Pesticide residues in cow milk consumed in São Paulo City (Brazil)

Residues of pesticides were surveyed in 132 samples of cow milk collected from bulk transports (38 samples of raw milk) and market (94 samples of pasteurised milk). These samples were analysed by the multiresidue analytical method DFG S19 for pesticide contamination. More than 70 active substances were studied and the identification and quantification were made by gas chromatographic technique. The results showed that 0.76% of samples were contaminated with HCH (alpha isomer) and 10.60% with endosulfan (alpha and beta isomers). Both pesticides, endosulfan and HCH, found in milk samples, indicated their use in agriculture practices, although legislation in Brazil does not permit the use of HCH since 1985 and endosulfan can be used only in a few crops. These compounds should not be present in milk because there are implications on human health. Organophosphorus, carbamates, pyrethroids, herbicides, and fungicides were not detected in cow's milk samples.     

Ozone-induced foliar injury in saplings of Psidium guajava 'Paluma' in São Paulo, Brazil

Psidium guajava 'Paluma' was evaluated under field conditions as a tropical bioindicator species of ozone (O(3)). Three exposures of 90 days each were performed (June 21, 2004-March 19, 2005). In each one of them, saplings of 'Paluma' (n=30) were exposed to ambient air at a site in S?o Paulo (Brazil) with high ozone concentrations, and in a greenhouse with charcoal-filtered air. Ozone-like visible foliar injuries were observed during the winter, spring and summer exposures, when AOT40 reached 6166ppbh, 3504ppbh and 4828ppbh, respectively. No injuries were observed in the plants kept under filtered air. The injuries consisted in red stippling on adaxial leaf surfaces. They did not cover the veins and appeared first in older leaves, becoming more intense as the exposure period increased. Injury incidence, severity, and the cumulative exposure threshold at injury onset varied among the exposure periods. AOT40 explained partly the incidence, severity and leaf injury index LII (r(2)=0.52, 0.39, 0.38, respectively, p=0.002). The results confirm the potential of the species as an O(3)-sensitive bioindicator.     

Physicochemical characteristics of atmospheric aerosol during winter in the São Paulo Metropolitan area in Brazil

In order to characterize atmospheric aerosol in the São Paulo Metropolitan Area, aerosols were sampled during the winter months of August 1999 and August 2000. A micro-orifice uniform deposit impactor (MOUDI) was used. Samples were submitted to gravimetry, as well as to proton-induced X-ray emission (PIXE), carbon (black and organic) and ion-chromatography analysis. These analyses supplied information about mass concentrations and physicochemical properties of the particles. Due to the higher humidity, which can increase soluble particles diameters, and reduced atmospheric stagnation seen in 2000, average PM₁₀ concentrations were higher (105 μg m⁻³) in the winter of 1999 than in the winter of 2000 (60 μg m⁻³). The PIXE analysis revealed metals and metal compounds, soil-derived elements, Si-rich particles, sulfates, carbonates, chlorides and other anthropogenic air-borne particles, supposing molecules in their usual composition. Mass balance for PM_2.5 revealed significant participation of organic and black carbon, probably resulting from diesel burning by the heavy-duty fleet.     

Dioxins and furans in the atmosphere of São Paulo City, Brazil

Air samples were collected simultaneously at three urban sites in São Paulo City, Brazil, in winter, spring, summer and fall (in 2000 and 2001). Andersen PUF samplers were used for gas and particles sequential sampling. Samples were analyzed using HRGC/HRMS according to US EPA Method 8290. The greater metropolitan area of São Paulo is the largest industrialized region of Latin America and has a highly polluted atmosphere. Concentrations of dioxins and furans, which are well-known toxic chemicals, ranged from 1.14 pg m⁻³ to 13.8 pg m⁻³ (0.047 pg I-TEQ m⁻³ to 0.751 pg I-TEQ m⁻³). Principal component analysis showed that all the variables are highly correlated with one another except the 2,3,7,8-TCDD one. This is consistent with the similar concentration profiles observed for the tetra, penta, hexa, hepta and octa-homologous groups of the three sampling sites studied. At all sites, the most abundant compounds were the hepta and octa congeners. The 2,3,4,7,8-PeCDF accounted for 37–46% of the total toxicity and the 2,3,7,8-TCDD accounted for 7–16%. Highest mass concentrations of PCDD/Fs were found in the site where there is influence of industrial activities and heavy vehicular traffic fueled by gasohol, diesel, and ethanol.     

