Feasibility of gas chromatography-atmospheric pressure photoionization-high-resolution mass spectrometry for the analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in environmental and feed samples.

In this work, the suitability of atmospheric pressure photoionization (APPI) has been assessed for the determination of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) by gas chromatography-high-resolution mass spectrometry (GC-HRMS). The APPI of target compounds has been tested in both positive and negative ion modes. Under positive ion mode, the analytes generated the molecular ion, which was favoured using dopants that promote charge exchange gas-phase reactions (i.e., benzene), while in negative ion mode, the ion [M-Cl+O]- for PCDFs and dl-PCBs were mainly formed, providing the best results using benzene and diethyl ether as dopants, respectively. Concerning PCDDs, highly chlorinated congeners were mainly ionized by means of the [M-Cl]- ion, whereas [M-Cl+O2]- was the base peak for tetraCDD and [M-Cl+O]- for penta- and hexaCDDs. Method quality parameters, in accordance with the current EU Regulation guidelines for food and feed analysis, showed the good performance of the two GC-APPI-HRMS (Orbitrap) methods since they provided high detection capability (low fg levels), good linearity, and satisfactory precision (RSD% < 9%). In addition, the GC-APPI-HRMS (Orbitrap) methods were validated by analysing selected environmental and feed samples and the results were compared to those obtained using conventional GC-EI-HRMS, demonstrating the good performance in the analysis of the target compounds. Hence, the GC-APPI-HRMS technique can be proposed as alternative to the conventional methods for the determination of PCDD/Fs and dl-PCBs in environmental and feed matrices.

Atypical presentation of invasive meningococcal disease caused by serogroup W meningococci.

Neisseria meningitidis, a gram-negative diplococcus, is typically an asymptomatic coloniser of the oropharynx and nasopharynx. Passage of N. meningitidis into the bloodstream can cause invasive meningococcal disease (IMD), a potentially life-threatening illness with rapid onset that generally presents as meningitis, septicemia or both. Serogroup W IMD has been increasing in prevalence in recent years, and observations suggest that it may present with atypical signs and symptoms. Herein, a literature search was performed to identify trends in atypical serogroup W IMD presentation in order to review those that are most prevalent. Findings indicate that the most prevalent atypical presentations of serogroup W IMD include acute gastrointestinal (GI) symptoms, septic arthritis and bacteremic pneumonia or severe upper respiratory tract infection, notably epiglottitis. Atypical clinical presentation is associated with higher case fatality rates and can lead to misdiagnoses. Such risks highlight the need for clinicians to consider IMD in their differential diagnoses of patients with acute GI symptoms, septic arthritis or bacteremic pneumonia, primarily in regions where serogroup W is prevalent.

Large impacts, past and future, of ozone-depleting substances on Brewer-Dobson circulation trends: A multi-model assessment.

Substantial increases in the atmospheric concentration of well-mixed greenhouse gases (notably CO2), such as those projected to occur by the end of the 21st century under large radiative forcing scenarios, have long been known to cause an acceleration of the Brewer-Dobson circulation (BDC) in climate models. More recently, however, several single-model studies have proposed that ozone-depleting substances might also be important drivers of BDC trends. As these studies were conducted with different forcings over different periods, it is difficult to combine them to obtain a robust quantitative picture of the relative importance of ozone-depleting substances as drivers of BDC trends. To this end we here analyze - over identical past and future periods - the output from 20 similarly-forced models, gathered from two recent chemistry-climate modeling intercomparison projects. Our multi-model analysis reveals that ozone-depleting substances are responsible for more than half of the modeled BDC trends in the two decades 1980-2000. We also find that, as a consequence of the Montreal Protocol, decreasing concentrations of ozone-depleting substances in coming decades will strongly decelerate the BDC until the year 2080, reducing the age-of-air trends by more than half, and will thus substantially mitigate the impact of increasing CO2. As ozone-depleting substances impact BDC trends, primarily, via the depletion/recovery of stratospheric ozone over the South Pole, they impart seasonal and hemispheric asymmetries to the trends which may offer opportunities for detection in coming decades.

Long-term monitoring programme of polychlorinated dioxins and polychlorinated furans in ambient air of Catalonia, Spain (1994-2015).

