Precipitation chemistry in the coast of the Metropolitan Region of Rio de Janeiro, Brazil

Precipitation chemistry was studied in the Metropolitan Region of Rio de Janeiro (MRRJ). This study reveals that rainwater in the MRRJ is affected by emissions of air pollutants and provides essential data for future estimates of regional biogeochemical cycles and the impacts of acid deposition on tropical ecosystems. The volume-weighted mean (VWM) pH was 4.77, varying from 3.50 to 6.85. Sea-salt aerosols were the dominant sources of the Na+, Cl- and Mg2+. Excess SO4(2-), Ca2+ and K+ comprised 82, 91, and 87% of their total VWM concentrations, respectively. There were very strong correlations (r > 0.75, P > 0.01) for NO3- and H+, NO3- and excess(exc-)SO4(2-), NH4+ and exc-K+, and exc-SO4(2-) and exc-Ca2+, suggesting causal relationships between these ion pairs. The VWM concentrations of all major ions, except H+, were higher in the dry season, with dry to wet VWM concentration ratios varying from 1.1 (NH4+) to 4.7 (for total K+).     

Atmospheric BTX and polyaromatic hydrocarbons in Rio de Janeiro, Brazil

Polycyclic aromatic and monoaromatic (benzene, toluene and xylene, or BTX) hydrocarbons were monitored in Rio de Janeiro, Brazil, during the summer of 1998/1999. The levels of these aromatic chemicals decreased with distance from main roads, indicating mobile sources are the main pollutant emitters in this Latin American city. Benzo[ghi]perylene/indeno[1,2,3-cd]pyrene and benzene/toluene ratios corroborate this idea. However, higher benzene/toluene ratios at one of the major access routes into the city suggest pollutant inputs from a nearby refinery. Literature data were reviewed in order to outline differences and similarities among sources and levels of aromatic pollutants in large urban agglomerations worldwide. Concentrations of benzo[a]pyrene and benzene, which are well-known carcinogenic chemicals, were relatively low in Rio de Janeiro. This fact was attributed to specific atmospheric conditions during the tropical summer and differences in vehicle fuel composition.     

Coarse and fine aerosol source apportionment in Rio de Janeiro,Brazil

The metropolitan area of Rio de Janeiro is one of the twenty biggest urban agglomerations in the world, with 11 million inhabitants in the metropolitan area, and has a high population density, with 1700 hab. km^?2. For this aerosol source apportionment study, the atmospheric aerosol sampling was performed at ten sites distributed in different locations of the metropolitan area from September/2003 to December/2005, with sampling during 24 h on a weekly basis. Stacked filter units (SFU) were used to collect fine and coarse aerosol particles with a flow rate of 17 L min^?1. In both size fractions trace elements were analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) as well as water-soluble species by Ion-Chromatography (IC). Also gravimetric analysis and reflectance measurements provided aerosol mass and black carbon concentrations. Very good detection limits for up to 42 species were obtained. Mean annual PM₁₀ mass concentration ranged from 20 to 37 μg m^?3, values that are within the Brazilian air quality standards. Receptor models such as principal factor analysis, cluster analysis and absolute principal factor analysis were applied in order to identify and quantify the aerosol sources. For fine and coarse modes, circa of 100% of the measured mass was quantitatively apportioned to relatively few identified aerosol sources. A very similar and consistent source apportionment was obtained for both fine and coarse modes for all 10 sampling sites. Soil dust is an important component, accounting for 22–72% and for 25–48% of the coarse and fine mass respectively. On the other hand, anthropogenic sources as vehicle traffic and oil combustion represent a relatively high contribution (52–75%) of the fine aerosol mass. The joint use of ICP-MS and IC analysis of species in aerosols has proven to be reliable and feasible for the analysis of large amount of samples, and the coupling with receptor models provided an excellent method for quantitative aerosol source apportionment in large urban areas.     

