The occurrence of perfluorinated compounds (PFCs) in human blood is known to be widespread; nevertheless, the sources of exposure to humans, including infants, are not well understood. In this study, breast milk collected from seven countries in Asia was analyzed (n=184) for nine PFCs, including perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA). In addition, five brands of infant formula (n=21) and 11 brands of dairy milk (n=12) collected from retail stores in the United States were analyzed, for comparison with PFC concentrations previously reported for breast milk from the U.S. PFOS was the predominant PFC detected in almost all Asian breast milk samples, followed by perfluorohexanesulfonate (PFHxS) and PFOA. Median concentrations of PFOS in breast milk from Asian countries varied significantly;the lowest concentration of 39.4 pg/mL was found in India, and the highest concentration of 196 pg/mL was found in Japan. The measured concentrations were similarto or less than the concentrations previously reported from Sweden, the United States, and Germany (median, 106-166 pg/mL). PFHxS was found in more than 70% of the samples analyzed from Japan, Malaysia, Philippines, and Vietnam, at mean concentrations ranging from 6.45 (Malaysia) to 15.8 (Philippines) pg/mL PFOA was found frequently only in samples from Japan; the mean concentration for that country was 77.7 pg/mL. None of the PFCs were detected in the infant-formula or dairy-milk samples from the U.S. except a few samples that contained concentrations close to the limit of detection. The estimated average daily intake of PFOS by infants from seven Asian countries, via breastfeeding, was 11.8 +/- 10.6 ng/kg bw/ day; this value is 7-12 times higher than the estimated adult dietary intakes previously reported from Germany, Canada, and Spain. The average daily intake of PFOA by Japanese infants was 9.6 +/- 4.9 ng/kg bw/day, a value 3-10 times greater than the estimated adult dietary intakes reported from Germany and Canada. The highest estimated daily intakes of PFOS and PFOA by infants from seven Asian countries studied were 1-2 orders of magnitude below the tolerable daily intake values recommended by the U.K. Food Standards Agency.
Statistical analysis of heavy metal concentrations in sediment was studied to understand the interrelationship between different parameters and also to identify probable source component in order to explain the pollution status of selected estuaries. Concentrations of heavy metals (Cu, Zn, Cd, Fe, Pb, Cr, Hg and Mn) were analyzed in sediments from Juru and Jejawi Estuaries in Malaysia with ten sampling points of each estuary. The results of multivariate statistical techniques showed that the two regions have different characteristics in terms of heavy metals selected and indicates that each region receives pollution from different sources. The results also showed that Fe, Mn, Cd, Hg, and Cu are responsible for large spatial variations explaining 51.15% of the total variance, whilst Zn and Pb explain only 18.93 of the total variance. This study illustrates the usefulness of multivariate statistical techniques for evaluation and interpretation of large complex data sets to get better information about the heavy metal concentrations and design of monitoring network.
Incineration of industrial waste produces large quantities of bottom ash which are normally sent to secured landfill, but is not a sustainable solution. Use of bottom ash in engineering applications will contribute to sustainability and generate revenue. One way of using the industrial waste incineration bottom ash is in controlled low-strength material (CLSM). Use of bottom ash in CLSM has problems related to bleeding and excessive strength development and so an additive has to be used to control bleeding and strength development. The main objective of this research is to study the effect of kaolin addition on the performance of CLSM made using industrial waste incineration bottom ash. CLSM mixes were made with bottom ash, cement, and refined kaolin. Various tests were performed on the CLSM in fresh and hardened states including compressive strength, water absorption, California bearing ratio (CBR) and the tests for concentration of leachable substances on the bleed and leachate. The compressive strength of CLSM tested ranged from 0.11 to 9.86 MPa. CBR values ranged from 6 to 46, and water absorption values from 12 to 36%. It was shown that the addition of kaolin delayed the initial setting time of CLSM mixtures, reduced bleeding, lowered the compressive strength, and increased the values of water absorption, sorption, and initial surface absorption. The CLSM tested did not have corrosivity. It was shown that the hardened CLSM was non hazardous, and the addition of kaolin increased the concentration of heavy metals and salts in the bleed and leachate.
