Spectrochemical Analysis of Nutritional and Toxic Metals in Different Brands of Candies Using Advanced Diagnostic Approaches.

Candies are frequently consumed sweetened food products among children, and their consumption can expose them to potential toxins and contamination. The present study employed calibration-free-laser-induced breakdown spectroscopy (CF-LIBS) as a steadfast diagnostic technique to analyze the presence of nutritional and heavy metals in candies from various brands available in local markets in Haripur, Pakistan. A pulsed Nd-YAG laser was used to create a microplasma on the target surface. The emitted light was collected using a dedicated spectrometer to analyze and quantify the species present in the candies. The analysis revealed the presence of micronutrients, macronutrients, and trace toxic metals such as Ca, K, Mg, Fe, Na, Al, Pb, Cr, Mn, Zn, Cu, and Ni. The optimization of our LIBS system was achieved through a parametric dependence study. The confirmation of the assumption of local thermodynamic equilibrium was achieved by assessing McWhirter's criterion and considering the relaxation time and the diffusion length of atoms in plasma. The highest concentrations (measured in mg/kg) of Pb, Cr, and Mn were determined to be 15 mg/kg, 340 mg/kg, and 880 mg/kg, respectively. The levels of Pb and Cr were found to be well above the maximum accepted limit set by the WHO. Similarly, the concentration of Mn in S-4 and S-5 exceeded the permissible limits set by the WHO. However, Zn, Cu, and Ni were found within safe limits in all the collected samples. In addition, the abundance obtained through CF-LIBS was compared to the concentration of similar (duplicate) candies samples analyzed using a standard analytical technique like inductively coupled plasma-optical emission spectroscopy. Excellent harmony could be seen in both outcomes. Moreover, energy-dispersive X-ray spectroscopy (EDX) was also utilized to confirm the presence of detected toxins. The significance of our findings lies in creating awareness among the public about the health risks associated with consuming toxins through candies, thereby protecting numerous human lives.

Estimation and Quantification of Toxic Metals in Hugely Consumed Chicken Livers by Advanced Diagnostic Approaches.

Contamination of toxins in chicken's liver is a serious concern for human health owing to related threats of cytotoxicity and general pathologies after their digestion. The quantitative investigations were accomplished by calibration curves plotted for all the detected toxins via typical samples arranged in the known concentrations in the chicken liver's matrix. The chicken liver samples were collected from the Khyber Pakhtunkhwa province of Pakistan and found to contain heavy metals like Cu, Mn, Ni, Pb, and Zn. The analytical estimations were performed under the suppositions of local thermodynamic equilibrium (LTE) in terms of optical thin plasma. The maximum concentrations (parts per million) of Cu, Mn, Ni, Pb, and Zn were as 2.87 ± 0.02 ppm, 7.80 ± 0.13 ppm, 2.84 ± 0.02 ppm, 4.00 ± 0.08, and 83.5 ± 2.10 ppm respectively. Abundance of Cu, and Pb was found considerably beyond the maximum accepted boundary of WHO. Likewise, the level of Ni exceeded the permitted bounds of WHO in samples 01 and 02. To validate our laser-induced breakdown spectroscopy investigation, we approximated the abundance of identical (duplicate) chicken livers through digesting the specimens in suitable solvents by a typical technique such as inductively coupled plasma/optical emission spectrometry (ICP/OES) and the results acquired were in outstanding harmony. Furthermore, the existence of detected toxins was also checked using energy dispersive X-ray spectroscopy (EDX). It is worth stating that larger amounts of Cu, Ni, and Pb in poultry may cause a severe hazard to customers which required security actions and precautions. Our findings are extremely important to make an awareness among the people due to associated health hazards after the digestion of toxins through chicken liver and to protect numerous human lives.

Development of laser induced breakdown spectroscopy technique to study irrigation water quality impact on nutrients and toxic elements distribution in cultivated soil.

