丙硫克百威在几种土壤中的迁移和降解研究

对丙硫克百威在湖南几种土壤中的迁移和降解进行了研究。结果表明 :丙硫克百威在土壤中能被雨水淋溶迁移 ,在 2 0cm耕作土层中 ,丙硫克百威及其降解产物克百威要分布在 0～ 1 4cm范围内 ,丙硫克百威的使用 ,对地下水污染的可能性比较小。丙硫克百威在第四纪红土红壤、河潮土、河潮泥中半衰期分别为 6.3d、7.3d、8.8d。在施药 3 0d内 ,丙硫克百威在土壤中降解很快 ,化学降解作用要大于生物降解作用 ,其中部分降解产物为克百威、3 -羟基克百威 ,其中 3 -羟基克百威在丙硫克百威降解过程中产生甚微。克百威的继续降解随时间无明显的规律。     

Persistence, fate, and metabolism of [(14)C]metalaxyl in typical Indian soils

The biodegradation of ring-labeled [(14)C]metalaxyl in six Indian soils was examined. The total recovery of radioactivity from soil was 100 +/- 6% of the applied radioactivity. Volatile organics and (14)CO(2) were detected at lower levels. This suggests that neither mineralization nor volatilization is a major route of metalaxyl dissipation. The most rapid degradation of metalaxyl was observed in Bannimantap soil, in which the half-life of metalaxyl was 36 days. An inverse relationship was found when half-lives were plotted against microbial biomass and soil clay content. However, soil total organic carbon did not correlate with metalaxyl persistence. Five metabolites detected by thin-layer chromatography were more polar than metalaxyl.     

Capillary column gas chromatographic determination of dicamba in water, including mass spectrometric confirmation

A sensitive method is described for determining dicamba at low micrograms/L levels in ground waters by capillary column gas chromatography with electron-capture detection (GC-EC); compound identity is confirmed by gas chromatography-mass spectrometry (GC-MS) using selected ion monitoring. Dicamba residue is hydrolyzed in KOH to form the potassium salt. The sample is then extracted with ethyl ether which is discarded. The aqueous phase is acidified to pH less than 1 and extracted twice with ethyl ether. The combined ethyl ether extracts are concentrated, and the residue is methylated using diazomethane to form the corresponding dicamba ester. The derivatized sample is cleaned up on a deactivated silica gel column. The methylated dicamba is separated on an SE-30 capillary column and quantitated by electron-capture or mass spectrometric detection. Average recoveries (X +/- SD) for ground water samples fortified with 0.40 microgram/L of dicamba are 86 +/- 5% by GC-EC and 97 +/- 7% by GC-MS detections. The EDL (estimated detection limit) for this method is 0.1 microgram dicamba/L water (ppb).     

土壤中土霉素残留的高效液相色谱检测方法

为有效测定土壤中土霉素残留量,建立了固相萃取－高效液相色谱法提取以及测定潮土、红壤、紫色土中土霉素残留量的方法。土壤中土霉素残留经提取缓冲溶液进行有效提取,经过DVB固相萃取小柱纯化、无水甲醇洗脱和氮气流浓缩后,经HPLC测定。对提取缓冲液、流动相以及流动相pH值、有机相与无机相的比例以及流速等测定条件进行优化研究。结果表明：提取液为Na2EDTA-Mcllvaine,流动相为乙腈∶0.01mol/L磷酸二氢钠（pH值2.5,V∶V=10∶90）,温度25℃,流速1.2ml/min,检测波长350nm对3种不同性质的土壤中土霉素残留量的测定最为合适。应用本方法进行土壤中土霉素残留量的测定,土霉素含量与峰面积具有良好的线性关系,相关系数（n=9）分别为红壤0.997,紫色土0.995,潮土0.987;检出限分别为红壤0.11mg/kg,紫色土0.17mg/kg,潮土0.09mg/kg;回收率(n=18)分别为红壤80.7%~128.8%,紫色土70.5%~100.0%,潮土61.5%~103.9%;相对标准偏差(RSD, n=18)分别为红壤7.1%~28.2%,紫色土11.9%~38.1%,潮土4.1%~17.0％。本方法简便、准确,适合于测定不同土壤中土霉素残留量,结果可靠。     

Influence of pH and soil copper on adsorption of metalaxyl and penconazole by the surface layer of vineyard soils

