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Distribution and Behavior of Nonylphenol, Octylphenol, and Nonylphenol Monoethoxylate in Tokyo Metropolitan Area: Their Association with Aquatic Particles and Sedimentary Distributions
Abstract
Distributions of alkylphenols (APs) [i.e., nonylphenol (NP), octylphenol (OP)], and nonylphenol monoethoxylate (NP1EO) in wastewater effluents, river water, and riverine and bay sediments in the Tokyo metropolitan area were demonstrated. During sewage treatments, NP and OP were efficiently removed from the sewage effluents through activated sludge treatments. Greater removal for NP (93% on average) than OP (84% on average) was consistent with their partitioning behavior to particles in primary and secondary effluents. NP concentrations in the river water samples ranged from 0.051 to 1.08 microg/L with higher concentrations in summer and spring than in colder seasons. In the river water samples, approximately 20% of NP was found in the particulate phase. Organic carbon-normalized apparent partition coefficients (K'OC) for NP (10(5.22 +/- 0.38)) and OP (10(4.65 +/- 0.42)) were 1 order of magnitude higher than those expected from their octanol-water partition coefficients (K(OW)), indicating strong affinity of APs to aquatic particles. Among NP isomers, no significant differences in their K'OC values were suggested. This is consistent with surprisingly uniform isomer peak profiles among the technical standard and all the environmental samples analyzed. NP and OP were widely distributed in the river sediments in Tokyo, and relatively high concentrations (0.5-13.0 microg/g dry) of NP were observed in a long reach (approximately 10 km) in the Sumidagawa River. In situ production of APs in the river sediment was suggested. Seaward decreasing trend in APs concentration was observed from the estuary to the Tokyo Bay. APs were well preserved in a sediment core collected from the bay. The profile shows subsurface maximum of AP concentrations in the layer deposited around the mid-1970s. The recent decrease in AP concentrations can be attributed to the legal regulation of industrial wastewater in the early 1970s.
... The problem is particularly pronounced in the soil of sewage irrigation and sludge utilization areas, with NP concentrations as high as 8.83-65.17 mg/kg (Kwak et al., 2017;Isobe et al., 2001;Liu et al., 2016). In view of that, the environmental behaviour of NP in soils needs more attention. ...
... However, in some focal areas that are frequently contaminated with NP, especially sewage irrigated areas, sludge utilisation areas and highly industrialised areas, NP concentrations can reach up to 8.83-65.17 mg/kg (Kwak et al., 2017;Isobe et al., 2001;Liu et al., 2016). Several additional studies have been conducted to investigate the environmental behavior of NP at concentrations ranging from 0.2 mg/L to 5 mg/L Xu et al., 2022;Milinovic et al., 2015). ...
... In the adsorption isotherm experiments, the NP stock solution was diluted to concentrations of 0.1, 0.2, 0.5, 1, 2 and 4 mg/L by 0.01 M CaCl 2 solution, which represent some of the priority areas that are frequently contaminated with NP (Kwak et al., 2017;Isobe et al., 2001;Liu et al., 2016). The experimental conditions were kept consistent to those used in the kinetic experiments. ...
In the soil environment, microplastics (MPs) commonly coexist with organic pollutants such as nonylphenol (NP), affecting the migration of NP through adsorption/desorption. However, few studies have focused on the interaction between NP and MPs in soil, especially for MPs of different types and ageing characteristics. In this study, non-polar polypropylene (PP) and polar polyamide (PA) MPs were aged either photochemically (144 h) or within soil (60 days), then used to determine the effect of 5 % MPs on the adsorption behaviour of NP (0.1-4.0 mg/L) in soil. Results showed that both ageing processes significantly promoted the conversion of-CH 3 groups to CO and CO on the surface of PPMPs, while PAMPs exhibited amide groups changes and a reduction in average particle size due to ageing. Additionally, both ageing processes promoted the adsorption of NP by soil containing PPMPs, due to an increase in oxygen-containing functional groups and specific surface area. In contrast, the NP adsorption capacity of soil containing PAMPs decreased by 15.4 % following photochemical ageing due to hydrolysis of amide groups, but increased by 21.15 % after soil ageing due to reorganization of amide groups, respectively. The soil-PAMPs systems exhibited a stronger affinity for NP compared to the soil-PPMPs systems, which was primarily attributed to the dominant role of hydrogen bonding. NP was found to be distributed mainly on soil particles in the soil-PPMPs systems, while it tended to be adsorbed by MPs in the soil-PAMPs systems, especially in the soil aged MPs system. This study provides a comprehensive analysis of the complex effects of MPs on coexisting pollutants in soil environments, highlighting the effect of MP characteristics on the adsorption of organic pollutants, which is essential for understanding the transport behaviour of organic pollutants.
... There was a strong evidence reported that suspended particles hold the EDCs stronger comparing to sediment particles (Bowman et al. 2002). However, the residue level of phenolic EDCs could be accelerated by in situ transformation from parent chain, alkylphenol ethoxylates as reported by Isobe et al. (2001). There are variety factors influencing the adsorption of OP and NP in the sediment however, in the present, we only focused on total organic carbon (TOC) content in the sediment. ...
... As reported by previous literatures, the Koc' values for OP and NP were calculated in the range of 3.60 -5.43 and 3.88 -6.10, respectively (Isobe et al. 2001;Ying et al. 2003;Burgess et al. 2005;Pojana et al. 2007;Navarro et al. 2009;Zhang et al. 2011b;Arditsoglou & Vousta, 2012;Pignotti & Dinelli, 2018). The highest Koc' ...
... value for OP was reported in Thermaikos Gulf, Greece (Arditsoglou & Vousta, 2012) whereas, for NP in Sumidagawa River, Japan (Isobe et al. 2001 (Yang et al. 2020). Moreover, external factors such as hydrodynamic processes governing the aquatic system could also potentially influence the Koc' value (Navarro et al. 2009;Yang et al. 2011). ...
This study comprises of three main objectives in order to determine the occurrence of selected phenolic endocrine disrupting chemicals (EDCs) in three rivers of Terengganu. The first objective was to determine the occurrence and distribution of EDCs in water, sediment and fish collected from the rivers. The second objective was to investigate the bioaccumulation and partitioning of EDCs in the environment and the third objective was to evaluate the implications of EDCs on ecological and human health through risk assessments. Two targeted EDCs, namely 4-octylphenol (4-OP) and 4-nonylphenol (4-NP) were determined in the surface water, sediment and fish collected in the three rivers of Terengganu. The concentration orders for 4-OP and 4-NP can be expressed as 4-OP > 4-NP (water), 4-NP > 4-OP (sediment) and 4-OP > 4-NP (fish). This suggests that the level of 4-OP prevalence in the surface water and fish, whereas 4-NP in the sediment. Therefore, bioaccumulation uptake of EDCs from water to fish (bioconcentration factor, BCF) and sediment to fish (biota-sediment accumulation factor, BSAF) were thoroughly investigated in the present study. Based on the BCF and BSAF values, the bioaccumulation uptake in fish was proved to accumulate higher from water compared to sediment. On the other hand, the partitioning of EDCs in the environment was evaluated through sediment-water partition coefficient (log Kd) and carbon-normalized partition coefficient (log Koc’). 4-OP and 4-NP were favorable to be deposited in the sediment due to higher log Kd values. From the log Koc’ data obtained, total organic carbon was not the main factor influencing the distribution of EDCs in the sediment of Terengganu. The implication of EDCs through ecological and human health was critically evaluated through derived assessments. Risk quotient (RQ) and estrogen equivalent concentration (EEQ) were evaluated to address ecological risk whereas, estimated daily intake (EDI) and hazard quotient (HQ) for human health risk assessments. Overall, no potential risk of EDCs was imposed on ecological and human health in the three rivers of Terengganu due to low calculated assessment values (RQ < 1, EEQ <1, EDI < 1 and HQ < 1).
... APs, BPA, and TCS were monitored in river water in Tokyo ~20 years ago (Isobe et al., 2001;Nakada, 2003;Nakada et al., 2006) and some regulations have been passed (Ministry of the Environment, 2012; Ministry of Health, Labor and Welfare, 2016). To see the temporal trend of contamination and to evaluate the effectiveness of countermeasures, it is important to monitor the current levels of EDC pollution. ...
... The results of NP, BPA, and TCS in the present study (2016 -2019) were compared with those in previous studies conducted ~20 years ago (Isobe et al., 2001;Nakada, 2003;Nakada et al., 2006). This comparison is shown in Fig. 4. The monitoring of NP in the Tamagawa River and the Sumidagawa River was conducted in 1997 (Isobe et al., 2001). ...
... The results of NP, BPA, and TCS in the present study (2016 -2019) were compared with those in previous studies conducted ~20 years ago (Isobe et al., 2001;Nakada, 2003;Nakada et al., 2006). This comparison is shown in Fig. 4. The monitoring of NP in the Tamagawa River and the Sumidagawa River was conducted in 1997 (Isobe et al., 2001). TR12, TR14, and TR16 in the Tamagawa River and SR01, SR02, and SR04 in the Sumidagawa River were the same sampling points as the previous research and the concentration levels of NP for the six locations are presented in Fig. 4 and Fig. S2. ...
To analyze a wide range of phenolic endocrine disrupting chemicals, including alkylphenols, bisphenol A (BPA) and its analogues, triclosan (TCS), thymol, and phenolic UV filters, a direct acetylation method has been developed and applied to 116 river water samples and 40 sewage treatment plant (STP) effluent samples collected in 2016–2019 in Tokyo, Japan. This method can simultaneously derivatize a range of target chemicals to inert acetylates at an early stage in the analytical procedure. In this study, nonylphenol concentrations in the Tamagawa River (median 5.7 ng/L) and the Sumidagawa River (median 13.4 ng/L) were one order of magnitude lower than those 20 years ago. Similarly, the TCS and BPA concentrations (median 27.0 ng/L and 11.0 ng/L, respectively) decreased by ~80% compared to the values obtained in studies conducted ~20 years ago. These decreases can be attributed to reduced production due to the establishment of environmental standards and industrial self-regulation. Most target chemicals had higher concentrations in the STP effluents than in river water, indicating that STP effluents are major sources of the chemicals. However, BPA in the Tamagawa River exhibited a different spatial pattern. Namely, BPA concentrations in the STP effluents (~5 ng/L) in the middle and lower reaches were lower than those in the receiving water (~15 ng/L). Meanwhile, effluents from two upstream STPs had extremely high BPA concentrations of up to 158 ng/L, revealing effluents from these STPs as major sources of BPA in the Tamagawa River. There are several landfills in the upstream STP catchment area, and their leachate is likely to contribute to the high concentrations of BPA in the STP effluents and river water. This is consistent with the composition of BPA and its alternatives, including BPAP, BPZ, BPS, BPB, BPE, BPF, BPAF, in the effluents from the STPs. The upstream STPs showed a predominance of BPA, whereas the alternatives, such as BPS and BPF, were dominant in the STPs in the middle and lower reaches. The compositional difference can be ascribed to the recent replacement of BPA with alternatives and BPA leaching from plastic products dumped in the 1980s and 1990s.
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... EDCs enter the environment primarily through anthropogenic activities, and the occurrence, distributions, and fates of EDCs in aquatic environments have been reported worldwide (Ying et al., 2002a(Ying et al., , 2002bLangston et al., 2005;Barber et al., 2015;Im and L€ offler, 2016). The association between EDCs and suspended particulate matter (SPM) and/or sediment is a dominant geochemical control on the fate of EDCs in rivers and is primarily governed by the organic carbon (OC) contents of the sorbents (Lai et al., 2000;Isobe et al., 2001;Gong et al., 2012Gong et al., , 2016. Other important biogeochemical processes, such as biosorption and the accumulation of EDCs by plankton, have also been identified recently Staniszewska et al., 2015). ...
... Generally, EDCs were ubiquitous in the aquatic environment. High concentrations of NP were found in all samples, and they were 1e2 orders of magnitude higher than OP concentrations, which is consistent with previous reports (Isobe et al., 2001;Gong et al., 2012). Besides the EDC concentrations in this investigation were comparable with those in related reports on the Pearl River Delta (Peng et al., 2017;Gong et al., 2016), indicating that the basin is severely polluted with phenolic compounds, including APs (OP and NP) and BPA. ...
... The extensive accumulation of APs in sediments may also have been related to in-situ formation from precursors such as alkylphenol ethoxylates. For example, the transformation of nonylphenol ethoxylates to NP was found to be responsible for the higher sedimentary NP observed in a Japanese River (Isobe et al., 2001). The opposite trend was found for BPA logK d values, which exhibited the following trend: algae/water > SPM/water > sediment/water. ...
