Aspergillus niger as an eco-friendly agent for potassium release from K- bearing minerals: Isolation, screening and culture medium optimization using Plackett-Burman design and response surface methodology.

The potential of Aspergillus niger, to enhance non-exchangeable potassium (K+) release from mineral structures were investigated as a cost-effective and environmentally friendly alternative to traditional chemical fertilizers. Optimizing the culture medium for maximum K+ release, alongside identifying potential mechanisms of action of the A. niger including the production of various organic acids and pH reduction in the minerals feldspar and phlogopite, were among the primary objectives of the present study. K+ dissolution from feldspar and phlogopite in the presence of Aspergillus niger were examined through a two-step experiment; impact of different carbon sources (glucose, sucrose, and fructose) on K+ release using the Plackett-Burman design (PBD) with 12 experimental runs and effect of other independent variables including pH (ranging from 5 to 10), carbon concentration (3-12.3 g l-1), and incubation time (5-18 days) on K+ release using the central composite design (CCD). Our results indicated that the PBD demonstrated a strong predictive capacity (RMSE = 0.012-0.018 g l-1 and R2 = 0.85-0.89) for K+ release. According to the CCD model, pH exerted a significant positive influence on increasing soluble K+ release (P < 0.001). The highest levels of K+ release (157.8 and 175.3 mg l-1 in feldspar and phlogopite, respectively) were observed at the central levels (0) of time and carbon source, and at the +α level (+1.68) of pH. Furthermore, based on the CCD model, the optimal conditions for achieving high K+ release from feldspar and phlogopite in a medium were pHs of 10.36 and 10.31, sucrose concentrations of 11.23 and 11.32 g l-1, and incubation times of 15 and 18 days, respectively. The determination coefficients of the CCD model indicated that 89.5% and 92.6% of the changes in soluble K+ for feldspar and phlogopite, could be explained by this model, respectively. In the current study, the production of organic acids and the resulting pH reduction, along with the reduction in mineral particle size in feldspar and phlogopite, were identified as potential mechanisms influencing the enhancement of potassium solubility. The predominant acids in both feldspar and phlogopite were lactic acid (70.9 and 69.15 mg l-1) and citric acid (40.48 and 22.93 mg l-1), although the production levels of organic acids differed in the two minerals. Overall, our findings highlight the potential of A. niger to proficiently release non-exchangeable potassium from mineral matrices, indicating its promising potential in agricultural applications.

Intraspecific divergence in essential oil content, composition and genes expression patterns of monoterpene synthesis in Origanum vulgare subsp. vulgare and subsp. gracile under salinity stress.

BACKGROUND: Oregano (Origanum vulgare L.), one of the important medicinal plants in the world, has valuable pharmacological compounds with antimicrobial, antiviral, antioxidant, anti-inflammatory, antispasmodic, antiurolithic, antiproliferative and neuroprotective activities. Phenolic monoterpenes such as thymol and carvacrol with many medical importance are found in Oregano essential oil. The biosynthesis of these compounds is carried out through the methyl erythritol-4 phosphate (MEP) pathway. Environmental stresses such as salinity might improve the secondary metabolites in medicinal plants. The influence of salinity stress (0 (control), 25, 50 and 100 mM NaCl) on the essential oil content, composition and expression of 1-deoxy-D-xylulose-5-phosphate reductoisomerase (DXR), γ-terpinene synthase (Ovtps2) and cytochrome P450 monooxygenases (CYP71D180) genes involved in thymol and carvacrol biosynthesis, was investigated in two oregano subspecies (vulgare and gracile). RESULTS: Essential oil content was increased at low NaCl concentration (25 mM) compared with non-stress conditions, whereas it was decreased as salinity stress intensified (50 and 100 mM). Essential oil content was significantly higher in subsp. gracile than subsp. vulgare. The highest (0.20 mL pot-1) and lowest (0.06 mL pot-1) amount of essential oil yield was obtained in subsp. gracile at 25 and 100 mM NaCl, respectively. The content of carvacrol, as the main component of essential oil, decreased with increasing salinity level in subsp. gracile, but increased in subsp. vulgare. The highest expression of DXR, Ovtps2 and CYP71D180 genes was observed at 50 mM NaCl in subsp. vulgare. While, in subsp. gracile, the expression of the mentioned genes decreased with increasing salinity levels. A positive correlation was obtained between the expression of DXR, Ovtps2 and CYP71D180 genes with carvacrol content in both subspecies. On the other hand, a negative correlation was found between the expression of CYP71D180 and carvacrol content in subsp. gracile. CONCLUSIONS: The findings of this study demonstrated that both oregano subspecies can tolerate NaCl salinity up to 50 mM without significant reduction in essential oil yield. Also, moderate salinity stress (50 mM NaCl) in subsp. vulgare might increase the carvacrol content partly via increment the expression levels of DXR, Ovtps2 and CYP71D180 genes.

