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Photochemistry-based sample treatments as greener approaches for traceelement analysis and speciation Carlos Bendicho, Francisco Pena, Marta

Costas, Sandra Gil, Isela Lavilla Sample preparation and sample introduction in analytical systems are rapidly evolving towards greener, simpler and more cost effective methodologies with subsequent achievements in analytical characteristics (e.g., improved detection limits, fewer matrix effects and higher sample throughput). Implementation of ultraviolet irradiation can provide remarkable advantages in the area of traceelement analysis and speciation, since methods for removal of organic matter, decomposition of organic-metal complexes and vapor generation (VG) can be driven by photo-oxidation or photo-reduction processes with total or partial replacement of chemicals employed in conventional approaches. New interfaces for coupling chromatographic techniques with atomic and mass detectors based on photochemical VG are emerging and expanding the scope of hyphenated techniques for elemental speciation. In this overview, we provide insight into these new developments and survey the main applications. 2010 Elsevier Ltd. All rights reserved. 1. Introduction Ultraviolet (UV) irradiation can promote derivatization processes when applied to chemical substances, the most important being photo-oxidation [1] and photoreduction [2], which can benefit many areas. For example, photo-oxidation can be applied for remediation of wastewaters polluted by toxic organic compounds. Photo-reduction allows elimination of toxic elemental species (e.g., reduction of Cd(II), Hg(II) and Cr(VI)) or synthesis of volatile metal species (e.g., alkylderivatives, carbonyl-derivatives, and hydrides) with different applications in

industry. Photolytic and photocatalytic processes induced by UV irradiation have found several applications in analytical chemistry. They enhance analytical performance and have optimal characteristics from the perspective of green chemistry (Fig. 1). Thus, from well-established treatments for removal of organic matter to the more recently developed photo-chemical vapor generation (VG), simple and low-cost methods using batch or flow-through photoreactors can be implemented easily for total element determination as well as speciation, in the latter case using both chromatographic and non-chromatographic approaches.

Figure 1. Scheme showing both green and analytical aspects of photochemistry applied to trace-element analysis and speciation, and the main applications.

2. Oxidative processes induced by UV irradiation Oxidative properties of UV radiation have long been recognized. Photo-oxidation occurring in natural environments can be advantageous for decomposition of toxic substances. So-called advanced oxidation processes (AOPs) were originally employed as efficient and clean treatments to degrade chemical and biological contaminants for water remediation. The AOP concept was firstly defined by Glaze et al. In 1987, and includes those processes involving the generation of hydroxyl radical (OH*) as a powerful, non-selective oxidant (redox potential = 2.8 V), which attacks virtually all organic compounds. Several methods are available for generating OH* radicals. Examples of AOPs that involve UV irradiation are: use of UV irradiation alone or in combination with other reagents/energies (e.g., ultrasound/UV, UV/O3, UV/H2O2, O3/H2O2/UV); photo-Fenton methods; photocatalytic methods (e.g., UV/TiO2).

Table 1 shows the reaction pathways for the formation of oxidizing OH* radicals in different AOPs driven by UV irradiation. We will focus on the main AOPs used in analytical chemistry where UV radiation is involved. When UV light is employed in the presence of additional substances that facilitate the oxidation process (e.g., H2O2, O3, K2Cr2O7, K2S2O8 and HNO3), UV irradiation has a catalytic character (i.e. homogeneous processes). Direct photolysis of H2O2 is widespread and gives rise to the formation of OH* radicals (H2O2/UV method). Although the photochemical cleavage of H2O2 is conceptually the simplest method for producing OH* radicals, the low molecular absorptivity of H2O2 at 254 nm (i.e. the wavelength mainly generated with low-pressure lamps) limits the yield of OH*. This could be a problem mainly with aqueous media having high absorbance, since there could be competition for the radiation with the H2O2.

O3 is able to absorb UV radiation, giving rise to H2O2 as an intermediate, which yields OH* radicals. The addition of H2O2 to O3/UV oxidation (i.e. O3/H2O2/UV) speeds up the decomposition of ozone, which increases the rate of OH generation Table 1. Reaction pathways for the formation of oxidizing OH* radicals in different advanced oxidation processes (AOPs) driven by UV irradiation.