The occurrence and distributions of selected endocrine-disrupting chemicals (EDCs), along with related environmental factors, were investigated in two rivers and six reservoirs in the Pearl River Delta. The vertical profiles of aqueous 4-tert-octylphenol (OP), 4-nonylphenol (NP), and estrone (E1) were constant, with little change in concentration between the surface and the river bottom, while higher aqueous concentrations of bisphenol A (BPA) were found in the bottom layers of the rivers. OP and NP in suspended particulate matter (SPM) were transferred from the surface to the bed layer, ultimately accumulating in the sediment. However, the particulate profiles of BPA and E1 both featured increases from the surface to the bottom layers and attenuation in the river bed. Dissolved oxygen (DO), water temperature, and pH were negatively correlated with the EDC concentrations, and negative relationships between DO and distribution coefficient (Kd) values for OP and NP were found as well. This indicated that these environmental parameters were primarily responsible for the EDC vertical distribution and SPM-water partitioning in the rivers. Positive relationships were observed between chlorophyll a and EDCs in the particulate phase, and the algae/water Kd values for EDCs in reservoirs were comparable to the SPM/water and sediment/water Kd values from the rivers. These results suggest that algae played an important role in regulating the distribution of EDCs in surface waters. Moreover, relationships between UV absorbance and EDCs revealed that π-π interactions were among the dissolved organic carbon (DOC)-EDC binding mechanisms and that DOC fractions with higher degrees of aromaticity and humification possessed higher affinities towards EDCs.
... The occurrence of OP and NP has been reported in the river sediment of China (Wu et al., 2013;Zhong et al., 2017), Germany (Bolz et al., 2001;Micić & Hofmann, 2009), Japan (Isobe et al., 2001;, and Korea (Li et al., 2004). The occurrence was also reported in the marine sediment in China (Duan et al., 2014), Korea (Khim et al., 1999), Spain (Gorga et al., 2014;Salgueiro-González et al., 2015), Taiwan (Dong et al., 2015), and USA (Kannan et al., 2001(Kannan et al., , 2003. ...
... The residue concentrations are generally high in sediments due to the stability and long half-life of these EDCs (Isobe et al., 2001). Benthic communities could be directly impacted by the deposition of OP and NP in the sediments. ...
Sediment is the ultimate reservoir of effluent from landmasses. This includes octylphenol (OP) and nonylphenol (NP), two chemical compounds which are known with the ability to disrupt the normal functions of hormones in the organism. To our knowledge, no study of these compounds in the marine sediment of Malaysia has been published to date. Hence, this study presents the level of OP and NP in the sediment of the South China Sea and Malacca Strait, Malaysia. The extraction of compounds was done using the liquid–liquid extraction method and followed by clean-up using solid-phase extraction cartridges. The range of OP in Malacca Strait (1.00–27.16 ng/g dw) was greater than in the South China Sea (5.12–14.16 ng/g dw) whereas a similar range of NP was found in the South China Sea (1.32–23.76 ng/g dw) and Malacca Strait (0.79–27.59 ng/g dw). The concentration of both compounds was consistently high near Redang Island (E2A) and Penang (W32 and W43) suggesting continuous input of these chemicals from this nearby land. Risk quotient (RQ) values of OP showed the potential risk to benthic communities in 4/7 and 21/47 sampling points of the respective South China Sea and Malacca Strait. Both water bodies are located far from the wastewater effluent and yet able to retain these chemicals in their sediment. This suggests that the wastewater treatment system as well as dilution effects do not prevent these chemicals to be ended up in the marine environment.
... The concentrations of APEOs around 45 lg L −1 and up to 3970 ng g −1 were detected near treatment plants and in the sediments. One of the important metabolites of APEOs is 4-nonylphenol (NP), the NP and octylphenol (OP) which showed more toxicity and more persistent properties than of APEOs; therefore, concern has arisen and many studies in Spain, Japan, Germany, USA and Canada found the concentrations of NPS in river water up to 17.5 lg L −1 (Bennie et al. 1997;Buxton and Kolpin 2005;Isobe et al. 2001;Céspedes et al. 2008). ...
... Sorption is one of the processes that affect the fate of APEs in water. Their association with aquatic particles is well documented in the rivers and coastal environments and analyzed, for example, NP in water of Tokyo, and the concentrations ranged between 0.051 and 1.08 µg L −1 ; however, about 20% of NP was found in solid particles in the aqueous environment (Isobe et al. 2001). Ekelund et al. (1993) reported that the half-life of NP after biodegradation was 58 days in seawater and 35 days in aerobic water with sediment. ...
Detergents are water-soluble chemical cleaning agents which remove impurities and dust, and are made up of major chemical components i.e. surfactants, builders and additives. Detergents have emerged as major water pollutants that enter water bodies and food chain and therefore, can be hazardous to humans and other organisms. Detergent residues in water bodies come from residential areas (household detergents), runoff water of agricultural areas (herbicides and insecticides) and industrial effluents. The fundamentals on pretreatment and analysis of surfactants using various analytical approaches are discussed in detail in this chapter. In addition, levels of concentration of detergents and their degradation pathways in river, streams and lakes are also reviewed. It can be concluded that detergents are hazardous water pollutants and their components readily interfere with biological processes and therefore represents a highly toxic group of pollutants posing considerable toxicity to all aquatic organisms. It is, therefore, essential to develop accurate analytical procedures for qualitative and quantitative determination of detergents and their primary components and consequently their impact on organisms in the biosphere.
... The concentrations of APs in sediments tended to decrease from the inner to outer regions of the bay (Fig. 2c). This result is similar to previous studies showing a seaward decrease of APs in the sediments in the coastal area (Isobe et al., 2001). At river and creek sites, the greatest concentration of ΣAPs was detected at the C2 and C1 sites. ...
... In this study, the ratio of ST1/SD3 in the sediments of Ulsan Bay showed similar results to those of SDs/STs, indicating that there were fresh inputs of SOs at the sites C2 and U4 (Fig. S3). Finally, assuming that APs are produced through the degradation of APEOs after being introduced to the coastal environment, we evaluated whether there was a fresh influx of APs based on the ratios of APs and APEOs (Isobe et al., 2001). In brief, if the APEOs/ APs ratio exceeds 1, it would indicate a fresh influx of pollutants in the given site. ...
Contamination status of traditional and emerging persistent toxic substances (PTSs) in sediments and their major sources were investigated in Ulsan Bay, Korea. A total of 47 PTSs, including 15 traditional PAHs, ten styrene oligomers (SOs), six alkylphenols (APs), and 16 emerging PAHs (E-PAHs) were analyzed. Concentrations of traditional PAHs, SOs, and APs ranged from 35 to 1300 ng g⁻¹ dry weight (dw), 30 to 3800 ng g⁻¹ dw, and 30 to 430 ng g⁻¹ dw, respectively. For the last 20 years, PTSs contamination in the bay area has been improved. However, 12 E-PAHs were widely detected in sediments, with a maximum of 240 ng g⁻¹ dw (for benzo[e]pyrene) at the creek site. These E-PAHs seemed to originate from surrounding activities, such as biomass combustion, mobile sources, and diesel combustion. Due to environmental concerns for E-PAHs, further research on the potential toxicity, distribution, and behavior of these compounds should be implemented.
... NP concentrations in river water and sediments were 0.051 to 1.08 µg l -1 and 0.5 to 13 µg g -1 (dry weight), respectively. 210 Partitioning to particulates is preferential to NP over OP, which is explained by their hydrophobic character. A lack of oxygen in sediment has been shown to reduce the degradation rate of NP by half. ...
... A lack of oxygen in sediment has been shown to reduce the degradation rate of NP by half. 211 There is evidence of anaerobic degradation of NP 1 EO to NP in the whole sediment layer, 210 which has implications to benthic organisms. Sediment has been shown to sorb larger quantities of OP when the TOC content of clay and silt particles are high. ...
... Most of these studies focus on the SOC accessibility within the subsoil in the context of SOC stabilization but reduced SOC inaccessibility may also affect pollutant sorption processes. Since subsoils control the release of pollutants to groundwater systems (Isobe et al., 2001;Sepehrnia et al., 2018), the role of sorption processes of organic and hydrophobic pollutants to subsoil SOM are important in for risk assessments. For example, the SOM controlled hydrophobic sorption mechanisms could be affected by SOC occlusion and thus reduce the retention potential for hydrophobic pollutants in subsoils. ...
... In the past, NPEOs were used as domestic detergents, dispersing agents, and industrial as well as institutional cleaners (Berryman et al., 2004;Shao et al., 2005). Thus, NP was often detected in different environmental media such as water, sediments, sludge, biota, and soils (Heemken et al., 2001;Isobe et al., 2001). Since NP has an endocrine disrupting and carcinogenic potential (Roberts et al., 2006), it is included in the priority hazardous substance list of the European Union (Liao et al., 2014). ...
Subsoils control the release of hydrophobic pollutants to groundwater systems, but the role of subsoil soil organic carbon (SOC) in sorption processes of hydrophobic organic pollutants remains unclear. Thus, this study aimed to understand the role of subsoil SOC in sorption processes of 4-n-nonylphenol (NP) and perfluorooctanoic acid (PFOA) as model pollutants. To characterize the sorption behavior of NP and PFOA, 42 sub- and 54 topsoil samples were used for batch experiments. Differences in NP and PFOA sorption between sub- and topsoil samples and its mechanisms were identified using multiple regression analysis. Generally, the sorption of NP and PFOA was linear in all samples. The sorption of NP to soil samples (logKD = 1.78–3.68) was significantly higher and less variable than that of PFOA (logKD = −0.97–1.44). In topsoils, SOC content had the highest influence on NP and PFOA sorption. For NP, hydrophobic interactions between NP and SOC were identified as the most important sorption mechanism. For PFOA, hydrophobic as well as electrostatic interactions were determined depending on soil pH. In subsoils, the relevance of SOC content for pollutant sorption decreased drastically. For NP, not SOC content but rather SOC quality was relevant in SOC poor subsoils. For PFOA, clay and iron oxide content were found to be relevant for pollutant interactions with the solid phase. Thus, especially in SOC depleted subsoils, the sorption potential for PFOA remained unpredictable.
... The carbon normalised sediment-water partition coefficient (K oc ) was used for evaluating the capability of branched 4-APs and BPA to be absorbed by sediment from seawater (Isobe et al., 2001;Pojana et al., 2007). It can be calculated according to the following equation: ...
... for BPA (mean ¼ 3.8 ± 0.15). These parameters are in agreement with those reported in previous studies (Isobe et al., 2001;Pojana et al., 2007). As expected, the log K oc values decreased with increasing polarity (BPA<4-tOP < NP) (Navarro-Ortega et al., 2010;Xu et al., 2018). ...
The spatial and temporal distribution of selected endocrine disrupting compounds (4-tert-octylphenol, 4-n-octylphenol, 4-n-nonylphenol, nonylphenol, and bisphenol A) in two coastal areas of the Iberian Peninsula (Ria de Vigo and Mar Menor lagoon) were evaluated for the first time. Seawater and sediment samples collected during spring and autumn of 2015 were analysed using greener extraction techniques and liquid chromatography-tandem mass spectrometry. The presence of branched isomers (4-tert-octylphenol and nonylphenol) and bisphenol A in almost all seawater and sediment samples demonstrated their importance as pollutants in the frame of water policy, while no concentrations of linear isomers (4-n-octylphenol and 4-n-nonylphenol) were found. Higher seawater levels were observed in Mar Menor lagoon, especially in spring, associated with wastewater treatment plant effluents and nautical, agricultural and industrial activities. Similar sediment concentrations were measured in both studied areas, being nonylphenol levels five times higher than those measured for the other EDCs. Experimental sediment–water partition coefficients showed a moderate sorption of target compounds to sediments. Risk quotients for water compartment evidenced a moderate risk posed by nonylphenol, considering the worst-case scenario. For sediments, moderate risk related to 4-tert-octylphenol and high risk to nonylphenol were estimated. Occurrence, distribution and environmental impact of selected endocrine disrupting compounds in marine environment.
... Where C w is the concentration of the estrogen in water (ng/ l); C s is concentration of the estrogen in sediment (ng/kg); f oc is the organic carbon fraction in sediment (%); K p is the sediment-water partition coefficient (l/kg). K oc is the partition coefficient at laboratory conditions, and is predicted according to the model reported in previous studies (Gong et al. 2012;Isobe et al. 2001) as follows: ...
... It was further supported by the poor linear correlations between logK ow and logK oc for eight estrogens (summer: r = 0.21, p = 0.63; winter: r = 0.10, p = 0.81). This result agreed with the previous studies in the estuary from Jamaica Bay (Ferguson et al. 2001), North Tai Lake (Zhang et al. 2014a), Rivers from Tianjin Area (Lei et al. 2009) and Tokyo metropolitan area (Isobe et al. 2001). There are some possible explanations for this result. ...
Estrogens have been widely detected in water and might pose a potential threat to the aquatic ecosystem. However, little information is available about the occurrence, multi-phase fate and potential risks of estrogens in Hanjiang River (HR). In this work, the concentration, multi-phase distribution and risk assessment of eight estrogens were studied by investigating surface water and sediment samples from HR during two seasons. These samples were analyzed using the solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (LC-MS). The concentrations of eight estrogens were 4.5–111 ng/l in surface water and 1.7–113 ng/g dry weight in sediments. 4-nonylphenol (NP) was the predominant estrogen in both water and sediments. The estrogens showed significantly spatial variability, with the highest average concentration in the lower section of HR (p < 0.01, F > 12.21). Meanwhile, NP, 17α-estradiol (αE2), Bisphenol A (BPA) and 4-tert-octyphenol (OP) in surface water exhibited higher concentrations in summer than in winter (p < 0.05, F > 4.62). The sediment-water partition coefficients of estrogens suggested that these compounds partitioned more to particulate phase. Risk assessment indicated that estriol (E3) was the main contributor to the total estradiol equivalent concentration. Moreover, estrogen mixtures could pose high ecological risks to aquatic organisms in surface water. Overall, estrogens are ubiquitous in HR, and their potential ecological risks should not be neglected.