Methylmercury and total mercury in estuarine organisms from Rio de Janeiro, Brazil

Guanabara Bay (GB), located in the Rio de Janeiro State, is still a productive estuary on the south-eastern Brazilian coast. It is an ecosystem heavily impacted by organic matter, oil and a number of other toxic compounds, including Hg. The present study aimed to comparatively evaluate the aquatic total mercury (THg) and MeHg contamination, and the ratios of MeHg to THg (% MeHg), in 3 species of marine organisms, Micropogonias furnieri-carnivorous fish (N = 81), Mugil spp.--detritivorous fish (N = 20) and Perna perna--filter-feeding bivalves (N = 190), which are widely consumed by the population. A total of 291 specimens were collected at the bay in different periods between 1988 and 1998. THg concentrations were determined by cold vapour AAS with stannous chloride as a reducing agent. MeHg was extracted by dithizone-benzene and measured by GC-ECD. Analytical quality was checked through certified standards. All organisms presented both low THg and MeHg concentrations and they were below the maximum limit of 1,000 micrograms Hg.kg-1 wet wt. as established for human intake of predatory fish by the new Brazilian legislation. Carnivorous fish showed higher THg and MeHg concentrations, and also % MeHg in muscle tissues, than organisms with other feeding habits and lower trophic levels. The average of THg concentrations in carnivorous fish was 108.9 +/- 58.6 micrograms.kg-1 wet wt. (N = 61) in 1990 and 199.5 +/- 116.2 micrograms.kg-1 wet wt. (N = 20) in 1998, but they presented different total length and body weights. The average THg content in detritivorous fish was 15.4 +/- 5.8 micrograms.kg-1 wet wt., whereas THg concentrations ranged from 4.1 to 53.5 micrograms.kg-1 wet wt. for the molluscs. The THg and MeHg contents of mussel varied according to the sampling point and water quality. MeHg concentration in detritivorous fish was similar to MeHg concentration in molluscs, but there was a significant difference in the MeHg/THg ratio: the carnivorous fish presented higher MeHg percentages (98%) than the detritivorous fish (54%) and the molluscs (33%). Weight-normalised average concentration of THg in carnivorous fish collected in 1990 (0.18 +/- 0.08 microgram.g-1/0.7 kg wet wt.) and in 1998 (0.16 +/- 0.09 microgram.g-1/0.7 kg wet wt.) presented no significant difference (t = 1.34; P < 0.5). In conclusion, the low THg and MeHg concentrations in the organisms from the GB ecosystem, are related to its eutrophic conditions and elevated amounts of suspended matter. In this situation, Hg could be strongly complexed or adsorbed by the particulate, which would dilute the Hg inputs and reduce its residence time in the water column, with a consequent decrease in its availability to organisms.     

PCDD/F-contamination in a hexachlorocyclohexane waste site in Rio de Janeiro,Brazil

In the 1950s, a production plant of hexachlorocyclohexane (HCH) was established in Brazil with the main purpose of producing chemicals for vectors control. This factory was closed down in 1955 and around 300 tons of production residues were left behind in the open air. In 1995, the area was treated with lime to eliminate the HCH contamination. Soil sample gave a PCDD/F concentration of 13 900 ng I-TEQ/kg whereas samples from the neighborhood ranged from 0.19 to 2.08 ng I-TEQ/kg. PCDD/F levels in cow's milk samples varied from 4.1 to 6.5 pg I-TEQ/g of milk fat. High concentration in soil collected from the site suggests that treatment and recovery shall be made. Further dioxin monitoring is needed to better estimate the risk posed to local population through food consumption and soil usage.     

