Surface sediments along the south of Caspian Sea were collected to evaluate the contamination of heavy metals. The result ranged (μg/g, Fe% dw): Pb(13.06-33.48); Ni(18.01-69.63); Cd(0.62-1.5); Zn(30.11-87.88); Cu(5.86-26.37) and Fe(1.8-4%) respectively. Cadmium showed higher EF when compared to other sites. Geoaccumulation Index value for Cd in most stations was classified as moderately contaminated and moderately to strongly contaminated, as well as the average of I(geo) of Cd (1.77 ± 0.35) suggested that surface sediments of Caspian coast were moderately polluted by this metal. The result of the Pearson correlation showed that there were significant positive associations between Ni, Cd and Zn (r = 0.44-0.76; p < 0.01).
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.
This paper describes the concentration of selected heavy metals (Co, Cu, Ni, Pb, and Zn) in the Mamut river sediments and evaluate the degree of contamination of the river polluted by a disused copper mine. Based on the analytical results, copper showed the highest concentration in most of the river samples. A comparison with Interim Canadian Sediment Quality Guidelines (ICSQG) and Germany Sediment Quality Guidelines (GSQG) indicated that the sediment samples in all the sampling stations, except Mamut river control site (M1), exceeded the limit established for Cu, Ni, and Pb. On the contrary, Zn concentrations were reported well below the guidelines limit (ICSQG and GSQG). Mineralogical analysis indicated that the Mamut river sediments were primarily composed of quartz and accessory minerals such as chalcopyrite, pyrite, edenite, kaolinite, mica, and muscovite, reflected by the geological character of the study area. Enrichment factor (EF) and geoaccumulation index (Igeo) were calculated to evaluate the heavy metal pollution in river sediments. Igeo values indicated that all the sites were strongly polluted with the studied metals in most sampling stations, specifically those located along the Mamut main stream. The enrichment factor with value greater than 1.5 suggested that the source of heavy metals was mainly derived from anthropogenic activity such as mining. The degree of metal changes (δfold) revealed that Cu concentration in the river sediments has increased as much as 20 to 38 folds since the preliminary investigation conducted in year 2004.
The purpose of this paper are to determine the concentration of heavy metals namely cadmium (Cd), copper (Cu) and lead (Pb) in water and sediment; and to investigate the effect of sediment pH and sediment organic matter on concentration of cadmium, copper and lead in sediment at oxidation fraction. For this purpose the concentration of heavy metals were measured in water and sediments at 15 sites from Tasik Chini, Peninsular Malaysia. The sequential extraction procedure used in this study was based on defined fractions: exchangeable, acid reduction, oxidation, and residual. The concentration of heavy metals in residual fraction was higher than the other fractions. Among the non-residual fractions, the concentration of heavy metals in organic matter fraction was much higher than other fractions collected from all sampling sites. The pH of the sediment in all sites was acidic. The mean pH ranges from 4.8 to 5.5 with the higher value observed at site 15. Results of organic matter analysis showed that the percentage of organic matter present in sediment samples varies throughout the lake and all sites of sediments were relatively rich in organic matter ranging from 13.0% to 34.2%. The highest mean percentage of organic matter was measured at sampling site 15, with value of 31.78%.
Abundance and diversity of benthic macroinvertebrates as well as physico-chemical parameters were investigated in five rivers of the Juru River Basin in northern Peninsula Malaysia: Ceruk Tok Kun River (CTKR), Pasir River (PR), Permatang Rawa River (PRR), Kilang Ubi River (KUR), and Juru River (JR). The physico-chemical parameters and calculated water quality index (WQI) were significantly different among the investigated rivers (ANOVA, P<0.05). The WQI classified CTKR, PR, and JR into class III (slightly polluted). However, PRR and KUR fell into class IV (polluted). High diversity and abundance of macroinvertebrates, especially the intolerant taxa, Ephemeroptera, Plecoptera, and Trichoptera, were observed in the least polluted river, CTKR. Decreasing abundance of macroinvertebrates followed the deterioration of river water quality with the least number of the most tolerant taxa collected from PR. On the basis of composition and sensitivity of macroinvertebrates to pollutants in each river, the highest Biological Monitoring Working Party (BMWP) index score of 93 was reported in CTKR (good water quality). BMWP scores in PRR and JR were 38.7 and 20.1, respectively, classifying both of them into "moderate water quality" category. Poor water quality was reported in PR and KUR. The outcome of the multivariate analysis (CCA) was highly satisfactory, explaining 43.32% of the variance for the assemblages of macroinvertebrates as influenced by 19 physical and chemical variables. According to the CCA model, we assert that there were three levels of stresses on macroinvertebrate communities in the investigated rivers: Level 1, characterized of undisturbed or slightly polluted as in the case of CTKR; Level 2, characterized by a lower habitat quality (the JR) compared to the CTKR; and Level 3 showed severe environmental stresses (PRR, PR, and KUR) primarily contributed by agricultural, industrial, and municipal discharges.
