Behavior of titanium dioxide nanoparticles in Lemna minor growth test conditions.

Titanium dioxide nanoparticles (TiO(2) NPs) have raised concern of environmental risks due to their widespread applications, but little is known about the potential toxicity of TiO(2) NPs to aquatic plants. The aim of this work was to study the effects of TiO(2) NPs on Lemna minor and to study the behavior of TiO(2) NPs under modified ISO 20079 test conditions. TiO(2) NPs had a tendency to aggregate in ISO (Steinberg) growth medium, but modification of the standard growth medium enabled the exposure of L. minor to TiO(2) NPs. By dilution of the growth medium (1:10), and exposure under semi-static conditions with medium renewal every second or third day, the size of TiO(2) particles remained rather stable throughout the test period. TiO(2) NPs showed no adverse effect on the growth rate or chlorophyll a content of L. minor, even at a high exposure concentration of 5 mg L(-1) and extended exposure time of 14 days. TiO(2) NPs attached onto L. minor cell walls, but no cellular uptake was observed. Although TiO(2) NPs were not toxic to L. minor, the potential transfer of TiO(2) NPs in aquatic food chains, e.g. attached to the plant leaves and other biological surfaces may be of importance, causing exposure of other organisms and contributing to the environmental fate of nanoparticles.

Liquid chromatography-mass spectrometry for C60 fullerene analysis: optimisation and comparison of three ionisation techniques.

The increasing use and production of nanomaterials have led to growing concern over the release of new pollutants to the environment. Fullerenes have been a subject of intense research, both because of their unique chemistry and because of technological applications. The development of analytical methods to quantify the fullerenes in complex sample matrices is a crucial step in the study of their occurrence and exposure, and thus in risk assessment. This paper reports the development and optimisation of a method combining liquid chromatography with ion-trap mass spectrometry (LC-ITMS) for analysis of the fullerene C(60). Under the optimised chromatogram conditions, a C(18) analytical column had good selectivity for fullerenes C(60) and C(70), with retention times of 3.0 and 4.1 min, respectively. Mass spectrometric detection was tested and optimised using three common ionisation techniques-atmospheric-pressure chemical ionisation (APCI), atmospheric-pressure photoionisation (APPI), and electrospray ionisation (ESI). The molecular ion was most abundant for C (60) (-) (m/z=720) in APCI and APPI, whereas adduct ions were formed with the molecular ion in ESI. Finally, the performance of the three ionisation techniques examined was compared by use of five validation criteria. The instrument detection limit (8 ng mL(-1)), quantification limit (27 ng mL(-1)), detection sensitivity (90.2 ng mL(-1)), linear range (8-1,000 ng mL(-1)), and repeatability (15 %) of APPI make it the most promising ionisation technique for fullerene C(60) analysis.

Historical and current occurrence of microplastics in water and sediment of a Finnish lake affected by WWTP effluents.

Only scarce information is available about the abundance of microplastics (MPs) in Nordic lakes. In this study, the occurrence, types, and distribution of MPs were assessed based on the lake water and sediment samples collected from a sub-basin of Lake Saimaa, Finland. The main goal was to estimate the possible effect of the local wastewater treatment plant (WWTP) on the abundance of MPs in different compartments of the recipient lake area. Collected bottom sediment samples were Cs-137 dated and the chronological structure was utilized to relate the concentrations of MPs to their sedimentation years. Raman microspectroscopy was used for the MPs' identification from both sample matrices. In addition, MPs consisting of polyethylene (PE), polypropylene (PP) and polystyrene (PS) were quantified from lake water samples by pyrolysis-gas chromatography-mass spectrometry to provide a complementary assessment of MPs based on two different analysis methods, which provide different metrics of the abundance of microplastics. MPs concentrations were highest in sediment samples closest to the discharge site of WWTP effluents (4400 ± 620 n/kg dw) compared to other sites. However, such a trend was not found in lake water samples (0.7 ± 0.1 n/L). Overall, microplastic fibers were relatively more abundant in sediment (70%) than in water (40%), and the majority of detected microplastic fibers were identified as polyester. This indicates that a part of textile fibers passing the WWTP processes accumulate in the sediment close to the discharge site. In addition, the abundance of MPs was revealed to have increased slightly during the last 30 years.

