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1.
Standing water from carbofuran-treated Azolla plots showing accelerated degradation was further enriched by five repeated transfers to carbofuran-supplemented mineral salts medium. This enrichment culture developed from standing water of carbofuran-treated Azolla plot can utilise carbofuran as sole source of carbon and nitrogen. The enrichment culture was able to hydrolyse nearly 100% of [ring-14C]carbofuran to carbofuran phenol in five days, which accumulated in the medium, while the carbamate side-chain in [carbonyl-14C]carbofuran was readily mineralized to [14C]carbon dioxide. Enrichment culture was able to degrade carbofuran up to 1000 µg ml−1 levels in mineral salts medium with ease. © 1999 Society of Chemical Industry  相似文献   

2.
Soils which have been pretreated with carbofuran can degrade the insecticide more rapidly than untreated soils, with a consequent loss of efficacy. In laboratory studies, soils pretreated with carbofuran were found to degrade the chemical more rapidly than soils which were not so pretreated. When pretreated soils were sterilised, the rate of carbofuran degradation was much reduced, indicating that most of it was due to microbial action. Incubation of pretreated soil with [phenyl-U-14C]carbofuran led to the rapid disappearance of the parent compound (3 % left after seven days). Most of the 14C was accounted for as bound residue after seven days, whilst smaller amounts were recovered as carbon dioxide, 3-hydroxycarbofuran, 3-ketocarbofuran, and an unknown metabolite. Incubation of pretreated soil with [carbonyl-14C]carbofuran led to rapid loss of the parent compound and the recovery of 73% of 14C as carbon dioxide by five days. Most of the bound 14C (>90%) arising from [phenyl-U-14C]carbofuran treatment of pretreated soil was extracted by 1 M sodium hydroxide and about half of the extracted 14C was precipitated with ‘humic acids’ after acidification. These and other results suggest that the major metabolic route for carbofuran in pretreated soils involves hydrolysis of the ester bond leading to (1) release of carbofuran phenol which rapidly binds to soil organic matter and, (2) release of the carbonyl moiety which quickly degrades to generate carbon dioxide.  相似文献   

3.
Prediction of the fate of pesticides in soil is of interest from an environmental (pollution) as well as an agricultural (efficacy, carryover) viewpoint. Two environmental parameters that control microbial degradation of pesticides in soil are moisture and temperature. This study was designed to quantify the impact of soil water content and temperature on microbial degradation rates of the insecticide carbofuran (2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl methyl-carbamate). Carbofuran degradation was determined by monitoring the [ 14 C] carbondioxide production from soils amended with [carbonyl- 14 C]carbofuran. Soils were incubated at seven soil-water tensions over the range of 0–03 to 1–5 MPa, and at five temperatures (10°C to 30°C). The sigmoidal degradation kinetics observed from these incubations were modeled using a general saturation model. For the moisture experiments, maximum rate of hydrolysis and half-life (DT50) were accurately modeled by an exponential relationship. The response of carbofuran degradation to temperature was also well described by an exponential relationship, from which it was estimated that the Q10 associated with the maximum rate was 1.68, and the Q10 for DT50 was 1–89.  相似文献   

4.
Ammonium sulphate and urea, but not potassium sulphate, increased the persistence of carbaryl in a flooded laterite soil with a low native nitrogen content (0.04%), but not in an alluvial soil with a higher nitrogen content (0.11%). Thus, NH4+ but not SO42-, contributed to the increased persistence of carbaryl. Likewise, ammonium sulphate increased the persistence of carbofuran in the laterite soil, but not in the alluvial soil. Significant accumulations of 1-naphthol and 2,3-dihydro-2, 2-dimethylbenzofuran-7-ol (‘carbofuran phenol’), in soils treated with carbaryl or carbofuran, suggested hydrolysis as the major pathway of degradation. Treatment of the two soils with ammonium sulphate, urea or potassium sulphate led to a decrease in soil-bound residues and an increase in the respective hydrolysis products, compared with untreated soils. Sorption studies indicated that NH4+ and SO42- compete with carbaryl, 1-naphthol and carbofuran for sorption and exchange sites in the complex soil system. Evolution of [14C]carbon dioxide from ring-14C in carbaryl and carbofuran was negligible. Consequently, after 40 days, more than 50% of the 14C in [14C]carbaryl and [14C]carbofuran remained in the soils as hydrolysis products (1-naphthol or 2,3-dihydro-2,2-dimethylbenzofuran-7-ol) plus soil-bound residues.  相似文献   

