Determination of fungicide residues in field-grown strawberries following different fungicide strategies against gray mold (Botrytis cinerea)

In a 2 year experiment, residues in field-grown strawberries were investigated from the fungicides fenhexamid, pyrimethanil, tolylfluanid, and kresoxim-methyl resulting from different strategies, as regards the dose, number, and time of fungicide applications. Kresoxim-methyl was only used the first year and in full or no dose to control powdery mildew. In the first year, the highest concentrations analyzed were 0.66 mg kg(-1) for pyrimethanil and 0.63 mg kg(-1) for fenhexamid resulting from the use of recommended dose rates and a preharvest interval (PHI) of 10 days, thus not exceeding the Danish maximum residue limit (MRL) of 1 mg kg(-1). Tolylfluanid was used no later than 21 days before harvest, which left residue contents in the berries of 0.48 mg kg(-1), a value well below the MRL of 5 mg kg(-1). In the second year, fungicide residues found in the samples were generally lower, 0.39 and 0.03 mg kg(-1) for pyrimethanil and fenhexamid, respectively. No residues of kresoxim-methyl were found in any of the samples from the field trials, indicating that kresoxim-methyl residues had declined to a level well below the detection limit within the 28 day period between the last application and the harvest.     

Monitoring residues of carbendazim (applied as benomyl) and thiabendazole in Wellspur apples

Residues of benomyl (determined as carbendazim, widely accepted as MBC) and of thiabendazole in Wellspur apples were monitored after the apples were treated postharvest by immersion in a bath with each of the fungicides separately and stored under refrigeration. Whole fruit and pulp analyses were conducted over the period beginning 1 day after treatment and lasting up to 200 days afterwards. Under the conditions described, both benomyl (expressed as parts per million of carbendazim) and thiabendazole were found in the fruits in the following average amounts: 0.44 +/- 0.03 and 0.11 +/- 0.03 ppm benomyl (as carbendazim) in whole fruit and in pulp, respectively; 0.98 +/- 0.10 and 0.39 +/- 0.10 ppm thiabendazole in whole fruit and in pulp, respectively.     

Investigation on fungicide residues in greenhouse-grown strawberries

Maximum residue limits (MRL's) for different agricultural food products in Norway are harmonized with EU standards. In field-grown strawberries in Norway, tolylfluanid has a 7 day quarantine from last application to harvest, while other approved fungicides have 14 days quarantine. Greenhouse production of strawberries is newly introduced to the country. Residue levels in strawberries of the cultivar Korona grown in a commercial greenhouse were investigated 4, 7, and 14 days after application of eight different fungicides at rates recommended by the manufacturers and at half rates. Iprodione, tolylfluanid, and vinclozolin were tested in two experiments, while chinomethionat, chlorothalonil, imazalil, penconazole, and triadimefon were tested once. For chinomethionat, imazalil, iprodione, penconazole, and vinclozolin, the residue levels were below MRL 2 weeks after application. Application of triadimefon in normal rate gave residues below MRL 14 days after application. However, its metabolite, triadimenol, was above MRL at the same time. Tolylfluanid gave very high residue levels, and except from half concentration in the second experiment, all other residue levels were above MRL. Seven days after application, residues in both experiments were approximately 3 times higher than MRL when normal rate of tolylfluanid was applied. For chlorothalonil at the recommended rate, the residue level was above MRL at any sampling time, while half rate gave residues below MRL 14 days after treatment. In view of the present results, tolylfluanid, chlorothalonil, and triadimefon will need longer time from last application to harvest and/or reduced application rates in greenhouse-grown compared to field-grown strawberries. In addition or as an alternative, recommended rates could be lowered.     

