Tetraphasic polar organic chemical integrative sampler for the determination of a wide polarity range organic pollutants in water. The use of performance reference compounds and in-situ calibration.

In the present work, a homemade polar organic chemical integrative sampler (POCIS) was studied for the determination of 16 target analytes. The suitability of the combination of triphasic mixture (used in so called pesticides-POCIS) and octadecyl-functionalized silica gel (C18) as sorbent for POCIS was evaluated for the determination of alkylphenols (APs), several hormones, bisphenol-A (BPA), synthetic musk fragrances and herbicides such as trifluralin (Tri) and alachlor (Ala). With this purpose, POCIS laboratory calibration study, using a continuous-flow calibration system, was carried out in order to determine the uptake behavior and sampling rate (Rs) values for each target analyte. While the most hydrophobic compounds, (synthetic musk fragrances, some APs and Tri), showed poor linearity and low accumulation, a linear accumulation was observed for compounds whose logarithmic octanol-water partition coefficient (log Kow) ranged from 5.3 (4-tert-octylphenol, 4t-OP) to 3.1 (cis-androsterone, ADT). The Rs values obtained ranged from 0.190Lday-1 (4t-OP) to 0.042Lday-1 (BPA and equilin, EQ). The addition of C18 to the commonly used triphasic mixture increased the applicability of the POCIS sampler to compounds slightly more non-polar, such as 4t-OP. As far as we know, this is the first time that a combination of tetraphasic sorbent composed by the commercially available triphasic sorbent (Isolute ENV+polystyrene divinylbenzene and Ambersorb 1500 carbon dispersed on S-X3 Biobeads) and C18 was evaluated for passive sampling of the target analytes. The developed POCIS samplers were applied in field experiments from Halle (Germany) wastewater treatment plant (WWTP) effluent. Concerning the calculation of Rs values, the time weighted average (TWA) water concentration CWTWA values were determined considering three different approaches: (i) Rs from laboratory calibration (ii) Rs from laboratory calibration corrected with the use of performance reference compounds (PRCs) and (iii) Rs derived from field experiments or in-situ calibration. Several deuterated compounds such as, [2H3]-17ß-estradiol ([2H3]-E2), [2H4]-nonylphenol ([2H4]-NP), [2H4]-equilin ([2H4]-EQ), [2H3]-tonalide ([2H3]-AHTN) and [2H15]-musk xylene ([2H15]-MX) were also studied for their applicability as PRCs. Finally, a reasonable agreement between grab sampling and CWTWA was found when results from in-situ calibration were considered, but not when PRCs were used for correction.

Uptake of perfluorooctanoic acid, perfluorooctane sulfonate and perfluorooctane sulfonamide by carrot and lettuce from compost amended soil.

Sewage sludge, which acts like a sink for many pollutants, including metals, pathogens and organic pollutants, that are not completely removed in waste water treatment plants (WWTPs), is applied as a nutrient rich organic fertilizer in many agricultural applications. In the present work, carrot and lettuce crops were grown in two different compost amended soils fortified with perfluorooctanoic acid (PFOA), perfluorosulfonate acid (PFOS) and perfluorosulfonamide (FOSA) and cultivated in a greenhouse. The plants were harvested and divided into root core, root peel and leaves in the case of carrots and into heart and leaves for lettuces. Concentrations for all the different compartments were determined to assess the bioconcentration factors (BCFs) and the plant distribution of the target analytes. The highest carrot BCFs for PFOA and PFOS were determined in the leaves (0.6-3.4), while lower values were calculated in the core (0.05-0.6) and the peel (0.05-1.9) compartments. However, PFOA was taken up in the translocation stream and accumulated more than PFOS in the edible part of lettuce. FOSA was totally degraded in the presence of carrot; however, a lower FOSA degradation was observed in presence of the lettuce, which was dependent on the total organic carbon (TOC) content of the soil. The higher the TOC value, the higher the FOSA degradation observed. No degradation was observed in the crop absence. In the case of the carrot experiments, different polymeric materials (polyethersulfone, PES, polyoxymethylene, and silicone rod) were tested to predict the concentration in the cultivation media. A high correlation (r(2)>0.63) was observed for the BCFs in the PES and in the carrot core and peel for PFOA and PFOS. It could be, concluded that the PES can be used as a first approach for the determination of the uptake of compounds such as PFOS and PFOA in carrot.

