Estuary sediments are one of the important components of coastal ecosystems and have been regarded as a sink for various types of organic pollutants. Organic pollutants such as endocrine disrupting compounds (EDCs) which have been associated with various environmental and human health effects were detected in the estuary sediment at trace level. Considering various interferences that may exist in the estuarine sediment, a sensitive and selective method, capable of detecting multiclass EDC pollutants at the trace levels, needs to be developed and optimized to be applied for environmental analysis. A combination of Soxhlet extraction followed by offline solid phase extraction (SPE) cleaned up with detection based on LC triple quadrupole MS was optimized and validated in this study. The targeted compounds consisted of ten multiclass EDCs, namely, diclofenac, primidone, bisphenol A, estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), 4-octylphenol (4-OP), 4-nonylphenol (4-NP), progesterone, and testosterone. The method showed high extraction efficiency with percentage of recovery from 78% to 108% and excellent sensitivity with detection limit between 0.02ngg-1 and 0.81ngg-1. Excellent linearity from 0.991 to 0.999 was achieved for the developed compounds and the relative standard deviation was less than 18%, an indication of good precision analysis. Evaluation of the matrix effects showed ionization suppression for all the developed compounds. Verification of the method was carried out by analyzing the estuarine sediment collected from Langat River. The analyzed estuarine sediments showed a trace concentration of diclofenac, bisphenol A, progesterone, testosterone, primidone, and E1. However, E2, EE2, 4-OP, and 4-NP were below the method's detection limit. Diclofenac exhibited the highest concentration at 2.67ngg-1 followed by bisphenol A (1.78ngg-1) while E1 showed the lowest concentration at 0.07ngg-1.
The concentration profile, distribution and risk assessment of pharmaceutically active compounds (PhACs) in the coastal surface water from the Klang River estuary were measured. Surface coastal water samples were extracted using offline solid phase, applying polymeric C18 cartridges as extraction sorbent and measuring with liquid chromatography mass spectrometry-mass spectrometry (LC MS-MS) technique. Extraction method was optimized for its recovery, sensitivity and linearity. Excellent recoveries were obtained from the optimized method with percentage of recoveries ranging from 73 to 126%. The optimized analytical method achieved good sensitivity with limit of detection ranging from 0.05 to 0.15 ng L-1, while linearity of targeted compounds in the LC MS-MS system was more than 0.990. The results showed that amoxicillin has the highest concentration (102.31 ng L-1) followed by diclofenac (10.80 ng L-1) and primidone (7.74 ng L-1). The percentage of contribution (% of total concentration) for the targeted PhACs is in the following order; amoxicillin (92.90%) > diclofenac (3.95%) > primidone (1.23%) > dexamethasone (0.75%) > testosterone (0.70%) > sulfamethoxazole (0.33%) > progesterone (0.14%). Environmental risk assessment calculated based on deterministic approach (the RQ method), showed no present risk from the presence of PhACs in the coastal water of Klang River estuary. Nonetheless, this baseline assessment can be used for better understanding on PhACs pollution profile and distribution in the tropical coastal and estuarine ecosystem as well as for future comparative studies.
In this study, the distributions and sources of sediment-associated polycyclic aromatic hydrocarbons (PAHs) and hopanes in the Malaysian rivers and estuaries were evaluated. The concentrations of 16 USEPA PAHs varied from 225.5 to 293.9 (Perlis River), 195.2 to 481.2 (Kedah River), 791.2 to 1995.4 (Merbok River), 231.2 to 426.7 (Perak River), and 3803.2 to 7442.7 ng g(-1) (Klang River) dry weight. PAHs can be classified as moderate in the Perlis, Kedah, and Perak Rivers, moderate to high in the Merbok River, and high to very high in the Klang River. The comparison of PAHs with sediment quality guidelines (SQGs) indicates that occasionally adverse biological effects may occur from total PAHs, low molecular weight (LMW), and high molecular weight (HMW) PAHs at stations 1, 2, and 3 of the Klang River and from total PAHs at station 2 of the Merbok River. The diagnostic ratios of individual PAHs indicate both petrogenic and pyrogenic origin PAHs with significant dominance of pyrogenic sources in the study areas. The results suggest that Malaysian sediments had hopane ratios (C29/C30) similar to MECO suggesting MECO as a major source of the petroleum hydrocarbons found in the sediments, which is consistent with results reported in previous studies. These findings demonstrate that effective and improved environmental regulations in Malaysia have shifted the source of petroleum hydrocarbons from petrogenic to pyrogenic origin.