Residues of vinclozolin and procymidone after treatment of greenhouse grown lettuce,tomato and cucumber

Residues of the fungicides vinclozolin and procymidone, used to control the Botrytis cinerea disease, were studied in greenhouse grown lettuce, tomato and cucumber. Residue concentrations differed between the species of treated vegetables, and depended mostly on time of picking (harvest), size of fruits and mode of chemical application. The differences in concentration between one and two applications became smaller with time after application. The greatest differences occurred in lettuce. The residue contents in cucumber fruits assigned both for industrial and home processing (pickling) were higher than the legal limit (3 mg/kg). As a result of washing cucumbers, 22–24% of the residue was eliminated, and by peeling them 79–85% of the vinclozolin and procymidone residues were eliminated. Therefore it is reasonable that one or two applications of these fungicides should be used, with a time lapse of 14 days, but only with cucumbers intended for salad consumption. Vinclozolin residues, when used as vaporisation tablets, were in all cases 35–65% lower compared with the wettable powder (WP) formulation; however, the rate of of residue decrease was much slower. When applied in the form of vaporable tablets, the vinclozolin residue concentration was lower in all the sampled fruits in comparison with the WP formulation. The concentration of fungicide residues detected in winter tomato fruits was higher than that of the spring crop. Irrespective of vegetable the detected levels of fungicide residues were lower in ripe and bigger fruits than in green and smaller ones.     

Development of an immunoassay (ELISA) for the quantification of thiram in lettuce

Two competitive immunoassays, a laboratory assay based on microwell plates and a field test based on the use of polystyrene tubes, have been developed for the quantification of thiram in lettuces. Concerning the laboratory assay, the calibration curve for thiram had a linear range of 11 to 90 ng/mL and a detection limit of 5 ng/mL. Precision of the assay presented coefficient of variation values <9% and the recovery of thiram from lettuce averaged 89% across the range of the immunoassay method using 30 min extraction with water/acetone (50:50, v/v). The tube-based method was developed in order that an extract of lettuce, containing thiram at the MRL (8 ppm), would be found on the linear part of the standard curve. The calibration curve for thiram has a linear range of 100 to 800 ng/mL (1.39 to 11.1 ppm in lettuce) and a detection limit of 40 ng/mL.     

Effect of the addition of wine distillery wastes to vineyard soils on the adsorption and mobility of fungicides

In the present work, a study was made of the effect of the addition of liquid and solid wine distillery wastes (WLW and WSW) to vineyard soils on the adsorption and leaching of penconazole and metalaxyl, two fungicides of different hydrophobic character that are widely used in vine cultivation. The study of these processes is of great interest, since currently the green filter system is implemented simultaneously in vine cultivation and as an alternative to classic purification methods of such organic wastes. Three vineyard soils selected from the La Rioja region (NW Spain) were used. Adsorption isotherms of the 14C-labeled fungicides by the soils in aqueous medium and in WLW medium were obtained, together with the percolation curves of the fungicides in packed soil columns under saturated flow conditions. The adsorption and leaching of metalaxyl in a soil amended with WSW were also studied. The Freundlich Kf constants indicated an increase in the adsorption of both fungicides by the soils in WLW medium as compared to aqueous medium. The amounts of penconazole leached in the three soils when they were washed with water and WLW ranged between 3.18 and 39.3% and between 2.00 and 10.4%, respectively, of the total fungicide added to the columns. In the case of metalaxyl, these amounts represented 69.1-100 and 91.6-117%. Variations were also observed in the shape and parameters of the breakthrough curves obtained in both systems and in the presence of WSW. The soluble organic compounds of WLW must be retained by the soil components, creating new adsorbent hydrophobic surfaces, which increase the retention in the soil of the highly hydrophobic compound penconazole. In the case of metalaxyl, which is very water soluble, the soluble organic compounds of WLW seem to contribute to the increase in its leaching, whereas the WSW favors the opposite effect. The results obtained, indicating modifications in the adsorption and leaching of penconazole and metalaxyl in the presence of WLW and WSW, show that further studies should be carried out on the adsorption and mobility of the fungicides in soils from the vineyard zone, which in turn are used as a green filter purification system of wine wastes.     

Compatibility of Talaromyces flavus with potato seedpiece fungicides

The compatibility of conidia and ascospores of a wild-type isolate (TF1) and a benomyl-resistant biotype (TF1-1) of Talaromyces flavus with five fungicides recommended for use on potato seedpieces was investigated in the field and in vitro. The fungicides tested were captan, mancozeb, maneb, metiram and thiabendazole. In the field test, highest populations were recovered from TF1 treatments. Both the TF1 and the TF1-1 survived better in the field and were more tolerant of more fungicides when applied to the potato seedpieces as ascospores than as conidia. In the field, both fungi were most tolerant of thiabendazole and metiram and least tolerant of captan. Tolerance of fungicides in vitro was not consistent with field compatibility.     

