Occupational exposure to pesticide mixtures comprising active substance(s) and/or co-formulant(s) with known/possible endocrine-disrupting activity was assessed using long-term activity records for 50 professional operators representing arable and orchard cropping systems in Greece, Lithuania, and the UK. Exposure was estimated using the harmonised Agricultural Operator Exposure Model, and risk was quantified as a point of departure index (PODI) using the lowest no observed (adverse) effect level. Use of substances with known/possible endocrine activity was common, with 43 of the 50 operators applying at least one such active substance on more than 50% of spray days; at maximum, one UK operator sprayed five such active substances and 10 such co-formulants in a single day. At 95th percentile, total exposure was largest in the UK orchard system (0.041 × 10-2 mg kg bw-1 day-1) whereas risk was largest in the Greek cropping systems (PODI 0.053 × 10-1). All five cropping systems had instances indicating potential for risk when expressed at a daily resolution (maximum PODI 1.2-10.7). Toxicological data are sparse for co-formulants, so combined risk from complex mixtures of active substances and co-formulants may be larger in reality.
Emerging pollutants known as endocrine-disrupting compounds (EDCs) are a contemporary global issue, especially in aquatic ecosystems. As aquaculture production through mariculture activities in Malaysia supports food production, the concentration and distribution of EDCs in estuarine water ecosystems may have changed. Therefore, this current study aims to prepare a suitable and reliable method for application on environmental samples. Besides, this study also presented the occurrence of EDCs pollutant in Pulau Kukup, Johor, where the biggest and most active mariculture site in Malaysia takes place. Analytical methods based on a combination of solid-phase extraction with liquid chromatography tandem mass spectrometry (Solid-phase extraction (SPE)-LC-MS/MS) have been modified and optimised to examine the level of targeted EDCs contaminant. In the current study, this method displays high extraction recovery for targeted EDCs, ranging from 92.02% to 132.32%. The highest concentration detected is diclofenac (<0.47-79.89 ng/L) followed by 17β-estradiol (E2) (<5.28-31.43 ng/L) and 17α-ethynylestradiol (EE2) (<0.30-7.67 ng/L). The highest percentage distribution for the targeted EDCs in the current study is diclofenac, followed by EE2 and dexamethasone with the percentages of 99.44%, 89.53% and 73.23%, respectively. This current study can be a baseline assessment to understand the pollution profile of EDCs and their distribution in the estuarine water of the mariculture site throughout the world, especially in Malaysia. Owing to the significant concentration of targeted EDCs detected in water samples, the need for further monitoring in the future is required.
The study was performed to examine the occurrence of endocrine disrupting chemicals (EDCs), including four steroid estrogens, one plasticizer, and three preservatives in the Mahakam River, Indonesia. The physicochemical analysis of river water and sediment quality parameters were determined as well as the concentration of EDCs. The range of values for pH, total dissolved solids (TDS), dissolved oxygen (DO), biochemical oxygen demand (BOD), total suspended solids (TSS), nitrate, ammonium, phosphate, and oil/grease in river water and sediment were higher than recommended limits prescribed by the World Health Organization's Guidelines for Drinking-water Quality (GDWQ). Bisphenol A (BPA) was the most widely found EDC with the highest concentration level at 652 ng/L (mean 134 ng/L) in the river water and ranged from ND (not detected) to 952 ng/L (mean 275 ng/L) in the sediment. Correlation analysis to investigate the relationship between the EDCs' concentrations in water and sediment also revealed a significant correlation (R2 = 0.93) between the EDCs' concentrations. High concentrations of EDCs are found in urban and residential areas because these compounds are commonly found in both human and animal bodies, resulting in the disposal of EDCs into canals and rivers in urban and suburban areas, as well as livestock manure and waste that is generated from intensive livestock farming around the suburban area.