Weathered crude oil (WCO) removals in shoreline sediment samples were monitored for 60 days in bioremediation experimentation. Experimental modeling was carried out using statistical design of experiments. At optimum conditions maximum of 83.13, 78.06 and 69.92% WCO removals were observed for 2, 16 and 30 g/kg initial oil concentrations, respectively. Significant variations in the crude oil degradation pattern were observed with respect to oil, nutrient and microorganism contents. Crude oil bioremediation were successfully described by a first-order kinetic model. The study indicated that the rate of hydrocarbon biodegradation increased with decrease of crude oil concentrations.
Polychlorinated biphenyl (PCB) was detected as isomer groups (congener numbers 28, 52, 101, 118, 138, 153 and 180) in the coastal water and sediment of four stations around Shadegan wetland protected area in the northwestern part of the Persian Gulf. Total PCB concentration range was 8-375 ng/L in water and 3.4-50.2 μg/g in sediment. Concentration of different congeners and chromatogram indicates that the source of PCB in this area can be Clophen A60; it used for long time in Iranian electronic industries. Other chlorinated hydrocarbons such as lindane, DDT and their metabolites were also present in the samples.
Present study was conducted to evaluate current status of trace elements contamination in the surface sediments of the Johor Strait. Iron (2.54 +/- 1.24%) was found as the highest occurring element, followed by those of zinc (210.45 +/- 115.4 microg/g), copper (57.84 +/- 45.54 microg/g), chromium (55.50 +/- 31.24 microg/g), lead (52.52 +/- 28.41 microg/g), vanadium (47.76 +/- 25.76 microg/g), arsenic (27.30 +/- 17.11 microg/g), nickel (18.31 +/- 11.77 microg/g), cobalt (5.13 +/- 3.12 microg/g), uranium (4.72 +/- 2.52 microg/g), and cadmium (0.30 +/- 0.30 microg/g), respectively. Bioavailability of cobalt, nickel, copper, zinc, arsenic and cadmium were higher than 50% of total concentration. Vanadium, copper, zinc, arsenic and cadmium were found significantly different between the eastern and western part of the strait (p < 0.05). Combining with other factors, Johor Strait is suitable as a hotspot for trace elements contamination related studies.
Concentrations of 11 trace elements (V, Cr, Co, Ni, Cu, Zn, As, Ag, Cd, Pb, and U) were determined in the intertidal surface sediments of Peninsular Malaysia. The average trace element concentrations are ranked as follows: Zn>V>As>Cr>Pb>Cu>Ni>Co>U>g>Cd. Interim Sediment Quality Guidelines (ISQGs) employed in present study are the Australia and New Zealand joint guideline (ANZECC/ARMCANZ), and the Hong Kong authorities. From the pooled data, none of these trace elements have the average concentration above the ISQG-high values. However, As and Ag average concentrations were over the ISQG-low values. Some elements were found to have the average concentration above the ISQG-high and/or ISQG-low in certain locations, including Kampung Pasir Putih (JPP), Lumut Port (ALP), Kuala Perai (PKP), Port Dickson (NPD), and others. The lowest and highest concentrations in a specific sampling location and maritime area varied among the elements, variations that were greatly affected by natural and anthropogenic activities in a given area. For each trace element, there were various levels of concentration among the sampling locations and maritime areas. These patterns indicated pollutant sources of an element for each area perhaps derived from nearby areas and did not widely distributed to other locations. It is necessary for Malaysia to develop an ISQG for effective quick screening and evaluation of the coastal environment of Peninsular Malaysia.
