Sensitivity of the amide I band to matrix manipulation in bone: a Raman micro-spectroscopy and spatially offset Raman spectroscopy study.

The fracture resistance of bone arises from the hierarchical arrangement of minerals, collagen fibrils (i.e., cross-linked triple helices of α1 and α2 collagen I chains), non-collagenous proteins, and water. Raman spectroscopy (RS) is not only sensitive to the relative fractions of these constituents, but also to the secondary structure of bone proteins. To assess the ability of RS to detect differences in the protein structure, we quantified the effect of sequentially autoclaving (AC) human cortical bone at 100 °C (∼34.47 kPa) and then at 120 °C (∼117.21 kPa) on the amide I band using a commercial Raman micro-spectroscopy (µRS) instrument and custom spatially offset RS (SORS) instrument in which rings of collection fiber optics are offset from the central excitation fiber optics within a hand-held, cylindrical probe. Being clinically viable, measurements by SORS involved collecting Raman spectra of cadaveric femur mid-shafts (5 male & 5 female donors) through layers of a tissue mimic. Otherwise, µRS and SORS measurements were acquired directly from each bone. AC-related changes in the helical status of collagen I were assessed using amide I sub-peak ratios (intensity, I, at ∼1670 cm-1 relative to intensities at ∼1610 cm-1 and ∼1640 cm-1). The autoclaving manipulation significantly decreased the selected amide I sub-peak ratios as well as shifted peaks at ∼1605 cm-1 (µRS), ∼1636 cm-1 (SORS) and ∼1667 cm-1 in both µRS and SORS. Compared to µRS, SORS detected more significant differences in the amide I sub-peak ratios when the fiber optic probe was directly applied to bone. SORS also detected AC-related decreases in I1670/I1610 and I1670/I1640 when spectra were acquired through layers of the tissue mimic with a thickness ≤2 mm by the 7 mm offset ring, but not with the 5 mm or 6 mm offset ring. Overall, the SORS instrument was more sensitive than the conventional µRS instrument to pressure- and temperature-related changes in the organic matrix that affect the fracture resistance of bone, but SORS analysis of the amide I band is limited to an overlying thickness layer of 2 mm.

Assessment of spatially offset Raman spectroscopy to detect differences in bone matrix quality.

Since spatially offset Raman spectroscopy (SORS) can acquire biochemical measurements of tissue quality through light scattering materials, we investigated the feasibility of this technique to acquire Raman bands related to the fracture resistance of bone. Designed to maximize signals at different offsets, a SORS probe was used to acquire spectra from cadaveric bone with and without skin-like tissue phantoms attenuating the light. Autoclaving the lateral side of femur mid-shafts from 5 female and 5 male donors at 100 °C and again at 120 °C reduced the yield stress of cortical beams subjected to three-point bending. It did not affect the volumetric bone mineral density or porosity. Without tissue phantoms, autoclaving affected more Raman characteristics of the organic matrix when determined by peak intensity ratios, but fewer matrix properties depended on the three offsets (5 mm, 6 mm, and 7 mm) when determined by band area ratios. The cut-off in the thickness of the tissue phantom layers was ∼4 mm for most properties, irrespective of offset. Matching trends when spectra were acquired without phantom layers between bone and the probe, ν1PO43-/Amide III and ν1PO43-/(proline + OH-proline) were higher and lower in the non-treated bone than in the autoclaved bone, respectively, when the thickness of tissue phantom layers was 4 mm. The layers, however, caused a loss of sensitivity to autoclaving-related changes in ν3CO3/ν1PO43- and crystallinity. Without advanced post-processing of Raman spectra, SORS acquisition through turbid layers can detect changes in Raman properties of bone that accompany a loss in bone strength.

Impregnation of biochar with montmorillonite and its activation for the removal of azithromycin from aqueous media.

