In this article, an easy and quick method based on microwave assisted acid digestion technique prior to quantification using inductively coupled plasma mass spectrometry for the analysis of heavy metals in cocoa beans, cocoa powder and chocolate was established and validated for arsenic (As), cadmium (Cd), lead (Pb), and antimony (Sb). Limit of quantification for all elements were product dependent and varies from 7.84 to 194.52 µg/kg. The recoveries of the heavy metals at 250 and 1000 µg/kg spiking levels were ranged between 96.27-108.75%, 90.43-101.97% and 89.72-106.26% for cocoa beans, cocoa powder, and chocolate, respectively. Relative standard deviation values obtained were all below 20% and the expanded uncertainty measurements for the elements were less than 25%. The analysis of real samples found that the concentration level is far from the national alarming level except for cadmium in cocoa beans.
The concentration of nine trace elements were analyzed in the different tissue organs of commonly available crabs (Portunus sanguinolentus, Portunus pelagicus and Scylla serrate) and bivalve (Polymesoda erosa) species collected from the Miri coast, Borneo in order to evaluate the potential health risk by consumption of these aquatic organisms. Among the analyzed organs, metal accumulation was higher in the gill tissues. The essential (Cu and Zn) and non-essential (Pb and Cd) elements showed the highest (i.e. Zn) and lowest concentrations (i.e. Cd) in their tissue organs, respectively. The estimated daily intake and hazard indices of all metals in the muscle indicate that the measured values were below the provisional tolerable daily intake suggested by the joint FAO/WHO Expert Committee on Food Additives. Compared to Malaysian and international seafood guideline values the results obtained from the present study are lower than the permissible limits and safe for consumption.
An organometallic/silica nanocomposite of a 1D cylindrical assembly of a trinuclear gold(I)-pyrazolate complex ([Au(3)Pz(3)]) that was confined inside the nanoscopic channels of hexagonal mesoporous silica ([Au(3)Pz(3)]/silica(hex)), emitted red light with a luminescence center at 693 nm upon photoexcitation at 276 nm owing to a Au(I)-Au(I) metallophilic interaction. When a film of [Au(3)Pz(3)]/silica(hex) was dipped into a solution of Ag(+) in tetrahydrofuran (THF), the resulting nanocomposite material (Ag@[Au(3)Pz(3)]/silica(hex)) emitted green light with a new luminescence center at 486 nm, which was characteristic of a Au(I)-Ag(I) heterometallic interaction. Changes in the emission/excitation and XPS spectra of Ag@[Au(3)Pz(3)]/silica(hex) revealed that Ag(+) ions permeated into the congested nanochannels of [Au(3)Pz(3)]/silica(hex), which were filled with the cylindrical assembly of [Au(3)Pz(3)].
This study aimed to determine the spatial distribution of PM2.5 and PM10 collected in four regions (North, Central, South and East Coast) of Peninsular Malaysia during the southwest monsoon. Concurrent measurements of PM2.5 and PM10 were performed using a high volume sampler (HVS) for 24 h (August to September 2018) collecting a total of 104 samples. All samples were then analysed for water soluble inorganic ions (WSII) using ion chromatography, trace metals using inductively coupled plasma-mass spectroscopy (ICP-MS) and polycyclic aromatic hydrocarbon (PAHs) using gas chromatography-mass spectroscopy (GC-MS). The results showed that the highest average PM2.5 concentration during the sampling campaign was in the North region (33.2 ± 5.3 μg m-3) while for PM10 the highest was in the Central region (38.6 ± 7.70 μg m-3). WSII recorded contributions of 22% for PM2.5 and 20% for PM10 mass, with SO42- the most abundant species with average concentrations of 1.83 ± 0.42 μg m-3 (PM2.5) and 2.19 ± 0.27 μg m-3 (PM10). Using a Positive Matrix Factorization (PMF) model, soil fertilizer (23%) was identified as the major source of PM2.5 while industrial activity (25%) was identified as the major source of PM10. Overall, the studied metals had hazard quotients (HQ) value of <1 indicating a very low risk of non-carcinogenic elements while the highest excess lifetime cancer risk (ELCR) was recorded for Cr VI in the South region with values of 8.4E-06 (PM2.5) and 6.6E-05 (PM10). The incremental lifetime cancer risk (ILCR) calculated from the PAH concentrations was within the acceptable range for all regions.