The upper horizons of old vineyard soils have substantial copper contents due to the traditional use of copper-based fungicides. Total copper levels in eight vineyard soils in the Rías Baixas area of Galicia (northwestern Spain) ranged from 60 to 560 mg kg(-1) (mean +/- SD = 206 +/- 170 mg kg(-1)). The adsorption of the fungicides metalaxyl (pK(a) = 1.41) and penconazole (pK(a) = 2.83) by these soils was determined using fungicide solutions of pH 2.5 and 5.5, and desorption of fungicide adsorbed at pH 5.5 was also determined. In all cases, Freundlich equations were fitted to the data with R (2) > 0.96. Penconazole was adsorbed and retained more strongly than metalaxyl, with K(F) values more than an order of magnitude greater. In the desorption experiments, both fungicides exhibited hysteresis. Soil copper content hardly affected the adsorption of metalaxyl, but K(F) values for adsorption of penconazole increased at a rate of about 0.1 mL(n) (microg of penconazole)(1-n) (microg of Cu)(-1), which is attributed to the formation of Cu(2+)-penconazole complexes with greater affinity for soil colloids than penconazole itself. Because the dependence of K(F) for penconazole adsorption on copper content was the same at both pH values, complex formation appears not to have been affected by the solubilization of 6-17% of soil copper at pH 2.5. A similar copper dependence, or lack of dependence, was observed when 100-1000 mg kg(-1) of copper was added as Cu(NO(3))(2).2H(2)O to the solutions from which the fungicides were adsorbed.     

Solid-phase extraction of carbofuran, atrazine, simazine, alachlor, and cyanazine from shallow well water

Extraction of several nitrogen-containing pesticides from water on solid-phase C18 cartridges was rapid and accurate. One analyst can extract greater than 48 samples/day. Recovery efficiencies were 77, 95, 92, 90, and 99% with detection limits of 0.20, 0.05, 0.05, 0.20, and 0.10 micrograms/L for carbofuran, atrazine, simazine, alachlor, and, cyanazine, respectively. Extraction of the atrazine and simazine dealkylation products (deethylatrazine and deethylsimazine) was less efficient, e.g., 26 and 9%, respectively. Comparisons with 10 U.S. Geological Survey samples gave similar results.     

Influence of soil aging on sorption and bioavailability of simazine

Characterization of pesticide bioavailability, particularly in aged soils, is of continued interest because this information is necessary for environmental risk assessment. However, pesticide bioavailability in aged soils has been characterized by a variety of methods with limited success, due in part to methodological limitations. The objective of this study was to use solvent extraction methods to correlate simazine residue bioavailability in aged soils to simazine mineralization using a simazine-mineralizing bacterium. Soils from Brazil, Hawaii, and the midwestern United States were treated with UL-ring-labeled [14C]simazine and incubated for up to 8 weeks. At the end of each incubation period, soils were either incubated further, extracted with 0.01 M CaCl2, or extracted with aqueous methanol (80:20 v/v methanol/water). In a parallel experiment, after each incubation period, soils were inoculated with the bacterium Pseudomonas sp. strain ADP, which is capable of rapidly mineralizing simazine, and 14CO2 was determined. The inoculated soil samples were then extracted with 0.01 N CaCl2 and with aqueous methanol. This allowed for the evaluation of the bioavailability of aged simazine residues, without the contribution of simazine desorption from soil. Results of these studies indicated that simazine sorption to soil increased with aging and that amounts of simazine in aged soils extracted by 0.01 M CaCl2 and aqueous methanol were highly correlated to amounts of simazine mineralized by Pseudomonas sp. strain ADP. Consequently, 0.01 M CaCl2/methanol-extractable simazine in aged soils can be used to estimate bioavailable residues. This technique may be useful in determining the bioavailability of other s-triazine compounds in soils.     

基于实时荧光定量PCR技术的油气微生物勘探样品保存研究

针对一个油气藏和两个非油气藏上方的土壤剖面,围绕典型油气指示微生物甲烷氧化细菌,采用分子生态学技术比较了新鲜、自然风干和冷冻干燥3种处理下土壤中甲烷氧化细菌标靶基因pmoA的变化规律,研究了自然风干土壤能否用于油气资源微生物勘探.与新鲜土壤相比,自然风干和冷冻干燥显著降低了不同土壤剖面微生物总DNA含量,甲烷氧化细菌pmoA基因数量最多分别下降了90.7％和77.5％;然而,与非油气藏上方土壤剖面相比,自然风干和冷冻干燥处理后,油气藏上方不同土壤剖面依然检测到了大量的甲烷氧化细菌pmoA基因.本研究中,自然风干或冷冻干燥处理后的土壤适合于油气微生物勘探.     

