Poor efficacy of herbicides in biochar-amended soils as affected by their chemistry and mode of action

We evaluated wheat straw biochar produced at 450 °C for its ability to influence bioavailability and persistence of two commonly used herbicides (atrazine and trifluralin) with different modes of action (photosynthesis versus root tip mitosis inhibitors) in two contrasting soils. The biochar was added to soils at 0%, 0.5% and 1.0% (w/w) and the herbicides were applied to those soil-biochar mixes at nil, half, full, two times, and four times, the recommended dosage (H₄). Annual ryegrass (Lolium rigidum) was grown in biochar amended soils for 1 month. Biochar had a positive impact on ryegrass survival rate and above-ground biomass at most of the application rates, and particularly at H₄. Within any given biochar treatment, increasing herbicide application decreased the survival rate and fresh weight of above-ground biomass. Biomass production across the biochar treatment gradient significantly differed (p < 0.01) and was more pronounced in the case of atrazine than trifluralin. For example, the dose-response analysis showed that in the presence of 1% biochar in soil, the value of GR₅₀ (i.e. the dose required to reduce weed biomass by 50%) for atrazine increased by 3.5 times, whereas it increased only by a factor of 1.6 in the case of trifluralin. The combination of the chemical properties and the mode of action governed the extent of biochar-induced reduction in bioavailability of herbicides. The greater biomass of ryegrass in the soil containing the highest biochar (despite having the highest herbicide residues) demonstrates decreased bioavailability of the chemicals caused by the wheat straw biochar. This work clearly demonstrates decreased efficacy of herbicides in biochar amended soils. The role played by herbicide chemistry and mode of action will have major implications in choosing the appropriate application rates for biochar amended soils.     

Sorption–desorption of indaziflam and its three metabolites in sandy soils

Indaziflam is a relatively new herbicide for which sorption–desorption information is lacking, and nothing is available on its metabolites. Information is needed on the multiple soil and pesticide characteristics known to influence these processes. For four soils, the order of sorption was indaziflam (N-[1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 5.9, 1/n_f = 0.7, K_foc = 447; sandy loam: K_f = 3.9, 1/n_f = 0.9, K_foc = 276) > triazine indanone metabolite (N-[(1R,2S)-2,3-dihydro-2,6-dimethyl-3-oxo-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 2.1, 1/n_f = 0.8, K_foc = 177; sandy loam: K_f = 1.7, 1/n_f = 0.9, K_foc = 118) > fluoroethyldiaminotriazine metabolite (6-[(1R-1-Fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 28; sandy loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 22) = indaziflam carboxylic acid metabolite (2S,3R)-3-[[4-amino-6-[(1R)-1-fluoroethyl]-1,3,5-triazin-2-yl]amino]-2,3-dihydro-2-methyl-1H-indene-5-carboxylic acid) (sandy clay loam: K_f = 0.3, 1/n_f = 0.9, K_foc = 22; sandy loam: K_f = 0.5, 1/n_f = 0.8, K_foc = 32). The metabolites being more polar than the parent compound showed lower sorption. Desorption was hysteretic for indaziflam and triazine indanone metabolite, but not for the other two metabolites. Unsaturated transient flow K_d's were lower than batch K_d's for indaziflam, but similar for fluoroethyldiaminotriazine metabolite. Batch K_d's would overpredict potential offsite transport if desorption hysteresis is not taken into account.     