An inexpensive and environmentally friendly composite synthesized from rice husk, impregnated with montmorillonite and activated by carbon dioxide, was investigated for the removal of azithromycin from an aqueous solution. Various techniques were used to characterize adsorbents in detail. The sorption process was primarily regulated by the solution pH, pollutant concentration, contact duration, adsorbent dose, and solution temperature. The equilibrium data were best analyzed using the nonlinear Langmuir and Sips (R2 > 0.97) isotherms, which revealed that adsorption occurs in a homogenous manner. The adsorption capacity of pristine biochar and carbon dioxide activated biochar-montmorillonite composite was 33.4 mg g-1 and 44.73 mg g-1, respectively. Kinetic studies identified that the experimental data obeyed the pseudo-second-order and Elovich models (R2 > 0.98) indicating the chemisorption nature of adsorbents. The thermodynamic parameters determined the endothermic and spontaneous nature of the reaction. The ion exchange, π-π electron-donor-acceptor (EDA) interactions, hydrogen-bonding, and electrostatic interactions were the plausible mechanisms responsible for the adsorption process. This study revealed that a carbon dioxide activated biochar-montmorillonite composite may be used as an effective, sustainable, and economical adsorbent for the removal of azithromycin from polluted water.

Effect of ribose incubation on physical, chemical, and mechanical properties of human cortical bone.

Raman spectroscopy (RS) is sensitive to the accumulation of advanced glycation end-products (AGEs), and it measures matrix-sensitive properties that correlate with the fracture toughness of human cortical bone. However, it is unclear whether sugar-mediated accumulation of AGEs affects the fracture toughness of human cortical bone in a manner that is consistent with the negative correlations between amide I sub-peak ratios and fracture toughness. Upon machining 64 single-edge notched beam (SENB) specimens from cadaveric femurs (8 male and 7 female donors between 46 years and 61 years of age), pairs of SENB specimens were incubated in 15 mL of phosphate buffered saline with or without 0.1 M ribose for 4 weeks at 37 °C. After acquiring 10 Raman spectra per bone specimen (n = 32 per incubation group), paired SENB specimens were loaded in three-point bending at a quasi-static or a high loading rate approximating 10-4 s-1 or 10-2 s-1, respectively (n = 16 per incubation group per loading rate). While 2 amide I sub-peak ratios, I1670/I1640 and I1670/I1610, decreased by 3-5% with a 100% increase in AGE content, as confirmed by fluorescence measurements, the ribose incubation to accumulate AGEs in bone did not affect linear elastic (KIc) nor non-linear elastic (KJc) measurements of bone's ability to resist crack growth. Moreover, AGE accumulation did not affect the change in these properties when the loading rate changed. Increasing the loading rate increased KIc but decreased KJc. Ribose incubation did not affect mineral-related RS properties such as mineral-to-matrix ratios, Type B carbonate substitutions, and crystallinity. It did however increase the thermal stability of demineralized bone (differential scanning calorimetry), without affecting the network connectivity of the organic matrix (i.e., maximum slope during a hydrothermal isometric tension test of demineralized bone). In conclusion, RS is sensitive to AGE accumulation via the amide I band (plus the hydroxyproline-to-proline ratio), but the increase in AGE content due to ribose incubation was not sufficient to affect the fracture toughness of human cortical bone.

Role of biochar-based free radicals in immobilization and speciation of metals in the contaminated soil-plant environment.

The structure of biochar produced at various pyrolysis temperatures influences metal geochemical behavior. Here, the impact of wheat straw-derived biochar (300, 500, and 700 °C) on the immobilization and transformation of metals in the contaminated soil-plant system was assessed. The findings of the sequential extraction revealed that biochar additives had a substantial influence on the speciation of Cr, Ni, Pb, and Zn in the contaminated soil. The lowest F1 (exchangeable and soluble fraction) + F2 (carbonate fraction) accounted for Cr (44%) in WB-300, Ni (43.87%) in WB-500, Pb (43.79%), and Zn (49.78%) in WB-700 with applied amendments of their total amounts. The characterization results indicated that high pyrolysis temperatures (300-700 °C) increased the carbon-containing groups with the potential to adsorb metals from the soil-plant environment. The bioconcentration and translocation factors (BCF and TF) were less than 1, indicating that metal concentration was restricted to maize roots and translocation to shoots. Reactive oxygen species (ROS) intracellularly influence metal interactions with plants. Electron paramagnetic resonance (EPR) was performed to determine hydroxyl radical generation (•OH) in plant segments to assess the dominance of free radicals (FRs). Consequently, the formation of •OH significantly depends on the pyrolysis temperature and the interaction with a contaminated soil-plant environment. Thus, metal transformation can be effectively decreased in the soil-plant environment by applying WB amendments.