Wastewater irrigation: An opportunity for improving soil phosphorus availability; PHREEQC modeling and adsorption studies.

Wastewater, an alternative supply of water and nutrients, is being allocated as a priority for human population sustainability in arid and semi-arid regions. This work proposes phosphorus (P), a vital growth-limiting nutrient, adsorption behavior in wastewater irrigated agricultural soils in comparison to non-irrigated soils using laboratory batch experiments. The adsorption mechanism was assessed using different adsorption isotherm models. Saturation indices were modeled, using the hydro-geochemical transport code PHREEQC and MINTEQ geochemical software. Phosphorus buffering parameters were also calculated based on the standard equations. The equilibrium data were well fitted with the Freundlich isotherm model. The physical adsorption mechanism was found based on the calculated isotherm parameters. The maximum adsorption capacity was two times more in non-wastewater irrigated soils than irrigated. Results highlighted the effectiveness of wastewater irrigation in P availability in soil. Based on the PHREEQC modeling data, precipitation of Pb and Zn mineral phases was probable in soils by wastewater influence. Meanwhile, the precipitation of stable calcium phases, that affect the P sorption and/or co-precipitation, in non-wastewater irrigated soils was highlighted in the PHREEQC calculations. The standard buffer capacity (SBC) was 43 and 64 L kg-1 in wastewater irrigated soils and non-irrigated soils, respectively. Findings of the present study demonstrate the importance of wastewater reuse opportunities for agricultural application, especially soil P availability, and are helpful to minimize the environmental impacts of wastewater and solid waste.

The efficiency of nano-TiO2 and γ-Al2O3 in copper removal from aqueous solution by characterization and adsorption study.

Water pollution is a major global challenge given the increasing growth in the industry and the human population. The present study aims to investigate the efficiency of TiO2 and γ-Al2O3 nanoadsorbents for removal of copper (Cu(II)) from aqueous solution as influenced by different chemical factors including pH, initial concentration, background electrolyte and, ionic strength. The batch adsorption experiment was performed according to standard experimental methods. Various isotherm models (Freundlich, Langmuir, Temkin, and Dubinin-Radushkevich) were fitted to the equilibrium data. According to geochemical modeling data, adsorption was a predominant mechanism for Cu(II) removal from aqueous solution. Calculated isotherm equations parameters were evidence of the physical adsorption mechanism of Cu(II) onto the surface of the nanoparticles. The Freundlich adsorption isotherm model could well fit the experimental equilibrium data at different pH values. The maximum monolayer adsorption capacity of TiO2 and γ-Al2O3 nanosorbents were found to 9288 and 3607 mg kg-1 at the highest pH value (pH 8) and the highest initial Cu(II) concentration (80 mg L-1) respectively. Copper )Cu(II) (removal efficiency with TiO2 and γ-Al2O3 nanoparticles increased by increasing pH. Copper )Cu(II) (adsorption deceased by increasing ionic strength. The maximum Cu(II) adsorption (4510 mg kg-1) with TiO2 nanoparticles was found at 0.01 M ionic strength in the presence of NaCl. Thermodynamic calculations show the adsorption of Cu(II) ions onto the nanoparticles was spontaneous in nature. Titanium oxide (TiO2) nanosorbents could, therefore, serve as an efficient and low-cost nanomaterial for the remediation of Cu(II) ions polluted aqueous solutions.

Predicting soil nutrient contents using Landsat OLI satellite images in rain-fed agricultural lands, northwest of Iran.

