A primary lesion of advanced melanoma in pregnancy: case report and review of literature of the advanced cases in the last ten years.

INTRODUCTION: Pregnancy- associated melanoma (PAM) is reported between 2.8 and 5.0 per 100,000 pregnancies and approximately 35% of women with melanoma are of childbearing age. The diagnosis and treatment of melanoma during pregnancy needs a balance of risks and benefits for both maternal and fetal well-being. It is a type of malignancy, which requires a multidisciplinary approach, not limited to the obstetrician, but also to oncologists, neonatologists, pharmacists and psychologists. MATERIAL AND METHODS: We present a case of a 36-year-old pregnant woman, who was admitted to our 3rd level Unit of Obstetrics and Gynecology (ARNAS Garibaldi Nesima) at 27 weeks and 2 days of gestation, with a diagnosis of suspected infection, then diagnosed as an advanced melanoma, which caused a premature delivery. A review of the literature of the last ten years from the international electronic bibliographic databases PUBMED was performed following the PRISMA Statement (Preferred Reporting Items for Systematic Reviews and Meta-Analysis). The search was limited to studies reported in the English language. We only included articles that followed our eligibility criteria, represented by: pregnant women with a diagnosis of advanced melanoma in pregnancy, with special reference to maternal, fetal or perinatal outcomes. RESULTS: The patient was affected by an 11 cm pregnancy-associated melanoma in the lower part back, with 2 hepatic metastasis. Due to the quickly development of general symptoms of sepsis it was decided to perform an urgent C-section. For the systematic review, we found 11 articles of advanced clinical melanoma, providing data from 12 patients. Maternal-perinatal outcomes is different depending on gestational age, general clinical condition, stage at diagnosis. CONCLUSION: Advanced melanoma is usually associated with a higher rate of termination of pregnancy, If the pregnancy continues, for the mother is associated with an higher risk of Cesarean section, sepsis, maternal progression of disease; for the baby is associated with prematurity, low birth weight, neonatal metastatic disease, neonatal morbidity and mortality. The future aim of clinicians should be the creation of an international database of the clinical cases of pregnancy-associated melanoma, to evaluate the same data, to improve treatments, to develop common protocols, and, finally, to improve the obstetric and perinatal outcomes.

Medical and Legal Aspects of the Practice of Teledermatology in Spain. / Aspectos medicolegales de la práctica de la teledermatología en España.

Teledermatology is now fully incorporated into our clinical practice. However, after reviewing current legislation on the ethical aspects of teledermatology (data confidentiality, quality of care, patient autonomy, and privacy) as well as insurance and professional responsibility, we observed that a specific regulatory framework is still lacking and related legal aspects are still at a preliminary stage of development. Safeguarding confidentiality and patient autonomy and ensuring secure storage and transfer of data are essential aspects of telemedicine. One of the main topics of debate has been the responsibilities of the physicians involved in the process, with the concept of designating a single responsible clinician emerging as a determining factor in the allocation of responsibility in this setting. A specific legal and regulatory framework must be put in place to ensure the safe practice of teledermatology for medical professionals and their patients.

[Usefulness and efficiency of teledermoscopy in skin cancer management in primary care]. / Utilidad y eficiencia de la teledermatoscopia en el manejo del cáncer de piel en atención primaria.

OBJECTIVE: To evaluate the usefulness of teledermoscopy as a diagnostic and triage method for suspected skin cancer lesions between Primary Care and Dermatology. To analyse the reduction in the number of referrals and estimate the savings achieved. MATERIAL AND METHODS: Concordance study on a non-randomised case series. Descriptive observational study of teleconsultations sent from two Health Centres (urban and rural) to the reference Dermatology service in Cordoba (Spain) between January 2017 and April 2019. The diagnoses proposed by Primary Care before and after the use of dermatoscopy, and the diagnosis of the Dermatologist, along with other epidemiological variables were collected. Descriptive analysis and concordance study were performed. RESULTS: A total of 395 teleconsultations were made. The coefficient of agreement between the diagnoses of both specialists without using dermoscopy was 0.486. Using this technique the concordance was 0.641. A reduction in the number of referrals to Dermatology was 58%. A savings of 2,475€ in transfers by ambulance and 550 working hours were made. The most common diagnoses were basal cell carcinoma (20%; n=79) and seborrheic keratosis (15.2%; n=60). CONCLUSIONS: The addition of dermoscopy increases diagnosis concordance. Teledermatology is a useful system for patient triage and for decreasing the demand for hospital care, with an inherent resources saving.