.UV photo-oxidation in the presence of K2S2O8, a very strong oxidizing agent, has been widely applied in many speciation studies using on-line couplings between highperformance liquid chromatography (HPLC) and atomic or mass spectrometry for detection. The decomposition of S2O8-2 anion to yield sulfate radicals (SO4-*) can be initiated by UV light. Finally, strong oxidizing species (e.g., H2O2, O2 and OH*) are formed in aqueous media. Other potential catalysts (e.g., K2Cr2O7 or even Hg(II), Ce(IV)), more rarely employed for UV photo-oxidation, would be less attractive for laboratory applications, because of their poor greenness profile, as would other effective processes used for treatment of effluents containing organic pollutants (e.g., Fenton (i.e. H2O2/Fe2+)). The Fenton method is very effective for generation of OH* radicals and the reaction involves consumption of one Fe2+ ion for each OH* radical produced. When Fe2+ ions are added to the UV/H2O2 system, the process

is commonly called photo-Fenton-type oxidation. Both methods entail the use of large concentrations of Fe, which could be a potential interference when analytical applications are developed. Many organic compounds can be photo-oxidized to CO2 using TiO2 as catalyst. Photocatalytic oxidation relies on the photo-excitation of a semiconductor of the calcogenide type (e.g., oxides: TiO2, ZnO and ZrO2; sulfides: CdS and ZnS), when it is illuminated with photons whose energy is equal to or greater than their bandgap energy. Then, these photons are absorbed and create within the bulk electronhole pairs, which dissociate into free photoelectrons in the conduction band and photo holes in the valence band. These charge carriers are able to induce reduction or oxidation, respectively. 3. Analytical applications of AOPs involving UV irradiation Application of AOPs for sample preparation in analytical chemistry is very attractive, since environmentally benign oxidants and clean energies are employed, so AOPs can replace corrosive acids for sample digestion, chemical oxidants with toxic properties (e.g., K2Cr2O7) and catalysts (e.g., Hg(II) and Se). Apart from the replacement of concentrated mineral acids for sample treatment in inorganic analysis, other conditions of the operating procedures involved in AOPs (e.g., use of room temperature and pressure) enhance their green character. Use of AOPs brings additional benefits when dealing with ultratrace-element analysis (e.g., low risk of contamination and improved limits of detection (LODs) due to the lower blank levels achievable). Application of AOPs in analytical chemistry has mainly been focused on the following tasks: to remove organic matter from biological and environmental samples as an alternative to classical mineralization methods based on wet or dry ashing;

to destroy organometallic species with the aim of improving their detectability using chromatographic separation techniques coupled to atomic detectors for speciation analysis; and,

to destroy complexes formed between metal ions and natural organic matter (NOM) for the determination of total metal contents in natural waters by electro analytical techniques.

Table 2 shows a selected group of applications related to UV photo-oxidation for trace-element analysis and speciation. Table 2. Selected applications of UV photo-oxidation for trace-element analysis and speciation

3.1. Removal of organic matter While some techniques available for trace-element analysis can tolerate certain amounts of organic matter (e.g., flame-atomic absorption spectrometry, FAAS; electro thermal-atomic absorption spectrometry, ETAAS), others are much more sensitive to its presence (e.g., vapor-generation techniques), and, for

electronalytical techniques, total decomposition of organic matter is generally needed. Several AOPs have been applied for the removal of organic matter in order to avoid interferences prior to elemental analysis by atomic spectrometric techniques. In this sense, these methods can replace old mineralization methods based on the use of intensive attack with concentrated and corrosive acids. Suitable samples include different types of waters, biological fluids and aqueous extracts, although solid materials have also been tried. Thus, photo-oxidation procedures using UV/H2O2 were employed for decomposition of wine samples prior to metal determination by FAAS. UV irradiation was also employed for pretreatment of wines so that Pb-isotope ratios could be measured accurately. Compared to sample treatments by microwave-assisted digestion, UV needs smaller amounts of chemicals. A UV photolysis method was applied to decompose tea for elemental determination by ETAAS and ICP-OES. UV photolysis in the presence of H2O2 and HNO3 was applied to digest food samples for determination of Se by ETAAS. An important advantage of UV photolysis is the low blanks obtained. This benefits the use of extremely sensitive techniques (e.g., ICP-MS) for ultratrace-metal determinations. Thus, sample pre-treatment following UV photolysis was applied to several metals in urine and serum prior to determination by sector field-ICP-MS. Noble metals (e.g., Pd and Pt) present at physiological levels in urine and blood can also be determined by double-focusing magnetic sector field-ICP-MS with excellent LODs following UV photolysis for matrix decomposition. Acid digestion