A critical review on biochar-assisted free radicals mediated redox reactions influencing transformation of potentially toxic metals: Occurrence, formation, and environmental applications.

Potentially toxic metals have become a viable threat to the ecosystem due to their carcinogenic nature. Biochar has gained substantial interest due to its redox-mediated processes and redox-active metals. Biochar has the capacity to directly adsorb the pollutants from contaminated environments through several mechanisms such as coprecipitation, complexation, ion exchange, and electrostatic interaction. Biochar's electron-mediating potential may be influenced by the cyclic transition of surface moieties and conjugated carbon structures. Thus, pyrolysis configuration, biomass material, retention time, oxygen flow, and heating time also affect biochar's redox properties. Generally, reactive oxygen species (ROS) exist as free radicals (FRs) in radical and non-radical forms, i.e., hydroxyl radical, superoxide, nitric oxide, hydrogen peroxide, and singlet oxygen. Heavy metals are involved in the production of FRs during redox-mediated reactions, which may contribute to ROS formation. This review aims to critically evaluate the redox-mediated characteristics of biochar produced from various biomass feedstocks under different pyrolysis conditions. In addition, we assessed the impact of biochar-assisted FRs redox-mediated processes on heavy metal immobilization and mobility. We also revealed new insights into the function of FRs in biochar and its potential uses for environment-friendly remediation and reducing the dependency on fossil-based materials, utilizing local residual biomass as a raw material in terms of sustainability.

Assessing the influence of sewage sludge and derived-biochar in immobilization and transformation of heavy metals in polluted soil: Impact on intracellular free radical formation in maize.

As one of the most common ways to get rid of municipal waste, landfill leachate, waste with complicated compositions and high levels of contaminants, has become a significant threat to the world's environment. Here, the impact of sewage sludge (SS) and derived-biochar (SSB) amendments on the immobilization and potential mobility of heavy metals in a contaminated soil-plant system was investigated. The sequential fractionation findings showed that using SS-2%, SSB-2%, and SSBC-1% reduced the potential mobility of heavy metals while increasing the residual fraction in polluted soils. The translocation and bioconcentration factors showed that heavy metals were slightly transferred into shoots from roots and lowered accumulation in roots from contaminated soils. Fourier transform infrared (FTIR) and X-ray photoelectron spectrum (XPS) comprehensive characterization results indicated the significant role of applied amendments for heavy metals transformation from the exchangeable-soluble fractions to the least available form by lowering their mobility to confirm the adsorption-based complexes, which results in the surface adsorption of heavy metals with functional groups. The electron paramagnetic resonance (EPR) results indicated the dominance of reactive oxygen species (ROS) in the intracellular formation of hydroxyl radicals (•OH) in maize plant roots and shoots. ROS (•OH) generation plays a critical influence in the interaction between the physiological processes of plants and heavy metals. Moreover, all the amendments increased maize growth and biomass production. Our study suggests that alone and combined application of SS and SSB have great potential to remediate heavy metals contaminated soil for environmental sustainability.

Identifying Bone Matrix Impairments in a Mouse Model of Neurofibromatosis Type 1 (NF1) by Clinically Translatable Techniques.