Footprint of carbonyl compounds in hand scent by in-tube solid-phase microextraction coupled to nano-liquid chromatography/diode array detection.

In the present work, the footprint of carbonyl compounds in hand scent was achieved by a miniaturized method consisting of sampling with cotton gauze, extraction and derivatization using 2,4-dinitrophenylhydrazine (DNPH) and preconcentration, separation and detection by in-tube solid-phase microextraction (IT-SPME) coupled to nano-liquid chromatography/Uv-vis diode array detection. The coupling IT-SPME-nanoLC-DAD was solved by using a two-valve system: the first valve for loading the sample and the second one to perform IT-SPME. To this aim, a nanoparticle-based capillary column was employed. Firstly, the transfer time from the load loop to the NP-based capillary column in the IT-SPME system was optimized. Additionally, the conditioning and clean-up steps were also studied. For the chromatographic separation of DNPH derivatives, gradient elution mode (acetonitrile/water) and a C18 nanocolumn were employed. The detection limits achieved were between 0.5 and 1.5 µg/L and % rsd was lower than 5% for quantification limits. The proposed methodology gave rise to different chromatographic profiles of carbonyl compounds in the hand scent of several volunteers. These profiles were obtained by estimating the relative peak area of selected carbonyls in hand scent. Nonanal, decanal and dodecanal and other low polarity carbonyl compounds (unknown hydrazones) were detected in the odor profiles.

Ion-pair in-tube solid phase microextraction for the simultaneous determination of phthalates and their degradation products in atmospheric particulate matter.

An in-tube solid phase microextraction, coupled with high-performance liquid chromatography with diode array detection (IT-SPME-HPLC-DAD) method, has been developed for the simultaneous determination of 13 diesters (from dimethyl to dioctylphthalate plus diisobutyl, benzylbutyl, di-2-ethylhexyl, diisononyl and diisodecylphthalate) and 2 monoesters of phthalic acid (mono-butyl and mono-(2-ethylhexyl) phthalate) in particulate matter (PM10). Triethylamine at pH=3 was used as an ion-pair reagent with a double function, of regulating the chromatographic retention of the monoesters and the most hydrophilic diesters on a monolithic silica column, and of improving their extraction on a porous polymer with divinylbenzene-4-vinylpyridine capillary. The chromatographic separation was achieved in 13min. A previous ultrasound-assisted extraction from PM10filters was also optimized using methanol as solvent. The method detection limits were 0.09-0.52ngm-3, the inter-day precision at concentration of 20ngmL-1 was between 4.2% and 12.7% (n=15), and the average recovery was 87.3%. The average absolute IT-SPME recovery was 26.2% and the linear range reached up to 109ngm-3 for most analytes. The method was applied to PM10 samples from different environments collected in Galicia (Spain). DiBP was the major phthalate, followed by its isomer DnBP in urban sites and by DEP in the suburban area. In all samples, DEHP quantified correlates with the isomers of dibutylphthalate. Total PAE concentration was between 14.5 and 245.5ngm-3. To the best of our knowledge, this is the first time that a method allows the simultaneous determination of 13 phthalates and their degradation products in particulate matter.

A comparative study of extractant and chromatographic phases for the rapid and sensitive determination of six phthalates in rainwater samples.