Chenab River is one of the most important rivers of Punjab Province (Pakistan) that receives huge input of industrial effluents and municipal sewage from major cities in the Central Punjab, Pakistan. The current study was designed to evaluate the concentration levels and associated ecological risks of USEPA priority polycyclic aromatic hydrocarbons (PAHs) in the surface sediments of Chenab River. Sampling was performed from eight (n = 24) sampling stations of Chenab River and its tributaries. We observed a relatively high abundance of ∑16PAHs during the summer season (i.e. 554 ng g(-1)) versus that in the winter season (i.e. 361 ng g(-1)), with an overall abundance of two-, five- and six-ring PAH congeners. Results also revealed that the nitrate and phosphate contents in the sediments were closely associated with low molecular weight (LMW) and high molecular weight (HMW) PAHs, respectively. Source apportionment results showed that the combustion of fossil fuels appears to be the key source of PAHs in the study area. The risk quotient (RQ) values indicated that seven PAH congeners (i.e. phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)pyrene, chrysene and benzo(a)anthracene) could pose serious threats to the aquatic life of the riverine ecosystem in Pakistan.
Sediment cores and overlying water samples were collected at four sites in Tianjin Coastal Zone, Bohai Bay, to investigate nutrient (N, P and Si) exchanges across the sediment-water interface. The exchange fluxes of each nutrient species were estimated based on the porewater profiles and laboratory incubation experiments. The results showed significant differences between the two methods, which implied that molecular diffusion alone was not the dominant process controlling nutrient exchanges at these sites. The impacts of redox conditions and bioturbation on the nutrient fluxes were confirmed by the laboratory incubation experiments. The results from this study showed that the nutrient fluxes measured directly from the incubation experiment were more reliable than that predicted from the porewater profiles. The possible impacts causing variations in the nutrient fluxes include sewage discharge and land reclamation.
The response patterns of microbial functional genes involved in biogeochemical cycles to cadaver decay is a central topic of recent environmental sciences. However, the response mechanisms and pathways of the functional genes associated with the carbon (C) and nitrogen (N) cycling to cadaveric substances such as cadaverine and putrescine remain unclear. This study explored the variation of functional genes associated with C fixation, C degradation and N cycling and their influencing factors under cadaverine, putrescine and mixed treatments. Our results showed only putrescine significantly increased the alpha diversity of C fixation genes, while reducing the alpha diversity of N cycling genes in sediment. For the C cycling, the mixed treatment significantly decreased the total abundance of reductive acetyl-CoA pathway genes (i.e., acsB and acsE) and lig gene linked to lignin degradation in water, while only significantly increasing the hydroxypropionate-hydroxybutylate cycle (i.e., accA) gene abundance in sediment. For the N cycling, mixed treatment significantly decreased the abundance of the nitrification (i.e., amoB), denitrification (i.e., nirS3) genes in water and the assimilation pathway gene (i.e., gdhA) in sediment. Environmental factors (i.e., total carbon and total nitrogen) were all negatively associated with the genes of C and N cycling. Therefore, cadaverine and putrescine exposure may inhibit the pathway in C fixation and N cycling, while promoting C degradation. These findings can offer some new insight for the management of amine pollution caused by animal cadavers.
This is the first extensive report on linear alkylbenzenes (LABs) as sewage molecular markers in surface sediments collected from the Perlis, Kedah, Merbok, Prai, and Perak Rivers and Estuaries in the west of Peninsular Malaysia. Sediment samples were extracted, fractionated, and analyzed using gas chromatography mass spectrometry (GC-MS). The concentrations of total LABs ranged from 68 to 154 (Perlis River), 103 to 314 (Kedah River), 242 to 1062 (Merbok River), 1985 to 2910 (Prai River), and 217 to 329 ng g(-1) (Perak River) dry weight (dw). The highest levels of LABs were found at PI3 (Prai Estuary) due to the rapid industrialization and population growth in this region, while the lowest concentrations of LABs were found at PS1 (upstream of Perlis River). The LABs ratio of internal to external isomers (I/E) in this study ranged from 0.56 at KH1 (upstream of Kedah River) to 1.35 at MK3 (Merbok Estuary) indicating that the rivers receive raw sewage and primary treatment effluents in the study area. In general, the results of this paper highlighted the necessity of continuation of water treatment system improvement in Malaysia.