This study is focused mainly on impact of irrigation water quality in cultivated soil on distribution of essentials nutrients (Al, Mg, Ca, Fe, S, Si, Na, P, and K) and relatively toxic metals (As, Ba, Cr, Cu, Ti, Sn, Mn, Ni, and Zn) using an elegant Laser induced breakdown spectroscopy (LIBS) technique. A pulsed Nd:YAG laser operating at 1064 nm in conjunction with suitable detector was applied to record soil emission spectra. The abundance of these elements were evaluated via standard calibration curve Laser Induced Breakdown Spectroscopy (CC-LIBS) and calibration free Laser Induced Breakdown Spectroscopy (CF-LIBS) approaches. Quantitative analyses were accomplished under conjecture of local thermodynamic equilibrium (L.T.E) and optically thin plasma. The average electron temperatures were estimated by Boltzmann plot method for cultivated soil samples in 7800 to 9300 K range. The electron number density was ~ 1.11 × 1017 cm - 3 to 1.60 × 1017 cm - 3. Prior to application on soil samples, the experimental setup was optimized at the following parameters: pulsed energy = 60 mJpulse-1, sample to lens distance of 9.0 cm, and the gate delay of 3.5 µs. It is noteworthy that nutritional elements content of cultivated soils were found strongly dependent upon the irrigation water quality. The cultivated soil from industrial area was found rich of toxins while the cultivated land using tube well water contains toxins in least amount. Our LIBS findings were also validated by comparing its results with contents measured using a standard inductively coupled plasma optical emission spectroscopy (ICP-OES) method and both were found in excellent agreement. The present study could be highly beneficial for agricultural applications and for farmers to produce safe food products and higher crops yield.

Nutritional and toxic elemental analysis of dry fruits using laser induced breakdown spectroscopy (LIBS) and inductively coupled plasma atomic emission spectrometry (ICP-AES).

Quantitative investigation of essential and trace heavy elements present in health-beneficial dry fruits (Pistachio, Almonds, Black walnut, White walnut, and Cashew) was investigated using Laser Induced Breakdown Spectroscopy. For an accurate elemental exposure using LIBS technique, the local thermo-dynamical equilibrium of the laser induced plasma was established and verified using McWhirter criterion based on the electron number density in the plasma. Earlier to engage, our LIBS detector was optimized. For quantification of elements, standard calibration curves (CC)-LIBS method was applied. Using our LIBS system, the nutritional elements such as Al, Mg, Ca, Fe, K, Zn, and Na and toxins like Pb, Cr, and Cu were detected in dry fruits. The elemental quantification of dry fruit contents were validated using standard (ICP-AES) method and the relative accuracy of our experimental setup in comparison to ICP approach was in the ranging from 0.1 to 0.3 at 2.5-% error confidence.

Detection of nutritional and toxic elements in Pakistani pepper powders using laser induced breakdown spectroscopy.

In the current study, we applied laser induced breakdown spectroscopy (LIBS) to determine the elemental distribution of nutritional and trace heavy metals in pepper powders available in Pakistan using the standard calibration curve of laser induced breakdown spectroscopic (CC-LIBS) technique. The samples were found to contain elements such as K, Ca, Mg, Na, Fe, Zn, Al, Pb, Cu, and Cr. In addition, we also identified the atmospheric H-alpha line of hydrogen in the spectra, which was used to estimate the electron number density. To achieve a highly sensitive LIBS system to determine the trace amounts of nutritional and toxic metals in the pepper powders and to achieve the best limit of detection, the LIBS system was optimized by studying the dependency of the LIBS signal intensity on laser irradiance, variation in spacing between the focusing lens and target, as well as on the gate width. To justify the results of the LIBS study, we also determined the concentration of similar (duplicate) peppers by digesting the samples in appropriate solvents using a standard method such as inductively coupled plasma-optical emission spectrometry (ICP-OES). The minimum detection limit was obtained for trace heavy metals from the calibration curves. The results of LIBS displayed noteworthy conformity with those acquired from the ICP-OES analysis. The results of both the techniques clearly revealed that K was the most abundant element in all the peppers, followed by Ca, Mg, Na, Fe, Al, Pb, Zn, Cu, and Cr. The relative accuracy of our LIBS system for different species as compared with the ICP technique was in the range of 0.08-0.3 at 2.5% error confidence. Conclusively, the present work demonstrated the suitability of the LIBS technique due to its rapid, non-destructive, and eco-friendly approach for food security.

Spectral diagnosis of health hazardous toxins in face foundation powders using laser induced breakdown spectroscopy and inductively coupled plasma-optical emission spectroscopy (ICP-OES).