Dental enamel as biomarker for environmental contaminants in relevant industrialized estuary areas in São Paulo,Brazil

Heavy metal contamination is a long-standing and very well-known public health problem, and its exposure can cause damage to several organs of human body, especially on the central nervous system of young children and teenagers. The aim of this article is to evaluate lead, cadmium, and manganese contamination in 125 children from 6 to 13 years old living in contaminated areas during the period from 2006 to 2009 (São Vicente, Cubatão Downtown, Bertioga and Cubatão Pilões/Água Fria). This estuary area is the most important example of environmental degradation by chemicals from industrial sources. This is a cross-sectional study through clinical examinations and dental enamel tests. All mothers from these children lived in the area since before the pregnancy. Lead, cadmium, and manganese levels (μg/g) were measured on dental enamel samples through graphite furnace atomic absorption spectrometry, searching for the occurrence of heavy metals. The mean lead concentrations were 139.48 μg/g in Cubatão Pilões/Água Fria, 170.45 μg/g in Cubatão Downtown, 213.52 μg/g in São Vicente, and 151.89 μg/g in Bertioga. The mean cadmium concentrations were 10.83 μg/g in Cubatão Pilões/Água Fria, 12.58 μg/g in Cubatão Downtown, 10.92 μg/g in São Vicente, and 14.57 μg/g in Bertioga. The mean manganese concentrations were 23.49 μg/g in Cubatão Pilões/Água Fria, 30.90 μg/g in Cubatão Downtown, 41.46 μg/g in São Vicente, and 42.00 μg/g in Bertioga. Dental surface enamel may be used as an efficient biomarker of past environmental exposure to lead, manganese, and cadmium which are associated to well-known sources of heavy metal contamination. The results suggest that the evaluated children were exposed to sources of lead, cadmium, and manganese since before their conceptions. Although Bertioga initially was chosen as a control area of this study, it was also was verified to have heavy metal contamination on examined children.     

Zinc toxicity in the fish Cnesterodon decemmaculatus in the Paraná River and Río de La Plata Estuary

Acute static tests were performed to assess Zn toxicity on adults of Cnesterodon decemmaculatus (not sexed), a neotropical fish of wide distribution in the Río de la Plata basin. Tests were carried out with ZnCl2 dissolved in natural waters from the Lower Paraná River, the Río de la Plata Estuary, reconstituted waters of similar composition, tap and distilled waters. Median lethal concentration at 24 h was positively correlated to conductivity and the concentrations of Ca2+, Mg2+, and HCO3- (r=0.99, 0.96, 0.97, 0.99, p<0.05, respectively), being higher at the Río de la Plata Estuary (61.2 mg l(-1)) than at the Lower Paraná River (35.3 mg l(-1)). Contaminant load in the natural waters tested was similar at both sites, being Zn concentration 40 and 44 microg l(-1), respectively. An assay with reconstituted water of similar alkalinity to the estuary showed a simultaneous decrease in HCO3- and dissolved Zn, while the Zn speciation, predicted with a computer program, suggested that Zn2+ precipitated as ZnCO3. The effect of Ca2+ on Zn toxicity is also discussed. Zn toxicity was higher in the Río de la Plata Estuary water than in synthetic water of similar ionic composition (24-h LC50 = 93.2 mg l(-1)), suggesting the synergistic effect of other toxic pollutants such as metals, present in the former which were absent in the later.     

Low molecular weight carboxylic acids in an urban atmosphere: Winter measurements in São Paulo City,Brazil

