An alternative silicone-based passive sampling device to derive organotin concentrations in the aqueous phase.

Organotin compounds (OTs) are well studied in various environmental compartments, with a critical focus on the water column as their primary entry point into aquatic ecosystems. In this context, a method for the analysis of organotin (OTs) in water using silicone rubber-based passive sampling was optimized, validated, and field-tested. Validation covered crucial parameters, including the limit of detection (LOD), limit of quantification (LOQ), accuracy, precision, linearity, and matrix effect. The method was shown to be robust (R2 ≥ 0.99), with recoveries between 70.2 and 114.6%, and precise (CV < 12.8%) (N = 3). LODCw and LOQCw were ≤15 and ≤ 48 pg Sn L-1, respectively, for TBT and TPhT. The matrix effect showed to be low (>-20% ME < 20%) for all OTs but TPhT (69.4%). The silicone rubber-water partition coefficients (Log Ksr,w) were estimated at 3.37 for MBT, 3.77 for DBT, 4.17 for TBT, 3.49 for MPhT, 3.83 for DPhT, and 4.22 for TPhT. During the field study carried out between October 2021 and February 2022 at the entrance of the Port of Santos navigation channel (Southeastern Brazil), sampling rates ranged between 4.1 and 4.6 L d-1, and the equilibrium was achieved for MBT, DBT, MPhT, and DPhT after ∼45 days of deployment. The freely dissolved concentrations varied between 134 and 165 pg Sn L-1 for TBT, 388 and 610 pg Sn L-1 for DBT, and 1114 and 1509 pg Sn L-1 for MBT, while MPhT, DPhT, and TPhT were below the limit of detection. Results pointed out that J-FLEX® rubber-based passive sampling is a suitable and reliable alternative method for the continuous monitoring of OTs in the water column.

Analysis of drug of abuse compounds using passive sampling and ultrahigh-liquid chromatography coupled to mass spectrometry.

The present study proposes the monitoring of compounds of drugs of abuse through the use of passive samplers in water systems. Initially, four positive ion compounds of interest were determined according to national surveys, and then composite sampling and passive sampling were implemented using continuous-flow passive samplers containing two types of sorbents, the Empore disk and Gerstel Twister. Two study sites were established at the beginning and at the end of the middle Bogotá River basin. After 4 days, the sorbents were removed so that they could be desorbed and analyzed using UHPLC-MS in the laboratory. For the composite samples, the results were below the first calibration curve point (FCCP) of the chromatographic method, and for passive sampling, peaks of benzoylecgonine (BE) (21427.3 pg mL-1), methamphetamine (MET) (67101.5 pg mL-1), MDMA (ecstasy) (225844.8 pg mL-1) and 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) (15908.4 pg mL-1) were found. Therefore, passive sampling could be suggested as an alternative to composite sampling for the monitoring of compounds.

Fractionation and speciation of metals in lakes formed by abandoned clay pits from industrial effluents (Santa Gertrudes, São Paulo, Brazil) using the diffusive gradient in thin films (DGT) technique.

Environmental impacts caused by mining activities (mainly tailings and effluents) are presenting serious challenges for humanity worldwide. In Brazil, clay extraction activities in the Ceramic District of Santa Gertrudes (CDSG) have led to the formation of abandoned drainage wells causing environmental and human health concerns. In the 90's, it was discovered that in one of the production areas, known as the region of the lakes of Santa Gertrudes, several ceramic industries had contaminated lakes created by abandoned clay pits with industrial effluents containing toxic metals. In the present study, analysis of total and dissolved concentrations of Al, Cd, Co, Cu, Mn, Ni, Pb and Zn in the waters of these lakes were combined with the diffusive gradients in thin films (DGT) technique to assess the lability and bioavailability of the target elements, representing one of the first studies to investigate the real environmental impact of contamination caused by ceramic production wastes to an aquatic system. Furthermore, based on the total concentrations and main physicochemical characteristics of each lake, a speciation analysis was performed using the MINTEQ software which data was compared with other surface water systems. The results indicated the presence of metals associated with ceramic residues in total, dissolved and labile fractions. It was verified that Zn, Ni and Cu were the only target metals found in labile form and according to speciation were present in the form of "free" ions, and thus may present risk in terms of bioavailability, although the majority of the total concentrations are within the limits established by the national environmental agency.