with HNO3 followed by UV photolysis was recommended for determination of Pb in vinegar by ICP-MS and ETAAS [12]. UV and photocatalytic oxidation (UV/TiO2) assisted by microwaves was also proposed for decomposition of organic materials. This system provides digests with extremely low residual carbon. Another combined digestion system, described by Florian and Knapp, used hightemperature microwave- assisted UV digestion. Digestions of a variety of liquid samples (e.g., wastewater, body fluids and beverages) were performed inside closed vessels heated by microwaves that contained an electrodeless Cd discharge lamp for UV irradiation. Compared to open UV digestion devices, this system displayed a dramatic increase in mineralization efficiency and

decomposition times were reduced by a factor of 5. More extended is the use of UV/H2O2 irradiation as sample pre-treatment for trace-metal determinations by electroanalytical methods [15]. For example, anodic stripping voltammetry (ASV) is very sensitive to the presence of organic matter in the sample solution. Dissolved organic matter (DOM) is present in many natural waters (e.g., river, lake and estuarine waters, and coastal seawater). In sewage effluents, DOM contents are very high. Many organic compounds are electrochemically active and may cause interferences in the analyte signal unless they are removed. Humic acids form complexes with metal ions in freshwaters, so UV photolysis is mandatory prior to chelation with an ion-exchange resin (e.g., Chelex-100), which is typically employed for pre-concentration, so that total metal levels (e.g., Cd, Cu and Pb) are accurately determined. UV irradiation is also useful for determination of trace metals by ASV in other samples containing organic matter (e.g., aminoacid parenteral nutrition solutions or wines). UV photolysis was also applied prior to transitionmetal determination in wines by other

electroanalytical techniques (e.g., cathodic stripping voltammetry).

3.2. Degradation of organic metal species for direct metal determination The presence of metal complexes can give rise to errors when the total metal content is sought. AOPs allow not only oxidation of organic matter but also conversion of metal complexes into simple inorganic forms, which are amenable to many analytical techniques. Rodman et al. Used a photo-Fenton process to convert Cr(III) propionate a biomimetic Cr species into Cr(VI), so that the 1,5-diphenylcarbazide method could be applied for detection. Determination of Pd in solutions containing Pd catalysts suffers from interferences when well-established electroanalytical or optical methods are employed. UV/ H2O2 photo-oxidation was applied to decompose model Pd complexes (e.g., palladium (II) acetylacetonate [Pd(aca)2], palladium (II) acetate [Pd(OAc)2], and tris(dibenzyllideneacetone)dipalladium(0) [Pd2(dba)3]). Complexes formed between metal ions and DOM are hardly, or not all, accessible to voltammetric determination, so efficient mineralization of samples is needed prior to analysis. UV irradiation was also applied to metal release from complexes prior to electroanalytical determination. The use of UV irradiation together with a chemical oxidant, commonly named UV photo-oxidation, has been employed for degradation of metal species in order to facilitate use of VG techniques in atomic spectrometry. For example, thiomersal an Hg compound present in some pharmaceutical formulations, such as eye drops is destroyed by UV/H2O2 prior to cold VG. A very green approach is achieved, since sono-induced cold VG, which does not require typical reducing agents (e.g., SnCl2 or NaBH4) is, in turn, implemented. Selenomethionine and selenocysteine can easily be degraded upon UV irradiation, as UV photolysis is able to induce simultaneous oxidation of SeMet and SeCys,