Atmospheric gas and particle-phase carboxylic acids were measured during July 1996, Winter, in an urban area of São Paulo, a highly polluted Latin American city. Ion chromatography and capillary electrophoresis techniques were used to determine the species. As oxalic (36.2±21.4%), pyruvic (15.0±7.9%), β-hydroxy-butyric (9.15±9.00%) and glycolic (3.55±2.26%) acids were determined in aerosol particles, formic and acetic acids were determined both in the gaseous (4.36±2.70 and 3.66±2.63 ppbv, respectively) and particulate phases (17.8±12.4 and 18.2±9.8%, respectively). Approximately 98% of the total acetic and formic acids were in the gas-phase and the gas–aerosol equilibrium was influenced by high levels of relative humidity. Gaseous formic-to-acetic ratios fell in the 0.94–1.85 range. Photochemical production appeared to be a very likely source of the gaseous acetic and formic acid levels found in this investigation. Direct emissions, mainly motor exhaust of vehicles also contributed to their presence in air.The observed amounts of formic and acetic acids in the particle phase were comparable with those observed in other urban sites. Results from aerosol particles indicated lower concentrations of the carboxylic acids at night, but their diurnal and nocturnal variation were similar.Using a correlation matrix, it was possible to suggest some sources for the carboxylic acids in the particulate phase. During daytime, vehicular emission appeared to be the primary source of acetic acid, whereas formic and pyruvic acids should be formed photochemically. Moreover, emissions from biogenic primary sources appeared to be an important contribution to atmospheric concentrations of formic and glycolic acids. Presumably, the photooxidation of pyruvic and glycolic acids gave rise to the oxalic acid.No source for acetic and pyruvic acids at nighttime was possible to suggest. However, direct vehicular and biogenic emissions might be major sources of TOC in nocturnal measurements. Oxalic acid might result from vehicular emission, glycolic acid from biogenic emission and formic acid from both sources.     

Alkylphenols in sediments of the Atlantic Rainforest south-west of São Paulo, Brazil

Concentrations of technical 4-nonylphenol, 4-n-octylphenol, and 4-tert-octylphenol were investigated in surface water and sediment samples of four reservoirs southwest of S?o Paulo. Three of them (Takimoto 1, Takimoto 2, Pedro) were established in intensively cropped landscapes, one (Morro Grande) was surrounded by dense forests. Total alkylphenol concentrations in sediments generally ranged between 1 and 10 microgkg-1dw with 4-tert-octylphenol being the dominant alkylphenol. Because 4-tert-octylphenol concentration patterns at Takimoto 2, Pedro, and in the Morro Grande forest reservoir were found to be quite similar (upto 5 microgkg-1dw), this value is considered as the ubiquitous background level. In contrast, the Takimoto 1 sediments showed significantly higher 4-tert-octylphenol concentrations, possibly due to accelerated inputs from adjacent intensively cropped fields. Analysed alkylphenols were not detectable in water samples.     

Risk ranking of multiple-POPs in detritivorous fish from the Río de la Plata

To evaluate the bioaccumulation and the risk associated to consumption of lipid-rich detritivorous fish, a comprehensive set of organic pollutants (n = 213) including polychlorinated biphenyls (PCBs), dioxin like PCBs (dlPCBs), chlorinated pesticides (CHLPs), chlorobenzenes (CBzs), polybrominated diphenyl ethers (PBDEs), polychlorinated dibenzo dioxins and furans (PCDD/F), resolved (ALI) and unresolved aliphatic hydrocarbons (UCM) and linear alkyl benzenes (LABs) were analyzed in Sábalo fish (Prochilodus lineatus) collected in the polluted Metropolitan Buenos Aires coast and in migrating specimens. Fatty fish muscles (lipids: 74 ± 9.3% dry weight) contained homogeneous (24-51% variability) and very high-concentrations of organic pollutants ranging from 60 to 1300 μg g⁻¹ fresh weight (fw) ALI + UCM; 10-40 μg g⁻¹ fw LABs and PCBs; 0.1-1 μg g⁻¹ fw dlPCBs, DDTs, chlordanes, CBzs and PBDEs; 0.01-0.1 μg g⁻¹ fw mirex, endosulfans, aldrin, dieldrin, endrin and 0.07-0.2 ng g⁻¹ PCDD/F. Total toxicity equivalents (TEQs) ranged from 60 to 395 pg g⁻¹ fw (34 ± 17 and 213 ± 124 pg g⁻¹ TEQs for PCDD/F and dlPCBs respectively). These are among the highest concentrations reported for fish and point out the remarkable ability of Sábalo to feed on anthropogenic organic-enriched particles and tolerate a high pollutant load. Contaminant signatures show partial alteration with still abundant lower molecular weight components indicating that fish feeds directly in the outfalls. Consumption limits based on reference doses ranged from 0.1 (PCBs) to >12 000 g d⁻¹ (endosulfan) allowing a comprehensive risk-based ranking of contaminants in this long-range migrating, detritivorous fish.     