Active pharmaceutical ingredients (APIs) are typical endocrine disruptors found in common pharmaceuticals and personal care products, which are frequently detected in aquatic environments, especially surface water treated for drinking. However, current treatment technologies are inefficient for removing emerging endocrine disruptors, leading to the potential contamination of tap water. This study employed an optimized analytical method comprising solid-phase extraction and liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) to detect APIs in tap water in Putrajaya, Malaysia. Several therapeutic classes of pharmaceuticals and personal care products, including anti-inflammatory drugs (dexamethasone and diclofenac), antibiotics (sulfamethoxazole and triclosan), antiepileptics (primidone), antibacterial agents (ciprofloxacin), beta-blockers (propranolol), psychoactive stimulants (caffeine), and antiparasitic drugs (diazinon), were detected in the range of
Online preconcentration using electrokinetic supercharging (EKS) was proposed to enhance the sensitivity of separation for endocrine disrupting chemical (methylparaben (MP)) and phenolic pollutants (2-nitrophenol (NP) and 4-chlorophenol (CP)) in water sample. Important EKS and separation conditions such as the concentration of BGE; the choice of terminating electrolyte (TE); and the injection time of leading electrolyte (LE), sample, and TE were optimized. The optimum EKS-CE conditions were as follows: BGE comprising of 12 mM sodium tetraborate pH 10.1, 100 mM sodium chloride as LE hydrodynamically injected at 50 mbar for 30 s, electrokinetic injection (EKI) of sample at -3 kV for 200 s, and 100 mM CHES as TE hydrodynamically injected at 50 mbar for 40 s. The separation was conducted at negative polarity mode and UV detection at 214 nm. Under these conditions, the sensitivity of analytes was enhanced from 100- to 737-fold as compared to normal CZE with hydrodynamic injection, giving LOD of 4.89, 5.29, and 53 μg/L for MP, NP and CP, respectively. The LODs were adequate for the analysis of NP and CP in environmental water sample having concentration at or lower than their maximum admissible concentration limit (240 and 2000 μg/L for NP and CP). The LOD of MP can be suitable for the analysis of MP exists at mid-microgram per liter level, even though the LOD was slightly higher than the concentration usually found in water samples (from ng/L to 1 μg/L). The method repeatabilities (%RSD) were in the range of 1.07-2.39% (migration time) and 8.28-14.0% (peak area).
The occurrence and estrogenic activities of steroid estrogens, such as the natural estrone (E1), 17β estradiol (E2), and estriol (E3), as well as the synthetic 17α-ethynylestradiol (EE2), were investigated in eight sampling points along the Langat River (Malaysia). Surface water samples were collected at 0.5 m and surface sediment 0-5 cm from the river surface. Instrument analysis of steroid estrogens was determined by UPLC-ESI-MS with an ultra-performance liquid chromatograph (Perkin Elmer FX15) coupled to a Q Trap function mass spectrophotometer (model 3200: AB Sciex). Steroid estrogen concentrations were higher in the Langat River sediments than those in its surface water. In surface water, E1 was not detected in any sampling point, E2 was only detected in two midstream sampling points (range 0-0.004 ng/L), E3 in three sampling points (range 0-0.002 ng/L), and EE2 in four sampling points (range 0-0.02 ng/L). E1 and E2 were detected in sediments from all sampling points, E3 in five sampling points, while EE2 only in one midstream sample (3.29E-4 ng/g). Sewage treatment plants, farming waste, and agricultural activities particularly present midstream and downstream were identified as potential sources of estrogens. Estrogenic activity expressed as estradiol equivalents (EEQs) was below 1 ng/L in all samples for both surface water and sediment, indicating therefore a low potential estrogenic risk to the aquatic environment. Although the health risks are still uncertain for drinking water consumers exposed to low levels of steroid estrogen concentrations, Langat River water is unacceptable for direct drinking purposes without treatment. Further studies of endocrine disruptors in Malaysian waters are highly recommended.