In this work, we applied laser-induced breakdown spectroscopy (LIBS) to estimate the amount of toxic heavy metals (Pb, Cr, Ni) in five different brands of face foundation powders available in the local market using standard calibration curve (CC)-LIBS approach. These samples contain toxic elements like lead, chromium, nickel which are highly carcinogens to cause eczematous and atopic dermatitis. The strongest atomic transition lines of lead (405.7 line), chromium (425.4 nm line), and nickel (336.9 nm line) were used as spectral markers to simultaneously detect these three heavy metals in face powder samples. The LIBS experimental parameters (delay time, laser energy, and focusing lens to target spacing) were optimized to enhance the signal to noise ratio in the resulting LIBS spectra. The consequence of self-absorption on the marker peaks used in the LIBS analysis was investigated and found to be insignificant. We calibrated our LIBS system for these three heavy metals, whose levels were found above the permissible limits. The face foundation powder used every day augments up to considerable exposure of heavy metals in the human body which could cause many skin disorders. Our LIBS quantitative results were also cross-validated by analysis using a standard analytical technique known as inductively coupled plasma-optical emission spectroscopy (ICP-OES). This study is highly significant due to the excessive use of cosmetic products especially face powder that could affect the health of millions of people around the globe.

Electron number density conservation model combined with a self-absorption correction methodology for analysis of nanostructure plasma using laser-induced breakdown spectroscopy.

We studied laser ablation and plasma property evolution for a nickel (Ni) doped tin (Sn) oxide nanostructures target using laser-induced breakdown spectroscopy (LIBS). The transition metal Ni doped tin oxide nanostructures were synthesized by co-precipitation and hydrothermal methodologies. The size of prepared nanoparticles was verified by X-ray diffraction and transmission electron microscopy techniques. A frequency-doubled pulsed Nd:YAG laser with a wavelength of 532 nm was used to produce ablated plasma nanostructures. Ablation of doped and undoped nanostructures revealed salient-enhanced spectral emissions compared with their bulky counterparts. The emission lines of the constituent elements of doped material were used to find plasma parameters. The plasma temperature was estimated from a Boltzmann plot, and the electron number density was determined from the Saha-Boltzmann equation. The self-absorption effect has been observed in tiny plasma of nanostructures. The affected profiles of spectral lines of Ni and Sn nanoparticles due to self-absorption in LIBS spectra were corrected by the internal reference self-absorption correction (IRSAC) methodology. After correction of emitted line intensities by IRSAC, the electron number density (END) conservation approach was applied for quantitative analysis of doped nanostructures. In the END conservation approach, quantitative analysis of samples was carried out using electron number densities. Quantitative results derived from the END conservation approach at high and low concentrations exhibited good correlation when these were compared and validated with results from a conventional calibration free approach and the standard recognized energy dispersive X-ray technique.

Quantitative analysis of Fuller's earth using laser-induced breakdown spectroscopy and inductively coupled plasma/optical emission spectroscopy.

Fuller's earth, most commonly known as Multani Matti (clay) in Urdu, among its various utilizations is traditionally used in skin care cosmetics, particularly for removing blackheads and to treat oily skin. It is also used for improving skin complexion. In this paper, laser-induced breakdown spectroscopy (LIBS) was effectively employed for the quantitative investigation of various clay samples for their special uses. To get the LIBS spectra with an optimal signal-to-noise as well as for a more robust and accurate analytical investigation, different experimental parameters (laser energy, gate delay time, and the distance between target and focusing lens) were optimized before the experiments on actual samples. The analysis of emission spectra revealed the presence of many different elements, including Al, Ca, Fe, Mg, Mn, Na, K, Li, S, Si, and Zn. The electron number density and plasma temperatures were determined using the Stark broadened line profile and Boltzmann plot method, respectively. To determine the relative concentration of observed elements, we used an integrated intensity ratio method, integrated intensity of every line from all elements, and calibration free (CF)-LIBS. The prevailing condition of local thermodynamic equilibrium during the experimental executions was verified with multiple criteria. The spectral lines used in CF-LIBS were characterized for the influence from the self-absorption phenomenon, but the same was found insignificant. The findings of our LIBS system were found to agree excellently with the outcomes of the inductively coupled plasma/optical emission spectroscopy, thereby yielding a high statistical correlation factor and hence enlighten the significance of LIBS as a safe and reliable tool for elemental analysis of clay samples.

LIBS for the detection of lead in ready to use henna paste and nutrients in fresh henna leaves and cultivated soils.

