Determination of free fatty acids in soil and bryophyte plants by precolumn derivatization via HPLC with fluorescence detection and tandem mass spectrometry (HPLC-MS/MS)

A sensitive method for the determination of 30 kinds of free fatty acids (FFAs, C-1-C-30) with 1-[2-(p-toluenesulfonate)-ethyl]-2-phenylimidazole-[4,5-f] 9,10-phenan- threne (TSPP) as labeling reagent and using high performance liquid chromatography with fluorescence detection and identification by online postcolumn mass spectrometry with atmospheric pressure chemical ionization (APCI) source in positive-ion mode (HPLC/MS/APCI) has been developed. TSPP could easily and quickly label FFAs in the presence of K2CO3 catalyst at 90 degrees C for 30 min in N,N-dimethylformamide (DMF) solvent, and maximal labeling yields close to 100% were observed with a 5-fold excess of molar reagent. Derivatives were stable enough to be efficiently analyzed by high performance liquid chromatography. TSPP was introduced into fatty acid molecules and effectively augmented MS ionization of fatty acid derivatives and led to regular MS and MS/MS information. The collision induced cleavage of protonated molecular ions formed specific fragment ions at m/z [MH](+)(molecular ion), m/z [M'+CH2CH2](+)(M' was molecular mass of the corresponding FFA) and m/z 295.0 (the, mass of protonated molecular core structure of TSPP). Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C-8 column (4.6 x 150 mm, 5 mu m, Agilent) with a good baseline resolution in combination with a gradient elution. Linear ranges of 30 FFAs are 2.441 x 10(-3) to 20 mu mol/L, detection limits are 3.24 similar to 36.97 fmol (injection volume 10 mu L, at a signal-to-noise ratio of 3, S/N 3:1). The mean interday precision ranged from 93.4 to 106.2% with the largest mean coefficients of variation (R.S.D.) < 7,5%. The mean intraday precision for all standards was < 6.4% of the expected concentration. Excellent linear responses were observed with correlation coefficients of > 0.9991. Good compositional data could be obtained from the analysis of extracted fatty acids from as little as 200 mg of bryophyte plant samples.Therefore, the facile TSPP derivatization coupled with HPLC/MS/APCI analysis allowed the development of a highly sensitive method for the quantitation of trace levels of short and long chain fatty acids from biological and natural environmental samples.

Suitability of extractants for predicting available sulfur in natural grassland in the Inner Mongolia steppe of China

It was the objective of this study to compare the suitability of different extractants for predicting the availability of sulfur (S) in natural grassland in a sulfur response trial on three different soil types in the Inner Mongolia steppe of China. For soil analysis, seven different extractants have been employed. The inorganic SO4-S concentration was determined by ion chromatography. Additionally, in the Ca(H-2-PO4)(2) extract the total soluble S was determined employing turbidimetry. Weak salt solutions (0.15% CaCl2, Ca(H2PO4)(2), and KH2PO4) extracted similar amounts Of SO4-S. Extraction with 0.025 M KCl provided the lowest SO4-S values. Deionized water dissolved significantly more SO4-S in the control plots than most weak salt extractants. The concentration of soluble organic S decreased in the control plots after 100 days of plant growth, indicating that the organic S pool contributed significantly to the S nutrition of the forage crops. Significant relationships among the SO4-S in the soil determined in different extracts and crop yield, sulfur content in the forage, and total sulfur uptake were only found for the Ca(H2PO4)(2) extract. In general, the correlation coefficients proved to be unsatisfactory for field experimentation.

Jiangella gansuensis gen. nov., sp nov., a novel actinomycete from a desert soil in north-west China

A novel actinomycete strain, designated YIM 002(T), was isolated from a desert soil sample in Gansu Province, north-west China. This actinomycete isolate formed well-differentiated aerial and substrate mycelia. In the early stages of growth, the substrate mycelia fragmented into short or elongated rods. Chemotaxonomically, it contained LL-2,6-diaminopimelic acid in the cell wall. The cell-wall sugars contained ribose and glucose. Phospholipids present were phosphatidylinositol mannosides, phosphatidylinositol and diphosphatidylglycerol. MK-9(H-4) was the predominant menaquinone. The major fatty acids were anteiso C-15:0 (35.92%), anteiso C-17:0 (15.84%), iso C-15:0 (10.40%), iso C-16:0 (7.07%) and C(17:10)w8c (9.37%). The G+C content of the DNA was 70 mol%. Phylogenetic analysis and signature nucleotide data based on 16S rRNA gene sequences showed that strain YIM 002(T) is distinct from all recognized genera of the family Nocardioidaceae in the suborder Propionibacterineae. On the basis of the phenotypic and genotypic characteristics, it is proposed that isolate YIM 002(T) be classified as a novel species in a new genus, Jiangella gansuensis gen. nov., sp. nov. The type strain is YIM 002(T) (= DSM 44835(T) = CCTCC AA 204001(T) = KCTC 19044(T)).