Three-to-four percent of children with neurofibromatosis type 1 (NF1) present with unilateral tibia bowing, fracture, and recalcitrant healing. Alkaline phosphatase (ALP) enzyme therapy prevented poor bone mineralization and poor mechanical properties in mouse models of NF1 skeletal dysplasia; but transition to clinical trials is hampered by the lack of a technique that (i) identifies NF1 patients at risk of tibia bowing and fracture making them eligible for trial enrollment and (ii) monitors treatment effects on matrix characteristics related to bone strength. Therefore, we assessed the ability of matrix-sensitive techniques to provide characteristics that differentiate between cortical bone from mice characterized by postnatal loss of Nf1 in Osx-creTet-Off ;Nf1flox/flox osteoprogenitors (cKO) and from wild-type (WT) mice. Following euthanasia at two time points of bone disease progression, femur and tibia were harvested from both genotypes (n ≥ 8/age/sex/genotype). A reduction in the mid-diaphysis ultimate force during three-point bending at 20 weeks confirmed deleterious changes in bone induced by Nf1 deficiency, regardless of sex. Pooling females and males, low bound water (BW), and low cortical volumetric bone mineral density (Ct.vBMD) were the most accurate outcomes in distinguishing cKO from WT femurs with accuracy improving with age. Ct.vBMD and the average unloading slope (Avg-US) from cyclic reference point indentation tests were the most sensitive in differentiating WT from cKO tibias. Mineral-to-matrix ratio and carbonate substitution from Raman spectroscopy were not good classifiers. However, when combined with Ct.vBMD and BW (femur), they helped predict bending strength. Nf1 deficiency in osteoprogenitors negatively affected bone microstructure and matrix quality with deficits in properties becoming more pronounced with duration of Nf1 deficiency. Clinically measurable without ionizing radiation, BW and Avg-US are sensitive to deleterious changes in bone matrix in a preclinical model of NF1 bone dysplasia and require further clinical investigation as potential indicators of an onset of bone weakness in children with NF1. © 2022 American Society for Bone and Mineral Research (ASBMR).

Phyto-mediated photocatalysis: a critical review of in-depth base to reactive radical generation for erythromycin degradation.

Erythromycin (ERY), designated as a risk-prioritized macrolide antibiotic on the 2015 European Union watch list, is the third most commonly used antibiotic, most likely due to its ability to inhibit the protein. ERY has revealed record-high aquatic concentrations threatening the entire ecosystem and hence demands priority remedial measures. The inefficiency of various conventional ERY degradation methodologies opened up a gateway to advanced technologies. The conventional approach comprising of a chemically formulated, single photocatalyst has a major drawback of creating multiple environmental stresses. In this context, photocatalysis is grabbing tremendous attention as an efficient and cost-effective antibiotic treatment approach. Several studies have ascertained that ZnO, TiO2, Fe3O4, and rGO nanoparticles possess remarkable pollution minimizing operational capabilities. Additionally, composites are found much more effective in antibiotic removal than single nanoparticles. In this review, an attempt has been made to provide a comprehensive baseline for efficient reactive radical production by a phyto-mediated composite kept under a certain source of irradiation. Considerable efforts have been directed towards the in-depth investigation of rGO-embedded, phyto-mediated ZnO/TiO2/Fe3O4 photocatalyst fabrication for efficient ERY degradation, undergoing green photocatalysis. This detailed review provides photocatalytic nanocomposite individualities along with a hypothetical ERY degradation mechanism. It is assumed that derived information presented here will provoke innovative ideas for water purification incorporating green photocatalysis, initiating the construction of high-performance biogenic hierarchical nanocatalysts.

Compositional assessment of bone by Raman spectroscopy.

Raman spectroscopy (RS) is used to analyze the physiochemical properties of bone because it is non-destructive and requires minimal sample preparation. With over two decades of research involving measurements of mineral-to-matrix ratio, type-B carbonate substitution, crystallinity, and other compositional characteristics of the bone matrix by RS, there are multiple methods to acquire Raman signals from bone, to process those signals, and to determine peak ratios including sub-peak ratios as well as the full-width at half maximum of the most prominent Raman peak, which is nu1 phosphate (ν1PO4). Selecting which methods to use is not always clear. Herein, we describe the components of RS instruments and how they influence the quality of Raman spectra acquired from bone because signal-to-noise of the acquisition and the accompanying background fluorescence dictate the pre-processing of the Raman spectra. We also describe common methods and challenges in preparing acquired spectra for the determination of matrix properties of bone. This article also serves to provide guidance for the analysis of bone by RS with examples of how methods for pre-processing the Raman signals and for determining properties of bone composition affect RS sensitivity to potential differences between experimental groups. Attention is also given to deconvolution methods that are used to ascertain sub-peak ratios of the amide I band as a way to assess characteristics of collagen type I. We provide suggestions and recommendations on the application of RS to bone with the goal of improving reproducibility across studies and solidify RS as a valuable technique in the field of bone research.