In this study, a rapid, specific and sensitive multi-residue method based on acetonitrile extraction followed by dispersive solid-phase extraction (d-SPE) clean-up was implemented and validated for multi-class pesticide residues determination in palm oil for the first time. Liquid-liquid extraction followed by low-temperature precipitation procedure was evaluated in order to study the freezing-out clean-up efficiency to obtain high recovery yield and low co-extract fat residue in the final extract. For clean-up step, d-SPE was carried out using a combination of anhydrous magnesium sulphate (MgSO(4)), primary secondary amine, octadecyl (C(18)) and graphitized carbon black. Recovery study was performed at two concentration levels (10 and 100 ng g(-1)), yielding recovery rates between 74.52% and 97.1% with relative standard deviation values below 10% (n = 6) except diuron. Detection and quantification limits were lower than 5 and 9 ng g(-1), respectively. In addition, soft matrix effects (≤±20%) were observed for most of the studied pesticides except malathion that indicated medium (20-50%) matrix effects. The proposed method was successfully applied to the analysis of suspected palm oil samples.
Worldwide prohibitions on lead gasoline additives were a major international public health accomplishment, the results of which are still being documented in parts of the world. Although the need to remove lead from paints has been recognized for over a century, evidence reported in this article indicates that lead-based paints for household use, some containing more than 10% lead, are readily available for purchase in some of the largest countries in the world. Sixty-six percent of new paint samples from China, India, and Malaysia were found to contain 5000 ppm (0.5%) or more of lead, the US definition of lead-based paint in existing housing, and 78% contained 600 ppm (0.06%) or more, the limit for new paints. In contrast, the comparable levels in a nearby developed country, Singapore, were 0% and 9%. In examining lead levels in paints of the same brands purchased in different countries, it was found that some brands had lead-based paints in one of the countries and paints meeting US limits in another; another had lead-free paint available in all countries where samples were obtained. Lead-based paints have already poisoned millions of children and likely will cause similar damage in the future as paint use increases as countries in Asia and elsewhere continue their rapid development. The ready availability of lead-based paints documented in this article provides stark evidence of the urgent need for efforts to accomplish an effective worldwide ban on the use of lead in paint.
In this work the development of an inhibitive assay for copper using the molybdenum-reducing enzyme assay is presented. The enzyme is assayed using 12-molybdophosphoric acid at pH 5.0 as an electron acceptor substrate and NADH as the electron donor substrate. The enzyme converts the yellowish solution into a deep blue solution. The assay is based on the ability of copper to inhibit the molybdenum-reducing enzyme from the molybdate-reducing Serratia sp. Strain DRY5. Other heavy metals tested did not inhibit the enzyme at 10 mg l(-1). The best model with high regression coefficient to measure copper inhibition is one-phase binding. The calculated IC50 (concentration causing 50% inhibition) is 0.099 mg l(-1) and the regression coefficient is 0.98. The comparative LC50, EC50 and IC50 data for copper in different toxicity tests show that the IC50 value for copper in this study is lower than those for immobilized urease, bromelain, Rainbow trout, R. meliloti, Baker's Yeast dehydrogenase activity Spirillum volutans, P. fluorescens, Aeromonas hydrophilia and synthetic activated sludge assays. However the IC50 value is higher than those for Ulva pertusa and papain assays, but within the reported range for Daphnia magna and Microtox assays.
The accumulative partitioning of Pb and Cu in the Rhizophora apiculata was studied randomly in the Setiu mangrove forest, Terengganu. Samples of leaves, barks and roots were collected randomly from the selected studied species. Sediments between the roots of the sampled mangrove plants were also collected. The results from analysis for Rhizophora apiculata shows that the concentration of Pb and Cu were accumulated higher in root tissue compared to bark and leaf tissue but lower than surrounding sediment level. The average concentration of Cu for Rhizophora apiculata in leaf, bark, root and sediment was 2.73, 3.94, 5.21 and 9.42 mg I(-1), respectively. Meanwhile, the average concentration of Pb in leaf, bark, root and sediment was 1.43, 1.38, 2.05 and 11.66 mg l(-1), respectively. Results of concentration factors (CF) show that the overall the concentration of Pb and Cu were accumulated much higher in roots system of Rhizophora apiculata.
