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Prevalence, production, and ecotoxicity of chlorination-derived metformin byproducts in Chinese urban water systems

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Abstract

The widely used antidiabetic drug metformin has become an emerging contaminant of water systems. In a prior study, we demonstrated the marked mammalian toxicity of the disinfection-derived byproducts (DBPs) Y (yellow, C4H6ClN5) and C (colorless, C4H6ClN3), and here assess the distribution, formation, and ecotoxicity of these in Chinese urban water systems. A national tap water assessment showed that metformin and C concentrations were higher in large, dense urban areas and surface water sources than in sparsely populated areas and groundwater sources. Water types' analysis clearly showed that C derived from chlorination of metformin-contaminated water (up to 4308.5 ng/L) circulated from domestic water (0.7–9.7 ng/L) via sewage (2.3 ng/L in effluent) to surface water (0.6–3.5 ng/L). Simulated disinfection and aqueous stability results systematically showed rapid formation and 24 h stability of both byproducts, indicating high exposure odds for water users. Both byproducts showed clear but distinct toxic effects on the growth (72 h IC50, 0.6 mg/L for Y and 4.4 mg/L for C) and photosynthesis of the microalgae Pseudokirchneriella subcapitata at milligram levels. Combinedly, our work reveals that metformin byproducts have been disseminated to urban water cycle and contaminated tap water, increasing potential toxic risk for drinking water. Its outcomes provide a preliminary reference for future studies on the environmental fate and ecotoxicological effects of unintended DBPs formed in the chlorination of metformin-contaminated water.

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... Additionally, PPCPs introduced into the water supply are subject to HOCl-mediated chlorination and subsequent formation of CBPs. For example, common drugs including metformin, diclofenac, and tamoxifen entering freshwater sources are subject to direct chlorination causing drinking water contamination associated with largely unexplored implications for human health (126)(127)(128)(129). Likewise, chlorination of PPCPs including sunscreen ingredients such as the common UVAsunscreen avobenzone are associated with formation of a dichloro-species, and cosmetics are equally subject to chlorination with unexplored effects on human health (16,(130)(131)(132)(133)(134)(135). ...
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In this study we developed a systematic method for suspect screening and target quantification of the human pharmaceutical residues in water, via solid phase extraction (SPE) followed by liquid chromatography-high resolution mass spectrometry (LC-HRMS). We then proceeded to study the occurrences and distribution of the pharmaceuticals in the surface waters of Wuhan, China, by analyzing water samples from lakes, rivers and municipal sewage. Initially, 33 human pharmaceuticals were identified from East Lake without using purchasing standards. Of these, 29 were later confirmed by using standards, and quantified using the aforementioned SPE pretreatment method and LC-HRMS analysis in full MS scan mode. The 29 compounds included 8 antibiotics, 9 metabolites, and 12 miscellaneous pharmaceuticals. The highest proportions of pharmaceutical residues were detected downstream of the Yangtze River and in the lakes close to the central city. Metformin, cotinine, and trans-3-hydroxy cotinine, were frequently encountered in all the surface water samples. High concentrations (>120 ng/l) of caffeine, metformin, theobromine, and valsartan were detected in the surface water samples; the removal rates of these compounds in the municipal sewage treatment plant were also high. In contrast, although the concentrations of 4-AAA and metoprolol acid in the surface water were high, the removal rates of these residues in the sewage treatment plant were low.