Appraisal on the role of passive sampling for more integrative frameworks on the environmental risk assessment of contaminants.

Over time multiple lines of research have been integrated as important components of evidence for assessing the ecological quality status of water bodies within the framework of Environmental Risk Assessment (ERA) approaches. One of the most used integrative approaches is the triad which combines, based on the weight-of-evidence, three lines of research, the chemical (to identify what is causing the effect), the ecological (to identify the effects at the ecosystem level) and the ecotoxicological (to ascertain the causes of ecological damage), with the agreement between the different lines of risk evidence increasing the confidence in the management decisions. Although the triad approach has proven greatly strategic in ERA processes, new assessment (and monitoring) integrative and effective tools are most welcome. In this regard, the present study is an appraisal on the boost that passive sampling, by allowing to increase information reliability, can give within each of the triad lines of evidence, for more integrative ERA frameworks. In parallel to this appraisal, examples of works that used passive samplers within the triad are presented providing support for the use of these devices in a complementary form to generate holistic information for ERA and ease the process of decision-making.

Unexpected reduction in ozone levels in a mid-size city during COVID-19 lockdown.

The current study evaluated ozone levels through passive samplers installed in 4 different points in a medium-sized city (Rio Grande, Brazil) with naturally low NO2 levels during a week of COVID-19 lockdown. Additionally, we evaluated the consequences of this response with regard to human health risk assessment and reduction of hospital admissions and ozone-related deaths. The reduction in ozone levels, one month after the implementation of containment measures, varied between 26 and 64% (average of 44%), in the different studied sites. The reduction of human mobility during the pandemic reduced the levels of ozone in Rio Grande city and consequently will bring benefits to health services in the municipality. This unexpected reduction in O3 levels must be related to the low 'natural' levels of NO2 in the city, which make the contribution of other precursors important for the fluctuation of O3 levels.

Atmospheric PAHs in rural, urban, industrial and beach locations in Buenos Aires Province, Argentina: sources and health risk assessment.

The first atmospheric PAHs levels and associated inhalation cancer risk were assessed over southwest Buenos Aires region by deploying PUF disk PAS samplers. Eight sampling location included coastal zones, touristic beaches, and rural inland areas were considered. PUF disks were fortified with surrogate standards and extracted by automated Soxhlet prior to GC-MS analysis. Σ16 PAHs ranged from 1.13 to 44.5 ng m-3 (10.3 ± 9.8), while urban locations showed up to 10 times higher PAH levels than rural or beach locations. Direct sources of PAHs, such as intensive vehicle traffic, heating, and general combustion activities, were identified. PAHs with four to six rings (46.62%) were predominantly Flt, Pyr, BbF, and BkF, and carcinogenic risk was expressed by BaP (0.10 ± 0.07 ng m-3) and BaPTEQs (0.26 ± 0.22 ng m-3). Inhalation ECR (2.23E-5, WHO) presented the lowest risk at beach locations. Molecular ratios and PCA showed a strong dominance in pyrolytic sources, such as biomass and coal combustion, with a particular signature in fires at inland locations. Overall, this study demonstrated that PUF disk passive air sampling provided a sound and simple approach for tracking air PAHs, their sources and public health risks, bringing a cost-effective tool for pollution control measures, even at small and remote towns. This is particularly relevant in extensive countries with medium or low income, such as Argentina.

Evaluation of Illicit Drug Consumption by Wastewater Analysis Using Polar Organic Chemical Integrative Sampler as a Monitoring Tool.