Heavy metals pollution has become a great threat to the world. Since instrumental methods are expensive and need skilled technician, a simple and fast method is needed to determine the presence of heavy metals in the environment. In this study, an inhibitive enzyme assay for heavy metals has been developed using crude proteases from Coriandrum sativum. In this assay, casein was used as a substrate and Coomassie dye was used to denote the completion of casein hydrolysis. In the absence of inhibitors, casein was hydrolysed and the solution became brown, while in the presence of metal ions such as Hg²⁺ and Zn²⁺, the hydrolysis of casein was inhibited and the solution remained blue. Both Hg²⁺ and Zn²⁺ exhibited one-phase binding curve with IC₅₀ values of 3.217 mg/L and 0.727 mg/L, respectively. The limits of detection (LOD) and limits of quantitation (LOQ) for Hg were 0.241 and 0.802 mg/L, respectively, while the LOD and LOQ for Zn were 0.228 and 0.761 mg/L, respectively. The enzyme exhibited broad pH ranges for activity. The crude proteases extracted from Coriandrum sativum showed good potential for the development of a rapid, sensitive, and economic inhibitive assay for the biomonitoring of Hg²⁺ and Zn²⁺ in the aquatic environments.
This paper reports the corrosivity and leaching behavior of CLSM made using two different industrial wastes i.e. bottom ash from an incineration facility and quarry dust. The leachate samples were derived from fresh and hardened CLSM mixtures, and studied for leaching and electrical resistivity. The release of various contaminants and the consequent environmental impact caused by the contaminants were studied by the measurement of contaminants in the bleed, in the leachate at 28 days, and on the leachate derived from crushed block and whole block leaching done over a period of 126 days. Results indicated that the CLSM mixtures are non corrosive; diffusion was the leaching mechanism; and the contaminants were found to be moderate to low mobility.
Using manure collected from swine fed with diet containing antibiotics and antibiotic-free swine manure spiked with antibiotics are the two common methods of studying the degradation behavior of veterinary antibiotic in manure in the environment. However, few studies had been conducted to co-compare these two different antibiotic addition methods. This study used oxytetracycline (OTC) as a model antibiotic to study antibiotic degradation behavior in manure under the above two OTC addition methods. In addition, the role of microorganisms present in the manure on degradation behavior was also examined. The results showed that degradation half-life of OTC in manure from swine fed OTC (9.04 days) was significantly shorter than that of the manure directly treated with OTC (9.65 days). Concentration of 4-epi-OTC in manure from swine fed OTC peaked earlier than that in manure spiked with OTC, and the degradation rates of 4-epi-OTC and α-apo-OTC in the manure from swine fed OTC were faster, but the peak concentrations were lower, than those in manure spiked with OTC. Bacterial diversity and relative abundance of Bacillus cereus data demonstrated that sterilization of the manure before experiment significantly decreased OTC degradation rate in both of the addition methods. Results of the present study demonstrated that the presence of the metabolites (especially 4-epi-OTC) and microorganisms had significant influence on OTC degradation.
Heavy metal pollution has become a global concern due to accumulation in tissue and transferable effects to humans via the food chain. This study focused on monitoring the accumulation of cadmium (Cd) and lead (Pb) in surface soil and body content: bone, heart, brain, liver, lung, muscle, kidney, feathers, feces, and gizzard contents of house crow Corvus splendens in the Klang region, Malaysia. The results revealed the occurrence of Pb and Cd in all biological samples from house crows, food contents, and surface soil samples. Heart and kidney accrued high amounts of Cd, while high amounts of Pb were found to accumulate in bones and feathers. Major discrepancies were also discovered in the concentrations of metals between juvenile and adults, as well as female and male bird samples. Concentrations of Pb and Cd in house crow internal tissues correlated significantly with that of bird feathers, but none could be established with that of surface soil. In addition, a significant correlation was observed between Pb concentration in the internal tissues to that of the feces, but the same was not the case when compared with the surface soil concentration. Metal accrual in the house crows feathers and feces may be through a long-term transmission via the food chain, which are eliminated from feathers via molting. This may suggest the utility of molted breast feathers of house crow in the bio-monitoring of Cd and Pb contamination, whereas feces of house crow appear only to be suitable for the bio-monitoring of Pb contamination.