... In the case of water samples with low-suspended solid materials (SSM) (≤1 g/L), PAEs can be extracted through SPE without any prior filtration [29]. However, when dealing with higher levels of SSM, pre-filtration becomes essential, which may result in potential errors up to a 20% inclination of the total PAE concentration due to the contamination risks [30]. Commercial SPE cartridges are not the only option for use as the extractant in SPE. ...
Phthalates (PAEs) are a group of synthetic esters of phthalic acid compounds mostly used as plasticizers in plastic materials but are widely applied in most industries and products. As plasticizers in plastic materials, they are not chemically bound to the polymeric matrix and easily leach out. Logically, PAEs should be prevalent in the environment, but their prevalence, transport, fate, and effects have been largely unknown until recently. This has been attributed, inter alia, to a lack of standardized analytical procedures for identifying them in complex matrices. Nevertheless, current advancements in analytical techniques facilitate the understanding of PAEs in the environment. It is now known that they can potentially impact ecological and human health adversely, leading to their categorization as endocrine-disrupting chemicals, carcinogenic, and liver- and kidney-failure-causing agents, which has landed them among contaminants of emerging concern (CECs). Thus, this review article reports and discusses the developments and advancements in PAEs’ standard analytical methods, facilitating their emergence from obscurity. It further explores the opportunities, challenges, and limits of their advancements.
... Some organic substances are known to be affected by temperature changes; e.g. Manzano et al. (1999) found a correlation between the increased temperature and biodegradation of nonylphenol ethoxhylates in water, and increased temperature was suggested to facilitate conversion of nonylphenol ethoxylates to nonylphenols (Isobe et al., 2001). ...
Urban runoff is a significant pathway for the transport of diverse substances from the urban environment to receiving water bodies. Many of these substances are pollutants of environmental concern with potentially harmful effects on aquatic life. Detailed knowledge of the sources of pollutants entering stormwater runoff is needed to mitigate these effects.The overall aim of this doctoral thesis is therefore to provide new knowledge on the sources contributing to urban runoff pollution and to evaluate the specific contributions of micropollutants from two known major sources: building and structure surface materials, and vehicular activities. The work presented herein also (i) identifies pollutants that are expected to occur in runoff from buildings and other structure surfaces in the urban environment as well as in runoff from the road environment, (ii) estimates the concentrations of these pollutants released into runoff, and (iii) evaluates methods for identifying sources contributing to the pollution of urban stormwater runoff.
The novel work presented in the thesis includes a critical review of the literature on sources contributing to urban runoff pollution, laboratory leaching tests and open-air sampling of pilot panels of building and structure surface materials, and field sampling of urban roadside snow. The literature review was not restricted in terms of type of pollution, while the experiments focused on selected metals and organic micropollutants including phthalates, alkylphenols, bisphenol A, and polycyclic aromatic hydrocarbons (PAHs).
According to the literature review, atmospheric deposition, vehicular activities, and metallic building envelopes are the major pollution sources in the urban environment and have been studied far more extensively than other sources. Moreover, their dominance is likely to continue given their central roles in urban environments. The experimental results confirmed that vehicular activities were sources of octylphenols, bisphenol A, and phthalates as well as the metal(loid)s Sb and W, both of which were rarely determined in previous studies on urban runoff. Building and structure surface materials such as copper sheets, zinc sheets, and polyvinyl chloride (PVC) roofing membranes were found to release Cu, Zn, nonylphenols, and phthalates. Among alkylphenols, nonylphenols were predominantly found in building surface runoff while octylphenols occurred predominantly in roadside snow. Metals occurred more commonly in dissolved (<0.45 μm) form in building surface runoff than in roadside snow, where metals were mainly attached to particles.
A comparison of methods for identifying building surface materials contributing to runoff pollution showed that laboratory leaching tests were generally effective for source identification but not for estimating concentrations in actual runoff, whereas open-air pilot studies were resource-intensive but give results that agree well with analyses of real runoff. In addition, the release of pollutants from building surface materials subjected to in-situ ageing was investigated and the water quality of rainwater-induced runoff was compared to that of snowmelt-induced runoff; neither of these issues were adequately addressed in the previous literature. These studies showed that pollutant concentrations were generally higher in rain runoff than in snowmelt runoff and that pollutant releases from most materials and substances exhibited no decreasing or increasing trend over time. However, the release of nonylphenols from one of the PVCs did decrease over time, possibly because of washing out and material ageing.
... In addition, similar to other endocrinedisrupting chemicals (EDCs), most PAEs are hydrophobic (Net et al., 2015) and thus can exist in different aquatic phases, such as the dissolved water phase and the suspended particulate matter (SPM) phase (Qin et al., 2014;Tremblay et al., 2005). Researchers have elucidated that the sorption of EDCs onto aquatic particles has considerable impacts on their transportation and fate in the environment as well as their bioavailability and toxicity toward organisms (Isobe et al., 2001;Suffet et al., 1994). SPM in the aquatic environment is, therefore, crucial for the interlocking of EDCs within water, sediment, and food webs (Yang et al., 2016). ...
Phthalate esters (PAEs) are representative additives used extensively in plastics. In this study, 15 PAEs were investigated at the eight riverine outlets of the Pearl River Delta (PRD). The total concentrations of Σ15PAEs, including both the dissolved and particulate phases, ranged from 562 to 1460 ng/L and 679 ng/L-2830 ng/L in the surface and bottom layers, respectively. Dibutyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) dominated in the dissolved and suspended particulate matter (SPM) phases, respectively, accounting for >50 % and > 80 % of Σ15PAEs. Riverine input of wastewater from the PRD was possibly the primary source of the contamination. Higher levels of PAEs occurred at the eastern outlets than at the western ones. The dissolved and particulate PAEs varied seasonally, with significantly higher concentrations observed in the dry season than in the wet season. However, no significant differences of PAE levels in both phases were observed among low, medium, and high tides. The partitioning results demonstrated that SPM is important in the transportation of pollutants in estuaries, where more hydrophobic DEHP was predominantly transported by the SPM phase, while those more hydrophilic ones were regularly transported by the dissolved phase. The total annual flux of Σ15PAEs through the eight outlets to the SCS reached 1390 tons.
... Thus, NP is commonly found in higher concentrations in sediments than in aquatic environments (Brix et al., 2010;Soares et al., 2008). In addition, previous studies have shown that NP is persistent in sludges (Isobe et al., 2001;Marcomini et al., 2000;Shang et al., 1999) and that the distribution of pollutants in rivers' sediments are also related to some properties like organic carbon and the particle size distribution (Chokwe et al., 2017). NP is expected to be adsorbed into sediments due to its physicochemical properties, in particular its high K ow values (3.9-4.48) ...
Nowadays, water pollution represents a great concern due to population growth, industrialization, and urbanization. Every day hazardous chemical products for humans and aquatic organisms are disposed of arbitrarily from homes and industries. Even though detergents are considered an essential market, there is evidence of environmental impacts caused by surfactants like nonylphenol ethoxylate (NPE) and linear alkylbenzene sulfonates (LAS). Regulations about maximum allowable concentrations in sewage, surface water, and drinking water are scarce or null, mostly in developing countries like Latin American countries. Therefore, this review explores these two common toxic surfactants (NPE and LAS) and proposes a technological, innovative, and ecological perspective on detergents. Also, it establishes a starting point for industries to minimize adverse effects on humans and environmental health caused by these compounds.
... The K oc of NP in irrigated soil was 7.56 × 10 4 L·kg −1 in this study (Table 3), which was similar to the study on other agricultural soils with a similar magnitude of 10 3 -10 4 [56,57]. Likewise, the K oc of NP adsorbed in the sediments and suspended particles has an equal magnitude to that in this study, which was 10 4 -10 5 L·kg −1 [39,[58][59][60]. The adsorption of NP on soil is not only related to the organic matter [39], but also depends on the structures of the isomers. ...
Nonylphenol (NP) and bisphenol A (BPA) are two typical endocrine disrupter chemicals (EDCs) in reclaimed water. In this study, the adsorptions of NP, a branched NP (NP7) and BPA on reclaimed water-irrigated soils were studied by isothermal experiments, and the different environmental factors on their adsorptions were investigated. The results showed that the adsorptions of NP and NP7 on soils conformed to the Linear model, and the adsorption of BPA conformed to the Freundlich model. The adsorptions of NP, NP7 and BPA on soils decreased with increasing temperatures and pHs. Adsorption equilibrium constant (Kd or Kf) were maximum at pH = 3, temperature 25 °C and As(III)-soil, respectively. The adsorption capacity of NP, NP7 and BPA to soils under different cation valence were as follows: neutrally > divalent cations > mono-cations. Kd of NP7 on soil was less than that of NP under different pH and temperatures, while under different cation concentrations it was the inverse. Fourier Transform Infrared Spectrometer (FTIR) analysis showed alkyl chains of NP and BPA seemed to form van der Waals interactions with the cavity of soil. Results of this study will provide further comprehensive fundamental data for human health risk assessment of NP and BPA in soil.
... ng/L, respectively (Wang et al., 2012;Niu and Zhang, 2018). The concentration level is equivalent to that in Sumidagawa River (Japan, 50-1080 ng/L) (Isobe et al., 2001) and Glatt River (Switzerland, < 30-480 ng/L) (Ahel et al., 2000), and it is significantly lower than that in main rivers of the UK (up to 53, 000 ng/L) (Blackburn and Waldock, 1995). NP has a wide range of applications in detergent synthesis, papermaking, etc. ...
Due to the extensive use and pseudo-persistence of pharmaceuticals and personal care products (PPCPs), they are frequently detected in the aqueous environment, which has attracted global attention. In this paper, accumulation data of 81 PPCPs in surface water or sediment in China were reported. In addition, 20 kinds of PPCPs with high frequency were selected and their ecological risk assessment was conducted by risk quotient (RQs). The results indicated that the concentration detected in surface water and sediment ranged from ng/L (ng/kg) to μg/L (μg/kg) in China, which was similar to concentrations reported globally. However, contamination by certain PPCPs, such as caffeine, oxytetracycline, and erythromycin, was relatively high with a maximum concentration of more than 2000 ng/L in surface water. RQs revealed that 14 kinds of PPCPs pose no significant risk or low risk to aquatic organisms, while 6 kinds of PPCPs pose a high risk. Additionally, the pollution characteristics of PPCPs in each watershed are different. The Haihe River watershed and the central and lower Yangtze River were the regions of high concern for erythromycin. Triclosan has potential risks in the Pearl River watershed. This study determined the occurrence and risk of PPCPs in China in the past decade, providing a scientific basis for PPCPs pollution control and risk prevention.
... It has been shown to stay in biologically active state for a longer period of time in the body than that of natural estrogen (Montgomery-Brown and Reinhard, 2003). The estrogenic activity of nonylphenol is three times higher than that of DDT and causes deformities and reproductive problems in wildlife (Sharma and Fekete, 2005;Blackburn et al., 1999;Isobe et al., 2001). ...
Toxic chemical contaminants released from industrial, agricultural, and municipal sources continues to threaten aquatic ecosystems. Aquatic ecosystems act as the final sinks accumulating and transporting numerous chemicals such as octylphenol (OP), nonylphenol (NP) and bisphenol-A (BPA). These chemicals are undesirable as they have been reported to possess endocrine disrupting properties. This study therefore assessesthe distribution and bioaccumulation of endocrine disrupting chemicals (EDCs) in Lagos Lagoon. Water and sediment samples were collected at nine different locations on the lagoon. Five different species of fishes were also collected, identified and homogenized prior to sample pre-treatment. Samples were extracted, clean-up, derivatized and analysed by gas chromatography–mass spectrometry. Physicochemical properties of the samples were also determined. In the water samples, BPA was not detected in all the samples collected at the different locations while the concentrations of NP and OP ranged from ND-102 ng/L and ND-127 ng/L, respectively. The concentrations of the targeted compounds in the sediment samples ranged from ND- 5.08 μg/g BPA, ND-1.90 μg/g NP, and ND- 2.51 μg/g OP while the concentrations ranged from ND-1139 ng/g BPA, ND-476 ng/g NP, and ND-643 ng/g OP in the fish samples. This study revealed the occurrence of EDCs in Lagos lagoon water and their accumulation in biota therein, which can have detrimental effects on other organisms across the food chain. Thus, the need to monitor these endocrine disrupting chemicals is imperative. Keywords: EDCs; BPA; OP; NP; Lagos lagoon
... Fresh inputs of APs were evaluated based on the ratios of degraded chemicals (OP: octylphenol and NPs: nonylphenols) and fresh chemicals (OPEOs: octylphenol ethoxylates and NPEOs: nonylphenol ethoxylates) (Fig. 3c) (Isobe et al., 2001). Fresh inputs of OP were confirmed in February, April, and June. ...
