Monitoring the photochemical degradation of triclosan in wastewater by UV light and sunlight using solid-phase microextraction

Photo solid-phase microextraction (photo-SPME) is applied for the first time to study the photochemical behavior of an emerging pollutant, triclosan, in real contaminated wastewater samples using a solar simulator. In this study, water samples are extracted by SPME and then, the fiber coating is irradiated for a selected time. This on-fiber procedure, so-called photo-SPME, followed by gas chromatography-mass spectrometry makes it possible to study photodegradation kinetics and the generation of byproducts. Several photoproducts were identified in the real samples including the 2,8-dichlorodibenzo-p-dioxin, dichlorophenols and a compound tentatively identified as other DCDD congener or a dichlorohydroxydibenzofuran. Accordingly, it was possible to postulate main photodegradation mechanisms. Photo-SPME demonstrated slower kinetics in wastewater than in spiked ultrapure water probably due to the presence of dissolved organic matter. This technique was extensively compared with conventional aqueous photodegradation showing high similarity. The influence of pH on the triclosan photolysis and on the triclosan-dioxin conversion was also investigated in wastewater. Photodegradation of triclosan and formation of 2,8-DCDD occurred independently of sample pH. This study represents an advance in the use of photo-SPME to understand the photochemical fate of environmental organic pollutants and demonstrates its clear advantages with real samples.     

Determination of selected pharmaceuticals and caffeine in sewage and seawater from Tromsø/Norway with emphasis on ibuprofen and its metabolites

Selected pharmaceuticals, among them analgesics, ss-blockers and anti-depressants as well as caffeine, the anti-bacterial triclosan and the insect repellent N,N-diethyl-3-toluamide (DEET) were determined in different sewage samples (sewage treatment plants, hospital effluents) from Troms?/Norway and in seawater from Troms?-Sound, into which the sewage is discharged. While caffeine, triclosan, ibuprofen and its major metabolites hydroxy- and carboxy-ibuprofen were present in all sewage samples, additional pharmaceuticals were observed in sewage containing hospital effluents. Concentrations were in the range of 20-293 microg/l (caffeine), 0.2-2.4 microg/l (triclosan) and 0.1-20 microg/l (sum ibuprofen + metabolites). In seawater, only caffeine (7-87 ng/l), DEET (0.4-13 ng/l) and ibuprofen + metabolites (sum concentration < LOQ-7.7 ng/l) were detected. Ibuprofen and its metabolites hydroxy- and carboxy-ibuprofen were quantified individually by use of the respective reference compounds. Relative amounts of the three compounds were determined in different types of water showing characteristic patterns, with hydroxy-ibuprofen being the major component in sewage whereas carboxy-ibuprofen was dominant in seawater samples. The patterns which were compared to those observed in similar samples from Germany indicated different transformation behaviour under limnic and marine conditions.     

Biological degradation of triclocarban and triclosan in a soil under aerobic and anaerobic conditions and comparison with environmental fate modelling

Triclocarban and triclosan are two antimicrobial agents widely used in many personal care products. Their biodegradation behaviour in soil was investigated by laboratory degradation experiments and environmental fate modelling. Quantitative structure-activity relationship (QSAR) analyses showed that triclocarban and triclosan had a tendency to partition into soil or sediment in the environment. Fate modelling suggests that either triclocarban or triclosan "does not degrade fast" with its primary biodegradation half-life of "weeks" and ultimate biodegradation half-life of "months". Laboratory experiments showed that triclocarban and triclosan were degraded in the aerobic soil with half-life of 108 days and 18 days, respectively. No negative effect of these two antimicrobial agents on soil microbial activity was observed in the aerobic soil samples during the experiments. But these two compounds persisted in the anaerobic soil within 70 days of the experimental period.     