5.
Ring- and carboxyl-labelled [14C]2,4-D were incubated under laboratory conditions, at the 2 g/g level, in a heavy clay, sandy loam, and clay loam at 85% of field capacity and 20 1C. The soils were extracted at regular intervals for 35 days with aqaeous acidic acetonitrile, and analysed for [14C]2,4-D and possible radioactive degradation products. Following solvent extraction, a portion of the soil residues were combusted in oxygen to determine unextracted radioactivity as [14C]carbon dioxide. The remaining soil residues were then treated with aqueous sodium hydroxide, and the radioactivity associated with the fulvic and humic soil components determined. In all soils there was a rapid decrease in the amounts of extractable radioacitivity, with only 5% of that applied being recoverable after 35 days. All recoverable radioactivity was attributable to [14C]2,4-D, and no [14C]-containing degradation products were observed. This loss of extractable radioactivity was accompanied by an increase in non-extractable radioactivity. Approximately 15% of the applied radioactivity, derived from carboxyl-labelled [14C]2,4-D, and 30% from the ring-labelled [14C]2,4-D was associated with the soil in a non-extractable form, after 35 days of incubation. After 35 days, less than 5% of the radioactivity from the carboxyl-labelled herbicide, and less than 10% of the ringlabelled material, was associated with the fulvic components derived from the three soils. Less than 5% of the applied radioactivities were identifiable with any of the humic acid components. It was considered that during the incubation [14C]2,4-D did not become bound or conjugated to soil components, and that non-extractable radioactivity associated with the three soil types resulted from incorporation of radioactive degradation products, such as [14C]carbon dioxide, into soil organic matter.  相似文献   

6.
The biomineralization of [14C]glyphosate, both in the free state and as 14C-residues associated with soybean cell-wall material, was studied in soil samples from four different agricultural farming systems. After 26 days, [14C]carbon dioxide production from free glyphosate accounted for 34–51% of the applied radiocarbon, and 45–55% was recovered from plant-associated residues. For three soils, the cumulative [14C]carbon dioxide production from free glyphosate was positively correlated with soil microbial biomass, determined by substrate-induced heat output measurement and by total adenylate content. The fourth soil, originating from a former hop plantation, and containing high concentrations of copper from long-term fungicide applications, did not fit this correlation but showed a significantly higher [14C]carbon dioxide production per unit of microbial biomass. Although the cumulative [14C]carbon dioxide production from plant-associated 14C-residues after 26 days was as high as from the free compound, it was not correlated with the soil microbial biomass. This indicates that the biodegradation of plant-associated herbicide residues, in contrast to that of the free compound, involves different degradation processes. These encompass either additional steps to degrade the plant matrix, presumably performed by different soil organisms, or fewer degradation steps since the plant-associated herbicide residues are likely to consist mainly of easily degradable metabolites. Moreover, the bioavailability of plant-associated pesticide residues seems to be dominated by the type and strength of their fixation in the plant matrix. ©1997 SCI  相似文献   

7.
Laboratory studies on the formation of bound residues and on the degradation of the triazole fungicide propiconazole were conducted in two different soils. Soils treated with 14C-propiconazole were incubated at 22 degrees C and extracted exhaustively with a solvent at each sampling date until no further propiconazole was extracted. The solvent-extractable residues were used to measure propiconazole remaining in the soil, and the extracted soils were used to investigate bound residues of propiconazole. Mineralization of propiconazole was investigated by measuring [14C]carbon dioxide evolved from the soil samples. Formation of bound residues of propiconazole was higher in silty clay loam soil than in sandy loam soil, giving approximately 38 and 23% of the applied 14C, respectively. In contrast, the rates of degradation and mineralization of propiconazole were lower in silty clay loam soil than in sandy loam soil. Decreased extractability of the 14C residues with incubation time was observed with increased formation of bound residues. When the propiconazole remaining in the solvent-extractable residues was quantitatively measured by high-pressure liquid chromatographic analysis, the half-life value in sandy loam soil was about 315 days, while the half-life in silty clay loam soil exceeded the duration of the 1 year experimental period. Increased formation of bound residues was observed as propiconazole degraded with incubation time, suggesting that degradation products are involved in the formation of bound residues. Our study suggests that the formation of bound residues of propiconazole contributes to the persistence of this fungicide in soil.  相似文献   