Article
The North American Great Lakes are a vital natural resource that provide fish and wildlife habitat, as well as drinking water and waste assimilation services for millions of people. Tributaries to the Great Lakes receive chemical inputs from various point and non-point sources, and thus are expected to have complex mixtures of chemicals. However, our understanding of the co-occurrence of specific chemicals in complex mixtures is limited. To better understand the occurrence of specific chemical mixtures in the U.S. Great Lakes basin, surface water from 24 U.S. tributaries to the Laurentian Great Lakes was collected and analyzed for diverse suites of organic chemicals, primarily focused on chemicals of concern (e.g. pharmaceuticals, personal care products, fragrances, etc.). A total of 181 samples and 21 chemical classes were assessed for mixture compositions. Basin wide, 1,664 mixtures occurred in at least 25% of sites. The most complex mixtures identified were comprised of nine chemical classes and occurred in 58% of sampled tributaries. Pharmaceuticals typically occurred in complex mixtures, reflecting pharmaceutical-use patterns and wastewater facility outfall influences. Fewer mixtures were identified at lake or lake-influenced sites than at riverine sites. As mixture complexity increased, the probability of a specific mixture occurring more often than by chance greatly increased, highlighting the importance of understanding source contributions to the environment. This empirically-based analysis of mixture composition and occurrence may be used to focus future sampling efforts or mixture toxicity assessments. This article is protected by copyright. All rights reserved.
Article
Stable dispersion of nanoparticles with environmentally-friendly materials is important for their various applications including environmental remediation. In this study, we systematically examined the mechanisms of stable dispersion of two types of TiO2nanoparticles (TNPs) with anatase and rutile crystalline structures by naturally occurring dissolved organic matter (humic acid) at different pHs, including at, below and above the Point of Zero Charge (PZC). The results showed that stable dispersion of TNPs by humic acid (HA) at all pHs tested can only be achieved with the assistance of ultra-sonication. The dispersion of TNPs by HA differed at the three pHs tested. Generally, HA greatly decreased the hydrodynamic diameters of TNPs at a very low concentration. The dispersion of TNPs became relatively stable when the HA concentration exceeded 5 mg/L, indicating that this HA concentration is required for stable dispersion of TNPs. The mechanisms involved in dispersion of TNPs by HA included electrostatic repulsion, steric hindrance and hydrophobic interaction. Electrostatic repulsion was identified to be the dominant mechanism. The dispersion of TNPs was enhanced when HA was added before ultra-sonication to avoid the partly irreversible re-aggregation of TNPs after sonication. The crystalline phases and concentrations of TNPs were also found to influence their stable dispersion. The findings from this work enhance understanding of the combined effects of HA, pH, ultra-sonication and crystalline structures of TNPs on their stable dispersion. The mechanisms identified can improve applications of TNPs in environmental water pollution control.
Article
Iodide photolysis under UV illumination affords an effective method to produce hydrated electrons (eaq–) in aqueous solution. Therefore, UV/Iodide photolysis can be utilized for the reductive degradation of many recalcitrant pollutants. However, the effect of naturally occurring organic matter (NOM) such as humic and fulvic acids (HA/FA), which may impact the efficiency of UV/Iodide photoreduction, is poorly understood. In this study, the UV photoreductive degradation of perfluorooctane sulfonate (PFOS) in the presence of I⁻ and HA is studied. PFOS undergoes a relatively slow direct photoreduction in pure water, a moderate level of degradation via UV/Iodide, but a rapid degradation via UV/Iodide/HA photolysis. After 1.5 h of photolysis, 86.0% of the initial [PFOS] was degraded in the presence of both I⁻ and HA with a corresponding defluorination ratio of 55.6%, whereas only 51.7% of PFOS was degraded with a defluorination ratio of 4.4% via UV/Iodide illumination in the absence of HA. The relative enhancement in the presence of HA in the photodegradation of PFOS can be attributed to several factors: a) HA enhances the effective generation of eaq– due to the reduction of I2, HOI, IO3⁻ and I3⁻ back to I⁻; b) certain functional groups of HA (i.e., quinones) enhance the electron transfer efficiency as electron shuttles; c) a weakly-bonded association of I⁻ and PFOS with HA increases the reaction probability; and d) absorption of UV photons by HA itself produces eaq–. The degradation and defluorination efficiency of PFOS by UV/Iodide/HA process is dependent on pH and HA concentration. As pH increases from 7.0 to 10.0, the enhancement effect of HA improves significantly. The optimal HA concentration for the degradation of 0.03 mM PFOS is 1.0 mg L⁻¹.
