Understanding How Chemical Pollutants Arise and Evolve in the Brewing Supply Chain: A Scoping Review.

In this study, a critical review was carried out using the Web of ScienceTM Core Collection database to analyse the scientific literature published to date to identify lines of research and future perspectives on the presence of chemical pollutants in beer brewing. Beer is one of the world's most popular drinks and the most consumed alcoholic beverage. However, a widespread challenge with potential implications for human and animal health is the presence of physical, chemical, and/or microbiological contaminants in beer. Biogenic amines, heavy metals, mycotoxins, nitrosamines, pesticides, acrylamide, phthalates, bisphenols, microplastics, and, to a lesser extent, hydrocarbons (aliphatic chlorinated and polycyclic aromatic), carbonyls, furan-derivatives, polychlorinated biphenyls, and trihalomethanes are the main chemical pollutants found during the beer brewing process. Pollution sources include raw materials, technological process steps, the brewery environment, and packaging materials. Different chemical pollutants have been found during the beer brewing process, from barley to beer. Brewing steps such as steeping, kilning, mashing, boiling, fermentation, and clarification are critical in reducing the levels of many of these pollutants. As a result, their residual levels are usually below the maximum levels allowed by international regulations. Therefore, this work was aimed at assessing how chemical pollutants appear and evolve in the brewing process, according to research developed in the last few decades.

Comprehensive Review on Monitoring, Behavior, and Impact of Pesticide Residues during Beer-Making.

This paper reviews the impact of beer-making stages (malting, mashing, boiling, and fermentation) on the behavior of pesticide residues. The large use of pesticides on barley and hop could cause the occurrence of their residues in beer. The foremost factors influencing the stability of residues (pH, temperature, and water content) and the physical-chemical properties of pesticides (octanol-water partition coefficient, vapor pressure, and water solubility) are essential to know their final fate. Most pesticides show a decrease in the unhopped wort because they are adsorbed onto the spent grains after mashing. In addition, their concentrations decrease during boiling and fermentation. Generally, maltsters should dedicate particular attention to the residues of hydrophobic pesticides because they can remain on the malt. Contrarily, brewers should control residues of hydrophilic pesticides because they can be carried over into young beer, disturbing the quality and organoleptic properties (flavor, aroma, taste, or color) of the beer.

Solar photocatalytic reclamation of agro-waste water polluted with twelve pesticides for agricultural reuse.

This study aims to demonstrate a technically feasible alternative to remove pesticide residues from agro-waste water produced in farms from remnants in containers and treatment tanks, rinse in tanks after treatments, and cleaning of machines and equipment. For this, the photocatalyzed degradation of 12 pesticides commonly used on vegetables, vines, citrus and fruit crops was investigated in aqueous suspensions of TiO2 in tandem with Na2S2O8 at pilot plant scale under natural sunlight in Murcia (SE of Spain) during summer and winter seasons. Previously, preliminary experiments were carried out at laboratory scale using a photoreactor to optimize the photocatalyst (200 mg L-1) and oxidant (250 mg L-1) concentrations on the rate constants of the studied pesticides. The photodegradation of all pesticides can be modelled assuming a pseudo-first-order kinetics. The time needed for disappearance of 90% (DT90) of the studied pesticides, was lower than 4 h in summer in all cases with the exception of cyproconazole (4.9 h), while, cyproconazole (8.9 h), metalaxil (6.1 h) and propyzamide (7.9 h) showed DT90 higher than 6 h in winter. The reaction rate was enhanced 3-fold in summer season, which is directly correlated to the higher accumulated fluence per time received during this season (about a factor of 2.9 higher than in winter). In both cases, the higher and lower degradation rates were obtained for cyprodinil and cyproconazole, respectively. The total fluence to get a 90% reduction (H90) ranged from 4.6 to 5.2 J cm-2 (cyprodinil) to 71.5-76 J cm-2 (cyproconazole).

Trial of solar heating methods (solarization and biosolarization) to reduce persistence of neonicotinoid and diamide insecticides in a semiarid Mediterranean soil.