8.
Volatilization, mineralization, degradation and binding of soil-applied [14C]DDT were studied in three different soils from a tropical region of southern India subjected to solar irradiation and flooding for a period of 42 days. The soil types–red cotton soil, nursery soil and canal bank soil–differed in their organic carbon content, pH and texture. Under unflooded conditions, volatile losses were highest in the sandy canal bank soil. Flooding significantly enhanced volatilization, and this effect was maximal in the nursery soil, which had the highest organic carbon. The soils fully exposed to solar radiations in quartz tubes registered 1.5-1.8 times greater volatility. The volatilized organics contained appreciable quantities of DDE under both flooded and unflooded conditions. In addition, greater quantities of DDD volatilized from the flooded systems. The rate of formation of DDE was faster when soils were irradiated in quartz tubes. Mineralization remained minimal throughout the period of exposure and flooding the soil appeared to reduce further the [14C]carbon dioxide evolution. Canal bank soil exhibited the least mineralization and degradation. The data indicate that volatilization was significantly influenced by solar radiation and flooding to a much greater degree than by the differences in soil properties. Binding of DDT to soil was significantly increased by flooding the soil, thus leaving up to 33% of the initial DDT as bound residues in the nursery soil.  相似文献   

9.
Carbofuran was incubated in top‐soil and sub‐soil samples from a pesticide‐free site at a range of initial concentrations from 0.1 to 10 mg kg−1. Amounts of the incubated soils were removed at intervals over the subsequent 12 months, and the rate of degradation of a second carbofuran dose at 10 mg kg−1 was assessed. An applied concentration as low as 0.1 mg kg−1 to top‐soil resulted in more rapid degradation of the fresh addition of carbofuran for at least 12 months. The degree of enhancement was generally more pronounced with the higher initial concentrations. When the same study was conducted in sub‐soil samples from the same site, an initial dose of carbofuran at 0.1 mg kg−1 resulted in only small increases in rates of degradation of a second carbofuran dose. However, degradation rates in the sub‐soil samples were, in many instances, considerably greater than in the corresponding top‐soil samples, irrespective of pre‐treatment concentration or pre‐incubation period. Initial doses of 0.5 mg kg−1 and higher applied to sub‐soil successfully activated the sub‐soil microflora. Application of the VARLEACH model to simulate carbofuran movement through the soil profile indicated that approximately 0.01 mg kg−1 of carbofuran may reach a depth of 70 cm 400 days after a standard field application. The results therefore imply that adaptation of the sub‐soil microflora (c 1 m depth) by normal field rate applications of carbofuran is unlikely to occur. In experiments to investigate this in soils exposed to carbofuran in the field, there was no apparent relationship between top‐soil exposure and degradation rates in the corresponding sub‐soils. The results further confirmed that some sub‐soil samples have an inherent capacity for rapid biodegradation of carbofuran. The high levels of variability observed between replicates in some of the sub‐soil samples were attributed to the uneven distribution of a low population of carbofuran‐degrading micro‐organisms in sub‐surface soil. There was no apparent relationship between soil microbial biomass and degradation rates within or between top‐soil and sub‐soil samples. © 2001 Society of Chemical Industry  相似文献   

10.
The distribution and fate of [14C]carbofuran were studied in model earlyseason rice/fish and late-season rice/fish ecosystems after its application by respectively soil incorporation and broadcasting. The differences observed in the behaviour of the insecticide in these two rice/fish ecosystems indicated the important effect of the different application methods on the fate of the chemical in the environment. The radioactive residues in the paddy water, rice plants and fish were much lower when the pesticide was incorporated into the soil surface layer. An obvious vertical movement of carbofuran residues occurred in the paddy soil profile. Bound residues constituted the majority of the residues in the paddy soil, rice plants and fish tissues. 3-Hydroxy- and 3-ketocarbofuran and carbofuran phenol were tentatively identified as the main degradation products in the paddy water, paddy soil, rice plants and fish.  相似文献   