Triclosan in Fresh Water Fish Gibelion Catla from the Kaveri River,India, and Its Consumption Risk Assessment

Triclosan is a common antimicrobial agent that is found in significant levels in the aquatic environment and may elicit effects on aquatic organisms through unexpected modes of action. In this study, triclosan was quantified in fish from the Kaveri River, India, by using the gas chromatography and mass spectrometry technique and it was found in the range of 0.73–50 ng/g wet weight (ww). The mean bioaccumulation factor based on water (BAF_w 820) and sediment (BAF_s 2.12) in the Kaveri River showed that triclosan is accumulative in fish, and reflects its feeding behavior. The bioaccumulation indicates triclosan's persistence or prevalence throughout the river stretch. Human risk assessment through dietary intake demonstrated that the triclosan exposure is five orders of magnitude lower than the acceptable daily intake (50 μg/kg bw) and US EPA reference dose (300 μg/kg bw/day). This investigation is the first to report the bioaccumulation of triclosan in freshwater fish from India. Further, the results indicate that this fish acts as a biomarker of exposure for triclosan and thus shall be used to report triclosan pollution in the future.     

Tissue distribution of organochlorine pesticides in fish collected from the Pearl River Delta, China: implications for fishery input source and bioaccumulation

Fish tissues from different fishery types (freshwater farmed, seawater farmed and seawater wild) were analyzed for organochlorine pesticides (OCPs), with the aim to further our understanding of bioaccumulation, and reflect the state of different fishery environments. Significantly higher SigmaOCP levels were found in seawater farmed fish than others, and among three freshwater farmed species, the lowest levels occurred in filter-feeding fish (bighead carp). Liver contained the highest SigmaOCP levels, while no significant differences were found among other tissues. Among DDT components, p,p'-DDT was abundant in seawater fish, while for freshwater fish, p,p'-DDE was the predominant congeners, except for northern snakehead (34% for p,p'-DDE and 30% for p,p'-DDT). The new source of DDTs to freshwater fish ponds was partly attributed to dicofol, whereas sewage discharged from the Pearl River Delta and anti-fouling paint were likely the DDTs sources to seawater farmed fish.     

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag–Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag–PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72 h in freshwater (500–600 μg L⁻¹) and seawater (1300–1500 μg L⁻¹), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag⁺ (1.1, 400 and 0.11 μg L⁻¹, respectively), Ag–Cit (3.0, 2380 and 0.15 μg L⁻¹, respectively) and Ag–PVP (19.5, 3690 and 2.0 μg L⁻¹, respectively) varied widely, with toxicity in the order Ag⁺ > Ag–Cit > Ag–PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag⁺ or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.     

Determinations and residual characteristics of triclosan in household food detergents of Taiwan

Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) is a widely used antibacterial agent. However, it was concerned recently that triclosan might act as an antibiotic and will cause resistant bacterial strains. Furthermore, possible formation of toxic chloroform was also reported when the triclosan contained in household dishwashing soaps reacted with the chlorinated water. To assess the associate risks from possible exposures, concentrations of triclosan in household food detergents of Taiwan were determined in this study. High performance liquid chromatography (HPLC) with UV detector at 280 nm was used to analyze the triclosan in samples. Factors that might affect the residual characteristics of triclosan from detergents on dishware and fruits, including the concentrations of detergents used, the temperature and immersion time for water before the cleaning processes, the temperatures of water used for the cleaning processes, and the materials of dishware made of, were evaluated under the orthogonal experiment design by the Taguchi method. By the analysis of variance, the orders of importance of different parameters were determined. The concentrations of triclosan detected in household food detergents were found to be 1.7 x 10(-2) -5.6 x 10(-1) (triclosan/detergent, mg g(-1)). For residual characteristics, the concentration of detergents used as well as the materials of dishware were found to be the significant factors that will affect the triclosan left on the dishware. On the other hand, the concentration of triclosan in the detergents was found to be the only factor that will affect the triclosan left on fruits. The maximum dose of triclosan exposures from the use of household food detergents in Taiwan was also estimated in the study.     

