This study applied the use of sequential extraction technique and simple bioaccessibility extraction test to quantify the bioavailable fractions and the human bioaccessible concentration of metals collected from nine stations in surface sediment of the Langat River. The concentrations of total and bioaccessible metals from different stations were in the range of 0.49-1.04, 0.10-0.32 μg g-1 for T-Cd, Bio-Cd, respectively, and 12.9-128.03, 2.06-8.53 μg kg-1 for T-Hg, Bio-Hg, respectively. The results revealed highest R-Bio-Cd in Banting station (55.3 %), while the highest R-Bio-Hg was in Kajang station (49.61 %). The chemical speciation of Cd in most sampling stations was in the order of oxidisable-organic > residual > exchangeable > acid-reducible, while speciation of Hg was in the order of exchangeable > residual > oxidisable-organic > acid-reducible. The correlation matric of mean content showed that the TOM, particle size and Mg++ in polluted surface sediments was highly correlated with total mercury. The PCA showed that the main factors influencing the bioaccessibility of Hg in surface sediments were the sediment TOM, F1 (EFLE) and F3 (oxidation-organic), while the factor influencing the bioaccessibility of Cd was the F3 (oxidation-organic) and T-Cd.
The Bernam River is one of the most important rivers in Malaysia in that it provides water for industries and agriculture located along its banks. The present study was conducted to assess the level of contamination of heavy metals (Cd, Ni, Cr, Sn, and Fe) in surface sediments in the Bernam River. Nine surface sediment samples were collected from the lower, middle, and upper courses of the river. The results indicated that the concentrations of the metals decreased in the order of Sn > Cr > Ni > Fe > Cd (56.35, 14.90, 5.3, 4.6, and 0.62 μg/g(1) dry weight). Bernam River sediments have moderate to severe enrichment for Sn, moderate for Cd, and no enrichment for Cr, Ni, and Fe. The contamination factor (CF) results demonstrated that Cd and Sn are responsible for the high contamination. The pollution load index (PLI), for all the sampling sites, suggests that the sampling stations were generally unpolluted with the exception of the Bagan Tepi Sungai, Sabak Bernam, and Tanjom Malim stations. Multivariate techniques including Pearson's correlation and hierarchical cluster analysis were used to apportion the various sources of the metals. The results suggested that the sediment samples collected from the upper course of the river had lower metal concentrations, while sediments in the middle and lower courses of the river had higher metal concentrations. Therefore, our results can be useful as a baseline data for government bodies to adopt corrective measure on the issues related to heavy metal pollution in the Bernam River in the future.
An analytical method that facilitated the analysis of 11 pharmaceuticals residue (caffeine, prazosin, enalapril, carbamazepine, nifedipine, levonorgestrel, simvastatin, hydrochlorothiazide, gliclazide, diclofenac-Na, and mefenamic acid) with a single pre-treatment protocol was developed. The proposed method included an isolation and concentration procedure using solid phase extraction (Oasis HLB), a separation step using high-performance liquid chromatography, and a detection procedure that applies time-of-flight mass spectrometry. The method was validated for drinking water (DW), surface water (SW), sewage treatment plant (STP) influent and effluent, and hospital (HSP) influent and effluent. The limits of quantification were as low as 0.4, 1.6, 5, 3, 2.2 and 11 ng/L in DW, SW, HSP influent and effluent, STP effluent, and STP influent, respectively. On average, good recoveries higher than 75% were obtained for most of the target analytes in all matrices. Matrix effect was evaluated for all samples matrices. The proposed method successfully determined and quantified the target compounds in raw and treated wastewater of four STPs and three hospitals in Malaysia, as well as in two SW sites. The results showed that a number of the studied compounds pose moderate to high persistency in sewage treatment effluents as well as in the recipient rivers, namely; caffeine, simvastatin, and hydrochlorothiazide. Ten out of 11 compounds were detected and quantified in 13 sampling points. Caffeine was detected with the highest level, with concentrations reaching up to 9099 ng/L in STP influent.