Geochemical fractionation and spectroscopic fingerprinting for evaluation of the environmental transformation of potentially toxic metal(oid)s in surface-subsurface soils.

The contamination of soil by toxic metal(oid)s has emerged as a major concern worldwide, particularly in developing countries. A metals behavior in the soil environment is influenced by organic matter, mineral phases, and oxidation states in which a particular metal exists. However, the spectroscopic evidence of metal(oid)s interactions in soil with organic matter and mineral phases can induce an extensive understanding. The surface and sub-surface soils (0-50 cm) from four sites of upper Indus basin, Pakistan, were collected and analyzed by using FTIR (Fourier-transform infrared spectroscopy), XRD (X-ray diffraction) and XPS (X-ray photoelectron spectroscopy) in addition to ICP-MS (inductively coupled plasma mass spectrometry) and geochemical fractionation. Geochemical fractionation of metal(oid)s indicated that As, Cu, Ni, Pb, and Zn were mostly found in the potentially bioavailable fractions. However, an increase in the residual fraction was observed from top to bottom. The absorption bands of FTIR spectra were divided into three spectral regions 700-400, 1700-800, and 3700-2800 cm-1. The soil was found rich in organic matter and capable of retaining metals as abundant peaks were observed in the mid-infrared region. The mineralogical analysis of soil samples testified silicon oxides and zeolite as major mineral phases. The XPS spectra showed broad peaks of As(III), As2O3, As4S4, PbO2, and PbCo3. The study concludes that the source identification of metal(oid)s in the upper Indus is crucial to find out the particular source of contamination in the soil.

Recent trends in advanced oxidation process-based degradation of erythromycin: Pollution status, eco-toxicity and degradation mechanism in aquatic ecosystems.

Wide spread documentation of antibiotic pollution is becoming a threat to aquatic environment. Erythromycin (ERY), a macrolide belonging antibiotic is at the top of this list with its concentrations ranging between ng/L to a few µg/L in various global waterbodies giving rise to ERY-resistance genes (ERY-RGs) and ERY- resistance bacteria (ERY-RBs) posing serious threat to the aquatic organisms. ERY seems resistant to various conventional water treatments, remained intact and even increased in terms of mass loads after treatment. Enhanced oxidation potential, wide pH range, elevated selectivity, adaptability and greater efficiency makes advance oxidation processes (AOPs) top priority for degrading pollutants with aromatic rings and unsaturated bonds like ERY. In this manuscript, recent developments in AOPs for ERY degradation are reported along with the factors that affect the degradation mechanism. ERY, marked as a risk prioritized macrolide antibiotic by 2015 released European Union watch list, most probably due to its protein inhibition capability considered third most widely used antibiotic. The current review provides a complete ERY overview including the environmental entry sources, concentration in global waters, ERY status in STPs, as well as factors affecting their functionality. Along with that this study presents complete outlook regarding ERY-RGs and provides an in depth detail regarding ERY's potential threats to aquatic biota. This study helps in figuring out the best possible strategy to tackle antibiotic pollution keeping ERY as a model antibiotic because of extreme toxicity records.

Lithium from breast-milk inhibits thyroid iodine uptake and hormone production, which are remedied by maternal iodine supplementation.

BACKGROUND: Lithium is especially taken as a maintenance medication for Bipolar Disorder. In women with bipolar disorder, lithium is often effective during postpartum period, but breast-feeding for medicated mothers is controversial because of harmful effects for her child. At present, the biological mechanisms of lithium are not well-understood, affecting its usage and overall health implications. PROCEDURE: We developed a rat lithium and breast-feeding model at human therapeutic levels to study the effects of lithium exposure through breast-milk on pups' thyroid function. Novel laser analytical spectroscopy, along with traditional blood and immunohistochemical tests, were applied to further investigate the mechanisms behind the thyroid dysfunction. Maternal iodine supplementation was evaluated as a therapeutic method to address the pups' thyroid dysfunction. RESULTS: Pups exposed to lithium via breastmilk, even with the dam on a sub-therapeutic level, experienced weight gain, reduced blood thyroxine (T4 ), and elevated blood urea nitrogen, indicating effects on thyroid and kidney function. We show that lithium inhibited iodine uptake by thyroid follicles, initiating a mechanism that reduced iodination of tyrosine, thyroglobulin cleavage, and thyroid hormone production. Importantly, infant thyroid function can be significantly improved by administering supplementary iodine to the medicated dam's diet during breast-feeding. CONCLUSION: These results elucidate the mechanisms of lithium in thyroid function, provide valuable information on use postpartum, and suggest a clinically applicable remedy to side-effects. The results are particularly important for patients (and their infants) who respond well to lithium and need, or choose, to breast-feed.