Reductions in concentrations of persistent organic pollutants were observed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a comparison of two consecutive decades ending in December 31, 2015 (n = 413) and compiled from a 48-station long-term air-monitoring network in Catalonia, Spain. Reductions were observed in geometric mean concentration of total PCDD/Fs, decreasing at a rate of 11% yr-1. Results reflect the relative success of improved pollution control measures at industry and traffic locations. At traffic and industrial locations, PCDD/Fs were reduced by around 68% (from 70 to 22 fg I-TEQ/m3) and 66% (from 57 to 19 fg I-TEQ/m3), respectively. The highest concentration of 1196 fg I-TEQ/m3 was observed during the first decade at an industrial location. The highest concentration over the second decade was at a background location during winter (674 fg I-TEQ/m3). Winter observations are generally higher than those recorded in summer, as evident in an 8-year period of moderate PCDD/F levels (<250 fg I-TEQ/m3, n = 143). PCDD/F congener profiles were identified has having less chlorinated PCDD/F, indicating the presence of nearby combustion sources at selected locations. More long-term sampling campaigns, combined with network optimization and integration into a meteorological model, can offer a tool for future PCDD/Fs control measures in not only Catalonia - but also applicable to other areas.

Analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans in stack gas emissions by gas chromatography-atmospheric pressure chemical ionization-triple-quadrupole mass spectrometry.

A gas chromatography coupled to triple-quadrupole mass spectrometry (GC-(QqQ)MS/MS) including a soft-ionization through an atmospheric pressure chemical ionization (APCI) source based method was compared with the high resolution mass spectrometry (HRMS) standard reference method EN1948, for the analysis of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in stack gas emissions. The stack emission samples were collected, both, by manual method sampling (from 6 to 8h) and by long-term sampling systems (sampling time of several weeks). This work presents the first comparison of GC-(QqQ)MS/MS with APCI source with the European Standard EN1948 technique for stack gas emissions. Sample concentrations ranged from 0.5 to 596pg I-TEQ/Nm3. Comparative results in all investigated samples showed relative errors that were within ±15%. These results make GC-(QqQ)MS/MS with APCI suitable for the quantitative analysis of dioxins in the studied samples and create a real alternative tool to the reference sector GC-HRMS instruments.

Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples.

The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg µL(-1) (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40-10000 pg g(-1). GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices.

Polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like PCBs in commercialized food products from Colombia.

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) are commonly known as dioxins and are the most toxic members of persistent organic pollutants (POPs) because present a variety of health effects especially as promoting agent of growing and transformation of cancer cells. They are bio-accumulate in humans primarily via the diet, specifically by ingestion of foods that have high lipid content which are generally associated with foods of animal origin such as oils and fats and with fishery and dairy products. In Colombia the Ministry of Health and Social Protection which is the entity responsible for surveillance food conditions, has established maximum levels for dioxins and dl-PCBs in oils from animal and vegetable origins. Oils of vegetable and animal origin represent an appreciable intake in the country thus the presence of dioxins and dl-PCBs in these materials is a matter of concern because they can bioaccumulate in fat. In this contribution the levels of PCDD/Fs and dl-PCBs in olive, soybean, fish oil, butter and shrimp consumed in Colombia were determined using HRGC-HRMS and were compared with the maximum levels permitted in oil samples according to both the Colombian and European regulations. WHO-TEQ concentrations for PCDD/Fs and dioxin like PCBs ranged from 0.24 to 1.710pgWHO-TEQ PCDD/Fg(-1) of fat and from 0.050 to 3.000pgWHO-TEQ PCBg(-1) of fat, respectively. As expected, fish oils and shrimp present the highest WHO-TEQ PCDD/Fs and dl-PCBs values followed by butter and soybean oil sample, while the olive oil shows the lowest levels. In general, the vegetable oils show levels below the limits established by both the Colombian and European regulations. The levels from soybean oil found in this study were slightly higher than the threshold established both by the Commission Regulation European Union (EU) and the Colombian legislation, while fish oils showed concentrations above the European regulations. Furthermore, shrimp exhibited values below the maximum concentration levels established by the EU and Colombian regulation.

Environmental variation of PCDD/Fs and dl-PCBs in two tropical Andean Colombian cities using passive samplers.