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.     

广东合水水库淤积物直接利用对蔬菜种植效应的影响

利用网室盆栽试验,以当地大田土壤为对照,种植辣椒、生菜和油麦菜,探讨广东合水水库淤积物直接农业利用对蔬菜生长、营养元素吸收及品质的影响。结果表明,水库淤积物种植的辣椒、生菜和油麦菜的每盆产量分别为111.25、110.04和115.84g,但均显著低于当地大田土壤种植蔬菜的产量;水库淤积物种植的辣椒果实、生菜和油麦菜植株含水率在78%～82%之间,相对低于当地大田土壤种植的蔬菜含水量;从蔬菜营养元素吸收及品质情况来看,水库淤积物种植的蔬菜氮素吸收量、维生素C含量与大田土壤种植之间差异不明显,而磷、钾、钙和镁元素的吸收量不同程度的低于大田土壤种植,硝酸盐和可溶性糖含量在水库淤积物种植条件下的累积量相对高于大田土壤种植。综合考虑蔬菜产量、养分吸收量和品质情况,合水水库淤积物作为土壤种植蔬菜进行农业资源化利用具有一定的可行性,但要达到当地大田土壤种植条件下的蔬菜产量和更好的蔬菜品质,需要对淤积物进行一定程度的改良后再行利用。     

霜霉威吡虫啉腐霉利在结球生菜上的消解动态及相关因子的影响

通过开展结球生菜生产中所用主要农药--霜霉威、吡虫啉、腐霉利的消解规律研究,探讨生菜农药消解与农药种类、浓度及外部因子的关系,为结球生菜生产过程中的安全管理提供参考依据。以目前我国生产上主要使用的结球生菜品种--＂皇帝＂为材料,2007年春季露地种植,按霜霉威、腐霉利、吡虫啉最大推荐用量（计算浓度分别为1203.3、500.0、40.0mg·kg-1）和最大推荐用量的2倍（计算浓度分别为2406.6、1000.0、80.0mg·kg-1）两个农药剂量处理,分别于6月6日施药后当日、2、6、9d取样测定农药残留含量,并记录环境因子温度、光照的变化。结果表明,不论是按最大推荐用量还是最大推荐用量2倍喷施,吡虫啉、霜霉威、腐霉利在生菜上均表现为起始和最后阶段消解快、中间阶段消解平缓的特点;按日本肯定列表制度对生菜吡虫啉、霜霉威和腐霉利最大残留限量（分别为5.0、10.0和5.0mg·kg-1）要求,对于吡虫啉,即使按最大推荐用量2倍喷施,其喷施8h后的残留量仅为1.5mg·kg-1,说明春季露地生菜上喷施吡虫啉的安全性较高;对于霜霉威,按最大推荐用量喷施,施药6d后的残留量为10.7mg·kg-1,接近肯定列表制度的要求,施药9d后的残留量降至8．4mg·kg-1,表明霜霉威自喷药至采收的间隔期应至少在7d以上才可能是安全的;对于腐霉利,到试验结束时,不论何种喷施浓度,其残留量均超过5．0mg·kg-1的要求,其使用安全性需要引起重视。在影响吡虫啉、霜霉威、腐霉利在生菜上消解的因素方面,统计分析表明,外部因子（时间、温度、光照）对3种农药消解具有显著作用（P〈0．05）,农药种类在对其消解率影响方面达到极显著差异（P〈0．01）,其中吡虫啉最易消解,其次为霜霉威,腐霉利消解最慢,但3种农药喷施浓度的高低对各自消解率均无显著影响（P〉0．05）。     

Uptake of organic emergent contaminants in spath and lettuce: an in vitro experiment