This study aims to determine the concentration of sterols used as biomarkers in the surface microlayer (SML) in estuarine areas of the Selangor River, Malaysia. Samples were collected during different seasons through the use of a rotation drum. The analysis of sterols was performed using gas chromatography equipped with a flame ionisation detector (GC-FID). The results showed that the concentrations of total sterols in the SML ranged from 107.06 to 505.55 ng L(-1). The total sterol concentration was found to be higher in the wet season. Cholesterol was found to be the most abundant sterols component in the SML. The diagnostic ratios of sterols show the influence of natural sources and waste on the contribution of sterols in the SML. Further analysis, using principal component analysis (PCA), showed distinct inputs of sterols derived from human activity (40.58%), terrigenous and plant inputs (22.59%) as well as phytoplankton and marine inputs (17.35%).
A comprehensive monitoring survey for polycyclic aromatic hydrocarbons (PAHs) and phenolic endocrine disrupting chemicals (EDCs) utilizing mussels as sentinel organisms was conducted in South and Southeast Asia as a part of the Asian Mussel Watch project. Green mussel (Perna viridis) samples collected from a total of 48 locations in India, Indonesia, Singapore, Malaysia, Thailand, Cambodia, Vietnam, and the Philippines during 1994-1999 were analyzed for PAHs, EDCs including nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA), and linear alkylbenzenes (LABs) as molecular markers for sewage. Concentrations of NP ranged from 18 to 643 ng/g-dry tissue. The highest levels of NP in Malaysia, Singapore, the Philippines, and Indonesia were comparable to those observed in Tokyo Bay. Elevated concentrations of EDCs were not observed in Vietnam and Cambodia, probably due to the lower extent of industrialization in these regions. No consistent relationship between concentrations of phenolic EDCs and LABs were found, suggesting that sewage is not a major source of EDCs. Concentrations of PAHs ranged from 11 to 1,133 ng/g-dry, which were categorized as "low to moderate" levels of pollution. The ratio of methylphenanthrenes to phenanthrene (MP/P ratio) was >1.0 in 20 out of 25 locations, indicating extensive input of petrogenic PAHs. This study provides a bench-mark for data on the distribution of anthropogenic contaminants in this region, which is essential in evaluating temporal and spatial variation and effect of future regulatory measures.
This case study uses several univariate and multivariate statistical techniques to evaluate and interpret a water quality data set obtained from the Klang River basin located within the state of Selangor and the Federal Territory of Kuala Lumpur, Malaysia. The river drains an area of 1,288 km(2), from the steep mountain rainforests of the main Central Range along Peninsular Malaysia to the river mouth in Port Klang, into the Straits of Malacca. Water quality was monitored at 20 stations, nine of which are situated along the main river and 11 along six tributaries. Data was collected from 1997 to 2007 for seven parameters used to evaluate the status of the water quality, namely dissolved oxygen, biochemical oxygen demand, chemical oxygen demand, suspended solids, ammoniacal nitrogen, pH, and temperature. The data were first investigated using descriptive statistical tools, followed by two practical multivariate analyses that reduced the data dimensions for better interpretation. The analyses employed were factor analysis and principal component analysis, which explain 60 and 81.6% of the total variation in the data, respectively. We found that the resulting latent variables from the factor analysis are interpretable and beneficial for describing the water quality in the Klang River. This study presents the usefulness of several statistical methods in evaluating and interpreting water quality data for the purpose of monitoring the effectiveness of water resource management. The results should provide more straightforward data interpretation as well as valuable insight for managers to conceive optimum action plans for controlling pollution in river water.
This study evaluates the impact of anthropogenic activities on the Shahrood River using water physico-chemical variables and macroinvertebrates data sets obtained over a period of 12 months between February 2012 and February 2013 at 8 sampling sites. Biotic indices i.e. FBI and BMWP based on macroinvertebrates and physico-chemical indices (MPI, HPI and NSF-WQI) were employed to evaluate the water quality status in connection with natural- and human-induced pressures. Based on physico-chemical indices, water quality was categorized as low polluted level and it is suitable for drinking purposes. The water quality based on biotic indices was related to the anthropic activities; a clear deterioration of the water quality was observed from upstream to downstream sites. The water quality along the river changed from very good (class I; reference sites) to good (class II; midstream sites) and turned into moderate (class III) and poor (class IV) quality (downstream sites). These findings indicate that biotic indices are more powerful indicators in assessing water quality than physico-chemical indices. Allocapnia, Glossosoma and Hesperoperla were exclusively related to least disturbed sites, and Naididae, Orthocladiinae and Ecdyonurus were found in sites showing notable degradation. Our results recommended that the use of macroinvertebrates could be employed as a cost-effective tool for biomonitoring and controlling of polluted riverine ecosystems in the Middle East. Finally, the results from this study may be useful not only for developing countries, but also for any organization struggling to use macroinvertebrate based indices with restricted financial resources and knowledge.
