Sunteți pe pagina 1din 7

The Oxalic Acid Content in Selected Barley Varieties Grown in Poland, as well as in their Malts and Worts

Andrzej Brudzyski and Agnieszka Salamon*


ABSTRACT

J. Inst. Brew. 117(1), 6773, 2011 The purpose of this work was to try to answer the question What factors influence the oxalic acid content in barley, malt and wort? Samples of three malting barley varieties (Prestige, Sebastian and Jersey, registered and grown in Poland) were investigated for their oxalic acid content. Laboratory scale malting and kilning of these samples and investigation of their oxalic acid content were conducted. Furthermore, the oxalic acid content was analysed in worts obtained from these malts. Tested barley samples, originating from various regions of Poland, showed different oxalic acid contents, ranging from 17.2 to 66.8 mg/kg d.m. basis. A higher temperature of germination (an increase from 14C to 18C with the same length of time) resulted in a decrease in oxalic acid content in the resultant worts. In most cases a positive linear correlation was found between the oxalic acid content in the malts and worts, and the initial barley samples. Oxalic acid content in barley appears to depend on the growth region rather than on the variety, but the data was not sufficient to draw any firm conclusions on this subject. Key words: malt, malting barley, oxalic acid, wort.

INTRODUCTION
Calcium oxalate precipitations in beer are cited by some authors25,26 as the most important factor evoking gushing problems. There are others who maintain that oxalates are only one, among a wide variety of suspected factors, such as barley and malt contamination by filamentous fungi, mainly of the genus Fusarium, producing the gushing evoking hydrophobins19, some other surfaceactive substances, including a peptide from the fungus Nigrospora, a tetrapeptide from Penicillium, a glucopeptide from Stemphyllium, some barley proteins, metal ions, iron (Fe+2) and copper (Cu+2), isomerised hop extracts etc.12,20 Oxalic acid in beer comes mainly from malt7,25. Its content in barley malt usually ranges from 10 to 20 mg/100 g d.m. basis (but sometimes to twice this value). In lager worts, around 25 to 32 mg/L can be found.
Department of Beer, Malt and Pro-health Food Technology, Institute of Agricultural and Food Biotechnology, 36 Rakowiecka St., 02-532 Warsaw, Poland * Corresponding author. e-mail: ztpis@ibprs.pl
Publication no. G-2011-0218-1075 2011 The Institute of Brewing & Distilling

Barley (Hordeum vulgare) is classified as a low-oxalate plant and, like many other crops, produces and accumulates oxalic acid, but its biosynthesis, accumulation, and catabolism are not yet sufficiently known23. alikan4 reported that oxalic acid and its salts are produced and stored in different amounts in all parts of plants, but that their levels may vary depending on the age of the plant, the growing season and cultivation conditions. Formation of oxalic acid may occur by several metabolic pathways. Libert and Franceschi9 indicate that the main pathways of metabolism of oxalic acid are the tricarboxylic acid cycle (Krebs) and glyoxylate cycle. The precursor of oxalic acid may be oxalacetate, which cleaves into oxalate and acetate8. The literature reports show that microbiological infection caused by fungi may be a potential source of oxalic acid in some plants6,7,12,24. In malting, the humidity during germination of barley contributes to the development of microorganisms colonizing the grain and some fungi may be able to synthesize oxalic acid22. In recent years, new varieties of malting barley have been introduced, but there is little information on their levels of oxalic acid. A few authors5,7 have reported that the content of this acid in malt depends on the variety, growing conditions and the malting process.