Illicit drug abuse is a worldwide social and health problem, and monitoring illicit drug use is of paramount importance in the context of public policies. It is already known that relevant epidemiologic information can be obtained from the analysis of urban residual waters. This approach, named wastewater-based epidemiology (WBE), is based on the measurement of specific markers, resulting from human biotransformation of the target drugs, as indicators of the consumption of the compounds by the population served by the wastewater treatment installation under investigation. Drug consumption estimation based on WBE requires sewage sampling strategies that express the concentrations along the whole time period of time. To this end, the most common approach is the use of automatic composite samplers. However, this active sampling procedure is costly, especially for long-term studies and in limited-resources settings. An alternative, cost-effective, sampling strategy is the use of passive samplers, like the polar organic chemical integrative sampler (POCIS). POCIS sampling has already been applied to the estimation of exposure to pharmaceuticals, pesticides, and some drugs of abuse, and some studies evaluated the comparative performances of POCIS and automatic composite samplers. In this context, this manuscript aims to review the most important biomarkers of drugs of abuse consumption in wastewater, the fundamentals of POCIS sampling in WBE, the previous application of POCIS for WBE of drugs of abuse, and to discuss the advantages and disadvantages of POCIS sampling, in comparison with other strategies used in WBE. POCIS sampling is an effective strategy to obtain a representative overview of biomarker concentrations in sewage over time, with a small number of analyzed samples, increased detection limits, with lower costs than active sampling. Just a few studies applied POCIS sampling for WBE of drugs of abuse, but the available data support the use of POCIS as a valuable tool for the long-term monitoring of the consumption of certain drugs within a defined population, particularly in limited-resources settings.

Dynamic passive sampling of hydrophobic organic compounds in surface seawater along the South Atlantic Ocean east-to-west transect and across the Black Sea.

Mapping of hydrophobic organic compounds (HOCs) in surface seawater on an east-to-west transect of the South Atlantic Ocean (SAO) and across the Black Sea (BS) in 2016 was performed by a dynamic passive sampling device containing silicone-based passive samplers. In SAO as well as in BS the measurements confirmed freely dissolved concentrations of polychlorinated biphenyls, DDT and its metabolites, chlorobenzenes, cyclodiene pesticides, and brominated flame retardants in the range of units to low hundreds of pg per litre. The findings indicate that the spatial distribution of HOCs and emerging pollutants in the SAO and the BS is influenced by riverine inputs, ocean currents and atmospheric deposition from continental plumes. Observed concentration gradients indicate that eastern SAO receives DDT from sources in South Africa, whereas the emissions of endosulfan originate in South America. Elevated HOC concentrations in the northwestern BS are related to their discharge by rivers from the European continent.

Assessment of pesticides in water using time-weighted average calibration of passive sampling device manufactured with carbon nanomaterial coating on stainless steel wire.

The continued contamination of water sources by pesticides is a problem that involves the life of aquatic organisms and human health, especially in countries whose economy is based on agriculture. The need to know the quality of drinking water under these circumstances is a priority for the public health of any community. Passive sampling methods allow the determination of long-term environmental pollutants through a single sample collection, reducing time and cost of analyses. One advantage of passive sampling is that it is possible to calculate a time-weighted average (TWA) concentration value or an equilibrium concentration value, depending on the type of device used and the exposure time. Passive sampling techniques using carbon nanomaterials (CNMs) have a high potential for pesticide sampling in aquatic systems. A device for passive sampling manufactured with CNMs in a microextraction system and recyclable materials was calibrated in laboratory exposure conditions over 15 days. The calibration results showed linear accumulation periods between 5 and 10 days. Sampling rates were between 0.014 and 0.146 mL day-1. The sampler was field-tested in the San Francisco river basin in the state of Minas Gerais in Brazil for 7 days. This research allowed for the detection and calculation of TWA concentrations for organochlorine pesticides such as α-HCH, 4,4-DDE, and 4,4-DD in water sources. The manufactured device demonstrated greater sensitivity than the grab sampling processes for the detection of pesticides. The performed passive sampling system using gas chromatography/mass spectrometry (GC/MS) technique allowed for the collection, detection, identification, and quantification of 26 pesticides.

Pharmaceutical compound removal efficiency by a small constructed wetland located in south Brazil.

