高效液相色谱法测定发酵醪中的γ-氨基丁酸

建立了高效液相色谱测定发酵醪中γ-氨基丁酸(γ-aminobutyric acid,GABA)的方法。采用7%(V/V)乙酸水溶液对发酵醪进行预处理,以异硫氰酸苯酯为衍生剂,用反相C18柱为分离柱,柱温27°C,阶段洗脱,在254 nm下进行检测。结果表明,发酵醪中的GABA获得了很好的分离,GABA在0~1.5 mmol/L内线性相关性好,其线性方程为y=14106.5713x-258.2493(r=0.9993)。最小检测浓度为0.5μmol/L(RSD≤10%),组间样品测定相对误差为3.571%,加样平均回收率达到了99.038%。所建立的方法稳定、灵敏、重现性好,可用于测定发酵醪中的GABA。     

Layered double hydroxides as supports for the slow release of acid herbicides

A Mg/Al layered double hydroxide (LDH) was intercalated with the anionic herbicides 2,4-D, MCPA, and picloram by using three different methodologies: (i) direct synthesis (DS), (ii) regeneration (RE), and (iii) ion exchange (IE). The resulting complexes were characterized and assayed by batch release and column leaching tests, aiming at the controlled release of these herbicides. All the tested LDH-herbicide complexes displayed similar slow herbicide release properties in water, although the IE method seemed to result in complexes with a greater fraction of herbicide in a readily available form. Apparently, the LDH-herbicide complexes released most of the active ingredient present in the complexes at the end of the batch release experiment. This was attributed to the replacement of the intercalated herbicide by carbonate and hydroxyl anions from the aqueous solution. Compared to the free herbicides, the application of the three LDH-herbicide complexes (RE) to soil columns resulted in reduction in the maximum herbicide concentration in leachates and led to the retardation of herbicide leaching through the soil. All LDH-herbicide complexes presented an herbicidal efficacy similar to that of the free (technical) herbicides. Our results indicated the potential applicability of LDHs as supports for the preparation of slow release formulations of acid herbicides such as 2,4-D, MCPA, or picloram.     

Nanosized silica modified with carboxylic acid as support for controlled release of herbicides

Hexagonal mesoporous silica modified with carboxylic acid (SiAc) has been obtained by reaction between chloroacetic acid and 3-aminopropyltrimethoxysilane, which was immobilized on porous material by a sol-gel process in the presence of an n-dodecylamine template. SiAc was characterized by TG, FT-IR, (29)Si NMR, (13)C NMR, SEM, surface charge density, surface area and porous diameter, which proved that the carboxylic group was chemically bonded to an inorganic structure, and the material presented a nanometric structure with spheres <50 nm and porous diameter of 10 nm. Herbicides 2,4-D and picloram were anchored on SiAc porous gel to produce the materials named SiD and SiPi, respectively. The controlled release of picloram from the SiAc was less than that of 2,4-D. After 26 days of releasing, 4.43 × 10(-5) mol L(-1) of picloram was delivered by SiPi, and 5.0 × 10(-5) L(-1) was released from the SiD in 30 days.     

Denitrification in soil: Effects of herbicides

The effects of 20 herbicides on denitrification of nitrate in three soils were studied by determining the effects of 10 and 50μgg^?1 soil of each herbicide on the amounts of nitrate lost and the amounts of nitrite, N₂O and N₂ produced when soil samples were incubated anaerobically after treatment with nitrate. The herbicides used were butylate, EPTC, chlorpropham, propham, diuron, linuron, monuron, siduron, alachlor, trifluralin, 2,4-D amine, 2,4-D ester, atrazine, cyanazine, metribuzin, simazine, dalapon, chloramben, dicamba and dinoseb.None of the herbicides studied significantly affected denitrification of nitrate when applied at the rate of 10 μg g^?1 soil, but dinoseb increased the ratio of N₂ to N₂O in the gaseous products of denitrification when applied at this rate. Butylate, EPTC, diuron, simazine and dalapon had no significant effect on denitrification when applied at the rate of 50μgg^?1 soil, whereas metribuzin and dinoseb enhanced denitrification when applied at this rate. The influence of the other herbicides on denitrification when applied at the rate of 50μgg^?1soil depended on the soil, but all enhanced or inhibited denitrification in at least one soil.     