Quantification of different microplastic fibres discharged from textiles in machine wash and tumble drying.

Microplastic fibres released in synthetic cloth washing have been shown to be a source of microplastics into the environment. The annual emission of polyester fibres from household washing machines has earlier been estimated to be 150,000 kg in a country with a population of 5.5 × 106 (Finland). The objectives of this study were (1) to quantify the emissions of synthetic textile fibres discharged from five sequential machine washes (fibre number and length) and tumble dryings (fibre mass) and (2) to determine the collection efficiency of two commercial fibre traps. The synthetic fabrics were five types of polyester textiles, one polyamide and one polyacryl. The number of fibres released from the test fabrics in the first wash varied in the range from 1.0 × 105 to 6.3 × 106 kg-1. The fibre lengths showed that the fleece fabrics released, on average, longer fibres than the technical sports t-shirts. The mass of fibres ranged from 10 to 1700 mg/kg w/w in the first drying. Fibre emissions showed a decreasing trend both in sequential washes and dryings. The ratio of the fibre emissions in machine wash to tumble drying varied between the fabrics: the ratio was larger than one to polyester and polyamide technical t-shirts whereas it was much lower to the other tested textiles. GuppyFriend washing bag and Cora Ball trapped 39% and 10% of the polyester fibres discharged in washings, respectively.

Microplastics pollution in the Brahmaputra River and the Indus River of the Indian Himalaya.

Rivers act as temporary sinks of microplastics and a key medium allowing microplastics to enter the ocean. In this study, microplastics pollution in river shore sediment of the Indian Himalaya, including the Brahmaputra River and the Indus River was discussed. Sampling campaigns were performed in years 2018 and 2019. Sample pretreatment was performed using Na2WO4·2H2O for density separation and H2O2 for oxidation of organic material. Microplastics analysis was performed by using FTIR microscope. The smaller size of microplastics 20-150 µm were more abundant (531-3485 MP/kg in the Brahmaputra River and 525-1752 MP/kg in the Indus River) than microplastics in size range between 150 µm and 5 mm (20-240 MP/kg in the Brahmaputra River and 60-340 MP/kg in the Indus River). Microplastics were found in sediments of all sampling sites. Fragmented, secondary microplastics were dominant in the river shore sediment of the Indian Himalaya. This study contributes towards filling research gap of microplastics in India's freshwater source and highlights the importance of in-depth complete studies of microplastics in the rivers that act as pathways and sinks for microplastics.

Associations of urban air particulate composition with inflammatory and cytotoxic responses in RAW 246.7 cell line.

Epidemiological studies show heterogeneities in the particulate pollution-related exposure-effect relationships among cardiorespiratory patients, but the connection to chemical composition and toxic properties of the inhaled particles is largely unknown. To identify the chemical constituents and sources responsible for the diverse inflammatory and cytotoxic effects of urban air, fine (PM(2.5-0.2)) and coarse (PM(10-2.5)) particulate samples were collected during contrasting air pollution situations. We exposed mouse RAW 246.7 macrophages for 24 hrs to PM(2.5-0.2) and PM(10-2.5) samples from six European cities. The concentrations of proinflammatory cytokines (IL-6, TNFalpha), chemokine (MIP-2), and nitric oxide were measured from the cell culture medium, and the cytotoxicity was assayed. Spearman's correlations between the chemical constituents and cellular responses were analyzed. In the PM(2.5-0.2) size range, the tracers of photo-oxidation of organics in the atmosphere (oxalate, succinate, malonate), some transition metals (Ni, V, Fe, Cu, Cr), and insoluble soil constituents (Ca, Al, Fe, Si) correlated positively with the response parameters. In contrast, the tracers of incomplete biomass (monosaccharide anhydrides) and coal (As) combustion, and polycyclic aromatic hydrocarbons (PAHs), had negative correlations with the inflammatory activity. The compositions of PM(10-2.5) samples were more uniform and there were only occasional high correlations between the chemical constituents, endotoxin, and the response parameters. The present results suggest that the local sources of incomplete combustion and resuspended road dust are important producers of harmful fine particulate constituents that may, however, operate via diverse toxicity mechanisms. The results agree well with our recent findings in the mouse lung.