Morpho-chemical characterization and source apportionment of potentially toxic metal(oid)s from school dust of second largest populous city of Pakistan.

Interior settled dust is one of the greatest threats of potentially toxic metal(oid)s (PTMs) exposure to the children, especially in the school environment. Therefore, it is more worthy of having in-depth knowledge of compositional characteristics of school dust. Forty schools were selected of Lahore city for dust sampling. The school dust was analyzed to determine the PTMs (As, Cd, Cr, Cu, Ge, Mo, Ni, Pb, Sb, Sn, Sr, V, and Zn) concentrations using ICP-MS. The morphological characteristics, PTMs speciation, and mineralogy of school dust were examined using SEM with EDS, XPS, and XRD, respectively. Moreover, the geo-accumulation index (Igeo), potential ecological risk index (PERI), and multivariate statistical analysis were employed to assess the pollution levels, ecological risk, and source identification of PTMs, respectively. The Igeo indicated a heavily-extreme pollution level of Cd (Igeo = 4.92), moderate-heavy pollution of Zn (Igeo = 3.22), and Pb (Igeo = 2.78), and slight-moderate pollution of Cr (Igeo = 1.62), and Cu (Igeo = 1.53). The ecological risk has been found extremely high for Cd and moderately high for Pb and As, while potential ecological risk found extremely high posed by cumulatively all selected PTMs. Multivariate statistical analysis showed that sources of PTMs comprise of natural processes as well as several anthropogenic processes like vehicular emissions, agricultural and industrial activities. The SEM, XRD, and XPS analyses demonstrated the presence of airborne particles and PTMs containing minerals with several toxic chemical species in school dust. This study can help to develop strategies to reduce school indoor pollution and hence to establish an eco-friendly learning environment for children.

Rapid trace element analysis of microgram soft materials with cryogenic milling and laser ablation spectroscopy.

Trace element analysis of soft materials, to determine the content of low concentration elements, is important in many industries such as food quality control and medical biopsy analysis. Many of these applications would benefit from faster analysis with smaller sample requirements. Further, some natural samples are soft and have high water content, which brings challenges to element analysis. Here, we develop a cryogenic pelletization pretreatment to address those challenges. The soft samples are cryogenically milled, freeze-dried, and pelletized before elemental analysis. Analysis is performed by laser ablation spectroscopy, the combination of laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS), to rapidly analyze light and heavy analytes. For this initial study, aluminum (Al) content in soft samples is determined by LIBS and lead (Pb) content by LA-ICP-MS. The standard addition method is performed to build calibration curves for element quantification. The measurements are compared with a Hong Kong government certified acid digestion and ICP-MS procedure. The experiment is performed on standard reference materials and selected food samples. The relative errors compared with certified measurements are less than 10% for all samples, with Al content ranging from 63-1466 µg/g and Pb content from 0.37-2.35 µg/g (dry mass). Microscopy of pellets shows that laser ablation spectroscopy can be performed with 100 µg of sample (dry mass). Total analysis time from raw sample to final measurement, including preparation, is under 1 h. The results indicate that the laser ablation spectroscopy with cryogenic pelletization is a promising technique for many applications such as screening of small food samples for toxic metals and trace element analysis of millimeter biopsies.

Contrasting effects of biochar and hydrothermally treated coal gangue on leachability, bioavailability, speciation and accumulation of heavy metals by rapeseed in copper mine tailings.