Synthesis of dimethyl derivatives of imidazolinone herbicides: their use in efficient gas chromatographic methods for the determination of these herbicides

The dimethyl derivatives of imazaquin, imazapyr, imazmethapyr, imazethapyr, 2-[4,5 dihydro-1, 4-dimethyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-methoxymethyl- 3-pyridine carboxylic acid, 2-[4,5-dihydro-1,4 -dimethyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4-methyl benzoic acid, and 2-[4,5-dihydro-1,4-dimethyl-4-(1-methyl ethyl)-5-oxo-1H-imidazol-2-yl]-5-methyl benzoic acid were prepared and fully characterized. The availability of these derivatives has led to the development of efficient and multiresidue gas chromatographic methods for trace level analysis of imidazolinone herbicides in matrixes such as water, soybean, and soil.     

Culture of commercially obtained Lumbricus terrestris L.: Implications for sub-lethal ecotoxicological testing

The use of commercially purchased or field-collected earthworms of unknown age, exposure or pre-treatment in sub-lethal ecotoxicological studies is questionable. In this study, adult (clitellate) Lumbricus terrestris, obtained from 5 commercial suppliers in the UK and also field collected, were kept under controlled environmental conditions (15 °C and 24 h darkness) in a sterilised loam soil and fed horse manure. Survival, biomass and cocoon production was monitored every 4 weeks over 1 y. Marked differences were recorded in survival rates (ranging from 40-100% after 40 weeks) and cocoon production (ranging from 15.1 to 32.2 worm⁻¹ y⁻¹) between treatments. Biomass in all treatments (mean mass 4.32-5.61 g at the outset) increased with time to week 20 (maximum 6.7 g) and then declined steadily (3.23-4.7 g at week 52). This pattern was also observed in cocoon production and was considered to be a function of an initial period of acclimation (0-12 weeks) followed by a period of high production (12-36 weeks) under optimal conditions and then fatigue (36-52 weeks) caused by reproductive exhaustion. Results suggest that earthworm origin may influence the validity and reproducibility of sub-lethal ecotoxicological studies and where applicable laboratory-reared earthworms of known age and history are recommended as test subjects.     

Homogentisic acid: a phenolic acid as a marker of strawberry-tree (Arbutus unedo) honey.

Analysis of organic acids in strawberry-tree (Arbutus unedo) honey showed the presence of an unknown acid as the main constituent. This compound was isolated and identified as homogentisic acid (2, 5-dihydroxyphenylacetic acid) by MS and NMR techniques. Its average content in honey was 378 +/- 92 mg/kg. Analysis of nectar confirmed the floral origin of the compound found in honey. Since this acid was not detected in any of the different monofloral honeys, it could be used as a marker of strawberry-tree (A. unedo) honey.     

Free radicals in electron donor-acceptor reactions between a soil humic acid and photosynthesis inhibitor herbicides

Products obtained by interaction of a soil humic acid with a number of s-triazines and substituted ureas, well known to act as photosynthesis inhibitor herbicides, were studied by infrared (IR) and electron spin resonance (ESR) spectrometries. Analysis of spectroscopic results showed that single-electron transfer processes take place reasonably between ring or chain donor groups of the herbicide molecule and acceptor quinone units of the humic acid, thus producing additional unpairing of electrons in the resulting charge-transfer complexes. Experimental and theoretical considerations suggested the hypothesis that the investigated herbicides may react chemically with humic compounds by simulating analogous processes that take place on biological scale in chloroplasts, on the basis of similar electron donor-acceptor reactions involving free radicals.     