Assessment of organochlorine pesticide residues in Atlantic Rain Forest fragments, Rio de Janeiro, Brazil

A superficial water quality survey in a watershed of the Paraíba do Sul River, the main water supply for the most populated cities of southeastern Brazil, was held in order to assess the impact of the expansion of agricultural activity in the near border of the Atlantic Rain Forest. The aim of this study was to investigate the presence of priority organochlorine pollutants in soils and superficial waters of Atlantic rainforest fragments in Teresópolis, Rio de Janeiro State. Soil sample preparations were compared by using ultrasound, microwave assisted extraction and Soxhlet extraction. Recoveries of matrix spiked samples ranged from 70 to 130%. Analysis of a certified soil material showed recoveries ranging from 71 to 234%. Although low concentrations of organochlorine residues were found in water and soil samples, this area is of environmental importance and concern, thus demanding a monitoring program of its compartments.     

Heavy metals, PCDD/F and PCB in sewage sludge samples from two wastewater treatment facilities in Rio de Janeiro State, Brazil

Two sewage sludge samples collected from an urban as well as a rural area in Brazil and one sludge sample originating from the city of Balingen, Baden-Württemberg, South Germany, were investigated in respect to contamination with heavy metals, PCDD/F and PCB. The results were compared to PCDD/F and indicator-PCB mean values found in the region of Baden-Württemberg. The observed toxicity equivalents of PCDD/F found in the Brazilian samples, were below the upper limit specified by German legislation for final disposal or agricultural use in soils. Both the PCB and heavy metal values exceeded this limit. The PCDD/F congener/homologue profiles found in the Brazilian samples indicated that the urban sewage sludge shows a contamination where both chlorophenols and depositional sources appear to be contributing to the contamination pool. The enrichment of highly chlorinated PCDD/F groups in the sludge of semi-rural origin is probably due to transport phenomena effects. For the German sludge sample, depositional sources seem to be the main PCDD/F contamination pathway. Regarding PCB, both Brazilian samples show a homologue profile that indicates a contamination stemming from technical PCB formulations like Clophen A50 and Clophen A60 or equivalent.     

Induced alkoxyresorufin-O-dealkylases in tilapias (Oreochromis niloticus) from Guandu river, Rio de Janeiro, Brazil

The activity of fish monooxygenases has been extensively used as a monitoring tool to detect contamination of water bodies by cytochrome P450-inducing agents. In this study we evaluated the activities of ethoxy- (EROD), methoxy- (MROD) and pentoxy- (PROD) resorufin-O-dealkylases in the liver of Nile tilapias (Oreochromis niloticus) collected at the Guandu river, at a reference clean site (Lake 1) and at two other sampling sites (Lakes 2 and 3) in Rio de Janeiro state, Brazil. Alkoxyresorufin-O-dealkylases were measured fluorimetrically in the hepatic S9 fraction. EROD (17.7-fold), MROD (14.2-fold) as well as PROD activities were considerably higher in tilapias from Guandu river. A moderate increase of EROD (5.0-fold) and MROD (5.4-fold) was also found in tilapias from Lake 3. These findings suggest that Guandu river watershed, the main source of urban drinking water supply in Rio de Janeiro, is polluted with CYP1A-inducing xenobiotics. Furthermore, we also found a good linear relationship between EROD and MROD, a finding that agrees with the hypothesis that the two reactions are catalysed by the same CYP1A isoform in O. niloticus.     

Traffic and catalytic converter - related atmospheric contamination in the metropolitan region of the city of Rio de Janeiro, Brazil

In this work, 24-h PM10 samples were collected in Rio de Janeiro, Brazil, and analysed for trace elements (Cd, Ce, Cu, La, Mo, Ni, Pb, Pd, Rh, Sb and Sn). The sampling was carried out at five locations (Bonsucesso; Centro, downtown city; Copacabana; Nova Igua?u and Sumaré) with different traffic densities and anthropogenic activities. An analytical method based on the EPA method for the determination of trace elements in airborne particulate matter (PM), using ultrasonic-assisted extraction and inductively coupled plasma mass spectrometry (ICP-MS) was applied. Our results suggest that vehicular traffic is the most important source of environmental pollution at the studied sites. The presence of Mo, Pd and Rh in the analysed filters reflects an additional source of pollution caused by the erosion and deterioration of automotive catalytic converters.     