Intercomparison study on commonly used methods to determine microplastics in wastewater and sludge samples.

The harmonized procedures in terms of the sampling, sample treatment and identification of microplastics in different environmental samples are missing, which poses challenges to researchers to compare the results or to adopt 'the most effective' monitoring approach. Furthermore, in the related literature, the used procedures are rarely tested with spiked microplastics to predetermine their recovery rates. Without this knowledge, results should only be discussed as rough estimations of the real environmental concentrations of microplastics. In this study, six different methods previously used in microplastic studies of different media were tested with municipal wastewater and digested sludge samples, spiked with seven different types of plastic particles and fibres. Recovery rates, time consumption, advantages and disadvantages were assessed and most suitable treatment procedures (i.e. high recovery rates in short amount of time) were chosen for both wastewater and sludge. Suitability of staining with Rose Bengal was examined together with most efficient methods, but it did not improve the recovery of microplastics. In addition, the possible impacts of the treatments for identification with micro-Raman and FTIR microscope were assessed. Filtration with size fractioning was found to be the best method for both wastewater and sludge samples, with recovery rates of spiked microplastics around 91.4% and 92.9%, respectively.

Field evaluation of a new particle concentrator- electrostatic precipitator system for measuring chemical and toxicological properties of particulate matter.

BACKGROUND: A newly designed electrostatic precipitator (ESP) in tandem with Versatile Aerosol Concentration Enrichment System (VACES) was developed by the University of Southern California to collect ambient aerosols on substrates appropriate for chemical and toxicological analysis. The laboratory evaluation of this sampler is described in a previous paper. The main objective of this study was to evaluate the performance of the new VACES-ESP system in the field by comparing the chemical characteristics of the PM collected in the ESP to those of reference samplers operating in parallel. RESULTS: The field campaign was carried out in the period from August, 2007 to March, 2008 in a typical urban environment near downtown Los Angeles. Each sampling set was restricted to 2-3 hours to minimize possible sampling artifacts in the ESP. The results showed that particle penetration increases and ozone concentration decreases with increasing sampling flow rate, with highest particle penetration observed between 100 nm and 300 nm. A reference filter sampler was deployed in parallel to the ESP to collect concentration-enriched aerosols, and a MOUDI sampler was used to collect ambient aerosols. Chemical analysis results showed very good agreement between the ESP and MOUDI samplers in the concentrations of trace elements and inorganic ions. The overall organic compound content of PM collected by the ESP, including polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, and alkanes, was in good agreement with that of the reference sampler, with an average ESP -to -reference concentration ratio of 1.07 (+/- 0.38). While majority of organic compound ratios were close to 1, some of the semi-volatile organic species had slightly deviated ratios from 1, indicating the possibility of some sampling artifacts in the ESP due to reactions of PM with ozone and radicals generated from corona discharge, although positive and negative sampling artifacts in the reference filter sampler cannot be ruled out. CONCLUSION: The very good overall agreement between ESP and reference samplers makes it an attractive alternative to filters and biosamplers for chemical and toxicological evaluation of PM properties, including the possibility of conducting direct in vitro cell exposures. Moreover, the concentration enrichment of ambient aerosols by the VACES allows for short-term exposure studies, which preserve cell viability and enable studies to PM generated from specific sources and-or formation mechanisms in the atmosphere.

Chemical compositions responsible for inflammation and tissue damage in the mouse lung by coarse and fine particulate samples from contrasting air pollution in Europe.

Inflammation is regarded as an important mechanism in mortality and morbidity associated with exposures of cardiorespiratory patients to urban air particulate matter. We investigated the association of the chemical composition and sources of urban air fine (PM(2.5-0.2)) and coarse (PM(10-2.5)) particulate samples with the inflammatory activity in the mouse lung. The particulate samples were collected during selected seasons in six European cities using a high-volume cascade impactor. Healthy C57BL/6J mice were intratracheally instilled with a single dose (10 mg/kg) of the particulate samples. At 4, 12, and 24 h after the exposure, the lungs were lavaged and the bronchoalveolar lavage fluid (BALF) was assayed for indicators of inflammation and tissue damage: cell number, total protein, and cytokines (tumor necrosis factor [TNF]-alpha, interleukin [IL]-6, and KC). Dicarboxylic acids and transition metals, especially Ni and V, in PM(2.5-0.2) correlated positively and some secondary inorganic ions (NO3(-), NH4(+)) negatively with the inflammatory activity. Total organic matter and SO4(2-) had no consistent correlations. In addition, the soil-derived constituents (Ca2+, Al, Fe, Si) showed positive correlations with the PM(2.5-0.2)-induced inflammatory activity, but their role in PM(10-2.5) remained obscure, possibly due to largely undefined biogenic material. Markers of poor biomass and coal combustion, i.e., monosaccharide anhydrides and As, were associated with elevated PAH contents in PM(2.5-0.2) and a consistent immunosuppressive effect. Overall, our results support epidemiological findings that the local sources of incomplete combustion and resuspended road dust are important in urban air particulate pollution-related health effects.