Triclosan in individual human milk samples from Australia

Triclosan is a chlorinated phenol ether that has been in widespread use as a broad-spectrum antibacterial agent for four decades. When compared to the limited international data available on human body burden of triclosan, results from a pooled blood study suggested that triclosan concentrations in Australia were a factor two higher than observed in Sweden. This study determined triclosan levels in individual human milk samples (n = 151) collected between 2002 and 2005 from primiparous Australian mothers. It provided the first report of population triclosan levels and individual variation in Australia and gave a measure of infant exposure via breast feeding. The distribution of triclosan concentration was positively skewed, with 7.2% of the samples below the LOQ, 66% with a concentration of less than or equal to 1.0 ng g⁻¹ fresh weight and the remaining samples above 1 ng g⁻¹ reaching a maximum concentration of 19 ng g⁻¹ fresh weight. The mean and median triclosan concentrations were 1.3 ± 2.7 ng g⁻¹ f.w. and 0.26 ng g⁻¹ f.w., respectively. The results of this study showed high variability in triclosan concentrations between individuals and no correlations with maternal age (p = 0.094), maternal weight (p = 0.971) or infant age at the time of sample collection (p = 0.621). A large number of samples contained low or non-quantifiable concentrations of triclosan and so, in Australia, ubiquitous background exposure due to environmental sources is low. This means that body burden can be influenced by an individual’s use of triclosan containing product. Given that triclosan containing product use is continuing, it is important that monitoring in both humans and the environment is continued and that triclosan containing products are adequately labeled so that an individual can choose to avoid exposure.     

Degradation of 2,7-dichlorodibenzo-p-dioxin by Fe(3+)-H(2)O(2) mixed reagent

Fe(3+)-H(2)O(2) mixed reagent, but not Fe(2+)-H(2)O(2), was found to be capable of degrading 2,7-dichlorodibenzo-p-dioxin (DCDD). A reaction mixture of FeCl(3) (8 mM) and H(2)O(2) (1%) caused approximately 50% degradation within 6 h and >90% degradation within 24 h at 27 degrees C. Increasing the temperature remarkably stimulated degradation: at 70 degrees C, approximately 100% degradation was achieved within 15 min. When DCDD-treated model soil (5 micrograms/g) was conducted, approximately 100% of the DCDD was degraded within 30 min at 70 degrees C (both reagents were added every 10 min). These results suggest that Fe(3+)-H(2)O(2) mixed reagent may be a new tool for combating persistent environmental pollutants such as dioxins and polychlorinated biphenyls.     

Behavior and stability of organic contaminant droplets in aqueous solutions

The behavior of several hydrophobic organic compounds (HOCs) in water at concentrations close to and above their maximum solubility values was studied. For this purpose, solutions of benzene, toluene, xylene, trichloroethylene (TCE) and a mixture of them were prepared in excess in freshwater and in saltwater, and solution stability was examined. High organic concentrations were found to remain stable in both freshwater and saltwater. In saltwater, for example, toluene and xylene concentrations remained as high as 14 and 26 times their solubilities, respectively, over a period of 6 days, while in freshwater, their concentrations remained 8 and 30 times their solubilities over the same period. This phenomenon is attributed to the presence of stable organic droplets, which were observed using optical microscopy. In addition, the transport of HOC droplets through sand is demonstrated, using an experimental system consisting of a saltwater source reservoir connected by a porous inactive sand layer to a freshwater collector reservoir.     