MATERIALS AND METHODS


Materials Samples of spring malting barley varieties harvested in 2005, currently registered and cultivated in Poland, were the materials for the study. Three varieties (Jersey, Prestige and Sebastian) were investigated. These were grown in various parts of Poland, namely in the region of Pozna (Wielkopolska), in West Pomerania, in Lower Silesia and in the region of Zamo (Zamojszczyzna). Micromalting procedure The samples were malted in laboratory scale maltings at our institute using as a basis standard method 2.5.3.1 as described in the MEBAK methodology10. The procedure was slightly modified as to steeping and germination temperatures and time, to come nearer to industrial scale conditions. Steeping with aeration was performed until the water content in the various samples reached 41%, 43% and 45% according to the following: 1 day 5 h flood and 19 h air rest, 2 day 4 h flood and 20 h air rest, 3 day
VOL. 117, NO. 1, 2011 67

water spray to obtain grain moisture in the air phase. The steeping and germination temperatures of parallel malted samples were 1415C and 1819C. Samples for kilning were taken after 4, 6 and 8 days of germination. The malting was then terminated using an increasing kilning regime of 50C 16 h, 60C 1 h, 70C 1 h and 80C 5 h for a total 23 h. Dried samples were stored for further analysis. Mashing procedure Malt (50 g) was milled on a DLFU grinder (BhlerMiag, Germany) using a fine grind (0.2 mm) and a coarse grind (1.0 mm). Laboratory-scale mashings were carried out in a mashing bath LB 12 Electronic (Lochner Labor+Technik, Germany), programmed according to the EBC method 4.5.12 and heated to 45C prior to insertion of the beakers. Each beaker contained 50 g of ground malt and was mashed-in with 200 mL of deionised water, leading to a net mashing-in temperature of 45C. The mashing apparatus set the stirrers in motion and maintained a constant mashing temperature for 30 min. Thereafter, the mash temperature was increased at a rate of 1C/min until 70C. Deionised water (100 mL) previously heated to 70C was dispensed into each beaker, and the mash was kept for a further 60 min at that temperature. After mashing, the contents were cooled for a period between 10 and 15 min. The contents were adjusted to 450 g by the addition of cold deionised water. Filtration was performed using Whatman No. 1 fluted filter paper. Oxalic acid standards The oxalic acid standard was obtained from Fluka (Switzerland) in a crystalline powder form. A stock solution (250 mg/L) was prepared by dissolving 0.3 g of oxalic acid dihydrate in 1,000 mL of deionised water. The solution was left overnight at room temperature to ensure complete dissolution of the crystalline oxalic acid. A standard stock solution of oxalic acid, in volumes of 0.5, 5, 10 and 15 mL respectively, was transferred to four 100 mL volumetric flasks. The flasks were filled with water to the mark, and the working solutions were used to calibrate the standard curve in the chromatographic analysis. Standard stock and working solutions were prepared for each analysis. Chemicals for HPLC analysis All reagents were of analytical grade and were obtained from POCh (Poland), except for gluconic acid (50% aqueous solution) for synthesis which came from Merck (Germany) and acetonitrile HPLC from Lab-Scan (Ireland). Lithium borate/gluconate eluent was prepared according to the procedure of Waters (USA). Boric acid, lithium hydroxide monohydrate, gluconic acid and glycerine, from which the lithium borate/gluconate concentrate was prepared, were first dissolved in deionised water. The concentrate can be stored for up for 6 months at room temperature. The mobile phase was a lithium borate/gluconate concentrate and acetonitrile solution in deionised water (pH 8.5). The mobile phase was filtered through a 0.45 m membrane filter (Millipore, USA). Eluent was prepared for each analysis. In all analytical steps, highly purified (deionised) water generated by an automatic system of demineralization from EuroWaters (Denmark) was used.
68 JOURNAL OF THE INSTITUTE OF BREWING