We investigated the sedimentary pollution by persistent toxic substances (PTSs) and their potential impacts on the macrobenthic faunal community in the Geum River Estuary, South Korea. Sediment and benthic macrofauna samples were collected from eight sites every two months during the period of February to December in 2015. Target PTSs encompassed metals (Cd, Cr, Cu, Hg, Ni, Pb, and Zn), one metalloid (As), polycyclic aromatic hydrocarbons (PAHs), and alkylphenols (APs). The significant difference to the environment of the inner and outer parts of the estuary (p < 0.05) was found with relatively high concentrations of PTSs in sediment from the inner estuary. The concentrations of Cu and Zn exceeded the sediment quality guidelines of Korea representing a potential risk to aquatic organisms. The primary source of PAHs was by-products of diesel and gasoline combustion (37%), followed by a coke oven (32%) and oil-burning (31%). The macrofaunal community was spatially distinguished between the inner and outer parts of the estuary (p < 0.05), regardless of the season. In the inner part of the estuary, the density of the macrofaunal community was high, due to the increased opportunistic species and/or some indicator species (organic polluted or enrichment), implying that the given environment was disturbed. Among the environmental parameters analyzed by the distance-based linear model (DistLM), salinity, chlorophyll-a, and nutrient concentrations were found to be key factors controlling the changes in macrofaunal community structure. Such changes in the closed estuary system would indicate that each taxonomic group had to adjust to lower salinities and alternative food sources. Overall, the distribution of PTSs and macrozoobenthic communities in the Geum River Estuary collectively reflected the environmental gradients caused by surrounding activities in the inner part of the estuary together with direct effects by the irregular inflow of freshwater.
... NP and BPA mainly drain into water through industrial wastewater discharge, and developed cities may exhibit high levels of contamination [16,17]. The high hydrophobicity of NP and BPA allows them to be easily deposited in sludge after draining into water, and their long half-lives under anaerobic sediment make them difficult to degrade (mean halflife of 301 days for NP and little or no degradation of BPA within 70 days) [18][19][20][21][22]. The observation of NP in aquatic microcosms demonstrates that the sediment is the key sink of NP deposition. ...
Sediment cores were collected from four outlets in the Pearl River Estuary (Guangdong Province, China) and dated using the 210Pb method to investigate the pollution history of the area due to its relatively stable sedimentation status and hydrographic conditions in recent decades. The ages of the sediment cores were dated over 40 years (1968–2015). The concentrations at the four outlets ranged from 2.21 to 48.52 ng g−1 dw for nonylphenol and were non-detectable for 23.64 ng g−1 dw for bisphenol A (BPA), which exhibited a decreasing trend from north to south as well as seaward. The fluxes (2.84 to 112.91 ng cm−2 yr−1 and non-detectable to 59.33 ng cm−2 yr−1 for nonylphenol and bisphenol A, respectively) stabilized in the 1980s to 1990s due to the construction of sewage treatment systems. The fluxes increased again in the 21st century, which reached a peak ca. 2010 but declined in recent years due to the establishment of regulations and the decreasing number of industrial enterprises. Fluctuations in the pollution composition coincided with industrial development and governmental policies.
... Octylphenol polyethoxylates were not among the reference materials but are listed as components of AFFFs. 10,16 Octylphenol polyethoxylates persist in other environments including sediments, 62 surface waters including the Great Lakes, 63 river waters, 64 and estuaries; 62 as well as in municipal wastewaters. 60,65,66 Linear alcohol ethoxylates were detected in 4 of 10 groundwaters (sites G, H, I, and J; Table 2). ...
Aqueous film forming foams (AFFFs) are proprietary mixtures containing hydrocarbon surfactants and per-and polyfluoroalkyl substances (PFASs) that are used to extinguish hydrocarbon-based fuel fires. There is limited information on hydrocarbon surfactants in AFFFs and AFFF-contaminated groundwater even though hydrocarbon surfactants are more abundant (5-10% w/w) than PFASs (0.9-1.5% w/w) in AFFFs. Eight commercial AFFFs manufactured between 1988 and 2012 and ten AFFF-contaminated groundwaters collected from near source zones of fire-fighter training areas were analyzed for suspect hydrocarbon surfactants by liquid chromatography quadrupole time-of-flight mass spectrometry. A suspect list and a homologous series detection computational tool, enviMass, were combined to screen for hydrocarbon surfactants. Nine classes of hydrocarbon surfactants were detected in AFFFs including octylphenol polyethoxylates, linear alcohol ethoxylates, ethoxylated cocoamines, alkyl ether sulfates, alkyl amido dipropionates, linear alkyl benzene sulfonates, alkyl sulfates, and polyethylene glycols. Of those, six were also found in groundwater along with diethanolamines and alkyl amido betaines, which were not found in the eight archived AFFFs. This indicates that, although aerobically biodegradable, hydrocarbon surfactants likely persist in groundwater due to anaerobic aquifer conditions. To the best of our knowledge, this is the first screening for hydrocarbon surfactants in AFFFs and in AFFF-contaminated groundwater.
... Some organic substances are known to be affected by temperature changes; e.g. Manzano et al. (1999) found a correlation between the increased temperature and biodegradation of nonylphenol ethoxhylates in water, and increased temperature was suggested to facilitate conversion of nonylphenol ethoxylates to nonylphenols (Isobe et al., 2001). ...
Control of diffuse pollution is critical for achieving good surface water quality status. In this context, pollutant contributions from building materials have received increased attention in recent decades. This study examined the releases of metals, nonylphenols and phthalates from ten common building surface materials (installed in triplicates) into rainwater runoff from six rain events. The highest releases of metals were from copper and zinc sheets (average concentrations of 3090 μg/L Cu and 7770 μg/L Zn respectively), while other metal materials, e.g., Corten weathering steel, exhibited lower releases. PVC roofing released high concentrations of nonylphenols and phthalates (average concentrations of up to 26 μg/L nonylphenols and 455 μg/L Diisononyl phthalate, DINP) which have not been investigated in the earlier studies. Pollutant releases varied between events, likely because of weather conditions and rainfall characteristics. Study findings should be valuable for environmentally responsible applications of the existing building materials and the development of new ones, as well as the investigations and risk assessment of specific pollutants in stormwater.
... A further comparison with the worldwide data reported in the literature (Table S1) indicated that the NP concentrations were lower in our study sites (ranging between 1.16 and 324 ng/g dw) than in other coastal areas of Japan, China, and Greece (Arditsoglou and Voutsa, 2012;Chen et al., 2006;Duan et al., 2014;Isobe et al., 2001). Our values were comparable to the concentration ranges reported for coastal sediments from Poland but were higher than the concentrations in sediments from San Francisco Bay (Klosterhaus et al., 2013;Koniecko et al., 2014). ...
Alkylphenol ethoxylates (APEOs) are one of the most widely used classes of surfactants, but they are also ubiquitous environmental pollutants and known endocrin-disrupting chemicals. This study is the first to investigate the spatiotemporal variations and possible sources of APEOs and their metabolites, including nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs), in coastal sediments off southwestern Taiwan. The highest APEO concentration in the dry season was observed for the Kaohsiung coastal area, whereas the highest alkylphenol (AP) concentration in the wet season was found offshore at the Tainan Canal exit. No continuous accumulation of alkylphenol metabolites was evident in the area. One possible reason is that seasonal current and wind waves disperse the coastal pollutants. Application of multivariate statistical tools (hierarchical cluster analysis and principal component analysis) confirmed the role of rivers and the Tainan Canal in transporting contaminants to coastal environments, suggesting influences of industrial and human activities on APEO distribution. A further comparison with the predicted no-effect concentrations (PNECs) proposed by the European Union indicates that nonylphenol (NP) and octylphenol (OP) might pose potential ecological risks to the aquatic environment in the studied area. These findings provide useful information for environmental policy implementation and ecological assessments of different types of endocrine-disrupting chemicals and raise warnings about surfactant applications.
... Suède ( (Fenet et al., 2003). Des études japonaises ont démontré que la contamination des eaux de surface par les alkylphénols varie en fonction des saisons, les concentrations d'octylphénols étant plus élevées pendant la saison chaude au Japon (Isobe et al., 2001 ;Tsuda et al., 2000). Ceci pourrait s'expliquer par la hausse de l'activité microbienne à des températures plus élevées, qui entraînerait une dégradation accrue des octylphénols éthoxylés en octylphénols . ...
Les alkylphénols sont des composés à haut rendement, économiques et utilisés dans une grande variété de produits, notamment dans les détergents, les peintures et les résines. En raison de leur utilisation massive, ces composés sont rejetés en quantité importante dans l’environnement, principalement dans les milieux aquatiques. Il a été démontré qu’un produit de cette famille, le nonylphénol, possède un potentiel toxicologique en tant que perturbateur endocrinien. Bien que l’utilisation du nonylphénol ait été restreinte au Canada en 2001, les autres composés de la famille des alkylphénols (exemple : butylphénol et octylphénol) ne possèdent toujours pas de restriction, malgré leurs propriétés physico-chimiques et toxicologiques similaires, ce qui soulève des inquiétudes dans la communauté scientifique.
Dans ce contexte, l’objectif principal de cet essai est d’évaluer le danger écotoxicologique du butylphénol et de l’octylphénol pour le milieu aquatique et de proposer des solutions adaptées. Afin d’y parvenir, huit objectifs spécifiques ont été établis. Ils consistent à présenter la législation régissant les rejets d’alkylphénols ; décrire leurs propriétés physico-chimiques ; dresser un portrait de la production, de l’utilisation et des sources de rejets des alkylphénols ; détailler leur comportement et leur devenir dans les différents compartiments environnementaux ; évaluer l’ampleur de la contamination des alkylphénols dans l’environnement ; évaluer leur toxicité sur les organismes aquatiques ; évaluer le danger écotoxicologique des alkylphénols et proposer différentes solutions pour minimiser ou éliminer les risques environnementaux de ces composés, les comparer et recommander les options les plus pertinentes. Les réponses à ces objectifs sont détaillées dans des chapitres respectifs, soit du chapitre 2 à 9.
À la suite de la revue de littérature, une analyse du danger écotoxicologique du butylphénol et de l’octylphénol a été réalisée. Les résultats obtenus montrent que l’octylphénol représente un danger écotoxicologique élevé pour les écosystèmes aquatiques, compte tenu de son caractère persistant, bioaccumulable et toxique. Bien que le butylphénol représente un faible danger pour l’environnement aquatique, une attention particulière devrait tout de même lui être portée en raison des réponses oestrogéniques observées chez les organismes aquatiques exposés à ce composé. Ainsi, les solutions recommandées en lien avec la problématique étudiée dans le cadre de cet essai sont d’utiliser des substances alternatives, d’améliorer les technologies en place pour traiter les alkylphénols dans les stations d’épuration et d’instaurer une réglementation plus sévère. Il est également conseillé de mettre à jour l’information concernant les concentrations environnementales de ces composés et d’approfondir les connaissances actuelles, notamment sur les effets à long terme du butylphénol et de l’octylphénol.
... In our study, dry sediments were analysed and this difference may be explained by the degradation of NPEO or the effect of the regular change between wet (during and after storm event) and dry (between storm events) conditions. The predominance of NP is also due to its high affinity for particles (Isobe et al., 2001), and its high persistence (Chokwe et al., 2017). In term of ecological risk assessment, concentrations found can be compared with the Predicted No Effect Concentration (PNEC) for the sediment compartment of the European Union risk assessment report (EU, 2002), which was evaluated at 0.039 mg/kg corresponding to 39 ng/g. ...
One of the most adopted solutions in developed countries to manage stormwater is detention/retention basins which generate large quantities of sediments that have to be removed regularly. In order to manage them properly, accurate data are needed about their physical and chemical characteristics, particularly on micropollutant concentrations and their associated risk. This work consisted in a two-year sampling of dry sediments from a detention-settling basin. Priority substances, including pesticides, polybrominated diphenyl ethers (PBDE), alkylphenols and bisphenol A (BPA), were monitored. Different sites in the basin bottom were sampled in order to investigate spatial distribution of the contamination. Results show that the increase of the sediment thickness in the basin was heterogeneous with a maximum of 15 cm after two years. Pesticides and PBDE were, if detected, mainly found in low concentrations from 2 ng/g to 286 ng/g. Conversely, alkylphenols and bisphenol A were always quantified at concentrations varying from 6 ng/g to 3400 ng/g. These high levels suggest that these sediments should be managed with precautions. Spatial heterogeneity of alkylphenol ethoxylates and BPA concentrations was observed, with higher contamination of alkylphenol ethoxylates in anaerobic zones and BPA levels correlated with total organic carbon and in a lesser extent to fine particles. Forty four priority substances, including endocrine disruptors, were followed during two years in stormwater sediments from a dry detention basin.