and reduction of Se(VI) into Se(IV), which allows a speciation model to be established for determination of individual species of Se. The presence of organoselenium compounds in some biological samples makes acid digestion inefficient under typical conditions (e.g., microwave-assisted digestion with concentrated nitric acid), so it limits use of simple, sensitive analytical techniques for total Se determination (e.g., HG-AAS). This can be overcome using perchloric, sulfuric and nitric acid in the treatment, addition of strong oxidants (e.g., K2S2O8 and V2O5), or combining wet and dry oxidation, as in the method recommended by AOAC International. A greener method involves postdigestion UV irradiation, which, in turn, serves to pre-reduce Se (VI) into Se(IV), which is the hydridereactive Se species. UV photolysis of seawater allows accurate determination of total As by the hydride generation (HG) technique, since non-hydride reactive As (i.e. hidden As fraction), typically present in these samples is easily destroyed and converted into hydride-reactive As. Likewise, many marine organisms contain complex As compounds (e.g., AsB), which are very difficult to destroy under typical reaction conditions reached in closed vessels with concentrated acids. Efficient decompositions are especially important when HG systems combined with AAS or AFS detection are employed, since AsB and other As compounds present in those samples are non-reactive toward NaBH4 used as reducing agent. Metal speciation in natural freshwater and seawater has been performed using onsite photolysis and chelation/ preconcentration to avoid sample storage prior to inductively coupled plasma-mass spectrometry (ICP-MS). The speciation model allows the determination of total, labile and organically-bound dissolved metals. Pt determination at the picomolar (pM) level in estuarine waters was performed by cathodic stripping voltammetry (CSV) and isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). Unless photo-oxidation is carried out prior

to the CSV method, lower Pt levels were found as compared to ID-ICP-MS, indicating the occurrence of organically-complexed Pt species. 3.3. Degradation of organic metal species after HPLC separation UV photo-oxidation has also been applied as an efficient post-column treatment in coupling HPLC with several atomic detection systems using HG as an interface for speciation studies. Volatilization by hydride VG or cold VG is commonly employed, and leads to a significant increase in sensitivity and a decrease in matrix effects. After HPLC separation of different metal species, including inorganic species and organometals not all directly yielding a volatile hydride the eluent is carried to an on-line photoreactor where species are decomposed prior to HG with the NaBH4/NaOH-HCl system. These AOPs are intended to decompose non-hydride reactive species so that they can be detected with good sensitivity after chromatographic separation. On-line photo-oxidation provides a more stable analytical signal and lower baseline noise than other on-line treatments (e.g., on-line microwave-assisted digestion), since peak broadening is kept to a minimum and no bubbles form. Several applications have been reported for elements (e.g., As, Sb, Se, Sn and Hg). Usually, the UV/K2S2O8 system is employed so as to facilitate fast oxidation of organocompounds in on-line couplings. On-line photocatalytic oxidation with nanoTiO2/UV was also tried for the coupling between micro-LC and HG-ICP-MS for As speciation in urine samples. Fig. 2 shows representative instrumental set-ups for on-line photo-oxidation and photo-reduction for trace element analysis and speciation.

Figure 2. Typical instrumental set-ups for hyphenated techniques employed in applications of photo-oxidation and photo-reduction to traceelement analysis and speciation. A) Couplings of high-performance liquid chromatography (HPLC) to different detectors using an ultraviolet (UV) photo-oxidation interface prior to hydride generation. B) Couplings of HPLC to different detectors using a UV photoreduction interface (photo-catalysis reaction device, PCRD) for photo-chemical vapor generation. C) On-line photo-chemical vapor generation using flow-injection or sequential-injection approaches combined with several detection systems. 4. Reductive processes induced by UV irradiation UV irradiation can induce not only photo-oxidation but also photo-reduction. The presence of some organic substances can result in the formation of radicals (e.g., H* or CO*) that promote photo-reduction instead of stimulating oxidation. Low molecular-weight organic acids, used in conjunction with UV irradiation, have been shown to be very efficient for promoting reduction processes. In this way, ionic species of some metals, metalloids and non-metals can be reduced when subjected to UV irradiation, giving rise to volatile species in many cases (e.g., alkyls, carbonyls, hydrides and reduced metals).

Some examples of these processes can be found in nature. Thus, it has been demonstrated that methylation can be driven by photochemical reactions. For example, methylmercury can be synthesized from Hg (II) salts using sunlight in liquid media (e.g., acetic and propionic acids, methanol and ethanol) [49]. A methyl-Cr bond has been observed during photolysis of Cr (II) with tertiary butoxide radicals. Hence, alkyl derivatives can be photochemically synthesized in the presence of certain organic compounds. First experimental observations on photo-reduction were based on heterogeneous photocatalysis. Photocatalytic reactions were initiated by the photogenerated holes and electrons when the TiO2 photocatalyst was illuminated. The holes reacted with the adsorbed water or hydroxyl groups on the photocatalyst surface, forming the hydroxyl radicals (OH*), which were generally accepted to be responsible for initiating the oxidation pathway. However, electrons are responsible for initiating photoreduction reactions. During Photocatalytic reduction processes, the presence of a hole scavenger, usually an organic compound, is needed. For efficient photoreduction, it is desirable for the oxidation of the organic compound to be straightforward so that the reduction process is not retarded. There are other areas that can benefit from photoreduction (e.g., remediation of polluted water, design of green synthetic methods for alkyl-derivatives, and synthesis of gas precursors that are needed for chemical vapor deposition techniques in the semiconductor industry). Thus, photocatalytic reduction has been employed for removal of Se (IV) and Se (VI) toxic anions from waters, conversion of toxic Cr(VI) into Cr(III), reduction of toxic metals to their elemental state {e.g., Hg(II), Cd(II) and Ag(I)}. In most studies, formic acid has been used as a hole scavenger, since this compound is readily oxidized to CO2 with minimum formation of intermediate by-products. Other compounds investigated include sucrose, acetic acid, salicylic acid, methanol and ethanol.