Sample preparation The barley sample (ca. 20 g) was milled (coarse grist) on a Miag grinder (Miag, Germany) and malt samples on a disc mill (Bhler-Miag, Germany) using a fine grind (2 mm). Deionised water at room temperature (50 mL) was added to 10 g of flour in an Erlenmeyer flask (100 mL) and acidified to pH 2 using 1.0 M HCl. The mixture was homogenized for 2 min (17,500 rpm) on an Ultra-Turrax T25 Basic (IKA-WERKE, Germany). Then the flask containing a magnetic stirring bar was tightly capped and contents were stirred for 15 min (50C, 1,000 rpm). The extract was cooled to room temperature and centrifuged for 15 min at 20C (14,000 rpm) in MPW 375 (MPW Med. Instruments, Poland). The supernatant (ca. 23 mL) was filtered through a 0.45 m syringe filter (Waters, USA) prior to injection onto the HPLC column. The wort sample (20 mL) was pipetted into a 100 mL Erlenmeyer flask and 1.0 M HCl was added to promote dissolution of the calcium oxalate for the determination of total oxalic acid. The flask was tightly capped and placed for 15 min in an ultrasonic bath (Polsonic, Poland). Hydrochloric acid extract of wort was filtered through a 0.45 m syringe filter (Waters, USA). The prepared samples of barley, malt and wort were placed into autosample vials and capped for analysis. Determination of oxalic acid in barley, malt and wort Barleys, malts and worts were analysed for their oxalic acid content using the HPLC method with conductometric detection, according to the modified MEBAK method 3.10.211, using a Waters HPLC system (Alliance 2695 Separations Module, 432 Conductivity Detector, oven of column controlled by a 2414 Refractive Index Detector). Purified extracts (10 L) were separated using an IC-Pak A HR column (75 mm 4.6 mm 6 m) preceded by a guard column of the same packing material (Waters, USA). The column was maintained at 35C and eluted with a mobile phase (lithium borate/gluconate) at a flow rate of 1.0 mL/min. Peak detection was determined using a conductivity detector operated at a sensitivity setting of 10 S full-scale deflection. The results were integrated and analyzed by Empower2 software (Waters, USA). Other analytical methods Barley samples were also analysed for their malting quality. The moisture, sizing of grains, germination power and germination capacity were determined according to the Polish standard PN-R-74110:199817. General protein in malting barley by the Kjeldahl method was analysed according Polish standard PN-A-04018:197513. The laboratory scale malts and worts were analysed according to the Polish standards on fine grind and coarse grind extracts15, total and soluble proteins (Kolbach index)16 and friability of malt14. The malting yield, i.e. the percentage ratio of the amount of malt produced to the amount of barley used, was calculated on a dry matter basis. Statistical analysis All analyses were performed at minimum in duplicate. The mean and standard deviations for each analysis were

calculated and reported. Statistical analysis of results was performed using the Version No. 6.0 of software STATISTICA. A Students t-test was used to interpret the differences between the results of the oxalic acid content for samples of barley, malt and laboratory wort. Probability () values of 0.05 were considered significant. Correlation analysis was performed aiming at the qualification of linear dependence among two sets of data. The Pearsons correlation coefficient accepts the values in the range from 1.0 to 1.0 exclusively.

togram of an autosampler injection of a diluted malt sample. Quality parameters and oxalic acid content of barley, malt and wort All barley samples, prior to their use for malting, were analysed to ascertain their malting quality, which in all cases proved satisfactory (Table I). Humidity, according to the Polish standards, was normal for good malting barley, germinative energy was up to around 98%, protein content was at the proper level, i.e. between 9.3 and 11.4% d.m. basis, grading (fraction 2.5 mm) was above 88.2%, up to 96.2%. The oxalic acid content in the barleys is shown in Table II. The lowest oxalic acid level among barley samples, 17.2 mg/kg d.m. basis, was found in the variety Prestige grown in the region of Pozna. The highest level, 66.8 mg/kg d.m., was in the Sebastian variety barley grown in the region of Zamo (S.-E. part of Poland). Most of investigated barley samples showed an oxalic acid content between 39.5 and 65.3 mg/kg d.m. Compared to data cited by Wagner23, the oxalic acid content found in our barley samples seems to be quite low. Among most, with a confidence level ranging 95%, there were substantial statistical differences within the same variety.