Sediment samples were analyzed for di-(2-ethylhexyl) phthalate (DEHP), an organic endocrine disruptor, in Houjing River in southern Taiwan. The average DEHP concentration at 10 sampling locations, spanning from upper, middle, and lower segments of the stream, was calculated at 3.81+/-6.36mgkg(-1)drywt. Highest concentration was recorded at the Jhongsing Bridge (20.22mgkg(-1)drywt.) near the Dashe Industrial Park, followed by the Renwu Bridge (8.93mgkg(-1)drywt.) near the Renwu Industrial Park. The surface sediment concentration of DEHP was found to be higher in the dry season (October and December), and lower in the wet (flood) season (August), indicating that sources of DEHP remained active and continued to recharge the Houjing River. Vertical sediment core analysis revealed that highest concentration occurred at the depth of 40-60cm, indicating that historical discharges of DEPH may have been higher than recent years. Domestic comparison of DEHP concentrations in sediment from highest to lowest could be categorized as northern, southern, central, and eastern Taiwan, respectively, and seemed to be positively correlated with population density and/or industrial activity. Compared to other countries, DEHP concentration of the Houjing River was relatively higher than rivers studied in Japan, Germany, Italy, and Malaysia, and was relatively lower than the Aire and Trent Rivers in the United Kingdom.
A novel microextraction technique termed solid phase membrane tip extraction (SPMTE) was developed. Selected triazine herbicides were employed as model compounds to evaluate the extraction performance and multiwall carbon nanotubes (MWCNTs) were used as the adsorbent enclosed in SPMTE device. The SPMTE procedure was performed in semi-automated dynamic mode and several important extraction parameters were comprehensively optimized. Under the optimum extraction conditions, the method showed good linearity in the range of 1-100 microg/L, acceptable reproducibility (RSD 6-8%, n=5), low limits of detection (0.2-0.5 microg/L), and satisfactory relative recoveries (95-101%). The SPMTE device could be regenerated and reused up to 15 analyses with no analyte carry-over effects observed. Comparison was made with commercially available solid phase extraction-molecular imprinted polymer cartridge (SPE-MIP) for triazine herbicides as the reference method. The new developed method showed comparable or even better results against reference method and is a simple, feasible, and cost effective microextraction technique.
Dissolved organic matter (DOM) was characterised in water samples sampled in the Lower Kinabatangan River Catchment, Sabah, Malaysia between October 2009 and May 2010. This study aims at: (i) distinguishing between the quality of DOM in waters draining palm oil plantations (OP), secondary forests (SF) and coastal swamps (CS) and, (ii) identifying the seasonal variability of DOM quantity and quality. Surface waters were sampled during fieldwork campaigns that spanned the wet and dry seasons. DOM was characterised optically by using the fluorescence Excitation Emission Matrix (EEM), the absorption coefficient at 340 nm and the spectral slope coefficient (S). Parallel Factor Analysis (PARAFAC) was undertaken to assess the DOM composition from EEM spectra and five terrestrial derived components were identified: (C1, C2, C3, C4 and C5). Components C1 and C4 contributed the most to DOM fluorescence in all study areas during both the wet and dry seasons. The results suggest that component C4 could be a significant (and common) PARAFAC signal found in similar catchments. Peak M (C2 and C3) was dominant in all samples collected during wet and dry seasons, which could be anthropogenic in origin given the active land use change in the study area. In conclusion, there were significant seasonal and spatial variations in DOM which demonstrated the effects of land use cover and precipitation amounts in the Kinabatangan catchment.