This paper reports the use of solar heating techniques, solarization (S) and biosolarization (BS) as a strategy for the environmental restoration of soils containing neonicotinoid, acetamiprid (AC), imidacloprid (IM) and thiamethoxam (TH), and diamide, chlorantraniliprole (CL) and flubendiamide (FB) insecticide residues. For this, a semiarid Mediterranean soil (Haplic calcisol) was covered with low-density polyethylene (LDPE) during the hot season, to raise the maximal soil temperatures. Compost from sheep manure (CSM), meat-processing waste (MPW) and sugar beet vinasse (SBV) were used as organic wastes. The results showed that both S and BS increase insecticide disappearance rates compared with the non-disinfected soil, the increase in soil temperature and added organic matter playing a key role. The dissipation rates of TH and AC in soil were satisfactorily described by first-order (monophasic) kinetics, while IM, CL and FB showed a deviation from exponential behaviour. For them, the best results were obtained applying biphasic kinetics with a rapid initial degradation followed by a slower decline of their residues. The findings suggest that S and BS (especially using MPW) can be considered as a valuable tool for enhancing the detoxification of soils polluted with these insecticides.

Reclamation of Water Polluted with Flubendiamide Residues by Photocatalytic Treatment with Semiconductor Oxides.

The photodegradation of flubendiamide (benzenedicarboxamide insecticide), a relatively new insecticide was investigated in aqueous suspensions binary (ZnO of and TiO2 ) and ternary (Zn2 TiO4 and ZnTiO3 ) oxides under artificial light (300-460 nm) irradiation. Photocatalytic experiments showed that the addition of semiconductors, especially ZnO and TiO2 , in tandem with an electron acceptor (Na2 S2 O8 ) enhances the degradation rate of this compound in comparison with those carried out with catalyst alone and photolytic tests. The photocatalytical degradation of flubendiamide using ZnO/Na2 S2 O8 and TiO2 /Na2 S2 O8 followed first-order kinetics. In addition, desiodo-flubendiamide was identified during the degradation of flubendiamide. Finally, application of these reaction systems in different waters (tap, leaching and watercourse) showed the validity of the treatments, which allowed the removal of flubendiamide residues in these drinking and environmental water samples.

Assessment of agro-industrial and composted organic wastes for reducing the potential leaching of triazine herbicide residues through the soil.

In this study, we examined the effect of four different organic wastes--composted sheep manure (CSM), spent coffee grounds (SCG), composted pine bark (CPB) and coir (CR)--on the sorption, persistence and mobility of eight symmetrical and two asymmetrical-triazine herbicides: atrazine, propazine, simazine, terbuthylazine (chlorotriazines), prometon (methoxytriazine), prometryn, simetryn, terbutryn (methylthiotriazines), metamitron and metribuzin (triazinones). The downward movement of herbicides was monitored using disturbed soil columns packed with a clay loam soil (Hipercalcic calcisol) under laboratory conditions. For unamended and amended soils, the groundwater ubiquity score (GUS) was calculated for each herbicide on the basis of its persistence (as t½) and mobility (as KOC). All herbicides showed medium/high leachability through the unamended soils. The addition of agro-industrial and composted organic wastes at a rate of 10% (w:w) strongly decreased the mobility of herbicides. Sorption coefficients normalized to the total soil organic carbon (KOC) increased in the amended soils. These results suggest that used organic wastes could be used to enhance the retention and reduce the mobility of the studied herbicides in soil.

Abatement kinetics of 30 sulfonylurea herbicide residues in water by photocatalytic treatment with semiconductor materials.

Sulfonylurea herbicides (SUHs) are a family of environmentally compatible herbicides but their high water solubility, moderate to high mobility through the soil profile, and slow degradation rate make them potential contaminants of groundwater as demonstrated in this paper. The photodegradation of a mixture of 30 SUHs in aqueous suspensions of semiconductor materials (ZnO and TiO2 in tandem with Na2S2O8 as electron acceptor) under artificial light (300-460 nm) irradiation was investigated. As expected, the influence of both semiconductors on the degradation of SUHs was very significant in all cases. Photocatalytic experiments show that the addition of photocatalyst, especially for the ZnO/Na2S2O8 system, greatly improves the removal of SUHs compared with photolytic tests, significantly increasing the reaction rates. The first-order equation (monophasic model) satisfactorily explained the disappearance process although it overlooked small residues remaining late in the process. These residues are important from an environmental point of view and the Hoerl function (biphasic model), was a better predicter of the results obtained. In our conditions, the average time required for 90% degradation was about 3 and 30 min for ZnO/Na2S2O8 and TiO2/Na2S2O8 systems, respectively.