Multiresidue HPLC methods for phenyl urea herbicides in water

High-performance liquid chromatography (HPLC) methods for the determination of phenyl urea herbicides in water are described. The target compounds include chlortoluron, diuron, fluometuron, isoproturon, linuron, metobromuron, metoxuron, monuron, neburon, and siduron. Water was subjected to solid phase extraction (SPE) using either automated SPE with 47 mm C(18) Empore disks or on-line precolumn concentration. Herbicides were separated on a C(18) reversed phase column with an acetonitile-water gradient and were detected with either a diode array detector (DAD) or a postcolumn photolysis and derivatization (PPD) detector system. Photolysis converted the phenyl ureas to monoalkylamines that were derivatized to fluorescent isoindoles by reaction with o-phthalaldehyde and 2-mercaptoethanol. The DAD monitoring at 245 nm was linear over three decades with instrument detection limits of approximately 0.01 mg/L. SPE efficiency was between 48 and 70% in laboratory reagent water, but use of the internal standard quantitation method improved accuracy. High total dissolved solids and total organic carbon values in surface water improved recoveries relative to laboratory reagent water for all of the phenyl ureas. In Colorado River water spiked at 1 or 50 microg/L, mean recoveries ranged from 74 to 104%. Method detection limits (MDLs) ranged from 4 to 40 ng/L (parts per trillion) with the DAD instrument. PPD detection was highly specific but resulted in a slight loss in chromatographic efficiency and average MDLs approximately 5 times higher using a single set of detection conditions. The study indicates that methods based on SPE followed by HPLC with diode array or PPD detection have practical utility for trace analysis of phenyl ureas in drinking water or surface waters.     

施用碱稳定污泥污水土壤经γ-辐照后土壤溶液中Cu和Zn

Soil samples collected from several acid soils in Guangdong, Fujian, Zhejiang and Anhui provinces of the southern China were employed to characterize the chemical species of aluminumions in the soils. The proportion of monomeric inorganic Al to total Al in soil solution was in the range of 19% to 70%, that of monomeric organic Al (Al-OM) to total Al ranged from 7.7% to 69%, and that of the acid-soluble Al to total Al was generally smaller and was lower than 20% in most of the acid soils studied. The Al-OM concentration in soil solution was positively correlated with the content of dissolved organic carbon (DOC) and also affected by the concentration of Al³⁺. The complexes of aluminum with fluoride (Al-F) were the predominant forms of inorganic Al, and the proportion of Al-F complexes to total inorganic Al increased with pH. Under strongly acid condition, Al³⁺ was also a major form of inorganic Al, and the proportion of Al³⁺ to total inorganic Al decreased with increasing pH. The proportions of Al-OH and Al-SO₄ complexes to total inorganic Al were small and were not larger than 10% in the most acid soils. The concentration of inorganic Al in solution depended largely on pH and the concentration of total F in soil solution. The concentrat ions of Al-OM, Al³⁺, Al-F and Al-OH complexes in topsoil were higher than those in subsoil and decreased with the increase in soil depth. The chemical species of aluminumions were influenced by pH. The concentrations of Al-OM, Al³⁺, Al-F complexes and Al-OH complexes decreased with the increase in pH.     

Chemical composition of acid precipitation in Central Texas

Studies were undertaken to determine factors affecting composition of acidic precipitation formation in the Austin area of Central Texas. The study was initiated to determine background levels of acid and alkalinity producing constitutents in an area with elevated natural dust levels from nearby limestone rock formations. Results showed normal rainfall pH values of 6.5 to 6.6 in the area, with extreme variations from 5.8 to 7.3. Significant Ca levels of 1 to 4 mg 1^?1 were observed from probably natural origin which appeared to have a buffering effect on acidity. Significant sulfate and nitrate ion concentrations occurred during the early stages of rainfall where rainfall pH was dependent on calcium-sulfate ratio.     

Investigation of alternate herbicides for effective weed management in glyphosate-tolerant cotton

ABSTRACT

Glyphosate-resistant (GR) weeds are the biggest concern for all cotton stakeholders worldwide. Currently, 43 weeds species are resistant to glyphosate and the number is increasing at an alarming rate. Soil residual/pre-emergence (PRE) herbicides like Pendimethalin and S-metolachlor can be effectively used for the control of GR weeds; however, their use is very limited at farmer’s side due to the adoption of herbicide-tolerant technology with complete reliance on glyphosate. The present study was conducted to evaluate the performance of PRE and post-emergence (POST) herbicides in glyphosate-tolerant (GT) cotton. The herbicide treatments were pendimethalin and S-metolachlor as PRE-residual, and glyphosate was applied as POST at 20 days after sowing (DAS) either alone or in combination with other herbicides like S-metolachlor, pendimethalin, and haloxyfop. A second application of glyphosate was made at 35 DAS. Results revealed that pendimethalin and S-metolachlor treatments gave 100% suppression of all dominant weeds and increased lint yield by 310–350% as compared to weedy control. In contrast, glyphosate applied once and twice, gave weed biomass reduction of only 10–86%, and increased lint yield by 136–185% over weedy control. This research established that PRE application of pendimethalin and S-metolachlor can be included in the weed management program of GT cotton.     