Evaluation of the hydrogeochemical processes governing the heavy metal distribution and the associated health risk is important in managing and protecting the health of freshwater resources. This study mainly focused on the health impacts due to the heavy metals pollution in a known Cretaceous-Tertiary (K/T) contact region (Tiruchinopoly, Tamilnadu) of peninsular India, using various pollution indices, statistical, and geochemical analyses. A total of 63 samples were collected from the hard rock aquifers and sedimentary formations during southwest monsoon and analysed for heavy metals, such as Li, Be, Al, Rb, Sr, Cs, Ba, pb, Mn, Fe, Cr, Zn, Ga, Cu, As, Ni, and Co. Ba was the dominant element that ranged from 441 to 42,638 μg/l in hard rock aquifers, whereas Zn was the major element in sedimentary formations, with concentrations that ranged from 44 to 118,281 μg/l. The concentrations of Fe, Ni, Cr, Al, Cr, and Ni fell above the permissible limit in both of the formations. However, the calculated heavy metal evaluation index (HEI), heavy metal pollution index (HPI), and the degree of contamination (Cd) parameters were higher in the sedimentary formation along the contact zone of the K/T boundary. Excessive health risks from consumption of contaminated groundwater were mostly confined to populations in the northern and southwestern regions of the study area. Carcinogenic risk assessment suggests that there are elevated risks of cancer due to prolonged consumption of untreated groundwater. Ba, Sr, and Zn were found to be geochemically highly mobile due to the partitioning between the rock matrix and groundwater, aided by the formation of soluble carbonato-complexes. Factor analysis indicates that the metals are mainly derived from the host rocks and anthropogenic inputs are relatively insignificant. Overall, this study indicated that groundwater in K/T contact zones is vulnerable to contamination because of the favorable geochemical factors. Long-term monitoring of such contact zones is required to avert the potential health hazards associated with consumption of the contaminated groundwater.
This study determined the heavy metals (HMs) accumulation in different vegetables in different seasons and attributed a serious health hazard to human adults due to the consumption of such vegetables in Jhansi. The total amounts of zinc (Zn), lead (Pb), nickel (Ni), manganese (Mn), copper (Cu), cobalt (Co), and cadmium (Cd) were analysed in 28 composite samples of soil and vegetables (Fenugreek, spinach, eggplant, and chilli) collected from seven agricultural fields. The transfer factor (TF) of HMs from soil to analysed vegetables was calculated, and significant non-carcinogenic health risks due to exposure to analysed heavy metals via consumption of these vegetables were computed. The statistical analysis involving Principal Component Analysis (PCA) and Pearson's correlation matrix suggested that anthropogenic activities were a major source of HMs in the study areas. The target hazard quotient of Cd, Mn, and Pb for fenugreek (2.156, 2.143, and 2.228, respectively) and spinach (3.697, 3.509, 5.539, respectively) exceeded the unity, indicating the high possibilities of non-carcinogenic health risks if regularly consumed by human beings. This study strongly suggests the continuous monitoring of soil, irrigation water, and vegetables to prohibit excessive accumulation in the food chain.
Postoperative biliary strictures are the most common cause of benign biliary stricture in Western countries, secondary to either operative injury or bile duct anastomotic stricture following orthotopic liver transplantation (OLT). Surgery or endoscopic interventions are the mainstay of treatment for benign biliary strictures. We aim to report the outcome of 2 patients with refractory anastomotic biliary stricture post-OLT, who had successful temporary placement of a prototype removable covered self-expandable metal stent (RCSEMS). These 2 patients (both men, aged 44 and 53 years) were given temporary placement of a prototype RCSEMS (8.5 Fr gauge delivery system, 8 mm x 40 mm stent dimensions) in the common bile duct across the biliary stricture. There was no morbidity associated with stent placement and removal in these 2 cases. Clinical parameters improved after the RCSEMS placement. Long-term biliary patency was achieved in both the patients. No further biliary intervention was required within 14 and 18 mo follow-up after stent removal.