RESULTS AND DISCUSSION


Method performance The ion chromatographic assay was linear in the range of 1.2537.5 mg/L oxalic acid in a standard solution for wort, and was in the range of 5.0165.0 mg/kg for barley and malt. The coefficient of variation obtained by injecting samples of barley, malt and wort at three levels of oxalic acid content for the seven injections was 6.3%, 7.1% and 1.8%, respectively. Recovery with the HPLC method of determination of oxalic acid in samples of barley, malt and wort was under 100%. The lowest recovery was obtained for the malt (approx. 82%), and the highest for wort (approx. 92%). Figure 1 shows a typical chroma-

Fig. 1. Typical chromatogram of separation of diluted malt extract.


Table I. Selected quality parameters of malting barley harvest in 2005. Barley variety Growth region Germinative energy (3 days), % Germinative energy (5 days), % Moisture content, % Total proteins, % d.m. Sizing of grains ( 2.5 mm), % Region of Zamo 97 98 12.4 9.3 96.2 PRESTIGE West Pomerania 90 93 13.4 10.2 94.6 Region of Pozna 90 93 14.0 11.4 88.2 JERSEY Lower Silesia 89 91 13.0 10.2 92.4 SEBASTIAN Region of Zamo 90 91 13.1 9.4 93.5 Lower Silesia 95 97 12.9 10.3 90.9

VOL. 117, NO. 1, 2011

69

Analysis of the mean air temperatures and total precipitation in 200521 indicates that the region of Pozna (mean: 9.2C; 496 mm) and Lower Silesia (mean: 9.2C; 529 mm) were in comparison to West Pomerania (mean: 8.2C; 668 mm) and region of Zamo (mean: 8.3C; 771 mm) characterized by higher average temperatures and less rainfall. Therefore, it appears likely that warmer and less humid areas are favourable for the cultivation of barley with a lower oxalic acid content in the grain; examples are the barley varieties Prestige from the regions of Pozna and Sebastian from the Lower Silesia. This suggests that the level of oxalic acid in barley may depend on climatic conditions, as well as soil factors, as reported in a few publications57. Laboratory scale malting of the barley samples mentioned above was conducted under the following conditions: steeping up to 43% of water content and germination 6 days at 14C. In addition to the malting, yield was calculated. All results indicated good brewing quality parameters i.e., the extract yield ranged between 82.5 and 84.4% d.m. basis and the friability value was 8398%. The results are shown in Table III. The results of the oxalic acid analysis in the malts and worts were of the most interest for this study and these are presented in Table II. The lowest level of oxalic acid was found in a sample of malt obtained with the variety Prestige grown in the region of Zamo (20.4 mg/kg d.m.), and the highest was in a malt of the same variety from the region of Pozna (40.4 mg/kg d.m.). Consequently one could assume that the level of oxalic acid in the malt is associated with malting yield (Table III); the smaller the process loss (less rootlets), the less oxalic acid content in malt. Kanauchi et al.8 present a similar point of view. As for the oxalic acid content in worts, the two extremes were yielded by malt samples from barley grown in the Zamo region, namely the lowest from the Prestige variety (8.8 mg/L), and the highest from the Sebastian variety (16.0 mg/L).The results for the same varieties as

Prestige and Sebastian differed with statistical significance in both samples of barley and malt, as well as laboratory wort. In the two malt samples, Prestige from the Pozna region and Sebastian from Lower Silesia (Table II), the oxalic acid content was surprisingly higher than in the corresponding barley samples. It must be remembered that oxalic acid is a step link or element in the Krebs cycle and is released during germination9 and this may explain the increase in content. In contrast, in the remaining four malt samples the oxalic acid content was twofold lower than in the corresponding barley samples. One can only assume the same explanation as above, that during the germination processes the oxalic acid content may be variable. Some authors3,9 have reported the presence of oxalic acid in all plant tissues. However, it is also known that during growth, plants can both synthesize and decompose oxalic acid. It is noted that the enzymes capable of the oxidation and decarboxylation of oxalic acid, such as oxalate oxidase and oxalate decarboxylase, occur in plants. Consequently one could assume that during the germination of barley, that oxalic acid is accumulated in rootlets. To some extent this is shown as well by the increase of oxalate oxidase activity in germinating seeds3,8,9,18. This could also explain the decrease in oxalic acid content in some samples of kilned malt whose rootlets were already removed, as well as by the partial oxidation by the enzyme8. During barley germination there is also a growth of microorganisms including moulds. alikan and Cuming3 reported that some moulds produce oxalic acid and release it to the environment. This may contribute as well to the increase of oxalic acid content in the malt. The oxalic acid content in malt and wort and time of germination of barley The effect of time of germination of barley on the content of oxalic acid in malt and laboratory wort was investi-