Ever increasing demand for water resources for different purposes makes it essential to have better understanding and knowledge about water resources. As known, groundwater resources are one of the main water resources especially in countries with arid climatic condition. Thus, this study seeks to provide groundwater potential maps (GPMs) employing new algorithms. Accordingly, this study aims to validate the performance of C5.0, random forest (RF), and multivariate adaptive regression splines (MARS) algorithms for generating GPMs in the eastern part of Mashhad Plain, Iran. For this purpose, a dataset was produced consisting of spring locations as indicator and groundwater-conditioning factors (GCFs) as input. In this research, 13 GCFs were selected including altitude, slope aspect, slope angle, plan curvature, profile curvature, topographic wetness index (TWI), slope length, distance from rivers and faults, rivers and faults density, land use, and lithology. The mentioned dataset was divided into two classes of training and validation with 70 and 30% of the springs, respectively. Then, C5.0, RF, and MARS algorithms were employed using R statistical software, and the final values were transformed into GPMs. Finally, two evaluation criteria including Kappa and area under receiver operating characteristics curve (AUC-ROC) were calculated. According to the findings of this research, MARS had the best performance with AUC-ROC of 84.2%, followed by RF and C5.0 algorithms with AUC-ROC values of 79.7 and 77.3%, respectively. The results indicated that AUC-ROC values for the employed models are more than 70% which shows their acceptable performance. As a conclusion, the produced methodology could be used in other geographical areas. GPMs could be used by water resource managers and related organizations to accelerate and facilitate water resource exploitation.
Contamination by endocrine disrupting compounds (EDCs) concerns the security and sustainability of a drinking water supply system and human exposure via water consumption. This study analyzed the selected EDCs in source (river water, n = 10) and supply (tap water, n = 155) points and the associated risks. A total of 14 multiclass EDCs was detected in the drinking water supply system in Malaysia. Triclosan (an antimicrobial agent) and 4-octylphenol (a plasticizer) were only detected in the tap water (up to 9.74 and 0.44 ng/L, respectively). Meanwhile, chloramphenicol and 4-nonylphenol in the system were below the method detection limits. Bisphenol A was observed to be highest in tap water at 66.40 ng/L (detection: 100%; median concentration: 0.28 ng/L). There was a significant difference in triclosan contamination between the river and tap water (p
The aim of the present study was to appraise the levels of heavy metal contamination (Zn and Pb) in sediment of the Langat River (Selangor, Malaysia). Samples were collected randomly from 15 sampling stations located along the Langat River. The parameters measured were pH, redox potential, salinity, electrical conductivity, loss of ignition, cation exchanges capacity (Na, Mg, Ca, K), and metal ions (Zn and Pb). The geo-accumulation index (I geo) and contamination factor (C f) were applied to determine and classify the magnitude of heavy metal pollution in this urban river sediment. Results revealed that the I geo of Pb indicated unpolluted to moderately polluted sediment at most of the sampling stations, whereas Zn was considered to be within background concentration. The I geo results were refined by the C f values, which showed Pb with very high C f at 12 stations. Zinc, on the other hand, had low to moderate C f values. These findings indicated that the sediment of the Langat River is severely polluted with Pb. The Zn concentration at most sampling points was well below most sediment quality guidelines. However, 40% of the sampling points were found to have a Pb concentration higher than the consensus-based probable effect concentration of 128 mg/kg (concentrations above this value are likely to cause harmful effects). This result not only highlights the severity of Pb pollution in the sediment of the Langat River, but also the potential risk it poses to the environment.
The concentrations were ranged from 1.35 ± 0.16 to 2.22 ± 0.34 µg/g (dry weight) and 2.65 ± 0.34 to 4.36 ± 0.53 µg/g (dry weight) for Cd and Pb, respectively, in blood cockle Anadara granosa from four sites of Sabang River, namely, Kampung Sambir, Kampung Tambirat, Beliong Temple, and Kampung Tanjung Apong, which are located at Asajaya, Sarawak, Malaysia. All values exceeded safety limits set by Malaysian Food Regulation (1985). It may be the cause of serious human health problems after long term consumption. Thus, consumer should have consciousness about such type of seafood from mentioned sites and need further investigation.