The spatio-temporal variability of water quality associated with anthropogenic activities was studied for the Bertam River and its main tributaries within the Bertam Catchment, Cameron Highlands, Malaysia. A number of physico-chemical parameters of collected samples were analyzed to evaluate their spatio-temporal variability. Nonparametric statistical analysis showed significant temporal and spatial differences (p < 0.05) in most of the parameters across the catchment. Parameters except dissolved oxygen and chemical oxygen demand displayed higher values in rainy season. The higher concentration of total suspended solids was caused by massive soil erosion and sedimentation. Seasonal variations in contaminant concentrations are largely affected by precipitation and anthropogenic influences. Untreated domestic wastewater discharge as well as agricultural runoff significantly influenced the water quality. Poor agricultural practices and development activities at slope areas also affected the water quality within the catchment. The analytical results provided a basis for protection of river environments and ecological restoration in mountainous Bertam Catchment.
Perfluorinated compounds (PFCs) have been used for many years, and are distributed all over the world. This study focused on occurrences of PFCs, especially perfluorooctane sulfonate (PFOS) and perfluorooctonoic acid (PFOA) in Thai rivers and industrial estate discharges, while comparing results with rivers of other Asian countries (Japan, China, and Malaysia). Surveys were conducted in Chao Phraya River, Bangpakong River and three industrial estates. A solid phase extraction (SPE) and HPLC-ESI-MS/MS were used for the analysis of these chemicals. The average concentrations of PFOS and PFOA were 1.9 and 4.7 ng/L, respectively in Chao Phraya River, while lower concentrations were detected in Bangpakong River with the averages of 0.7 ng/L for both PFOS and PFOA. Higher concentrations were detected in all industrial estate discharges with the averages of 64.3 ng/L for PFOA and 17.9 ng/L for PFOS., Total loadings from three industrial estates were 1.93 g/d for PFOS and 11.81 g/d for PFOA. The concentration levels in Thai rivers were less than rivers in Japan, China, and Malaysia. However, PFCs loading rate of Chao Phraya River was much higher than Yodo River (Japan), due to the higher flow rate. The other six PFCs were found above the Limit of Quantification (LOQ) in most samples. PFHxS and PFNA were also highly detected in some river samples.
This study explores diatom community dynamics in a highly modified semi-arid temperate region river system characterised by inconsistent river flow. Various water and sediment environmental variables were assessed using a multi-faceted analysis approach to determine the spatio-temporal drivers of benthic diatom communities in the river system. Overall, the diatom community was generally dominated by pollution tolerant species, reflecting the anthropogenic intensity and activities on the river system. Diatom community composition was found to be largely determined by water column chemistry variables particularly nutrient concentrations in comparison to sediment chemistry and physical variables. Strong seasonal diatom species composition was also observed and this was driven by strong seasonal variations in nutrient loads and metal concentrations, a result of the variable water flow across the two seasons. However, the greater temporal variation in communities was observed in the smaller systems with the mainstream river system being more homogenous over time. In addition, diatom community composition and environmental variables were found to be different and more pronounced between streams and mainstream sites, than between canals and streams. The study highlights the complex interaction between water column, sediment and physical variables in determining the diatom species composition in small river systems. It also highlights the importance of river flow inconsistency as an indirect variable that alters primary drivers such as nutrient concentrations in the water column and heavy metal levels in the sediment.