This is the first publication on the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in riverine and coastal sediments in South East Asia where the rapid transfer of land-based pollutants into aquatic environments by heavy rainfall and runoff waters is of great concern. Twenty-nine Malaysian riverine and coastal sediments were analyzed for PAHs (3-7 rings) by gas chromatography mass spectrometry. Total PAHs concentrations in the sediment ranged from 4 to 924 ng/g. Alkylated homologues were abundant for all sediment samples. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P), an index of petrogenic PAHs contribution, was more than unity for 26 sediment samples and more than 3 for seven samples for urban rivers covering a broad range of locations. The MP/P ratio showed a strong correlation with the total PAHs concentrations, with an r2 value of 0.74. This ratio and all other compositional features indicated that Malaysian urban sediments are heavily impacted by petrogenic PAHs. This finding is in contrast to other studies reported in many industrialized countries where PAHs are mostly of pyrogenic origin. The MP/P ratio was also significantly correlated with higher molecular weight PAHs such as benzo[a]pyrene, suggesting unique PAHs source in Malaysia which contains both petrogenic PAHs and pyrogenic PAHs. PAHs and hopanes fingerprints indicated that used crankcase oil is one of the major contributors of the sedimentary PAHs. Two major routes of inputs to aquatic environments have been identified: (1) spillage and dumping of waste crankcase oil and (2) leakage of crankcase oils from vehicles onto road surfaces, with the subsequent washout by street runoff. N-Cyclohexyl-2-benzothiazolamine (NCBA), a molecular marker of street dust, was detected in the polluted sediments. NCBA and other biomarker profiles confirmed our hypothesis of the input from street dust contained the leaked crankcase oil. The fingerprints excluded crude oil, fresh lubricating oil, asphalt, and tire-particles as major contributors.
This study investigated polycyclic aromatic hydrocarbons (PAHs) pollution in surface sediments within aquaculture areas in Peninsular Malaysia using chemometric techniques, forensics and univariate methods. The samples were analysed using soxhlet extraction, silica gel column clean-up and gas chromatography mass spectrometry. The total PAH concentrations ranged from 20 to 1841 ng/g with a mean of 363 ng/g dw. The application of chemometric techniques enabled clustering and discrimination of the aquaculture sediments into four groups according to the contamination levels. A combination of chemometric and molecular indices was used to identify the sources of PAHs, which could be attributed to vehicle emissions, oil combustion and biomass combustion. Source apportionment using absolute principle component scores-multiple linear regression showed that the main sources of PAHs are vehicle emissions 54%, oil 37% and biomass combustion 9%. Land-based pollution from vehicle emissions is the predominant contributor of PAHs in the aquaculture sediments of Peninsular Malaysia.
Concentrations of Cd, Cu, Pb, Zn, Ni and Fe were determined in the surface sediments to investigate the distributions, concentrations and the pollution status of heavy metals in Dumai coastal waters. Sediment samples from 23 stations, representing 5 different site groups of eastern, central and western Dumai and southern and northern Rupat Island, were collected in May 2005. The results showed that heavy metal concentrations (in microg/g dry weight; Fe in %) were 0.88 (0.46-1.89); 6.08 (1.61-13.84); 32.34 (14.63-84.90); 53.89 (31.49-87.11); 11.48 (7.26-19.97) and 3.01 (2.10-3.92) for Cd, Cu, Pb, Zn, Ni and Fe, respectively. Generally, metal concentrations in the coastal sediments near Dumai city center (eastern and central Dumai) which have more anthropogenic activities were higher than those at other stations. Average concentration of Cd in the eastern Dumai was slightly higher than effective range low (ERL) but still below effective range medium (ERM) value established by Long et al. (Environmental Management 19(1):81-97, 1995; Environmental Toxicology Chemistry 17(4):714-727, 1997). All other metals were still below ERL and ERM. Calculated enrichment factor (EF), especially for Cd and Pb, and the Pollution load index (PLI) value in the eastern Dumai were also higher than other sites. Cd showed higher EF when compared to other metals. Geo-accumulation indices (I(geo)) in most of the stations (all site groups) were categorized as class 1 (unpolluted to moderately polluted environment) and only Cd in Cargo Port was in class 2 (moderately polluted). Heavy metal concentrations found in the present study were comparable to other regions of the world and based on the calculated indices it can be classified as unpolluted to moderately polluted coastal environment.