Pesticides residues in the Prochilodus costatus (Valenciennes, 1850) fish caught in the São Francisco River,Brazil

The objective of this study was to determine the levels of pesticides in the fish Prochilodus costatus caught in São Francisco River, one of most important rivers in Brazil. Thirty-six fish were captured in three different areas, and samples of the dorsal muscle and pooled viscera were collected for toxicological analysis. We evaluated the presence of 150 different classes of insecticides, fungicides, herbicides and acaricides by multiresidue analysis technique using liquid chromatography-tandem mass spectrometry (LC-MS/MS), with the limit of detection of 5 ppb. In this study, organophosphorus and carbamate pesticides were detected at the highest levels in the caught fish. Among the 41 organophosphorus pesticides surveyed, nine types were detected (chlorpyrifos, diazinon, dichlorvos, disulfoton, ethion, etrimfos, phosalone, phosmet and pyrazophos) in the muscle, viscera pool, or both in 22 (61.1%) fish. Sampled tissues of 20 (55.6%) fish exhibited at least one of the eight evaluated carbamate pesticides and their metabolites: aldicarb, aldicarb sulfoxide, carbaryl, carbofuran, carbosulfan, furathiocarb, methomyl and propoxur. Fungicides (carbendazim, benalaxyl, kresoxim-methyl, trifloxystrobin, pyraclostrobin and its metabolite BF 500 pyraclostrobin), herbicides (pyridate and fluasifop p-butyl), acaricide (propargite) and pyrethroid (flumethrin) were also detected. In conclusion, P. costatus fish caught in the São Francisco River contained residues of 17 different pesticides, in both muscles and the viscera pool, indicating heavy environmental contamination by pesticides in the study area.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State,Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the Northeastern part of São Paulo State, Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05–0.92, 0.12–11.01, 0.02–0.25 ng g⁻¹ dry wt, respectively, and in the surface water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l⁻¹, respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport.     

Suitability of Nicotiana tabacum 'Bel W3' for biomonitoring ozone in São Paulo, Brazil

Nicotiana tabacum 'Bel W3' is a widely used sensitive bioindicator for ambient ozone, but it is rarely used in tropical countries. Our goal was to determine the suitability of this plant for biomonitoring ozone in the city of S?o Paulo by evaluating the relationships between leaf necroses and ozone under field conditions and measurements of chlorophyll a fluorescence and antioxidants in plants exposed to different concentrations of ozone in closed chambers. While a weak linear relationship between leaf injury and ozone concentrations (R(2)=0.10) was determined in the field, a strong linear relationship was observed in the chamber experiments. Maximum leaf injury was observed in plants submitted to 40 ppb, which coincided with a significant decrease in fluorescence and total ascorbic acid. The relationship between leaf damage observed in the field and ozone was improved when the concentrations were limited to 40 ppb (R(2)=0.28).     

Relationship between leaf antioxidants and ozone injury in Nicotiana tabacum ‘Bel-W3’ under environmental conditions in São Paulo,SE – Brazil

Previous studies have reported that the extent of leaf injury in Nicotiana tabacum “Bel-W3” exposed to environmental conditions in the city of São Paulo is influenced by weather conditions. This influence may occur by means of antioxidant responses. Thus, this study aimed to evaluate whether daily antioxidant responses to environmental variations interfere on the progression of leaf injury on plants of this cultivar during their exposure in a state park of São Paulo and to determine a linear combination of variables, among antioxidants and environmental factors, which mostly explain this visible response. Plants were exposed at the mentioned site for 14 days in four different experiments. During each experiment, three plants were daily sampled to determine the accumulated percentage of leaf area affected by necrosis and antioxidant responses (concentrations of total ascorbic acid (AA) and activity of superoxide dismutase (SOD) and peroxidases (POD)). Ozone concentrations and weather conditions were also daily measured. Pearson correlations and multivariate analyses assessed the relationship between biological and environmental variables. Leaf injury appeared between the 3rd and 6th days of exposure and increased over the exposure periods. The daily concentrations of AA tended to decrease with time of exposure in all experiments, but the activity of SOD and POD oscillated during plant exposure. Positive correlations were observed between AA or SOD and O₃ concentrations, as well as negative correlations between AA and air temperature. The increasing percentage of leaf necrosis across the whole period was explained by decreasing levels of AA 2 days before injury estimation and by higher O₃ concentrations 5 days before (R² = 0.36; p < 0.001). The use of N. tabacum Bel-W3 as a bioindicator can be restricted by leaf antioxidant responses to both atmospheric contamination and weather conditions.     