Influence of pre-slaughtering feed restriction on muscle characteristics of farmed sea bass (Dicentrarchus labrax L.) during cold storage.

BACKGROUND: This paper deals with the consequences of dietary restriction or complete starvation before slaughtering on the biochemical and textural characteristics of sea bass muscle. RESULTS: Results showed that only severe feed restriction influenced negatively total body and individual organ weights, and these animals showed lower condition factor as well. Neither moderate feed restriction (up to 50% of the standard ration) kept for 30 days nor total starvation up to 12 days caused significant effects on fish weight and fillet yield. Muscle lipid content was lower in feed-restricted fish, although this parameter was not altered by starvation time. Differences between the two feeding strategies studied were observed in muscle textural and biochemical parameters, and the results point to an influence of the nutritional status on the post-mortem evolution of collagen and myofibrillar proteins, although firmness was not modified. CONCLUSIONS: Moderate feed restriction prior to slaughtering could be advisable in sea bass culture, given that no detrimental effects on fish quality or fish performance were noticed, whereas substantial amounts of feed can be saved.

Photocatalytic degradation of substituted phenylurea herbicides in aqueous semiconductor suspensions exposed to solar energy.

The photocatalyzed degradation of the biocides chlorotoluron, diuron, fluometuron, isoproturon and linuron (substituted phenylurea herbicides) was investigated in aqueous suspensions of ZnO, TiO2, WO3, SnO2 and ZnS at pilot plant scale under natural sunlight. Comparison of the five catalysts showed that ZnO is the most effective for catalyzing the removal of all the compounds studied. The primary degradation of the herbicides followed a pseudo-first order kinetics. In our conditions, the time required for 90% degradation ranged from 23 to 47min for isoproturon and linuron, respectively, when using the tandem ZnO/Na2S2O8. Eight transformation products were identified by HPLC-MS(2) during the experiments, although at the end of the photoperiod (240min), their concentrations were below detection limits. Based on derivative identification, the proposed metabolic pathways would involve N-demethylation and N-demethoxylation of the N-methoxy-N-methyl substituted ureas and N-demethylation of the N,N-dimethylurea-substituted compounds.

Photocatalytic transformation of sixteen substituted phenylurea herbicides in aqueous semiconductor suspensions: intermediates and degradation pathways.

The photocatalytic degradation of sixteen substituted phenylurea herbicides (PUHs) in pure water has been studied using zinc oxide (ZnO) and titanium dioxide (TiO(2)) as photocatalyst under artificial light irradiation. Photocatalytic experiments showed that the addition of these chalcogenide oxides in tandem with the oxidant (Na(2)S(2)O(8)) strongly enhances the degradation rate of these compounds in comparison with those carried out with ZnO and TiO(2) alone and photolytic tests. Comparison of catalysts showed that ZnO is the most efficient for the removal of such herbicides in optimal conditions and at constant volumetric rate of photon absorption in the photoreactor. Thus, the complete disappearance of all the studied compounds was achieved after 20 min of illumination in the ZnO/Na(2)S(2)O(8) system. The main photocatalytic intermediates detected during the degradation of PUHs were identified. The probable photodegradation pathways were proposed and discussed. The main steps involved: N-demethylation of the N,N-dimethylurea-substituted compounds followed of N-demethylation and N-demethoxylation of the N-methoxy-N-methyl-substituted ureas and hydroxylation of aromatic rings and their aliphatic side-chains of both, parent compounds and intermediates.

Gas chromatographic determination of pesticide residues in malt, spent grains, wort, and beer with electron capture detection and mass spectrometry.