Commercially available ready to use henna paste, procured from the local market in Pakistan were tested to find the level of hazardous element, lead present in the samples, using Laser Induced Breakdown Spectroscopy (LIBS). The source of lead in the ready to use henna is from the artificial chemical additives in henna paste, added to enhance the color and also to speed up the dying of the henna tattoo in hand, feet, and body. Henna tattooing is an inevitable practice in the social events in the cultures of the Indian subcontinent and the Arabian Peninsula. The frequent reckless use of henna, particularly lavishly administering it to the children is quite dangerous, although the level of lead found in the commercially available ready to use henna samples are within the permissible safe level. For the sensitive detection and quantification of lead, various experimental and plasma parameters in the LIBS detection system were optimized and the system was calibrated. The quantitative analysis of lead, carried out in five different samples of ready to use henna, using LIBS revealed that the concentration of lead in these samples is between 5.5 ±â€¯0.2 mg Kg-1 and 16.0 ±â€¯0.2 mg Kg-1. Moreover, LIBS elemental analysis of natural henna leaves, cultivated in Sindh and Punjab regions of Pakistan, and also the soils taken from the locations of cultivation were carried out and a correlation in the elemental compositions between the henna leaves and the cultivated soil in the proximity were studied. The quantitative analysis of LIBS results were validated by atomic absorption spectroscopy (AAS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES).

Optimized laser-induced breakdown spectroscopy for the determination of high toxic lead in edible colors.

An optimized laser-induced breakdown spectroscopy (LIBS) system was utilized as a robust tool for the detection of high toxic lead (Pb) in often used edible colors available in local markets. Edible colors are extensively used in different food stuffs and sweet dish items. To attain a highly sensitive LIBS system for the determination of trace amounts of toxic Pb in edible colors and to achieve the best detection limit, various parametric dependence studies were performed. The quantitative determinations were accomplished under the condition of local thermodynamic equilibrium in terms of optically thin plasma. Besides toxic Pb, other elements like Ca, Mg, Fe, and Na were also detected in edible colors. To estimate the concentration of toxic lead in edible colors, calibration curves were plotted by preparing standard samples of different lead concentrations in an edible colors matrix. Results of the LIBS technique were compared with the outcomes of the same samples studied using a standard analytical technique of inductively coupled plasma-optical emission spectroscopy to confirm the contemporary LIBS setup. The color samples were found above the safe permissible level due to the mass of toxic lead. Limit of detection of the LIBS setup was found at 0.86+/-0.03 ppm for toxic lead present in edible color samples.

Optimized laser-induced breakdown spectroscopy for determination of xenobiotic silver in monosodium glutamate and its verification using ICP-AES.

Laser-induced breakdown spectroscopy (LIBS) was applied as a potential tool for the determination of xenobiotic metal in monosodium glutamate (MSG). In order to achieve a high-sensitivity LIBS system required to determine trace amounts of metallic silver in MSG and to attain the best detection limit, the parameters used in our experiment (impact of focusing laser energy on the intensity of LIBS emission signals, the influence of focusing lens distance on the intensity of LIBS signals, and time responses of the plasma emissions) were optimized. The spectra of MSG were obtained in air using a suitable detector with an optical resolution of 0.06 nm, covering a spectral region from 220 to 720 nm. Along with the detection of xenobiotic silver, other elements such as Ca, Mg, S, and Na were also detected in MSG. To determine the concentration of xenobiotic silver in MSG, the calibration curve was plotted by preparing standard samples having different silver abundances in an MSG matrix. The LIBS results of each sample were cross-verified by analyzing with a standard analytical technique such as inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Both (LIBS and ICP-AES) results were in mutual agreement. The limit of detection of the LIBS setup was found to be 0.57 ppm for silver present in MSG samples.

Determination of lead content in drilling fueled soil using laser induced spectral analysis and its cross validation using ICP/OES method.

A detection system based on Laser Induced Breakdown Spectroscopy (LIBS) was designed, optimized, and successfully employed for the estimation of lead (Pb) content in drilling fueled soil (DFS) collected from oil field drilling areas in Pakistan. The concentration of Pb was evaluated by the standard calibration curve method as well as by using an approach based on the integrated intensity of strongest emission of an element of interest. Remarkably, our investigation clearly demonstrated that the concentration of Pb in drilling fueled soil collected at the exact drilling site was greater than the safe permissible limits. Furthermore, the Pb concentration was observed to decline with increasing distance away from the specific drilling point. Analytical determinations were carried out under the assumptions that laser generated plasma was optically thin and in local thermodynamic equilibrium (LTE). In order to improve the sensitivity of our LIBS detection system, various parametric dependence studies were performed. To further validate the precision of our LIBS results, the concentration of Pb present in the acquired samples were also quantified via a standard analytical tool like inductively coupled plasma/optical emission spectroscopy (ICP/OES). Both results were in excellent agreement, implying remarkable reliability for the LIBS data. Furthermore, the Limit of detection (LOD) of our LIBS system for Pb was estimated to be 125.14 mg L-1.