The fate of pharmaceuticals during the treatment of effluents is of major concern since they are not completely degraded and because of their persistence and mobility in environment. Indeed, even at low concentrations, they represent a risk to aquatic life and human health. In this work, fourteen pharmaceuticals were monitored in a constructed wetland wastewater treatment plants (WWTP) assessed in both influent and effluent samples. The basic water quality parameters were evaluated, and the removal efficiency of pharmaceutical, potential for bioaccumulation, and the impact of WWTP were assessed using Polar Organic Chemical Integrative Sampler (POCIS) and biofilms. The pharmaceutical compounds were quantified by High Performance Liquid chromatography coupled to mass spectrometry. The sampling campaign was carried out during winter (July/2018) and summer (January/2019). The WWTP performed well regarding the removal of TSS, COD, and BOD5 and succeeded to eliminate a significant part of the organic and inorganic pollution present in domestic wastewater but has low efficiency regarding the removal of pharmaceutical compounds. Biofilms were shown to interact with pharmaceuticals and were reported to play a role in their capture from water. The antibiotics were reported to display a high risk for aquatic organisms.

The use of biomimetic tools for water quality monitoring: passive samplers versus sentinel organisms.

To evaluate the performance of artificial and biological integrative sampling strategies, dissolved concentrations of polychlorinated biphenyl (PCBs) and metals (Cu and Mn) were measured with passive sampler devices (PSD) enclosing hydrophobic and chelating phases, and Asiatic clams were transplanted to a polluted area in the Rio de la Plata. Water concentrations based on PSD were compared with spot water samples collected at 0, 15, 32, and 63 days of exposition. PCBs and metals displayed linear accumulation kinetics both in PSDs and bivalves, but with different slopes. PCBs slopes were 2-27 times higher in bivalves (0.3-7.9 vs. 0.1-2.6 ng g-1 d-1 in PSDs) reflecting active filtration and uptake from particles, colloids, and dissolved phase, whereas metal slopes were 2.5-11 times lower in bivalves (0.04-0.18 vs. 0.10-2.00 µg g-1 d-1 in PSDs) suggesting metal bioregulation. Truly dissolved PCB concentrations from PSD (4.0-6.9 ng.l-1) represented average 13±4 % of PCB concentrations from filtered spot water samples reflecting the operational discrimination of the PSD diffusion membrane on competing dissolved and colloidal organic phases. In contrast, PSD dissolved Cu concentrations (2.3-8.2 µg l-1) were equivalent to the spot water values (3.2-3.8 µg l-1) suggesting that Cu speciation was adequately integrated by passive sampling. On the other hand, PSD-dissolved Mn concentrations (49±38 µg l-1) were higher (p<0.05) than those from spot water samples (7±11µg l-1) possibly due to phase changes of Mn distribution related to variable redox conditions in the water. Results evidenced that the PSDs are efficient accumulators of metals and organic compounds from the truly dissolved fraction.

Passive sampling of toluene (and benzene) in indoor air using a semipermeable membrane device.

The distribution and concentration of organic compounds in the environment have attracted great interest mainly due to their capability of bioaccumulation, dispersion, and danger to living organisms. Factors such as urbanization, population growth, and the emergence of new technologies contribute to the increase in pollutant emissions, especially volatile organic compounds (VOCs), such as benzene, toluene, ethylbenzene, and xylenes (BTEX). These compounds are emitted by several sources, becoming more common in work environments, influencing indoor air quality (IAQ), which can cause health damage, in addition to increasing the likelihood of cancer development. In this context, we developed a semipermeable membrane device (SPMD), consisting of low density polyethylene membrane (8 cm long × 3 cm wide), filled with 3 mL of acetonitrile, for passive sampling of toluene (and benzene) in gas phase. With this configuration, the SPMD needed 24 h exposure to the indoor air in order to achieve equilibrium. The target compounds were quantified in the acceptor phase by HPLC-DAD. The optimized SPMD was tested for the collection of toluene and benzene in six chemistry laboratories at Fluminense Federal University and in five nail salons in the city of Niterói, in the state of Rio de Janeiro, Brazil. The developed sampling method was able to identify the analytes in the indoor air of the studied environments, and was easy to operate, with no need to clean up the extracts, allowing their direct injection into the chromatographic system.

Influence of some physicochemical parameters on the passive sampling of copper (II) from aqueous medium using a polymer inclusion membrane device.