A method for the simultaneous determination of 9 pesticides (dinitroanilines, organophosphorus, triazoles, and pyrimidines) in several products (malt, spent grains, wort, and beer) of the beer industry is reported. Solid samples (malt and spent grains) are extracted by homogenization with a water-hexane mixture, and the pesticides are partitioned with dichloromethane. Liquid samples (wort and beer) are extracted by sonication with a hexane-dichloromethane mixture. Determination of pesticide residues was made by capillary gas chromatography with an electron capture detector (ECD). Confirmation of the compounds was performed by gas chromatography/ion trap mass spectrometry in the selected ion monitoring mode. Detection limits for GC-ECD varied from 0.2 to 5.5 pg for trifluralin and malathion, respectively. Recoveries of the pesticides from spiked samples ranged from 81.2 to 113.7% with a relative standard deviation between 3.4-7.5%. The method presents good linearity over the studied range (0.005-2 microg/mL). The proposed method is rapid and reliable and can be useful for routine monitoring during brewing.

Influence of fungicide residues on the primary fermentation of young lager beer.

The effect of four sterol biosynthesis-inhibiting fungicides added to the pitching wort on the evolution of several organoleptic parameters during the primary fermentation of young lager beer was assessed. Pyrimidine (nuarimol and fenarimol) and triazole (myclobutanil and propiconazole) fungicides were individually supplied to the pitching wort to obtain a concentration of 1 mg/L. A marked influence in the fermentation rate was observed for the samples with propiconazole residues. From the fourth day onward, the fermentation prematurely ceased (stuck fermentation), and therefore, statistical significant differences were found in fermented extract, alcohol content, fermentable carbohydrates, pH, color, and total polyphenol and flavonoid contents of beer. Myclobutanil residues are only influenced in the total polyphenol and flavonoid contents, while differences in the analyzed parameters were not noticeable for the samples containing nuarimol and fenarimol residues in comparison with the blank sample.

Decay of dinitroaniline herbicides and organophosphorus insecticides during brewing of lager beer.

This article examines the fate of four pesticides that can be present during the brewing of lager beer. For this purpose, malted barley was spiked at 2 mg/kg with pendimethalin and trifluralin (dinitroaniline herbicides) and fenitrothion and malathion (organophosphorus insecticides). Analyses of pesticide residues were carried out by a gas chromatograph with an electron capture detector, and their identity was confirmed by gas chromatography-mass spectrometry. Cleanup was necessary for the malt and spent grain samples. Beginning with mashing and ending with the final product 4 months later, various samples (spent grain, sweet wort, brewer wort, and beer) were taken to determine the concentration of the targeted residual pesticides during the various beer making phases. In all cases, the residual levels recorded in sweet wort sampled after the mashing phase were below the respective maximum residue limits established by Spanish legislation for barley. Significant proportions of pesticide residues (17 to 40%) were retained on the spent grain. Applying the standard first-order kinetics equation (r > 0.91), the half-lives obtained for the four compounds during the storage of the spent grain (3.5 months) varied from 138 days (fenitrothion) to 192 days (malathion and pendimethalin). Herbicide residues practically disappeared (<0.3%) after wort boiling, whereas the percentages of the remaining insecticides, fenitrothion and malathion, ranged from 3.5 to 4.3%, respectively, at this time. No residues of dinitroaniline compounds were detected in young beer, whereas there was a significant reduction in fenitrothion (58%) and malathion (71%) residues during fermentation. Lagering and filtering processes also reduced the content of the organophosphorus insecticides (33 to 37%). Finally, after the storage period (3 months), the content of fenitrothion was reduced by 75%, with malathion residues being below its detection limit.

Behavior of myclobutanil, propiconazole, and nuarimol residues during lager beer brewing.

Over a 4 month brewing process, the fate of three fungicides, myclobutanil, propiconazole, and nuarimol, was studied in the spent grain, brewer wort, and final beer product. Only the residual level of myclobutanil after the mashing step was higher than its maximum residue limit (MRL) on barley. A substantial fraction was removed with the spent grain in all cases (26-42%). The half-life times obtained for the fungicides during storage of the spent grains ranged from 82 to 187 days. No significant influence of the boiling stage on the decrease of the fungicide residues was demonstrated. During fermentation, the content reduction varied from 20 to 47%. After the lagering and filtration steps, no significant decrease (<10%) was observed in any of the residues. Finally, during storage of the beer (3 months), the amounts of fungicides fell by 25-50% of their respective concentrations in the finished beer.