Passive air-sampling data of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) taken in Manizales (a medium-sized city) and Bogotá (a megacity), Colombia, were analyzed in order to identify potential sources of pollution and the possible influence of meteorological variables like temperature and precipitation. The results indicate important differences in levels of PCDD/Fs and dl-PCBs between Bogotá and Manizales, attributed to differences in site characteristics and potential local/regional sources. Higher PCDD/Fs concentrations were observed in Bogotá (373fg/m(3)) compared to those observed in Manizales, with mean levels ranging from 64fg/m(3) in a residential zone to 151fg/m(3) around a vehicular-influenced area. Higher dl-PCBs concentrations were observed in the industrial area of Manizales compared to those observed in Bogotá, with mean levels of 6668fg/m(3) and 4388fg/m(3) respectively. In terms of PCDD/Fs congener distribution, there was a predominance of octachlorodibenzodioxin (OCDD) followed by 1,2,3,4,6,7.8-heptachlorodibenzofuran (HpCDF) congeners, with both cities showing higher levels in zones of high vehicular activity. Industrial influence was most evident in dl-PCB levels. In comparison to the mean levels of dl-PCB congeners obtained in the vehicular zones of Bogotá and Manizales, the industrially influenced sampling stations showed higher concentrations of dl-PCB congeners. Passive sampling results suggested that congener concentration profiles are characteristic of their different emission sources, and can be used to distinguish between their industrial or vehicular origins.

Long-term sampling of dioxin-like substances from a clinker kiln stack using alternative fuels.

The aim of this work is to characterize atmospheric emissions of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) from a cement production plant where the existing clinker production line was completely replaced by a new state-of-the-art installation. The project started in April 2008 with the installation of a long-term sampling system in the stack of the clinker kiln that used petroleum coke as fuel; PCDD/PCDF and dl-PCB emissions were then evaluated for a two year period. To carry out the second part of the study, in 2010 the sampling system was moved to the new installation in which, apart from conventional fuel, recovered derived fuel (RDF) and WWTP sludge were used as alternative fuels. For both the old and new clinker kilns, PCDD/PCDF emission values were well below the limit established by the European Waste Incineration Directive 2000/76/CE (EWID) of 100 pg I-TEQ/Nm(3); values ranged from 0.43 to 2.02 and from 0.07 to 3.31 pg I-TEQ/Nm(3), respectively. dl-PCBs accounted for approximately 25% of the WHO-TEQ toxicity. These results prove that the installation is capable of reducing PCDD/PCDF and dl-PCB emissions when alternative fuels are integrated into the process. In the case of PCDDs/PCDFs, the major contributions to total TEQ were usually from 2,3,7,8-TCDD (owing to its relative abundance) and 2,3,4,7,8-PeCDF (due to its high I-TEF of 0.5); while for dl-PCBs, the major contribution was from PCB-126. The slight shift in the congener profile between the old and new installations was characterized and a regression model was proposed for dl-PCB emissions depending on the RDF flow rate in the clinker.

PCDD/PCDF and dl-PCB in the ambient air of a tropical Andean city: passive and active sampling measurements near industrial and vehicular pollution sources.

Concentration gradients were observed in gas and particulate phases of PCDD/F originating from industrial and vehicular sources in the densely populated tropical Andean city of Manizales, using passive and active air samplers. Preliminary results suggest greater concentrations of dl-PCB in the mostly gaseous fraction (using quarterly passive samplers) and greater concentrations of PCDD/F in the mostly particle fraction (using daily active samplers). Dioxin-like PCB predominance was associated with the semi-volatility property, which depends on ambient temperature. Slight variations of ambient temperature in Manizales during the sampling period (15°C-27°C) may have triggered higher concentrations in all passive samples. This was the first passive air sampling monitoring of PCDD/F conducted in an urban area of Colombia. Passive sampling revealed that PCDD/F in combination with dioxin-like PCB ranged from 16 WHO-TEQ2005/m(3) near industrial sources to 7 WHO-TEQ2005/m(3) in an intermediate zone-a reduction of 56% over 2.8 km. Active sampling of particulate phase PCDD/F and dl-PCB were analyzed in PM10 samples. PCDD/F combined with dl-PCB ranged from 46 WHO-TEQ2005/m(3) near vehicular sources to 8 WHO-TEQ2005/m(3) in the same intermediate zone, a reduction of 83% over 2.6 km. Toxic equivalent quantities in both PCDD/F and dl-PCB decreased toward an intermediate zone of the city. Variations in congener profiles were consistent with variations expected from nearby sources, such as a secondary metallurgy plant, areas of concentrated vehicular emissions and a municipal solid waste incinerator (MSWI). These variations in congener profile measurements of dioxins and dl-PCBs in passive and active samples can be partly explained by congener variations expected from the various sources.