Trace analysis of benzophenone-type UV filters in water and their effects on human estrogen and androgen receptors.

To carry out risk assessments of benzophenone-type UV filters (BPs), fast and accurate analytical methods are crucial to determine and monitor levels in the environment. This study presents an LC-MS/MS method that requires minimal sample preparation and yet can identify 10 different BPs in environmental samples such as surface or wastewater resulting in a LOQ range from 2 to 1060 ng/L. The method suitability was tested through environmental monitoring, which showed that, BP-4 is the most abundant derivative found in the surface waters of Germany, India, South Africa and Vietnam. BP-4 levels correlate with the WWTP effluent fraction of the respective river for selected samples in Germany. Peak values of 171 ng/L for 4-hydroxybenzophenone (4-OH-BP), as measured in Vietnamese surface water, already exceed the PNEC value of 80 ng/L, elevating 4-OH-BP to the status of a new pollutant that needs more frequent monitoring. Moreover, this study reveals that during biodegradation of benzophenone in river water, the transformation product 4-OH-BP is formed which contain structural alerts for estrogenic activity. By using yeast-based reporter gene assays, this study provides bio-equivalents of 9 BPs, 4-OH-BP, 2,3,4-tri-OH-BP, 4-cresol and benzoate and complements the existing structure-activities relationships of BPs and their degradation products.

Natural Zeolites for the Sorption of Ammonium: Breakthrough Curve Evaluation and Modeling.

The excessive use of ammonium fertilizer and its associated leakage threatens aquatic environments around the world. With a focus on the treatment of drinking water, the scope of this study was to evaluate and model the breakthrough curves for NH4+ in zeolite-filled, fixed-bed columns. Breakthrough experiments were performed in single- and multi-sorbate systems with the initial K+ and NH4+ concentrations set to 0.7 mmol/L. Breakthrough curves were successfully modeled by applying the linear driving force (LDF) and Thomas models. Batch experiments revealed that a good description of NH4+ sorption was provided by the Freundlich sorption model (R2 = 0.99), while unfavorable sorption was determined for K+ (nF = 2.19). Intraparticle diffusion was identified as the rate limiting step for NH4+ and K+ during breakthrough. Compared to ultrapure water, the use of tap, river, and groundwater matrices decreased the treated bed volumes by between 25% and 69%-as measured at a NH4+ breakthrough level of 50%. The concentrations of K+ and of dissolved organic carbon (DOC) were identified as the main parameters that determine NH4+ sorption in zeolite-filled, fixed-bed columns. Based on our results, the LDF and Thomas models are promising tools to predict the breakthrough curves of NH4+ in zeolite-filled, fixed-bed columns.

Primary and ultimate degradation of benzophenone-type UV filters under different environmental conditions and the underlying structure-biodegradability relationships.

Ten common benzophenone-based UV filters (BPs), sharing the same basic structure and differing only in their substituents, were investigated with respect to their primary and ultimate biodegradability. This study was carried out in order to gain deeper insights into the relationship between structure and biodegradability. The primary biodegradation of the selected BPs was studied in river water at environmentally relevant concentrations (1 µg/L) while varying specific, crucial environmental conditions (aerobic, suboxic, supplementation of nutrients). For this purpose, both batch and column degradation tests were performed, which allowed a systematic study of the effects. Subsequently, the ultimate biodegradation, i.e. the potential to achieve full mineralization of BPs, was examined according to OECD guideline 301 F. The results indicate that mineralization is limited to derivatives in which both aromatic rings contain substituents. This hypothesis was supported by docking simulations showing systematic differences in the orientation of BPs within the active site of the cytochrome P450 enzyme. These differences in orientation correspond to the substitution pattern of the BPs. This study provides valuable insights for assessing the environmental hazards of this class of trace organic compounds.

Structure-related endocrine-disrupting potential of environmental transformation products of benzophenone-type UV filters: A review.

Benzophenone-type UV filters (BPs) represent a very diverse group of chemicals that are used across a range of industrial sectors around the world. They are found within different environmental compartments (e.g. surface water, groundwater, wastewater, sediments and biota) at concentrations ranging from ng/L to mg/L. Some are known as endocrine disruptors and are currently within the scope of international regulations. A structural alert for high potential of endocrine disrupting activity was assigned to 11 BP derivatives. Due to the widespread use, distribution and disruptive effects of some BPs, knowledge of their elimination pathways is required. This review demonstrates that biodegradation and photolytic decomposition are the major elimination processes for BP-type UV filters in the environment. Under aerobic conditions, transformation pathways have only been reported for BP, BP-3 and BP-4, which are also the most common derivatives. Primary biodegradation mainly results in the formation of hydroxylated BPs, which exhibit a structure-related increase in endocrine activity when compared to their parent substances. By combining 76 literature-based transformation products (TPs) with in silico results relating to their receptor activity, it is demonstrated that 32 TPs may retain activity and that further knowledge of the degradation of BPs in the environment is needed.

Portable Analyzer for On-Site Determination of Dissolved Organic Carbon-Development and Field Testing.

Dissolved organic carbon (DOC) is a sum parameter that is frequently used in water analytics. Highly resolved and accurate DOC data are necessary, for instance, for water quality monitoring and for the evaluation of the efficiency of treatment processes. The conventional DOC determination methods consist of on-site sampling and subsequent analysis in a stationary device in a laboratory. However, especially in regions where no or only poorly equipped laboratories are available, this method bears the risk of getting erroneous results. For this reason, the objective of the present study was to set up a reliable and portable DOC analyzer for on-site analysis. The presented DOC system is equipped with an electrolysis-based decomposition cell with boron-doped diamond electrodes (BDD) that oxidizes the organic compounds to carbon dioxide. Within this study, the influence of different electrode materials and the composition of the applied electrolytes on the DOC decomposition in an undivided electrolytic cell were systematically investigated. Furthermore, some technical aspects of the portable prototype are discussed. After a detailed validation, the prototype was used in an ongoing monitoring program in Northern India. The limit of detection is 0.1 mg L-1 C with a relative standard deviation of 2.3% in a linear range up to 1000 mg L C-1. The key features of the portable DOC analyzer are: No need for ultra-pure gases, catalysts or burning technology, an analyzing time per sample below 5 min, and a reliable on-site DOC determination.

Sorption of cationic organic substances onto synthetic oxides: Evaluation of sorbent parameters as possible predictors.

Knowledge on the sorption behavior of cationic organic substances in aquatic systems is vital for their risk assessment due to the increasing detection of such chemicals in the hydrosphere. Their sorption behavior is strongly influenced by sorption processes onto mineral surfaces (e.g., oxides, clays). To contribute to the development of prediction tools, the impact of sorbent characteristics on the sorption strength was studied in a highly-idealized model system. In addition to the properties of the solid phase, the concentration of other ions in direct competition for sorption sites and the molecular structure of the sorbate were changed to separate ion exchange and non-ion exchange processes. The study includes in total 120 systematic column experiments using five extensively characterized synthetic oxides (three silica gels, two aluminum oxides), three probe molecules (two structurally related cationic substances, one neutral compound), and four distinctively different NaCl concentrations. The results show that the concentration of OH groups on the sorbent surface is a meaningful descriptor for the observed variations in sorption capacity onto different oxides. Compound-specific linear correlations were obtained, enabling the prediction of sorption coefficients. In addition, a more complex sorption behavior of organic cations compared to uncharged molecules were observed as demonstrated by the sorption results at different electrolyte concentrations. Thus, the study provides an important step towards a better principal mechanistic understanding of organic cation sorption. However, further work using other sorbents including natural ones and other probe molecules is needed to verify the identified relationships within the scope of developing reliable prediction models for cation sorption.

Production of a bisdemethylated microcystin variant by Planktothrix rubescens.

Reservoir samples from a bloom of Planktothrix rubescens were analyzed by ELISA and LC-MS/MS. The comparison of the results of both methods points to the presence of a microcystin variant not yet available as analytical standard and therefore, not detectable by LC-MS/MS analysis. It is proposed that the unknown cyanotoxin variant is a bisdemethylated microcystin variant, presumably [Asp3,Dha7]-microcystin-RR. [Asp3,Dha7]-MC-RR has not been described for a bloom of P. rubescens before.

Sorption of organic cations onto silica surfaces over a wide concentration range of competing electrolytes.

The fundamental understanding of organic cation-solid phase interactions is essential for improved predictions of the transport and ultimate environmental fates of widely used substances (e.g., pharmaceutical compounds) in the aquatic environment. We report sorption experiments of two cationic model compounds using two silica gels and a natural aquifer sediment. The sorbents were extensively characterized and the results of surface titrations under various background electrolyte concentrations were discussed. The salt dependency of sorption was systematically studied in batch experiments over a wide concentration range (five orders of magnitude) of inorganic ions in order to examine the influence of increasing competition on the sorption of organic cations. The organic cation uptake followed the Freundlich isotherm model and the sorption capacity decreases with an increase in the electrolyte concentration due to the underlying cation exchange processes. However, the sorption recovers considerably at high ionic strength (I>1M). To our knowledge, this effect has not been observed before and appears to be independent from the sorbent characteristics and sorbate structure. Furthermore, the recovery of sorption was attributed to specific, non-ionic interactions and a connection between the sorption coefficient and activity coefficient of the medium is presumed. Eventually, the reasons for the differing sorption affinities of both sorbates are discussed.

Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations.

Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel.

Vacuum-UV radiation at 185 nm in water treatment--a review.

The vacuum-UV radiation of water results in the in situ generation of hydroxyl radicals. Low-pressure mercury vapor lamps which emit at 185 nm are potential sources of VUV radiation. The scope of this article is to give an overview of the application of VUV radiation at 185 nm for water treatment including the transformation of inorganic and organic water constituents, and the disinfection efficiency. Another focus is on the generation of ozone by VUV radiation from oxygen or air and the application of the produced ozone in combination with VUV irradiation of water in the VUV/O3 process. The advantages and limitation of the VUV process at 185 nm as well as possible applications in water treatment are outlined.

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment.

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na(+) and Ca(2+) on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH=7. Isotherms for the beta-blocker metoprolol were obtained by sediment-water batch tests over a wide concentration range (1-100000 µg L(-1)). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n=0.9), indicating slightly non-linear behavior. Results show that the influence of Ca(2+) compared to Na(+) is more pronounced. A logarithmic correlation between the Freundlich coefficient K(Fr) and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface.

UV-based advanced oxidation processes for the treatment of odour compounds: efficiency and by-product formation.

The occurrence of the taste and odour compounds geosmin and 2-methyl isoborneol (2-MIB) affects the organoleptic quality of raw waters from drinking water reservoirs worldwide. UV-based oxidation processes for the removal of these substances are an alternative to adsorption and biological processes, since they additionally provide disinfection of the raw water. We could show that the concentration of geosmin and 2-MIB could be reduced by VUV irradiation and the combination of UV irradiation with ozone and hydrogen peroxide in pure water and water from a drinking water reservoir. The figure of merit EE/O is an appropriate tool to compare the AOPs and showed that VUV and UV/O(3) yielded the lowest treatment costs for the odour compounds in pure and raw water, respectively. Additionally, VUV irradiation with addition of ozone, generated by the VUV lamp, was evaluated. The generation of ozone and the irradiation were performed in a single reactor system using the same low-pressure mercury lamp, thereby reducing the energy consumption of the treatment process. The formation of the undesired by-products nitrite and bromate was investigated. The combination of VUV irradiation with ozone produced by a VUV lamp avoided the formation of relevant concentrations of the by-products. The internal generation of ozone is capable to produce ozone concentrations sufficient to reduce EE/O below 1 kWh m(-3) and without the risk of the formation of nitrite or bromate above the maximum contaminant level.

Role of cation exchange processes on the sorption influenced transport of cationic ß-blockers in aquifer sediments.

The influence of cation exchange processes on the transport behavior of the cationic ß-blockers atenolol and metoprolol was investigated by applying saturated laboratory column experiments. Breakthrough curves using natural sediments under different competitive conditions were generated and resulting sorption coefficients were compared. For the cationic species of atenolol (at pH = 8), the existence and dominating role of cation exchange processes were demonstrated by varying calcium concentrations. No effect of atenolol concentration on its retardation was observed within a wide concentration range. The breakthrough curve comparison of atenolol and the more hydrophobic metoprolol under constant conditions showed a significantly stronger retardation for metoprolol than for atenolol. However, additional non-polar interactions cannot explain the observed differences as they are determined to be negligible for both compounds. Due to the dominating role of cation exchange processes for the cationic species on overall sorption, a simple prediction of ß-blocker transport in the subsurface by using K(OC) values derived from log K(OW)-log K(OC) correlations is not feasible.

Sorption influenced transport of ionizable pharmaceuticals onto a natural sandy aquifer sediment at different pH.

The pH-dependent transport of eight selected ionizable pharmaceuticals was investigated by using saturated column experiments. Seventy-eight different breakthrough curves on a natural sandy aquifer material were produced and compared for three different pH levels at otherwise constant conditions. The experimentally obtained K(OC) data were compared with calculated K(OC) values derived from two different logK(OW)-logK(OC) correlation approaches. A significant pH-dependence on sorption was observed for all compounds with pK(a) in the considered pH range. Strong retardation was measured for several compounds despite their hydrophilic character. Besides an overall underestimation of K(OC), the comparison between calculated and measured values only yields meaningful results for the acidic and neutral compounds. Basic compounds retarded much stronger than expected, particularly at low pH when their cationic species dominated. This is caused by additional ionic interactions, such as cation exchange processes, which are insufficiently considered in the applied K(OC) correlations.

Adsorption of geosmin and 2-methylisoborneol onto powdered activated carbon at non-equilibrium conditions: influence of NOM and process modelling.

The adsorption of the taste and odour (T&O) compounds geosmin and 2-methylisoborneol (2-MIB) onto powdered activated carbon (PAC) has been studied under conditions which are typical for a drinking water treatment plant that uses reservoir water for drinking water production. The reservoir water as well as the pre-treated water (after flocculation) contains NOM that competes with the trace compounds for the adsorption sites on the carbon surface. Although the DOC concentrations in the reservoir water and in the pre-treated water were different, no differences in the competitive adsorption could be seen. By using two special characterisation methods for NOM (adsorption analysis, LC/OCD) it could be proved that flocculation removes only NOM fractions which are irrelevant for competitive adsorption. Different model approaches were applied to describe the competitive adsorption of the T&O compounds and NOM, the tracer model, the equivalent background compound model, and the simplified equivalent background compound model. All these models are equilibrium models but in practice the contact time in flow-through reactors is typically shorter than the time needed to establish the adsorption equilibrium. In this paper it is demonstrated that the established model approaches can be used to describe competitive adsorption of T&O compounds and NOM also under non-equilibrium conditions. The results of the model applications showed that in particular the simplified equivalent background compound model is a useful tool to determine the PAC dosage required to reduce the T&O compounds below the threshold concentration.

Photoinitiated oxidation of geosmin and 2-methylisoborneol by irradiation with 254 nm and 185 nm UV light.

The degradation of geosmin and 2-methylisoborneol (2-MIB) by UV irradiation at different wavelengths was investigated under varying boundary conditions. The results showed that conventional UV radiation (254 nm) is ineffective in removing these compounds from water. In contrast to the usual UV radiation UV/VUV radiation (254+185 nm) was more effective in the removal of the taste and odour compounds. The degradation could be described by a simple pseudo first-order rate law with rate constants of about 1.2 x 10(-3) m(2)J(-1) for geosmin and 2-MIB in ultrapure water. In natural water used for drinking water abstraction the rate constants decreased to 2.7 x 10(-4) m(2)J(-1) for geosmin and 2.5 x 10(-4) m(2)J(-1) for 2-MIB due to the presence of NOM. Additionally, the formation of the by-product nitrite was studied. In the UV/VUV irradiation process up to 0.6 mg L(-1) nitrite was formed during the complete photoinitiated oxidation of the odour compounds. However, the addition of low ozone doses could prevent the formation of nitrite in the UV/VUV irradiation experiments.

Identification and expression analyses of putative sesquiterpene synthase genes in Phormidium sp. and prevalence of geoA-like genes in a drinking water reservoir.

The occurrence of taste and odor problems in drinking water supplies is a widespread phenomenon. From a Saxonian water reservoir we isolated a cyanobacterial species which was classified as Phormidium sp. Under laboratory conditions it produced an earthy-musty smell due to the synthesis of geosmin. The only genes shown to be involved in geosmin biosynthesis are cyc2 and geoA of Streptomyces. Based on the alignment of Cyc2 with a putative sesquiterpene synthase of Nostoc punctiforme, a degenerate primer pair was designed. By PCR, we could amplify two similar genes in Phormidium sp., which we named geoA1 and geoA2. Their expression was studied by reverse transcription-PCR. This revealed that both genes are expressed at 20 degrees C and a light-dark cycle of 12 h. Expression was not detectable at the end of a 24-h dark period. To analyze the prevalence of geoA1 and geoA2 in samples from the phytobenthos, we generated PCR fragments with the same degenerate primer pair. Fifty-five different sequences that might represent geoA variants were obtained. The GC content ranged from 42% to 67%, suggesting that taxonomically very different bacteria might contain such genes.

Sorption of phenols onto sandy aquifer material: the effect of dissolved organic matter (DOM).

The influence of dissolved organic matter (DOM) on the sorption of four phenols, 2,4,6-trichlorophenol (2,4,6-TCP), pentachlorophenol (PCP), 2,4-dinitrophenol (2,4-DNP) and 2-methyl-4,6-dinitrophenol (2-M-4,6-DNP), onto sandy aquifer material at different pH values was investigated using flow through column experiments. The pH-dependent sorption of the chlorinated phenols 2,4,6-TCP and PCP was not significantly affected by DOM (measured as dissolved organic carbon, DOC), whereas in the case of nitrophenols a significant lower retardation was found, depending on the DOC concentration and pH value of the aqueous solution. Sorption decreases with increasing DOC concentration, which indicates a binding of these compounds by DOM. The degree of sorption reduction depends on the pH value and increases with increasing fraction of neutral species. The different behaviour of nitrophenols in comparison to the chlorophenols is assumed to be a result of specific charge-transfer interactions. A combined sorption and complex formation model was used to describe the effect of pH and DOC concentration on the sorption of nitrophenols onto aquifer material and to estimate binding coefficients of neutral nitrophenols on DOM.