Six phthalic acid esters were determined in rainwater samples, from which a very low sample volume was collected. This method combines on-line in-tube solid-phase microextraction coupled to high-performance liquid chromatography with a diode-array detector. In order to obtain a short analysis time and to reduce the consumption of organic solvents, two chromatographic phases (C18 monolithic and cyanopropyl silica) are compared. Although three critical pairs are found, faster separation, good resolution and lower pressures are achieved using C18 monolithic column. In order to achieve a simple and sensitive method, two commercial capillaries (a porous polymer with divinylbenzene-4-vinylpyridine and a liquid-phase capillary with 95% poly(dimethylsiloxane)-5% poly(diphenylsiloxane)) are tested for the extraction process. Due to great differences of hydrophobicity among the six phthalates, the selection of a modifier is necessary for a good extraction. The best conditions are achieved using 5 mL of sample containing 40% methanol in a 70 cm-long porous polymer capillary. The procedural blanks are controlled and taken into account in the calculation of the detection limits. Except for dimethylphthalate, the method detection limits are in the range from 0.2 to 0.9 ng mL-1 and the inter-day precision is between 5.3% and 12.5%. The recoveries were within the range of 71%-101%. Rainwater samples are analyzed in order to examine the dilution effect and washout of phthalates in the atmosphere. Dibutyl phthalate is the predominant phthalate found and di-(2-ethylhexyl) phthalate is detected in all analyzed samples.

Evaluating the risk of ovarian cancer before surgery using the ADNEX model: a multicentre external validation study.

BACKGROUND: The International Ovarian Tumour Analysis (IOTA) group have developed the ADNEX (The Assessment of Different NEoplasias in the adneXa) model to predict the risk that an ovarian mass is benign, borderline, stage I, stages II-IV or metastatic. We aimed to externally validate the ADNEX model in the hands of examiners with varied training and experience. METHODS: This was a multicentre cross-sectional cohort study for diagnostic accuracy. Patients were recruited from three cancer centres in Europe. Patients who underwent transvaginal ultrasonography and had a histological diagnosis of surgically removed tissue were included. The diagnostic performance of the ADNEX model with and without the use of CA125 as a predictor was calculated. RESULTS: Data from 610 women were analysed. The overall prevalence of malignancy was 30%. The area under the receiver operator curve (AUC) for the ADNEX diagnostic performance to differentiate between benign and malignant masses was 0.937 (95% CI: 0.915-0.954) when CA125 was included, and 0.925 (95% CI: 0.902-0.943) when CA125 was excluded. The calibration plots suggest good correspondence between the total predicted risk of malignancy and the observed proportion of malignancies. The model showed good discrimination between the different subtypes. CONCLUSIONS: The performance of the ADNEX model retains its performance on external validation in the hands of ultrasound examiners with varied training and experience.

A novel and cost-effective method for the determination of fifteen polycyclic aromatic hydrocarbons in low volume rainwater samples.

A novel single-step method was developed for the determination of 15 polycyclic aromatic hydrocarbons (PAHs) at ultratrace levels in rainwater by on-line in-tube solid-phase microextraction (IT-SPME) coupled to high-performance liquid chromatography-photodiode array-fluorescence detection. This paper is focused on a study of the IT-SPME coupling and optimization, its application to rainwater and other environmental waters and the stability of PAH rainwater solutions. In order to solve the different extractive behavior of PAHs, several IT-SPME parameters were optimized, with the type and percentage of organic modifier playing a decisive role. In the kinetic study on stability of PAH solutions, the organic modifier has proven to be effective as a preservative, avoiding the loss of the higher-molecular weight PAHs. The proposed method presents a wide interval of linearity (10-1500ngL(-1)) and a good relative standard deviation between 3.4% and 14.6% for the PAHs analyzed. Detection and quantification limits between 2.3 and 28ngL(-1) and 5.7 and 65ngL(-1) were obtained respectively, taking into account the values of the procedure blanks. Recoveries for different kinds of real water samples were within the range of 72-110%. Low and medium-molecular weight PAHs predominate in daily and monthly rainwater samples analyzed. In comparison with other methods reported, the proposed method achieves a significant reduction of the sample volume, the organic solvent consumption and time of sample treatment, allowing a cost-effective analysis of environmental waters. The method is especially suitable for samples from the precipitation events of low intensity or short duration for which sample volume is limiting.

