Controlling lead release due to uniform and galvanic corrosion - An evaluation of silicate-based inhibitors.

Silicates have been added to drinking water for decades, both to sequester iron/manganese and as a corrosion control treatment for lead. But the mechanisms by which they might act to limit lead release are not well understood. We evaluated the effects of two silicate formulations on lead release due to uniform and galvanic corrosion over a wide range of pH and dissolved inorganic carbon concentrations. We compared these results to better-characterized systems, with added ortho- or polyphosphate and in an inhibitor-free control. Independent of pH, silicates did not consistently mitigate lead release due to either uniform or galvanic corrosion. Furthermore, lead carbonates appeared to determine lead solubility in the presence of sodium silicate. While silicate treatment did promote the formation of a nanometer-thick silicon layer on lead and a decrease in crystallite size at the scale surface, these changes did not inhibit lead release. But unlike polyphosphate-which is known to form soluble complexes with lead and disperse particulate metals-high ratio silicate did not exacerbate lead release. Metasilicate did exacerbate lead release, especially at pH 7 and 5 mg DIC/L; this suggests that silicate formulation may have an important effect on the dispersion of lead-rich particles.

Impact of sodium silicate on lead release and colloid size distributions in drinking water.

Sodium silicates have been used in drinking water treatment for decades as sequestrants and corrosion inhibitors. For the latter purpose they are poorly understood, which presents a potential public health risk. We investigated a common sodium silicate formulation as a treatment for lead release and compared it to orthophosphate, a well-established lead corrosion control treatment. We also compared the size distributions of colloids generated in silicate and orthophosphate-treated systems using field flow fractionation with multielement detection. At a moderate dose of 24 mg SiO2/L, sodium silicate yielded a median lead release of 398 µg/L, while orthophosphate yielded 67 µg Pb/L. At an elevated dose of 48 mg SiO2/L, sodium silicate dispersed corrosion scale in cast iron pipe sections and lead service lines, resulting in a substantial release of colloidal iron and lead. In the silicate-treated system, a silicon-rich coating occurred at the lead-water interface, but lead carbonate remained the major corrosion product and appeared to control lead levels. These data suggest that, as a corrosion control treatment for lead, sodium silicate is inferior to orthophosphate in circumneutral pH water with low alkalinity. And, as with polyphosphate, excess silicate can be highly detrimental to controlling lead release.

Effects of a central metal on the organization of 5,10,15,20-tetra-(p-chlorophenyl)-rare earth porphyrin hydroxyl compound at the air/water interface and in Langmuir-Blodgett films.

Langmuir monolayers and Langmuir-Blodgett (LB) films of 5,10,15,20-tetra-(p-chlorophenyl) terbium/gadolinium porphyrin hydroxyl compound (TbOH and GdOH) and their mixtures with stearic acid (SA) in a molar ratio of 1:1 were investigated by Brewster angle microscopy (BAM), ultraviolet-visible (UV-vis), and infrared (IR) spectroscopy and atomic force microscopy (AFM). pi-A isotherms showed that well-defined Langmuir monolayers were formed at an air/water interface for the porphyrins and their mixture with SA. The BAM observations suggest that the pi-pi interaction between the GdOH molecules is stronger than that between the TbOH molecules. This result can be further confirmed by the AFM measurements. After the introduction of SA, the pi-pi interaction between the TbOH molecules is broken and thus two phases formed in the mixed LB film. However, it cannot break the stronger pi-pi interaction between the GdOH molecules. Therefore, no phase separation is observed in the GdOH/SA LB film. IR reflection-absorption (RA) spectra showed that the COOH groups of SA are partly converted to COO(-) groups, suggesting that there is an interaction between MOH and SA in the films. This interaction leads the benzene rings of TbOH to rotate toward parallel to the substrate and those of GdOH to rotate toward perpendicular to the substrate. All these results have demonstrated that the central metal ions have great effects on the organization and formation of the films.

Formation and stability of rare earth metalloporphyrin monolayer films on amino-terminated silanized quartz surfaces studied by ultraviolet-visible and X-ray photoelectron spectroscopy.