11.
The persistence of carbofuran (2, 3-dihydro-2, 2-dimethylbenzofuran-7-yl methylcarbamate) and the β- and γ-isomers of HCH (hexachlorocyclohexane) applied to surface (oxidised) and sub-surface (reduced) layers of a flooded soil was studied using radiolabelled insecticides. In one experiment, these compounds were placed in the surface (2–5 mm) and sub-surface (10–15 cm) layers of 10-day flooded soil columns. HCH isomers were unstable under flooded soil conditions irrespective of their placement, but disappeared slightly faster when applied to the sub-surface layer, possibly due to the more reduced conditions prevailing. In contrast, sub-surface-applied carbofuran was more stable than surface-applied carbofuran. The decreased stability of surface-applied carbofuran may be due to a relatively higher pH in the surface layer and in the flood water which was in immediate contact with the surface layer. In another experiment, surface and sub-surface soil samples were collected from a rice field which had been flooded for 30 days. These soils were then again flooded under laboratory conditions prior to addition of carbofuran and β-HCH. Upon submergence, both surface and sub-surface soil samples attained almost equally reduced conditions. In flooded surface soil samples, more rapid degradation not only of carbofuran but also of β-HCH occurred, compared with similarly incubated sub-surface soil samples.  相似文献   

12.
The degradation of the wild oat herbicide flamprop-methyl [methyl DL -N-benzoyl-N-(3-chloro-4-fluorophenyl)alaninate] in four soils has been studied under laboratory conditions using 14C-1abelled samples. The flamprop-methyl underwent degradation more rapidly than its analogue flamprop-isopropyl. However, similar degradation products were formed, namely the corresponding carboxylic acid and 3-chloro-4-fluoroaniline. The latter compound occurred mainly as ‘bound’ forms although evidence was obtained of limited ring-opening to give [14C]carbon dioxide. The time for depletion of 50% of the applied herbicide was approximately 1-2 weeks in sandy loam, clay and medium loam soils and 2-3 weeks in a peat soil.  相似文献   

13.
Mineralisation of the phenylurea herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) and two of its known metabolites, 3-(4-isopropylphenyl)-1-methylurea (monodesmethyl-isoproturon) and 4-isopropylaniline, was studied in Danish agricultural soils with or without previous exposure to isoproturon. A potential for rapid mineralisation of isoproturon and the two metabolites was present in soils sampled from three plots within an agricultural field previously treated regularly with the herbicide, with 34-45%, 51-58% and 33-36% of the added [phenyl-U-14C]isoproturon, [phenyl-U-14C]monodesmethyl-isoproturon and [phenyl-U-14C]4-isopropylaniline metabolised to [14C]carbon dioxide within 30 days at 20 degrees C. In contrast, such extensive mineralisation of these three compounds was not observed within this period in soils sampled from two other agricultural fields without previous treatment with isoproturon. The mineralisation patterns indicated growth-linked metabolism of the three compounds in the previously exposed soils, and doubling times for [14C]carbon dioxide production ranged from 1.6 to 3.2, 1.0 to 2.1 and 1.3 to 1.7 days for isoproturon, monodesmethyl-isoproturon and 4-isopropylaniline, respectively. The ability to mineralise [phenyl-U-14C]isoproturon to [14C]carbon dioxide was successfully sub-cultured to a fresh mineral medium which provided isoproturon as sole source of carbon and nitrogen. One of the soils sampled from an agricultural field not previously treated with isoproturon showed accelerated mineralisation of [phenyl-U-14C]4-isopropylaniline toward the end of the experiment, with a doubling time for [14C]carbon dioxide production of 7.4days. This study indicates that the occurrence of rapid mineralisation of the phenyl ring of isoproturon to carbon dioxide is related to previous exposure to the herbicide, which suggests that microbial adaptation upon repeated isoproturon use may occur within agricultural fields.  相似文献   