Survey of volatile organic compounds associated with automotive emissions in the urban airshed of São Paulo,Brazil

The Metropolitan Region of São Paulo (MRSP), Brazil, is one of the largest metropolitan areas in the world (population 17 million, approx.) and relies heavily on alcohol-based fuels for automobiles. It is estimated that about 40% of the total volume of fuel is ethanol with some vehicles using pure ethanol and others a gasoline/ethanol blend. As such, São Paulo is an excellent example of an oxygenates-dominated airshed of mobile sources and is most likely indicative of the future in heavily populated areas in the US such as Los Angeles where “oxy-fuels” are becoming an important replacement for the conventional pure petroleum-based fuels. In this work, we surveyed the ambient air to identify and quantify the organic compounds associated with the evaporative and exhaust emissions of these fuels and to begin to understand the potential for human exposure. Because this was an initial test without detailed prior knowledge of the airshed of the area, we applied two different air sampling methods for various time periods to assess the ambient concentrations of a variety of polar and nonpolar volatile organic compounds (VOCs). For quality assurance (QA), we collected all the samples in duplicate (whole-air samples in Summa canisters and adsorbent-based samples on Perkin-Elmer Air Toxics tubes) at various flow rates to test performance. All samples were collected over identical time frames, typically for 1-, 2-, and 4-h periods per day at six different locations over a period of 1 week. Overall São Paulo results demonstrate that mean concentrations of single-ring aromatics are 2–3 times higher, volatile aldehydes are 5–10 times higher, and simple alcohols 10–100 times higher as compared to results of a recent study performed by EPA in the Los Angeles basin. C₄–C₁₁ n-alkanes were only slightly elevated in São Paulo.     

Vertical fluxes and accumulation of PCBs in coastal sediments of the Río de la Plata estuary, Argentina

Settling particles and underlying sediments collected at 1, 2.5 and 4 km along offshore transects in the urbanized sector of the Río de la Plata were analyzed to evaluate the sources and accumulation of PCBs. Total PCB concentrations range from <0.1 to 100 ng g(-1) and include variability associated to North-South and offshore gradients reflecting the impact of coastal discharges. Highest concentrations were recorded in the industrialized Central area close to Buenos Aires (61+/-37 ng g(-1) at 1 km) relative to cleaner northern stations (3.6+/-2.2 ng g(-1)) and southward sites (37+/-2.8 ng g(-1)), affected by transport of particulate PCBs by coastal currents. Sediment traps deployed in the Central area revealed large depositional fluxes of total matter (361+/-124 gm(-2)day(-1)) and PCBs (26+/-19 microg m(-2)day(-1)) and high sedimentation rates (5.0+/-1.7 cm yr(-1)). Uniform PCB concentrations (66-89 ng g(-1)) down to 20 cm in sediment cores suggest continued PCB discharges during the last 4 years. PCB composition was dominated by hexa (43+/-6.4%), hepta (23+/-5.1%) and pentachlorobiphenyls (21+/-5.5%) with lower proportions tri-tetra (7.4+/-5.4%) and higher chlorinated congeners (5.1+/-3.3%). A consistent weathering pattern with loss of 3-5 chlorobiphenyls and enrichment in higher chlorinated PCBs corresponding to a shift from a 1:1 to a 1:3 1254:1260 Aroclor mixture, was observed offshore. A principal component analysis performed with the relative contribution of PCB congener classes confirmed the offshore weathering pattern indicating that transformer oils containing Aroclor 1254-1260 are the most probable sources. Sediment inventories, sediment trap fluxes and Fugacity II calculations indicate an accumulation approximately 500-800 kg PCB in superficial sediments of this coastal environment.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 1-aliphatic hydrocarbons

