Temporal characterisation of river waters in urban and semi-urban areas using physico-chemical parameters and chemometric methods

Three sampling campaigns were carried out in rivers located at two hydrographic basins affected by urban and semi-urban areas around the Metropolitan area of A Coruña (ca. 500,000 inhabitants, NW-Spain) to study local and temporal variations of 21 physicochemical parameters (pH, conductivity, Cl⁻, SO₄²⁻, SiO₂, Ca²⁺, Mg²⁺, Na⁺, K⁺, hardness, NO₃⁻, NO₂⁻, NH₄⁺, COD, PO₄³⁻, Zn²⁺, Cu²⁺, Mn²⁺, Pb²⁺, alkalinity and acidity) in 23 sampling points. The temporal evolution of the water quality was assessed by matrix augmentation principal components analysis (MA-PCA) and parallel factor analysis (PARAFAC). Moreover, classical principal components analysis (PCA) (one per sampling campaign) was applied with exploratory and comparison purposes. The first factor of the different studies comprised variables associated to the mineral content and it differentiated the samples according to their hydrographic basins. The second factor was mainly associated to organic matter, from domestic wastes and decomposition of natural debris. The temporal evolution of the water quality was mostly related to seasonal increments of the physicochemical parameters defining the decomposition of the organic matter.The three models applied (PCA, MA-PCA and PARAFAC) led to similar conclusions, nonetheless, MA-PCA excelled, since the refolding of scores provided more straightforward and convenient overview of sample time and geographical variations than individual PCA and it is more flexible and adaptable to environmental studies than PARAFAC.     

A new tool for inorganic nitrogen speciation study: simultaneous determination of ammonium ion, nitrite and nitrate by ion chromatography with post-column ammonium derivatization by Nessler reagent and diode-array detection in rain water samples

The paper presents a new method for a simultaneous determination of inorganic nitrogen species in the oxidized (NO₂⁻, NO₃⁻) and reduced (NH₄⁺) form in rain water samples. The method is based on a system of nitrogen species separation employing ion exchange and diode-array detection. The ions are separated in a strong ion-exchanger, nitrites and nitrates are determined directly at 208 and 205 nm, respectively, while the ammonium ions are determined in the column hold-up time after a post-column derivatization by the Nessler reagent, at 425 nm. The use of a diode-array detector permits a simultaneous identification of the inorganic nitrogen species in 8 min. The detection limits obtained are: NO₂⁻, 0.1 mg L⁻¹; NO₃⁻, 0.05 mg L⁻¹; NH₄⁺, 1 mg L⁻¹. The method proposed has been successfully used for speciation analysis of inorganic nitrogen in precipitation.     

A new family of delocalized lipophilic cations

A new family of delocalized lipophilic cations containing one to three carbimino, sulfimino and phosphinimino units with Cl⁻, Br⁻, HF₂⁻ and Me₃SiF₂⁻ as counterions has been designed. The compounds synthesized demonstrate high performance and thermal stability in the ‘Halex’ fluorination reactions. For the first time sulfur tetrachloride pregenerated at −78°C was successfully applied in reactions with N-nucleophiles to afford straightforwardly sulfonium chlorides with three S-N bonds.     

‘Total fluorine’ analysis of seed of Australian Gastrolobium spp. showing temporal, spatial and morphological variation

Alkali-fusion in conjunction with a fluoride selective electrode were used to quantify ‘total fluorine’, being organic fluorine + inorganic fluoride, for the seed of 13 species of Gastrolobium from south-west Western Australia. Intact seed covering spatial and temporal distributions, as well as G. bilobum, G. calycinum and G. parviflorum seed dissected into cotyledons and testa + aril, were analysed. Analysis found significant intra-and inter-species variation, both temporally and spatially, with intact seed concentrations ranging from 1.6 ± 0.3 mg kg⁻¹ in G. spinosum from Mundaring to 1063.9 ± 77.8 mg kg⁻¹ for G. cuneatum from Torbay. Approximately 87% of the ‘total fluorine’ was found to be in the seed cotyledons. Additional analysis detected little inorganic fluoride, indicating the majority of fluorine in the seed is organically bound. Parent compound(s) of the fluorine, seed toxicity and the implications of the results for seed chemical defense are discussed.     