Local warming about 1.3 degrees C in alpine meadow has no effect on root vole (Microtus oeconomus L.) population during winter

The influence of air and soil warming on root vole (Microtus oeconomus L.) population was studied in winter period in top open chambers (OTC) (0.8-1.8 m(2) warmed by conical fiberglass material and situated in alpine meadow (3250 m) at Qinghai-Tibet Plateau, China. The OTCs were distributed on an area of 30 x 30 m of experimental warming site; another site of the same area was a control one. The root vole population was investigated on two pairs of sites in "low-grazing" and "high-grazing" (by sheep) parts of the meadow; mark-recapture method was used. The winter-season averaged air and soil temperature inside of the chambers were 1.3 degrees C higher than the temperature outside the chambers. The warming in the chambers had no statistically significant effect on root vole numbers, on average body mass of individual, and on average body mass of males and females. In conclusion, as small as 1.3 degrees C warming of soil and air introduced locally and on small (several m(2)) scale, in the alpine meadow habitat in winter period, has possibly no effect on root vole numbers and biomass.

Grazing intensity alters soil respiration in an alpine meadow on the Tibetan plateau

Grazing intensity may alter the soil respiration rate in grassland ecosystems. The objectives of our study were to (1) determine the influence of grazing intensity on temporal variations in soil respiration of an alpine meadow on the northeastern Tibetan Plateau; and (2) characterise, the temperature response of soil respiration under different grazing intensities. Diurnal and seasonal soil respiration rates were measured for two alpine meadow sites with different grazing intensities. The light grazing (LG) meadow site had a grazing intensity of 2.55 sheep ha(-1), while the grazing intensity of the heavy grazing (HG) meadow site, 5.35 sheep ha(-1), was approximately twice that of the LG site. Soil respiration measurements - showed that CO2 efflux was almost twice as great at the LG site as at the HG site during the growing season, but the diurnal and seasonal patterns of soil respiration rate were similar for the two sites. Both exhibited the highest annual soil respiration rate in mid-August and the lowest in January. Soil respiration rate was highly dependent on soil temperature. The Q(10) value for annual soil respiration was lower for the HG site (2.75) than for the LG site (3.22). Estimates of net ecosystem CO2 exchange from monthly measurements of biomass and soil respiration revealed that during the period from May 1998 to April 1999, the LG site released 2040 g CO2 m(-2) y(-1) to the atmosphere, which was about one third more than the 1530g CO2 m(-2) y(-1) released at the HG site. The results suggest that (1) grazing intensity alters not only soil respiration rate, but also the temperature dependence of soil CO2 efflux; and (2) soil temperature is the major environmental factor controlling the temporal variation of soil respiration rate in the alpine meadow ecosystem. (C) 2003 Elsevier Ltd. All fights reserved.