In recent years, photo-reduction has received increasing attention for useful generation of elemental species for analysis. The main applications of photoreduction in trace-element analysis and speciation are: (1) UV photo-reduction of endogenous elemental species so that they are converted into other species amenable to the detection technique; (2) Photochemical VG (photo-CVG), with replacement of conventional reducing agents used for hydride VG and cold VG; and, (3) Design of new interfaces for photo-VG for hyphenation between HPLC and atomic or mass detectors. Table 3 shows a selected group of applications of UV photo-reduction for traceelement analysis and speciation. Table 3. Selected applications of UV photo-reduction for trace element analysis and speciation

5. Analytical applications of UV photo-reduction processes 5.1. Pre-reduction of elemental species Several studies have been performed where UV irradiation is employed for prereduction of analyte species to a specific one that is amenable to detection.

Since Se(VI) is not hydride-reactive, UV pre-reduction of Se(VI) to Se(IV) is mandatory prior to HG or application of electroanalytical techniques. Traditional prereduction approaches for Se(VI) include boiling with 56 mol/L HCl for 1530 min under reflux or heating in the presence of HCl + HBr or KBrO3 + HBr mixtures. Both chromatographic and non-chromatographic strategies have been developed for speciation of Se(VI), Se(IV), and sometimes Se(-II) (i.e. organic Se), mainly in natural waters. For example, UV irradiation without a photocatalyst has been employed in both on-line and batch systems for the reduction of Se(VI) to Se(IV). Pre-reduction of Se(VI) has also been tried in applications where an oxidative pretreatment (e.g., acid digestion) is applied first, hence replacing the traditional prereduction step based on. Likewise, Se(IV) is the electroactive species, so a prereduction from Se(VI) to Se(IV) is required when electrochemical techniques are employed for detection. Some applications have been published concerning Se determination and speciation by electroanalytical techniques following UV reduction of Se(VI) [53]. Prereduction of Se(VI) to Se(IV) was also performed for determination of total Se and Se(IV) by ETAAS following single-drop microextraction [54]. In this, SeH2 was generated in a vial using the NaBH4-NaOH/HCl system and collected onto an aqueous microdrop containing Pd(II). For pre-reduction of Se(VI) to Se(IV), the use of a TiO2 photocatalyst could be beneficial, especially with on-line systems. Clearly, less stringent conditions (i.e. low temperature reaction, less amounts of reagents) involved in UV pre-reduction makes it a greener approach than thermal treatments. 5.2. Photochemical vapor generation Volatile-phase sample introduction in atomic detectors has been a research area of great activity in recent decades, with a number of benefits for analytical methodology (e.g., reduced matrix effects as a consequence of the efficient analyte