Adsorption and analysis of the insecticides thiamethoxam and indoxacarb in hawaiian soils

A method was developed for the simultaneous extraction and analysis of the insecticides indoxacarb and thiamethoxam from five Hawaiian soils. Using pressurized fluid extraction followed by liquid chromatography, optimized recoveries from the five soils were obtained ranging from 80% +/- 5 to 101% +/- 10 for thiamethoxam, and 83% +/- 6 to 106% +/- 7 for indoxacarb. Aging studies also showed strong binding of indoxacarb to all soils tested after 30 days, while thiamethoxam remained quite available for extraction during the length of the study (90 days). Freundlich constant (K(f)) and empirical value (n) for thiamethoxam sorption on Lihue soil were 0.007391 mmol((1-1/)(n)).L(1/)(n).g(-1) and 1.1377, respectively; K(f) and n were 0.007844 mmol((1-1/)(n)).L(1/)(n).g(-1) and 0.8473, respectively, on Wahiawa soil. The organic carbon adsorption constant (Koc) of thiamethoxam was 0.53 in Lihue soil and 0.23 in Wahiawa soil.     

磷灰石和石灰稳定化修复对污染土壤铜和镉垂直迁移的影响

大量改良材料被用于重金属污染土壤的稳定化修复,但是不同用量的改良材料长期田间修复后重金属总量和有效态在不同土层的垂直分布特征鲜有研究涉及。本研究采集不同剂量的磷灰石和石灰稳定化修复的0~13、13~30和30~50 cm土层污染土壤,考察铜和镉总量及有效态含量在不同土层的分布特征。结果表明:随着磷灰石和石灰用量的增加,显著降低了0~13 cm土层土壤交换性酸和交换性铝,增加了土壤全钙的含量,且磷灰石处理提高了土壤全磷和速效磷含量。0~13 cm土层土壤pH、总铜和总镉含量均随着磷灰石和石灰用量的增加而逐渐增加,但是降低了13~30和30~50 cm土层土壤总铜和总镉含量。3个土层中铜和镉有效态含量均随着磷灰石和石灰用量的增加而显著降低,其中23.2 g/kg磷灰石处理和4 g/kg石灰处理土壤有效态铜含量降低85.1%和92.0%,有效态镉降低18.8%和23.5%。相关性分析表明,土壤pH和铜镉总量是影响铜镉有效性的主要因素。可见,磷灰石和石灰的应用使铜和镉较好地固定在土壤表层,减少铜和镉向下层土壤的淋溶,降低了铜和镉的有效性。     

Determination of ethalfluralin in canola seed, meal, and refined oil by capillary gas chromatography with mass selective detection

Ethalfluralin is a herbicide that is effective for weed control on a wide variety of crops, including canola. A method is described for the determination of ethalfluralin residues in canola seed, meal, and refined oil. Residues are extracted from canola sample matrixes with acetonitrile. An aliquot of the extract is diluted with water and purified by C(18) solid-phase extraction prior to analysis by capillary gas chromatography with mass selective detection. For all three sample matrixes, the method has a validated limit of quantitation of 0.02 microg/g and a limit of detection of 0.006 microg/g. Recoveries averaged 96 +/- 7% for canola seed, 87 +/- 6% for canola meal, and 89 +/- 5% for refined oil. In a magnitude-of-residue study, canola seed from field plots that had been treated with ethalfluralin at one to three times the maximum label rate for weed control were found to contain no detectable residue of the herbicide.     

Simultaneous analysis of free and conjugated estrogens, sulfonamides, and tetracyclines in runoff water and soils using solid-phase extraction and liquid chromatography-tandem mass spectrometry

The ability to monitor multiple analytes from various classes of compounds in a single analysis can increase throughput and reduce cost when compared to traditional methods of analyses. This method for analyzing free (parent estrogen) and conjugated estrogens (metabolites) along with sulfonamides and tetracyclines utilizes a high pH (10.4) mobile phase with an ammonium hydroxide buffer for both positive- and negative-mode electrospray ionization. A single-step sample preparation by solid-phase extraction (SPE) was used to isolate and concentrate all analytes simultaneously. The analytical method was developed and validated for recoveries at 3 concentration levels for water and soil and produced recoveries of 42-123% and 21-105% respectively. Method detection limits ranged from 0.3 to 1.0 ng/L for water samples and 0.01 to 0.1 ng/g for soils. The method quantification limit ranged from 0.9 to 3.3 ng/L for water samples and 0.06 to 0.7 ng/g for soils. The single-point standard addition calibration procedure was validated across a linear range of MQL to 100 ng/L with ≥82% accuracy against a matrix matched standard curve. Furthermore, sorption of tetracyclines onto glassware was investigated and minimized by 10% using nitric acid-rinsed glassware, while separation parameters were further optimized based on retention time and signal responses. This method has been used for the quantification of estrogens, tetracyclines, and sulfonamides in soil and runoff waters with multiple compounds detected simultaneously in a single analysis.     