Nowadays, two of the endocrine disrupting compounds (EDCs) in the group of alkylphenols (APs), nonylphenol (4-NP) and octylphenol (4-t-OP), have attracted great scientific and regulatory attention mainly due to concerns about their aquatic toxicity and endocrine disrupting activity. This paper investigated the occurrence, distribution behavior, fate, and removal of 4-NP and 4-t-OP in liquid and solid phases of three full-scale wastewater treatment plants (WWTPs) with different treatment technologies comparatively. In this context, (i) advanced biological WWTP, (ii) wastewater stabilization pond (WSP), and (iii) constructed wetland (CW) were utilized. In all three investigated WWTPs, the concentrations of 4-NP (219.9–19,354.4 ng/L) in raw wastewater were higher than those of 4-t-OP (13.9–2822.4 ng/L). Within the scope of annual average removal efficiencies, 4-NP was treated highly in advanced biological WWTP (93.5 %), while it was almost not treated in WSP (3.1 %) and treated with negative removal (<0 %) in CW. While 4-t-OP was treated at a similar removal rate (93.5 %) to 4-NP in advanced biological WWTP, it was treated moderately in WSP (52.5 %) and very poorly in CW (12.4 %). It has been determined that the most important removal mechanism of both 4-NP and 4-t-OP in WWTPs is biodegradation, followed by sorption onto sewage sludge. According to the mass balance performed in advanced biological WWTP, the biodegradation rates for 4-NP and 4-t-OP were found to be 70.4 % and 86.6 %, respectively, while the sorption onto sewage sludge were determined to be 23.3 % and 6.8 %. One of the critical findings obtained within the scope of the study is that while the concentrations of both metabolites, especially 4-NP, in wastewater and sewage sludge, decreased considerably under aerobic conditions, on the contrary, their concentrations increased significantly under anaerobic conditions. Both compounds were detected at higher concentrations in primary sludge compared to secondary sludge in advanced biological WWTP, while in WSP, they were determined at higher concentrations in anaerobic stabilization pond sludge compared to facultative stabilization pond sludge. Besides, it was also determined that the sorption behavior of these alkylphenols is much more dominant than desorption.
Phthalates (PAEs) are the class of lipophilic chemicals, which are used as additives in the manufacturing of plastics. It results in presence of PAEs in water and beverages because of their migration capacity. Their presence has attracted considerable attention due to their potential impacts on ecosystem functioning and public health. In addition, an enormous number of research articles have been published between 2000 and 2020, which have been identified and their results have been tabulated displaying PAEs analyzed, matrices, sample preparation, analytical method used, the limit of detection (LOD), and recovery percentages. Numerous sample preparation and analytical methods are found which are suitable for the reliable determination of the PAEs. The analysis of the PAEs is difficult due to their ubiquitous presence and their complexity, therefore suitable precautions, should be taken into account. In this review, we provide an overview of various pre-treatment measures and detection methods for PAEs in several types of water and beverages, mainly focusing on the last 20 years published works have been discussed. Pre-treatment methods mainly include liquid-liquid extraction (LLE), solid-phase extraction (SPE), solid-phase microextraction (SPME), liquid-phase microextraction (LPME), and many more rare techniques. Chromatographic and non-chromatographic techniques coupled with or without diodes, spectrophotometers, and detectors, have been described. The concept of “green analytical chemistry” for PAE determination has also been discussed. Hereby, the limitations and challenges in these applications are also included.
Endocrine-disrupting compounds (EDCs) enter lakes mainly through river inflow. However, the occurrence, transport and fate of EDCs in the overlying water, suspended particulate matter (SPM) and sediment of inflowing rivers remain unclear. This study investigated the load of seven EDCs in a complex river-lake system of the Taihu Lake Basin during different seasons, with the aims of revealing the transport routes of EDCs and identifying the contributions from different sources. The results indicated that the levels of the seven EDCs in the wet season with high temperature and dilution effects were generally lower than those in the other seasons. EDC enrichment in the sediment was largely affected by the transport and fate of SPM. Moreover, the estrogenic activity and risks of EDCs were the highest in SPM. The mass loadings of particulate EDCs carried by SPM were 2.6 times that of overlying water. SPM plays a vital role in the transport and fate of EDCs in complex river-lake systems and thereby deserves more attention. Nonpoint sources, particularly animal husbandry activities and untreated domestic sewage, were the main sources of EDCs, amounting to 61.5% of the total load.
Alkane/water (logPalk) partitioning systems are gaining relevance in applied surfactant science but there is still a challenge to calculate logPalk values for surfactants. In this contribution, a simple method of calculating logPalk at sub‐micellar concentrations for a wide range of nonionic surfactants is presented, using a linear combination of octanol/water partition and hydrogen‐bonding contribution parameters of surfactants. These two parameters can be easily calculated using many commercial or open‐access software packages. The model requires a critical folding chain length factor to account for entropic effects arising from conformational behavior of the ethylene‐oxide chain for alcohol ethoxylate surfactants. This observation is substantiated by conducting a conformational lipophilicity study by molecular dynamics simulations of two alkylphenol ethoxylates as model surfactants. Polydispersity is not seen as a major factor in calculating the logPalk of surfactants. The model is shown to outperform previously published methods and can be applied directly in surfactant research and regulatory submissions when experimental data are not available.
Endocrine-disrupting chemicals (EDCs) are widespread contaminants that severely affect the endocrine systems of living organisms. In addition to the conventional instrument-based approaches for quantifying organic pollutants, a monitoring method using transgenic plants has also been proposed. Plants carrying a recombinant receptor gene combined with a reporter gene represent a system for the easy detection of ligands that specifically bind to the receptor molecule. Here, the EDC detection sensitivity of transgenic Arabidopsis plants expressing the medaka (Oryzias latipes) estrogen receptor (mER) and green fluorescent protein (GFP) genes, was assessed. Four transgenic Arabidopsis lines, obtained by transformation with expression plasmids constructed using combinations of two types of the ligand-binding domains of mER, the DNA-binding domain of LexA and the transactivation domain of VP16 in the chimeric receptors, showed significant induction of GFP when germinated on a medium contaminated with 1 ng/mL 4-t-octylphenol (OP). The most sensitive XmEV19-2 plants detected 0.1 ng/mL OP and 1 pg/mL 17β-estradiol. GFP expression was suppressed by the insecticides imidacloprid and fipronil, whereas perfluorooctanesulfonic acid induced it at 0.1 ng/mL. Experiments with river water-based medium showed that XmEV19-2 can be used for monitoring polluted waters, detecting OP at concentrations as low as 5 ng/mL. Notably, XmEV19-2 showed a significant decrease in root length when grown on 0.1 ng/mL OP. mER transgenic plants can be a promising tool for simple monitoring of EDCs, without the need for extraction and concentration steps in sample preparation.
A novel strategy of W modification was applied to overcome the disadvantages of Ag3PO4. Ultra-active Ag3PO4 with different W doping ratios were successfully synthesized by facile chemical precipitation method, among which 0.5%W-AP showed the best results. Meanwhile, the stability and yield were enhanced. XRD, Raman and ESR etc. were employed to investigate the morphology, structure and optical properties of samples. It was proved W⁶⁺ entered into the Ag3PO4 lattice, occupied the position of P⁵⁺ and doped in the form of WO4²⁻. The significant improvement of photocatalytic performance of W doped Ag3PO4 was attributed to the change of morphology, the decrease of particle size, the increase of crystallinity, the shrink of band gap energy and the reduction of photo-induced carriers recombination rate with W doping. The photocatalytic mechanism analysis showed h⁺ was the main oxidative species in the photocatalytic process, •O2⁻ and •OH played minor roles. Under visible light irradiation, the impacts of the important operating parameters on the typical phenolic pollutants, phenol and bisphenol A, were evaluated with 0.5%W-AP. It was confirmed that 68% and 82% of phenol and bisphenol A were respectively degraded within 15 min and 40 min under optimized photocatalytic parameters: 0.4 g/L catalyst dosage, 20 mg/L pollutant concentration, pH 5.7 and 125 mW/cm² irradiation intensity, and the corresponding K′ were 2.14 and 5.50 times of undoped samples. This work provides a new approach for effective degradation towards phenolic pollutants by Ag3PO4 with ultra-high photocatalytic activity, high applicability and enhanced stability and yield.
Aquatic products, which are among the most important sources of animal protein, contain proteins, vitamins, and a variety of trace elements, thus occupying an indispensable part of a reasonable diet. China is the largest consumer market of aquatic products in the world. The quality and safety of aquatic products are closely related not only to the healthy development of the aquaculture industry, but also to people's health. However, the presence of harmful substances has a bearing on the quality and safety of aquatic products in the overall process, including breeding, processing, storage, and transportation. These harmful substances are enriched in aquatic products and are transferred to humans via the food chain. Accurate determination of such harmful substances in aquatic product samples is imperative because of their complex matrices and extremely low concentrations. Many efficient sample preparation techniques such as liquid-liquid extraction, solid-phase extraction, and QuEChERS (quick, easy, cheap, effective, rugged, and safe method) with different configurations have been developed and widely employed for preconcentration in different matrices of aquatic products. Meanwhile, solid-phase microextraction has been demonstrated to be advantageous for some volatile and ultra-trace harmful substances. Suitable sample preparation techniques are important for effectively removing matrix interferences as well as for improving the sensitivity and accuracy of the method. It is important to develop appropriate sample preparation techniques for different target compounds in aquatic products. The harmful substances in aquatic products can be segregated into three categories according to their sources: (1) environmental pollutants in aquatic products; (2) substances acquired during aquaculture, transportation, and processing; (3) biotoxins in aquatic products. This article reviews the progress in sample pretreatment techniques for three harmful substances in aquatic products over the past decade. Various sample pretreatment techniques have been summarized and described, including liquid-liquid extraction, solid-phase extraction, solid-phase microextraction, QuEChERS, and magnetic solid-phase extraction. In addition, the merits and demerits of these techniques and future research directions are discussed. Finally, we reviewed the progress in functionalized materials for the preparation of aquatic product samples. With the increasing demand for aquatic products, quick, sensitive, and practical detection methods, such as surface-enhanced Raman scattering (SERS) are gaining importance. SERS has great potential for fast and accurate on-site detection of harmful substances in aquatic products. Several nondestructive sample pretreatment techniques have also been developed for harmful substances in aquatic products. The application and development of these techniques will guarantee the safety of aquatic products. Moreover, in vivo solid-phase microextraction is a potential method for aquatic product analysis. This technique integrates sampling, extraction, and enrichment into a single step, thus significantly reducing the processing time, labor, and cost. Overall, with the development and application of sophisticated materials and techniques, we can expect theoretical and practical advances in aquatic product analysis.
While the coastal pollution of persistent toxic substances (PTSs) has been widely documented, information on offshore environments remains limited. Here, we investigated the spatial distribution and sources of PTSs in the offshore sediments (n = 34) of South Korea. Sediment samples collected from the Yellow Sea (n = 18), the South Sea (n = 10), and the East Sea (n = 6), in 2017–18 were analyzed for a total of 71 PTSs. Target compounds include 31 PCBs, 15 PAHs, 9 emerging PAHs (e-PAHs), 10 styrene oligomers (SOs), and 6 alkylphenols (APs). Sedimentary PCBs showed relatively low concentrations with no significant difference across the three seas (0.16–6.9 ng g⁻¹ normalized organic carbon, OC). Low-chlorinated PCBs (tri- and tetra Cl-CBs) were predominant (mean: 77%), primarily indicating atmospheric inputs. PAHs widely accumulated in the three seas with low to moderate level (22–250 ng g⁻¹ OC), and dominated by high molecular weight PAHs (4–6 rings). PMF analysis revealed coast-specific PAHs sources; i.e., originated from mainly coke production (77%) in the Yellow Sea, vehicle emissions (68%) in the South Sea, and fossil fuel combustion (49%) in the East Sea. SOs showed significant contamination than other PTSs, with elevated concentrations in the Yellow Sea (mean: 350 ng g⁻¹ OC). APs showed a similar regional distribution to SOs, but concentrations were much lower (mean: 17 ng g⁻¹ OC). SOs and APs seemed to be introduced from rivers and estuaries on the west coast of Korea, where industrial and municipal activities are concentrated, then might be transported to offshore through tide or currents. Overall, the novel data presented for various PTSs in offshore Korean sediments warrant the necessity of a long-term monitoring effort and urgent management practice to protect marine ecosystem.
Nonylphenol (NP) is analkylphenolic compound classified as an endocrine disrupter capable of interfering with the hormonal system of different aquatic organisms. It is mainly originated from degradation of Nonylphenol Ethoxylates. Due to its physical and chemical characteristics, it is persisted in sewage sludge and river sediments. In river water and sediments the concentration of NP is 4 µg/l and 1 mg/kg, respectively. The fate and occurrence of NP in the environment is clearly correlated with different anthropogenic activities like wastewater treatment, land-filling and sewage sludge recycling. Different types of aquatic vertebrates and invertebrates are trashily affected by the NP. The impact of the NP on the fish as follows: decrease in male fertility, altered sex ratio, reducing hatching rate. Also different types of alteration are occurred in haematological, biochemical and histopathological parameters. Due the bioaccumulation properties the human beings are dangerously affected by the NP.