Table II. Oxalic acid content in samples of barley from various growing regions in Poland, as well as in the malts and worts.* Barley variety Growth region Oxalic acid in barley, mg/kg d.m. Oxalic acid in malt, mg/kg d.m. Oxalic acid in wort (per wort 8.6Plato), mg/L
* Values

PRESTIGE Region of Zamo 39.5 20.4 1.4a 8.8 0.4a 1.0a West Pomerania 65.3 34.0 1.3b 12.5 0.2b 1.1b Region of Pozna 17.2 40.4 0.2c 14.2 0.4c 0.5c

JERSEY Lower Silesia 60.6 27.4 0.4d 11.1 0.2d 1.5b,d

SEBASTIAN Region of Zamo 66.8 28.4 0.2d,e 16.0 0.2e 2.5d,e Lower Silesia 17.3 0.4b,c,f 35.9 0.6b,f 13.2 0.5b,c,f

in rows followed by the same letter are not significantly different at a confidence level of 95%.

Table III. Physicochemical parameters of malt samples from various crop regions in Poland obtained during the malting process.* Barley variety Growth region Extract fine grind, % d.m. Extract difference, % Total protein, % d.m. Wort soluble protein, % d.m. Kolbach Index, % Friability, % Malting yield, %
* Malting

PRESTIGE Region of Zamo 83.8 0.2 8.8 4.70 53 96 89.4 West Pomerania 82.5 0.9 10.1 4.56 47 92 91.5 Region of Pozna 83.4 3.2 10.6 4.69 44 83 93.2

JERSEY Lower Silesia 82.9 1.1 9.3 4.75 51 94 90.8

SEBASTIAN Region of Zamo 84.4 0.9 8.6 4.72 55 98 86.6 Lower Silesia 83.4 1.1 9.5 4.77 50 90 89.9

parameters: humidity 43%, germination 6 days, temperature 14C.

70

JOURNAL OF THE INSTITUTE OF BREWING

gated on the samples of the barley variety Prestige from the region of Zamo and the variety Sebastian of Lower Silesia. Data is shown in Fig. 2. Table IV presents the results of the physicochemical quality of the malts produced from selected samples of malting barley varieties and malting yield. Malts obtained under equal conditions of laboratory malting were similar and conformed to standard quality. Their friability was quite high (above 80%), and the Kolbach index sometimes a bit too high or even flatly overrun (4453%). Better qualities were shown in malts obtained from the barley variety Prestige grown in the Zamo region. Remarkably the malts obtained from barley variety Sebastian, grown in Lower Silesia region, were twice as rich in oxalic acid, compared to malts from the variety Prestige grown in the Zamo region. Generally, it was observed that germination for 6 days, compared to samples that were germinated for 4 days, contributed to a decrease in oxalic acid in the malt. However, contrary to expectation, the longer germination time, up to 8 days, did not contribute to a further decline. The drop in oxalate content observed in day 6 of the germination could be the result of simultaneous growth of oxalate oxidase activity as well as of the transfer of oxalic acid to the rootlets. The accumulation in day 8 may be the result