14.
Nutrient-agar plates containing isoxaben (500 mg litre(-1)) were used to isolate isoxaben-metabolising bacteria from four European soils incubated with the herbicide under laboratory conditions. In flask experiments, inoculation of a basal salts medium containing nitrogen and [phenyl-U-14C]isoxaben with an isolate (B2b) resulted in 33% recovery of the initial radioactivity as [14C]carbon dioxide after 2 weeks. A major metabolite identified by GC-MS and NMR analysis as 3-(1-ethyl-1-methylpropyl)isoxazol-5-ylamine accumulated both in basal salts and nutrient broth media. 2,6-Dimethoxybenzoic acid, a suspected metabolite of isoxaben, was not detected in either liquid media. However, the capability of the B2b isolate to use 2,6-dimethoxybenzoic acid as a source of carbon was demonstrated. Soil inoculation with the B2b strain resulted in an increase in the recovery of [14C] carbon dioxide from both [phenyl-U-14C] and [isoxazole-5-14C]isoxaben. The metabolite identified as 3-(1-ethyl-1-methylpropyl)isoxazole-5-ylamine only accumulated if the soil was autoclaved before inoculation. This metabolite was rapidly mineralized by the microflora of a natural soil without history of isoxaben treatment. Homology patterns of sequenced 16S rDNA between isoxaben-transforming isolates and reference strains showed that the four isolates identified belonged to the genus Microbacterium.  相似文献   

15.
The spatial variability in mineralization of atrazine, isoproturon and metamitron in soil and subsoil samples taken from a 135-ha catchment in north France was studied. Fifty-one samples from the top layer were taken to represent exhaustively the 31 agricultural fields and 21 soil types of the catchment. Sixteen additional samples were collected between depths of 0.7 and 10 m to represent the major geological materials encountered in the vadose zone of the catchment. All these samples were incubated with 14C-labelled atrazine under laboratory conditions at 28 degrees C. Fourteen selected surface samples which exhibited distinctly different behaviour for atrazine dissipation (including sorption and mineralization) were incubated with 14C-isoproturon and 14C-metamitron. Overall soil microbial activity and specific herbicide degradation activities were monitored during the incubations through measurements of total carbon dioxide and 14C-carbon dioxide respectively. At the end of the incubations, extractable and non-extractable (bound) residues remaining in soils were measured. Variability of herbicide dissipation half-life in soil surface samples was lower for atrazine and metamitron (CV < 12%) than for isoproturon (CV = 46%). The main contributor to the isoproturon dissipation variability was the variability of the extractable residues. For the other herbicides, spatial variability was mainly related to the variability of their mineralization. In all cases, herbicide mineralization half-lives showed higher variability than those of dissipation. Sorption or physicochemical soil properties could not explain atrazine and isoproturon degradation, whose main factors were probably directly related to the dynamics of the specific microbial degradation activity. In contrast, variability of metamitron degradation was significantly correlated to sorption coefficient (K(d)) through correlation with the sorptive soil components, organic matter and clay. Herbicide degradation decreased with depth as did the overall microbial activity. Atrazine mineralization activity was found down to a depth of 2.5 m; beyond that, it was negligible.  相似文献   

16.
The potential to mineralize 2,4‐dichlorophenoxyacetic acid (2,4‐D), mecoprop, isoproturon and terbuthylazine was studied in soil and aquifer chalk sampled at an agricultural field near Aalborg, Denmark. Laboratory microcosms were incubated for 258 days under aerobic conditions at 10 °C with soil and chalk from 0.15–4.45 m below the surface. The [ring‐U14C]‐labeled herbicides were added to obtain a concentration of 6 µg kg?1 and mineralization was measured as evolved [14C]carbon dioxide. The herbicides were readily mineralized in soil from the plough layer, except for terbuthylazine, which was mineralized only to a limited extent. In the chalk, lag periods of at least 40 days were observed, and a maximum of 51%, 33% and 6% of the added 2,4‐D, mecoprop and isoproturon, respectively, were recovered as [14C]carbon dioxide. Large variations in both rate and extent of mineralization were observed within replicates in chalk. No mineralization of terbuthylazine in chalk was observed. As a measure of the general metabolic activity towards aromatic compounds, [ring‐U14C]‐benzoic acid was included. It was readily mineralized at all depths. © 2000 Society of Chemical Industry  相似文献   