Fluorescent PET chemosensors for lithium

The synthesis of the chiral diaza-9-crown-3 derivatives 1 (S,S) and 2 (R,R) is described. These sensors were designed as luminescent chemosensors for lithium where the fluorescence emission from the naphthalene moieties was ‘switched on’ upon Li⁺ recognition by the crown ether moiety in organic solvents, showing excellent selectivity over other group I and group II cations. Even though the recognition of Li⁺ was not achieved in water (pH 7.4) or aqueous alcohol solution, the fluorescence (which was switched on at pH 7.4) was substantially modulated by spherical anions, where the fluorescence emission was quenched in the presence of Br⁻ and I⁻ but less by Cl⁻ and not by acetate. This indicates that the emission was quenched by heavy-atom affect. The recognition of Li⁺ was also investigated by ¹H NMR in CD₃CN and by observing the changes in the circular dicromism spectra. For the former, the resonances for the crown ether moiety and α-methyl protons adjacent to the ring were sifted upfield and broadened, whereas for 1 the intensity of the CD signal for the π-π transition was substantially modulated upon Li⁺ recognition.     

Sequential cloud point extraction for the speciation of mercury in seafood by inductively coupled plasma optical emission spectrometry

A novel nonchromatographic speciation technique for the speciation of mercury by sequential cloud point extraction (CPE) combined with inductively coupled plasma optical emission spectrometry (ICP-OES) was developed. The method based on Hg²⁺ was complexed with I⁻ to form HgI₄²⁻, and the HgI₄²⁻ reacted with the methyl green (MG) cation to form hydrophobic ion-associated complex, and the ion-associated complex was then extracted into the surfactant-rich phase of the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114), which are subsequently separated from methylmercury (MeHg⁺) in the initial solution by centrifugation. The surfactant-rich phase containing Hg(II) was diluted with 0.5 mol L^− 1 HNO₃ for ICP-OES determination. The supernatant is also subjected to the similar CPE procedure for the preconcentration of MeHg⁺ by the addition of a chelating agent, ammonium pyrrolidine dithiocarbamate (APDC), in order to form water-insolvable complex with MeHg⁺. The MeHg⁺ in the micelles was directly analyzed after disposal as describe above. Under the optimized conditions, the extraction efficiency was 93.5% for Hg(II) and 51.5% for MeHg⁺ with the enrichment factor of 18.7 for Hg(II) and 10.3 for MeHg⁺, respectively. The limits of detection (LODs) were 56.3 ng L^− 1 for Hg(II) and 94.6 ng L^− 1 for MeHg⁺ (as Hg) with the relative standard deviations (RSDs) of 3.6% for Hg(II) and 4.5% for MeHg⁺ (C = 10 μg L⁻¹, n = 7), respectively. The developed technique was applied to the speciation of mercury in real seafood samples and the recoveries for spiked samples were found to be in the range of 93.2–108.7%. For validation, a certified reference material of DORM-2 (dogfish muscle) was analyzed and the determined values are in good agreement with the certified values.     

Three different fluorescent responses to transition metal ions using receptors based on 1,2-bis- and 1,2,4,5-tetrakis-(8-hydroxyquinolinoxymethyl)benzene