The effect of metals on environmental health is well documented and monitoring these and other pollutants is considered an important part of environmental management. Developing countries are yet to fully appreciate the direct impacts of pollution on aquatic ecosystems and as such, information on pollution dynamics is scant. Here, we assessed the temporal and spatial dynamics of stream sediment metal and nutrient concentrations using contaminant indices (e.g. enrichment factors, pollution load and toxic risk indices) in an arid temperate environment over the wet and dry seasons. The mean sediment nutrient, organic matter and metal concentration were highest during the dry season, with high values being observed for the urban environment. Sediment contaminant assessment scores indicated that during the wet season, the sediment quality was acceptable, but not so during the dry season. The dry season had low to moderate levels of enrichment for metals B, Cu, Cr, Fe, Mg, K and Zn. Overall, applying the sediment pollution load index highlighted poor quality river sediment along the length of the river. Toxic risk index indicated that most sites posed no toxic risk. The results of this study highlighted that river discharge plays a major role in structuring temporal differences in sediment quality. It was also evident that infrastructure degradation was likely contributing to the observed state of the river quality. The study contributes to our understanding of pollution dynamics in arid temperate landscapes where vast temporal differences in base flow characterise the riverscape. Such information is further useful for contrasting sediment pollution dynamics in aquatic environments with other climatic regions.
The aim of this study was to investigate and apply supported ionic liquid membrane (SILM) in two-phase micro-electrodriven membrane extraction combined with high performance liquid chromatography-ultraviolet detection (HPLC-UV) for pre-concentration and determination of three selected antidepressant drugs in water samples. A thin agarose film impregnated with 1-hexyl-3-methylimidazolium hexafluorophosphate, [C6MIM] [PF6], was prepared and used as supported ionic liquid membrane between aqueous sample solution and acceptor phase for extraction of imipramine, amitriptyline and chlorpromazine. Under the optimized extraction conditions, the method provided good linearity in the range of 1.0-1000μgL(-1), good coefficients of determination (r(2)=0.9974-0.9992) and low limits of detection (0.1-0.4μgL(-1)). The method showed high enrichment factors in the range of 110-150 and high relative recoveries in the range of 88.2-111.4% and 90.9-107.0%, for river water and tap water samples, respectively with RSDs of ≤7.6 (n=3). This method was successfully applied to the determination of the drugs in river and tap water samples. It is envisaged that the SILM improved the perm-selectivity by providing a pathway for targeted analytes which resulted in rapid extraction with high degree of selectivity and high enrichment factor.
Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytical methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world's rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals.
A study was conducted to investigate the influence of Asian monsoon on chlorophyll-a (Chl-a) content in Sabah waters and to identify the related oceanographic conditions that caused phytoplankton blooms at the eastern and western coasts of Sabah, Malaysia. A series of remote sensing measurements including surface Chl-a, sea surface temperature, sea surface height anomaly, wind speed, wind stress curl, and Ekman pumping were analyzed to study the oceanographic conditions that lead to large-scale nutrients enrichment in the surface layer. The results showed that the Chl-a content increased at the northwest coast from December to April due to strong northeasterly wind and coastal upwelling in Kota Kinabalu water. The southwest coast (Labuan water) maintained high concentrations throughout the year due to the effect of Padas River discharge during the rainy season and the changing direction of Baram River plume during the northeast monsoon (NEM). However, with the continuous supply of nutrients from the upwelling area, the high Chl-a batches were maintained at the offshore water off Labuan for a longer time during NEM. On the other side, the northeast coast illustrated a high Chl-a in Sandakan water during NEM, whereas the northern tip off Kudat did not show a pronounced change throughout the year. The southeast coast (Tawau water) was highly influenced by the direction of the surface water transport between the Sulu and Sulawesi Seas and the prevailing surface currents. The study demonstrates the presence of seasonal phytoplankton blooms in Sabah waters which will aid in forecasting the possible biological response and could further assist in marine resource managements.
Influences of river hydrodynamic behaviours on hydrochemistry (salinity, pH, dissolved oxygen saturations and dissolved phosphorus) were evaluated through high spatial and temporal resolution study of a sandbar-regulated coastal river. River hydrodynamic during sandbar-closed event was characterized by minor dependency on tidal fluctuations, very gradual increase of water level and continual low flow velocity. These hydrodynamic behaviours established a hydrochemistry equilibrium, in which water properties generally were characterized by virtual absence of horizontal gradients while vertical stratifications were significant. In addition, the river was in high trophic status as algae blooms were visible. Conversely, river hydrodynamic in sandbar-opened event was tidal-controlled and showed higher flow velocity. Horizontal gradients of water properties became significant while vertically more homogenised and with lower trophic status. In essence, this study reveals that estuarine sandbar directly regulates river hydrodynamic behaviours which in turn influences river hydrochemistry.