This study was conducted to assess the levels of toxic metals like arsenic (As), chromium (Cr), cadmium (Cd), and lead (Pb) in water and sediments of the Pasur River in Bangladesh. The ranges of Cr, As, Cd, Pb in water were 25.76-77.39, 2.76-16.73, 0.42-2.98 and 12.69-42.67 μg/L and in sediments were 20.67-83.70, 3.15-19.97, 0.39-3.17 and 7.34-55.32 mg/kg. The level of studied metals in water samples exceeded the safe limits of drinking water, indicating that water from this river is not safe for drinking and cooking. Certain indices, including pollution load index (PLI) and contamination factor (Cif) were used to assess the ecological risk. The PLI indicated progressive deterioration of sediments by the studied metals. Potential ecological risks of metals in sediment indicated low to considerable risk. However, the Cif values of Cd ranged from 0.86 to 8.37 revealed that the examined sediments were strongly impacted by Cd. Considering the severity of potential ecological risk (PER) for single metal (Eir), the descending order of contaminants was Cd > Pb > As > Cr. According the results, some treatment scheme must formulate and implement by the researchers and related management organizations to save the Pasur River from metals contamination.
This article describes design and application of feed-forward, fully-connected, three-layer perceptron neural network model for computing the water quality index (WQI)(1) for Kinta River (Malaysia). The modeling efforts showed that the optimal network architecture was 23-34-1 and that the best WQI predictions were associated with the quick propagation (QP) training algorithm; a learning rate of 0.06; and a QP coefficient of 1.75. The WQI predictions of this model had significant, positive, very high correlation (r=0.977, p<0.01) with the measured WQI values, implying that the model predictions explain around 95.4% of the variation in the measured WQI values. The approach presented in this article offers useful and powerful alternative to WQI computation and prediction, especially in the case of WQI calculation methods which involve lengthy computations and use of various sub-index formulae for each value, or range of values, of the constituent water quality variables.
Seven sulfonamides, trimethoprim, five macrolides, lincomycin and three tetracyclines were measured in 150 water samples of sewage, livestock and aquaculture wastewater, and river and coastal waters, in five tropical Asian countries. The sum of the concentrations of the target antibiotics in sewage and heavily sewage-impacted waters were at sub- to low-ppb levels. The most abundant antibiotic was sulfamethoxazole (SMX), followed by lincomycin and sulfathiazole. The average concentration of SMX in sewage or heavily sewage-impacted waters was 1720 ng/L in Vietnam (Hanoi, Ho Chi Minh, Can Tho; n=15), 802ng/L in the Philippines (Manila; n=4), 538 ng/L in India (Kolkata; n=4), 282 ng/L in Indonesia (Jakarta; n=10), and 76 ng/L in Malaysia (Kuala Lumpur; n=6). These concentrations were higher than those in Japan, China, Europe, the US and Canada. A predominance of sulfonamides, especially SMX, is notable in these tropical countries. The higher average concentrations, and the predominance of SMX, can be ascribed to the lower cost of the antibiotics. Both the concentration and composition of antibiotics in livestock and aquaculture wastewater varied widely. In many cases, sulfamethazine (SMT), oxytetracycline (OTC), lincomycin, and SMX were predominant in livestock and aquaculture wastewater. Both human and animal antibiotics were widely distributed in the respective receiving waters (i.e., the Mekong River and Manila Bay). SMT/SMX ratios indicate a significant contribution from livestock wastewater to the Mekong River and nearby canals, with an estimated ~10% of river water SMX derived from such wastewater. Mass flow calculations estimate that 12 tons of SMX is discharged annually from the Mekong River into the South China Sea. Riverine inputs of antibiotics may significantly increase the concentration of such antibiotics in the coastal waters.