separation, high sensitivity as a result of the enhanced transport yield of analyte to the detector, improved selectivity, and speciation ability when coupled to chromatographic separations). Chemical VG (CVG) methods comprise alkylation reactions (Grignard, aqueous ethylation), halides, dithiocarbamates, carbonyls, elemental vapors and volatile oxides, and the more extended, volatile covalent hydrides. Simplification of analytical methods along with other trends within the context of clean methods are stimulating new alternatives to classical VG methods, replacing chemical reagents (e.g., sodium borohydride) with a number of shortcomings (i.e. instability, ability to reduce transition-metal ions to their elemental state, which catalyzes hydride decomposition, variable reaction yields depending on the oxidation state, among the most relevant) by synthetic pathways with the intervention of UV radiation. Photogeneration of volatile derivatives from elemental species is an emerging research area, which expands the scope for introducing volatile samples in atomic spectrometry. Photo-reduction processes can be implemented in a way similar to CVG with detectors (e.g., AAS, AFS, ICP-OES and ICP-MS) and also to hyphenated techniques for post-column derivatization in HPLC. The first work demonstrating the reduction of an ion to a volatile hydride was reported by Kikuchi and Sakamoto for the conversion of inorganic Se into SeH2 photocatalyzed by TiO2 in formic acid medium. Later on, several studies were concerned with the effect of the experimental conditions on photo-reduction of both Se(IV) and Se (VI) to SeH2. A first analytical application of inorganic Se photo-reduction to yield volatile Se compounds was given by Guo et al. These authors pointed out that the TiO2 photocatalyst could be unnecessary when reactions involve low concentrations of Se, as is the case in ultratrace analysis.

Generation of volatile Se compounds (e.g., SeCO, SeH2, (CH3)2Se and (CH3CH2)2Se) upon UV irradiation in the presence of low molecular-weight organic acids was performed in a flow-through reactor directly coupled to the detector. Several papers concerning photo-CVG for Se have been published, including AAS detection with continuous flow and flowinjection/stopped-flow sample introduction, as well as ICP-MS. Although Se and Hg are the elements for which most studies have been reported, photogeneration can be extended to other elements (e.g., Te, As, Bi, Hg, Sb, Cd, Sn, transition metals (Ni, Cu, Co, Fe), noble metals (Au, Pt, Pd, Ag, Rh) and nonmetals (I, S)). Thus, useful analytical signals were obtained for the above elements using ICP-MS with time-of-flight (ICP-TOF-MS). Mechanisms for photo-CVG have been established for a few elements (e.g., Se, Hg, As, Ni, Co and I). Usually, GC-MS has been applied for identification of photogenerated species. Volatile As species (e.g., trimethylarsine, triethylarsine, tripropylarsine,

methylarsine, dimethylarsine, dimethylethylarsine and diethylmethylarsine) have been identified, depending on the organic acid or acid mixtures, with a conversion yield of 75% at best. The photogeneration of water-soluble As species from As(III) in the presence of HOAc has also been studied. Some 13 organoarsenic species were identified when multi-dimensional LC was combined off line with electrospray mass spectrometry (ES-MS). An aspect to be more deeply studied is the type of organic acid necessary to provide the appropriate radicals. Most studies report the use of simple organic acids (e.g., formic or acetic), but the performance of more complex acids (e.g., EDTA) may need further consideration,

since radical formation may be reached with much lower acid concentration apart from its beneficial effect concerning the removal of transition-metal interferences. Cold VG is the preferred method worldwide for tracemercury determination because of its sensitivity and simplicity, and freedom from interferences. Hg(II) is easily reduced to Hg(0) by TiO2/UV photocatalysis using methanol as hole scavenger. UV reduction without resorting to the use of a photocatalyst has been reported by several workers. Speciation approaches can be according to the different behaviors of inorganic and methyl-mercury toward UV irradiation, so Hg(II) is efficiently reduced when natural room light is applied, whereas the sum Hg+ + MeHg+ can be obtained after UV irradiation. This strategy has also been used by combining UV reduction and conventional CVG with SnCl2 for speciation of Hg2+ and MeHg+ by AAS. The conversion efficiency for both reduction mechanisms is estimated to be near 100%. In these photo-CVG systems, formic acid is usually employed as a precursor to drive the reduction of Hg species. There are alternative organic precursors to assist the UV reduction of Hg species acetaldehyde, glycol and glycerol). Mercaptoethanol was also applied as a precursor for photo-reduction of Hg species with AFS detection. TiO2/UV photocatalysis was also tried in this work. A further step to a totally green cold VG method involved sample matrix-assisted photo-CVG. In this case, the method was useful for samples containing ethanol (e.g., wines). In general, flow systems have been employed for developing photo-CVG applications. A batch method was reported where UV and ultrasound irradiation (e.g., methanol, formaldehyde,