Strengths and weaknesses of in-tube solid-phase microextraction: A scoping review.

In-tube solid-phase microextraction (in-tube SPME or IT-SPME) is a sample preparation technique which has demonstrated over time its ability to couple with liquid chromatography (LC), as well as its advantages as a miniaturized technique. However, the in-tube SPME perspectives in the forthcoming years depend on solutions that can be brought to the environmental, industrial, food and biomedical analysis. The purpose of this scoping review is to examine the strengths and weaknesses of this technique during the period 2009 to 2015 in order to identify research gaps that should be addressed in the future, as well as the tendencies that are meant to strengthen the technique. In terms of methodological aspects, this scoping review shows the in-tube SPME strengths in the coupling with LC (LC-mass spectrometry, capillary LC, ultra-high-pressure LC), in the new performances (magnetic IT-SPME and electrochemically controlled in-tube SPME) and in the wide range of development of coatings and capillaries. Concerning the applicability, most in-tube SPME studies (around 80%) carry out environmental and biomedical analyses, a lower number food analyses and few industrial analyses. Some promising studies in proteomics have been performed. The review makes a critical description of parameters used in the optimization of in-tube SPME methods, highlighting the importance of some of them (i.e. type of capillary coatings). Commercial capillaries in environmental analysis and laboratory-prepared capillaries in biomedical analysis have been employed with good results. The most consolidated configuration is in-valve mode, however the cycle mode configuration is frequently chosen for biomedical analysis. This scoping review revealed that some aspects such as the combination of in-tube SPME with other sample treatment techniques for the analysis of solid samples should be developed in depth in the near future.

A capillary liquid chromatography method for benzalkonium chloride determination as a component or contaminant in mixtures of biocides.

A method for quantifying benzalkonium chloride (BAK), an alkyl dimethyl benzyl ammonium compound, in several biocides formulations is proposed. A tertiary amine like N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine (TA) and a straight-chain alkyl ammonium compound like trimethyl-tetradecyl ammonium chloride (TMTDAC), have been employed as trade surfactants besides BAK. Two capillary analytical columns with different polarities are tested: inertsil CN-3 capillary column (150mm×0.5mm i.d., 3µm particle diameter) and a non endcapped Zorbax C18 capillary column (35mm×0.5mm i.d., 5µm particle diameter). This latter column provided the best separation of the BAK homologues in less than 12min using acetonitrile:acetate buffer (50mM, pH 5) 85:15 at 20µLmin(-1). The proposed method combines on-line in-tube solid-phase microextraction (IT-SPME) coupled to capillary liquid chromatography (CapLC) and UV diode array detection. Matrix effect was present when TA were in excess to BAK. If TMTDAC is the co-biocide, matrix effect is always present. A decreasing of analytical response mainly for C12-BAK homologue was found using both chromatographic columns. The charged amount of mixture in the system was the most important parameter for obtaining reliable results. 1mL was the on line processed sample volume optimum for concentrations lower than 35µgmL(-1) of total surfactants. LODs were 0.03µgmL(-1) and 0.006µgmL(-1) for C12-BAK and C14-BAK, respectively. This method is also of use to evaluate the unwanted presence of BAK in biocide formulations due to industrial processes.

Trichinella pseudospiralis in the Iberian peninsula.

Nematode worms of the genus Trichinella are zoonotic parasites circulating in most continents, including Europe. In Spain, Trichinella spiralis and Trichinella britovi are highly prevalent in wildlife but seldom in domestic pigs. In Portugal, only T. britovi was documented in wild carnivores. In the period 2006-2013 in Spain, 384 (0.0001%) pigs and 1399 (0.20%) wild boars (Sus scrofa) were positive for Trichinella spp. larvae, which were identified as T. spiralis or T. britovi. In 2014, Trichinella pseudospiralis larvae were isolated from a wild boar hunted in the Gerona province, Cataluña region, North-East of Spain, near the border to France. This is the first report of T. pseudospiralis in the Iberian peninsula, which suggests a broad distribution area of this zoonotic nematode in Europe. Since larvae of this Trichinella species do not encapsulate in the host muscles, they can be detected only by artificial digestion of muscle samples. T. pseudospiralis is the only Trichinella species infecting both mammals and birds. Birds can spread this pathogen over great distances including islands triggering new foci of infections in areas previously considered at low risk for this pathogen.