Endocrine disrupting compound (EDC) contamination in food is a global concern. Concerning potential environmental and human health exposed to EDCs via food intake, an experiment was conducted on the selected EDCs concentration in the mariculture fish, Trachinotus blochii (golden pomfret), Lutjanus campechanus (snapper), and Lates calcarifer (sea bass) at Pulau Kukup, Johor. Mariculture activity at Pulau Kukup involves active export of fishes to Singapore and Indonesia. The recovery of BPA (bisphenol A), 4OP (4-octylphenol), and 4NP (4-nonylphenol) were 61.54%-93.00%, 16.79%-17.13%, and 61.24%-71.49%, respectively. Relatively high concentration of BPA was recorded in T. blochii (0.322ng/g), followed by L. calcarifer (0.124ng/g) and L. campechanus (0.023ng/g). Furthermore, 4OP and 4NP were detected only in T. blochii at concentrations of 0.084ng/g and 0.078ng/g, respectively. The results of the present study provide insights on monitoring and managing mariculture activity in relation to environmental protection and food safety.
The presence and distribution of endocrine-disrupting chemicals (EDCs) in the mariculture fish from Pulau Kukup, Johor of Malaysia have been studied along with the impact on human health. Six different species of mariculture fish were collected, due to their high consumption in the Asian region-especially Malaysia, to assess their levels of EDCs. The highest concentration of EDCs detected in the muscle was dexamethasone (2.37-15.84 ng/g) and (0.77-13.41 ng/g), in the liver was dexamethasone (<2.54-43.56 ng/g) and progesterone (2.23-9.78 ng/g), and in the reproductive organ are dexamethasone (<2.54-37.23 ng/g) and caffeine (0.21-18.92 ng/g). The human health risk assessment in the current study suggested that there is no potential risk to the consumer because the hazard index was below 1 (HI
Endocrine disrupting compounds (EDCs) are an emerging environmental concern and commonly occur as a mixture of compounds. The EDC mixture can be more toxic than any single compound. The present study analyses EDCs in surface water in the case of an urban tropical river, the Langat River, using the multiresidue analytical method of solid phase extraction and liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS). The Langat River is used as a drinking water source and is treated for Malaysian drinking water supply. A total of 14 EDCs i.e. five hormones, seven pharmaceuticals, one pesticide, and one plasticizer were detected. Caffeine was observed to be highest at 19.33 ng/L, followed by bisphenol A and diclofenac at 8.24 ng/L and 6.15 ng/L, respectively. Using a conservative risk quotient (RQ) method, EDCs were estimated for having negligible risks under acute and chronic exposure (RQ
Endocrine-disrupting compounds (EDCs) such as hormones, pesticides, phenolic compounds, and pharmaceuticals compounds can cause adverse effects on humans, animals, and other living organisms. One of the largest mariculture areas situated in Pulau Kukup, Johor, Malaysia, is actively involved in exporting marine fish to other countries worldwide. This paper aims to provide baseline data on the level of EDC pollutants found in mariculture sediments in Malaysia since no reports have investigated this issue. Calculated samples recovered are between 50.39 and 129.10% at 100 ng/g spiking level. The highest concentration in the sediment samples was bisphenol A (0.072-0.389 ng/g dry weight) followed by diethylstilbestrol (<0.208-0.331 ng/g dry weight) and propranolol (<0.250-0.275 ng/g dry weight). Even though the concentrations of the targeted compounds obtained were low, their effects could become more evident longer term, which raises not only environmental health concerns but the potential risk to humans.
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
In the work presented here, photocatalytic systems using TiO2 and ZnO suspensions were utilized to evaluate the degradation of resorcinol (ReOH). The effects of catalyst concentration and solution pH were investigated and optimized using multivariate analysis based on response surface methodology. The results indicated that ZnO showed greater degradation and mineralization activities compared to TiO2 under optimized conditions. Using certain radical scavengers, a positive hole, together with the participation of hydroxyl radicals, were the oxidative species responsible for ReOH degradation on TiO2 whereas, the ZnO photocatalysis occurred principally via hydroxyl radicals. Some hitherto unreported pathway intermediates of ReOH degradation were identified using gas chromatography-mass spectrometry. A tentative reaction mechanism for the formation of these intermediates was proposed. Moreover, the figure-of-merit electrical energy per order was employed to estimate the electrical energy consumption.