Article
Pharmaceuticals and personal care products are released into aquatic environments, largely as a result of ineffectual removal during wastewater treatment. Here we present a screening strategy based on the use of three commercially available mass spectral databases, combined into a single searchable entity and parallelized by cluster computing. In addition to this, a targeted solid phase extraction method with Ultra High Pressure Liquid Chromatography coupled to quadrupole time of flight mass spectrometry (UHPLC-QTOF) was used to quantify 99 pharmaceuticals in South African surface water on a national level. Limits of quantification were in the low ng/L range for the majority of the compounds and it was found that nationally both Lamotrigine and Nevirapine occurred most often. Prednisolone and Ritonavir were present at the highest average concentration; 623 and 489 ng/L respectively. It is however shown that more than 50% of the targets chosen for analysis are not detectable in any of the samples, which highlights the utility of untargeted, database driven screening; prior to the use of costly analytical standards. Untargeted screening detected 45% of the compounds detected in targeted mode, and furthermore tentatively identified a total of 4273 unique compounds across the samples. Automatically triggered MS/MS analyses yielded 92 unique hits with greater than 95% confidence. It is therefore suggested that untargeted screening should precede the targeted approach as a matter of economy and to guide the selection of targets for quantification. There is however great room for improvement in current commercial database search methodologies as a large bottleneck exists due to processing time.
Article
Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are two widely used polyfluorinated compounds (PFCs) and are persistent in the environment. This study for the first time systematically investigated their toxicities and the underlying mechanisms to Escherichia coli. Much higher toxicity was observed for PFOA than PFOS, with the 3 h half growth inhibition concentrations (IC50) determined to be 10.6 ± 1.0 and 374 ± 3 mg L−1, respectively, while the bacterial accumulation of PFOS was much greater than that of PFOA. The PFC exposures disrupted cell membranes as evidenced by the dose-dependent variations of cell structures (by transmission electron microscopy observations), surface properties (electronegativity, hydrophobicity, and membrane fluidity), and membrane compositions (by gas chromatogram and Fourier transform infrared spectroscopy analyses). The increases in the contents of intracellular reactive oxygen species (ROS) and malondialdehyde and the activity of superoxide dismutase indicated the increment of oxidative stress induced by the PFCs in the bacterial cells. The fact that the cell growth inhibition was mitigated by the addition of ROS scavenger (N-acetyl cysteine) further evidenced the important role of oxidative damage in the toxicities of PFOS and PFOA. Eighteen genes involved in cell division, membrane instability, oxidative stress, and DNA damage of the exposed cells were up or down expressed, indicating the DNA damage by the PFCs. The toxicities of PFOS and PFOA to E. coli were therefore ascribed to the membrane disruption, oxidative stress, and DNA damage induced cell inactivation and/or death. The difference in the bactericidal effect between PFOS and PFOA was supposed to be related to their different dominating toxicity mechanisms, i.e., membrane disruption and oxidative damage, respectively. The outcomes will shed new light on the assessment of ecological effects of PFCs.
Article
Wastewater-based epidemiology (WBE) applies advanced analytical methods to quantify drug residues in wastewater with the aim to estimate illicit drug use at the population level. Transformation processes during transport in sewers (chemical and biological reactors) and storage of wastewater samples before analysis are expected to change concentrations of different drugs to varying degrees. Ignoring transformation for drugs with low to medium stability will lead to an unknown degree of systematic under- or overestimation of drug use, which should be avoided. This review aims to summarize the current knowledge related to the stability of commonly investigated drugs and, furthermore, suggest a more effective approach to future experiments. From over 100 WBE studies, around 50 mentioned the importance of stability and 24 included tests in wastewater. Most focused on in-sample stability (i.e., sample preparation, preservation and storage) and some extrapolated to in-sewer stability (i.e., during transport in real sewers). While consistent results were reported for rather stable compounds (e.g., MDMA and methamphetamine), a varying range of stability under different or similar conditions was observed for other compounds (e.g., cocaine, amphetamine and morphine). Wastewater composition can vary considerably over time, and different conditions prevail in different sewer systems. In summary, this indicates that more systematic studies are needed to: i) cover the range of possible conditions in sewers and ii) compare results more objectively. To facilitate the latter, we propose a set of parameters that should be reported for in-sewer stability experiments. Finally, a best practice of sample collection, preservation, and preparation before analysis is suggested in order to minimize transformation during these steps.