Recently polymer inclusion membranes (PIMs) have been proposed as materials for passive sampling, nonetheless a theoretical base to describe the mass transfer process through those materials, under such conditions of monitoring, has not been elucidated. Under the assumption that: (i) the transport of the metal ion occurs at steady state conditions, (ii) the concentration gradients are linear, and (iii) the kinetics of the chemical reactions in the extraction process on the membrane are elemental; an equation for the passive sampling of copper (II) using a PIM system containing Kelex-100 as carrier is derived. The prediction capacity of this sampler under different conditions of temperature, metal concentration, flow velocity, ionic strength and pH is analyzed as well. Among the dependencies of the PIM on the physicochemical conditions, effects of concentration, temperature and flow velocity tend to increment copper (II) flux across the membrane, being the parameter temperature the one with the most pronounced effect at T ≥ 30 °C. Ionic strength had no great effect on passive sampler response, however the sampler is dependent on the acidity of the medium. The comparable metal ion concentrations estimated from the PIM sampler to those obtained by direct measurements of the sampling medium suggest that PIMs can be robust materials when used as passive sampler devices.

Passive Sampling of Persistent Organic Pollutants in Four Coastal Aquatic Systems of Puerto Rico: A Pilot Study.

Little is known about the presence and effects of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in Puerto Rico's waters. Four coastal aquatic systems were investigated using low-density polyethylene passive sampling for PCBs and OCPs in water and its overlying air. The highest total freely dissolved and gaseous concentrations of PCBs were found in Guánica Bay, with 4000 pg/L and 270 pg/m3, respectively. Five OCPs were detected, mainly in water, with greatest concentrations (pg/L) in Guánica Bay: α-HCH (7400), p,p'-DDE (390), aldrin (2000), dieldrin (420), and endrin (77). The compound α-HCH was also measured at elevated water concentrations in Condado Lagoon (5700 pg/L) and Laguna Grande (2900 pg/L). Jobos Bay did not show values of concern for these persistence organic pollutants. Levels of PCBs and OCPs in water, particularly in Guánica Bay, exceeded USEPA ambient water quality criteria values representing a human health risk regarding consumption of aquatic organisms.

Development of an analytical methodology for the determination of organochlorine pesticides by ethylene-vinyl acetate passive samplers in marine surface waters based on ultrasound-assisted solvent extraction followed with headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry.

A novel strategy for the analysis of 20 organochlorine pesticides (OCPs) monitoring in marine surface waters through ethylenevinyl acetate (EVA) passive samplers was developed and validated. The approach is based on the coupled of ultrasound-assisted solvent extraction (UASE) and headspace solid-phase microextraction (HS-SPME) as extraction method for OCPs from EVA samplers. The UASE-HS-SPME method was optimized with a 27-4 Plackett-Burman design, while the significant factors (salting out, temperature and extraction time) were optimized using a central composite design (CCD) combined with desirability function (DF). The OCPs detection was performed using multiple reaction monitoring (MRM) by gas chromatography-tandem mass spectrometry (GC-MS/MS). The optimum experimental conditions comprised: salting out: 23% wv-1 NaCl, temperature: 75°C and extraction time: 55 min. The optimized method was validated in terms of linearity (R2>0.9946), recovery (>61%) and inter-day and intra-day reproducibility (<19%) for 20 OCPs studied. The limits of detection (LODs) were ranging from 0.01 ng for α-hexachlorocyclohexane and 0.27 ng for endrin aldehyde. Finally, the methodology was tested in marine surface seawater of Southern Chile using EVA samplers, where twelve OCPs were detected at ultra-trace levels (ngL-1).

Occurrence of persistent organic pollutants in air at different sites in the province of Córdoba, Argentina.