Cylinder-shaped NaY zeolite was used as an adsorbent for eradicating both heavy metal ions (Cu2+, Zn2+, Ni2+, and Co2+) and proteins from the waste streams. As a pseudo-metal ion affinity adsorbent, NaY zeolite was used in the capture of heavy metal ions in the first stage. The amount (molar basis) of metal ions adsorbed onto NaY zeolite decreased in the order of Cu2+ > Zn2+ > Co2+ > Ni2+. Bovine serum albumin (BSA) was utilized as a model of proteins used in the waste adsorption process by NaY zeolite. The adsorption capacities of NaY zeolite and Cu/NaY zeolite for BSA were 14.90 mg BSA/g zeolite and 84.61 mg BSA/g zeolite, respectively. Moreover, Cu/NaY zeolite was highly stable in the solutions made of 2 M NaCl, 500 mM imidazole or 125 mM EDTA solutions. These conditions indicated that the minimal probability of secondary contamination caused by metal ions and soluble proteins in the waste stream. This study demonstrates the potential of Cu/NaY zeolite complex as an efficient pseudo-metal chelate adsorbent that could remove metal ions and water-soluble proteins from wastewater concurrently.
Metanilate-layered double hydroxide nanohybrid compound was synthesized for controlled release purposes through co-precipitation method of the metal cations and organic anion. The effect of various divalent metal cations (M2+), namely Zn2+, Mg2+ and Ca2+ on the formation of metanilate-LDH nanohybrids, in which metanilate anion was intercalated into three different layered double hydroxide (LDH) systems; Zn-Al, Mg-Al and Ca-Al were investigated. The syntheses were carried out with M2+ to Al3+ initial molar ratio, R of 4. The pH of the mother liquor was maintained at pH 7.5 and 10 during the synthesis, and the resulting mixture was aged at around 70 degrees C for about 18 h. The intercalation of metanilate anion into the host was found to be strongly influenced by the M2+ that formed the inorganic metal hydroxide layers. Under our experimental condition, the formation of the nanohybrid materials was found to be more feasible for the Zn-Al than for the other two systems, in which the former showed well-ordered layered organic-inorganic nanohybrid structure with good crystallinity. Intercalation is confirmed by the expansion of the interlayer spacing to about 15-17 A when metanilate was introduced into the interlamellae of Zn-Al LDHs. In addition, CHNS and FTIR analyses also support that metanilate anion has been successfully intercalated into the interlamellae of the inorganic LDH. Apart from M2+, this study also shows that the initial pH of the mother liquor plays an important role in determining the physicochemical properties of the resulting nanohybrids, especially the mole fraction of the Zn2+ substituted by the Al3+ ion in the LDH inorganic sheets which in turn controlled the loading percentage of the organic anion, surface properties and the true density. Preliminary study shows that LDH can be used to host beneficial guests, active agent with controlled release capability of the guests. Generally the overall process is governed by pseudo second order kinetic but for the first 180 min, the release process can be slightly better described by parabolic diffusion than the other models.
This study is the first to demonstrate dimensional optimization of nanowire-complementary metal-oxide-semiconductor inverter. Noise margins and inflection voltage of transfer characteristics are used as limiting factors in this optimization. Results indicate that optimization depends on both dimensions ratio and digital voltage level (Vdd). Diameter optimization reveals that when Vdd increases, the optimized value of (Dp/Dn) decreases. Channel length optimization results show that when Vdd increases, the optimized value of Ln decreases and that of (Lp/Ln) increases. Dimension ratio optimization reveals that when Vdd increases, the optimized value of Kp/Kn decreases, and silicon nanowire transistor with suitable dimensions (higher Dp and Ln with lower Lp and Dn) can be fabricated.