Article
As an environmental contaminant of anthropogenic origin metformin is present in the high ng/L- up to the low μg/L-range in most surface waters. Residues of metformin may lead to the formation of disinfection by-products during chlorine disinfection, when these waters are used for drinking water production. Investigations on the underlying chemical processes occurring during treatment of metformin with sodium hypochlorite in aqueous medium led to the discovery of two hitherto unknown transformation products. Both substances were isolated and characterized by HPLC-DAD, GC-MS, HPLC-ESI-TOF, (1)H-NMR and single-crystal X-ray structure determination. The immediate major chlorination product is a cyclic dehydro-1,2,4-triazole-derivate of intense yellow color (Y; C4H6ClN5). It is a solid chlorimine of limited stability. Rapid formation was observed between 10 °C and 30 °C, as well as between pH 3 and pH 11, in both ultrapure and tap water, even at trace quantities of reactants (ng/L-range for metformin, mg/L-range for free chlorine). While Y is degraded within a few hours to days in the presence of light, elevated temperature, organic solvents and matrix constituents within tap water, a secondary degradation product was discovered, which is stable and colorless (C; C4H6ClN3). This chloroorganic nitrile has a low photolysis rate in ambient day light, while being resistant to heat and not readily degraded in the presence of organic solvents or in the tap water matrix. In addition, the formation of ammonia, dimethylamine and N,N-dimethylguanidine was verified by cation exchange chromatography. Copyright © 2015 Elsevier Ltd. All rights reserved.
Article
Activated carbon is used in many drinking water facilities because it can remove a broad spectrum of contaminants (e.g., herbicides, pesticides, heavy metals, etc.) or to replace anthracite coal in dual media filters. In the last years, liquid chlorine has been substituted by chlorine dioxide (ClO2) because, for instance, it can remove natural organic matter in raw water without formation of harmful disinfection by-products. Interest in chlorine dioxide is due to formation of chlorite (ClO−2) which can be potentially toxic for humans. In this study, the authors investigated the applicability of two activated carbons coming from different matrices (coconuts and bituminous) as technology for chlorite removal. The activated carbons were tested at different conditions (virgin and pre-loaded with some substances) in order to simulate full-scale working situations, and their Freundlich isotherms were determined. The results show a good affinity of virgin carbons in chlorite removal (about 80%), but the pre-loading significantly affected the efficiency in chlorite removal process, reducing it to only 19%. Moreover, an investigation on main removal mechanism used by the carbons for chlorite removal was done. Results show that activated carbons used both reduction and adsorption processes.
Article
A gas-tight system for toxicity testing of highly volatile chemicals with the green algaChlamydomonas reinhardtii was developed. The procedure permits maintenance of constant and defined concentrations of the tested compounds in the vessels. To ensure sufficient CO2-supply, new bipartite test vessels were used. These vessels allowed spatial separation of a HCO3-/CO 3 (2-) buffer used for CO2 supply and the alga culture to avoid growth inhibition due to ionic strength. Several volatile chlorinated hydrocarbons have been tested. Their EC10 values were several orders of magnitude lower than those obtained with open test systems.