were applied for fast photo-reduction of Hg species and gasliquid separation of the freshly formed Hg(0), respectively. Other elements (e.g., Ni, Co and I) have received increased attention in regard to photo-CVG. UV irradiation of solutions containing Ni2+ led to the formation of Ni(CO)4 with a 95% efficiency. Photogeneration of volatile Ni(CO)4 was applied for determination of Ni by ETAAS following in-atomizer trapping. Recently, a carbonylated Co species was synthesized upon UV irradiation of inorganic Co solutions. After preconcentration in a cryogenic trap, the Co volatile species was re-volatilized and introduced to an ICP-MS, although generation efficiency was lower than for Ni(CO)4. Speciation strategies can be implemented in several ways when using photoreduction processes. Thus, nonchromatographic approaches make use of the different efficiency of photo-reduction reactions. Some examples can be found in the literature (e.g., for Hg and Se). Thus, a scheme for speciation of Se(IV), Se(VI), SeMet and SeCys based on selective photo-reactions and sono-reactions was proposed. Nano-TiO2 was used for photo-CVG under temperature control in the nonchromatographic speciation of Se(IV) and Se(VI) by AFS and ICP-MS. Recently, very sensitive determinations of non-metals (e.g., I) following photo-CVG were reported. 5.3. UV photo-reduction in hyphenated techniques and other applications Hyphenated systems have been described where UV irradiation fulfils different functions. In some hyphenated systems that include an HG interface,

photochemical reactions provide the species amenable to HG by conventional systems.

On-line UV/TiO2 photocatalysis was employed prior to electrochemical VG as an interface between HPLC and AFS for speciation of Se. UV/nano-TiO2 photocatalysis was employed as an interface between HPLC and ICP-MS for photo-CVG of Se species, thereby eliminating conventional HG with the NaBH4/NaOH-HCl system. An HPLC-UV/nano-TiO2-ICP-MS coupling was described for speciation of Hg(II) and Me-Hg+ using a short cation-exchange column. Fig. 2 shows typical instrumental set-ups employed to implement UV photoreduction on-line. Other analytical approaches take advantage of photogeneration of volatile elemental species. For example, a modified spray chamber that incorporates an UV photolysis unit was proposed to enhance sampleintroduction efficiency in ICPMS. Enhancement factors of 240 were achieved for Ag, As, Se, Sb, Hg, I, Bi, Pb and Sn in the presence of formic, acetic and propionic acids. Liquid-phase microextraction has also been employed following photogeneration of Se(Me)2 in the presence of HOAc, although other acids (e.g., formic, citric, oxalic and EDTA) were also tried. A microdrop used for collection of the Se vapors was injected into a graphite tube for ETAAS determination. Formic and acetic acids at 0.6 mol/L concentration were required but, with citric and EDTA, a concentration as low as 1 mmol/L could be used, yet longer extraction times were needed with them. An LOD as low as 20 pg/mL Se could be obtained. 6. Conclusions Implementation of UV irradiation in sample-preparation and sample-introduction systems provides remarkable improvements in analytical characteristics as well as green methods for trace-element analysis and speciation.

For many applications, photo-oxidation can provide several benefits (e.g., minimum use of chemicals, low blanks and efficient decomposition of organic matter and metal complexes that interfere with the analytical measurement). Photo-reduction processes, particularly photo-CVG, are expanding very fast, offering new avenues for enhancing introduction of vapors into atomic detectors (e.g., AAS, ICP-OES, AFS and ICP-MS). A variety of volatile metal species (e.g., hydrides, carbonyls and alkyl derivatives) can be photogenerated depending on the organic precursor added to the medium. Apart from the removal of traditional chemicalreducing agents and acids, sensitivity is usually improved and matrix effects are diminished, yet more studies are required to understand fully the mechanisms of the photochemical reactions involved. Further research is also needed to extend photo-CVG to more elements, not only to those addressed by conventional CVG (e.g., Hg and Se). Thus, recent applications include Co, I and Ni, and experimental evidence points to photo-CVG being applicable to other transition and noble metals. Photochemical reactions have increased the scope of speciation analysis, since both chromatographic and nonchromatographic approaches can be applied. Hyphenated techniques have taken advantage of photo-oxidation and photoreduction to break down non-hydride reactive species or to generate vapors directly, respectively. In some cases, both processes can be accomplished at the same time, hence providing very efficient systems for speciation (e.g., decomposition of organic Hg species and further photo-CVG from Hg2+). Improvements in photocatalytic processes are also expected, mainly with the use of new nano-materials. Other possibilities regarding the design of manifolds (flow injection and sequential injection) incorporating on-line photo-reduction and

additional processes (e.g., separation and preconcentration) for sample pretreatment remain to be explored.