17.
The spatial variability in the mineralisation rate of linuron [N-(3,4-dichlorophenyl)-N'-methoxy-N'-methylurea] was studied within a previously treated Danish agricultural field by sampling soils from eleven different plots randomly distributed across an area of 20 x 20 m. The soils were characterised with respect to different abiotic and biotic properties including moisture content, organic matter content, pH, nutrient content, bacterial biomass, potential for mineralisation of MCPA [(4-chloro-2-methylphenoxy)acetic acid] and linuron. Five soils had a potential for mineralisation of linuron, with 5-15% of the added [ring-U-14C]linuron metabolised to 14CO2 within 60 days at 10 degrees C, while no extensive mineralisation of linuron was observed in the six remaining soils within this period. A TLC analysis of the methanol-extractable residues showed no development of 14C-labelled metabolites from linuron in any of the samples. Multivariate analysis was conducted to elucidate relationships between the intrinsic properties of single soil samples and initial rate of linuron mineralisation. The analysis indicated that important soil parameters in determining the spatial heterogeneity included the C(total)/N(total) ratio, pH and the water-extractable potassium contents, with the first of these highly negatively correlated and the last two highly positively correlated to the initial linuron mineralisation rate. This study shows that enhanced biodegradation of linuron may develop with successive field treatments, but that considerable in-field spatial heterogeneity in the degradation rate still exists. Combined with a parallel enrichment study focused on the underlying microbial processes, the present results suggest that intrinsic soil properties affect the linuron-metabolising bacterial population and thereby determine the spatial variability in the linuron mineralisation activity.  相似文献   

18.
A 140-day laboratory incubation, using surface soil from a long-term soybean tillage study, evaluated tillage influence on [14C]metribuzin degradation. Higher plant residue conditions in no-tillage (NT) soil inhibited metribuzin mineralization to [14C]carbon dioxide as compared to metribuzin degradation patterns observed in conventional tillage (CT) soil. At 140 days, relative abundance of extractable 14C components in NT included polar metabolites > metribuzin = deaminated metribuzin (DA) = deaminated diketometribuzin (DADK), while in CT, components included metribuzin > polar metabolites > DADK?DA. Conditions in NT apparently inhibited polar 14C degradation, and resulted in its accumulation, while in CT polar 14C degradation proceeded relatively rapidly. For both NT and CT, more 14 C was measured in an unextractable fraction than in any other fraction. A greater portion of the unextractable fraction in NT was associated with decomposed plant residue than in CT. Surface accumulation of crop residue, such as occurs under NT, provided a soil environment which altered metribuzin degradation patterns.  相似文献   

19.
The aim of this study was to investigate the spatial variability in degradation and mineralization of atrazine and isoproturon in subsurface samples taken from sandy loam soils overlying gravel terraces which form part of a groundwater protection zone. Percussion drilling was used to obtain samples from 11 boreholes (maximum depth 3 m). Unlabelled atrazine or isoproturon, and ring-14C-labelled atrazine or isoproturon were added to samples, incubated at 25 degrees C for up to 16 weeks, and analyzed for the residual herbicide or [14C]carbon dioxide. All samples showed the potential to degrade these herbicides, although the percentage degradation decreased by a factor of 2-3 from the surface soil to a depth of 3 m. This was associated with a decrease in organic matter content, but there was no change in the potential to mineralize acetate, indicating that specific changes in the catabolic ability of the microbial population occurred with depth. The capacity of samples to mineralize atrazine and isoproturon to carbon dioxide decreased markedly with depth, with no mineralization potential observed at a depth of 80 cm.  相似文献   

20.
The effects of application rate, volume, solvent and soil moisture content on the kinetics of mineralization and degradation, of [14C] permethrin have been studied in a sandy loam soil under standard laboratory conditions. During the incubation period, up to 32 days, the temperature and moisture level of the soil were controlled. Apart from the effects of application rate, which have been widely reported, application volume had the most significant effect on mineralization rate and T1/2. [14C]Permethrin, at a level of a 1 mg kg?1 in the soil, applied in 100 μl of methanol, resulted in the evolution of 14% of the applied radiochemical as [14C] carbon dioxide over 30 days. The same level applied in 1000 μl mineralized at a faster rate, with 30% [14C]carbon dioxide evolved over 30 days. The test chemical applied to soil in methanol mineralized at a significantly faster rate than a similar concentration applied in ethanol. There was no significant difference when comparing applications made using acetonitrile with those using methanol or ethanol. The addition of formulation ingredients resulted in little or no variation in mineralisation rate compared to an equivalent application volume of methanol/water.  相似文献   

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