Effect of temperature on the disappearance of four triazine herbicides in environmental waters.

The influence of temperature on the disappearance of four s-triazine herbicides, terbuthylazine, simazine, atrazine and prometryn was studied in sea, river and groundwaters spiked with approx. 5 mg l(-1) of each during long-term laboratory incubation. Residues were analyzed by GC-NPD and confirmed by GC-MSD. No clean-up was necessary and a micro on-line method for the determination of herbicide residues was used. The results showed that temperature had little effect on the behaviour of the four herbicides in river and seawaters but strongly affected their behaviour in groundwater. Simazine was the most readily affected compound in sea, river and groundwaters, while terbuthylazine and atrazine were the most persistent in all cases, especially in riverwater. Half-lives ranged from 41 days (constant rate = 0.017 days(-1)) to 196 days (constant rate = 0.003 days(-1)) for simazine (40 degrees C) and terbuthylazine (20 degrees C), respectively, in riverwater. Only for terbuthylazine in riverwater was the remaining percentage at the end of the experiment higher than 50% (58%, 3.21 mg l(-1)). In the other cases, the remaining percentage varied from 4% (0.20 mg l(-1), 40 degrees C) to 43% (2.25 mg l(-1), 20 degrees C) for simazine and terbuthylazine, respectively, in groundwater.

Persistence of four s-triazine herbicides in river, sea and groundwater samples exposed to sunlight and darkness under laboratory conditions.

The persistence of terbuthylazine, simazine, atrazine and prometryn (s-triazine herbicides) was studied in sea, river and groundwaters during long-term laboratory incubation (127 days) under different laboratory conditions (light-darkness at 20 degrees C). Analysis of herbicides was performed by GC-NPD and their identity was confirmed by GC-MSD. A micro on-line method for the isolation of herbicide residues was used. The results showed that light had little effect on the removal of the four herbicides in riverwater but had a marked effect on their removal from sea and groundwater. Surprisingly, this removal appeared to be inversely proportional to the concentration of dissolved organic materials. In general, the degradation order was similar in sea and riverwaters; simazine was the most readily degraded compound (t(1/2)= 29-49 days), while terbuthylazine was the most persistent with the longest half-lives (76-331 days). In groundwater, terbuthylazine also showed greater persistence but prometryn was the compound with a fastest degradation rate, half-lives ranged from 88 days for prometryn to approximately 100 days for the other three compounds in light conditions and 263-366 days for prometryn and terbuthylazine, respectively, in darkness. Only for terbuthylazine was the remaining percentage at the end of the experiment higher than 50% under light conditions in riverwater, while in the other cases, the remaining percentage varied from 7 to 43% for simazine in seawater and atrazine in groundwater, respectively. Finally, a greater persistence was observed in groundwater for the four compounds.

Persistence of simazine and terbuthylazine in a semiarid soil after organic amendment with urban sewage sludge.

The persistence of two herbicides, simazine and terbuthylazine, and appearance of their principal dealkylated chloro-s-triazine metabolites have been studied in agricultural soil after the addition of urban sewage sludge as organic amendment. Both herbicides and metabolites were monitored during long-term laboratory incubation (140 days) and analyzed by gas chromatography with a nitrogen-phosphorus detector (GC-NPD). Residues were confirmed by gas chromatography with a mass selective detector (GC-MSD). A sonication microextraction method was used to extract the compounds. The organic amendments used were urban sewage sludge and the humic fraction of this sludge, to increase the organic matter content of the soil from 1% to 2%. For both compounds, simazine and terbuthylazine, the degradation began earlier in the amended soils. Simazine showed a higher dissipation rate than terbuthylazine, the percentage of the former at the end of the experiment being lower than 2% in all cases, while for terbuthylazine the corresponding percentage ranged from 5% to 46%. Organic amendment, mainly its humic fraction, caused a certain stabilization of terbuthylazine in the soil, but did not greatly influence the residual amount of simazine at the end of the experiment. The periodic aeration of the soil caused a greater degradation in the case of terbuthylazine. Only mono-deethylsimazine and deethylterbuthylazine were isolated from the soil during the time the experiment lasted, while the di-deethylated metabolite of simazine was not found.