Endocrine disrupting compounds (EDCs) have been widely reported as potential carcinogenic threats to the human population. The release of EDCs to environmental compartments, such as water, sediment, and biota, has been monitored extensively. Considering the typically low levels of EDC concentrations found in environmental samples and the complexity of biota matrices, the main challenge is with the extraction and cleanup of samples, as well as with finding a sensitive enough instrumentation system for analyte detection. This paper presents a review of recent trends in the analysis of EDCs in environmental matrices. The focus of this review is three classes of environmentally important EDCs; namely, pharmaceuticals, estrogenic hormones, and alkylphenol compounds. Discussions about state-of-the-art instrumentation and sample preparation techniques, as well as a review of sample storage and preservation, are highlighted. Overall, the use of LC-MS-MS as an instrumentation technique has increased over the past 15 years.
The occurrence, level, and distribution of multiclass emerging organic contaminants (EOCs) in fish and mollusks from the Klang River estuary were examined. The targeted EOCs for this assessment were phenolic endocrine disrupting compounds (bisphenol A, 4-OP, and 4-NP), organophosphorous pesticides (quinalphos, chlorpyrifos, and diazinon), estrogenic hormones (E2, E1, and EE2), and pharmaceutically active chemicals (primidone, sulfamethoxazole, dexamethasone, diclofenac, amoxicillin, progesterone, and testosterone). Results from this study showed that the prevalent contamination of the Klang River estuary by EOCs with diclofenac, bisphenol A, progesterone, and amoxicillin were predominantly detected in fish and mollusks. Among the EOCs, diclofenac and progesterone had the highest concentrations in fish and mollusk samples, respectively. The concentrations of diclofenac and progesterone in fish and mollusk samples range from 1.42 ng/g to 10.76 ng/g and from 0.73 ng/g to 9.57 ng/g, respectively. Bisphenol A should also be highlighted because of its significant presence in both fish and mollusks. The concentration of bisphenol A in both matrices range from 0.92 ng/g to 5.79 ng/g. The calculated hazard quotient (HQ) for diclofenac, bisphenol A, and progesterone without consideration to their degradation byproduct were less than one, thus suggesting that the consumption of fish and mollusks from the Klang River estuary will unlikely pose any health risk to consumers on the basis of the current assessment. Nonetheless, this preliminary result is an important finding for pollution studies in Malaysian tropical coastal ecosystems, particularly for organic micropollutant EOCs, and can serve as a baseline database for future reference.
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, 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) followed by diclofenac (10.80 ng L) and primidone (7.74 ng L). 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.
Pesticide contamination in the environment is a contemporary global issue. As agricultural production through crop planting in Malaysia now supports both energy and food productions, the concentration and distribution of pesticides in surface water may have changed. Therefore, this study assesses the concentration and distribution of organophosphorus pesticides (quinalphos, diazinon and chlorpyrifos) contamination in the Langat River, Selangor. The Langat River Basin is one of the most populated river basins in Malaysia. As a result, it is surrounded by various environmental stresses of which agricultural activity is a dominant cause. An analytical method has been developed and optimised based on solid-phase extraction and high-performance liquid chromatography, coupled with a diode array detector (SPE-HPLC-DAD). This method allowed for the determination and quantification of selected organophosphorus pesticides. The optimised method displays a high mean recovery for both quinalphos and diazinon (100.21 and 100.15 %, respectively) but relatively low recovery for chlorpyrifos (32.40 %). The low recovery of chlorpyrifos is due to limitations in the determination of multi-residues in a single analytical run, optimisation of chromatographic conditions and the recovery of each compound. The method detection limit was found to be 0.003 μg/L for quinalphos and diazinon, and 0.006 μg/L for chlorpyrifos. Sample analyses revealed the occurrence of quinalphos, diazinon and chlorpyrifos in the Langat River with chlorpyrifos found to have the highest mean concentration of 0.0202 μg/L. The quinalphos and diazinon sample concentrations were 0.0178 μg/L and 0.0094 μg/L, respectively. The concentrations of organophosphorus pesticides in this monitoring study were found to be below the Maximum Contaminant Levels (MCLs) established under the European Union (Drinking Water) Regulation 2014. This study was the first to detect concentrations of quinalphos and diazinon in the Langat River, Selangor.
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