Soil nutrients are the key factors in soil fertility, which have important roles in plant growth. Determining soil nutrient contents, including macro and micronutrients, is of crucial importance in agricultural productions. Conventional laboratory techniques for determining soil nutrients are expensive and time-consuming. This research was aimed to develop linear regression (LR) models for remote sensing of total nitrogen (TN) (mg/kg), available phosphorous (AP) (mg/kg), available potassium (AK) (mg/kg), and micronutrients such as iron (Fe) (mg/kg), manganese (Mn) (mg/kg), zinc (Zn) (mg/kg), and copper (Cu) (mg/kg) extracted by DTPA in rain-fed agricultural lands in the northwest of Iran. First, 101 soil samples were collected from 0-30 cm of these lands and analyzed for selected nutrient contents. Then a linear regression along with principal component analysis was conducted to correlate soil nutrient contents with reflectance data of different Landsat OLI bands. Finally, the spatial distributions of soil nutrients were drawn. The results showed that there were linear relationships between soil nutrient contents and standardized PC1 (ZPC1). The highest significant determination coefficient with an R2 value of 0.46 and the least relative error (%) value of 11.97% were observed between TN and ZPC1. The accuracy of the other LR's developed among other soil nutrient contents and remotely sensed data was relatively lower than that obtained for TN. According to the results obtained from this study, although remote sensing techniques may quickly assess soil nutrients, new techniques, technologies, and models may be needed to have a more accurate prediction of soil nutrients.

Increasing medicinal and phytochemical compounds of coneflower (Echinacea purpurea L.) as affected by NO3-/NH4+ ratio and perlite particle size in hydroponics.

Medicinal plants are considered as one of the most important sources of chemical compounds, so preparing a suitable culture media for medicinal plant growth is a critical factor. The present study is aimed to improve the caffeic acid derivatives and alkylamides percentages of Echinacea purpurea root extract in hydroponic culture media with different perlite particle size and NO3-/NH4+ ratios. Perlite particle size in the growing media was varied as very coarse perlite (more than 2 mm), coarse perlite (1.5-2 mm), medium perlite (1-1.5 mm), fine perlite (0.5-1 mm), and very fine perlite (less than 0.5 mm) in different ratios to peat moss (including pure perlite, 50:50 v/v, 30:70 v/v, and pure peat moss). Two NO3-/NH4+ ratios (90:10 and 70:30) were tested in each growing media. All phytochemical analyses were performed according to standard methods using high performance liquid chromatography (HPLC). It was found that the E. purpurea grown in the medium containing very fine-grade perlite with 50:50 v/v perlite to peat moss ratio had the maximum caffeic acid derivatives, including chicoric acid (17 mg g-1 DW), caftaric acid (6.3 mg g-1 DW), chlorogenic acid (0.93 mg g-1 DW), cynarin (0.84 mg g-1 DW), and echinacoside (0.73 mg g-1 DW), as well as, alkylamides (54.21%). The percentages of these phytochemical compounds increased by decreasing perlite particle size and increasing of NO3-/NH4+ ratio. The major alkylamide in the E. purpurea root extract was dodeca-2E, 4E, 8Z-10 (E/Z)-tetraenoic acid isobutylamide in all treatments, ranging from 31.12 to 54.21% of total dry weight. It can be concluded that optimizing hydroponic culture media and nutrient solution has significant effects on E. purpurea chemical compounds.

Soil fertility, chemical properties, and pollutant removal efficiency of Salicornia europaea in response to different times and duration of wastewater irrigation.

Halophytes are the good candidates in coastal saline areas which could be irrigated with wastewater. The purpose of this study was to evaluate the soil-water-plant system under control and wastewater irrigation (containing toxic elements and organic matter) at three durations (vegetative, flowering, and reproductive stages) and two exposure times (2 and 4 days in each stage). The results obtained in the experimental tests for wastewater irrigation indicated that the Salicornia is efficient for the removal of chemical oxygen demand (61%), biochemical oxygen demand (74%), total suspended solids (47.6%), and ammoniacal nitrogen (64%) at the reproductive stage. At the same time, the average nitrate concentration increased to 51.3 mg L-1 with more solids. Regardless of wastewater irrigation duration, irrigation with wastewater significantly increased organic matter, nitrogen, phosphorus, and potassium of the soil. The Mg2+ and Ca2+ contents in the aboveground biomass of the plants were also high ranged from 0.58 to 1%, and 0.43 to 0.68 mg g-1 DW, respectively. All the exchangeable cations other than Na+ were higher for wastewater irrigation at the flowering stage. Plants maintained noticeably higher Ca2+/Na+ and K+/Na+ ratios in the roots than those in the shoots except for 4 days after the reproductive stage. S. europaea is well adapted to grow in wastewater irrigation and can tolerate hypoxic conditions through improving water and soil quality.