Determination of toxic and essential metals in rock and sea salts using pulsed nanosecond laser-induced breakdown spectroscopy.

A spectrometer based on pulsed nanosecond laser-induced breakdown spectroscopy (LIBS) was employed for the quantitative determination of heavy and essential metals in salts from various sources available in Pakistan. Six salt samples were collected from sea salt and rock salt. Toxic metals (Cu, Cd, and Ni) and other microessentials (Fe, Ca, Co, Mg, Mn, S, and Zn) were investigated from the recorded spectra. The detection system was calibrated using a parametric dependence study. The quantitative analyses were accomplished under the assumption of local thermodynamic equilibrium and optically thin plasma. The results by the LIBS technique were in agreement with the outcomes of the same samples studied using a more standard approach like inductively coupled plasma-atomic emission spectroscopy (ICP-AES). When the concentrations of heavy and essential metals were calculated using a calibration-free LIBS method that does not need a standard salt specimen and dilution, both LIBS and ICP-AES were also in good agreement. The limit of detection of the experimental set up was determined for the observed heavy metals in the studied samples.

Synthesis, antileishmanial activity and docking study of N'-substitutedbenzylidene-2-(6,7-dihydrothieno[3,2-c]pyridin-5(4H)-yl)acetohydrazides.

A series of N'-substitutedbenzylidene-2-(6,7-dihydrothieno[3,2-c]pyridin-5(4H)-yl)acetohydrazide derivatives is synthesized and evaluated for antileishmanial activity against Leishmania donovani promastigotes. Compounds 9a and 9i were shown significant antileishmanial when compared with standard sodium stilbogluconate. Antimicrobial study revealed that compound 9b has potent as well as broad spectrum antibacterial activity when compared with ampicillin and compound 9e showed promising antifungal activity when compared with miconazole. Also, none of the synthesized compounds showed cytotoxicity up to tested concentration. Further, docking study against pteridine reductase 1 enzyme of L. donovani showed good binding interactions. ADME properties of synthesized compounds were also analyzed and showed potential to develop as good oral drug candidates.

Anterior tension - free repair versus posterior preperitoneal repair for recurrent hernia.

OBJECTIVE: To compare anterior tension-free approach with posterior preperitoneal repair for complications and early recurrence. DESIGN: A randomized clinical trial. PLACE AND DURATION OF STUDY: Combined Military Hospital, Muzaffarabad and Rawalpindi, from March 1997 to December 2002. PATIENTS AND METHODS: Sixty-seven patients with unilateral recurrent inguinal scrotal and irreducible hernias, were randomized to either anterior tension-free or posterior preperitoneal repair. Patients with primary inguinal hernia, patients with class11/111 obesity (BMI > 35) and ASA grade 3 and beyond were excluded. For posterior repair, preperitoneal space was entered through a transverse lower abdominal incision placed 3 cms above inguinal ligament. Anterior repair was done by standard Lichtenstein technique. Forty-two patients were operated under spinal anesthesia while 25 patients had general anesthesia. Follow-up was on 7th and 12th postoperative day, at third month, and then yearly for two years. Main outcome measures were postoperative pain and recovery; postoperative complications related to wound, testicles, sensory nerves; and recurrence. RESULTS: Thirty-four patients had anterior tension-free hernioplasty while 33 patients had posterior preperitoneal repair. Mean operating time was longer for anterior preperitoneal repair as compared to posterior repair (70.1min vs. 62.6 min, p = 0.1). Pain score and hospital stay was same for both groups. Return to normal activity was not significantly different being 14.1 days for anterior and 13 days for posterior repair (p= 0.07). Heavy duties were also resumed after statistically non-significant interval, 34.6 days for anterior, and 33 days for posterior repair (p = 0.09). Complication rate in anterior hernioplasty group was 17.6% while in preperitoneal group it was 3% ( p=0.001). There was no recurrence in either group after a mean follow-up of 2 years. CONCLUSION: Open preperitoneal repair and anterior tension-free repair were equivalent in terms of postoperative pain, recovery and early recurrence rate. Considering fewer testicular complications with posterior repair, it should be the procedure of choice for repair of recurrent groin hernia in men.