The dipod 1,2-bis(8-hydroxyquinolinoxymethyl)benzene (3) and tetrapod 1,2,4,5-tetrakis(8-hydroxyquinolinoxymethyl)benzene (5) have been synthesized through nucleophilic substitution of respective 1,2-bis(bromomethyl)benzene (2) and 1,2,4,5-tetra(bromomethyl)benzene (4) with 8-hydroxyquinoline (1). For comparison, 1,3,5-tris(8-hydroxyquinolinoxymethyl)benzene derivatives (7a and 7b) have been obtained. The complexation behavior of these podands towards Ag⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, and Cd²⁺ metal ions has been investigated in acetonitrile by fluorescence spectroscopy. The sterically crowded 1,2,4,5-tetrapod 5 displays unique fluorescence ‘ON-OFF-ON’ switching through fluorescence quenching (λ_max 395 nm, switch OFF) with <1.0 equiv of Ag⁺ and fluorescence enhancement (λ_max 495 nm, switch ON) with >3 equiv Ag⁺ and can be used for estimation of two different concentrations of Ag⁺ at two different wavelengths. The addition of Cu²⁺, Ni²⁺, and Co²⁺ metal ions to tetrapod 5 causes fluorescence quenching, i.e., ‘ON-OFF’ phenomena at λ_max 395 nm for <10 μM (1 equiv) of these ions but addition of Zn²⁺ and Cd²⁺ to tetrapod 5 results in fluorescence enhancement with a gradual shift of λ_em from 395 to 432 and 418 nm, respectively. Similarly, dipod 3 behaves as an ‘ON-OFF-ON’ switch with Ag⁺, an ‘ON-OFF’ switch with Cu²⁺, and an ‘OFF-ON’ switch with Zn²⁺. The placement of quinolinoxymethyl groups at the 1,3,5-positions of benzene ring in tripod 7a-b leads to simultaneous fluorescence quenching at λ_max 380 nm and enhancement at λ_max 490 nm with both Ag⁺ and Cu²⁺. This behavior is in parallel with 8-methoxyquinoline 8. The rationalization of these results in terms of metal ion coordination and protonation of podands shows that 1,2 placement of quinoline units in tetrapod 5 and dipod 3 causes three different fluorescent responses, i.e., ‘ON-OFF-ON’, ‘ON-OFF’, and ‘OFF-ON’ due to metal ion coordination of different transition metal ions and 1, 3, and 5 placement of three quinolines in tripod 7, the protonation of quinolines is preferred over metal ion coordination. In general, the greater number of quinoline units coordinated per metal ion in 5 compared with the other podands points to organization of the four quinoline moieties around metal ions in the case of 5.     

A new terpyrrolic analogue of dipyrrolylquinoxalines: an efficient optical-based sensor for anions in organic media

The synthesis and X-ray structural characterization of a new terpyrrolic analog of dipyrrolylquinoxaline (DPQ) is described that contains two pyrrole anion recognition groups bridged by a central 1,2-linked pyrrole. Relative to the ‘parent’ DPQ system, this new terpyrrolic scaffold acts as an improved colorimetric and fluorescent sensor for halide and dihydrogen phosphate anions in organic media. This enhancement is particularly dramatic in the case of H₂PO₄⁻ (studied as its tetrabutylammonium salt); in CH₂Cl₂ it is bound with an affinity constant, K, of 17,500 M⁻¹ by the terpyrrole of this report vs. 80 M⁻¹ in the case of DPQ. The present findings thus support the emerging notion that a range of pyrrole-based anion recognition and sensing systems may be produced by replacing the central quinoxaline spacer in DPQs by other bridging subunits and that these new receptors may have properties that differ dramatically from their DPQ ‘parents’.     

Preparation and properties of a new solid state borate ion selective electrode and its application

A new borate ion selective electrode using solid salts of Ag₃BO₃, Ag₂S and Cu₂S has been developed. Detailed information is provided concerning the composition, working pH and conditioning of the electrode. An analytically useful potential change occurred from 1 × 10⁻⁶ to 1 × 10⁻¹ M borate ion. The slope of the linear portion was 31 ± 2 mV/10-fold changes in borate concentration. The measurements were made at constant ionic strength (0.1 M NaNO₃) and at room temperature. The effect of Cl⁻, Br⁻, NO₃⁻, SO⁼₄, H₂PO₄⁻ anions and K⁺, Na⁺, Cu²⁺, Ag⁺, Ca²⁺ cations on borate response is evaluated and it was found that only Ag⁺ had a small interference effect. The lifetime of the electrode was more than two years, when used at least 4-5 times a day, and the response time was about 20-30 s. Borate content in waste water of borax factory, tap water of a town situated near to the borax factory and city tap water far from these mines were also determined. The validation was made with differential pulse polarography for the same water sample, and high consistency was obtained.     

Sensitive and robotic determination of bromate in sea water and drinking deep-sea water by headspace solid-phase micro extraction and gas chromatography–mass spectrometry

A robotic method has been established for the determination of bromate in sea water and drinking deep-sea water. Bromate in water was converted into volatile derivative, which was measured with headspace solid-phase micro extraction and gas chromatography–mass spectrometry (HS-SPME GC–MS). Derivatization reagent and the HS-SPME parameters (selection of fibre, extraction/derivatization temperature, heating time and; the morality of HCl) were optimized and selected. Under the established conditions, the detection and the quantification limits were 0.016 μg L⁻¹ and 0.051 μg L⁻¹, respectively, and the intra- and inter-day relative standard deviation was less than 7% at concentrations of 1.0 and 10.0 μg L⁻¹. The calibration curve showed good linearity with r² = 0.9998. The common ions Cl⁻, NO₃⁻, SO₄²⁻, HPO₄²⁻, H₂PO₄⁻, K⁺, Na⁺, NH₄⁺, Ca²⁺, Mg²⁺, Ba²⁺, Mn⁴⁺, Mn²⁺, Fe³⁺ and Fe²⁺ did not interfere even when present in 1000-fold excess over the active species. The method was successfully applied to the determination of bromate in sea water and drinking deep-sea water.     

Coupled Li/Nb and O/F ordering on the Na and Cl sites of the average NaCl structure of Li4NbO4F

The average, as well as the cation and anion ‘disordered’, crystal structure of Li₄NbO₄F has been carefully investigated via coupled neutron and X-ray powder diffraction studies as well as via electron diffraction studies. The existence of a spectacular highly structured diffuse intensity distribution in the latter provides strong evidence for coupled Li¹⁺/Nb⁵⁺ and O²⁻/F⁻ ordering on the Na and Cl sites of the average NaCl structure of Li₄NbO₄F. Bond valence sum calculations have been used to investigate local crystal chemistry as well as to suggest plausible local crystal chemical constraints while ab initio DFT based theoretical calculations of a 2×2×2 supercell have been carried out in order to provide additional insight into the local crystal chemistry of this compound.     

Ultra-sensitive determination of cyanide in surface water by gas chromatography–tandem mass spectrometry after derivatization with 2-(dimethylamino)ethanethiol

A gas chromatography–tandem mass spectrometric (GC–MS/MS) method has been established for the determination of cyanide in surface water. This method is based on the derivatization of cyanide with 2-(dimethylamino)ethanethiol in surface water. The following optimum reaction conditions were established: reagent dosage, 0.7 g L⁻¹ of 2-(dimethylamino)ethanethiol; pH 6; reaction carried out for 20 min at 60 °C. The organic derivative was extracted with 3 mL of ethyl acetate, and then measured by using GC–MS/MS. Under the established conditions, the detection and quantification limits were 0.02 μg L⁻¹ and 0.07 μg L⁻¹ in 10-mL of surface water, respectively. The calibration curve had a linear relationship relationship with y = 0.7140x + 0.1997 and r² = 0.9963 (for a working range of 0.07–10 μg L⁻¹) and the accuracy was in a range of 98–102%; the precision of the assay was less than 7% in surface water. The common ions Cl⁻, F⁻, Br⁻, NO₃⁻, SO₄²⁻, PO₄³⁻, K⁺, Na⁺, NH₄⁺, Ca²⁺, Mg²⁺, Ba²⁺, Mn⁴⁺, Mn²⁺, Fe³⁺, Fe²⁺ and sea water did not interfere in cyanide detection, even when present in 1000-fold excess over the species. Cyanide was detected in a concentration range of 0.07–0.11 μg L⁻¹ in 6 of 10 surface water samples.     

Reaction of Selectfluor (F-TEDA-BF4) with chloromethylated-DABCO monocation salts (X = BF4, NTf2) and other nitrogen bases (Et3N; piperidine; basic ionic liquid); unexpected formation of symmetrical [N−H−N] trication salts

Selectfluor reacts with N-chloromethylated DABCO monocation BF₄ or NTf₂ salts in MeCN (rt to 80 °C) to give symmetrical [N−H−N]⁺ trication salts. The same dimeric adducts are formed via the reaction of Selectfluor with Et₃N, piperidine, or a basic-IL (imidazolium with an alkyl-piperidine tether). The resulting stable salts were studied by multinuclear NMR, ¹⁵N/¹H HMBC, electrospray-MS, and by chemical reactivity. This hitherto unreported reactivity behavior contrasts the well documented ‘transfer fluorination’ by Selectfluor to quinuclidine and the quinuclidinic nitrogen of cinchona alkaloids.     

Hydrogen bonded H3O, H2O, HF, F in fluoride metalates (Al, Cr, Fe, Zr, Ta) templated with tren (tris-(2-aminoethyl)amine)

The environment of H₃O⁺, H₂O, HF and F⁻ species (non-bonded to metals) is considered in fluoride metalates which crystallise from the (Al(OH)₃, Cr(OH)₃, FeF₃, ZrF₄, Ta₂O₅)-tren-HF_aq·-ethanol systems (microwave heating at 190 °C during 1 h). The presence of (H₃O)(H₂O)₆⁺ clusters or H₃O⁺ cations, of isolated or associated H₂O molecules, of (HF₂)⁻ and F⁻ anions is evidenced. The thermal stability of the solids depends strongly on the nature of the hydrogen-bonded species associated with the preceding cations or anions and on the formation of water ribbons or layers.     

Highly sensitive and selective amperometric sensors for nanomolar detection of iodate and periodate based on glassy carbon electrode modified with iridium oxide nanoparticles

Iridium oxide nanoparticles are grown on a glassy carbon electrode by electrodepositing method. The electrochemical behavior and electrocatalytic activity of modified electrode towards reduction of iodate and periodate are studied. The reductions of both ions occur at the unusual positive peak potential of 0.7 V vs. reference electrode. The modified electrode is employed successfully for iodate and periodates detection using cyclic voltammetry, hydrodynamic amperometry and flow injection analysis (FIA). In the performed experiments, flow injection amperometric determination of iodate and periodate yielded calibration curves with the following characteristics: linear dynamic range up to 100 and 80 μM, sensitivity of 140.9 and 150.6 nA μM⁻¹ and detection limits of 5 and 36 nM, respectively. The repeatability of the modified electrode for 21 injections of 1.5 μM of iodate solution is 1.5%. The interference effects of NO₂⁻, NO₃⁻, ClO₃⁻, BrO₃⁻, ClO₄⁻, SO₄²⁻, Cu²⁺, Zn²⁺, Mn²⁺, Mg²⁺, Cd²⁺, Ca²⁺, Na⁺, K⁺, NH₄⁺ and K⁺, CH₃COO⁻ and glucose were negligible at the concentration ratio of more than 1000. The obtained attractive analytical performance together with high selectivity and simplicity of the proposed method provide an effective and e novel modified electrode to develop an iodate and periodate sensor. Sensitivity, selectivity, the liner concentration range and the detection limit of the developed sensor are all much better than all known similar sensors in the literature for iodate and periodate determination.     

Development of the diffusive gradient in thin films technique for the measurement of labile mercury species in waters

The diffusive gradients in thin films (DGT) technique, utilizing resin gel with ion-exchange resin Duolite GT73 and new ion-exchange resin Ambersep GT74, was investigated for the accumulation of four mercury species (Hg²⁺, CH₃Hg⁺, C₂H₅Hg⁺, C₆H₅Hg⁺). The diffusion coefficients of mercury species in agarose gel calculated on the basis of Fick’s Law were mercury species-specific. The diffusion coefficients of Hg²⁺ and CH₃Hg⁺ at 25 °C (9.07 ± 0.23 × 10⁻⁶ cm² s⁻¹ and 9.06 ± 0.30 × 10⁻⁶ cm² s⁻¹, respectively) were very similar, but the diffusion coefficients of C₂H₅Hg⁺ (6.87 ± 0.23 × 10⁻⁶ cm² s⁻¹) and C₆H₅Hg⁺ (3.86 ± 0.19 × 10⁻⁶ cm² s⁻¹) were significantly lower. Influence of experimental conditions (pH, selected cations, chlorides and humic substance) on mercury species accumulation by DGT was studied. The DGT technique was applied to river water spiked with mercury species.     

Determination of water-soluble inorganic and organic species in atmospheric fine particulate matter

The use of ion chromatography (IC) in conjunction with ultrasonic extraction is described for the routine analysis of water-soluble major inorganic ions and organic acids in atmospheric fine particles (PM_2.5). Both the extraction method and the IC analysis were validated using NIST SRM 1648 (urban particulate matter). In addition, the reliability of the IC method was established by intercomparison of results obtained with those from suitable alternative analytical techniques (atomic absorption spectrometry (AAS), proton-induced X-ray emission (PIXE) spectrometry, and UV-Visible spectrophotometry). The validated IC method was successfully applied for field monitoring of PM_2.5 particles collected in Singapore over an extended period of time. The IC analysis revealed that the concentrations of individual ions were in the order, SO₄²⁻ > NH₄⁺ > NO₃⁻ > Na⁺ > K⁺ > Cl⁻, respectively. Among the major ionic components, SO₄²⁻ contributed 50% to the measured water-soluble aerosol mass followed by NH₄⁺ (16.5%) and NO₃⁻ (9.0%). The cations Na⁺, K⁺, Mg²⁺, and Ca²⁺ accounted for 24% of the total water-soluble mass. The IC analysis was performed to quantify the organic acids, which typically account for a small fraction of water-soluble organic compounds in PM_2.5. Oxalate was found to be the dominant species among the organic acids measured in this work.     

Rational design of a colorimetric and ratiometric fluorescent chemosensor based on intramolecular charge transfer (ICT)

A simple colorimetric and ratiometric fluorescent anion sensor 1, 3,6-dichloro-1,8-dinitrocarbazole, was rationally designed and synthesized on basis of the mechanism of intramolecular charge transfer (ICT). In DMSO solutions of 1, the presence of AcO⁻, F⁻ and H₂PO₄⁻ gave birth to the formation of a 2:1 host-to-guest complex, which was synchronously accompanied by a ‘naked-eye’ color change from light yellow to purple, a red-shift of the absorption spectrum and a blue-shift of the emission spectrum.     

Effects of chloride ions on electrochemical reactions of manganese(III) complexes

Electrochemical reactions of manganese(III) complexes, Mn^III(L)X (L; salen, salpn, 5-NO₂–salen or 5-NO₂–salpn, X; Cl, Br or NO₂) and Mn^III(L’)₂X (L’; N-Bu-sal, N-Oct–sal, N-Oct–5-Br–sal or N-Oct–5-NO₂–sal, X; Cl or Br), were investigated by voltammetry at a glassy carbon electrode in the absence/presence of Cl⁻ in acetonitrile solution. By the addition of Cl⁻, oxidation processes of Mn^III(L)X and Mn^III(L’)₂X have been found to be improved from quasi-reversible to reversible, and their oxidation products, [Mn^IV(L)X]⁺ and [Mn^IV(L’)₂X]⁺, were stabilized by the combination with Cl⁻ resulting in [Mn^IV(L)Cl₂] and [Mn^IV(L’)₂Cl₂], respectively. On the other hand, the reduction processes of Mn^III(L)X and Mn^III(L’)₂Cl were not so significantly affected by Cl⁻ as those observed for their oxidation. Other types of manganese(III) complexes and iron(III) complex were also investigated. The present study may clarify the role of Cl⁻ being involved in OEC (oxygen-evolving center) in photosystem II.     

Ion-exclusion chromatography with the direct UV detection of non-absorbing inorganic cations using an anion-exchange conversion column in the iodide-form

An ion-exclusion chromatographic method for the direct UV detection of non-absorbing inorganic cations such as sodium (Na⁺), ammonium (NH₄⁺) and hydrazine (N₂H₅⁺) ions was developed by connecting an anion-exchange column in the I⁻-form after the separation column. For example, NH₄⁺ is converted to a UV-absorbing molecule, NH₄I, by the anion-exchange column in the I⁻-form after the ion-exclusion separation on anion-exchange column in the OH⁻-form with water eluent. As a result, the direct UV detection of Na⁺, NH₄⁺ and N₂H₅⁺ could be successfully obtained as well as the well-resolved separation. The calibration graphs of the analyte cations detected with UV at 230 nm were linear in the range of 0.001-5.0 mM. The detection limits at S/N = 3 of the cations were below 0.1 μM. This method was applied to real water analysis, the determination of NH₄⁺ in river and rain waters, or that of N₂H₅⁺ in boiler water, with the satisfactory results. This could be applied also to low- or non-absorbing anions such as fluoride or hydrogencarbonate ions by the combination of a weakly acidic cation-exchange resin in the H⁺-form as the separation column and the anion-exchange conversion column.