The fight against environmental pollution by organic compounds has today become a primary necessity for public authorities to ensure sustainable development. This work highlights the removal of 4-nonylphenol (4-NP) in aqueous solution onto two chemically activated carbons (ACs) by optimizing some parameters that influence the adsorption process. Central composite design with four centre points was used to optimize the process variables. The concentration of 4-NP solution, adsorbent dosage, stirring time and solution pH on the adsorption capacity were considered while the response measured was the quantity of 4-NP adsorbed. The AC obtained by treatment with sulfuric acid was named NSST and that obtained by treatment with phosphoric acid was named NSPT. Optimal conditions for 4-NP removal were as follows: 4-NP concentration 180 mg/L and 100 mg/L for NSST and NSPT respectively. Adsorbent dosage (100 mg), solution pH (9) and stirring time (120min) were the same for both adsorbents. These optimal conditions resulted in 30.740 and 39.490 mg/g removal for NSST and NSPT respectively. A quadratic model for 4-NP removal was proposed and from it, analysis of variance was approximately in accordance with expectations. Correlation coefficients R² and R²adj were of 91.00 and 81.32 % for NSPT material and 87.81 and 74.69 % for NSST material. Experimental data obtained from optimal conditions were validated with different isotherms and kinetic models to evaluate the solute interaction behavior and nature of adsorption. A pseudo-second order non-linear kinetic model best described the adsorption kinetics of 4-NP removal onto the ACs. Freundlich's isotherm best described the removal of 4-NP onto NSST and the Langmuir's isotherm did the same with the NSPT.
Nonylphenol (NP) and bisphenol A (BPA) are two typical endocrine disrupter chemicals (EDCs) in the reclaimed water. The adsorptions of NP, a branched NP (NP7) and BPA on reclaimed water-irrigated soils were studied by isothermal experiments, and the different environmental factors on their adsorptions were investigated. The results showed that the adsorptions of NP and NP7 on soils conformed to Linear model, and the adsorption of BPA conformed to Freundlich model. The adsorptions of NP, NP7 and BPA on soils decreased with the increasing temperatures and pHs, while increased with the cation valence. Adsorption equilibrium constant (K d or K f ) were maximum at pH=3, temperature 25℃ and As (Ⅲ)-soil, respectively; The adsorption capacity of NP, NP7, and BPA to soils increased in accordance with cation valence: trivalent cations > divalent cations > mono- cations. K d of NP7 on soil was less than that of NP under the different pH and temperatures; while under different cations concentrations, it was inverse. Fourier Transform Infrared Spectrometer (FTIR) analysis showed alkyl chains of NP and BPA seemed to form van der Waals interactions with the cavity of soil. Results of this study will provide further comprehensive fundamental data for human health risk assessment of nonylphenol in the soil.
Endocrine-disrupting chemicals (EDCs) serve as agents that could damage the endocrine systems in human bodies. The EDCs can be introduced into an aquatic system via physicochemical reactions by nature and anthropogenic activities mainly including pharmaceuticals and industrial discharges. Generally, concentrations of EDCs in the Pearl River fall in higher ranges than those in other lakes and rivers in China and around the world. The potential hazards of the EDCs in the Pearl River have been thoroughly assessed in the last two decades but not comprehensively compared. This review aimed to discuss the detected concentration levels of EDCs in the surface water and sediment of the Pearl River respectively and conducted the risk assessment for residents along the Pearl River. Among EDCs, six important groups of chemicals (estrone, 17β-estradiol, nonylphenol, octylphenol, bisphenol A, and triclosan) were selected for analysis in this review due to their environmental ubiquity and toxicity in the Pearl River. The risk assessment indicated there was no potential negative impact of target EDCs on human health via water ingestion.
The concentrations and distributions of selected alkylphenols (APs; 4-nonylphenols, 4-n-octylphenol, 4-tert-octylphenol, 4-tert-butylphenol and 2,4-di-tert-butylphenol) in water, sediment and aquatic organism samples in the Pearl River networks were determined using gas chromatography-mass spectrometry. The results showed that 4-nonylphenols (NPs) were dominant in both water samples and sediment samples. For APs, downtown and populated regions showed higher concentrations than rural regions; furthermore, the concentrations of APs in eastern tributaries were higher than those in western tributaries. In aquatic organism samples, the content range of APs, NPs, and octylphenols (OPs; 4-n-octylphenol and 4-tert-octylphenol) were 174.74–648.10 ng/g, 143.95–582.51 ng/g, and 8.10–37.10 ng/g, respectively, with mean values of 346.52, 281.90, and 24.13 ng/g, accordingly. The accumulated level of APs in nine different species of aquatic organism species declined as follows: perch (Lateolabrax japonicus) > bighead fish (Aristichthys nobilis) > silver carp (Hypophthalmichthys molitrix) > carp (Cyprinus carpio) > barbel chub (Squaliobarbus curriculus) > shellfish (Corbicula fluminea) > grass carp (Ctenopharyngodon idellus) > cyprinid fish (Megalobrama hoffmanni) > shrimp (Macrobranchium nipponense). Carnivorous and filter-feeding fish tended to accumulate more APs than other dietic fish, shellfish and shrimps.
Coastal waters are the critical ecologically fragile regions under the influence of the fastest economic developing pace and the extensive anthropogenic activities in coastal zone. Little information on the seasonal distribution, risks, and sources of endocrine disrupting chemicals (EDCs) which are emerging contaminants to pose potential risks at very low concentrations in coastal waters at continental-scale is available. This study investigated the coastline-based distribution, risks, and sources of target EDCs in coastal water of China. EDCs in coastal waters of China showed significant spatio-temporal variation with phenolic compounds serving as predominant EDCs. Bisphenol A (BPA) was detected in all water samples with average concentration of 449.2/186.3 ng/L in winter/summer while estrone was the main steroidal estrogen with the average concentration of 87.2/2.7 ng/L in winter/summer. EDCs in coastal waters of South China Sea Area showed higher concentrations. EDCs in coastal waters exerted high ecological risks and estrone/BPA averagely accounted for over 61%/71% of total risk quotient in winter/summer. Average estradiol equivalent concentration of all target EDCs reached 68.87/1.76 ng/L in winter/summer. EDCs in coastal waters did not pose potential non-cancer health risks for humans. The positive matrix factorization (PMF) model was firstly used to identify and quantify possible sources of EDCs. The PMF analysis showed that wastewater and sewage might be the main source for EDCs in coastal waters. EDCs in coastal waters showed high estradiol equivalent concentration and ecological risks at continental-scale, highlighting that EDCs contamination has become a crucial stress affecting the sustainable development of coastal regions.
In this long-term field study, to restore a dried river ecosystem, reclaimed water was used as a supplementary water source. The main aim of this study was to investigate the accumulation and migration potential of EDCs in groundwater during long-term utilization of reclaimed water and the changes in microbial community during the removal of EDCs. A long-term field study was conducted in order to ascertain the temporal and spatial distribution of four selected endocrine-disrupting chemicals (EDCs) in an underground aquifer in the Chaobai watershed, where reclaimed water is the primary water source. Anew, the microbial community structure at different groundwater depths, along with related environmental factors were also determined. Based on the results obtained from this long-term study, it was found that the EDCs in the surface water of the Chaobai river have entered a depth of 80 m in the groundwater aquifers, within a distance of 360 m from the river. The vertical profiles of the concentrations of bisphenol A (BPA), 4-nonylphenol (NP), estrone (E1), and estriol (E3) decreased significantly from the surface to different groundwater depths with first-order attenuation rates of 0.0416, 0.0343, 0.0498, and 0.0173 m-1. The aquifer depth, water temperature, conductivity, and coexisting anions correlated well with the distribution of EDCs in groundwater.
Purpose:
Nonylphenol (NP) is one widely distributed representative of environmental estrogens that disturb reproductive activities, bone metabolism and brain function through interfering diverse signal pathways leading to hormone metabolic dysfunctions, immunologic derangement, and tumorigenesis. Few of previous studies have observed the subacute toxicity on rodents, and little has been focused on the mechanism underneath the toxicities observed.
Methods:
The 32 male Sprague-Dawley (SD) rats were randomly divided into four groups, the negative control group (corn oil) NP low, medium and high dose groups [30, 90, 270 mg/(kg·d)]. SD rats administrated with different dosage of NP every other day for 28d. Elisa and RT-PCR was employed to observe estrogen metabolism markers or mRNA expressions.
Results:
In serum, NP exposure caused testosterone (T) (p < 0.001), progesterone (PROG) (p < 0.05) and estrone (E1) (p < 0.05) increased. In testicle, NP exposure caused T (p < 0.001), PROG (p < 0.05), E1 (p < 0.05), 17β-estradiol (E2) (p < 0.05) and ERα mRNA (p < 0.01) increased, while P450 aromatizing enzyme (p < 0.001) decreased in NPL and ERβ mRNA (p < 0.001) decreased in NPM and NPH. In liver, NP exposure caused 17β-HSD2 mRNA (p < 0.01) increased, while P450 aromatizing enzyme decreased (p < 0.05).
Conclusion:
NP exposure exhibited general and estrogenic toxicity in rats through disturbing estrogen secretion network and estrogen receptor expression network, inducing abnormal metabolism of estrogen, whether in serum, liver and testicle.
An estrogen-inducible screen was developed in yeast (Saccharomyces cerevisiae) in order to assess whether surfactants and their major degradation products are estrogenic. The DNA sequence of the human estrogen receptor (hER) was integrated into the yeast genome, which also contained expression plasmids carrying estrogen-responsive sequences (ERE) controlling the expression of the reporter gene lac-Z (encoding the enzyme β-galactosidase). Thus, in the presence of estrogens, β-galactosidase is synthesized and secreted into the medium, where it causes a color change from yellow to red. This recombinant strain was used to determine whether representatives of major surfactant classes and some of their principal degradation products possess estrogenic activity. The results were compared to the effects of the main natural estrogen 17β-estradiol. None of the parent surfactants tested possessed estrogenic activity. However, one class of surfactants, the alkylphenol polyethoxylates, degrade to persistent metabolites that were weakly estrogenic. Another group of degradation products, the sulfophenyl carboxylates, which are derived from the biodegradation of linear alkylbenzene sulfonates, do not appear to possess estrogenic activity.
The concentration of an environmental estrogen (4-nonylphenol) was determined in suspended solids and large volume water samples (501) collected from a major sewage treatment plant (STP) and two sites located on the lower Fraser River in British Columbia, Canada. The collection of suspended solids and large volume water samples was conducted concurrently using an in situ continuous flow centrifuge and solid phase extraction. The phase partitioning profile and log Koc of 4-nonylphenol were determined in the STP effluent and the Fraser River receiving environment. The data indicate the following: i) in situ continuous flow centrifugation and solid phase extraction techniques are appropriate methods for the determination of trace levels of 4-nonylphenol in suspended solids and water ii) the highest concentrations of 4-nonylphenol were measured in the STP final effluent iii) 4-nonylphenol showed preferential partitioning to the suspended solid phase in the STP effluent sample and iv) elevated levels of 4-nonylphenol were detected in the Fraser River receiving environment downstream of the STP.
Concentrations of vitellogenin (VTG) in serum of wild male ¯ounder (Pleuronectes yoko-hamae) were investigated, as a biomarker for environmental estrogens in marine waters, from January 1997 to May 1998 in Tokyo Bay, Japan (n 130) and from a reference site in Hok-kaido, Japan, far from urban areas (about 40 km from Hakodate city) from March 1997 to June 1998 (n 62). Statistically higher concentrations of serum VTG were detected in wild male ¯ounder collected in Tokyo Bay (range: 25±2200 ng ml À1) compared to ®sh from Hok-kaido (range: 31±91 ng ml À1) throughout the entire sampling period. Three out of 20 males collected o Haneda, in the inner part of Tokyo Bay, showed testes containing small numbers of oocytes. This intersex condition was not found among males collected from the reference site. This study suggests that the abnormally high levels of VTG and the presence of oocytes Marine Environmental Research 49 (2000) 37±53 www.elsevier.com/locate/marenvrev 0141-1136/00/$-see front matter # 2000 Elsevier Science Ltd. All rights reserved. P I I : S 0 1 4 1-1 1 3 6 (9 9) 0 0 0 4 7-1 in the testis of male ¯ounder collected from Tokyo Bay could be the eect of environmental estrogens. #
Nonylphenol polyethoxylates and their refractory metabolites, including nonylphenol, are on the second Priority Substances List (PSL2) to determine if they are 'toxic' as defined under the Canadian Environmental Protection Act. This study addresses the need for data on their occurrence in raw sewage, final effluents and sludge in Canada. Samples of raw sewage, final effluent and sludge were collected from 16 wastewater treatment plants across Canada in 1995 and 1996. These samples were analyzed for 4-nonylphenol (4-NP), nonylphenol ethoxylate (NP1EO), nonylphenoldiethoxylate (NP2EO) and 4-tert-octylphenol (4-t-OP). Measurable quantities of these chemicals were found in almost all raw sewage and sludge samples. In the raw sewage, concentrations ranged from < 0.005 to 21 μg/L for 4-t-OP, from 0.69 to 155 μg/L for 4-NP, from 2.9 to 43 μg/L for NP1EO and from 0.26 to 24 μg/L for NP2EO. Sludge concentrations (based on dry weight) ranged from < 0.010 to 20 μg/g, from 8.4 to 850 μg/g, from 3.9 to 437 μg/g and from 1.5 to 297 μg/g for 4-t-OP, 4-NP, NP1EO and NP2EO, respectively. Of the final effluent samples, 60% contained detectable amounts of 4-t-OP and concentrations ranged from < 0.005 to 0.37 μg/L. Almost all of the final effluent samples had detectable levels of 4-NP, NP1EO and NP2EO. The 4-NP concentrations varied from < 0.020 to 13 μg/L, NP1EO was found in the range of 0.072 to 26 μg/L and NP2EO was found in the range of 0.099 to 21 μg/L.