of slowing of both these processes. Such fluctuations of enzyme activity during germination are normal1. The extension of germination time from 6 to 8 days was followed in the Sebastian variety from Silesia with an increase in oxalic acid content from 35.9 to 49.1 mg/kg d.m. Similar results were obtained for the Prestige variety. It is assumed that this phenomenon may be linked with the decrease of activity of oxalic acid oxidase at the end of the germination period. This finding does not conform to other data from the literature8, but the germinating barley kernel is a living organism and its physiology can vary with even slightly changing conditions. Data from Table IV and Fig. 2 show that with the increase of enzyme activities linked to malt modification, i.e. endo--glucanases, proteases and amylases, some decrease of oxalic acid content in related worts was observed. This is difficult to explain as there are many factors involved. The temperature of germination of malting barley grains and oxalic acid content in malt and laboratory wort The effect of temperature of germination on the oxalic acid content in the malt and wort was also studied. Quality parameters of malts from the Prestige and Sebastian varieties, harvested in the Zamo region and malted at two different temperatures, are presented in Table V. The corresponding content of oxalic acid in the barley and malt (mg/kg d.m.) and in the wort of 8.6Plato (mg/L), are shown at the Fig. 3. These data show substantial differences in the oxalic acid content between the samples of both barley varieties germinated at the two different temperatures. The Sebastian variety malted at 14C, contained 28.4 mg/kg d.m., which was 9.3 mg/kg d.m. less than in the sample germinated at 18C. For the Prestige variety, non-substantial but contrary differences were found. As expected, malts germinated at a lower temperature were characterized by slightly better quality and by a lower malting loss than the samples malted at 18C. The level of steeping of barley and oxalic acid content in malt and wort Malts produced from the barley variety Prestige, harvested in the Pozna region, were studied to determine if there was a correlation between the degree of steeping,

Fig. 2. Oxalic acid content in barley, malt and wort, with three germination times using the barley varieties Prestige from region of Zamo and Sebastian of Lower Silesia (steeping of barley up to 43% humidity, temperature of germination 14C). Values followed by the same letter are not significantly different at a confidence level of 95%.

Table IV. Quality parameters of malt samples depending on germination time of varieties Prestige from the region of Zamo and Sebastian of Lower Silesia.* Barley variety Growth region Malt germination, days Extract fine grind, % d.m. Extract difference, % Total protein, % d.m. Wort soluble protein, % d.m. Kolbach Index, % Friability, % Malting yield, %
* Malting

PRESTIGE Region of Zamo 4 days 83.9 0.5 9.0 4.41 49 87 91.3 6 days 83.8 0.2 8.8 4.70 53 96 89.4 8 days 84.1 0.5 9.0 4.46 50 95 91.3 4 days 83.6 1.7 9.8 4.50 46 82 91.5

SEBASTIAN Lower Silesia 6 days 83.4 1.1 9.5 4.77 50 90 89.9 8 days 83.5 0.8 10.0 4.42 44 90 90.4

parameters: humidity 43%, temperature of germination 14C.

VOL. 117, NO. 1, 2011

71

Table V. Quality parameters of malt samples depending on temperature of germination of varieties Prestige and Sebastian from the region of Zamo.* Barley variety Growth region Temperature of germination, C Extract fine grind, % d.m. Extract difference, % Total protein, % d.m. Wort soluble protein, % d.m. Kolbach Index, % Friability, % Malting yield, %
*

PRESTIGE Region of Zamo 14C 83.8 0.2 8.8 4.70 53 96 89.4 18C 83.2 0.5 8.9 4.15 47 97 88.0

SEBASTIAN Region of Zamo 14C 84.4 0.9 8.6 4.72 55 98 86.6 18C 83.0 0.2 9.0 4.49 50 97 86.4

Malting parameters: humidity 43%, germination 6 days.

Table VI. Quality parameters of malt samples depending on steeping level of variety Prestige from the region of Pozna.* Barley variety (Growth region) Malt steeping level, % Extract fine grind, % d.m. Extract difference, % Total protein, % d.m. Wort soluble protein, % d.m. Kolbach Index, % Friability, % Malting yield, %
* Malting

PRESTIGE (Region of Pozna) 41% 81.3 1.3 10.6 4.57 43 83 92.5 43% 83.4 0.9 10.6 4.69 44 85 93.2 45% 81.2 0.5 10.8 4.17 39 86 90.8

parameters: temperature of germination 14C, germination 6

days.