A study on the quality of water abstracted for potable use was conducted in the Selangor River basin from November 2008 to July 2009. Seven sampling sites representing the intake points of water treatment plants in the basin were selected to determine the occurrence and level of 15 organochlorine pesticides (OCPs), six phthalate esters (PAEs) and bisphenol A (BPA). Results indicated OCPs were still detected regularly in 66.1 % of the samples with the Σ(15)OCPs ranging from 0.6-25.2 ng/L. The first data on PAEs contamination in the basin revealed Σ(6)PAEs concentrations were between 39.0 and 1,096.6 ng/L with a median concentration of 186.0 ng/L while BPA concentration ranged from <1.2 to 120.0 ng/L. Although di-n-butyl phthalate was detected in all the samples, concentrations of di-ethyl(hexyl)phthalate were higher. Sampling sites located downstream recorded the highest concentrations, together with samples collected during the dry season. Comparison of the detected contaminants with the Department of Environment Water Quality Index (DOE-WQI) showed some agreement between the concentration and the current classification of stream water. While the results suggest that the sites were only slightly polluted and suitable to be used as drinking water source, its presence is cause for concern especially to the fragile firefly "Pteroptyx tener" ecosystem located further downstream.
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.
Fishes are a major protein food source for humans, with a high economic value in the aquaculture industry. Because endocrine disrupting compounds (EDCs) have been introduced into aquatic ecosystems, the exposure of humans and animals that depend on aquatic foods, especially fishes, should be seriously considered. EDCs are emerging pollutants causing global concern because they can disrupt the endocrine system in aquatic organisms, mammals, and humans. These pollutants have been released into the environment through many sources, e.g., wastewater treatment plants, terrestrial run-off (industrial activities, pharmaceuticals, and household waste), and precipitation. The use of pharmaceuticals, pesticides, and fertilizers for maintaining and increasing fish health and growth also contributes to EDC pollution in the water body. Human and animal exposure to EDCs occurs via ingestion of contaminated matrices, especially aquatic foodstuffs. This paper aims to review human EDC exposure via fish consumption. In respect to the trace concentration of EDCs in fish, types of instrument and clean-up method are of great concerns.
This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).
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.
Steroid estrogens, such as estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethinylestradiol (EE2), are natural and synthetic hormones released into the environment through incomplete sewage discharge. This review focuses on the sources of steroid estrogens in wastewater treatment plants (WWTPs). The mechanisms and fate of steroid estrogens throughout the entire wastewater treatment system are also discussed, and relevant information on regulatory aspects is given. Municipal, pharmaceutical industry, and hospitals are the main sources of steroid estrogens that enter WWTPs. A typical WWTP comprises primary, secondary, and tertiary treatment units. Sorption and biodegradation are the main mechanisms for removal of steroid estrogens from WWTPs. The fate of steroid estrogens in WWTPs depends on the types of wastewater treatment systems. Steroid estrogens in the primary treatment unit are removed by sorption onto primary sludge, followed by sorption onto micro-flocs and biodegradation by microbes in the secondary treatment unit. Tertiary treatment employs nitrification, chlorination, or UV disinfection to improve the quality of the secondary effluent. Activated sludge treatment systems for steroid estrogens exhibit a removal efficiency of up to 100%, which is higher than that of the trickling filter treatment system (up to 75%). Moreover, the removal efficiency of advance treatment systems exceeds 90%. Regulatory aspects related to steroid estrogens are established, especially in the European Union. Japan is the only Asian country that implements a screening program and is actively involved in endocrine disruptor testing and assessment. This review improves our understanding of steroid estrogens in WWTPs, proposes main areas to be improved, and provides current knowledge on steroid estrogens in WWTPs for sustainable development.