A survey of the concentrations of nonylphenol ethoxylates (NPnEO) and their metabolites in wastewater samples collected from a Canadian sewage treatment plant using primary and secondary treatment is presented. Twenty-four-hour composite raw sewage, primary effluent and final effluent samples were collected monthly over a one-year period. Levels of NPnEO (n = 1 to 17) and their metabolites, nonylphenol (NP) and nonylphenoxy carboxylic acids (NPnEC), in these samples were determined by HPLC and GC/MS methods. While ca. 85% of the total alkylphenolics in raw sewage are ethoxylates, the major component (nearly 80%) in the final effluent was in the form of carboxylic acids. During this study period, the median total alkylphenolic concentrations in raw sewage and final effluent were 526 and 248 nmol/L, respectively, representing an overall elimination rate of 53%. The estimated daily discharge of the nonylphenolics to the aquatic environment varied from 15 to 44 moles, with a median value of 20 moles. These data suggested that conventional sewage treatments are ineffective in the removal of the surfactant-derived metabolites.
The concentration of an environmental estrogen (4-nonylphenol) was determined in suspended solids and large volume water samples (501) collected from a major sewage treatment plant (STP) and two sites located on the lower Fraser River in British Columbia, Canada. The collection of suspended solids and large volume water samples was conducted concurrently using an in situ continuous flow centrifuge and solid phase extraction. The phase partitioning profile and log Kco of 4-nonylphenol were determined in the STP effluent and the Fraser River receiving environment. The data indicate the following: i) in situ continuous flow centrifugation and solid phase extraction techniques are appropriate methods for the determination of trace levels of 4-nonylphenol in suspended solids and water ii) the highest concentrations of 4-nonylphenol were measured in the STP final effluent iii) 4-nonylphenol showed preferential partitioning to the suspended solid phase in the STP effluent sample and iv) elevated levels of 4-nonylphenol were detected in the Fraser River receiving environment downstream of the STP.
The distribution of linear alkylbenzenes (LABs) and linear alkylbenzenesulfonates (LASs) in river sediments, suspended river particles, domestic wastes, and waste effluents around the Tokyo city area was investigated. LABs as well as LASs with alkyl carbon chain lengths in the range from 10 to 14 were found in all environmental samples and LAS-type synthetic detergents examined. These results indicate that LABs are carried into aquatic environments as a result of the use of synthetic detergents around the Tokyo metropolitan area. Further results are (1) LABs in urban river sediments originate predominantly from untreated domestic wastes, final effluents contributing only a minor portion of the LABs in sediments, (2) the isomeric composition of the LABs changes systematically during biodegradation, and (3) the ratio of LAS to LAB decreases as follows: commercial synthetic detergents > suspended particles in domestic wastes > river sediments > Tokyo Bay sediments.
Concentrations of the weakly oestrogenic degradation products of alkylphenol polyethoxylate (APE) surfactants (nonylphenol, octylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate) were measured in water and sediments from British rivers and estuaries collected during 1994 and 1995. In addition, a series of samples of tissues of wild fish from the River Aire, and from a laboratory dosing experiment were analysed for alkylphenols, to assess the degree of bioaccumulation of these compounds. Measurable concentrations of APE residues were recorded in the River Aire (15–76 μg/l total extractable alkylphenols), the River Mersey (6–11 μg/l) and the Tees estuary (up to 76 μg/l). These levels exceed, or are close to, the no observed effect concentration for the induction of vitellogenesis in caged trout (5–20 μg/l total extractable alkylphenols), and may be sufficient to exert an oestrogenic effect on fish populations in these areas. A sediment sample from Bingley on the River Aire contained 15 μg/g (dry weight) nonylphenol, and concentrations in sediments from the Tees and Mersey estuaries exceeded 1 μg/g. These rivers receive a variety of trade waters via sewage treatment works (STW) effluents containing significant concentrations of APE. Elsewhere, concentrations in water and sediments were near or below limits of detection and biological effects are unlikely, suggesting that any oestrogenic effects observed in sewage outfalls and rivers not directly impacted by APE-containing trade-waters may be caused by other chemicals. Analysis of samples of trout muscle taken from a tank dosed at 65 μg/l nonylphenol indicated a bioaccumulation factor of between 90 and 125 after 3 weeks exposure. Samples of wild fish from the River Aire contained up to 0.8 μg/g nonylphenol in the muscle, a tissue bioaccumulation factor of approximately 50 relative to measured concentrations in water samples. A series of fish samples taken from offshore for food quality assurance purposes contained no detectable levels of APE residues (0.05–0.1 μg/g nonylphenol).
The atmospheric occurrence of nonylphenols and tert-octylphenol has been assessed at three sites in the lower Hudson River Estuary (LHRE). The samples (n = 186) were taken from June to December of 1998. Gas-phase nonylphenol (NP) concentrations at a coastal site (Sandy Hook) ranged from below the detection limit (DL) to 56.3 ng m-3, while concentrations at a suburban site (New Brunswick) ranged from 0.13 to 81 ng m-3. Gas-phase concentrations of tert-octylphenol (tOP) ranged from <DL to 1.0 ng m-3 at Sandy Hook and from 0.01 to 2.5 ng m-3 at New Brunswick. NPs and tOP exhibited seasonal dependence with higher gas-phase concentrations during summer than during fall and early winter. Temperature explained 40−62% of the variability in the log (gas phase) NP and tOP concentrations. Assessment of the influence of local wind direction on atmospheric NP concentrations provided evidence for the predominance of local sources rather than long-range transport. Based on simultaneous water and over-water gas-phase samples and subsequent estimation of air−water exchange fluxes, volatilization and advection to the Atlantic Ocean accounted for 40 and 26% of the removal of NPs from the water column of the LHRE, respectively. The estimated half-life of NPs in the water column of the LHRE was 9 days.
Although poly(oxyethylene)alkylphenyl ether (APE) nonionic surfactants with longer ethylene oxide (EO) chain than 2 can be the important pollutants in natural aquatic environments as the potential precursor of alkylphenol, an endocrine disrupting chemical, little attention has been paid to those. Water samples were seasonally collected at five sites of each of the three main rivers in Tokyo. APE with different alkyl chains were separated and fractionated using a reversed-phase adsorption enrichment technique with gradient elution in high performance liquid chromatography (HPLC). After the concentration of each fraction, EO chain length (polymerization degree of EO) in APE was determined by electrospray ionization mass spectrometry (ESI/MS). The results indicated that, in three main river waters in Tokyo, poly(oxyethylene)nonylphenyl ether (NPE) was the dominant pollutant among APE, total NPE concentrations with different EO chain lengths were 2−6 nM in summer and 10−35 nM in winter, and its peak in the abundance of NPE components with different EO chain lengths was at 5−8 EO units in winter and shifted to 2−5 units in summer. Laboratory biodegradation experiments using filtered and NPE-spiked river water confirmed that seasonal changes in the abundance of NPE components with different EO chain lengths would be mainly caused by increased bacterial activity due to high water temperature, producing mainly the persistent nonylphenol diethoxylate.
Masan Bay, located on the southeast coast of Korea, is a long and narrow inlet of a semi-closed bay that receives industrial and municipal wastewaters from the cities of Masan and Changwon. In this study, sediments collected from 28 locations on Masan Bay were analyzed for total organic carbon (TOC), nonylphenol (NP), octylphenol (OP), bisphenol A (BPA), organochlorine pesticides (HCB, HCHs, CHLs, and DDTs), individual polychlorinated biphenyl (PCB) congeners, and 16 polycyclic aromatic hydrocabons (PAHs) to characterize their spatial distribution and contamination status. Concentrations of NP in sediment ranged from 113 to 3890 ng/g on a dry weight basis (dry wt), whereas concentrations of OP and BPA were, on average, 20−110-fold less than those of NP. PAHs were predominated by 4−6-ring compounds with concentrations in the range of 54.1−1100 ng/g dry wt. Concentrations of PCBs in sediment, which were predominated by tetra- and pentachlorobiphenyl congeners, ranged from 10.3 to 148 ng/g, dry wt. Among different OC pesticides analyzed, concentrations of DDTs were the greatest, ranging from 0.4 to 12.6 ng/g dry wt. NP concentrations were greater at coastal locations proximal to the discharges of creeks from inland areas, whereas the concentrations of PCBs and PAHs were greater near the sites of industrial and shipping activities. Concentrations of target analytes were not related to TOC. Although the mean concentrations of PCBs and PAHs in sediments were less than the suggested sediment quality guidelines (SQG), their concentrations in some locations were close to or above the SQG for toxic effects in benthic organisms.
Determination of polychlorinated biphenyls (PCBs) and nonylphenols (NoPhs) in the Sea of Japan not only points out the extent of marine pollution but also helps to understand the deep sea structure of that semi-enclosed “small ocean”. Using an in-situ filtration/extraction technique, two vertical profiles (deep water and shallow coastal water) and two space-integrated surface profiles were taken. Concentrations of ∑CBs (sum of 30 individual congeners) in solution were between 0.1 and 1.2 pg dm-3 and in suspension were between 0.2 and 1.5 pg dm-3; those of ∑NoPhs in solution were 2−150 pg dm-3 and below detection limits in suspension. The concentrations of ∑CBs and nonylphenols in solution as well as the compositions of the CB mixtures in solution in the vertical profile indicates a vertical structure similar to the situation in the open ocean as suggested by Kim (Biogeochemical processes in the North Pacific; Tsunogai, S., Ed.; Japan Marine Science Foundation: Tokyo 1996; pp 41−51). The concentrations of CBs in solution were determined primarily by characteristics of the water bodies involved, solution−suspension interactions playing only a minor role. Principal component analyses of the data revealed a relation between deep and bottom waters and surface waters of the nearby region.
Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), naphthalenes (PCNs), biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and nonylphenol (NP) were measured in a dated sediment core collected from Tokyo Bay, Japan, in order to study the history of contaminant inputs and fluxes. Concentrations of organochlorine compounds measured in this study increased gradually from the beginning of the early 1900s, reached a maximum in the early 1980s, and decreased steadily until the 1990s. The profile of isomer/congener compositions of PCDDs/DFs and PCNs varied with depth, which suggested that the sources of input of these compounds varied at different periods. The possible changing sources of PCDDs/DFs and PCNs to the environment are discussed in the context of the concentration trends and congener-specific data. The composition of PCB congeners was uniform at the top 40 cm, which corresponded to the period of usage of technical PCB mixtures, suggesting that the major single source of PCBs in sediments was technical preparations. All of the above organochlorines were detected in sediment sections collected at 90 cm depth, which corresponded to the early 1900s, suggesting the occurrence of these compounds in pre-industrial sediments. The vertical profile of PAHs was similar to that found for organochlorines with the highest concentrations occurring in the early 1980s. The vertical profile of NP concentrations was different from those observed for restricted compounds such as PCBs and PAHs. NP concentrations were greater in surface sediments (0−12 cm) than those in subsurface sediments (12−30 cm). In general, the profile of residues of organic compounds reflected production and usage trends of the respective compounds, although there was a time lag of a few years between peak periods of usage and deposition in coastal sediments. Improvements in emission controls in the late 1980s and the early 1990s appear to have been effective in reducing the inputs of organic residues to the environment; however, the concentrations of several organochlorines in surface sediments are still greater than those found in sediments from the 1970s.
Alkylphenol polyethoxylates are a major class of nonionic surfactants that are microbially degraded in sewage treatment plants (STPs) and sediments to more toxic and hydrophobic alkylphenols. Recent data on the estrogenic activity of alkylphenols has prompted interest in the distribution of these compounds in the aquatic environment. Sediment samples were collected from several sites (n = 28) at industrialized and pristine regions of Lake Huron, Lake Erie, and Lake Ontario, USA and Canada, and analyzed for concentrations of 4-nonylphenol (NP) and 4-(tert)-octylphenol (OP). Also, sludge samples were taken from a secondary STP in Whitby, Ontario, Canada. Sediment and sludge samples and analytical standards were prepared for analysis by gas chromatography–mass spectrometry in selected ion mode by combined acetylation and supercritical fluid extraction. Concentrations of NP were up to 37 μg/g in sediments and >300 μg/g in the sewage sludge. Concentrations of OP were up to 23 μg/g in sediment and 21 μg/g in the sewage sludge. These data indicate that alkylphenols are distributed widely in sediments in the lower Great Lakes. However, concentrations of NP were present at high (μg/g) levels only in sediments near urban and industrialized centers.
A comprehensive monitoring study, sponsored by the Chemical Manufacturers Association and designed in cooperation with the
Environmental Protection Agency (EPA), measured the levels of nonylphenol (NP) and its ethoxylates (NPE) in 30 rivers. The
sites, all receiving municipal or industrial wastewater, were selected at random from EPA’s United States river reach database
by a statistical procedure. Water column and bottom sediment samples were collected along a perpendicular transect at each
site. All samples were assayed for NP and NPE1, and the higher ethoxylates (NPE2 to NPE17) were determined in the water samples. Analysis was by high-performance liquid chromatography (HPLC) with fluorescence detection
of microgram quantities of NPE obtained by extractive steam distillation (NP and NPE1) or a dualcolumn extraction procedure (NPE2 to NPE17). Sample collection and analytical procedures were validated according to rigorous EPA guidelines, and quality assurance
standards were met throughout the study. NP and NPE concentrations in river water were mostly (60 to 75% of the samples) below
their detection limits (about 0.1 ppb for NP, NPE1, and NPE2; 1.6 ppb for NPE3–17). The highest levels found were about 1 ppb for NP, NPE1, and NPE2, 15 ppb for NPE3–17. A majority of sediment samples contained detectable amounts of NP and NPE1, ranging up to 3000 ppb for NP and 170 ppb for NPE1. Sediment interstitial water concentrations of NP were estimated to be similar to concentrations in the water column.