The concentration, distribution, and risk assessment of parabens were determined in the surface water of the Terengganu River, Malaysia. Target chemicals were extracted via solid-phase extraction, followed by high-performance liquid chromatography analysis. Method optimization produced a high percentage recovery for methylparaben (MeP, 84.69 %), ethylparaben (EtP, 76.60 %), and propylparaben (PrP, 76.33 %). Results showed that higher concentrations were observed for MeP (3.60 μg/L) as compared with EtP (1.21 μg/L) and PrP (1.00 μg/L). Parabens are ubiquitously present in all sampling stations, with >99 % of detection. Salinity and conductivity were the major factors influencing the level of parabens in the surface water. Overall, we found no potential risk of parabens in the Terengganu River ecosystem due to low calculated risk assessment values (risk quotient
A comprehensive geochemical study was conducted in the Sibuti River estuary by considering water, suspended solids (SS), and sediment samples from 36 stations during southwest monsoon (SWM) and northeast monsoon (NEM). In this study, the distribution of in situ parameters, major ions, nutrients, trace metals, and isotopes (δD, δ18O) were analyzed in water samples, whereas sediments and SS were studied for trace metals. The distribution revealed that suspended solids were the major carrier of Cd, Zn, and Mn, whereas sediments worked as a major source of Co, Cr, Ba, Se, Cu, and Pb. Na-Cl water type and ion exchange dominated the lower part of the estuary during both seasons. However, the mixed mechanism of Ca-Cl, Ca-Mg-Cl, and higher weathering indicated reverse ion exchange in the intermediate and upper parts of the estuary. Isotopic signatures of δD and δ18O in estuarine water indicate that the precipitation over the Limbang area dominates during SWM, whereas higher evaporation was confirmed during NEM. The factor analysis revealed that seawater influence in the estuary majority controlled the water chemistry irrespective of seasons. Major ions were mainly regulated by the tidal influence during the low flow time of the river (SWM), whereas the mixing mechanism of weathering and seawater controlled the concentrations during NEM. Nutrients such as NO3, SO42-, NH3, and NH4+ mainly originated from the agricultural fields and nitrification along with ammonification were responsible for the recycling of such nutrients. Trace metals except Cd were found to be geogenic in nature and originating mainly from the oxidation of pyrites present in the sandstone and mudstones of the Sibuti Formation. Redox condition was catalyzed by microorganisms near the river mouth, whereas Al-oxyhydroxides and Fe-oxyhydroxides complexes in the intermediate and upper part under oxygenated conditions controlled the absorption of metals. Overall, the estuary was found to be absorptive in nature due to ideal pH conditions and was confirmed by the saturation index (SI) of minerals.
A novel sol-gel hybrid methyltrimethoxysilane-tetraethoxysilane (MTMOS-TEOS) was produced and applied as sorbent for solid phase extraction (SPE). Five selected organophosphorus pesticides (OPPs) were employed as model compounds to evaluate the extraction performance of the synthesized sol-gel organic-inorganic hybrid MTMOS-TEOS. Analysis was performed using gas chromatography-mass spectrometry. Several important SPE parameters were optimized. Under the optimum extraction conditions, the method using the sol-gel organic-inorganic hybrid MTMOS-TEOS as SPE sorbent showed good linearity in the range of 0.001-1 μg L(-1), good repeatability (RSD 2.1-3.1%, n=5), low limits of detection at S/N=3 (0.5-0.9 pg mL(-1)) and limit of quantification (1-3 pg mL(-1), S/N=10). The performance of the MTMOS-TEOS SPE was compared to commercial C18 Supelclean SPE since C18 SPE is widely used for OPPs. The MTMOS-TEOS SPE method LOD was 500-600 × lower than the LOD of commercial C18 SPE. The LOD achieved with the sol-gel organic-inorganic hybrid MTMOS-TEOS SPE sorbent allowed the detection of these OPPs in drinking water well below the level set by European Union (EU) at 0.1 μg L(-1) of each pesticides. The developed MTMOS-TEOS SPE method was successfully applied to real sample analysis of the selected OPPs from several water samples and its application extended to the analysis of several fruits samples. Excellent recoveries and RSDs of the OPPs were obtained from the various water samples (recoveries: 97-111%, RSDs 0.4-2.8%, n=3) and fruit samples (recoveries: 96-111%), RSDs 1-4%, n=5) using the sol-gel organic-inorganic hybrid MTMOS-TEOS SPE sorbent. Recoveries and RSDs of OPPs from river water samples and fruit samples using C18 Supelclean SPE sorbent were 91-97%, RSD 0.9-2.6, n=3 and 86-96%, RSD 3-8%, n=5, respectively). The novel sol-gel hybrid MTMOS-TEOS SPE sorbent demonstrate the potential as an alternative inexpensive extraction sorbent for OPPs with higher sensitivity for the OPPs.