Uptake of polybrominated diphenyl ethers by carrot and lettuce crops grown in compost-amended soils.

The uptake of polybrominated diphenyl ethers (PBDEs) by carrot and lettuce was investigated. Degradation of PBDEs in soil in the absence of the plants was discarded. Different carrot (Nantesa and Chantenay) and lettuce (Batavia Golden Spring and Summer Queen) varieties were grown in fortified or contaminated compost-amended soil mixtures under greenhouse conditions. After plant harvesting, roots (core and peel) and leaves were analyzed separately for carrot, while for lettuce, leaves and hearts were analyzed together. The corresponding bioconcentration factors (BCFs) were calculated. In carrots, a concentration gradient of 2,2',3,4,4',5'-hexabromodiphenyl ether (BDE-138) became evident that decreased from the root peel via root core to the leaves. For decabromodiphenyl ether (BDE-209) at the low concentration level (7 and 20 ng g(-1)), the leaves incorporated the highest concentration of the target substance. For lettuce, a decrease in the BCF value (from 0.24 to 0.02) was observed the higher the octanol-water partition coefficient, except in the case of BDE-183 (BCF = 0.51) and BDE-209 (BCF values from 0.41 to 0.74). Significant influence of the soils and crop varieties on the uptake could not be supported. Metabolic debromination, hydroxylation or methylation of the target PBDEs in the soil-plant system was not observed.

Matrix solid-phase dispersion of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogues in lettuce, carrot and soil.

In the present work, a novel analytical method for the simultaneous determination of ten polybrominated diphenyl ethers (PBDEs), eight methoxylated PBDEs (MeO-PBDEs) and seven hydroxylated PBDEs (OH-PBDEs) in soil, lettuce and carrot samples was developed. The procedure was based on matrix solid-phase dispersion (MSPD) followed by gas chromatography coupled to negative chemical ionization-mass spectrometry (GC-NCI-MS). Under optimum conditions, 0.5g of sample (freeze-dried in the case of lettuce and carrot samples) was dispersed with 0.5g of octadecyl-functionalized silica (C18) and 1.75g of acidified silica (10% H2SO4, w/w) was used as clean-up sorbent. A two-step fractionated elution was carried out. First, PBDEs and MeO-PBDEs were eluted in 75:25% (v/v) n-hexane/dichloromethane mixture and, then, the retained OH-PBDEs were eluted in pure dichloromethane. Both extracts were analyzed by GC-NCI-MS separately, in the case of OH-PBDEs after derivatization with N-methyl-N-(trimethylsilyl) trifluoroacetamide. The developed method was validated in terms of accuracy for soil, lettuce and carrot matrices, spiked at two fortification levels (5 and 25ngg(-1)). After correction with the corresponding surrogate, apparent recovery values (defined as the recovery obtained after correction with the corresponding surrogate) were in the 80-129% range. Precision (as relative standard deviation) in the 1-21% range and method detection limits (MDLs) in the 0.003 and 0.3ngg(-1) range for soil and in the 0.003-0.4ngg(-1) range (dry weight) for lettuce and carrot samples were obtained. For PBDEs the method was also validated with a standard reference material (SRM-2585) of house dust. Finally, the method was applied for the determination of target analytes in soil, lettuce and carrot.

Matrix effect during the membrane-assisted solvent extraction coupled to liquid chromatography tandem mass spectrometry for the determination of a variety of endocrine disrupting compounds in wastewater.

Membrane-assisted solvent extraction (MASE) coupled to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) was studied for the determination of a variety of emerging and priority compounds in wastewater. Among the target analytes studied certain hormones (estrone (E1), 17ß-estradiol (E2), androsterone (ADT), 17α-ethynyl estradiol (EE2), diethylstilbestrol (DES), equilin (EQ), testosterone (TT), mestranol (MeEE2), 19-norethisterone (NT), progesterone (PG) and equilenin (EQN)), alkylphenols (APs) (4-tert-octylphenol (4tOP), nonylphenol technical mixture (NPs) and 4n-octylphenol (4nOP)) and BPA were included. The work was primarily focused in the LC-MS/MS detection step, both in terms of variable optimization and with respect to the matrix effect study. Both, electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) were assessed both in the negative and positive mode, including the optimization of MS/MS operating conditions. The best results were obtained, in most of the cases, for ESI using 0.05% ammonium hydroxide as buffer solution in the mobile phase, composed with methanol and water. Under optimum detection conditions, matrix effect during the detection step was thoroughly studied. Dilution, correction with deuterated analogues and clean-up of the extracts were evaluated for matrix effect correction. Clean-up with Florisil together with correction with deuterated analogues provided the most satisfactory results, with apparent recoveries in the 57-136% range and method detection limits in the low ngL(-1) level for most of the analytes. For further validation of the method, two separated extraction procedures, the above mentioned MASE, and conventional solid phase extraction (SPE) were compared during the analysis of real samples and comparable results were successfully obtained for E1, E2, EE2, DES, NT, TT, EQ, PG, BPA, ADT, 4nOP, 4tOP, NPs and EQN.