Human health is threatened by significant emissions of heavy metals into the urban environment due to various activities. Various studies describing health risk analyses on soil and dust have been conducted previously. However, there are limited studies that have been carried out regarding the potential health risk assessment of heavy metals in urban road dust of < 63-μm diameter, via incidental ingestion, dermal contact, and inhalation exposure routes by children and adults in developing countries. Therefore, this study evaluated the health risks of heavy metal exposure via ingestion, dermal contact, and inhalation of urban dust particles in Petaling Jaya, Malaysia. Heavy metals such as lead (Pb), chromium (Cr), zinc (Zn), copper (Cu), and manganese (Mn) were measured using dust samples obtained from industrial, high-traffic, commercial, and residential areas by using inductively coupled plasma mass spectrometry (ICP-MS). The principal component and hierarchical cluster analysis showed the dominance of these metal concentrations at sites associated with anthropogenic activities. This was suggestive of industrial, traffic emissions, atmospheric depositions, and wind as the significant contributors towards urban dust contamination in the study sites. Further exploratory analysis underlined Cr, Pb, Cu, and Zn as the most representative metals in the dust samples. In accommodating the uncertainties associated with health risk calculations and simulating the reasonable maximum exposure of these metals, the related health risks were estimated at the 75th and 95th percentiles. Furthermore, assessing the exposure to carcinogenic and non-carcinogenic metals in the dust revealed that ingestion was the primary route of consumption. Children who ingested dust particles in Petaling Jaya could be more vulnerable to carcinogenic and non-carcinogenic risks, but the exposure for both children and adults showed no potential health effects. Therefore, this study serves as an important premise for a review and reformation of the existing environmental quality standards for human health safety.
Assessment of eco-toxicant using bioluminescent bacterial assay is a widely used and globally accepted method. In this work, a new luminescent bacterium was isolated from squid (Loligo duvauceli) and identified as Photobacterium leiognathi strain AK-MIE using 16S rRNA, phylogeny analysis. The predicted optimum conditions by RSM were 2.76% (w/v) NaCl, 2.28% (w/v) peptone, 0.34% (w/v) yeast extract, and pH 6.83 with 541,211.80 RLU of luminescent production whereas the predicted optimum conditions by ANN were 2.21% (w/v) NaCl, 2.27% (w/v) peptone, 0.39% (w/v) yeast extract, and pH 6.94 which produced 541,986.20 RLU. The validation analysis of both RSM and ANN show 0.60% and 0.69% deviation from the predicted results indicating that both models provided good quality predictions with ANN showing a superior data fitting capability for non-linear regression analysis. Toxicity tests show strain AK-MIE was sensitive to mercury (concentration causing 50% inhibition or IC50 of 0.00978 mgL-1), followed by cadmium (IC50 of 0.5288 mgL-1), copper IC50 of (0.8117 mgL-1), silver (IC50 of 1.109 mgL-1), and lead (IC50 of 10.71 mgL-1) which are more sensitive than previously isolated luminescent bacteria, suggesting that strain AK-MIE has the potential to be used in toxicity assessment of heavy metals in the environment. Based on the field trial results, several sediment samples from industrial areas in Bangi, Selangor managed to inhibit the bioluminescence of strain AK-MIE. Validation method carried out using ICP-MS proved the presence of several toxic heavy metal elements.
Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are widely used in products, and are known for their water and grease repellent properties. The persistence nature and potential toxicity of these substances have raised substantial concerns about health effects. Regarding humans, food consumption has reportedly been a significant source of exposure for both compounds. Hence, this study was performed to develop and validate an analytical method for PFOS and PFOA in egg yolks using liquid chromatographic tandem mass spectrometry (LC-MS/MS) followed by the determination of concentration of both compounds in the yolk of poultry eggs in Malaysia. A total of 47 poultry egg yolk samples were extracted by a simple protein precipitation technique using acetonitrile. The analytical method was developed using LC-MS/MS and validated based on the Food and Drug Administration (FDA)'s Bioanalytical Method Validation guidelines. The results revealed that PFOS was quantitatively detected in six samples, with the concentration range between 0.5 and 1.01 ng g-1. Among these, five samples were from home-produced chicken eggs, and one sample was from a quail egg. The levels of PFOA in all samples were below the quantifiable limit (<0.1 ng g-1). This indicated that the contamination of PFCs in poultry eggs were mostly attributed to the nature of free foraging animals, which had direct contact with the contaminants in soil and feed. In conclusion, a fast and robust analytical method for analyzing PFOS and PFOA in egg yolk samples using LC-MS/MS was successfully developed and validated. The presence of these emerging contaminants in this study signified widespread pollution in the environment.