西藏高原草原化嵩草草甸生态系统呼吸及碳平衡

The soil respiration and net ecosystem productivity of Kobresia littledalei meadow ecosystem was investigated at Dangxiong grassland station, one grassland field station of Lhasa Plateau Ecosystem Research Station. Soil respiration and soil heterotrophic respiration were measured at the same time by using Li6400-09 chamber in growing season of year 2004. The response of soil respiration and its components, i.e. microbial heterotrophic respiration and root respiration to biotic and abiotic factors were addressed. We studied the daily and seasonal variation on Net Ecosystem carbon Exchange (NEE) measured by eddy covariance equipments and then the regression models between the NEE and the soil temperature. Based on the researches, we analyzed the seasonal variation in grass biomass and estimated NEE combined the Net Ecosystem Productivity with heterogeneous respiration and then assessed the whether the area is carbon source or carbon sink. 1.Above-ground biomass was accumulated since the grass growth started from May; On early September the biomass reached maximum and then decreased. The aboveground net primary production (ANPP) was 150.88 g m~" in 2004. The under-ground biomass reached maximum when the aboveground start to die back. Over 80% of the grass root distributed at the soil depth from 0 to 20cm. The underground NPP was 1235.04 g m"2.. Therefore annual NPP wasl.385X103kg ha"1, i.e.6236.6 kg C ha"1. 2. The daily variation of soil respiration showed single peak curve with maximum mostly at noon and minimum 4:00-6:00 am. Daily variations were greater in June, July and August than those in September and October. Soil respiration had strong correlation with soil temperature at 5cm depth while had weaker correlation with soil moisture, air temperature, surface soil temperature, and so on. But since early September the soil respiration had a obviously correlation with soil moisture at 5cm depth. Biomass had a obviously linearity correlation with soil respiration at 30th June, 20th August, and the daytime of 27th September except at 23lh October and at nighttime of 27th September. We established the soil respiration responding to the soil temperature and to estimate the respiration variation during monsoon season (from June through August) and dry season (May, September and October). The regression between soil respiration and 5cm soil temperature were: monsoon season (June through August), Y=0.592expfl()932\ By estimating , the soil daily respiration in monsoon season is 7.798gCO2m"2 and total soil respiration is 717.44 gCC^m" , and the value of Cho is 2.54; dry season (May, September and October), Y=0.34exp°'085\ the soil daily respiration is 3.355gCO2m~2 and total soil respiration is 308.61 gCC^m", and the value of Cho is 2.34. So the total soil respiration in the grown season (From May to October) is 1026.1 g CO2IT1"2. 3. Soil heterogeneous respiration had a strong correlation with soil temperature especially with soil temperature at 5cm depth. The variation range in soil heterogeneous respiration was widely. The regression between soil heterogeneous respiration and 5cm soil temperature is: monsoon season, Y=0.106exp ' 3x; dry season, Y=0.18exp°"0833x.By estimating total soil heterotrophic respiration in monsoon season is 219.6 gCC^m"2, and the value of Cho is 3.78; While total soil heterogeneous respiration in dry season is 286.2 gCCbm"2, and the value of Cho is 2.3. The total soil heterotrophic respiration of the year is 1379.4kg C ha"1. 4. We estimated the root respiration through the balance between soil respiration and the soil heterotrophic respiration. The contribution of root respiration to total respiration was different during different period: re-greening period 48%; growing period 69%; die-back period 48%. 5. The Ecosystem respiration was relatively strong from May to October, and of which the proportion in total was 97.4%.The total respiration of Ecosystem was 369.6 g CO2 m" .we got the model of grass respiration respond to the soil temperature at 5cm depth and then estimated the daytime grass respiration, plus the nighttime NEE and daytime soil respiration. But when we estimated the grass respiration, we found the result was negative, so the estimating value in this way was not close. 6. The estimating of carbon pool or carbon sink. The NPP minus the soil heterogeneous respiration was the NEE, and it was 4857.3kg C o ha"1, which indicated that the area was the carbon sink.

Estimation of soil organic partition coefficients: from retention factors measured by soil column chromatography with water as eluent

The retention factors (k) of 104 hydrophobic organic chemicals (HOCs) were measured in soil column chromatography (SCC) over columns filled with three naturally occurring reference soils and eluted with Milli-Q water. A novel method for the estimation of soil organic partition coefficient (K-oc) was developed based on correlations with k in soil/water systems. Strong log K-oc versus log k correlations (r>0.96) were found. The estimated K-oc values were in accordance with the literature values with a maximum deviation of less than 0.4 log units. All estimated K-oc values from three soils were consistent with each other. The SCC approach is promising for fast screening of a large number of chemicals in their environmental applications. (C) 2002 Elsevier Science B.V. All rights reserved.

Influence of methanol on retention of hydrophobic organic chemicals in soil leaching column chromatography

The influence of methanol in methanol-water mixed eluents on the capacity factor (P), an important parameter which could depict leaching potential of hydrophobic organic chemicals (HOCs) in soil leaching column chromatography (SLCC), was investigated. Two reference soils, GSE 17201 obtained from Bayer Landwirtschaftszentrum, Monheim, Germany and SP 14696 from LUFA, Spencer, Germany, were used as packing materials in soil columns, and isocratic elution with methanol-water mixtures at different volume fractions of methanol (phi) were tested. Shortterm exposure of the column (packed with the GSE 17201 soil) to the eluents increased solute retention by a certain (23% log-unit) degree evaluated through a correlation with the retention on the same soil column but unpreconditioned by methanol-containing eluents. Long-term exposure of soil columns to the eluents did not influence the solute retention. A log-linear equation, log k' = log k'(w) - Sphi, could well and generally describe the retention of HOCs in SLCC. For the compounds of homologous series, logk'(w), had good linear relationship with S, indicating the hydrophobic partition mechanism existing in the retention process. (C) 2002 Elsevier Science Ltd. All rights reserved.