A new LaCo0.71(1)V0.29(1)O2.97(3) perovskite containing vanadium in octahedral sites: synthesis and structural and magnetic characterization.

In the course of an investigation to prepare the hypothetic new double perovskite La(3)Co(2)VO(9) with Co(2+) and V(5+) in octahedral sites, we obtained the new simple perovskite LaCo(0.71(1))V(0.29(1))O(2.97(3)) as the main phase. The pure compound was then synthesized by the citrate decomposition method. The crystal structure was studied by X-ray (PXRD) and powder neutron diffraction (PND). Physical properties were characterized by X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and thermogravimetric analysis (TGA). Rietveld refinements were performed in the orthorhombic space group Pnma (#62). Refined cell parameters were a = 5.4762(2) Å, b = 7.7609(2) Å and c = 5.5122(1) Å. Magnetization measurements showed that this perovskite is an antiferromagnet with a Neel temperature of 15 K. At high T the magnetization follows the Curie-Weiss law corrected by temperature independent paramagnetism (TIP) showing an effective magnetic moment of 3.03µ(B) well described by the contribution of Co(2+) (HS), Co(3+) (IS), V(3+) and V(4+) ions. The crystallographic formula was refined by PND and oxidation state distribution was determined by the combination of PND, XAS, TGA and magnetic measurements.

Development of a polydimethylsiloxane-thymol/nitroprusside composite based sensor involving thymol derivatization for ammonium monitoring in water samples.

This report describes a polydimethylsiloxane (PDMS)-thymol/nitroprusside delivery composite sensor for direct monitoring of ammonium in environmental water samples. The sensor is based on a PDMS support that contains the Berthelot's reaction reagents. To prepare the PDMS-thymol/nitroprusside composite discs, thymol and nitroprusside have been encapsulated in the PDMS matrix, forming a reagent release support which significantly simplifies the analytical measurements, since it avoids the need to prepare derivatizing reagents and sample handling is reduced to the sampling step. When, the PDMS-thymol/nitroprusside composite was introduced in water samples spontaneous release of the chromophore and catalyst was produced, and the derivatization reaction took place to form the indothymol blue. Thus, qualitative analysis of NH4(+) could be carried out by visual inspection, but also, it can be quantified by measuring the absorbance at 690 nm. These portable devices provided good sensitivity (LOD<0.4 mg L(-1)) and reproducibility (RSD <10%) for the rapid detection of ammonium. The PDMS-NH4(+) sensor has been successfully applied to determine ammonium in water samples and in the aqueous extracts of particulate matter PM10 samples. Moreover, the reliability of the method for qualitative analysis has been demonstrated. Finally, the advantages of the PDMS-NH4(+) sensor have been examined by comparing some analytical and complementary characteristics with the properties of well-established ammonium determination methods.

Determination of carbonyl compounds in particulate matter PM2.5 by in-tube solid-phase microextraction coupled to capillary liquid chromatography/mass spectrometry.

In this paper, a new procedure based on in-tube solid phase microextraction (IT-SPME)-capillary liquid chromatography hyphenated to mass spectrometry detection by using microelectrospray ionisation (CapLC-MS), has been reported. The device was proposed to quantify 12 carbonyl compounds (10 aliphatic aldehydes, an unsaturated aldehyde and a ketone) derivatized with 2,4-dinitrophenylhidrazine (DNPH) reagent in aqueous extracts of PM2.5. This methodology involves the on-line preconcentration of DNPH-carbonyl compounds derivatives coupled to the CapLC-MS system, efficiently providing appropriate sensitivity for the determination of the target analytes. Detection limits for the analytes ranged between 0.9 and 8.2 ng L(-1). These values represent a remarkable improvement over the existing methods since PM2.5 analysis can be carried out avoiding off-line preconcentration steps. The procedure is also proved useful for analysing water samples. Under the optimised conditions, IT-SPME-CapLC-MS shows satisfactory recovery values (80-90%) for spiked samples.