Although a myriad of organic microcontaminants may occur in irrigation waters, little attention has been paid to their incorporation in crops. In this work, a systematic approach to assess the final fate of both ionizable and neutral organic contaminants taken up by plants is described. In vitro uptake of triclosan (TCS), hydrocinnamic acid (HCA), tonalide (TON), ibuprofen (IBF), naproxen (NPX), and clofibric acid (CFA) were studied in lettuce ( Lactuca sativa L) and spath ( Spathiphyllum spp.) as model plants. After 30 days incubation, analyte depletion from the culture medium was 85-99% (lettuce) and 51-81% (spath). HCA, NPX, and CFA exhibited the highest depletion rate in both plant species. Lettuce plant tissue analysis revealed an accumulation of all compounds except for HCA. These compounds reached a peak in tissue concentration followed by a sudden drop, probably due to the plant detoxification system and analyte depletion from the culture medium. Kinetic characterization of the uptake and detoxification processes was fitted to a pseudo-first-order rate. Compounds with a carboxylic group in their structure exhibited higher uptake rates, possibly due to the contribution of an ion trap effect. Molecular weight and log K(ow) played a direct role in uptake in lettuce, as proven by the significant correlation of both properties to depletion and by the correlation of molecular weight to kinetic uptake rates.     

施肥对酸性菜园土壤莴笋硝酸盐和叶片养分形态的效应

通过田间试验研究了3种酸性菜园土壤(强酸性、酸性和微酸性土壤)不同氮磷钾配比及其与硝酸盐复合控制剂配施对莴笋产量、硝酸盐及叶片养分形态的影响。结果表明,莴笋产量以微酸性土>酸性土>强酸性土,酸性和强酸性土壤上配施硝酸盐复合控制剂可使莴笋显著增产(达6.2％～18.2％),而微酸性土壤则相反。HNK配施硝酸盐复合控制剂在3种土壤上分别降低莴笋茎和叶硝酸盐含量25.1％～76.3％和3.1％～27.7％(微酸性土除外),降低作用以茎>叶,以HNK+C2处理效果最好。莴笋叶片硝酸盐含量以酸性土壤>微酸性土壤>强酸性土壤,茎中硝酸盐以酸性土壤为最高。莴笋叶片氮、磷、钾形态分别以蛋白氮、非蛋白磷、非蛋白钾为主,HNK配施硝酸盐复合控制剂(HNK+C3除外)提高莴笋叶片蛋白氮占全氮、蛋白磷占全磷和蛋白钾占全钾的比例。莴笋叶片硝酸盐含量与全氮、蛋白氮、全磷、蛋白磷和蛋白钾含量呈极显著负相关。     

不同红外补光模式对植物工厂生菜生长及品质的影响

试验在密闭植物工厂内进行,以0:00-12:00照射的白色LED光为基础光,在保证生菜正常生长的前提下以两种峰值波长的LED红外光(850nm和930nm)作为补充光,通过调节红外光补光的时间点使之与白光形成半重叠(S)、全重叠(O)、不重叠(N)3种模式,分别为Fr_(930)S、Fr_(850)S、Fr_(930)O、Fr_(850)O、Fr_(930)N、Fr_(850)N共6个处理,各处理白光及红外光的光强度、供光时长均一致,且处理间的耗电量也基本一致。通过测定各处理生菜生长及品质指标,以分析不同红外光对生菜的作用是否独立或依赖于基础光,以及在相同耗电量下红外光的最佳补光模式。结果表明:(1)同一峰值波长的红外光在不同补光模式下对生菜的生长和品质影响各异;而同一补光模式下,不同峰值波长红外光对生菜的生长及品质的影响也存在差异。(2)6个处理中,850nm红外光独立于白光补光时,生菜地上食用部分的鲜重最高;而生菜粗蛋白和可溶性糖含量均在850nm红外光半重叠模式下最高;930nm独立补光时生菜Vc含量最高,硝酸盐含量最低。因此,实际生产中,在耗能基本一致的前提下,可根据生产目的对红外光的种类及其相对于基础光的补光模式进行选择和调节。     

Effect of methyl jasmonate on phenolic compounds and carotenoids of romaine lettuce (Lactuca sativa L.)