Fluorescence properties of humic acid interaction products with s-triazine and bipyridilium herbicides and their Cu complexes: a multivariate approach

Purpose

Excitation–emission matrices spectroscopy (EEMS) of soil humic acids (HAs) contains large amount of information on their properties, as well as on the dynamics related to their intra- and inter-molecular interactions. The objective of this research was (i) to show that EEMS represents a useful tool to investigate the molecular and mechanistic aspects of HA adsorbing capacity towards atrazine (A) and paraquat (P) with or without Cu²⁺ ions and (ii) to evaluate if additional information on these mechanisms can be obtained by combining EEMS with principal component analysis (PCA).

Materials and methods

HAs have been isolated from soil samples collected in a citrus field at three locations, within the plant rows (HAa); between the rows (HAb) and in a adjacent, control soil (HAc). Interaction products were obtained between each HA and A and P, with or without Cu ions. Elemental analysis and Fourier-transorm Infrared Spectroscopy were applied to support fluorescence data. Fluorescence spectra were recorded on aqueous solutions, and fluorescence intensity (FI) values were normalized using a quinine sulphate standard. PCA analysis was performed using the software STATGRAPHICS Centurion XV.I.

Results and discussion

The EEM spectra of the three unreacted HAs are characterized by the presence of two fluorophores α and β, in the region of longer wavelengths pairs (EEWP). The EEM spectra of the HA-A interaction products are featured by the same two fluorophores, with FI values decreased of about 50%, whereas those of the HA-P interaction products show a unique peak, γ, at intermediate EEWP. Finally, the EEM spectra of HA-A-Cu²⁺ show, with respect to HA-A samples, a blue shift of the α peak with an additional decrease of FI values (about 60%) and the disappearance of the peaks β, whereas those of HA-P-Cu²⁺ feature, in comparison with those of HA-P, a small red-shift of the peak γ. PCA data suggest that Cu ions do not affect the interaction mechanism between HA and P, whereas it appears to exercise a strong influence on interaction between HA and A.

Conclusions

The results obtained indicate that EEMS allows direct measurements of the adsorbing capacity of HA towards atrazine and paraquat. Additional information obtained by PCA analysis show that Cu ions behave like a good antagonist in preventing the formation of ionic bonds between HA and atrazine, whereas Cu is not able to affect the prevalent mechanism of HA interaction with paraquat, which is a charge-transfer bond.

     

Multiresidue method for determining substituted urea herbicides in foods by liquid chromatography

A method is described for determining substituted urea herbicides in foods. The residues are extracted from the product with methanol, and the food coextractives are removed by using solvent partitioning and Florisil column chromatography. The extract is analyzed using liquid chromatography with postcolumn photodegradation, chemical derivatization with orthophthalaldehyde, and spectrofluorometry. Recoveries were determined by spiking 8 different food products with 6 phenylureas--chlorbromuron, chloroxuron, diuron, fluometuron, linuron, and metobromuron--at 0.05 and 0.5 ppm. Three determinations were made at each level for each product. Average recovery at 0.05 ppm was 95% (with a standard deviation of 7.9%), and at 0.5 ppm, 98% (with a standard deviation of 6.9%).     

Hydrolysis of sulfonylurea herbicides in soils and aqueous solutions: a review

Sulfonylureas are a unique group of herbicides used for controlling a range of weeds and some grasses in a variety of crops and vegetables. They have been extremely popular worldwide because of their low mammalian toxicity, low use rate, and unprecedented herbicidal activity. Knowledge about the fate and behavior of sulfonylurea herbicides in the soil-water environment appears to be of utmost importance for agronomic systems and environmental protection. Because these herbicides are applied at a very low rate, and their mobility is greatly affected by the chemicals' anionic nature in alkaline soils, a thorough understanding of their degradation/hydrolysis processes and mechanisms under aqueous and soil systems is important. This review brings together published information on the hydrolysis of several sulfonylureas in aqueous and soil solutions that includes the effects of pH, temperature, functional relationship between pH vs hydrolysis rate constants, and hydrolysis behavior of sulfonylureas in the presence of minerals. In addition, the transformations of sulfonylureas in soil, under laboratory and field experiments, have been discussed in connection with the compounds' varied structural features, i.e., sulfonylueas that are with or without the pyridinic, pyrimidine, and triazinic ring.     