Occurrence, identification and removal of microplastic particles and fibers in conventional activated sludge process and advanced MBR technology.

Wastewater treatment plants (WWTPs) are acting as routes of microplastics (MPs) to the environment, hence the urgent need to examine MPs in wastewaters and different types of sludge through sampling campaigns covering extended periods of time. In this study, the efficiency of a municipal WWTP to remove MPs from wastewater was studied by collecting wastewater and sludge samples once in every two weeks during a 3-month sampling campaign. The WWTP was operated based on the conventional activated sludge (CAS) process and a pilot-scale membrane bioreactor (MBR). The microplastic particles and fibers from both water and sludge samples were identified by using an optical microscope, Fourier Transform Infrared (FTIR) microscope and Raman microscope. Overall, the retention capacity of microplastics in the studied WWTP was found to be 98.3%. Most of the MP fraction was removed before the activated sludge process. The efficiency of an advanced membrane bioreactor (MBR) technology was also examined. The main related finding is that MBR permeate contained 0.4 MP/L in comparison with the final effluent of the CAS process (1.0 MP/L). According to this study, both microplastic fibers and particles are discharged from the WWTP to the aquatic environment.

Heterogeneities in inflammatory and cytotoxic responses of RAW 264.7 macrophage cell line to urban air coarse, fine, and ultrafine particles from six European sampling campaigns.

We investigated the cytotoxic and inflammatory activities of size-segregated particulate samples (particulate matter, PM) from contrasting air pollution situations in Europe. Coarse (PM10-2.5), fine (PM2.5-0.2), and ultrafine (PM0.2) particulate samples were collected with a modified Harvard high-volume cascade impactor (HVCI). Mouse RAW 264.7 macrophages were exposed to the samples for 24 h. Selected inflammatory mediators, nitric oxide (NO) and cytokines (tumor necrosis factor alpha [TNFalpha], interleukin 6 [IL-6], macrophage inflammatory protein-2 [MIP-2]), were measured together with cytotoxicity (MTT test), and analysis of apoptosis and cell cycle (propidium iodide staining). The PM10-2.5 samples had a much higher inflammatory activity than the PM2.5-0.2 and PM0.2 samples, but the PM2.5-0.2 samples showed the largest differences in inflammatory activity, and the PM0.2 samples in cytotoxicity, between the sampling campaigns. The PM2.5-0.2 samples from traffic environments in springtime Barcelona and summertime Athens had the highest inflammatory activities, which may be related to the high photochemical activity in the atmosphere during the sampling campaigns. The PM0.2 sample from wintertime Prague with proven impacts from local coal and biomass combustion had very high cytotoxic and apoptotic activities and caused a distinct cell cycle arrest. Thus, particulate size, sources, and atmospheric transformation processes affect the toxicity profile of urban air particulate matter. These factors may explain some of the heterogeneity observed in particulate exposure-response relationships of human health effects in epidemiological studies.

Release of polyester and cotton fibers from textiles in machine washings.

Microplastics are widely spread in the environment, which along with still increasing production have aroused concern of their impacts on environmental health. The objective of this study is to quantify the number and mass of two most common textile fibers discharged from sequential machine washings to sewers. The number and mass of microfibers released from polyester and cotton textiles in the first wash varied in the range 2.1 × 105 to 1.3 × 107 and 0.12 to 0.33% w/w, respectively. Amounts of released microfibers showed a decreasing trend in sequential washes. The annual emission of polyester and cotton microfibers from household washing machines was estimated to be 154,000 (1.0 × 1014) and 411,000 kg (4.9 × 1014) in Finland (population 5.5 × 106). Due to the high emission values and sorption capacities, the polyester and cotton microfibers may play an important role in the transport and fate of chemical pollutants in the aquatic environment.