The purpose of this research was to examine the influence of hydrothermally treated coal gangue (HTCG) with and without biochar (BC) on the leaching, bioavailability, and redistribution of chemical fractions of heavy metals (HMs) in copper mine tailing (Cu-MT). An increase in pH, water holding capacity (WHC) and soil organic carbon (SOC) were observed due to the addition of BC in combination with raw coal gangue (RCG) and HTCG. A high Cu and other HMs concentration in pore water (PW) and amended Cu-MT were reduced by the combination of BC with RCG and/or HTCG, whereas individual application of RCG slightly increased the Cu, Cd, and Zn leaching and bioavailability, compared to the unamended Cu-MT. Sequential extractions results showed a reduction in the exchangeable fraction of Cu, Cd, Pb, and Zn and elevation in the residual fraction following the addition of BC-2% and BC-HTCG. However, individual application of RCG slightly increased the Cu, Cd, and Zn exchangeable fractions assessed by chemical extraction method. Rapeseed was grown for the following 45 days during which physiological parameters, metal uptake transfer rate (TR), bioconcentration factor (BCF), and translocation factor (TF) were measured after harvesting. In the case of plant biomass, no significant difference between applied amendments was observed for the fresh biomass (FBM) and dry biomass (DBM) of shoots and roots of rapeseed. However, BC-2% and BC-HTCG presented the lowest HMs uptake, TR, BCF (BCFroot and BCFshoot), and TF for Cu, Cd, Cr, Ni, Pb, and Zn in rapeseed among the other amendments compared to the unamended Cu-MT. Overall, these findings are indicative that using biochar in combination with RCG and/or HTCG led to a larger reduction in HMs leaching and bioavailability, due to their higher sorption capacity and could be a suitable remediation strategy for heavy metals in a Cu-MT.

Single red blood cell analysis reveals elevated hemoglobin in poikilocytes.

Abnormally shaped red blood cells (RBCs), called poikilocytes, can cause anemia. At present, the biochemical abnormalities in poikilocytes are not well understood. Normal RBCs and poikilocytes were analyzed using whole-blood and single-cell methods. Poikilocytes were induced in rat blood by intragastrically administering titanium dioxide (TiO2) nanoparticles. Complete blood count and inductively coupled plasma mass spectrometry analyses were performed on whole-blood to measure average RBC morphology, blood hemoglobin (HGB), iron content, and other blood parameters. Follow-up confocal Raman spectroscopy was performed on single RBCs to analyze cell-type-specific HGB content. Two types of poikilocytes, acanthocytes and echinocytes, were observed in TiO2 blood samples, along with normal RBCs. Acanthocytes (diameter 7.7 ± 0.5 µm) and echinocytes (7.6 ± 0.6 µm) were microscopically larger (p < 0.05) than normal RBCs (6.6 ± 0.4 µm) found in control blood samples (no TiO2 administration). Similarly, mean corpuscular volume was higher (p < 0.05) in TiO2 whole-blood (70.70 ± 1.97 fl) than in control whole-blood (67.42 ± 2.03 fl). Poikilocytes also had higher HGB content. Mean corpuscular hemoglobin was higher (p < 0.05) in TiO2 whole-blood (21.84 ± 0.75 pg) than in control whole-blood (20.8 ± 0.32 pg). Iron content was higher (p < 0.001) in TiO2 whole-blood (697.0 ± 24.5 mg / l) than in control whole-blood (503.4 ± 38.5 mg / l), which supports elevated HGB as iron is found in HGB. HGB-associated Raman bands at 1637, 1585, and 1372 cm - 1 had higher (p < 0.001) amplitudes in acanthocytes and echinocytes than in RBCs from control blood and normal RBCs from TiO2 blood. Further, the 1585-cm - 1 band had a lower (p < 0.05) amplitude in normal RBCs from TiO2 versus control RBCs. This represents biochemical abnormalities in normal appearing RBCs. Overall, poikilocytes, especially acanthocytes, have elevated HGB.

Biochar-assisted transformation of engineered-cerium oxide nanoparticles: Effect on wheat growth, photosynthetic traits and cerium accumulation.