Article
The role of terrestrial humic substances as electron shuttles in bioreduction processes has gained broad acceptance as recognition has grown that the ability to transfer electrons to humic materials is distributed widely among microorganisms in nature. A fundamental property of humic substances pertinent to their mediation of reductive transformations is the maximum moles of electron charge they can transfer to an added oxidant, a parameter for which the name Reducing Capacity has been suggested. A number of different operational definitions of this important parameter have appeared in the literature recently, leading to conflicting terminology that has not heretofore been rationalized. In this paper, we present a consistent set of independent definitions of Reducing Capacity and develop laboratory methodologies for applying them, illustrating our concepts and methods with representative International Humic Substances Society (IHSS) humic acids that have been widely studied in connection with electron shuttling. Our principal results are: (1) non-negligible Reducing Capacity for humic acid (HA) maintained under oxic conditions, indicating that important reductant functional groups persist in humic substances, and (2) Reducing Capacity of chemically-reduced HA equal, within experimental precision, to that for microbially-reduced HA, indicating that chemical reduction can be used as a convenient laboratory method to assess the capacity of HA to be reduced by microorganisms. Our results also demonstrate that complexed Fe contributes negligibly to the Reducing Capacity of HA. We further illustrate our proposed definitions by applying them to interpret some published field data on the Reducing Capacity profile of HA measured in a freshwater lake sediment exhibiting a pronounced redox zonation.
Article
In recent years, much attention has been focused on developing heterogeneous catalyst for Fenton or photo-Fenton process to reuse the catalyst and avoid the possible pollution caused by the metal ions in the solution. Through cation exchange reaction, hydroxyl-Fe pillared bentonite (H-Fe-P-B) was successfully prepared as a solid catalyst for UV-Fenton process. Compared with raw bentonite, the content of iron, interlamellar distance and external surface area of H-Fe-P-B increased remarkably. Heterogeneous UV-Fenton catalytic degradation of azo-dye Acid Light Yellow G (ALYG) was investigated in aqueous using UVA (365nm) light as irradiation source. The effects of H2O2 concentration, catalyst dosage, initial pH and temperature on degradation of ALYG were studied in detail. The results demonstrated that the H-Fe-P-B had high catalytic activity. In optimal operation conditions, more than 98% discoloration and 65% TOC removal of 50mg/L ALYG could be achieved after 120min treatment. The iron leaching rates of H-Fe-P-B were all below 0.6% in multiple runs in the degradation of ALYG, which indicated that the heterogeneous catalyst had long-term stability and activity. Another advantage of this catalyst was its strong surface acidity, which made the range of pH for heterogeneous UV-Fenton system extended from 3.0 to 9.0. The results indicated that the H-Fe-P-B was a promising catalyst for heterogeneous UV-Fenton system.
Article
Metformin, an antidiabetic drug with one of the highest consumption rates of all pharmaceuticals worldwide, is biologically degraded to guanylurea in wastewater treatment plants. Due to high metformin influent concentrations of up to 100 μg/L and its high but incomplete degradation both compounds are released in considerable amounts of up to several tens of μg/L into recipient rivers. This is the first systematic study on their environmental fate and the effectiveness of treatment techniques applied in waterworks to remove metformin and guanylurea from surface water influenced raw waters. The concentrations in surface waters depend strongly on the respective wastewater burden of rivers and creeks and are typically in the range of about 1 μg/L for metformin and several μg/L for guanylurea but can reach elevated average concentrations of more than 3 and 20 μg/L, respectively. Treatment techniques applied in waterworks were investigated by an extended monitoring program in three facilities and accompanied by laboratory-scale batch tests. Flocculation and activated carbon filtration proved to be ineffective for removal of metformin and guanylurea. During ozonation and chlorination experiments with waterworks-relevant ozone and chlorine doses they were partly transformed to yet unknown compounds. The effectiveness of the treatment steps under investigation can be ordered chlorination > ozonation > activated carbon filtration > flocculation. However, most effective for removal of both compounds at the three full-scale waterworks studied proved to be an underground passage (riverbank filtration or artificial groundwater recharge). A biological degradation is most likely as sorption can be neglected. This is based on laboratory batch tests conducted with three different soil materials according to OECD guideline 106. Since such treatment steps were implemented in all three drinking water treatment plants, even traces of metformin and its metabolite guanylurea could not be detected at the end of the treatment trains. Both can only be expected in finished drinking water if surface influenced raw water is used by direct abstraction without underground passage.