Adenosine Deaminase Activity in Soils

Adenosine deaminase activity in six soil samples was measured. One g of moist soil was incubated with 0.02 M adenosine in 0.1 M phosphate buffer (pH 7.6) and toluene in a shaking water bath (30°C) for 72 h. Inosine and NH₂ ⁺ were detected in the filtrate as degradation products of adenosine; inosine was identified by paper chromatography, and NH₂ ⁺ was determined by Nessler’s method.

The adenosine deaminase activity in soils was completely inhibited by autoclaving (120°C, 15 min).

The relation between substrate concentration and reaction rate followed the Michaelis-Menten equation.

The optimum pH for adenosine deaminase activity in soils ranged from about 7 to 8.

The adenosine deaminase activity in soils ranged from about 1.51 to 4.33 munit (nmol per min) per g of dry soil at 30°C.     

Bovine serum albumin and Triton X-100 greatly increase phosphomonoesterases and arylsulphatase extraction yield from soil

Extraction of arylsulphatase (aryS), acid (acP) and alkaline phosphomonoesterase (alkP) from six different soils using sodium pyrophosphate (0.14 M, pH 7.1) yielded brown extracts displaying enzymatic activity mostly below detection limit. Tris-HCl (50 mM, pH 7.5) gave an extraction yield, on average, lower than 0.5%, but addition of Triton X-100 or bovine serum albumine (BSA) to Tris buffer increased the extraction yield 2-8 times. When both Triton X-100 and BSA were added to the buffer, the extraction yield was more than additive and reached 2-13% for acP, 2-5% for alkP and 3-6% for aryS, depending on the soil. In addition, these extracts were colourless or at most light yellow, showing that besides the high yield enzymes were extracted along with negligible amounts of humic substances.     

Changes in soil microflora in response to repeated applications of some pesticides

The effects of pesticides on soil microflora were studied on arable soils that had received repeated applications of carbofuran and carbosulfan (insecticides), iprodione and vinclozolin (fungicides), and MCPA, simazine and paraquat (herbicides). Carbofuran at single and 5-fold treatments did not show any detectable detrimental effects on soil microbial biomass, but single application of carbosulfan produced a significant biomass reduction. There were dramatic reductions in soil microbial biomass following vinclozolin application, and this was due to a reduction in fungal biomass; iprodione showed less obvious biomass trends. MCPA and simazine caused no detectable effects to the microflora, but repeated paraquat application significantly lowered soil microbial biomass (chiefly fungal biomass). The results indicate that there may be substantially different effects on soil biomass produced by single or repeated applications of pesticides.     

Gas Chromatography–Mass Spectroscopy Analysis of Carbofuran and Its Metabolite 3-Hydroxy-carbofuran in Maize and Soil in Field

In this article, a simple and efficient method using gas chromatography–mass spectrometry (GC-MS) was developed to determine carbofuran and 3-hydroxy carbofuran in maize and soil. Field experiments were carried out to investigate the dissipation of carbofuran and its metabolite 3-hydroxy carbofuran in soil and maize plants and their accumulation in maize. Results showed that the half-lives of carbofuran were 4.7 and 5.3 days in maize plants and 8.5 and 7.6 days in soil for Beijing and Jinan trial sites, respectively. The final residues of carbofuran and 3- hydroxy carbofuran in the soils and maize grain were not detected. This study suggests that carbofuran is acceptable to apply to maize in the recommended dosage and can be a good alternative to other highly toxic insecticides.     