Growth and biochemical parameters of Cicer arietinum L. grown on amended fly ash

Growth and metal accumulation were investigated in two Cicer arietinum L. varieties (var. CSG-8962 and var. C-235) when grown in various combinations of fly ash (FA) amended with garden soil (GS), press mud (PM) or saw dust (SD). In addition, the levels of photosynthetic pigments, nitrate reductase (NR) activity, cysteine, non-protein thiols (NP-SH), and ascorbic acid were studied. FA amended with GS or PM led to a 5–10 times increase in biomass compared to FA control and was most pronounced in the less metal tolerant variety CSG-8962. Amendment of FA with either GS or PM only moderately increased the contents of some essential metals whereas the non-essential Cd and Cr remained similar or decreased slightly compared to FA control. FA combined with either GS or PM increased the amount of photosynthetic pigments and was largely absent when SD was added to FA. Improved nitrogen availability led to increased nitrate reductase (NR) activity with all amendments but less so with SD. Metal stress indicating parameters were generally reduced (cysteine and non-protein thiols) or unchanged (ascorbic acid). In conclusion, of the tested ameliorants both GS and PM greatly improved growth of C. arietinum making FA a suitable component of plant growth substrates.     

Monitoring of toxic elements present in sludge of industrial waste using CF-LIBS

Industrial waste is one of the main causes of environmental pollution. Laser-induced breakdown spectroscopy (LIBS) was applied to detect the toxic metals in the sludge of industrial waste water. Sludge on filter paper was obtained after filtering the collected waste water samples from different sections of a water treatment plant situated in an industrial area of Kanpur City. The LIBS spectra of the sludge samples were recorded in the spectral range of 200 to 500 nm by focusing the laser light on sludge. Calibration-free laser-induced breakdown spectroscopy (CF-LIBS) technique was used for the quantitative measurement of toxic elements such as Cr and Pb present in the sample. We also used the traditional calibration curve approach to quantify these elements. The results obtained from CF-LIBS are in good agreement with the results from the calibration curve approach. Thus, our results demonstrate that CF-LIBS is an appropriate technique for quantitative analysis where reference/standard samples are not available to make the calibration curve. The results of the present experiment are alarming to the people living nearby areas of industrial activities, as the concentrations of toxic elements are quite high compared to the admissible limits of these substances.     

Comparative assessment of Azolla pinnata and Vallisneria spiralis in Hg removal from G.B. Pant Sagar of Singrauli Industrial region, India

The aim of the present work was to monitor the Hg pollution in water and sediments of G.B. Pant Sagar located in Singrauli Industrial Region, India and to suggest the efficient aquatic plants for its phytoremediation. The study assessed the comparative potential of a free floating water fern Azolla pinnata and submerged aquatic macrophyte Vallisneria spiralis to purify waters polluted by Hg. Six days laboratory experiments have been conducted to mark the percentage removal of Hg at initial concentration of 0.1, 0.5, 1.0 and 3.0 mg L(-1). The percentage removal of Hg was higher for A. pinnata (80-94%) than V. spiralis (70-84%). Likewise, the Hg accumulated in dry mass was much higher for A. pinnata and a high correlation (R(2) = 0.91 for A. pinnata and 0.99 for V. spiralis) was obtained between applied Hg doses and accumulated amounts in biomass. A concentration dependent decrease in chlorophyll a, protein, RNA, DNA and nutrients (NO(3-) and PO(4)(3-)) uptake was detected in A. pinnata and V. spiralis due to Hg toxicity. The decrease was more prominent in Azolla than Vallisneria. The results recommended the use of A. pinnata and V. spiralis to ameliorate the industrial effluents (thermal power, chlor-alkali and coal mine effluent) contaminated with Hg.     

Dye reduction-based electron-transfer activity monitoring assay for assessing microbial electron transfer activity of microbial fuel cell inocula