Overview of extraction, clean-up and detection techniques for the determination of organic pollutants in sewage sludge: a review.

Priority pollutants constitute only a part of the large chemical pollution puzzle where the number of potentially hazardous chemicals that reaches the environment is very wide and new substances are constantly being developed and released. Among them, a diverse group of unregulated pollutants, many times called "emerging" contaminants, including pharmaceuticals and personal care products (PPCPs), is found. This group of emerging contaminants constitutes a broad class of chemicals widely used in daily life, such as synthetic fragrances, UV filters, antiseptics, antioxidants and insect repellents. The large amount of them and other emerging contaminants consumed in modern society contribute as well to a wide range of contamination in the aquatic environment, introduced mainly through wastewater treatment plants (WWTPs). The agricultural application of sewage sludge has become the most widespread method for its disposal, since it is the most economical outlet for sludge and offers the opportunity to recycle plant nutrients and organic matter to soil for crop production. However, due to the presence of metals, organic contaminants and pathogenic bacteria in sewage sludge, concern has increased about the human exposure to priority and emerging pollutants via crops cultivated in sewage/compost-amended soils. Because of the potentially dangerous consequences of the presence of those contaminants in the environment, data concerning the concentration, fate and behavior of those pollutants is urgently necessary. With this purpose in mind, sensitive and robust analytical methods for complex matrices such as sewage sludge are necessary in order to obtain reliable data that help us to understand the risk of agricultural use of sewage sludge. The present manuscript reviews the different approaches present in the literature for determining organic pollutants (priority and emerging) in sewage sludge. A review of the last ten years has been performed and the three main steps of an analytical procedure (extraction, clean-up and analysis) have been reviewed.

Solid-phase extraction combined with large volume injection-programmable temperature vaporization-gas chromatography-mass spectrometry for the multiresidue determination of priority and emerging organic pollutants in wastewater.

In the present work the simultaneous extraction for the multiresidue determination in wastewater samples of organic compounds such as polychlorinated biphenyls (PCBs), polybrominated biphenyls (PBBs), pesticides, polycyclic aromatic hydrocarbons (PAHs), phthalate esters (PEs), alkylphenols (APs), bisphenol A (BPA) or hormones included in different lists of priority and emerging pollutants because of their action as endocrine disrupting compounds (EDCs) was developed. Different solid phase extraction (SPE) variables such as the nature of the solid phase (Oasis-HLC, C18 and Lichrolut), the sample volume, the addition of MeOH and NaCl, the pH of the water phase and the volume of the eluent solvent were optimized in order to analyze simultaneously the priority and emerging families of pollutants mentioned above. Good recoveries were obtained for Milli-Q water (80-120%), however, since the use of deuterated analogues and dilution of the sample did not correct the matrix effect, additional SPE clean-up step using Florisil® cartridges was necessary to obtain good results for wastewater samples (80-125%). In order to improve the limits of detection (LODs), large volume injection (LVI) using programmable temperature vaporizer (PTV) coupled to gas chromatography-mass spectrometry (GC-MS) was also optimized. Since analytes losses in the case of the most volatile congeners occurred during the derivatization step and no separation of the derivatized and the non-derivatized analytes was possible during SPE elution, two different injections were optimized for each analyte group. LODs were in good agreement with those found in the literature and relative standard deviations (RSDs) were in the 10-25% range for Milli-Q and 12-30% for wastewater samples. The method was finally applied to the determination of target analytes in three different wastewater treatment plants (WWTPs, Bakio, Gernika and Galindo (Spain)) and in one water purification plant (WPP) in Zornotza (Spain).

Selective allergy to lobster in a case of primary sensitization to house dust mites.