Occurrence of triclosan in plasma of wild Atlantic bottlenose dolphins (Tursiops truncatus) and in their environment

The presence of triclosan, a widely-used antibacterial chemical, is currently unknown in higher trophic-level species such as marine mammals. Blood plasma collected from wild bottlenose dolphins (Tursiops truncatus) in Charleston, SC (CHS) (n = 13) and Indian River Lagoon, FL (IRL) (n = 13) in 2005 was analyzed for triclosan. Plasma concentrations in CHS dolphins ranged from 0.12 to 0.27 ng/g wet weight (mean 0.18 ng/g), with 31% of the sampled individuals having detectable triclosan. The mean IRL dolphin plasma concentrations were 0.072 ng/g wet weight (range 0.025–0.11 ng/g); 23% of the samples having detectable triclosan. In the CHS area, triclosan effluent values from two WWTP were both 190 ng/L and primary influents were 2800 ng/L and 3400 ng/L. Triclosan values in CHS estuarine surface water samples averaged 7.5 ng/L (n = 18) ranging from 4.9 to 14 ng/L. This is the first study to report bioaccumulation of anthropogenic triclosan in a marine mammal highlighting the need for further monitoring and assessment.     

特殊工况下船舶生活污水处理的试验研究

采用厌氧复合床反应器与接触氧化、接触沉淀相结合的工艺,针对实船条件下可能出现的重启动、倾斜、海水及淡水海水交替冲洗厕所和水力负荷增加等情况,进行了特殊工况下船舶生活污水处理的试验研究.结果表明,该组合工艺在设计条件下(HRT为5 h)重启动速度较快,可用于海水冲厕所产生的高盐度污水处理,耐受淡水海水交替变化的盐度冲击负荷变化能力较强,具有一定的水力负荷增加潜力,并且不受倾斜影响.     

Triclosan in individual human milk samples from Australia

Triclosan is a chlorinated phenol ether that has been in widespread use as a broad-spectrum antibacterial agent for four decades. When compared to the limited international data available on human body burden of triclosan, results from a pooled blood study suggested that triclosan concentrations in Australia were a factor two higher than observed in Sweden. This study determined triclosan levels in individual human milk samples (n = 151) collected between 2002 and 2005 from primiparous Australian mothers. It provided the first report of population triclosan levels and individual variation in Australia and gave a measure of infant exposure via breast feeding. The distribution of triclosan concentration was positively skewed, with 7.2% of the samples below the LOQ, 66% with a concentration of less than or equal to 1.0 ng g⁻¹ fresh weight and the remaining samples above 1 ng g⁻¹ reaching a maximum concentration of 19 ng g⁻¹ fresh weight. The mean and median triclosan concentrations were 1.3 ± 2.7 ng g⁻¹ f.w. and 0.26 ng g⁻¹ f.w., respectively. The results of this study showed high variability in triclosan concentrations between individuals and no correlations with maternal age (p = 0.094), maternal weight (p = 0.971) or infant age at the time of sample collection (p = 0.621). A large number of samples contained low or non-quantifiable concentrations of triclosan and so, in Australia, ubiquitous background exposure due to environmental sources is low. This means that body burden can be influenced by an individual’s use of triclosan containing product. Given that triclosan containing product use is continuing, it is important that monitoring in both humans and the environment is continued and that triclosan containing products are adequately labeled so that an individual can choose to avoid exposure.     

A field study of triclosan loss rates in river water (Cibolo Creek, TX)

Triclosan (TCS) is an anti-microbial agent used in down-the-drain consumer products. Following sewage treatment some of the triclosan will enter receiving waters. This study was designed to determine the die-away rate of triclosan released into a river as part of the sewage treatment plant effluent matrix. The study was conducted in Cibolo Creek, a moderate sized stream (discharge approximately 0.1 m(3)s(-1)) located in South Central Texas. Triclosan was analyzed from samples collected upstream of the sewage treatment plant, the sewage treatment plant effluent, and the river downstream from the effluent discharge. The first-order loss rate of parent triclosan from the water column was calculated from measured data (0.06 h(-1)) and this rate corresponded to a 76% reduction in triclosan over an 8 km river reach below the discharge. Mathematical modeling indicated that sorption and settling accounted for approximately 19% of total triclosan loss over 8 km. When removing sorption and settling, the remaining amount of triclosan had an estimated first-order loss rate of 0.25 h(-1). This loss rate was presumably due to other processes such as biodegradation and photolysis. These data show that loss of parent triclosan from the water column is rapid. Additional data are needed to fully document loss mechanisms.     