Contamination of persistent organochlorines (OCs) such as PCBs (polychlorinated biphenyls), DDT and its metabolites (DDTs), HCH (hexachlorocyclohexane) isomers (HCHs), chlordane compounds (CHLs), and HCB (hexachlorobenzene) were examined in mussels collected from coastal waters of Asian countries such as Cambodia, China, Hong Kong, India, Indonesia, Japan, Korea, Malaysia, Philippines, Far East Russia, Singapore, and Vietnam in 1994, 1997, 1998, 1999, and 2001 to elucidate the contamination status, distribution and possible pollution sources and to assess the risks on aquatic organisms and human. OCs were detected in all mussels collected from all the sampling sites investigated. Considerable residue levels of p,p(')-DDT and alpha-HCH were found in mussels and the concentrations of DDTs and HCHs found in mussels from Asian developing countries were higher than those in developed nations suggesting present usage of DDTs and HCHs along the coastal waters of Asian developing countries. On the other hand, lower concentrations of PCBs detected in mussels from Asian developing countries than those in developed countries indicate that PCBs contamination in mussels is strongly related to industrial and activities. To our knowledge, this is a first comprehensive report on monitoring OCs pollution in the Asia-Pacific region.
Phthalate esters are used in a wide variety of consumer products, and human exposure to this class of compounds is widespread. Nevertheless, studies on dietary exposure of human to phthalates are limited. In this study, to assess the daily intakes of phthalate esters and the possible adverse health impacts, different food samples were collected from three areas of Cambodia, one of the poorest countries in the world. The ∑phthalate ester concentrations in Kampong Cham, Kratie and Kandal provinces ranged from 0.05 to 2.34 (median 0.88) μgg(-1), 0.19-1.65 (median 0.86) μgg(-1) and 0.24-3.05 (median 0.59) μgg(-1) wet weight (ww), respectively. Di-2-Ethylhexyl phthalate (DEHP) and diisobutyl phthalate (DiBP) were the predominant compounds among all foodstuffs. The estimated daily intake (EDI) of phthalate esters for the general population in Kampong Cham, Kratie and Kandal was 34.3, 35.6 and 35.8μgkg(-1) bw d(-1), respectively. The dietary daily intake of DEHP, benzylbutyl phthalate (BBP) and di-n-butyl phthalate (DBP) in Kampong Cham, Kratie and Kandal were below the tolerable daily intakes (TDI) imposed by the European Food Safety Authority (EFSA) and reference doses (RfD) imposed by The United States Environmental Protection Agency (USEPA). Rice contributed the greatest quantity of DEHP to the daily intake in Cambodia so may deserve further exploration. To our knowledge, this is the first study to investigate the occurrence and the daily intakes of phthalate esters in Cambodia.
With rapid urbanization and large-scale industrial activities, modern human populations are being increasingly subjected to chronic environmental heavy metal exposures. Elemental uptake in tooth dentine is a bioindicator, the uptake occurring during the formation and mineralization processes, stored to large extent over periods of many years. The uptake includes essential elements, most typically geogenic dietary sources, as well as non-essential elements arising through environmental insults. In this study, with the help of the Dental Faculty of the University of Malaya, a total of 50 separate human teeth were collected from dental patients of various ethnicity, age, gender, occupation, dietary habit, residency, etc. Analysis was conducted using inductively coupled plasma-mass spectrometry (ICP-MS), most samples indicating the presence of the following trace elements, placed in order of concentration, from least to greatest: As, Mn, Ba, Cu, Cr, Pb, Zn, Hg, Sb, Al, Sr, Sn. The concentrations have been observed to increase with age. Among the ethnic groups, the teeth of ethnic Chinese showed marginally greater metal concentrations than those of the Indians and Malays, the teeth dentine of females generally showing greater concentrations than that of males. Greater concentrations of Hg, Cu and Sn were found in molars while Pb, Sr, Sb and Zn were present in greater concentrations in incisors. With the elevated concentration levels of heavy metals in tooth dentine reflecting pollution from industrial emissions and urbanization, it is evident that human tooth dentine can provide chronological information on exposure, representing a reliable bio-indicator of environmental pollution.