Effect-based assessment of toxicity removal during wastewater treatment.

Wastewaters contain complex mixtures of chemicals, which can cause adverse toxic effects in the receiving environment. In the present study, the toxicity removal during wastewater treatment at seven municipal wastewater treatment plants (WWTPs) was investigated using an effect-based approach. A battery of eight bioassays was applied comprising of cytotoxicity, genotoxicity, endocrine disruption and fish embryo toxicity assays. Human cell-based CALUX assays, transgenic larval models and the fish embryo toxicity test were particularly sensitive to WWTP effluents. The results indicate that most effects were significantly reduced or completely removed during wastewater treatment (76-100%), while embryo toxicity, estrogenic activity and thyroid disruption were still detectable in the effluents suggesting that some harmful substances remain after treatment. The responsiveness of the bioassays was compared and the human cell-based CALUX assays showed highest responsiveness in the samples. Additionally, the fish embryo toxicity test and the transgenic larval models for endocrine disrupting effects showed high responsiveness at low sample concentrations in nearly all of the effluent samples. The results showed a similar effect pattern among all WWTPs investigated, indicating that the wastewater composition could be rather similar at different locations. There were no considerable differences in the toxicity removal efficiencies of the treatment plants and no correlation was observed with WWTP characteristics, such as process configuration or sludge age. This study demonstrated that a biotest battery comprising of multiple endpoints can serve as a powerful tool when assessing water quality or water treatment efficiency in a holistic manner. Rather than analyzing the concentrations of a few selected chemicals, bioassays can be used to complement traditional methods of monitoring in the future by assessing sum-parameter based effects, such as mixture effects, and tackling chemicals that are present at concentrations below chemical analytical detection limits.

Influences of water properties on the aggregation and deposition of engineered titanium dioxide nanoparticles in natural waters.

With the increasing usage of titanium dioxide nanoparticles (NPs), their release into the environment makes it important to understand their transport, fate and behaviour in natural waters. In this study, aggregation and deposition of TiO2 NPs were studied during a 3-h period by using a dynamic light scattering instrument and a UV-vis spectrophotometer, respectively. TiO2 NPs were spiked in 34 lake and 5 brackish water samples at an initial concentration of 10 mg L-1. Depending on the physicochemical properties of the natural waters, TiO2 NPs exhibited different colloidal stability. In brackish waters with high salinity, TiO2 NPs were prone to aggregate and settled rapidly. Whereas under conditions of humic and humus-poor lake waters, TiO2 NPs were suspended in water column for a longer time without remarkable change in particle size and concentration. Deposition likely occurred in nutrient-rich lakes which had high amount of nitrogen and phosphorus accompanied by high values of conductivity, alkalinity, pH and turbidity. Linear regression analysis revealed the statistically significant relationships (p ≤ 0.008) between the TiO2 NPs stability and these water properties. Our study makes a better understanding of the water properties that control the aggregation and deposition of TiO2 NPs in complex natural waters.

Estrogenic activity in Finnish municipal wastewater effluents.

Effluents from wastewater treatment plants (WWTPs) are a major source of estrogenic compounds to the aquatic environment. In the present work, estrogenic activities of effluents from eight municipal WWTPs in Finland were studied. The main objectives of the study were to quantify the concentrations of selected estrogenic compounds, to evaluate their contribution to estrogenic potency and to test the feasibility of the commercial bioassays for wastewater analysis. The effluent samples were analyzed by two in vitro tests, i.e. ERα-CALUX(®) and ELISA-E2, and by liquid chromatography mass spectrometry for six estrogenic compounds: estrone (E1), 17ß-estradiol (E2), estriol (E3), 17α-ethinylestradiol (EE2), 17α-estradiol and bisphenol A (BPA). Estrogenic effects were found in all of the effluent samples with both of the bioassays. The concentrations measured with ELISA-E2 (8.6-61.6 ng/L) were clearly higher but exhibited a similar pattern than those with chemical analysis (E2

Chemical composition, mass size distribution and source analysis of long-range transported wildfire smokes in Helsinki.