The occurrence of persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of six sites with different emission sources in the province of Córdoba, Argentina, was analyzed. The sites included urban, industrial, agricultural, and mountain areas. Samples were collected using passive air samplers (PAS) consisting of polyurethane foam disks (PUF). Samples were analyzed for 12 PAHs, 31 polychlorinated biphenyls (PCBs), 12 organochlorine pesticides (OCPs), and 11 polybrominated diphenyl ethers (PBDEs). The concentrations of PAHs in the atmosphere were elevated at urban sites and were even higher at the industrial site. With respect to OCPs, it was observed that the concentrations of endosulfan were greater at the agricultural site (AGR) (416 ± 4 pg m-3). For hexachlorocyclohexanes (HCHs), only the alpha isomer was detected and there were minimal differences between the different sampling sites (5.9-13.3 pg m-3). In the case of dieldrin, the highest concentrations (33.6 pg m-3) were found at the mountain site, which may have been due to its use for insect control. Although heptachlor epoxide was not detected, the concentration of heptachlor was significantly higher at the agricultural and downtown sites (∼ 3.6 pg m-3). Regarding DDTs, the isomers p,p'-DDT and p,p'-DDE showed the highest concentrations at the mountain site (ΣDDT 120 ± 12 pg m-3) and downtown site (ΣDDT 157 ± 62 pg m-3). The relationship between the isomers suggested that at the downtown site, the contribution of this pesticide to the environment was recent, probably for the control of diseases vectors. The congener pattern of PBDEs was dominated by BDE-47, and BDE-99 at all sites, with the downtown site having the highest concentrations of compound esters (ΣPBDEs 118 ± 38 pg m-3). Finally, high concentrations of PCBs were found at the industrial site (ΣPCBs 1677 ± 134 pg m-3), and the predominating homologs were 5-Cl and 6-Cl, in contrast to the other sites where PCBs were dominated by 3-Cl and 4-Cl. This is the first study of POPs carried out in the province of Córdoba.

Evaluation of a semi-permeable membrane device (SPMD) for passive sampling of solar filters from swimming pool waters and determination by HPLC-DAD.

Sunscreens are used to protect skin against ultraviolet radiation, avoiding the damages that can be caused by it. However, in vitro and in vivo studies report that some organic substances employed as sunscreens can alter the biological effects of several hormones. Therefore, a methodology for passive sampling using a semipermeable membrane device (SPMD) was developed for the extraction and preconcentration of some organic compounds employed in sunscreen formulations, such as benzophenone (BZP), 2-hydroxy-4-methoxybenzophenone (BZP-3), 3-(4-methylbenzylidene)-camphor (4-MBC), 2-ethylhexyl-4-methoxycinnamate (4-MCN), 2-ethylhexyl salicylate (EHS), and homomethyl salicylate (HMS), from swimming pool waters where exposure to these substances is unintended. The determination of these analytes in the acceptor phase was performed using high performance liquid chromatography with diode array detection (HPLC-DAD). The optimization of the methodology included the evaluation of several variables, such as type and volume of acceptor phase, dimensions and time of exposure of the SPMD, sample pH, and volume. The optimum conditions for the collection of the solar filters were achieved with an 8-cm device filled with 3.0 mL of acetonitrile and without adjustment of the sample pH, which was approximately 5.8. The collection time was 24 h. Afterwards, some parameters of merit of the developed method were determined. The working range for BZP, BZP-3, 4-MBC, 4-MCN, EHS, and HMS was established as 25-500 µg L-1. The methodological limits of detection and quantification for these analytes were 0.2-1.0 µg L-1 and 0.7-3.1 µg L-1, respectively. Quantification of the analytes was performed on four samples collected from different swimming pools. Recovery tests were performed with the samples spiked with 100 µg L-1 of each substance, and recovery percentages in the range of 75-116% were obtained. The performance of the SPMD was also verified through the determination of BZP-3, EHS, and HMS in a swimming pool water sample intentionally contaminated with a commercial sunscreen.

New passive sampling device for effective monitoring of pesticides in water.

The extensive use of pesticides promotes environmental contamination, mainly in surface and ground waters. However, they remain at very low concentration and present wide degradation level requiring the use of efficient devices for pesticides passive sampling. In this study, a new in situ passive sampling device was developed for monitoring and estimating time-weighted average (TWA) of pesticides in waters. The device was made with simple, recyclable and cheap materials. The sampling system involves the liquid phase microextraction technique with hollow fiber in two-phases mode. Pesticides determination was done by gas chromatography coupled to mass spectrometry. The method was optimized and validated for the determination of 29 pesticides in water, showing good linearity in the range between 0.012 and 40.00 µg L-1 with determination coefficients of R2 > 0,9649. Limit of detection (LOD) ranged from 0.009 to 0.557 µg L-1 and limit of quantification (LOQ) from 0.012 to 0.802 µg L-1. The recoveries of spiked pesticides in water samples were in the range from 96 to 130%. The method was applied to forty environmental water samples collected at São Francisco river basin, Brazil. The highest detection frequency was found for the pesticides 4,4-DDE, 4,4-DDD and propazine. They were detected in more than 20 percent of the samples.

