/A325. The absorption values of and -acids extracts are maximal at 325 nm and minimal at 275 nm. Oxidised - and -acids extracts have maximum absorption at about 250-280 nm. Oxidation of the hops is accompanied by a decrease in A325 and an increase in A275, therefore the HSI ratio increases. This ratio may be used to adjust the hopping rates for old hops that have lost up to 35% of their initial of - and -acids /4/. MATERIAL AND METHODS Experiments were carried out on four Slovenian hop varieties Savinjski Golding, Aurora, Bobek, Celeia and German variety Magnum which were grown in Savinja Vally region. Immediately after picking (technological ripeness) and drying we determinated Hop Storage Index (HSI) according to method ASBC H-6,12 and -acids content with method EBC 7.4. Samples were than packed into woven polypropylene bags (containing cca. 100 g hops in cones) and stored in cold-storage chamber at 0C and in dark place at 20C respectevely. The analyses were performed after one, two, three and six months. To determine changes of acids content and HIS in time of physiological ripeness, 30 plants of each cultivar were left on the field and were picked and analysed in same time intervals (after one, two and three months).

RESULTS AND DISCUSSION Results show comparison of storage stability and Hop Storage Index on varietes Savinjski Golding (SG), Celia (CE), Aurora (AU), Bobek (BO) and Magnum (MA), stored in coldstorage chamber at 0C and in dark place at +20C. Results are expresed in % relative of acids content decrease and % relative of HSI increase. As shown in Figure 1, after one month of storage at 0C -acids content remained unchanged with all varieties, after two months a slight decrease is noted with varieties Celeia, Bobek and Magnum. After three months we can see some decrease in all varieties (ranging from 2 % rel Aurora up to 5,3 % rel - Bobek). After six months of storage the changes were still quite small, ranging from 8 % rel - Magnum to 17,3% rel - Bobek. That practically means that with variety Bobek -acids content lowered from starting 5,8% w/w to 4,8% w/w, which is a decrease in 1% w/w after six months.

Storage at +200C (see Figure 2) causes a decrease in -acids content with all varieties (from 3,2 % rel - Magnum to 13,8% rel - Bobek). During later storage -acids content decreases further and ranges from 26,6% rel - Aurora to 39,7 % rel - Bobek. In terms of w/w, the starting -acids content lowered from 5,8% w/w to 3,5% w/w which represented the loss of 2,3% w/w. When compared to loss of -acids content in time of physiological ripening (Figure 3) and storage at +20C, we found comparable values after three months of physiological ripening and six months of storage. With variety Magnum we also noted an increase in -acids content after one month of ripening for 10,3% rel which indicated that at the time of picking (August 30th, 2002) this variety has not reached technological ripeness. Hop Storage Index expresed in % rel increase (Figure 4) has increased after two months of storage in cold-storage chamber only with variety Bobek for 2,1% rel, after three months increases were noted with all varieties from 2% rel Magnum to 3,1% rel Bobek. After six months increases ranged from 27,6 % rel - Aurora to 47,6 % rel Bobek. According to HSI, expressed as A275/A325, which was with Aurora 0,37 and with Bobek 0,56, these hops could still be regarded as fresh hops that have acceptable brewing value. Figure 5 shows that % rel increase of HSI in hops stored in unsatisfactory conditions rises in all varieties after one month and increases further with time. After six months % rel increase of HSI ranges from 52,3% rel - Magnum to 69,3% rel Bobek. In terms of A275/A325 HSI ranged from 0,54 Magnum to 0,74 Bobek. After one month of physiological ripening we noted no increase in HSI (Figure 6), after two months values were comparable to HSI measured after three months of storage in cold-storage chamber. After three months of physiological ripening the increase in HSI was considerably lower than after six months of storage in cold-storage chamber and also after three months of storage at +20C. The results also show that plants of all varieties that were left on the field after time of their technological ripeness to the time of physiological ripeness (end of November) had their HSI, expresed as A275/A325 from 0,29 Magnum to 0,35 Bobek. The later shows that late-picked hops preserve their HSI and could be regarded as fresh hops with good brewing value, while the -acids content loss ranges from 13,5% rel Magnum to 31,7% rel Bobek. CONCLUSIONS Brewing value of hops after storage is affected by three basic contributors: time, temperature, and hop damage.To preserve good brewing value of raw hops and hop products (-acids content , Hop Storage Index) it is important to store hops until further processing or sale in a cold store cold storage chamber at 0C. Losses of -acids content in raw hops of varieties Savinjski Golding, Celeia, Aurora, Bobek and Magnum after six months of storage at 0C were quite low, the average loss was 11,9% rel. Losses of -acids content in raw hops of varieties Savinjski Golding, Celeia, Aurora, Bobek and Magnum after six months of storage at +20C were high, the average loss was 31,1% rel.