Optimizing hydroponic culture media and NO3-/NH4+ ratio for improving essential oil compositions of purple coneflower (Echinacea purpurea L.).

Medicinal plants represent a valuable commodity due to beneficial effects of their natural products on human health, prompting a need for finding a way to optimize/increase their production. In this study, a novel growing media with various perlite particle size and its mixture with peat moss was tested for hydroponic-based production of Echinacea purpurea medicinal plant under greenhouse conditions. The plant growth parameters such as plant height, total fresh leave weight, fresh root weight, total biomass, total chlorophyll, leaf area, and essential oil compositions were assessed. Perlite particle size in the growing media was varied from very coarse (more than 2 mm) to very fine (less than 0.5 mm), and the ratio between perlite and peat moss varied from 50:50 v/v to 30:70 v/v. In addition, two nitrate (NO3-) to ammonium (NH4+) ratios (90:10 and 70:30) were tested for each growing media. The medium containing very fine-grade perlite and 50:50 v/v perlite to peat moss ratio was found to be most optimal and beneficial for E. purpurea performance, resulting in maximal plant height, fresh and dry weight, leaf surface area, and chlorophyll content. It was also found that an increase in NO3-/NH4+ ratio caused a significant increase in plant growth parameters and increase the plant essential oil content. The major terpene hydrocarbons found in extract of E. purpurea with the best growth parameters were germacrene D (51%), myrcene (15%), α-pinene (12%), ß-caryophyllene (11%), and 1-Pentadecene (4.4%), respectively. The percentages of these terpene hydrocarbons were increased by increasing of NO3-/NH4+ ratio. It can be concluded that decreasing the perlite particle size and increasing the NO3-/NH4+ ratio increased the plant growth parameters and essential oil compositions in E. purpurea.

The Salicornia europaea potential for phytoremediation of heavy metals in the soils under different times of wastewater irrigation in northwestern Iran.

The use of wastewater for irrigation usually leads to the buildup of potentially toxic elements (PTEs) in soils. The objective of this study was to assess the capacity of Salicornia europaea L. to uptake heavy metal when irrigated with wastewater at the vegetative, flowering, and reproductive stages of S. europaea for 2 and 4 days (in each stage) in the coastal saline area of Lake Urmia. The concentrations of heavy metals were detected in irrigated water, soil, and plant samples, while transfer factor (TF), bioconcentration factor (BCF), and bioaccumulation factor (BAF) were calculated. The results revealed that metal concentrations in the wastewater were above the permissible limits. The wastewater irrigation caused higher shoot biomass despite the high uptake of PTEs. Levels of Fe and Cu in plants were higher when irrigated with wastewater at the reproductive stage as compared to flowering and vegetative stages. The TF of wastewater-irrigated plants was higher at the flowering stage. TF of different metals at the flowering stage were in order of Zn > Pb > Ni > Cd > Cu, while the BCF increased in the order Cd > Cu > Zn > Ni > Pb. The BAF of the investigated PTEs at the flowering stage increased in the order Cd > Pb > Ni > Zn > Cu. In conclusion, higher Pb and Zn in the shoot indicated that the plant exhibited the phytoextraction mechanism, while Salicornia used a phytostabilization mechanism for roots-Cu, Ni, and Cd.

Application of diatomite for sorption of Pb, Cu, Cd and Zn from aqueous solutions: kinetic, thermodynamic studies and application of response surface methodology (RSM).

Contamination of water and soil with toxic metals is a serious environmental issue. To study the Pb, Cu, Cd, and Zn sorption behavior by diatomite, batch experiments were carried out with increasing levels of initial concentration (0-200 mg/L) under different contact times (0-360 min) and temperatures (283, 293, 303, and 313 K). The effects of concentration (0-200 mg/L), pH (3-6), and ionic strength (0.01-0.06 mol/L) on the sorption were modeled using response surface methodology (RSM). Results showed that adsorption data were well-fitted by the Langmuir equation. The sorption of metals intensified by increasing initial concentration and pH but ionic strength had inverse effect. High value for R2 (0.99) and adjusted R2 (0.99) showed that the removal of ions can be described by response surface method. One-way ANOVA showed (p-value < 0.0001) that quadratic model is the best model for determining the interaction of variables. The values of the sorption energy parameter from Dubinin-Radushkevich model (E < 8 kJ K-1  mol-1 ) and negative values of ∆G showed that the sorption of the metals was physical and spontaneous. The positive values of enthalpy (ΔH) indicated that the sorption reaction of metals was endothermic at 283-313 K. PRACTITIONER POINTS: Applications of diatomite increased the sorption of Pb, Cd, Zn, and Cu from aqueous solutions. Diatomite, as low-cost adsorbent, had significant potential to sorption of ions. The sorption of heavy metals by adsorbent intensified by increasing initial concentration and pH but ionic strength had inverse effect. High value for R2 (0.99) and adj-R2 (0.99) showed that removal of metals can be described by response surface method (RSM) and the initial concentration of metal was the most significant factor.