Consumption of iced beverages is common in Malaysia although specific research focusing on its safety parameters such as presence of faecal coliforms and heavy metal elements remains scarce. A study conducted in Kelantan indicated that faecal coliforms were detected in the majority of the ice cube samples analyzed, largely attributable to improper handling. Hence, it was found pertinent to conduct similar study in other parts of the country such as Johor Bahru if the similar pattern prevailed. Therefore, this present cross sectional study which randomly sampled ice cubes from 30 permanent food outlets in Taman Universiti, Johor Bahru for detecting contamination by faecal coliforms and selected heavy metal elements (lead, copper, manganese and zinc) acquires significance. Faecal coliforms were detected in 11 (36.67%) of the samples, ranging between 1 CFU/100 mL to > 50 CFU/100 mL; two of the samples were grossly contaminated (>50 CFU/100 mL). Interestingly, while positive detection of lead was observed in 29 of the 30 ice cube samples (mean: 0.511±0.105 ppm; range: 0.489-0.674 ppm), copper, manganese and zinc were not detected. In addition, analysis on commercially bottled mineral water as well as in tap water samples did not detect such contaminations. Therefore, it appears that (1) contamination of faecal coliforms in ice cubes in food outlets in Malaysia may not be sporadic in pattern but rather prevalent and (2) the source of water used for manufacturing the ice cubes that contained significant amount of lead would suggest that (3) it was neither originated from the treated tap water supply nor bottled mineral water or (4) perhaps contaminated during manufacturing process. Further studies exploring the source of water used for manufacturing these ice cubes as well as the handling process among food operators deserve consideration.
Enterobacter tabaci 4M9 (CCB-MBL 5004) was reported to have plant growth-promoting and heavy metal tolerance traits. It was able to tolerate more than 300 mg/L Cd, 600 mg/L As, and 500 mg/L Pb and still maintained the ability to produce plant growth-promoting substances under metal stress conditions. To explore the genetic basis of these beneficial traits, the complete genome sequencing of 4M9 was carried out using Pacific Bioscience (PacBio) sequencing technology. The complete genome consisted of one chromosome of 4,654,430 bp with a GC content of 54.6% and one plasmid of 51,135 bp with a GC content of 49.4%. Genome annotation revealed several genes involved in plant growth-promoting traits, including the production of siderophore, indole acetic acid, and 1-aminocyclopropane-1-carboxylate deaminase; solubilization of phosphate and potassium; and nitrogen metabolism. Similarly, genes involved in heavy metals (As, Co, Zn, Cu, Mn, Se, Cd, and Fe) tolerance were detected. These support its potential as a heavy metal-tolerant plant growth-promoting bacterium and a good genetic resource that can be employed to improve phytoremediation efficiency of heavy metal-contaminated soil via biotechnological techniques. This, to the best of our knowledge, is the first report on the complete genome sequence of heavy metal-tolerant plant growth-promoting E. tabaci.
Quantitative indices are classically employed to evaluate the contamination status of metals with reference to the baseline concentrations. The baselines vary considerably across different geographical zones. It is imperative to determine the local geochemical baseline to evaluate the contamination status. No study has been done to establish the background concentrations in tropical rivers of this region. This paper reports the background concentrations of metals in water and sediment of the Baleh River, Sarawak, derived based on the statistical methods where the areas possibly disturbed are distinguished from the undisturbed area. The baseline levels of six elements in water determined were Al (0.34 mg/L), Fe (0.51 mg/L), Mn (0.12 mg/L), Cu (0.01 mg/L), Pb (0.03 mg/L), and Zn (0.05 mg/L). Arsenic and selenium were below the detection limit. For sediment, the background values were established according to statistical methods including (mean + 2σ), iterative 2σ, cumulative distribution frequency, interquartile, and calculation distribution function. The background values derived using the iterative 2σ algorithm and calculated distribution function were relatively lower. The baseline levels calculated were within the range reported in the literatures mainly from tropical and sub-tropical regions. The upper limits proposed for nine elements in sediment were Al (100,879 mg/kg), Cr (75.45 mg/kg), Cu (34.59 mg/kg), Fe (37,823 mg/kg), Mn (793 mg/kg), Ni (22.88 mg/kg), Pb (27.26 mg/kg), Zn (70.64 mg/kg), and Hg (0.33 mg/kg). Quantitative indices calculated suggest low risk of contamination at the Baleh River.
This study aimed to evaluate the spatial and temporal distribution of heavy metals (Cd, Cr, Cu, Co, Fe, Pb, Ni, V, and Zn) in the sediments of Bayan Lepas Free Industrial Zone of Penang, Malaysia. Ten sampling stations were selected and sediment samples were collected during low tide (2012-2013). Metals were analyzed and the spatial distribution of metals were evaluated based on GIS mapping. According to interim sediment quality guidelines (ISQG), metal contents ranged from below low level to above high level at different stations. Based on the geoaccumulation index (Igeo) of sediment, sampling stations were categorized from unpolluted to strongly polluted. The enrichment factor (EF) of metals in the sediment varied between no enrichment to extremely high enrichment. The potential ecological risk index (RI) indicated Bayan Lepas FIZ was at low risk.