Fig. 3. Oxalic acid content in samples of barley, malt and wort with two temperatures of germination using the barley varieties Prestige and Sebastian from cultivation of the region of Zamo (humidity 43%, germination 6 days). Values followed by the same letter are not significantly different at a confidence level of 95%.

The highest level of oxalic acid was found with a steeping degree of 45%. In general, the steeping degree was of little impact on the oxalic acid level in malts and worts. A statistically significant difference ( 0.05) was found between samples of steeping degree 41% and 45%. The content of the oxalic acid in the wort also differed significantly. The test correlation between the oxalic acid content in barley, malt and wort Test results of one variant of this study (humidity 43%, temperature 14C, germination 6 days) and other samples (unpublished data) indicated a relationship between the content of oxalic acid in the barley, malt and laboratory wort. The data show a strong degree of dependence between the amount of oxalic acid in the malt and its content in wort. For these data sets of variables, a high positive correlation was obtained, indicated by Pearsons factor (rxy = 0.793). The dependence was statistically significant at a confidence level of 95%. As would be expected, there was a positive linear dependence between the increase of oxalic acid content in barley, malt and resultant wort (Table VII).

Fig. 4. Oxalic acid content in samples of malt and wort obtained from malting barley variety Prestige grown in the region of Pozna, depending on steeping level (temperature 14C, germination 6 days). Oxalic acid content in sample barley - 17.2 mg/kg d.m. Values followed by the same letter are not significantly different at a confidence level of 95%.

CONCLUSIONS
The quantitative determination of oxalic acid content in barleys, malts and worts was possible due to use of an HPLC method with conductometric detection. Good precision and good repeatability characterized the results obtained using this analytical method. The oxalic acid content in samples of the same barley variety, coming from various regions of Poland, differed significantly. No

measured by water content in barley after this operation (an important malt quality parameter) as well as the oxalic acid content in the malt and wort. The results are shown in Fig. 4 and Table VI.
72 JOURNAL OF THE INSTITUTE OF BREWING

Table VII. Pearsons linear correlation factors (rxy) between the oxalic acid content in barley, malt and laboratory wort (n = 26).* Oxalic acid in malting barley Oxalic acid in malting barley Oxalic acid in malt Oxalic acid in wort (8.6Plato)
* Statistically

Oxalic acid in malt 1 0.793*

Oxalic acid in wort (8.6Plato)

1 0.515* 0.729*

significant dependence at 0.05.

influence of barley variety on the oxalic acid content in malt was confirmed. The most important quantities of oxalic acid were found in the laboratory worts obtained from malts of the Sebastian variety. Steeping (attained humidity) and the temperature of malt germination appeared to have little influence on the oxalic acid level in malts and worts. Laboratory worts obtained from malts germinated at 18C were poorer in oxalic acid content than malts germinated at 14C. A high linear positive correlation between the oxalic acid content in malts and worts was observed and these dependencies were statistically significant.
REFERENCES 1. Agu, R. C. and Palmer, G. H., The effect of temperature on the endosperm modification of sorghum and barley during malting. Process Biochem., 1997, 32, 501-507. 2. Analytica EBC 4.5.1 Extract of Malt: Congress Mash, Fachverlag Hans Carl: Nrnberg. 2004. 3. alikan, M. and Cuming, A.C., Spatial specificity of H2O2generating oxalate oxidase gene expression during wheat embryo germination. Plant J., 1998, 15, 165-171. 4. alikan, M., The metabolism of oxalic acid. Turk. J. Zool., 2000, 24, 103-106. 5. Havlov, P., ernoch, I., Prma, J. and Mikulkov, R., Oxalate content in a barley caryopsis, in malt and beer (Abstract 4th International Symposium on Brewing and Malting). Kvas. Prm., 2004, 50(7-8), 198-212. 6. Havlov, P., Lancov, K., Vov, M., Havel, J. and Hajlov, J., The effect of fungicidal treatment on selected quality parameters of barley and malt. J. Agric. Food Chem., 2006, 54, 13531360. 7. Jacob, F., Calcium-oxalic acid technological importance. Brauwelt Int., 2000, 18, 58-59. 8. Kanauchi, M., Milet, J. and Bamforth, C. W., Oxalate and oxalate oxidase in malt. J. Inst. Brew., 2009, 115, 232-237. 9. Libert, B. and Franceschi, V.R., Oxalate in crop plants. J. Agric. Food Chem., 1987, 35, 926-938. 10. MEBAK 2.5.3.1 Kleinmlzung, In: Brautechnische Analysenmethoden. Vol. I, Selbstverlag der Mitteleuropische Brautechnische: Freising, 1997. 11. MEBAK 3.10.2 Anionen. Bromide, Chlorid, Fluorid, Nitrat, Oxalat, Phosphat und Sulfat in Wasser, Malz, Hopfen, Wrze