We investigated the fabrication of self-assembled monolayers of 5,10,15,20-tetra-(p-chlorophenyl)-porphyrin metal hydroxyl compounds (MOH; M=Gd, Tb, Er, Lu) on amino-terminated silanized quartz surfaces using ultraviolet-visible (UV-vis) and X-ray photoelectron spectroscopy (XPS). The orientation of MOH molecules in the films, the kinetics of the adsorption of MOH from a chloroform solution on an amino-terminated quartz substrate, and the stability of the metalloporphyrin films under natural light, UV light, and acidic and basic conditions were studied by UV-vis spectroscopy. The results indicate that the central metal is crucial in the formation of self-assembled porphyrin films and that the stability of the MOH SAMs also depends on the central metal. Under natural and UV light irradiation conditions, the stability of the MOH SAMs depends on the strength of the M-N bonds between the central metal and pyrrole nitrogens or between the central metal and the axial ligand. In the acidic conditions, the UV-vis spectra of the MOH SAMs show decreases in the absorbance and blue shifts. These spectral changes lead us to suggest that the four M-N bonds between the central metal and the pyrrole nitrogens of the porphyrins are cleaved and the resulted porphyrins are protonated under acidic conditions. Thus, it is likely that the protonated porphyrins and MOH form pi-pi complexes with a parallel stacking of the macrocycles through the electrostatic attractive interaction in the SAMs, resulting in the blue shifts of the Soret bands of the SAMs.

Ultraviolet-visible and surface-enhanced Raman scattering spectroscopy studies on self-assembled metalloporphyrin films on organic monolayer-modified ultra-thin silver substrates.

A self-assembled monolayer (SAM) film of 5,10,15,20-tetra-(para-chlorophenyl)-porphyrin terbium (or lutetium) hydroxy compound (TbOH/LuOH) fabricated on a silver substrate premodified with a SAM of 4-mercaptopyridine (PySH) was studied by ultraviolet-visible (UV-Vis) spectroscopy and surface-enhanced Raman scattering (SERS) spectroscopy. PySH can modify the substrate and deliver its pyridyl group pointing out from the silver surface. Thus, we can investigate the effects of the central metals of the metalloporphyrins in the formation of the composite films. For the TbOH-PySH composite film, a new absorption band arising from TbOH appears at 425 nm, and a band at 512 nm due to the PySH-modified silver substrate shifts to a longer wavelength (538 nm). The results suggest that TbOH is successfully assembled on the top of PySH-modified silver film and that there is an interaction between TbOH and PySH in the film. The frequency shifts and relative intensity changes of bands due to PySH in the SERS spectra imply the coordination of the pyridyl group on Tb in the SAM. As for the LuOH-PySH composite film, its SERS spectrum shows bands arising from both the LuOH and PySH moieties, indicating that LuOH is assembled on the PySH-modified silver film. Furthermore, a band at 1221 cm(-1) due to the in-plane C-H bending mode of PySH disappears, implying that the pyridyl moiety of PySH becomes more parallel to the silver surface upon the formation of the LuOH-PySH composite film. Additionally, an absorption band at 515 nm shifts to a longer wavelength (541 nm) and becomes broad upon the formation of the composite film, suggesting an interaction between LuOH and PySH in the film. By comparing the spectral changes between the two self-assembled composite films, we find that the central metal is crucial in the formation of the composite films. The structure and orientation of the composite films depend on the central metal of the metalloporphyrin compounds.

Novel method for preparing controllable and stable silver particle films for surface-enhanced Raman scattering spectroscopy.

A new surface-enhanced Raman scattering (SERS) active substrate has been developed based on our previous study. Small silver nanoparticles on a quartz slide can be enlarged by using a mixture of commercially available reagents called Silver Enhancer and Initiator. The optical properties and characteristics of the new substrate have been investigated by ultraviolet-visible (UV-Vis) spectroscopy and atomic force microscopy (AFM). The results indicate that the small silver nanoparticles grow and some silver aggregates emerge on the quartz slide after the slide is immersed into the Silver Enhancer and Initiator Mixture (SEIM). The average diameter of the silver nanoparticles on the substrate becomes approximately double after the immersion into SEIM for 20 s. 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was used as a Raman probe to evaluate the enhancement ability of the new silver substrate. It has been found that the SERS intensity can be increased about 10 times by using the substrate treated by SEIM compared with that without being treated by SEIM. Interestingly enough, the SERS enhancement increases with time. This may be due to the reorganization of silver nanoparticles on the quartz surface. The new substrate can remain active for more than 90 days. The adsorption mode of BPENB on the new substrate and the dependence of the BPENB configurations on the concentration of BPENB in methanol solution have also been investigated by SERS or UV-Vis spectroscopy. The SERS spectra of a self-assembled monolayer (SAM) BPENB film adsorbed on a silver substrate treated by SEIM show that BPENB molecules are chemically absorbed through the Ag-N bond. Consequently, a nearly perpendicular orientation of BPENB on the silver surface is proposed. The SERS spectra of BPENB SAMs on the new substrates fabricated from methanol solutions with different concentrations are compared. The concentration dependence of the SERS spectra reveals that the BPENB molecules are adsorbed on the silver film as monomers when the film is prepared from the solution with a lower concentration (<4 x 10(-6) M) and as aggregates when it is prepared from the solution with a higher concentration (>1 x 10(-5) M).