Microbial fuel cells (MFC) utilize microbes as catalysts to convert chemical energy to electricity. Inocula used for MFC operation must therefore contain active microbial population. The dye reduction-based electron-transfer activity monitoring (DREAM) assay was employed to evaluate different inocula used in MFCs for their microbial bioelectrical activity. The assay utilizes the redox property of Methylene Blue to undergo color change from blue to colorless state upon microbial reduction. The extent of Methylene Blue reduction was denoted as the DREAM assay coefficient. DREAM assay was initially performed on a microbial culture along with the growth curve and estimation of colony forming units (CFUs). DREAM coefficient correlated to the CFU/mL obtained over time as growth progressed. The assay was then extended to water samples (domestic sewage, lake and a man-made pond) serving as inocula in MFCs. Domestic wastewater gave the highest DREAM coefficient (0.300 ± 0.05), followed by pond (0.224 ± 0.07) and lake (0.157 ± 0.04) water samples. Power density obtained conformed to the DREAM coefficient values, with the three samples generating power densities of 46.45 ± 5.1, 36.12 ± 3.2 and 25.08 ± 4.3 mW/m² respectively. We have also studied the role of addition of various carbon sources and their concentrations towards improving the sensitivity of the assay. The DREAM assay is a rapid, easy-to-perform and cost-effective method to assess inocula for their suitability as anolytes in terms of electron transfer potential in MFCs.     

Intracellular cyanobiont Richelia intracellularis: ultrastructure and immuno-localisation of phycoerythrin,nitrogenase, Rubisco and glutamine synthetase

In marine tropical or subtropical plankton the filamentous, heterocyst-forming cyanobacterium Richelia intracellularis forms a symbiosis with the diatom Rhizosolenia clevei. An ultrastructural analysis of the apex of Rhizosolenia clevei showed that the cytoplasm in that particular part of the cell was present only where the cyanobiont was located. The cyanobiont was, however, always outside the host cytoplasm. Vegetative cells as well as the heterocysts of the cyanobiont were devoid of gas vesicles and cyanophycin granules, while carboxysomes and large glycogen granules were common. The cyanobacterial cell wall apparently remained intact in both vegetative and heterocyst cells. In green excitation light the heterocysts and vegetative cells emitted a bright yellow fluorescence, indicating that both cell types possessed high concentrations of the pigment phycoerythrin (PE) commonly associated with photosystem (PS) II. The presence of this pigment in both cell types was verified by immunogold localisation. Using the same technique, the nitrogenase (dinitrogenase reductase) enzyme was shown to be exclusively present in the heterocysts, while Rubisco was localised primarily to the carboxy-somes, which were only detected in vegetative cells. Using an antiserum against the ammonia assimilating enzyme glutamine synthetase (GS), we could demonstrate very low levels of this enzyme, indicating repression of GS in the cyanobiont.     

Response of antioxidants in sunflower (Helianthus annuus L.) grown on different amendments of tannery sludge: its metal accumulation potential

The interaction of metals present in tannery waste and their tolerance in the plants of sunflower (Helianthus annuus L.) was studied in the present paper under field conditions. Effects of 100% tannery sludge and various amendments of tannery sludge (10%, 25%, 35%, 50%, 75%) along with one set of control were studied on the physiological and biochemical parameters of the plant along with their metal accumulation potential after 30, 60 and 90 d after sowing. The plants of H. annuus were found effective in the accumulation of metals (Cr, Fe, Zn and Mn) in roots, shoots and leaves, however, the level of toxic metal, Cr was found below detection limit in the seeds of the plant. The oil was extracted from the seeds of the plant and the level of oil content was increased up to 35% tannery sludge as compared to control followed by decrease at higher tannery sludge ratio. An increase in the chlorophyll, protein, cysteine, non-protein thiol and sugar contents was observed at the lower amendment of tannery sludge at initial exposure periods followed by decrease than their respective controls. Malondialdehyde content in the roots and leaves was increased beyond 50% sludge amendments at all the exposure periods as compared to control. However, proline and ascorbic acid contents of the roots and leaves of the plant increased at all the exposure periods and sludge amendments, compared to their respective controls.     

Simultaneous determination of imidacloprid, thiacloprid, and thiamethoxam in soil and water by high-performance liquid chromatography with diode-array detection

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C18 cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 +/- 4.2% for thiamethoxam, 99 +/- 4.2% for imidacloprid and 94 +/- 1.4% for thiacloprid. The recoveries for water samples ranged from 87 +/- 3.4% for thiamethoxam to 97 +/- 3.9% for imidacloprid and 97 +/- 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5g), and 2, 2, 0.5, micro/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively.