Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.

SOLUTIONS (2013SOLUTIONS ( to 2018) is a European Union Seventh Framework Programme Project (EU-FP7) that aims to deliver a solution-oriented conceptual framework for the evidence-based development of environmental policies with regard to water quality and its protection against contamination. This project will integrate innovative chemical and effect-based monitoring tools with a full set of exposure, effect and risk assessment models and strategies to assess abatement options. Uniquely, SOLUTIONS takes advantage of (i) expertise of leading European scientists of major FP6/FP7 projects on chemicals in the water cycle, (ii) access to the infrastructure necessary to investigate the large basins of the Danube and Rhine as well as relevant Mediterranean basins as case studies, and (iii) innovative approaches for stakeholder dialogue and support. In particular, the EU Water Framework Directive (WFD) Common Implementation Strategy (CIS) working groups, International River Commissions, and water works associations will be directly supported with consistent guidance for the early detection, identification, prioritization, and abatement options for chemicals in the water cycle. A set of predictive models and tools will support stakeholders' management decisions by benefiting from the wealth of data generated from monitoring and chemical registration. SOLUTIONS will provide a specific emphasis on concepts and tools for the impact and risk assessment of complex mixtures of emerging pollutants, their metabolites and transformation products. Analytical and effect-based screening tools will be applied together with ecological assessment tools for the identification of toxicants and their impacts. Beyond state-of-the-art monitoring and management, tools will be elaborated allowing risk identification for aquatic ecosystems and human health. The SOLUTIONS approach will provide transparent and evidence-based suggestions of River Basin Specific Pollutants for the case study basins and support future review of priority pollutants under the WFD as well as potential abatement options.

Aromatic amines are one of the most important classes of compounds contributing to surface water mutagenicity due to their widespread occurrence as precursors and transformation products of dyes, pharmaceuticals, agrochemicals, and other compound classes. In this study, we implemented a workflow including novel analytical and data evaluation methods aiming to identify aromatic amines in six mutagenic wastewater effluents from a chemical-industrial area in Germany, collected by the passive sampler Blue Rayon. We identified 14 amines including the two potent mutagenic aromatic amines 2,3- and 2,8-phenazinediamine, which were reported for the first time as environmental contaminants. These two isomers accounted between 4.2 and 86% of the mutagenicity of the blue rayon extracts and may be byproducts of dye production at the studied site.

The reaction of Cp*ZrF 3 (1) (Cp* ) η 5 -C 5 Me 5 ) and AlMe 3 resulted in the formation of cis-{[Cp*ZrMe(µ 2 -F)][(µ 2 -F) 2 AlMe 2 ]} 2 (6) and [(Cp*Zr) 3 Al 6 Me 8 (µ 3 -CH 2 ) 2 (µ 4 -CH) 4 (µ 3 -CH)] ( 7), respectively. Analogously, (η 5 -C 5 Me 4 Et)ZrF 3 (3) reacts with AlMe 3 in a molar ratio of 1:5 with methane elimination to give the Zr 3 Al 6 C 7 cluster of composition {[(η 5 -C 5 Me 4 Et)Zr] 3 Al 6 Me 8 -(µ 3 -CH 2 ) 2 (µ 4 -CH) 4 (µ 3 -CH)} ( 8), which has been characterized by elemental analysis and 1 H NMR and mass spectrometry. Reaction of 2 equiv of AlMe 3 with Cp* 2 ZrF 2 (2) leads quantitatively to Cp* 2 ZrMe 2 (12). Reaction of Cp*HfF 3 (4) with AlMe 3 in an equimolar ratio gives {[Cp*HfMe (µ 2 -F)][(µ 2 -F) 2 AlMe 2 ]} 2 (9) stereospecifically as its cis isomer in high yield. 9 crystallizes in the space group P2 1 /c with four molecules in the elemental cell (Z ) 16). From the reaction of 1 equiv of Cp*HfF 3 (4) with 3 equiv of AlMe 3 , Cp*HfMe 3 (10) can be obtained in a yield of 85%. As a byproduct of this reaction the Hf 3 Al 6 C 7 cluster [(Cp*Hf) 3 -Al 6 Me 8 (µ 3 -CH 2 ) 2 (µ 4 -CH) 4 (µ 3 -CH)] ( 11) can be isolated in a yield of 5%. The characterization of 11 by single-crystal X-ray diffraction and 1 H, 13 C NMR and mass spectroscopic data will be discussed. Cp*TaF 4 (5) reacts with a 5-fold excess of AlMe 3 , leading quantitatively to Cp*TaMe 4 (13) without further decomposition via C-H activation processes.

Complexes [M(q5-CSMeS)F3] (M = Zr 2, Hf 9, [Zr(qS-CsHs)F2] 7 and [Hf(qS-CsMe&F2] 8 are obtained by treating the corresponding metal alkyls with [tmpy-(HF)z] (tmpy = 2,4,64rimethylpyridine); using an excess of [tmpy.(HF)2] in the preparation of 2 and 5 leads to the complexes [Htmpy][ (M(q5-CsMes)F2)(p-F)3] (M = Zr 3, Hf 6), respectively and a crystal structure determination of 3 confirms its ionic nature; [Ti(qS-C5Mes)C12F] 10 and 2 were synthesised also from their corresponding alkyls by alkyl-fluorine exchange using Me3SnF.Versatile fluorinating reagents for the syntheses of organometallic fluorides are limited. 1 However, recently we found that Me3SnF or Bun3SnF are suitable fluorinating reagents for high yield preparations of cyclopentadienyl substituted fluorides of group 4 metals by chlorine-fluorine metathesis reactions.2 In order to increase the synthetic methods for preparing organo metal fluorides we were interested to study whether it is possible to introduce fluorine into a metal centre by the reaction of organo metal alkyls using HF with elimination of the corresponding hydrocarbons.Due to the hydrolytic sensitivity of organometallic alkyls of the early transition metals, adducts of Lewis acids should be used preferentially instead of anhydrous HF. The reaction of HF-BF3 has been studied for synthesising [Zr( q5-C5H5)2F2]3 and [Ta(CH2But3)F2]4 using [ZrMe2(q5-C5H5)2] and [Ta(=CH-But)(CH2But3], respectively. To the best of our knowledge no HF adducts of tertiary amines, [R3N.(HF),],5 have been used as fluorinating reagents for the preparation of organometallic fluorides. Herein, we report on the results of our investigations studying the reactions of organo transition metal alkyls with [R3N.(HF),]. Compounds [R3N-(HF),] are mild HF transfer reagents which do not corrode glassware surfaces. Anhydrous systems are obtained by distillation or sublimation of the adducts. 2,4,6-Trimethylpyridine (tmpy) and HF form a solid adduct of composition [tm~y.(HF)~] after sublimation [50 "C (1 Pa)].? The reaction of [Zr(CH2Ph)3(q5-C5Me5)] 16 with an equimolar amount of [tmpy.(HF)2] at room temp. resulted in the formation of the zirconium complex [Zr(q5-C5Me5)F3]2 2 and unreacted starting material instead of the mixed complex [Zr(CH2Ph)(qSC5Me5)F2] [Scheme l(a)]. 'H and '9F NMR spectra showed that the compounds 1 and 2 are present in a molar ratio of 1 : 2 indicating that both HF molecules of [tmpy-(HF)2] are active in (a) 3 [MR3(r15-C5Me5)1 + 3 [tmPY (HF)d i ' [MR3(r15-C5Me5)1 + 2 [M(r15-C5Me5)F31 1(4) 2(5) M = Zr(Hf); R = CH2Ph 1 or Me 4 Scheme 1 Reagents and conditions: i, toluene, room temp., 1 h, -3 tmpy, -6 RH the metathesis reaction. Hence, as expected, treatment of 1 with 1.5 equiv. of [tm~y-(HF)~] affords 2 in a quantitative yield [Scheme I@)]. However, for the preparation of 2 in accordance to Scheme l(b) an excess of [trnpy-(HF)z] has to be avoided. Reaction of 1 with 3 equiv. of [tmpy.(HF)2] leads to the complex [Htmpyl-[ { Zr(q5-C5Mes)F2]2(pF)3] 3 in high yield (Scheme 2).Single crystals of 3 suitable for ...