Self-assembled metal colloid films: two approaches for preparing new SERS active substrates.

In this paper, we propose two new approaches for preparing active substrates for surface-enhanced Raman scattering (SERS). In the first approach (method 1), one transfers AgI nanoparticles capped by negatively charged mercaptoacetic acid from a AgI colloid solution onto a quartz slide and then deoxidizes AgI to Ag nanoparticles on the substrate. The second approach (method 2) deoxidizes AgI to Ag nanoparticles in a colloid solution and then transfers the Ag nanoparticles capped by negatively charged mercaptoacetic acid onto a quartz slide. By transfer of the AgI/Ag nanoparticles from the colloid solutions to the solid substrates, the problem of instability of the colloid solutions can largely be overcome. The films thus prepared by both approaches retain the merits of metal colloid solutions while they discharge their shortcomings. Accordingly, the obtained Ag particle films are very suitable as SERS active substrates. SERS active substrates with different coverages can be formed in a layer-by-layer electrostatic assembly by exposing positively charged surfaces to the colloid solutions containing oppositely charged AgI/Ag nanoparticles. The SERS active substrates fabricated by the two novel methods have been characterized by means of atomic force microscopy (AFM) and ultraviolet-visible (UV-vis) spectroscopy. The results of AFM and UV-vis spectroscopy show that the Ag nanoparticles grow with the increase in the number of coverage and that most of them remain isolated even at high coverages. Consequently, the surface optical properties are dominated by the absorption due to the isolated Ag nanoparticles. The relationship between SERS intensity and surface morphology of the new active substrates has been investigated for Rhodamine 6G (R6G) adsorbed on them. It has been found that the SERS enhancement depends on the size and aggregation of the Ag particles on the substrates. Especially, we can obtain a stronger SERS signal from the substrate prepared by method 1, implying that for the metal nanoparticles capped with stabilizer molecules such as mercaptoacetic acid, the in situ deoxidization in the film is of great use in preparing SERS active substrates. Furthermore, we have found that the addition of Cl- into the AgI colloid solution changes the surface morphology of the SERS active substrates and favors stronger SERS enhancement.

Raman spectroscopic investigation of the single-monolayer Langmuir-Blodgett film of C16NaphOH and C10AzoNaphC4N-SDS.

Raman spectra were measured for Langmuir-Blodgett (LB) films of C(16)NaphOH and C(10)AzoNaphC(4)N-SDS on Calcium Fluorite substrate for the first time. In order to find out favorable excitation condition, Raman spectra of the single and multi-monolayer LB films excited at different lines at 244, 514, 633 and 778 nm are recorded and compared in the present study. Raman spectrum of the monolayer LB film of C(16)NaphOH excited by 244 nm demonstrate that excellent signal to noise is achieved even for one monolayer LB film with an extremely short integrating time as 60 s because of being resonantly enhanced, while no meaningful spectra were recorded under the same condition for the monolayer LB film of C(10)AzoNaphC(4)N-SDS because of burning. Using a HeNe 633 nm excitation the problem with strong substrate fluorescence was partially solved, since under these conditions this fluorescence is mainly outside the fingerprint region of the LB film molecules (1000-2000 cm(-1)). Therefore by using the HeNe laser excitation, Raman spectra with high signal to noise ratio of LB films of C(16)NaphOH were collected and shown in this paper. These findings stress again the necessity to define an appropriate Raman system for this special application of LB film diagnosis.

Surface-enhanced Raman spectroscopy study on the structure changes of 4-mercaptopyridine adsorbed on silver substrates and silver colloids.

Surface-enhanced Raman scattering (SERS) of 4-mercaptopyridine (4-mpy) adsorbed on HNO3 etched silver foil, chemically deposited silver films (silver mirror) and silver colloids were measured. The SERS study has revealed that 4-mpy was adsorbed onto the three kinds of silver surfaces by a sulfur-silver bond with the plane of pyridine ring being normal to the silver substrates. The structure of 4-mpy adsorbed on the silver surfaces depends largely on the pH values of environment. When the pH values of the environment are changed, the structure of 4-mpy adsorbed on silver surfaces can easily be altered through a protonation or deprotonation reaction occurring on the N atom of the pyridine ring, and the modified structure shows unique characters on the SERS spectrum. Owing to the remarkable enhancement ability of SERS technique and characteristic spectrum of different species, a monolayer of 4-mpy assembled on a silver mirror holds potential as a H+ sensor for highly sensitive detection of the proton concentration in an aqueous solution.