Article
Nonylphenol is a metabolic intermediate from the microbial transformation of detergents used worldwide. While nonylphenol shows some acute toxicity, it is also able to mimic important hormones resulting in the disruption of several processes by interfering with the signals that control the overall physiology of the organism. The effect of the pollutant nonylphenol (NP) through the trophic chain was studied. Microalgae Isochrysis galbana was able to bioconcentrate NP 6940 times, where 77% of initial NP (100microgl(-1)) is accumulated intracellularly after 1-h incubation. Crustacean Artemia fransiscana showed 25% higher growth when fed with NP-rich algae. However, Artemia metabolized almost all NP ingested and only traces of NP could be found in the organism, eliminating future NP effects. Zebrafish (Brachydanio rerio) were affected by the presence of 171microgg(-1) of NP in the diet, showing higher levels of the hormone vitellogenin and lower levels of cytochrome P450 activity. These results showed that organisms placed in the first level of trophic chain are able to significantly bioconcentrate the pollutant and endocrine disruptor NP. These grassed organisms affect the growth of crustacean. Moreover, the organisms placed on the top of some trophic chains, such as fish, could be affected by the presence of NP in their food, in both the hormone levels and metabolic enzymes. This work shows that the environmental presence of NP should be considered as a risk for the organisms living in an ecosystem.
Article
The effect of nonylphenol (NP) on growth, photochemistry and biochemistry of two green microalgae, Chlorella vulgaris and Selenanstrum capricornutum, and their ability to degrade NP were compared. The 96 h EC50 of C. vulgaris and S. capricornutum were greater than 4.0 and 1.0 mg L(-1) NP, respectively, suggesting that the former species was more tolerant to NP. Both microalgae acclimated to NP stress through down-regulating their photosynthetic activities, including antenna size (chlorophyll a content), maximal photochemistry (Fv/Fm) and the light absorbed by PSII (ABS/CS0), but the dissipation of energy from reaction centres (DI0/RC) increased with the increase of NP concentrations. In C. vulgaris, the changes of these parameters were more significant than in S. capricornutum and recovered completely after a 96 h exposure. The antioxidant responses, such as GSH content, CAT and POD activities in C. vulgaris increased with the increase of NP concentrations after a 24h exposure, but these changes disappeared with exposure time and recovered to the control levels after 96 h. In S. capricornutum, although GSH content, CAT and POD activities also increased when exposed to low- to moderate-NP concentrations, these values were significantly reduced at a high concentration (4 mg L(-1)) even after a 96 h exposure, indicating its antioxidant responses were significantly delayed. It is clear that the more NP-tolerant species, C. vulgaris, acclimated better with a faster recovery of its photosynthetic activity from the NP-induced damage, and exhibited more efficient and rapid responses to NP-induced oxidative stress. C. vulgaris also had a higher NP degradation ability than S. capricornutum.
Article
Adsorption of natural organic matter (NOM) on nanoparticles (NPs) is important for evaluating their transport, transfer, and fate in the environment, which will also affect sorption of hydrophobic organic compounds (HOCs) by NPs and thereby potentially alter the toxicity of NPs and the fate, transport, and bioavailability of HOCs in the environment. Therefore, the adsorption behavior of humic acids (HA) by four types of nano-oxides (i.e., TiO2, SiO2, Al2O3, and ZnO) was examined in this study to explore their interaction mechanisms using techniques including Fourier transform infrared (FTIR) spectroscopy and elemental, zeta potential, and surface area analyses. Adsorption of HA was observed on nanosized TiO2, Al2O3, and ZnO but not on nano-SiO2. Furthermore, HA adsorption was pH-dependent. HA adsorption by nano-oxides was mainly induced by electrostatic attraction and ligand exchange between HA and nano-oxide surfaces. Surface hydrophilicity and negative charges of nano-oxides affected their adsorption of HA. However, the maxima of HA adsorption on nano-oxides were limited by the surface area of nano-oxides. HA phenolic OH and COOH groups were responsible for its ligand exchange with nano-TiO2 and nano-ZnO, respectively, while either HA COOH or HA phenolic/aliphatic OH was responsible for its ligand exchange with nano-Al2O3. HA adsorption decreased the micropore surface area of nano-oxides but not the external surface area because of the micropore blockage. HA adsorption also decreased the zeta potential of nano-oxides, indicating that HA-coated nano-oxides could be more easily dispersed and suspended and more stable in solution than uncoated ones because of their enhanced electrostatic repulsion.