Special episodes of long-range transported particulate (PM) air pollution were investigated in a one-month field campaign at an urban background site in Helsinki, Finland. A total of nine size-segregated PM samplings of 3- or 4-day duration were made between August 23 and September 23, 2002. During this warm and unusually dry period there were two (labelled P2 and P5) sampling periods when the PM2.5 mass concentration increased remarkably. According to the hourly-measured PM data and backward air mass trajectories, P2 (Aug 23-26) represented a single, 64-h episode of long-range transported aerosol, whereas P5 (Sept 5-9) was a mixture of two 16- and 14-h episodes and usual seasonal air quality. The large chemical data set, based on analyses made by ion chromatography, inductively coupled plasma mass spectrometry, X-ray fluorescence analysis and smoke stain reflectometry, demonstrated that the PM2.5 mass concentrations of biomass signatures (i.e. levoglucosan, oxalate and potassium) and of some other compounds associated with biomass combustion (succinate and malonate) increased remarkably in P2. Crustal elements (Fe, Al, Ca and Si) and unidentified matter, presumably consisting to a large extent of organic material, were also increased in P2. The PM2.5 composition in P5 was different from that in P2, as the inorganic secondary aerosols (NO3-, SO4(2-), NH4+) and many metals reached their highest concentration in this period. The water-soluble fraction of potassium, lead and manganese increased in both P2 and P5. Mass size distributions (0.035-10 microm) showed that a large accumulation mode mainly caused the episodically increased PM2.5 concentrations. An interesting observation was that the episodes had no obvious impact on the Aitken mode. Finally, the strongly increased concentrations of biomass signatures in accumulation mode proved that the episode in P2 was due to long-range transported biomass combustion aerosol.

Chemical and microbial components of urban air PM cause seasonal variation of toxicological activity.

The chemical and microbial composition of urban air particulate matter (PM) displays seasonal variation that may affect its harmfulness on human health. We studied the in vitro inflammatory and cellular metabolic activity/cytotoxicity of urban air particulate samples collected in four size-ranges (PM10-2.5, PM2.5-1, PM1-0.2, PM0.2) during four seasons in relatively clean urban environment in Helsinki, Finland. The composition of the same samples were analyzed, including ions, elements, PAH compounds and endotoxins. In addition, microbial contribution on the detected responses was studied by inhibiting the endotoxin-induced responses with Polymyxin B both in the PM samples and by two different bacterial strains representing Gram-positive and -negative bacteria. Macrophage cell line (RAW 264.7) was exposed to the size segregated particulate samples as well as to microbe samples for 24h and markers of inflammation and cytotoxicity were analyzed. The toxicological responses were dependent on the dose as well as size range of the particles, PM10-2.5 being the most potent and smaller size ranges having significantly smaller responses. Samples collected during spring and autumn had in most cases the highest inflammatory activity. Soil components and other non-exhaust particulate emissions from road traffic correlated with inflammatory responses in coarse particles. Instead, PAH-compounds and K(+) had negative associations with the particle-induced inflammatory responses in fine particles, suggesting the role of incomplete biomass combustion. Endotoxin content was the highest in PM10-2.5 samples and correspondingly, the largest decrease in the responses by Polymyxin B was seen with the very same samples. We found also that inhibitory effect of Polymyxin B was not completely specific for Gram-negative bacteria. Thus, in addition to endotoxin, also other microbial components may have a significant effect on the toxicological responses by ambient particulate matter.

Chemical and in vitro toxicologic characterization of wintertime and springtime urban-air particles with an aerodynamic diameter below 10 microm in Helsinki.