Simultaneous determination of ochratoxin A and cyclopiazonic,mycophenolic, and tenuazonic acids in cornflakes by solid-phase microextraction coupled to high-performance liquid chromatography

A solid-phase microextraction (SPME) method, coupled to liquid chromatography with diode array UV detection (LC-UV/DAD), for the simultaneous determination of cyclopiazonic acid, mycophenolic acid, tenuazonic acid, and ochratoxin A is described. Chromatographic separation was achieved on a propylamino-bonded silica gel stationary phase using acetonitrile/methanol/ammonium acetate buffer mixture (78:2:20, v/v/v) as mobile phase. SPME adsorption and desorption conditions were optimized using a silica fiber coated with a 60 microm thick polydimethylsiloxane/divinylbenzene film. Estimated limits of detection and limits of quantitation ranged from 3 to 12 ng/mL and from 7 to 29 ng/mL, respectively. The method has been applied to cornflake samples. Samples were subjected to a preliminary short sonication in MeOH/2% KHCO(3) (70:30, v/v); the mixture was evaporated to near dryness and reconstituted in 1.5 mL of 5 mM phosphate buffer (pH 3) for SPME followed by LC-UV/DAD. The overall procedure had recoveries (evaluated on samples spiked at 200 ng/g level) ranging from 74 +/- 4 to 103 +/- 9%. Samples naturally contaminated with cyclopiazonic and tenuazonic acids were found; estimated concentrations were 72 +/- 9 and 25 +/- 6 ng/g, respectively.     

Comparison of ammonium lactate,sodium bicarbonate and double calcium lactate methods for extraction of phosphorus from wetland peat soils

Procedures for routine analysis of soil phosphorus (P) have been used for assessment of P status, distribution and P losses from cultivated mineral soils. No similar studies have been carried out on wetland peat soils. The objective was to compare extraction efficiency of ammonium lactate (P-AL), sodium bicarbonate (P-Olsen), and double calcium lactate (P-DCaL) and P distribution in the soil profile of wetland peat soils. For this purpose, 34 samples of the 0–30, 30–60 and 60–90 cm layers were collected from peat soils in Germany, Israel, Poland, Slovenia, Sweden and the United Kingdom and analysed for P. Mean soil pH (CaCl₂, 0.01 M) was 5.84, 5.51 and 5.47 in the 0–30, 30–60 and 60–90 cm layers, respectively. The P-DCaL was consistently about half the magnitude of either P-AL or P-Olsen. The efficiency of P extraction increased in the order P-DCaL<P-AL≤P-Olsen, with corresponding means (mg kg^?1) for all soils (34 samples) of 15.32, 33.49 and 34.27 in 0–30 cm; 8.87, 17.30 and 21.46 in 30–60 cm; and 5.69, 14.00 and 21.40 in 60–90 cm. The means decreased with depth. When examining soils for each country separately, P-Olsen was relatively evenly distributed in the German, UK and Slovenian soils. P-Olsen was linearly correlated (r=0.594, P=0.0002) with pH, whereas the three P tests (except P-Olsen vs P-DCaL) significantly correlated with each other (P=0.0178≤0.0001). The strongest correlation (r=0.617, P=0.0001) was recorded for P-AL vs P-DCaL) and the two methods were inter-convertible using a regression equation: P-AL=?22.593+5.353 pH+1.423 P-DCaL, R ² =0.550.     

Simultaneous determination of alachlor, metolachlor, atrazine, and simazine in water and soil by isotope dilution gas chromatography/mass spectrometry

A multiresidue method was developed for the simultaneous determination of low parts per billion (ppb) concentrations of the herbicides alachlor, metolachlor, atrazine, and simazine in water and soil using isotope dilution gas chromatography/mass spectrometry (GC/MS). Known amounts of 15N,13C-alachlor and 2H5-atrazine were added to each sample as internal standards. The samples were then prepared by a solid phase extraction with no further cleanup. A high resolution GC/low resolution MS system with data acquisition in selected ion monitoring mode was used to quantitate herbicides in the extract. The limit of detection was 0.05 ppb for water and 0.5 ppb for soil. Accuracy greater than 80% and precision better than 4% was demonstrated with spiked samples.     

Determination of bentazone, dichlorprop, and MCPA in different soils by sodium hydroxide extraction in combination with solid-phase preconcentration

A method for the extraction of bentazone, dichlorprop, and MCPA in three selected Norwegian soils of different textures is described. Initially three different extraction methods were tested on one soil type. All methods gave recoveries >80% for the pesticide mixture, but extraction with sodium hydroxide in combination with solid-phase preconcentration was used for further recovery tests with soils of different properties spiked at four herbicide concentration levels (0.001-10 microg/g of wet soil). The method was rapid and easy and required a minimum of organic solvents. The recoveries were in the range of 82-109, 80-123, and 45-91% for the soils containing 1.4 (Hole), 2.5 (Kroer), and 37.8% (Froland) organic carbon, respectively. Limits of quantification using GC-MS were 0.0003 microg/g of wet soil for bentazone and 0.0001 microg/g of wet soil for both dichlorprop and MCPA.