Glyphosate (GLY) and glufosinate (GLUF) are non-selective translocated herbicides that are used in agricultural and non-agricultural land worldwide. The extensive use of GLY and GLUF may lead to their accumulation in soil, which causes soil pollution and affects the soil micro-ecological environment; the accumulated GLY and GLUF also migrate to groundwater via leaching. However, GLY, GLUF, and their metabolites are highly water-soluble and lack chromogenic and fluorescent groups, making them difficult to analyze. Currently, derivatization methods are mostly used to detect GLY, GLUF, and their metabolites. However, these methods also have some drawbacks, such as complex operation, long time consumption, and poor stability. In addition, these compounds are easily passivated and made inactive in soil; they also react with organic matter, humic acid, metal oxides, and heavy metal ions, making their extraction from soil difficult. To date, the method for the determination of GLY, GLUF, and their metabolites in soil is limited. Therefore, it is necessary to establish a quick and sensitive method to determine the residues of GLY, GLUF, and their metabolites in soil. In this study, a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed for the determination of GLY, GLUF, and their metabolites in soil. Parameters like extraction solvent, extraction temperature, extraction time, and adsorbents, which affected the extraction efficiencies, were optimized. Finally, the soil samples were extracted with 0.5 mol/L ammonia solution in a bath shaker at 50 ℃, and then centrifuged at 10000 r/min for 5 min. The supernatant was filtered through 0.2-μm syringe filters and then determined by HPLC-MS/MS. A Dikma Polyamino HILIC column (150 mm×2.0 mm, 5 μm) was used for chromatographic separation with good peak shape and high response of the target compounds. Ammonium acetate (0.2 mmol/L) with 0.07% ammonia aqueous solution and acetonitrile were used as the mobile phase. The flow rate of the elute was 0.25 mL/min. MS/MS was conducted under multiple reaction monitoring (MRM) mode using an electrospray ionization (ESI) source, and was quantified by the external standard method using matrix-matched calibration curves. All the target compounds were ionized in the negative ionization mode. The linear ranges of GLY and its metabolites were between 5.0 and 500 μg/L, and those of GLUF and its metabolites were between 2.0 and 500 μg/L. Linear correlation coefficients were greater than 0.99. The limit of detection (LOD) and limit of quantification (LOQ) were assessed using signal-to-noise (S/N) ratios of 3 and 10, respectively. The LOD and LOQ values of both GLY and (aminomethyl)phosphonic acid (AMPA) were 4.0 and 13.3 μg/kg, respectively. The LOD and LOQ values of GLUF, MPP, and N-acetyl glufosinate (NAG) were 2.0 and 6.7 μg/kg, respectively. Method accuracy was acquired by recovery test at three spiked levels (0.02, 0.05, 0.2 mg/kg). The average recoveries of five targets spiked in soil with low organic matter content were 74.2%-101%, and the relative standard deviation (RSD) was 0.93%-6.8%; the average recoveries of the five targets spiked in soil with high organic matter content were 90.8%-116%, and the RSD was 0.40%-7.1%. The established method was used to determine 20 soil samples in peach orchard, and the detection rates of AMPA, GLY, MPP, GLUF and NAG were 45%, 25%, 10%, 5% and 5%, respectively. The maximum residues were 147, 35.2, 154, 21.6 and 11.0 μg/kg, respectively. This method is simple, rapid, green, inexpensive, allows pretreatment without organic reagents, and affords high accuracy, high sensitivity, and good reproducibility. The method is suitable for testing a large number of soil samples with different organic matter contents. It can provide reliable technical support for the study of residue status and environmental behavior in soil.
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This chapter focuses on the schematic description of sulfur (S) cycle at global level and in soil–plant–atmosphere systems. Knowledge of this cycle helps in understanding the accumulation and turnover of organic S in soils. The chapter also summarizes the knowledge concerning the quantity, forms, distribution, and turnover of organic S in soils. Chemical fractionation provides information about the nature of organic S, yet it does not provide a true reflection of the biological reactivity of the different forms of S in soil where the whole system is heterogenous and complex. The method that fractionates soil organic S into different pools according to their biological and biochemical lability is very informative. Microbial biomass-S is the most active component of soil organic S. The relationships and interactions between organic C, N, and S cycles in soil are examined through the perspective of microbial activity.
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The capacity to accumulate cadmium (Cd) and zinc (Zn) was compared in Thlaspi goesingense and four populations of Thlaspi caerulescens . Two populations of T. caerulescens were grown in hydroponics at five concentrations of Cd. In addition, plants were grown in pots containing compost in which three different concentrations of Cd and two concentrations of Zn were added. A field trial was conducted to compare Zn and Cd uptake by three populations of T. caerulescens on nine selected plots of the Woburn Market Garden Experiment (UK) which had been contaminated to different degrees with heavy metals owing to past applications of sewage sludge. Results show that the four populations of T. caerulescens had the same ability to hyperaccumulate Zn but were significantly different in terms of Cd accumulation. Two populations of T. caerulescens from Southern France accumulated much more Cd than the populations from Prayon (Belgium) and Whitesike (UK). Generally, uptake of Cd was not decreased by increased concentrations of Zn in the substrate. These results indicate that the mechanisms of Cd and Zn hyperaccumulation are not identical in this species. This is the first report of hyperaccumulation of Cd by T. goesingense , but the growth of this species was markedly reduced by the large concentrations of Zn in the substrate. Future work should focus on the differences between Cd and Zn uptake in hyperaccumulator plants at the species and population level.
Summary Berkheya coddii is a fast‐growing, high biomass nickel (Ni) hyperaccumulator plant that has recently attracted attention for its possible use in the phytoextraction of Ni. The mechanisms of Ni accumulation, however, are not well understood in this plant. Plants were grown hydroponically in varying Ni concentrations to assess the uptake and distribution of Ni, and other metals, at the whole plant level. X‐ray microanalyses (EDXA) of frozen hydrated tissues were conducted to determine the distribution of Ni at the cellular level in the leaves. Most Ni was found in the shoots, especially in the leaves. Leaf Ni concentration increased with age, whereas older stem sections had lower Ni concentrations than new growth. EDXA analyses revealed that the cuticle of the upper epidermis had a significantly higher Ni concentration than the rest of the leaf. The Ni concentrations in the other leaf tissues were not significantly different. This pattern of distribution contrasts sharply with some other hyperaccumulator species that commonly show a preferential accumulation of Ni and other metals in the vacuoles of the epidermal cells.
Atmospheric SO2 emissions in the UK and globally increased 6- and 20-fold, respectively, from the mid-1800s to the 1960s resulting in increased S deposition, acid rain, and concurrent acidification of terrestrial and aquatic ecosystems. Structural analyses using synchrotron-based X-ray near-edge spectroscopy (XANES) on humic substance extracts of archived samples from the Rothamsted Park Grass Experiment reveal a significant (R2 = -0.58; P < 0.05; N = 7) shift in soil organic sulfur (S) forms, from reduced to more oxidized organic S between 1876 and 1981, even though soil total S contents remained relatively constant. Over the last 30 years, a decrease in emissions and consequent S deposition has again corresponded with a change of organic S structures of humic extracts-reverting in the direction of their early industrial composition. However, the observed reversal lagged behind reductions in emissions by 19 years, which was computed using cross correlations between time series data (R2 = 0.66; P = 0.0024; N = 11). Presently, the ratio of oxidized-to-reduced organic S in humic substance extracts is nearly double that of early industrial times at identical SO2 emission loads. The significant and persistent structural changes of organic S in humic substances as a response to SO2 emissions and S deposition may have effects on recuperation of soils and surface waters from acidification.
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