OBJECTIVES: The chemical composition and toxicity of wintertime urban-air particulate matter with an aerodynamic diameter of <10 microm (PM10), derived mostly from long-range transport and local combustion sources, were compared with those of springtime PM10 derived mostly from the resuspension of road dust. METHODS: Water-soluble ions and elements and polycyclic aromatic hydrocarbons (PAH) were analyzed from seasonally pooled PM10 samples collected at a busy traffic site in Helsinki in 1999. These PM10 samples were also tested for cytotoxicity [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide test] and the production of proinflammatory cytokines [tumor necrosis factor alpha (TNF-alpha) and interleukin 6 (IL-6)] and nitric oxide (NO) in the mouse macrophage cell line RAW 264.7. Their oxidative capacity and the associated DNA (deoxyribonucleic acid) damage were investigated by electron paramagnetic resonance and the formation of 8-hydroxy-2'-deoxyguanosine (8-OH-DG) in isolated calf thymus DNA, respectively. RESULTS: The late wintertime and springtime PM10 had similar compositions of water-soluble ions and elements, but the winter PM10 had a higher content of PAH. The spring PM10 was a much more potent inducer of TNF-alpha and IL-6 production than the winter PM10 was, but there were no consistent differences in cytotoxic potency. In contrast, the winter PM10 was a significantly more potent inducer of NO production and 8-OH-DG formation. The large cytokine responses to the spring PM10 were caused by its insoluble fraction and largely inhibited by the endotoxin antagonist polymyxin B. The transition metal chelator deferoxamine did not modify the proinflammatory or cytotoxic responses to the PM10 samples. CONCLUSIONS: The toxicity profile of urban-air PM10 changed with season in a subarctic climate. Particulate-bound endotoxin from soil gram-negative bacteria is suggested as a highly proinflammatory constituent of springtime resuspended road dust.

Particle induced toxicity in relation to transition metal and polycyclic aromatic hydrocarbon contents.

Exposure to ambient particulate matter (PM) is statistically significantly associated with morbidity and mortality. The objectives of this study were (a) to investigate in vivo pulmonary and systemic cytotoxicity and inflammatory activity in compromised animals exposed to PM and (b) to investigate the relationships of the outcomes to the chemical compositions of particular polycyclic aromatic hydrocarbons (PAH) and transition metals in the PM. The PM samples were collected in European cities representing contrasting situations. Exposure of spontaneously hypertensive rats (7 mg of PM/kg) resulted in pulmonary inflammation, cellular toxicity and the induction of blood fibrinogen. Coarse PM generally caused stronger effects per mg than fine particles. Positive correlations between lactate dehydrogenase, proteins, and some inflammation parameters and the particle metal and PAH content were found. PM rich in PAH also led to increased blood fibrinogen. Removal of particles but not the organics (i.e., PAH) of a sample led to reduced inflammation in the lungs. The present study highlights the importance of metals as well as PM-bound PAH in particle biological outcomes. It supports the hypothesis that, on an equal mass basis, particle health effects differ due to differences in compositions and size.

Effects of solubility of urban air fine and coarse particles on cytotoxic and inflammatory responses in RAW 264.7 macrophage cell line.

We investigated the inflammatory and cytotoxic activities of the water-soluble and -insoluble as well as organic-solvent-soluble and -insoluble fractions of urban air fine (PM(2.5-0.2)) and coarse (PM(10-2.5)) particulate samples. The samples were collected with a high volume cascade impactor (HVCI) in 7-week sampling campaigns of selected seasons in six European cities. Mouse macrophage cells (RAW 264.7) were exposed to the samples for 24 h. The production of nitric oxide (NO) and proinflammatory cytokines (TNFalpha, IL-6), and cytotoxicity (MTT-test, apoptosis, cell cycle) were measured. The inflammatory and cytotoxic responses in both size ranges were mostly associated with the insoluble particulate fractions. However, both the water- and organic-solvent-soluble particulate fractions induced TNFalpha production and apoptosis and had some other cytotoxic effects. Soil-derived water-soluble and -insoluble components of the chemical PM(2.5-0.2) mass closure had consistent positive correlations with the responses, while the correlations were negative with the secondary inorganic anions (NO(3)(-), NH(4)(+), non-sea-salt SO(4)(2-)) and particulate organic matter (POM). With the PM(10-2.5) samples, sea salt and soluble soil components correlated positively with the induced toxic responses. In this size range, a possible underestimation of the insoluble, soil-related compounds containing Si and Ca, and biological components of POM, increased uncertainties in the evaluation of associations of the mass closure components with the responses. It is concluded that insoluble components of the complex urban air particulate mixture exert the highest inflammatory and cytotoxic activities in the macrophage cell line but, at the same time, they may operate as carriers for active water- and lipid-soluble components.