Losses of -acids content in physiologically riped hops are comparable to values measured in hops picked at the time of technological ripeness and stored in warehouse for six months at +20C. The average loss of -acids content was 27,2% rel. After six months of storing raw hops in cold warehouse at 0C, all the varieties have their HSI, expressed as A275/A325 in ranges of fresh hops. After six months of storing raw hops in an unsatisfactory warehouse at +20C, HSI expressed as A275/A325 lies in ranges of aged hops, indicating poor brewing value. In three months period of physiological ripening oxidation processes run slower than during storing at +20C. According to HSI, expressed as A275/A325, the late picked hops are regarded as fresh hops.

Zusammenfassung Der Brauwert des Hopfens nach der Lagerung wird von drei grundlegenden Faktoren beeinflusst: Zeit, Temperatur und Schdigung des Hopfens. Zur Erhaltung eines guten Brauwertes von Rohhopfen und Hopfenprodukten (-Suregehalt, HSI-Index [Hop Storage Index, Hopfenlager-Index]) ist es wichtig, den Hopfen bis zur weiteren Verarbeitung oder zum Verkauf in einem khlen Lager bzw. Khllager bei 0 C zu lagern. Der mittlere Verlust des -Suregehalts beim Rohhopfen der Sorten Savinjski Golding, Celeia, Aurora, Bobek und Magnum nach sechs Monaten Lagerung bei 0 C war mit 11,9 % (rel.) recht gering. Der mittlere Verlust des -Suregehalts beim Rohhopfen der Sorten Savinjski Golding, Celeia, Aurora, Bobek und Magnum nach sechs Monaten Lagerung bei +20 C war mit 31,1 % (rel.) hoch. Der Verlust des -Suregehalts bei physiologisch gereiftem Hopfen waren mit den gemessenen Werten fr Hopfen vergleichbar, der zum Zeitpunkt der technologischen Reife geerntet und im Lager fr sechs Monate bei +20 C gelagert wurde. Der mittlere Verlust des -Suregehalts betrug 27,2 % (rel.). Nach einer sechsmonatigen Lagerzeit des Rohhopfens im Khllager bei 0 C haben alle Sorten ihren HSI, in A275/A325 ausgedrckt, in der Grenordnung von Frischhopfen. Nach sechsmonatiger Lagerzeit in einem unzureichenden Lager bei +20 C liegt der in A275/A325 ausgedrckte HSI im Bereich gealterten Hopfens, was einen schlechten Brauwert anzeigt. Nach einer dreimonatigen physiologischen Reifezeit verlaufen die Oxidationsprozesse langsamer als whrend einer Lagerung bei +20 C. Nach dem HSI-Wert, als A275/A325 ausgedrckt, wird spt geernteter Hopfen als Frischhopfen betrachtet.

REFERENCES /1/ Narziss, L.: Die Tecnologie der Wrzebereitung 6. Auflage, 1985, 68-69, 63-77 /2/ Virant, M., Pavlovic,M.: A quality circle from a hop grower to a brewer. Proceedings of the Technical Commission I. H. G. C. of the XLVIII th International Hop Growers Congress. Canterbury, England 6.-10.August 2001. /3/ Nickerson, G.B., Likens, S. T.: Journal of the American Society of Brewing Chemists,

1979, 34 184. /4/ Stevens, T. J.: Brewing Science &Tecnology, Series II, Volume 1 Hops, 1987, 101-112. /5/ Foster, A.: The Quality Chain from hops to hop product. . Proceedings of the Technical Commission I. H. G. C. of the XLVIII th International Hop Growers Congress. Canterbury, England 6.-10.August 2001. /6/ Skinner, R. N.&authors: The Effect of Storage temperature on the Stability of the alpha acid content of baled hops. Journa the Institute of Brewing 83, 1977, 290-294. /7/ Hough, J.S.&authors: Malting and Brewing Science, Vol 2, 1982. /8/ Garetz, M.: How to get and keep your hops optimum value. BrewingTechniques, January/February 1994 /9/ Hops and Hop Products, EBC Manual of Good Practice,1997, 25-36, 162. /10/ Scheer, F. M.: The Hop Storage Index. Is it importatnt for Homebrewers. Boscos Nashville. /11/ Foster, A.: Significance of crop year in qualitative assessment of hop product. Brauwelt Internatioonal I/2001, 32-37 /12/ Foster, A.: Die Marktstellung des Hallertauer Hopfens: Derzeitige Situation und Mglichkeiten zur Verbesserung. Hopfen-Rundschau Nummer 4, 1996, 90-94. /13/ Hopfenveredlung St. Johann: Unser kaltlagerservice fr Hopfenprodukte in Hopfenpelletwerk St. Johann 09/2001. /14/ Analytica EBC, 1998 Methods 7 Hops 7.4. /15/ American Society of Brewing Chemists, Methods

Alpha acids decreases in % relative cold storage 0 0 C (Figure 1)

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Hop Storage Index increases in % relative cold storage 00C (Figure 4)

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Hop Storage Index increases in % relative storage at +200C (Figure 5)

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Hop Storage Index increases in % relative physiological ripeness (Figure 6)

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