Article
The acute toxicity of N-nitrosodimethylamine (DMN) and N-nitrosodiethylamine (DEN) was determined for three groups of aquatic organisms: algae, invertebrates, and fish. Toxicity of DMN and DEN to algae was assessed as a repression in the growth rate of either Selenastrum capricornutum or Anabaena flos-aquae in static bioassay tests. DMN and DEN concentrations of 1-10 ppm depressed algal growth in all cases. Invertebrate toxicity was determined in 96-h static bioassay tests with Dugesia dorotocephala and Gammarus limnaeus. The data indicated that these organisms are not highly susceptible to nitrosamine toxicity. The 96-h LC50s for D. dorotocephala were 1365 and 1490 ppm for DMN and DEN, respectively. Similar studies with G. limnaeus indicated LC50s of 330 and 500 ppm for DMN and DEN, respectively. Fish toxicity was also determined in 96-h statis bioassays with the fathead minnow (Pimephales promelas). Acute toxicities were calculated as LC50s of 940 and 775 ppm for DMN and DEN, respectively. Algae were calculated as LC50s of 940 and 775 ppm for DMN and DEN, respectively. Algae were quite sensitive to relative low levels of volatile nitrosamines, but higher organisms (invertebrates and fish) were relatively insensitive.
Article
The stability of diluted solutions of sodium hypochlorite was studied. Sodium hypochlorite 1% solutions were diluted (1:8, 1:12, and 1:20) and stored at room temperature in a window exposed to sunlight in amber-glass, two-liter bottles that were two-thirds full. Samples were taken 25 times throughout a six-month study period; bottles were opened only on sampling days. An iodometric titration was used to determine the percent available chlorine in each sample. Least-squares regression analyses of the percent available chlorine yielded lines with negative slopes for each dilution (-7.7 X 10(-6), -8.1 X 10(-6), and -1.5 X 10(-6) for the 1:8, 1:12, and 1:20 dilutions, respectively). Using the fastest degradation rate (from the 1:12 dilution), 5.24% of available chlorine would be lost per year. The concentration of sodium hypochlorite would therefore remain above 90% of the initial concentration for 22.9 months. It is concluded that sodium hypochlorite solution stored in amber-glass bottles should carry a 23-month expiry date on chemical stability.
Article
Working with primary-source freshwater drinking samples from the Clinch and Tennessee Rivers, we have developed a tissue-based biosensor detection system that uses naturally occurring aquatic photosynthetic tissue as the sensing material for detection of chemical antagonists in the water. Sensor readout is based on well-known principles of fluorescence induction by living photosynthetic tissue. The Clinch River is the main source of drinking water for Oak Ridge, Tennessee, while the Tennessee River is a major source for the city of Knoxville. We have successfully detected algae in every sample that we examined and readily monitored changes in the characteristic fluorescence induction curves when the samples were exposed to potassium cyanide (KCN), methyl parathion (MPt), N'(3,4-dichlorophenyl)-N,N-dimethylurea (DCMU), and paraquat. The percentage decreases in photochemical yields observed in Tennessee River samples after a 24-min exposure to KCN, MPt, and DCMU were, respectively, 21.89+/-0.76, 3.28+/-0.18, and 14.77+/-1.81. For a site at the Clinch River, the percentage decreases were 22.78+/-1.63, 8.32+/-0.21, and 17.71+/-1.32 (Table 1). The unique aspect of this approach to real-time water quality monitoring is that unlike conventional sensing devices, this sensor material is external to the detecting instrument and is continuously refreshed. These biosensors may be used as continuous rapid-warning sentinels for detection of chemical warfare agents in sunlight-exposed drinking water supplies.
Pharmaceuticals suppress algal growth and microbial respiration and alter bacterial communities in stream biofilms
  • Rosi-Marshall