Contribution to the understanding of biologic concentrations of arsenic in children living in an urban area from Rio de Janeiro,Brazil

Environmental Science and Pollution Research - There are few studies about children’s environmental exposure to arsenic (As) in Brazil, most of them being in mining regions. The objective of...     

A novel approach for characterization of polycyclic aromatic hydrocarbon (PAH) pollution patterns in sediments from Guanabara Bay, Rio de Janeiro, Brazil

A novel multivariate method based on principal component analysis of pre-processed sections of chromatograms is used to characterize the complex PAH pollution patterns in sediments from Guanabara Bay, Brazil. Five distinct sources of 3- to 6-ring PAHs could be revealed. The harbour is the most contaminated site in the bay, its plume stretches in a South West to North East direction and the chemical profile indicates mainly pyrogenic sources mixed with a fraction of high-molecular-weight petrogenic PAHs. Rio São João de Meriti is the second largest source of PAHs, and introduces mainly a fraction of low-molecular-weight petrogenic PAHs from the western region of Rio de Janeiro. The sites close to the ruptured pipeline at the Duque de Caxias Refinery show a distinctive pollution pattern indicating a heavy petroleum fraction. The method also led to the identification of new potential indicator ratios also involving coeluting peaks (e.g., triphenylene and chrysene).     

Atmospheric levels of aldehydes and BTEX and their relationship with vehicular fleet changes in Rio de Janeiro urban area

A comprehensive monitoring campaign to assess aldehydes and BTEX concentrations was performed during 12 months, in the Tijuca district (Rio de Janeiro), an area with commercial activities and a high flux of vehicles. The mean concentrations of formaldehyde and acetaldehyde were 151 and 30 ppb, respectively. The high formaldehyde/acetaldehyde ratio was attributed to extensive use of compressed natural gas (CNG). The number of CNG vehicles in the metropolitan Region of Rio de Janeiro increased from 23000 in January 2001 to 161000 in January 2005. Monitoring data show that, for the same period, methane and formaldehyde concentrations increased while NO(x) and CO levels diminished. Mean concentrations for benzene, toluene, ethylbenzene, m,p-xylene and o-xylene, were 1.1, 4.8, 3.6, 10.4 and 3.0 micro gm(-3), respectively. Benzene and toluene concentrations were lower than the values determined in 1996, for the same location. The levels of ethylbenzene and xylenes determined in this work are similar to values obtained in 1996. This fact may be explained as a consequence of changes in the gasoline composition.     

PM2.5–10, PM2.5 and associated water-soluble inorganic species at a coastal urban site in the metropolitan region of Rio de Janeiro

The concentrations of PM_2.5−10, PM_2.5 and associated water-soluble inorganic species (WSIS) were determined in a coastal site of the metropolitan region of Rio de Janeiro, Southeastern Brazil, from October 1998 to September 1999 (n=50). Samples were dissolved in water and analyzed for major inorganic ions. The mean (± standard deviation; median) concentrations of PM_2.5−10 and PM_2.5 were, respectively, 26 (± 16; 21) μg m⁻³ and 17 (± 13; 14) μg m⁻³. Their mean concentrations were 1.7–1.8 times higher in dry season (May–October) than in rainy season (November–April). The WSIS comprised, respectively, 34% and 28% of the PM_2.5−10 and PM_2.5 masses. Chloride, Na⁺ and Mg²⁺ were the predominant ions in PM_2.5−10, indicating a significant influence of sea-salt aerosols. In PM_2.5, SO₄²⁻ (∼97% nss-SO₄²⁻) and NH₄⁺ were the most abundant ions and their equivalent concentration ratio (SO₄²⁻/NH₄⁺ ∼1.0) suggests that they were present as (NH₄)₂SO₄ particles. The mean concentration of (NH₄)₂SO₄ was 3.4 μg m⁻³. The mean equivalent PM_2.5 NO₃⁻ concentration was eight times smaller than those of SO₄²⁻ and NH₄⁺. The PM_2.5 NO₃⁻ concentration in dry season was three times higher than in rainy season, probably due to reaction of NaCl (sea salt) with HNO₃ as a result of higher levels of NO_y during the dry season and/or reduced volatilization of NH₄NO₃ due to lower wintertime temperature. Chloride depletion was observed in both size ranges, although more pronouncely in PM_2.5.     