The spatial distributions of Na, Mg, K, Ca, Cr, Fe, Ni, Cu, Zn, As, Se and Pb in Hemibagrus sp. from Selangor River and a reference site were determined with inductively coupled plasma-mass spectrometer, in comparison to the levels in their surrounding water body and sediments. The results demonstrated significant differences in elemental accumulation pattern in different fish tissues originated from both sites. The variations observed were mainly subjected to their metabolic activities, and also the influence of the surrounding medium. In general, the liver tends to accumulate higher concentration of metals followed by the gills, and muscle tissues. The data also indicate associations between the concentrations of metal contaminants measured in the fish and the levels observed at the sites. The concentrations of hazardous metals As, Se and Pb in all the studied tissues reflect the influence of anthropogenic inputs. This suggests the potential utility of widely available Hemibagrus sp. as a valuable bioindicator of metal pollution in environmental monitoring and assessment.
Activity concentrations of primordial radionuclides in sand samples collected from the coastal beaches surrounding Penang Island have been measured using conventional γ-ray spectrometry, while in-situ γ-ray doses have been measured through use of a portable radiation survey meter. The mean activity concentrations for 226Ra, 232Th and 40K at different locations were found to be less than the world average values, while the Miami Bay values for 226Ra and 232Th were found to be greater, at 1023±47 and 2086±96Bqkg̶ 1 respectively. The main contributor to radionuclide enrichment in Miami Bay is the presence of monazite-rich black sands. The measured data were compared against literature values and also recommended limits set by the relevant international bodies. With the exception of Miami Bay, considered an elevated background radiation area that would benefit from regular monitoring, Penang island beach sands typically pose no significant radiological risk to the local populace and tourists visiting the leisure beaches.
Rapid socioeconomic development in the Linggi River Basin has contributed to the significant increase of pollution discharge into the Linggi River and its adjacent coastal areas. The toxic element contents and distributions in the sediment samples collected along the Linggi River were determined using neutron activation analysis (NAA) and inductively coupled plasma-mass spectrometry (ICP-MS) techniques. The measured mean concentration of As, Cd, Pb, Sb, U, Th and Zn is relatively higher compared to the continental crust value of the respective element. Most of the elements (As, Cr, Fe, Pb, Sb and Zn) exceeded the freshwater sediment quality guideline-threshold effect concentration (FSQG-TEC) value. Downstream stations of the Linggi River showed that As concentrations in sediment exceeded the freshwater sediment quality guideline-probable effect concentration (FSQG-PEC) value. This indicates that the concentration of As will give an adverse effect to the growth of sediment-dwelling organisms. Generally, the Linggi River sediment can be categorised as unpolluted to strongly polluted and unpolluted to strongly to extremely polluted. The correlation matrix of metal-metal relationship, principle component analysis (PCA) and cluster analysis (CA) indicates that the pollution sources of Cu, Ni, Zn, Cd and Pb in sediments of the Linggi River originated from the industry of electronics and electroplating. Elements of As, Cr, Sb and Fe mainly originated from motor-vehicle workshops and metal work, whilst U and Th originated from natural processes such as terrestrial runoff and land erosion.
As many studies are exploring the association between ingestion of bioactive compounds and decreased risk of non-communicable diseases, the scientific community continues to show considerable interest in these compounds. In addition, as many non-nutrients with putative health benefits are reducing agents, hydrogen donors, singlet oxygen quenchers or metal chelators, measurement of antioxidant activity using in vitro assays has become very popular over recent decades. Measuring concentrations of total phenolics, flavonoids, and other compound (sub)classes using UV/Vis spectrophotometry offers a rapid chemical index, but chromatographic techniques are necessary to establish structure-activity. For bioactive purposes, in vivo models are required or, at the very least, methods that employ distinct mechanisms of action (i.e., single electron transfer, transition metal chelating ability, and hydrogen atom transfer). In this regard, better understanding and application of in vitro screening methods should help design of future research studies on 'bioactive compounds'.