Marine sediment cores and surface grabs were collected from the Strait of Georgia, British Columbia, Canada, near the Iona municipal outfall and were analyzed for nonylphenol (NP) and its ethoxylate compounds (NPnEOs). The authors used normal-phase liquid chromatography with electrospray mass spectrometric detection to determine concentrations of ethoxylates from n = 1 to n = 19. Over half the NPnEO inventory in marine sediments resides in ethoxylates of chain length greater than n = 2, suggesting that analyses limited to short-chain ethoxylates (n = 2) are under-reporting total NPnEO by a factor of 2. The NPnEO vertical profiles and oligomer distributions in dated sediment cores suggest that little degradation occurs once these compounds enter the sediments: the half-life for these compounds is estimated to be greater than 60 yr. The lack of change in NPnEO oligomer distribution with age suggests that degradation by chain shortening does not occur significantly. A rough inventory shows that over 30 t of NPnEO resides in Fraser River Delta sediments near the Iona municipal outfall and that the entire Strait of Georgia sediments contain over 170 t of NPnEO.
The behaviour of nonylphenol polyethoxylate surfactants (NPnEO) and their metabolites in the Glatt River, Switzerland was studied. Discharge of secondary effluents from municipal sewage plants into the river was the predominant source of the investigated compounds. The majority of nonylphenolic compounds in the Glatt River were in the form of persistent metabolites, the most abundant being nonylphenoxy carboxylic acids. Distribution of the various classes of nonylphenolic compounds in the river was influenced to differing extents by biological and physico-chemical processes and was dependent on the compound class and the season. Biotransformation appears to be the predominant mechanism determining the fate of nonylphenolic compounds. High concentrations of lipophilic metabolites in river sediments indicate the importance of physico-chemical processes on the distribution of the nonylphenolic chemicals in natural waters.
The study investigates pollution by micro-organic contaminants in riverine systems in NE England with the following four key objectives: (1) to establish the range and concentrations of micro-organic compounds in relation to land use; (2) investigate how the type and concentrations of micro-organics can vary seasonally; (3) compare bed-sediment and suspended-sediment concentrations, and to (4) assess the use of `whole-water' samples as indicators of environmental water quality in particular with respect to the ecotoxicological impact of contaminant-laden sediments within fluvial systems. Waters, bed- and suspended sediments were collected from six freshwater tributaries of the Humber river at quarterly intervals during the period July 1995–1996. A wide range of micro-organic contaminants were analyzed by GC/MS and GC/NPD, chosen on the basis of information provided through the UK Land Ocean Interaction Study (LOIS) core monitoring and additional data regarding water quality and land-use within the catchment. Thirty compounds were targeted including a range of pesticide groups, e.g. triazines, organophosphorus and synthetic pyrethroids, in addition to other compounds of concern including polyaromatic hydrocarbons, e.g. fluoranthene and pyrene, and a surfactant residue, nonylphenol. The results show the presence of a wide range of micro-organic contaminants associated with river sediments. The high concentration of compounds associated with both bed and suspended sediments appears unrelated to the concentrations measured in the dissolved phase. Greater concentrations of contaminants are found associated with the industrial southern rivers, Aire, Calder and Don. However, considerable temporal variation in the concentrations associated with sediment has been shown. It is suggested that these variations reflect a number of factors such as differences in land-use and the effect of the seasonal application of contaminants in addition to differences in the sediment characteristics and hence the potential of the sediment to remove or release a contaminant. It is shown that river sediments can act as a `sink' and potential secondary source of micro-organic contaminants within fluvial systems. The implication of such an association is also shown to be significant in terms of the ecotoxicological impact of micro-organic contaminants. This is demonstrated for cis- and trans-permethrin for which the calculated porewater concentrations in some rivers are sufficient to cause adverse effects on benthic fauna.
A preliminary survey of concentrations of nonylphenol and octylphenol in rivers and estuaries in England and Wales was undertaken to establish environmental concentrations and to support a biological field programme. The analytes were quantified by GC/MS in MID mode after concentration onto C18 solid phase extraction columns. A concentration of 330 μg/l total nonylphenol was found in wastewaters from a sewage treatment works discharging into the river Aire, and up to 180 μg/l was measured at sites on the same river. Nonylphenol concentrations in the river Aire exceed Daphnia chronic effect levels and approach acute toxicity levels. Elsewhere, concentrations in rivers and sewage effluents were in the range <0.2−12 μg/l total nonylphenol and are below chronic effect levels. Estuarine concentrations were considerably lower. The highest concentrations were recorded in the outer Tees estuary (5.2 μg/l nonylphenol, 13 μg/l octylphenol) and in the Mersey estuary (up to 0.32 μg/l nonylphenol). Over 30% of the samples contained <0.1 μg/l total nonylphenol, and octylphenol was present only in the Tees.
Specific analytical techniques were used to study the behaviour of alkylphenol polyethoxylate surfactants (APnEO) in several full-scale mechanical-biological sewage treatment plants in the Glatt Valley, Switzerland. Both parent compounds and the major metabolic products were quantified. Untreated sewage and primary effluents contained considerable amounts of surfactant-derived nonylphenolic compounds (3.0–9.6% of the dissolved organic carbon). Parent nonylphenol polyethoxylates (nEO = 3–20) were efficiently eliminated during biological treatment. However, the overall rate of biodegradation was limited due to the formation of biorefractory metabolites, including nonylphenol (NP), nonylphenol mono- and diethoxylate (NP1EO, NP2EO) and nonylphenoxy carboxylic acids (NPEC). The abundance of a particular metabolite was very dependent on the treatment conditions. Studies of the mass flows of nonylphenolic compounds in sewage treatment plants indicated that their fate was determined not only by microbial transformation, but also by physicochemical processes.
Laboratory batch techniques were used to study the sorptive behaviour of 4-t-octylphenol (OP), a xenobiotic with oestrogenic properties, to sediments from three English rivers of contrasting water quality. Samples were taken from industrially polluted lower reaches of the Aire and Calder rivers, in the Humber catchment, as well as a rural reach of the River Thames, in Oxfordshire in the South of England. The results showed that given either sufficient time or mixing, a large proportion of OP in solution will sorb to the bed-sediments, with distribution coefficients (Kd) of 6–700 l kg−1 and organic carbon normalised partition coefficients (Koc) 3500–18 000 l kg−1. The sediments which sorbed the highest quantities of OP had higher total organic carbon and a greater proportion of clay and silt particles. There was evidence in some bed-sediments of a sorption-desorption hysteresis effect between OP and sediment. The suspended sediments, on a carbon for carbon basis, adsorbed 5–35 times more OP than their respective bed-sediments in the Aire and Calder rivers: microscopic examination suggested that the suspended sediments were predominantly organic aggregates. The suspended sediments of the Thames adsorbed far less OP than those of the Aire and Calder: microscopic examination revealed these suspended sediments to be largely algae. The work predicts that suspended sediments may play a key role in the fate of OP in the industrial reaches of English Rivers. In the comparatively rural reach of the Thames, a higher proportion of OP might be predicted to remain free in solution.
Nonylphenol and its ethoxylates are on the second priority substances list (PSL2) to determine if they are ‘toxic’ as defined under the Canadian Environmental Protection Act. This study addresses the need for data on their occurrence in surface waters and sediments in Canada. Samples of surface water from 35 sites in the Laurentian Great Lakes basin and the upper St. Lawrence River were analyzed for 4-nonylphenol (4-NP), nonylphenol ethoxylate (NPE1), nonylphenol diethoxylate (NPE2) and 4-tert-octylphenol (4-t-OP). Bottom sediment samples from nine heavily industrialized sites were also analyzed for the same chemicals. Measurable quantities of 4-NP and 4-t-OP were found in 24% of all water samples. Values ranged from <0.010 μg to 0.92 μg/l and from <0.005 to 0.084 μg/l for 4-NP and 4-t-OP, respectively. Of the surface water samples, 58% were found to contain NPE1 and 32% contained NPE2. Their concentrations ranged from <0.020 to 7.8 μg/l for NPE1 and from <0.020 to 10 μg/l for NPE2. All nine sediment samples contained 4-nonylphenol, with values ranging from 0.17 to 72 μg/g (dry weight). The majority of sediment samples also contained detectable levels of the other contaminants. A total of 66% of sediments had detectable amounts of NPE1 and concentrations ranged from <0.015 to 38 μg/g (dry weight), 66% of sediments had detectable amounts of NPE2 and values ranged from <0.015 to 6.0 μg/g (dry weight) and 89% of sediment samples had detectable amounts of 4-t-OP and values ranged from <0.010 to 1.8 μg/g (dry weight). The highest concentrations of the analytes found are well below acute toxicity thresholds, but in some cases there may be cause for concern with regard to long-term effects on reproductive health of fish.
The acute and chronic toxicity of nonylphenol to the freshwater invertebrate Daphnia magna has been determined. The acute 24 and 48 h EC50 values, based on immobilization, were 0.30 and 0.19 mg/l, respectively, using mean measured concentrations. In a separate study, effects of nonylphenol on survival, growth and reproduction of D. magna were measured over a period of 21 days. The no observed effect concentration (NOEC), based on mean measured concentrations, was found to be 0.024 mg/l. This is approximately one order of magnitude below the acute value and one order of magnitude higher than the highest reported environmental levels.
Partition coefficients of octylphenol (OP), nonylphenol (NP) and nonylphenol ethoxylates (NPnEO, n = 1–3) were determined for and systems. In the octanol/water system, logarithmic values of the partition coefficients (log KOW) for the phenols were 4.12 and 4.48 for OP and NP, respectively. Slightly lower lipophilicity was found for APnEO with log KOW values of NP1EO, NP2EO and NP3EO around 4.2. The corresponding values in hexane/water system were approximately 0.8 logarithmic units lower but showed essentially the same ratio between NP and NPnEO as it was observed in the octanol water system. An attempt was made to estimate octanol/water partition coefficients for higher OPnEO and NPnEO oligomers. Application of reversed-phase HPLC for this purpose resulted in a significant overestimation. Alternatively, octanol/water partition coefficients for the higher APnEO oligomers were estimated (i) using an equation that correlates log KOW with solubility and (ii) converting the respective partition coefficients to the octanol/water coefficients.
On the basis of solid-phase extraction, a simple procedure for determining simultaneously two aromatic surfactant classes, i.e., linear alkylbenzene sulfonates (LAS) and nonylphenol polyethoxylates (NPEO), as well as their biodegradation intermediates in raw and treated sewages is presented. This procedure involved passing 10 and 100 mL of an influent and effluent water sample, respectively, through a 1-g graphitized carbon black (GCB) extraction cartridge. By exploiting the presence of positively charged active centers on the GCB surface, we succeeded in fractionating the complex mixture of the analytes considered by differential elution. The first fraction contained NPEO and nonylphenol (NP). The second fraction contained the carboxylated biotransformation products of NPEO, i.e., nonylphenoxy carboxylic acids (NPEC). Finally, the last fraction contained LAS and their metabolites, i.e., carboxylic sulfophenyl acids (SPC). By suitably adjusting the chromatographic conditions, any group of analytes was subfractionated and quantified by liquid chromatography with fluorometric detection. Recoveries of all compounds of interest ranged between 89 % and 99%. This procedure was empolyed for 1 year to assess monthly the concentrations of the analytes considered in raw and treated sewages of a mechanical-biological treatment plant.
U.S. and European regulators and researchers disagree over risks of a common class of surfactants.
It is becoming evident that an increasing number of widely used industrial and agricultural chemicals are estrogenic. The biodegradation products of a major group of nonionic surfactants, the alkylphenol polyethoxylates, are one such group. Some of these chemicals are widespread aquatic pollutants, and bioconcentrate in aquatic biota. Exposure of male rainbow trout (Oncorhynchus mykiss) to four different alkylphenolic chemicals caused synthesis of vitellogenin, a process normally dependent on endogenous estrogens, and a concomitant inhibition of testicular growth. The magnitude of these estrogenic effects was dependent on the estrogenic potency of the chemical, the stage of reproductive development of the fish, and the concentration of the chemical in the water. These results support the contention that exposure of wildlife to environmentally persistent estrogenic chemicals can result in deleterious reproductive consequences.
Anaerobically treated sewage sludge was found to contain extraordinarily high concentrations of 4-nonylphenol, a metabolite derived from nonionic surfactants of the nonylphenol polyethoxylate type. Concentrations in activated sewage sludge, in mixed primary and secondary sludge, and in aerobically stabilized sludge were substantially lower, suggesting that the formation of 4-nonylphenol is favored under mesophilic anaerobic conditions. Because 4-nonylphenol may be highly toxic to aquatic life, further research is needed on the fate of 4-nonylphenol after sludge is disposed of in the environment.