The effect of exogenous methyl jasmonate (MeJA) on antioxidative compounds of romaine lettuce ( Lactuca sativa L.) was investigated. Lettuces were treated with various MeJA solutions (0, 0.05, 0.1, 0.25, and 0.5 mM) before harvest. Total phenolic compounds content and antioxidant capacity of romaine lettuce significantly increased after MeJA treatments (0.1, 0.25, and 0.5 mM). The total content of phenolic compounds of the romaine lettuce treated with 0.5 mM MeJA (31.6 microg of gallic acid equivalents/mg of dry weight) was 35% higher than that of the control. The increase in phenolic compound content was attributed to a caffeic acid derivative and an unknown phenolic compound, which also contributed to increased antioxidant capacity. The induction of phenylalanine ammonia-lyase (PAL) activity by the MeJA treatment indicated that phenolic compounds were altered due to the activation of the phenylpropandoid pathway. Total content of carotenoids, including lutein and beta-carotene, of the MeJA-treated lettuce did not change after 8 days of treatment, whereas the content of the control without MeJA decreased after 8 days. This research indicated that preharvest application of MeJA could increase the nutritional value of romaine lettuce under determined conditions discussed in this work.     

LED绿光对生菜生长和品质的影响

在全人工光型植物工厂内以水培奶油生菜（Lactuca sativa L.）为试验材料,运用光质及光强可调节的LED植物生长灯,以8：00-24：00照射强度为200μmol·m-2·s-1的白光为基础光（对照W）,依次以强度为50（WG50）、100（WG100）、150μmol·m?2·s?1（WG150）的绿光取代相等强度的白光照射生菜,并测定生菜叶片生物量、形态、叶片数以及叶绿素、硝态氮、维生素C、可溶性糖、粗纤维和淀粉的含量,以探究绿光对生菜生长及品质的影响,为LED绿光的供光策略提供参考。结果表明：（1）在50μmol·m-2·s-1的绿光处理下,生菜地上部叶绿素含量显著高于对照,地上部干重较对照提高3.69%。（2）随着绿光强度的增加和基础白光强度的减弱,生菜地上部可溶性糖和维生素C含量均呈现先升高后降低的趋势,二者均在WG50处理下达到最高,并显著高于对照（P＜0.05）,而在WG150处理下达到最低,并显著低于对照（P＜0.05）。（3）与对照相比,绿光处理均降低了生菜叶片中淀粉、粗纤维以及硝酸盐的含量,其中硝酸盐含量在WG50处理下达到最低。说明50μmol·m-2·s-1强度的绿光有促进生菜干物质积累以及提升生菜品质的作用。     

Application of an electronic nose to predict total volatile bases in capelin (Mallotus villosus) for fishmeal production

An electronic nose was used as a rapid technique to monitor changes in the headspace gas above capelin (Mallotus villosus) during storage at 0 and 5 degrees C. At both temperatures, refrigeration was compared with an ice/seawater cooling system. At 5 degrees C, the effect of added 0.2% acetic acid was also tested. Electronic nose measurements were compared to measurements of total volatile bases (TVB), gas chromatography of volatile compounds, and sensory analysis. TVB analysis indicated less spoilage in seawater/ice systems than in refrigeration, but the other measurements indicated more spoilage in the seawater system compared to refrigeration. The possibility of using only a few sensors in the electronic nose to predict TVB was studied using partial least squares regression and a saturated generalized linear model. The results reported herein indicate that rapid electronic nose measurements, which require no sample preparation, can be used to predict the TVB value of the raw material stored under different conditions.     