Biomonitoring perfluorinated compounds in Catalonia,Spain: concentrations and trends in human liver and milk samples

Background, aim and scope  

Perfluorinated compounds (PFCs) are global environmental pollutants that bioaccumulate in wildlife and humans. Laboratory experiments have revealed toxic effects such as delayed development, humoral suppression, and hepatotoxicity. Although numerous human blood levels have been reported, little is known about distribution in the human body. Knowledge about PFC distribution and accumulation in the human body is crucial to understanding uptake and subsequent effects as well as to conduct risk assessments. The present study reports PFC levels in human liver and breast milk from a general population living in Catalonia, Spain. Liver and milk levels are compared to previously reported levels in blood from the same geographic area as well as to other existing reports on human liver and milk levels in other countries.     

Mercury and its relation with selenium in the liver of Dall's porpoises (Phocoenoides dalli) off the Sanriku coast of Japan

Liver samples of 22 Dall's porpoises (Phocoenoides dalli) collected off the Sanriku coast of Japan were analyzed for investigation on bioaccumulation of total mercury (SigmaHg), organic mercury (OrgHg), inorganic mercury (InHg) and selenium (Se). In the liver, detoxification of Hg was evident by transformation of OrgHg. Se showed different Hg detoxification patterns in the liver with a threshold range of hepatic SigmaHg concentration of about 20-30 microg/g dry weight. The molar ratios of Se/InHg or Se/SigmaHg were obviously higher than 1 when hepatic SigmaHg levels were less than the range, while both ratios were close to 1 when SigmaHg levels were higher than the threshold, suggesting a mechanism by detoxification of OrgHg into less toxic mercuric selenide (HgSe) forms in the latter.     

Distribution of hydrocarbons in recent marine sediments off the coast of Baja California

Concentrations of linear or n-hydrocarbons, polycyclic aromatic hydrocarbons (PAHs) and unresolved complex mixture (UCM), were measured in recent marine sediments in 24 stations off the coastal region at the Mexico-USA border. The average concentration found for n-hydrocarbons was 15 microg g(-1), with a maximum of 70.6 microg g(-1) and minimum of 0.8 microg g(-1). The average concentration for UCM was 37 microg g(-1) with a maximum of 220.5 microg g(-1) and a minimum below detection levels. For the PAHs, the average concentration was 0.4 microg g(-1), with a maximum of 1.93 microg g(-1). Maxima and minima are consistent with previous studies in northern stations. A North to South gradient distribution is reported. Cluster analysis supports the hypothesis of a North to South transport. The sources of hydrocarbons appeared to be mainly anthropogenic. No significant correlation was found between particle size and hydrocarbon content, PAHs or UCM. Deposition of the n-hydrocarbons and UCM was apparently dictated by closeness to point sources as a poor correlation was found with organic content (r=0.27-0.32 alpha=0.05) and with grain size of sediments (r=0.019-0.079 alpha=0.05). Distribution of PAHs was found to decrease toward the coast. Possible sources of these materials are discussed. Grain size distribution suggest the general direction of main flow of material for the area studied.     