Combining poly(dimethyldiphenylsiloxane) and nitrile phases for improving the separation and quantitation of benzalkonium chloride homologues: In-tube solid phase microextraction-capillary liquid chromatography-diode array detection-mass spectrometry for analyzing industrial samples.

The retention and separation of four homologues of benzalkonium chloride (alkyl (C12, C14, C16, C18) dimethylbenzylammonium chloride) have been studied in poly(dimethyldiphenylsiloxane) (TRB) and nitrile capillary phases, respectively. Under the optimized conditions (50% acetonitrile in processed samples, 35% of diphenyl content of the TRB, capillary length 43cm and water:methanol 60:40 as replacing solvent), the extraction efficiency was similar for all the homologues with satisfactory reproducibility and independently of the amount and proportion of homologues. Industrial samples with high viscosity or with complex composition and washes waters have been analyzed without previous treatment. The coupling of IT-SPME-CapLC-DAD to MS detection allowed the determination of the minority homologues (C16 and C18) in the industrial samples and washes waters. No matrix effect was found.

Single step electrochemical synthesis of hydrophilic/hydrophobic Ag5 and Ag6 blue luminescent clusters.

Well-defined Ag(5) and Ag(6) dodecanethiol/tetrabutyl ammonium-protected clusters were prepared by a one-pot electrochemical method. Ag clusters show bright and photostable emissions. The presence of a dual capping renders the silver clusters soluble in both organic and aqueous solvents.

Ion-pair in-tube solid-phase microextraction and capillary liquid chromatography using a titania-based column: application to the specific lauralkonium chloride determination in water.

A quick, miniaturized and on-line method has been developed for the determination in water of the predominant homologue of benzalkonium chloride, dodecyl dimethyl benzyl ammonium chloride or lauralkonium chloride (C(12)-BAK). The method is based on the formation of an ion-pair in both in-tube solid-phase microextraction (IT-SPME) and capillary liquid chromatography. The IT-SPME optimization required the study of the length and nature of the stationary phase of capillary and the processed sample volume. Because to the surfactant character of the analyte both, the extracting and replacing solvents, have played a decisive role in the IT-SPME optimized procedure. Conditioning the capillary with the mobile phase which contains the counter ion (acetate), using an organic additive (tetrabutylammonium chloride) added to the sample and a mixture water/methanol as replacing solvent (processed just before the valve is switched to the inject position), allowed to obtain good precision of the retention time and a narrow peak for C(12)-BAK. A reversed-phase capillary based TiO(2) column and a mobile phase containing ammonium acetate at pH 5.0 for controlling the interactions of cationic surfactant with titania surface were proposed. The optimized procedure provided adequate linearity, accuracy and precision at the concentrations interval of 1.5-300 µg L(-1) .The limit of detection (LOD) was 0.5 µg L(-1) using diode array detection (DAD). The applicability of proposed IT-SPME-capillary LC method has been assessed in several water samples.

Improving methodological aspects of the analysis of five regulated haloacetic acids in water samples by solid-phase extraction, ion-pair liquid chromatography and electrospray tandem mass spectrometry.