A new approach based on the integration of the free liquid membrane (FLM) into electrokinetic supercharging (EKS) was demonstrated to be a new powerful tool used in order to enhance online preconcentration efficiency in capillary electrophoresis (CE). A small plug of water immiscible organic solvent was used as a membrane interface during the electrokinetic sample injection step in EKS in order to significantly enhance the analyte stacking efficiency. The new online preconcentration strategy was evaluated for the determination of paraquat and diquat present in the environmental water samples. The optimised FLM-EKS conditions employed were as follows: hydrodynamic injection (HI) of 20mM potassium chloride as leading electrolyte at 50mbar for 75s (3% of the total capillary volume) followed by the HI of tris(2-ethylhexyl) phosphate (TEHP) as FLM at a 1mm length (0.1% of the capillary volume). The sample was injected at 10kV for 360s, followed by the HI of 20mM cetyl trimethylammonium bromide (CTAB) as terminating electrolyte at 50mbar for 50s (2% of the total capillary volume). The separation was performed in 12mM ammonium acetate and 30mM NaCl containing 20% MeOH at +25kV with UV detection at 205nm. Under optimised conditions, the sensitivity was enhanced between 1500- and 1866-fold when compared with the typical HI at 50mbar for 50s. The detection limit of the method for paraquat and diquat was 0.15-0.20ng/mL, with RSDs below 5.5%. Relative recoveries in spiked river water were in the range of 95.4-97.5%. A comparison was also made between the proposed approach with sole preconcentration of the field-enhanced sample injection (FASI) and EKS in the absence of the FLM.
Influence of deforestation on biodiversity of aquatic organisms was investigated in a stream in the Ulu Sedili Forest Reserve. The stream was monitored five (5) times from December 2011 until December 2012 with 2-month intervals. Sampling of benthic communities was carried out using rectangular dip net while water quality study using a YSI ProPlus meter and the rest were done in the laboratory. Physicochemical parameters and water quality index (WQI) calculation showed no significant difference among the investigated events. WQI classified the Berasau River between Class II (good) to III (moderate) of river water quality. In total, 603 individuals representing 25 taxa that were recorded with Decapods from genus Macrobrabchium were widely distributed. Several intolerant taxa, especially Ephemeroptera and Odonata, were also observed in this river. According to Pearson's correlation analysis, the richness and diversity indices were generally influenced by water quality parameters represented by WQI (P
Since landfilling is the common method of waste disposal in Malaysia, river water is greatly exposed to the risk of contamination from leachate unless proper leachate management is carried out. In this study, leachates from three different types of landfills, namely active uncontrolled, active controlled and closed controlled, were characterized, and their relationships with river water chemistry were examined monthly for a year. The influence of leachate on river water chemistry from each type of landfill depended on many factors, including the presence of a leachate control mechanism, leachate characteristics, precipitation, surface runoff and the applied treatment. The impact of leachate from an active uncontrolled landfill was the highest, as the organic content, NH(4)(+)-N, Cd and Mn levels appeared high in the river. At the same time, influences of leachate were also observed from both types of controlled landfills in the form of inorganic nitrogen (NH(4)(+)-N, NO(3)(-)-N and NO(2)(-)-N) and heavy metals (Fe, Cr, Ni and Mn). Improper treatment practice led to high levels of some contaminants in the stream near the closed controlled landfill. Meanwhile, the active controlled landfill, which was located near the coastline, was exposed to the risk of contamination resulting from the pyrite oxidation of the surrounding area.
Metallothionein (MT) concentrations in gill and liver tissues of Oreochromis mossambicus were determined to assess biological response of fish to levels of some metals. Metal concentrations in gill and liver tissues of O. mossambicus ranged from 0.6 to 2.6 for Cd, 16 to 52 for Zn, 0.5 to 17 for Cu and 2 to 67 for T-Hg (all in μg/g wet weight, except for T-Hg in ng/g wet weight). Accumulation of Cd, Zn, Cu and Hg (μg/g wet weight) in the liver and gills of O. mossambicus were in the order of liver > gills. The concentrations of Cd, Zn, Cu and Hg in fish tissues were correlated with MT content. The increases in MT levels from the reference area Puchong Tengah compared to the polluted area Kampung Seri Kenangan were 3.4- and 3.8-fold for gills and livers, respectively. The results indicate that MT concentrations were tissue-specific, with the highest levels in the liver. Therefore, the liver can act as a tissue indicator in O. mossambicus in the study area.