Assessment of polychlorinated biphenyls (PCBs) in cheese from Rio Grande do Sul, Brazil

Polychlorinated biphenyls (PCBs) are among the most toxic environmental pollutants. Food, especially animal based, has been described as the major source for human exposure to PCBs. We investigated PCB levels (congeners 10, 28, 52, 153, 138, and 180) in cheese from 14 cities of Rio Grande do Sul, Brazil. The fat was extracted using sodium sulfate and petroleum ether, and PCBs purification was conducted using florisil and hexane. The identification and quantification were made in a gas chromatograph with microelectron capture detector (GC-microECD). PCB congeners were found (lower bound data as ngg(-1) fat) in the following rank: 52 (15.75)>180 (4.91)>28 (3.43)>153 (3.00)>10 (2.38)>138 (1.37). Summation operatorPCB contamination ranged from 0 to 78.32 ngg(-1) fat. Differences in PCB levels between industrialized (33.32 ngg(-1) fat) and homemade (26.58 ngg(-1) fat) cheese and between two different regions (36.19 vs. 26.95 ngg(-1) fat) were not statistically significant. For university students, the estimated daily intake (EDI) of PCBs from cheese ranged from 0 to 3.13 pgkg(-1) b.w. EDI was significantly higher for industrialized than homemade cheese, and for cheese from Mountain/Porto Alegre region than from Santa Maria/South/Western region. No sample exceeded maximum level of PCBs allowed in dairy products in the European Community.     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia usneoides (L.) in an industrialized area in Rio de Janeiro state, southeast Brazil--Part II: PCB and PAH

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic bromeliad species as biomonitor and measuring bulk deposition rates of polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH). For the sum of PCB, overall deposition rates were between 17 and 314 ng/(m2 day) in winter and between 43 and 81 ng/(m2 day) in summer, respectively. Deposition rates of dioxin-like PCBs ranged from 0.14 to 2.8 pg WHO-TEQ/(m2 day) in winter and from 0.90 to 4.3 pg WHO-TEQ/(m2 day) in summer. PCB deposition rates (total PCB and WHO-TEQ) were in the same range in winter in V.R. and PNI. In summer, contamination levels in V.R. were 6-10-folds higher than in PNI. PCB concentrations in biomonitor samples from V.R. and PNI were in the same range in summer and in winter. Concentrations of total PCB ranged from 14 to 95 microg/kg dry matter (d.m.) in winter and from 18 to 27 microg/kg d.m. in summer, respectively. The TEQ values were between 1.7 and 4.1 ng WHO-TEQ/kg d.m. in winter and between 1.9 and 2.9 ng WHO-TEQ/kg d.m. in summer. PCB concentrations of di-ortho PCB but not of non-ortho PCB were a factor of 2-4 lower in summer in both areas. PCB congener profiles resembled those from technical formulations. The profiles shifted to the higher chlorinated congeners in summer, probable due to revolatilisation of the lighter components at higher temperatures. PCB profiles in biomonitor resembled those from deposition samples and the shift to the heavier congeners in summer was even more pronounced. PAH deposition rates were in a similar range in both areas (131-2415 ng/(m2 day)). PAH levels in biomonitor samples from V.R. were about one order of magnitude higher than in samples from PNI indicating the impact of local sources. PAH profiles revealed stationary thermal processes as main source of contamination in V.R. whereas in PNI, biomass burning seems to be the main contamination source.     

Distributions of polyhalogenated compounds in Hudson River (New York, USA) fish in relation to human uses along the river

PCBs (as Aroclor concentrations) have been extensively examined in fish along the Hudson River, but other xenobiotic chemicals in fish have had limited assessment. This study determined concentrations and congener distributions of polybrominated diphenyl ethers (PBDEs), polybrominated and polychlorinated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs and PCDD/Fs), and polychlorinated biphenyls (PCBs) in smallmouth bass and striped bass taken from a 385 km reach of the Hudson River. Concentrations of PBDEs and PCBs in smallmouth bass, and PCBs in striped bass, were positively related to human uses of the compounds in the basin. Generally low levels of PCDD/Fs were found. One striped bass, however, contained elevated 2,3,7,8-TCDD, indicating exposure to a known source in the adjacent Newark Bay-Passaic River basin. PBDDs were generally below detection. PBDFs were present in four of 18 smallmouth bass, but were not detected in striped bass. Dioxin-like PCBs contribute most to 2,3,7,8-TCDD toxic equivalents in 29 of 30 samples.