Kinetic effects on the interactions of Rh(III) with humic acids as determined using size-exclusion chromatography (SEC)

The anthropogenic inputs of Rh in the environment—together with other platinum group elements—have increased considerably during the last 20–30 years. However, thermodynamics and kinetics on the interaction of Rh with natural organic and inorganic ligands are still poorly characterized. Here, we report the time-dependent speciation of rhodium chlorides spiked to model freshwater with and without the presence of humic substances. Rhodium species were determined using size-exclusion chromatography-inductively coupled plasma mass spectrometry (SEC-ICP-MS). Results indicate that organic matter can effectively bind rhodium, but the extremely slow reaction kinetics of Rh plays a significant role on its speciation in natural waters. Accordingly, formation of Rh-organic complexes from spiked rhodium chlorides required around 15 days to reach equilibrium; this should be taken into account in those laboratory experiments where the biological interactions of Rh, using spiked samples, are studied. Regarding Rh inorganic speciation in freshwater, the available thermodynamic constants predict the dominance of the neutral trihydroxo and negatively charged tetrahydroxo rhodium complexes over typical pHs (6–8); our results, however, indicate only the presence of negatively charged hydroxocomplexes at pH 7. Reexamination of the Rh stability constants suggest that these hydroxylated rhodium complexes may also dominate its inorganic speciation in seawater.     

Removal and formation of chlorinated triclosan derivatives in wastewater treatment plants using chlorine and UV disinfection

Triclosan, a common antimicrobial agent, may react during the disinfection of wastewater with free chlorine to form three chlorinated triclosan derivatives (CTDs). This is of concern because the CTDs may be photochemically transformed to tri- and tetra-chlorinated dibenzo-p-dioxins when discharged into natural waters. In this study, wastewater influent, secondary (pre-disinfection) effluent, and final (post-disinfection) effluent samples were collected on two occasions each from two activated sludge wastewater treatment plants, one using chlorine disinfection and one using UV disinfection. Concentrations of triclosan and three CTDs were determined using ultra performance liquid chromatography-triple quadrupole mass spectrometry with isotope dilution methodology. Triclosan and the CTDs were detected in every influent sample at levels ranging from 453 to 4530 and 2 to 98 ng L⁻¹, respectively, though both were efficiently removed from the liquid phase during activated sludge treatment. Triclosan concentrations in the pre-disinfection effluent ranged from 36 to 212 ng L⁻¹, while CTD concentrations were below the limit of quantification (1 ng L⁻¹) for most samples. In the treatment plant that used chlorine disinfection, triclosan concentrations decreased while CTDs were formed during chlorination, as evidenced by CTD levels as high as 22 ng L⁻¹ in the final effluent. No CTDs were detected in the final effluent of the treatment plant that used UV disinfection. The total CTD concentration in the final effluent of the chlorinating treatment plant reached nearly one third of the triclosan concentration, demonstrating that the chlorine disinfection step played a substantial role in the fate of triclosan in this system.     

Occurrence and distribution of triclosan in the German Bight (North Sea)

The potential of triclosan (TCS) acting as an endocrine disruptor has led to growing concern about the presence of TCS in the environment. In this study, seawater samples were collected from the German Bight during sampling campaigns conducted with the German research ships Gauss and Ludwig Prandtl. TCS was determined both in the dissolved phase and in the suspended particulate matters with concentrations ranging 0.8-6870 pg L⁻¹ and <1-95 pg L⁻¹, respectively. High concentrations of TCS were present in the estuaries of the Elbe and the Weser, indicating significant input of TCS by the river discharge. The correlation coefficient (R²) between the dissolved concentration and salinity was 0.79 for the data obtained from the Gauss cruise, showing an obvious declining trend from the coast to the open sea.     