Allergy to only 1 kind of seafood is uncommon. We report a case of selective allergy to lobster. We studied a 30-year-old man who suffered generalized urticaria, facial erythema, and pharyngeal pruritus after eating lobster. He had a more than 10-year history of mild persistent asthma and sensitization to house dust mites. The study was performed by skin prick test, and prick-prick test, oral food challenge, specific immunoglobulin (Ig) E determinations by CAP (Phadia, Uppsala, Sweden) and ADVIA-Centaur (ALK-Abelló, Madrid, Spain), and IgE-immunoblotting. The patient's serum recognized 2 allergens of around 198 kDa and 2 allergens of around 65 kDa from the lobster extract, allergens of around 15, 90, and 120 kDa from Dermatophagoides pteronyssinus extract, and allergens of around 15 and 65 kDa from Dermatophagoides farinae extract. Serum did not recognize purified shrimp tropomyosin. Immunoblot-inhibition assay results indicated cross-reactivity between lobster and mite allergens. This is the first report of selective allergy to lobster.

[An analysis of long-term computerized prescriptions for those over and under 65 at a health center]. / Análisis de la prescripción crónica informatizada en mayores y menores de 65 años en un centro de salud.

OBJECTIVES: To analyse the origin, diagnoses and types of medicine used in computerised long-term prescription at our centre, which are classified by age distribution; and to extract, if possible, use parameters for monitoring internal activities. DESIGN: Descriptive study. SETTING: Zumaia Health Centre (Guipúzcoa). PATIENTS: 976 patients divided into those over and those under 65, included in the programme of long-term treatment cards. MEASUREMENTS AND MAIN RESULTS: 54% of patients were over 65 and 46% under. Average medicines per patient were 3.24 and 2.23, respectively. 34% of long-term prescription originated in primary care, although primary care was only the main indicator to a significant degree in group K (CIAP) diagnoses for under-65's. The commonest diagnoses belonged to group K, independently of the origin of the prescription. The most prescribed medicines were those in groups M and C (IMC), significantly higher in the over-65's. CONCLUSIONS: Only one third of the prescriptions originated in PC. A significant reversal of this tendency was observed in young people with chronic group K pathologies. The indication of long-term treatment for psychological problems often escapes the public health system; when the PC doctor indicates this treatment, he/she usually does so on the basis of symptomatic conditions. Monitoring new cases could help us find the efficacy of the corrective measures introduced, both at the level of structural innovations and changes in care procedure.

[Orthopedic treatment of nocturnal acroparesthesias in primary care]. / Tratamiento ortopédico de las acroparestesias nocturnas en atención primaria.

OBJECTIVE: To report the experience gained from the systematic use of a splint immobilising at night the flexion or extension of the carpus of patients affected by nocturnal acroparaesthesiae. DESIGN: Descriptive, observational study. SETTING: Two urban Health Centres. PATIENTS OR OTHERS PARTICIPANTS: Twenty-two patients were studied. These were 6 men and 16 women who attended during the period from June 1991 and June 1992 because of nocturnal acroparaesthesiae in the area innervated by the median nerve. INTERVENTIONS: The treatment used was to immobilize with a splint the flexion and extension of the carpus during the night. After three weeks the results were evaluated. MEASUREMENTS AND MAIN RESULTS: Disappearance of the symptomatology occurred in 8 cases (36.4%). In 10 cases (45.5%), the intensity or frequency of the acroparaesthesiae lessened and in the remaining 4 (18.2%) the symptoms persisted. No significant differences in the therapeutic results could be shown when the patients were grouped in line with clinical or exploratory findings. CONCLUSIONS: On account of the absence of side-effects, its low cost and its being accessible and bloodless, we recommend this treatment as the initial model of therapeutic intervention in Primary Care, while other diagnostic and/or therapeutic possibilities are considered.

[Prolonged febrile syndrome as a manifestation of Coxiella burnetii infection, presentation of infrequent clinical cases]. / Síndrome febril prolongado como manifestación de infección por Coxiella burnetii, presentando casos clínicos poco frecuentes.

We present two cases of infection by Coxiella burnetii which developed with sustained fever symptoms. During its evolution, the first case presented granulomatous hepatitis, whereas the second case presented left Cosofemoral Arthritis. We describe the clinical-evolutive characteristics of these clinical forms and within the evolution of the chronic forms of Q fever.