Concentration of butyltin compounds (BTs), including tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) and total tin (SigmaSn) were determined in green mussel (Perna viridis), 10 species of muscle fish and sediment from coastal waters of Malaysia. BTs were detected in all these samples ranging from 3.6 to 900 ng/g wet wt., 3.6 to 210 ng/g wet wt., and 18 to 1400 ng/g dry wt. for mussels, fish and sediments, respectively. The concentrations of BTs in several locations of this study were comparable with the reported values from some developed countries and highest among Asian developing nations. Considerable concentration of BTs in several locations might have ecotoxicological consequences and may cause concern to human health. The parent compound TBT was found to be highest than those of its degradation compounds, DBT and MBT, suggesting recent input of TBT to the Malaysian marine environment. Significant positive correlation (Spearman rank correlation: r2=0.82, P<0.0001) was found between BTs and SigmaSn, implying considerable anthropogenic input of butyltin compounds to total tin contamination levels. Enormous boating activities may be a major source of BTs in this country, although aquaculture activities may not be ignored.
Mining activities are responsible for the elevated input levels of suspended sediment and hazardous metals into the riverine ecosystem. These have been shown to threaten the riverine fish populations and can even lead to localized population extinction. To date, research on the effects of mining activities on fish has been focused within metal contamination and bioaccumulation and its threat to human consumption, neglecting the effects of suspended sediment. This paper reviews the effects of suspended sediment and metal pollution on riverine ecosystem and fish population by examining the possibilities of genetic changes and population extinction. In addition, possible assessments and studies of the riverine fish population are discussed to cope with the risks from mining activities and fish population declines.
Soil serves as a major reservoir for contaminants as it posseses an ability to bind various chemicals together. To safeguard the members of the public from an unwanted exposure, studies were conducted on the sediments and soil from water bodies that form the major sources of domestic water supply in northern peninsular Malaysia for their trace element concentration levels. Neutron Activation Analysis, using Nigeria Research Reactor-1 (NIRR-1) located at the Centre for Energy Research and Training, Zaria, Nigeria was employed as the analytical tool. The elements identified in major quantities include Na, K, and Fe while As, Br, Cr, U, Th, Eu, Cs, Co, La, Sm, Yb, Sc, Zn, Rb, Ba, Lu, Hf, Ta, and Sb were also identified in trace quantities. Gamma spectroscopy was also employed to analyze some soil samples from the same area. The results indicated safe levels in terms of the radium equivalent activity, external hazard index as well as the mean external exposure dose rates from the soil. The overall screening of the domestic water sources with relatively high heavy metals concentration values in sediments and high activity concentration values in soil is strongly recommended as their accumulation overtime as a consequence of leaching into the water may be of health concern to the members of the public.
Central composite design (CCD) and response surface methodology (RSM) were employed to optimize four important variables, i.e. amounts of oil, bacterial inoculum, nitrogen and phosphorus, for the removal of selected n-alkanes during bioremediation of weathered crude oil in coastal sediments using laboratory bioreactors over a 60 day experimentation period. The reactors contained 1 kg soil with different oil, microorganisms and nutrients concentrations. The F Value of 26.89 and the probability value (P < 0.0001) demonstrated significance of the regression model. For crude oil concentration of 2, 16 and 30 g per kg sediments and under optimized conditions, n-alkanes removal was 97.38, 93.14 and 90.21% respectively. Natural attenuation removed 30.07, 25.92 and 23.09% n-alkanes from 2, 16 and 30 g oil/kg sediments respectively. Excessive nutrients addition was found to inhibit bioremediation.