Soil nutrients status affected by simple and enriched biochar application under salinity conditions.

In order to study the effect of biochar application as simple and enriched, on the soil nutrients status in the salinity conditions, a research was conducted as a factorial arrangement based on completely randomized design (CRD) with three replicates. The biochar (grape pruning residues) was applied in three levels (0, 2% biochar, and 2% enriched biochar by rock phosphate and cow manure). Also, the salinity treatment was considered in three levels (2, 4.5, and 9 dSm-1). After treating the soil, it was incubated in polyethylene containers for a 70-day period at 25 °C and 70% field capacity moisture regime. The results showed that salinity significantly affected the soil pH, electrical conductivity (EC), calcium, magnesium, sodium, basal respiration, and nitrifying bacteria frequency (P < 0.001) and chloride concentration (P < 0.01). Also, the biochar significantly affected the pH, organic carbon, concentration of total nitrogen, phosphorous, solution potassium, sodium, iron, zinc, copper, basal respiration, and nitrifying bacteria frequency (P < 0.001) of the soil. The interaction effect of biochar and salinity levels was significant on soil sodium concentration (P < 0.01) and pH (P < 0.05). In comparison with the control treatment, the enriched biochar, decreased soil pH (about 1.4%) and increased the phosphorous, iron, and zinc up to 36%, 29%, and 36%, respectively and simple biochar increased the Nitrogen and Potassium up to 46% and 48%, respectively. In general, it was concluded that both types of the biochars lowered the sodium concentration of the soil in different salinity levels due to high potential of biochar for sodium absorption which this ability may be considered in saline soils remediation.

Distribution of phosphorous pools in western river sediments of the Urmia Lake basin, Iran.

Impact of anthropogenic loading of phosphorous (P) to an aquatic ecosystem can be qualitatively assessed by measuring the buildup and distribution of P in sediments and by differentiating bioavailable and recalcitrant P pools. Distribution of P pools in sediments is affected by the physico-chemical properties including specific elements, particle size distribution, pH, electrical conductivity (EC), and carbonate content. We applied X-ray fluorescence and scanning electron microscopy (SEM) methods to characterize sediments from western rivers in the Urmia Lake basin in Iran with a particular focus on properties that are relevant to P speciation. Phosphorous pools were sequentially extracted into operationally defined exchangeable (EXCH-P), iron and aluminum oxide-bound (Fe/Al-P), calcium-bound (Ca-P), and residual (RES-P) P pools. In river sediments, the size of P pool was found to be in the order of Ca-P > RES-P > Fe/Al-P > EXCH-P indicating small fraction of bioavailable P pool and Ca-P minerals being the most dominant P sink. Carbonate-related properties had an inverse relationship with bioavailable P pools in the river sediments studied. The principal component analysis (PCA) of the sequential extraction data with sediment properties revealed that four principal components described 82.7% of total variation. Similarly, particle size-related properties were found to have the highest eigenvalues in the first PC. Electron diffraction spectra (EDS) and X-ray fluorescence (XRF) analyses showed a largely uniform distribution of P in the upstream sediment. However, limited evidence of local enrichment of P with Fe, Al, and Ca contents was observed in the downstream river sediments. Correlation of Fe/Al-P pool size with Al2O3 and SiO2 contents indicated that P was associated with Al oxide and clay minerals in the sediment matrix. Overall, the results from this study provide insights into the variability of upstream and downstream river processes and their relationship with P pools with regard to their bioavailability. These results are expected to be useful in assessing the potential impact of P loading on the aquatic ecosystem in the Urmia Lake basin.