Salinity and nutrient modulate soil bacterial communities in the coastal wetland of the Yellow River Delta,China

The Yellow River Delta is the largest and youngest estuarine and coastal wetland in China and is experiencing the most active interactions of seawater and freshwater in the world. Bacteria played multifaceted influence on soil biogeochemical processes, and it was necessary to investigate the intermodulation between the soil factors and bacterial communities. Soil samples were collected at sites with different salinity degree, vegetations, and interference. The sequences of bacilli were tested using 16S rRNA sequencing method and operational taxonomic units were classified with 97% similarity. The soil was highly salinized and oligotrophic, and the wetland was nitrogen-restricted. Redundancy analysis suggested that factors related with seawater erosion were principal to drive the changes of soil bacterial communities and then the nutrient level and human disturbance. A broader implication was that, in the early succession stages of the coastal ecosystem, seawater erosion was the key driver of the variations of marine oligotrophic bacterial communities, while the increasing nutrient availability may enhance in the abundance of the riverine copiotrophs in the late stages. This study provided new insights on the characteristics of soil bacterial communities in estuarine and coastal wetlands.

     

Evaluation of aquatic plants for removing polar microcontaminants: a microcosm experiment

Microcosm wetland systems (5 L containers) planted with Salvinia molesta, Lemna minor, Ceratophyllum demersum, and Elodea canadensis were investigated for the removal of diclofenac, triclosan, naproxen, ibuprofen, caffeine, clofibric acid and MCPA. After 38 days of incubation, 40-99% of triclosan, diclofenac, and naproxen were removed from the planted and unplanted reactors. In covered control reactors no removal was observed. Caffeine and ibuprofen were removed from 40% to 80% in planted reactors whereas removals in control reactors were much lower (2-30%). Removal of clofibric acid and MCPA were negligible in both planted and unplanted reactors. The findings suggested that triclosan, diclofenac, and naproxen were removed predominantly by photodegradation, whereas caffeine and naproxen were removed by biodegradation and/or plant uptake. Pseudo-first-order removal rate constants estimated from nonlinear regressions of time series concentration data were used to describe the contaminant removals. Removal rate constants ranged from 0.003 to 0.299 d(-1), with half-lives from 2 to 248 days. The formation of two major degradation products from ibuprofen, carboxy-ibuprofen and hydroxy-ibuprofen, and a photodegradation product from diclofenac, 1-(8-Chlorocarbazolyl)acetic acid, were followed as a function of time. This study emphasizes that plants contribute to the elimination capacity of microcontaminants in wetlands systems through biodegradation and uptake processes.     

Photocatalytic oxidation of triclosan

In the spring of 2003, there was an outbreak of the severe respiratory syndrome (SARS) in Hong Kong. Health concerns have thus triggered an increased and predominant use of various types of household cleansing agents such as triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol). However, it has been reported recently that triclosan could be photochemically converted to toxic 2,8-dichlorodibenzo-p-dioxin (2,8-Cl(2)DD) in the environment. It is therefore necessary to develop environmentally friendly methods for the treatment of triclosan. To this end, photocatalytic degradation of triclosan in aqueous solution was conducted using TiO(2) (Degussa P25) under irradiation of UV light (lambda < 365 nm). It was found that triclosan could be degraded by this approach. Hydrogen peroxide was added to enhance the degradation process, and the optimal initial hydrogen peroxide concentration for triclosan degradation was 0.005% (w/v). Product identification indicated that triclosan oxidation occurred at its phenol moiety and yielded quinone and hydroquinone intermediates. The formation of a dichlorophenol intermediate in triclosan degradation suggested bond-breaking of the ether linkage occurred during the process. Moreover, no chlorinated dibenzo-p-dioxin congener was detected. These findings confirm that the photocatalytic degradation of triclosan is an environmentally friendly process.