The extensive use of nano-fabricated products in daily life is releasing a large volume of engineered nanoparticles (ENPs) in the environment having unknown consequences. Meanwhile, little efforts have been paid to immobilize and prevent the entry of these emerging contaminants in the food chain through plant uptake. Herein, we investigated the biochar role in cerium oxide nanoparticles (CeO2NPs) bioaccumulation and subsequent translocation in wheat (Triticum aestivum L.) as well as impact on growth, photosynthesis and gas-exchange related physiological parameters. Results indicated that CeO2NPs up to 500 mg L-1 level promoted the plant growth by triggering photosynthesis, transpiration and stomatal conductance. Higher NPs concentration (2000 mg CeO2NPs L-1) has negatively affected the plant growth and photosynthesis related processes. Conversely, biochar amendment with CeO2NPs considerably reduced (~9 folds) the plants accumulated contents of Ce even at 2000 mg L-1 exposure level of CeO2NPs through surface complexation process and alleviated the phyto-toxic effects of NPs on plant growth. XPS and FTIR analysis confirmed the role of biochar-mediated carboxylate and hydroxyl groups bonding with CeO2NPs. These findings provides an inside mechanistic understanding about biochar interaction with nano-pollutants to inhibit their bioavailability to plant body.

A comprehensive review of climate change impacts, adaptation, and mitigation on environmental and natural calamities in Pakistan.

The devastations and damages caused by climate change are apparent across the globe, specifically in the South Asian region where vulnerabilities to climate change among residents are high and climate change adaptation and mitigation awareness are extremely low. Pakistan's low adaptive capacity due to high poverty rate, limited financial resources and shortage of physical resources, and continual extreme climatic events including varying temperature, continual flooding, melting glaciers, saturation of lakes, earthquakes, hurricanes, storms, avalanches, droughts, scarcity of water, pest diseases, human healthcare issues, and seasonal and lifestyle changes have persistently threatened the ecosystem, biodiversity, human communities, animal habitations, forests, lands, and oceans with a potential to cause further damages in the future. The likely effect of climate change on common residents of Pakistan with comparison to the world and their per capita impact of climate change are terribly high with local animal species such as lions, vultures, dolphins, and tortoise facing extinction regardless of generating and contributing diminutively to global GHG emissions. The findings of the review suggested that GHG emissions cause climate change which has impacted agriculture livestock and forestry, weather trends and patterns, food water and energy security, and society of Pakistan. This review is a sectorial evaluation of climate change mitigation and adaption approaches in Pakistan in the aforementioned sectors and its economic costs which were identified to be between 7 to 14 billion USD per annum. The research suggested that governmental interference is essential for sustainable development of the country through strict accountability of resources and regulation implemented in the past for generating state-of-the-art climate policy.

Divisional disparities on climate change adaptation and mitigation in Punjab, Pakistan: local perceptions, vulnerabilities, and policy implications.

Climate change is a global challenge faced by everyone, but the developing countries are highly vulnerable to variations in the environment. This research focuses on the Punjab province of Pakistan and evaluates the impacts and consequences of climate change on general public at local and divisional level. In order to cope with the impacts of climatic changes at all levels, especially divisional level, raising reliable awareness and dispersing actionable knowledge regarding mitigating and adapting measures is significantly important. Therefore, recognition of information gaps, improvements in the level of alertness, and development of preventive measures in each sector is imperative. The impacts of climate change are observed across the country through gradual increase in temperature, human health issues, pest diseases, droughts, floods, and irregular weather patterns leading to changes in lifestyles, and these issues are likely to continue in the future. The main cause of climate change in Punjab, Pakistan, can be attributed to excessive release of greenhouse gases (GHG) into the atmosphere due to human activities involving inefficient energy usage, rapid urban expansion, improper waste management, industrial development, increasing transportation, agricultural activities, and livestock mismanagement. The findings of this study revealed that transportation sector is the major source of GHG emissions in the country, followed by industrialization and waste, at national, as well as divisional, level. The extent of impacts of climate change at divisional level is distinguishable and displayed a direct relationship with climate, geography, variation of effects, and modes of production in various regions of Punjab. The study strategically investigated all nine divisions of the province for comprehensive understanding of climate change phenomenon, and the results indicated that nearly three-fourths of the respondents have never indulged in taking steps towards climate change mitigation and adaptation. The study adopted a mixed (qualitative and quantitative) approach where the findings can act as set of guidelines for governmental authorities in formulating, assisting in preparation, instructing, and guiding policies for climate change mitigation and adaptation at national, local, and divisional levels. Graphical abstract.