The temporal variability and bioaccumulation dynamics of C_12–25 n-alkanes, isoprenoids and unresolved aliphatic hydrocarbons (UCM) were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the sewage impacted Buenos Aires coastal area. Fish muscles contain huge amounts of n-C_12–25 (165 ± 93, 70 ± 48 or 280 ± 134 μg g⁻¹, dry, fresh and lipid weight, respectively) and UCM (931 ± 560, 399 ± 288 and 1567 ± 802 μg g⁻¹) reflecting the chronic bioaccumulation of fossil fuels from sewage particulates. On a temporal basis, lipid normalized aliphatic concentrations peaked by the end of 2001–2002 during the rainiest period over the last four decades (1750 vs. 1083 ± 4.6 mm in 1999, 2004 and 2005), reflecting an enhanced exposition due to massive anthropogenic fluxes from Metropolitan Buenos Aires in wet years. The hydrocarbon composition in fish muscles is enriched in n-C_15–17 and isoprenoids relative to a fresh crude oil and settling particulates, with fresher signatures during the 2001–2002 maxima. Fish/settling material bioaccumulation factors (BAFs: 0.4–6.4 dry weight or 0.07–0.94 lipid-organic carbon) plotted against K_ow showed a parabolic pattern maximizing at n-C_14–18 and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log K_ow: 7.2–9.9), intermediate-size C_14–18 n-alkanes and C_15–20 isoprenoids (MW: 198–282; length: 17.9 to 25.4 Å) with melting points ranging from −19.8 to 28 °C. The uptake efficiency is inversely correlated to melting points and increased from 75% for n-C₂₅ to above 90% for n-C_14–15 and isoprenoids.     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 2-Polychlorinated biphenyls

The temporal variability and bioaccumulation dynamics of individual PCBs were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the polluted Buenos Aires coastal area. Fish muscles contain high concentrations of total PCBs (11+/-7.2, 4.6+/-3.4 or 19+/-13 microg g(-1), dry, fresh and lipid weight, respectively) reflecting chronic bioaccumulation from sewage-industrial particulates. On a temporal basis, lipid normalized PCBs concentrations peaked by the end of 2001-2002 coincident with the rainiest period over the last four decades and shortly after PCB prohibition in the country, reflecting massive discharges to the coastal ecosystem. PCB composition in fish muscles show a prevailing contribution of hexachlorobiphenyls (35+/-4.2%), followed by hepta (23+/-3.0%), penta (20+/-3.6%), tri-tetra (16+/-4.8%) and minor proportions of octa-decachlorobiphenyls (5.7+/-3.1%) similar to an Aroclor 1242-1254-1260 1:2:4 mixture. During 2001-2002 maxima fish showed an enrichment in tri-tetrachlorobiphenyls ( approximately 1242-1254-1260 1:1:1 mixture) denoting a fresher signature. Fish/settling material lipid-organic carbon accumulation factors (BSAFs: 2.4-46, average: 21+/-10) plotted against kow showed a parabolic trend (BSAFs=-0.38 log kow2 + 5.16 log kow -15.85; R2=0.46) maximizing at hexa, hepta and octachlorobiphenyl 203 with reduced bioaccumulation of a few hepta (170, 191) and most octa-decachlorobihenyls suggesting limited intestinal absorption.     

Ground-level ozone mapping in large urban areas using multivariate statistical analysis: application to the São Paulo Metropolitan Area

A statistical study on the behavior of ground-level O3 concentration in different regions of a large urban area was carried out, with emphasis on pollutant gas concentrations and meteorological variables. The study was based on data generated by a network of measuring stations distributed throughout the S?o Paulo Metropolitan Area, in regions with different characteristics of traffic and economic activities. The combined application of principal component analysis and clustering techniques to data collected from 1997 until 2000 has led to the identification of implicit relationships between variables that have been associated with dominant processes related to O3 formation in different locations. Similarities between different regions of the city have also been detected and associated with local characteristics. The results indicate that the application of such statistical techniques to data collected in large urban areas enables the grouping of different regions according to their behavior in terms of O3 levels, as well as the identification of dominant processes in each group. These techniques are thus important in the planning of air pollution policies, especially in the case of O3, a pollutant that is not directly related to pollution levels alone.