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C-18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) = XYZ(0) + mV(1)/100 + spi* + bbeta(m) + aalpha(m), was applied to analyze capacity factors (k'), soil organic partition coefficients (K-oc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control log K-oc, log P, and log k' (on soil and on C-18) are the solute size (V-1/100) and hydrogen-bond basicity (beta(m)). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpha(m)). Log k' on soil and log K-oc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C-18 and log P have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, log k' values on C-18 have good correlations with log P (r > 0.97), while log k' values on soil have good correlations with log K-oc (r > 0.98). Two K-oc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC. (C) 2002 Elsevier Science Ltd. All rights reserved.

Prediction of soil adsorption coefficients from retention parameters on three reversed-phase liquid chromatographic columns

Reversed-phase high-performance liquid chromatographic (RP-HPLC) retention parameters, which are determined by the intermolecular interactions in retention process, can be considered as the chemical molecular descriptors in linear free energy relationships (LFERs). On the basis of the characterization and comparison of octadecyl-bonded silica gel (ODS), cyano-bonded silica gel (CN), and phenyl-bonded silica gel (Ph) columns with linear solvation energy relationships (LSERs), a new multiple linear regression model using RP-HPLC retention parameters on ODS and CN columns as variables for estimation of soil adsorption coefficients was developed. It was tested on a set of reference substances from various chemical classes. The results showed that the multicolumn method was more promising than a single-column method was for the estimation of soil adsorption coefficients. The accuracy of the suggested model is identical with that of LSERs.

Retention behavior of hydrophobic organic chemicals as a function of temperature in soil leaching column chromatography

To study the transport mechanism of hydrophobic organic chemicals (HOCs) and the energy change in soil/solvent system, a soil leaching column chromatographic (SLCC) experiment at an environmental temperature range of 20-40 degreesC was carried out, which utilized a reference soil (SP 14696) packed column and a methanol-water (1:4 by volume ratio) eluent. The transport process quickens with the increase of column temperature. The ratio of retention factors at 30 and 40 degreesC (k'(30)/k'(40)) ranged from 1.08 to 1.36. The lower enthalpy change of the solute transfer in SLCC (from eluent to soil) than in conventional reversed-phase liquid chromatography (e.g., from eluent to C-18) is consistent with the hypothesis that HOCs were dominantly and physically partitioned between solvent and soil. The results were also verified by the linear solvation energy relationships analysis. The chief factor controlling the retention was found to be the solute solvophobic partition, and the second important factor was the solute hydrogen-bond basicity, while the least important factors were the solute polarizability-dipolarity and hydrogen-bond acidity. With the increase of temperature, the contributions of the solute solvophobic partition and hydrogen-bond basicity gradually decrease, and the latter decreases faster than the former. (C) 2002 Elsevier Science Ltd. All rights reserved.

Soil column chromatography for correlation between capacity factors and soil organic partition coefficients for eight pesticides

A soil column chromatographic method was developed to measure the capacity factors (k') of pesticides, in which soil acted as a stationary phase and methanol-water mixture as an eluent. The k' values of eight pesticides, including three insecticides (methiocarb, azinphos-methyl, fenthion), four fungicides (triadimenol, fuberidazole, tebuconazole, pencycuron), and one herbicide (atrazine), were found to be well fitted to a retention equation, ln k'=ln k(w)'-S-phi. Due to similar interactions of solutes with soil and solvent in both sorption determination and retention experiment, log k' has a good linear correlation with log K-oc for the eight pesticides from different classes, in contrast with poor correlation between log k' from C-18 column and log K-oc. So the method provides a tool for rapid estimation of K-oc from experimental k'. (C) 1999 Elsevier Science Ltd. All rights reserved.

Soil differentiation using fingerprint Fourier transform infrared spectroscopy, chemometrics and genetic algorithm-based feature selection

Elliott, G. N., Worgan, H., Broadhurst, D. I., Draper, J. H., Scullion, J. (2007). Soil differentiation using fingerprint Fourier transform infrared spectroscopy, chemometrics and genetic algorithm-based feature selection. Soil Biology & Biochemistry, 39 (11), 2888-2896. Sponsorship: BBSRC / NERC RAE2008