12. 13. 14. 15. 16. 17. 18. 19. 20. 21.

22.

23. 24. 25. 26.

und Bier, In: Brautechnische Analysenmethoden. Vol. III, Selbstverlag der Mitteleuropische Brautechnische: Freising, 1996. Pellaud, J., Gushing-State of the Art. In: J. De Clerck Chair X. Bacteria, Yeasts and Moulds in Malting and Brewing. 15-18th September 2002, Leuven. Polish standard: PN-A-04018:1975 Agricultural food products. Determination of nitrogen by the Kjeldahl method and expressing as protein. Polish standard: PN-A-79083-4:1998 Brewery malt. Test methods. Determination of malt friability. Polish standard: PN-A-79083-6:1998 Brewery malt. Test methods. Determination of extract contents, extract difference, malt saccharificating, wort run-off time and brightness. Polish standard: PN-A-79083-9:1998 Brewery malt. Test methods. Determination of general protein and soluble protein content and Kolbachs number calculating. Polish standard: PN-R-74110:1998 Barley. Test methods. Requena, L. and Bornemann, S., Barley (Hordeum vulgare) oxalate oxidase is a manganese-containing enzyme. Biochem. J., 1999, 343, 185-190. Sarlin, T., Nakari-Setl, T., Linder, M., Penttil, M. and Haikara, A., Fungal hydrophobins as predictors of the gushing activity of malt. J. Inst. Brew., 2005, 111, 105-111. Schur, F., Gushing tendency and foam stability. Brauwelt Int., 2001, 19, 302-304. Stan fitosanitarny rolin uprawnych w Polsce w roku 2007 i spodziewane wystpienie agrofagw w 2008. In: Opracowanie zbiorowe. F. Walczak, Ed., Instytut Ochrony Rolin: Pozna 2008. Stempniewicz, R. and Witkowska, D., Aktywnoci enzymatyczne kultur starterowych jako kryterium selekcji szczepw o potencjalnym zastosowaniu w sodownictwie. VIII Szkoa Technologii Fermentacji pt. Enzymy w piwowarstwie dzi i jutro. 26-29th March 2003, Jamrozowa Polana. Wagner, G. J., Vacuolar deposition of ascorbate-derived oxalic acid in barley. Plant Physiol., 1981, 67, 591-593. Winkelmann, L., The gushing puzzle a success story. Brauwelt Int., 2004, 22, 343-345. Zepf, M. and Geiger, E., Gushing problems caused by calcium oxalate (1). Brauwelt Int., 2000, 18, 473-475. Zepf, M. and Geiger, E., Gushing problems caused by calcium oxalate (2). Brauwelt Int., 2001, 19, 420-421.

(Manuscript accepted for publication September 2010)

VOL. 117, NO. 1, 2011

73

S-ar putea să vă placă și