Haloacetic acids (HAAs) are organic pollutants originated from the drinking water disinfection process, which ought to be controlled and minimized. In this work a method for monitoring haloacetic acids (HAAs) in water samples is proposed, which can be used in quality control laboratories using the techniques most frequently available. Among its main advantages we may highlight its automated character, including minimal steps of sample preparation, and above all, its improved selectivity and sensitivity in the analysis of real samples. Five haloacetic acids (HAA5) were analyzed using solid-phase extraction (SPE) combined with ion-pair liquid chromatography and tandem mass spectrometry. For the optimization of the chromatographic separation, two amines (triethylamine, TEA and dibutylamine, DBA) as ion pair reagents were compared, and a better selectivity and sensitivity was obtained using DBA, especially for monohaloacetic acids. SPE conditions were optimized using different polymeric adsorbents. The electrospray source parameters were studied for maximum precursor ion accumulation, while the collision cell energy of the triple quadrupole mass spectrometer was adjusted for optimum fragmentation. Precursor ions detected were deprotonated, dimeric and decarboxylated ions. The major product ions formed were: ionized halogen atom (chloride and bromide) and decarboxylated ions. After enrichment of the HAAs in Lichrolut EN adsorbent, the limits of detection obtained by LC-MS/MS analysis (between 0.04 and 0.3 ng mL(-1)) were comparable to those obtained by GC-MS after derivatization. Linearity with good correlation coefficients was obtained over two orders of magnitude irrespective of the compound. Adequate recoveries were achieved (60-102%), and the repeatability and intermediate precision were in the range of 2.4-6.6% and 3.8-14.8%, respectively. In order to demonstrate the usefulness of the method for routine HAAs monitoring, different types of water samples were analyzed. In swimming pool water samples the ∑HAAs were determined between 76 and 154 ng mL(-1).

On-line analysis of carbonyl compounds with derivatization in aqueous extracts of atmospheric particulate PM10 by in-tube solid-phase microextraction coupled to capillary liquid chromatography.

A new device for carbonyl compounds based on coupling on-line and miniaturizing both, sample pretreatment and chromatographic separation, is reported. Two capillary columns, a GC capillary column (95% methyl-5% phenyl substituted backbone, 70 cm × 0.32 mm i.d., 3 µm film thickness) in the injection valve for in-tube solid-phase microextraction (IT-SPME) and a Zorbax SB C18 (150 mm × 0.5 mm i.d., 5 µm particle diameter) LC capillary column were employed. Different combinations of IT-SPME and derivatization using 2,4-dinitrophenylhydrazine (DNPH) were examined for mixtures containing 15 carbonyl compounds (aliphatic, aromatic and unsaturated aldehydes and ketones). A screening analysis of aqueous extracts of atmospheric particulate PM(10) was carried out. Moreover, the possibility of coupling IT-SPME and conventional liquid chromatography is also tested. Derivatization solution and IT-SPME coupled to capillary liquid chromatography provided the best results for achieving the highest sensitivity for carbonyl compounds in atmospheric particulate analysis. Detection limits (LODs) using a photodiode array detector (DAD) were ranged from 30 to 198 ng L(-1), improving markedly those LODs reported by conventional SPME-LC-DAD.

Simultaneous determination of carbonyl compounds and polycyclic aromatic hydrocarbons in atmospheric particulate matter by liquid chromatography-diode array detection-fluorescence detection.

Simultaneous analysis of 24 carbonyl compounds (alkanals, unsaturated, dicarbonylic and aromatic aldehydes and ketones) derivatized with 2,4-dinitrophenylhydrazine and 16 polycyclic aromatic hydrocarbons (PAHs) using a photodiode-array (PDA) and a fluorescence (FL) detector in series is proposed. The separation is carried out with a reversed-phase column and gradient elution using four solvents (acetonitrile, water, tetrahydrofuran and methanol) in less than 35 min. Several critical pairs of carbonyl compounds with 3 and 4 carbon atoms and different functional groups, isomers of tolualdehyde, aromatic and aliphatic aldehydes were conditional on the gradient elution. Common pre-treatment for two groups of compounds consists in a step of extraction and derivatization in aqueous medium and a further clean-up using a polymeric phase SPE and concentration in a mixture of dichloromethane:methanol. A pre-concentration factor of 50 was achieved by this procedure. Acetone and formaldehyde blanks were minimized and remain controlled with a specific cleaning of glass material and washing the SPE cartridge. The limits of detection (LOD) ranged from 0.006 to 0.18 ng mL(-1) for PAHs and from 2.4 to 10.1 ng mL(-1) for carbonyl compounds and method precision was