Comparative sorption and leaching study of the herbicides fluometuron and 4-chloro-2-methylphenoxyacetic acid (MCPA) in a soil amended with biochars and other sorbents

Biochar, the solid residual remaining after the thermochemical transformation of biomass for carbon sequestration, has been proposed to be used as a soil amendment, because of its agronomic benefits. The effect of amending soil with six biochars made from different feedstocks on the sorption and leaching of fluometuron and 4-chloro-2-methylphenoxyacetic acid (MCPA) was compared to the effect of other sorbents: an activated carbon, a Ca-rich Arizona montmorillonite modified with hexadecyltrimethylammonium organic cation (SA-HDTMA), and an agricultural organic residue from olive oil production (OOW). Soil was amended at 2% (w/w), and studies were performed following a batch equilibration procedure. Sorption of both herbicides increased in all amended soils, but decreased in soil amended with a biochar produced from macadamia nut shells made with fast pyrolysis. Lower leaching of the herbicides was observed in the soils amended with the biochars with higher surface areas BC5 and BC6 and the organoclay (OCl). Despite the increase in herbicide sorption in soils amended with two hardwood biochars (BC1 and BC3) and OOW, leaching of fluometuron and MCPA was enhanced with the addition of these amendments as compared to the unamended soil. The increased leaching is due to some amendments' soluble organic compounds, which compete or associate with herbicide molecules, enhancing their soil mobility. Thus, the results indicate that not all biochar amendments will increase sorption and decrease leaching of fluometuron and MCPA. Furthermore, the amount and composition of the organic carbon (OC) content of the amendment, especially the soluble part (DOC), can play an important role in the sorption and leaching of these herbicides.     

Analysis and detection of the herbicides dimethenamid and flufenacet and their sulfonic and oxanilic acid degradates in natural water

Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufenacet [N-(4-fluorophenyl)-N-(1-methylethyl)-2-(5-(trifluoromethyl)-1,3,4-thiadiazol-2-yl)oxy] were isolated by C-18 solid-phase extraction and separated from their ethanesulfonic acid (ESA) and oxanilic acid (OXA) degradates during their elution using ethyl acetate for the parent compound, followed by methanol for the polar degradates. The parent compounds were detected using gas chromatography-mass spectrometry in selected-ion mode. The ESA and OXA degradates were detected using high-performance liquid chromatography--electrospray mass spectrometry (HPLC-ESPMS) in negative-ion mode. The method detection limits for a 123-mL sample ranged from 0.01 to 0.07 microg/L. These methods are compatible with existing methods and thus allow for analysis of 17 commonly used herbicides and 18 of their degradation compounds with one extraction. In a study of herbicide transport near the mouth of the Mississippi River during 1999 and 2000, dimethenamid and its ESA and OXA degradates were detected in surface water samples during the annual spring flushes. For flufenacet, the only detections at the study site were for the ESA degradates in samples collected at the peak of the herbicide spring flush in 2000. The low frequency of detections in surface water likely is due to dimethenamid and flufenacet being relatively new herbicides. In addition, detectable amounts of the stable degradates have not been detected in ground water.     

ATP-sulphurylase: An enzymatic marker for biological sulphate reduction?

Adenosine triphosphate-sulphurylase (ATPS) plays a major role in dissimilatory sulphate reduction. In this study, the level of ATPS activity was monitored in a time course study using a biosulphidogenic batch bioreactor system. A coincident decrease in ATPS activity with a decline in sulphate concentration and an increase in sulphide concentration as biosulphidogenesis proceeded was observed. Flask studies further showed sulphate to be stimulatory to ATPS, while sulphide proved to be inhibitory. The effect of ions (Ca²⁺, Cl⁻, Fe²⁺ and Zn²⁺) on the ATPS activity was also investigated. Most of the ions studied (Ca²⁺, Cl⁻ and Fe²⁺) were stimulatory at lower concentrations (40-120 mg/l) but proved toxic at higher concentrations (>120 mg/l). In contrast, Zn²⁺ was inhibitory even at low concentrations (?40 mg/l). ATPS may potentially be used as an enzymatic marker for biological sulphate reduction in sulphate-rich wastewaters and natural environments (anaerobic systems such as soils and sediments found in freshwater and marine systems), providing all residual sulphide and interfering ions are removed using a simple preparative step.