Antimicrobial properties of Quercus ilex L. proanthocyanidin dimers and simple phenolics: evaluation of their synergistic activity with conventional antimicrobials and prediction of their pharmacokinetic profile

The antibacterial and antifungal activities of an ample number of phenolic compounds isolated from Quercus ilex leaves, belonging to the classes of flavonoids, proanthocyanidins, and phenolic acids, are discussed. The isolation of A type proanthocyanidin, (+)-epigallocatechin-(2β→O→7, 4β→8)-(+)-catechin is reported for the first time. Its structure was established by means of highfield NMR (correlation spectroscopy, heteronuclear single quantum correlation, heteronuclear multiple bond correlation, and rotating frame Overhauser effect spectroscopy) and MS spectral analyses, while its absolute configuration was determined by circular dichroism measurements. The isolated compounds were tested for their antimicrobial effects against eight human bacterial species and 14 fungal species. In a second step, the most potent compounds were tested in combination with the conventional fungicides, bifonazole and ketoconazole, to evaluate possible synergistic effects. Results showed that proanthocyanidins 3 and 4 when combined with bifonazole and ketoconazole increase the activity of both of these conventional fungicides. Moreover, the pharmacokinetic profile of the isolated compounds was investigated using computational methods.     

Rapid detection of tetracyclines and their 4-epimer derivatives from poultry meat with bioluminescent biosensor bacteria

Tetracycline (TC) specific luminescent bacterial biosensors were used in a rapid TC residue assay sensitized to meet the EU maximum residue limit (MRL) for TC residues in poultry muscle tissue (100 microg kg(-1)) by membrane-permeabilizing and chelating agents polymyxin B and EDTA. Sensitivities of 5 ng g(-1) for doxycycline, 7.5 ng g(-1) for chlortetracycline, and 25 ng g(-1) for tetracycline and oxytetracycline were reached. Except for doxycycline, the MRLs of these tetracyclines include their 4-epimer metabolites. In the biosensor assay, all four 4-epimers showed induction capacity and antimicrobial activity, and antimicrobial activity was also observed in the inhibition assay, although with lower efficiency than that of the corresponding parent compound in both assays. The biosensor assay is an inexpensive and rapid high-throughput screening method for the detection of 4-epimer TC residues along with their parent compounds.     

Effect of differential N and S competition in inter- and sole cropping of Brassica species and lettuce on glucosinolate concentration

Field and greenhouse pot experiments were conducted to evaluate the potential to use intercropping as an alternative method to increase glucosinolates in Brassicas by manipulating nitrogen (N) and sulfur (S) balance by intercropping with lettuce (Lactuca sativa L. var. capitata). In both experiments, four combinations of N and S fertilization were used. In the field experiment no effect of intercropping on the total glucosinolate concentration was found as the growing lettuce was strongly inhibited by the presence of broccoli (Brassica oleracea L. var. italic). In contrast to this, in the pot experiment both total and individual glucosinolate concentrations in red leaf mustard (Brassica juncea L.) increased by intercropping. Fertilization treatments influenced glucosinolate concentrations in both experiments, and an interaction between N and S fertilization was noticed.     

Determination of anthraquinone in technical material,formulations, and lettuce by high performance liquid chromatography

Foraging on lettuce seeds and seedlings by horned larks (Eremophila alpestris) causes millions of dollars in losses to the California lettuce crop annually. Anthraquinone (AQ; 9,10-anthracenedione) has been shown to deter pest birds from consuming the seeds and seedlings of several plant species and was evaluated as a repellent to horned larks when applied to lettuce seedlings. A set of analytical methods using simple liquid extraction followed by high-performance liquid chromatography analysis were developed for the quantitation of AQ as technical material, as an active ingredient in a commercial formulation, and as a residue in lettuce plants. The methods were easy, reliable, and repeatable. AQ recoveries from control formulation fortified to concentrations of either 24 or 600 mg g(-)(1) were 99 (+/-1.2%) and 98% (+/-1.2%), respectively, with a control formulation method limit of detection (MLOD) of 0.50 mg g(-)(1). Control lettuce tissues from three growth stages were AQ-fortified to concentrations of 0.50 and 500 microg g(-)(1). The resulting AQ recoveries for the two fortification levels were 99 (+/-8.5) and 89% (+/-1.5%) for 11 day old seedlings, 95 (+/-2.6%) and 86% (2.1%) for 16 day old plants, and 92 (+/-1.4%) and 93% (+/-1.1%) for adult head lettuce cover leaves, respectively. The MLODs for the same three lettuce tissues were 0.055, 0.058, and 0.077 microg g(-)(1), respectively. These methods were used to quantify AQ residues from field-grown, treated lettuce and associated fortified quality control samples.