Quantificação de benzeno, tolueno, etilbenzeno e xilenos no ar de ambientes internos / Quantification of benzene, toluene, ethylbenzene and xylenes in the air of indoor environments

RESUMO A poluição do ar não está restrita a ambientes abertos, podendo existir elevadas concentrações de poluentes do ar derivados do petróleo, como o benzeno, tolueno, etilbenzeno e xilenos (BTEX), em ambientes internos. Os BTEX, mesmo quando presentes em baixas concentrações, na ordem de parte por bilhão (ppb), causam problemas à saúde humana. O objetivo deste trabalho foi aplicar uma técnica de quantificação dos BTEX, no nível de ppb, em apenas oito horas de amostragem em um ambiente interno. Para tal fim, foram usados tubos amostradores passivos associados a análise por dessorção térmica, cromatografia gasosa e espectrometria de massas. O método de calibração desse sistema analítico também foi apresentado. O uso dessa metodologia permitiu quantificar os BTEX em um laboratório de pesquisa de motores de combustão, em concentrações de 4,64, 7,87, 10,47 e 21,36 ppb respectivamente. Esses resultados estão próximos da faixa encontrada em ambientes internos por outros estudos no Brasil. A avaliação dos BTEX no laboratório de combustão, além de levar apenas 16 horas, somando a amostragem e análise das amostras, confirmou a sensibilidade da metodologia usada.

ABSTRACT Air pollution is not restricted to open air areas. High concentrations of petroleum-based air pollutants may occur, such as benzene, toluene, ethylbenzene and xylenes (BTEX), in indoor environments. The BTEX, even in low concentrations, of the order of parts per billion (ppb), cause human health problems. The objective of this work was to apply a technique of measurement of BTEX, at ppb level, using only eight hours of sampling in an indoor environment. To this end, passive tube samplers were used associated with analysis by thermal desorption, gas chromatography and mass spectrometry. The calibration method applied to this analytical system was also presented. The use of this method allowed the quantification of BTEX in a combustion engines research laboratory, at concentrations of 4.64, 7.87, 10.47 and 21.36 ppb, respectively. These results are close to the range found by other indoor studies in Brazil. The evaluation of BTEX in the combustion laboratory, besides it only takes 16 hours, considering the sampling and the analysis procedures, confirmed the sensitivity of the methodology used.

Applying no-depletion equilibrium sampling and full-depletion bioaccessibility extraction to 35 historically polycyclic aromatic hydrocarbon contaminated soils.

Assessing the bioaccessibility of organic pollutants in contaminated soils is considered a complement to measurements of total concentrations in risk assessment and legislation. Consequently, methods for its quantification require validation with historically contaminated soils. In this study, 35 such soils were obtained from various locations in Switzerland and Cuba. They were exposed to different pollution sources (e.g., pyrogenic and petrogenic) at various distance (i.e., urban to rural) and were subject to different land use (e.g., urban gardening and forest). Passive equilibrium sampling with polyoxymethylene was used to determine freely dissolved concentrations (Cfree) of polycyclic aromatic hydrocarbons (PAHs), while sorptive bioaccessibility extraction (SBE) with silicone rods was used to determine the bioaccessible PAH concentrations (Cbioacc) of these soils. The organic carbon partition coefficients of the soils were highest for skeet soils, followed by traffic, urban garden and rural soils. Lowest values were obtained from soil exposed to petrogenic sources. Applicability of SBE to quantify Cbioacc was restricted by silicone rod sorption capacity, as expressed quantitatively by the Sorption Capacity Ratio (SCR); particularly for soils with very high KD. The source of contamination determined bioaccessible fractions (fbioacc). The smallest fbioacc were obtained with skeet soils (15%), followed by the pyrogenically influenced soils, rural soils, and finally, the petrogenically contaminated soil (71%). In conclusion, we present the potential and limitations of the SBE method to quantify bioaccessibility in real soils. These results can be used for additional development of this and similar bioaccessibility methods to guarantee sufficient sorption capacity to obtain reliable results.