This study reports the concentrations and congener partners of polychlorinated biphenyls (PCBs) in commercially available paints. Polycyclic-type pigments containing dioxazine violet (pigment violet (PV) 23, PV37) and diketopyrrolopyrrole (PR254, PR255) were found to contain PCB-56, PCB-77, PCB-40, PCB-5, and PCB-12, and PCB-6, PCB-13, and PCB-15, respectively, as major congeners. Dioxazine violet is contaminated with by-products during synthesis from o-dichlorobenzene, which is used as a solvent during synthesis, and diketopyrrolopyrrole is contaminated with by-products during synthesis from p-chlorobenzonitrile. The concentration of PCBs in paint containing PV23 or PV37 was 0.050-29 mg/kg, and toxic equivalency (TEQ) values ranged 1.1-160 pg-TEQ/g. The concentration of PCBs in paint containing PR254 or PR255 was 0.0019-2.4 mg/kg. Naphthol AS is an azo-type pigment, and PCB-52 was detected in paint containing pigment red (PR) 9 with 2,5-dichloroaniline as its source. PCB-146, PCB-149, and PCB-153 were identified from paint containing PR112 produced from 2,4,5-trichloroaniline, as major congeners. These congeners have chlorine positions similar to aniline, indicating that these congeners are by-products obtained during the synthesis of pigments. The concentrations of PCBs in paints containing PR9 and PR112 were 0.0042-0.43 and 0.0044-3.8 mg/kg, respectively. The corresponding TEQ for PR112 was 0.0039-8.6 pg-TEQ/g.
17α-ethynylestradiol (EE2) is a synthetic hormone, which is a derivative of the natural hormone, estradiol (E2). EE2 is an orally bio-active estrogen, and is one of the most commonly used medications for humans as well as livestock and aquaculture activity. EE2 has become a widespread problem in the environment due to its high resistance to the process of degradation and its tendency to (i) absorb organic matter, (ii) accumulate in sediment and (iii) concentrate in biota. Numerous studies have reported the ability of EE2 to alter sex determination, delay sexual maturity, and decrease the secondary sexual characteristics of exposed organisms even at a low concentration (ng/L) by mimicking its natural analogue, 17β-estradiol (E2). Thus, the aim of this review is to provide an overview of the science regarding EE2, the concentration levels in the environment (water, sediment and biota) and summarize the effects of this compound on exposed biota at various concentrations, stage life, sex, and species. The challenges in respect of EE2 include the extension of the limited database on the EE2 pollution profile in the environment, its fate and transport mechanism, as well as the exposure level of EE2 for better prediction and definition revision of EE2 toxicity end points, notably for the purpose of environmental risk assessment.
A variety of trace metals were measured in the egg contents of three clutches of Chelonia mydas collected from Kuala Terengganu state in Peninsular Malaysia. We quantified Mn, Cu, Zn, Se (essential trace metals) and As (anthropogenic pollutant) at several developmental stages obtained by incubating eggs at two different temperatures (27 °C and 31 °C). The incubation temperatures were chosen because they produce predominantly male or predominantly female hatchlings, respectively. The eggs were removed from the sand and washed before being placed in incubators, to ensure that the only possible source of the detected metals was maternal transfer. Other metals: Mo, Co, Ni, Cd, Sn, Sb, Hg, Tl and Pb (all non-essential metals) were detected at concentrations below the lower limit of quantitation (LLOQ). Trace metal concentrations, particularly [Zn], increased during development, other metals (Cu, As, Se and Cr) accumulated to a lesser degree than zinc but no significant differences were observed between the incubation temperatures at any stage of incubation. To date, only a few studies on trace metals in turtle embryos and hatchlings have been reported; this study will provide basic knowledge on the accumulation of trace metals during development at two different incubation temperatures.