The presence of toxic polonium-210 (Po-210) in the environment is due to the decay of primordial uranium-238. Meanwhile, several studies have reported elevated Po-210 radioactivity in the rivers around the world due to both natural and anthropogenic factors. However, the primary source of Po-210 in Langat River, Malaysia might be the natural weathering of granite rock along with mining, agriculture and industrial activities. Hence, this is the first study to determine the Po-210 activity in the drinking water supply chain in the Langat River Basin to simultaneously predict the human health risks of Po-210 ingestion. Therefore, water samples were collected in 2015⁻2016 from the four stages of the water supply chain to analyze by Alpha Spectrometry. Determined Po-210 activity, along with the influence of environmental parameters such as time-series rainfall, flood incidents and water flow data (2005⁻2015), was well within the maximum limit for drinking water quality standard proposed by the Ministry of Health Malaysia and World Health Organization. Moreover, the annual effective dose of Po-210 ingestion via drinking water supply chain indicates an acceptable carcinogenic risk for the populations in the Langat Basin at 95% confidence level; however, the estimated annual effective dose at the basin is higher than in many countries. Although several studies assume the carcinogenic risk of Po-210 ingestion to humans for a long time even at low activity, however, there is no significant causal study which links Po-210 ingestion via drinking water and cancer risk of the human. Since the conventional coagulation method is unable to remove Po-210 entirely from the treated water, introducing a two-layer water filtration system at the basin can be useful to achieve SDG target 6.1 of achieving safe drinking water supplies well before 2030, which might also be significant for other countries.
Luminescence-based assays for toxicants such as Microtox, ToxAlert, and Biotox have been used extensively worldwide. However, the use of these assays in near real time conditions is limited due to nonoptimal assay temperature for the tropical climate. An isolate that exhibits a high luminescence activity in a broad range of temperatures was successfully isolated from the mackerel, Rastrelliger kanagurta. This isolate was tentatively identified as Photobacterium sp. strain MIE, based on partial 16S rDNA molecular phylogeny. Optimum conditions that support high bioluminescence activity occurred between 24 and 30°C, with pH 5.5 to 7.5, 10 to 20 g/L of sodium chloride, 30 to 50 g/L of tryptone, and 4 g/L of glycerol as the carbon source. Assessment of near real time capability of this bacterial system, Xenoassay light to monitor heavy metals from a contaminated river running through the Juru River Basin shows near real time capability with assaying time of less than 30 minutes per samples. Samples returned to the lab were tested with a standard Microtox assay using Vibrio fishceri. Similar results were obtained to Xenoassay light that show temporal variation of copper concentration. Thus, this strain is suitable for near real time river monitoring of toxicants especially in the tropics.
Cyclodextrin-ionic liquid polymer (βCD-BIMOTs-TDI) is a new class of macroporous material and has great potential to be used as an SPE adsorbent material for extraction of phenols in river water samples. Six phenols, as model analytes, were extracted on a βCD-BIMOTs-TDI SPE cartridge, and then, eluted with 2 mL of methanol containing 1% acetic acid. The optimum experimental condition was 15 mL of sample volume (sample at pH 6) and 2 mL of methanol containing 1% acetic acid as an eluent solvent. The eluent concentration was determined by using Gas Chromatography-Flame Ionization Detector (GC-FID). Under optimized condition, high sensitivity (detection limits 0.23-0.35 µg/L) and good recoveries (87-116%) were achieved with satisfactory relative standard deviation (RSD) (0.1-1.7%). The developed βCD-BIMOTs-TDI-SPE was then compared with other adsorbents, and the obtained results showed that the βCD-BIMOTs-TDI exhibited higher extraction recovery due to the unique structure and properties. Finally, the βCD-BIMOTs-TDI was applied as a solid phase extraction sorbent for phenols determination under optimized condition, in river and tap waters, prior to the GC-FID separation.