Claudio Bilos

Sources, distribution and variability of airborne trace metals in La Plata City area, Argentina

Airborne particulate trace metals have been measured bimonthly during day and night hours in four permanent stations located in residential, industrial and commercial sectors of La Plata City region, to characterize the sources and variability of atmospheric inputs. Airborne trace metal regional averages (Pb 64 +/- 62, Cu 30 +/- 27, Mn 26 +/- 20, Zn 273 +/- 227, Fe 1183 +/- 838, Ca 5343 +/- 3614, Mg 1472 +/- 967, Cr 4.3 +/- 2.4, Ni 3.2 +/- 3.5 and Cd 0.41 +/- 0.42 ng/m3) are comparable to the values reported for not grossly polluted cities and below the general trend described for urban particulates. Two- and three-way analysis of variance and variance components tests (P < 0.05) were performed to assess the contribution of the diurnal (day vs. night), spatial (inter-station) and temporal (inter-month) components of variability. Trace metal concentrations followed the behavior of total suspended particles with higher concentrations during the day and at the Downtown station and lower at the Residential site. In general, spatial and temporal variations prevailed over diurnal differences. Spatial differences were clearly most significant for Pb, which presented higher values at the Downtown site reflecting the importance of motor exhaust inputs. In contrast, diurnal differences were more important for Mn due to increased dust resuspension during day hours. A seasonal trend with concentrations usually increasing during winter months and decreasing in spring-summer was also detected. Enrichment factors (EF) were calculated to evaluate anthropogenic versus natural element sources. High EF (21-376) were obtained for Pb, Zn, Cd and Cu reflecting the importance of anthropic inputs. The comparison with EF calculated for high-emitting vehicle particle emissions indicated that motor exhausts are the most important source of these elements in La Plata region. In contrast, the EF calculated for Mn, Cr, Ni, Ca and Mg were low (1.3-7.5) suggesting chiefly natural sources, i.e. soil-derived dusts.

Trace metals in suspended particles, sediments and Asiatic clams (Corbicula fluminea) of the Rio de la Plata Estuary, Argentina

Suspended particulate matter (SPM), sandy sediments and Asiatic clams were collected at seven sites along 150 km of the Río de la Plata coast to assess the magnitude of trace metal pollution in the area. Metal concentrations in SPM (Cu: 7.4-109; Cr: 75-408; Mn: 525-1341 microg(-1)), sediments (Cr: 16-27; Zn: 26-99; Mn: 221-489 microg(-1)) and bivalves (Cd: 0.5-1.9; Ni: 1.3-6.4; Cr: 1.3-11; Mn: 15-81; Cu: 28-89; Zn: 118-316 microg g(-1)) are comparable to those reported for other moderately polluted world rivers. Cu levels in Asiatic clams are among the highest, similar to those reported for heavily polluted sites. SPM Cu and Cr concentrations displayed a clear geographical trend with values increasing with proximity to major urban centers. Sediments showed a less clear pattern possibly due to their coarse nature (>98% sand) and higher proportion of mineral-associated residual metals. The clams showed a complex pattern due to the variability introduced by size-related factors and the natural dynamics of SPM in the estuary. Cr and Mn showed an apparent reverse industrial trend with higher concentrations in clams collected at distant stations near the turbidity maximum zone, possibly reflecting enhanced particle retention. Cu, Cd and Ni showed no clear geographical pattern, whereas Zn increased in the clams collected in the most industrialized area. A significant relationship with clam size was observed for Cu (positive) and Zn (negative) suggesting different physiological requirements for both metals with age. A principal component analysis confirmed these geographical and size-related trends.

Environmental toxicity assessment in the Paraná river delta (Argentina): simultaneous evaluation of selected pollutants and mortality rates of Corbicula fluminea (Bivalvia) early juveniles

Water and sediment samples were collected in the lower Paraná delta at four sites with different levels of exposure to pollution to evaluate the anthropogenic impact through chemical analyses and mortality bioassays. Individual polychlorinated biphenyls, chlorinated pesticides, aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, and heavy metals were measured in waters, porewaters and sediments. The same three phases were also subjected to toxicity assays with straight-hinged juveniles of Corbicula fluminea. Concentrations of several pollutants were above levels recommended for the protection of aquatic life: in waters, Zn, Cu and Cr were 1.6-4.9 times higher, whereas in the sediments Cr was 1.8-3.6, and benzo(a)pyrene was 2.8-5.6 times higher. Pollutant concentrations followed a clear geographic pattern with highest values in the densely populated area of the Reconquista and Luján rivers, lower levels in the San Antonio, and lowest loadings in the remote Paraná de las Palmas. This gradient was adequately matched by the pattern of mortality rates of C. fluminea early juveniles, which were highest in the Reconquista-Luján (40-93%) and lowest (and not significantly different from the control) in the Paraná (3.3-23%). Mortality rates also increased from surface waters (3.3-53%), to porewaters (12-73%), to sediments (23-93%). Although toxicity was probably mainly due to dissolved contaminants, agreement between chemical and biological evidence of pollution was best for the sediment compartment, whereas porewater and surface water showed a higher degree of variability.

Bioaccumulation of Polychlorinated Biphenyls and Chlorinated Pesticides by the Asiatic Clam Corbicula fluminea; Its Use as Sentinel Organism in the Rio de La Plata Estuary, Argentina

Individual PCBs and chlorinated pesticides (CHLPs) were determined in water, suspended particles (SPM), sediments, and Asiatic clams to study their bioaccumulation kinetics and evaluate the usefulness of the clams as sentinel organisms. Bioaccumulation depended on the routes of uptake and bioavailability determined by compound hydrophobicity. CHLPs were mainly present in the dissolved phase, showed a positive correlation between the bivalve-water BAFs and K ow s and reached steady-state levels before 70 days in a caging experience. These facts reflect an efficient water-gill partitioning process. In contrast, PCBs were only detected in the SPM, showed essentially K ow independent bivalve-sediment and bivalve-SPM BAFs with the lowest values for super-hydrophobic heptachlorobiphenyls 174, 180, and 170, and did not reach steady-state levels during a 140-day exposure period. This suggests that the uptake was hindered by their stronger affinity for SPM and the interference of steric factors during intestine absorption. Corbicula fluminea are reliable sentinel organisms and showed clear geographical trends along 150 km of the Rio de La Plata coast : a progressive decrease of PCB levels and more degraded patterns dominated by recalcitrant congeners, i.e., 153, were observed with increasing distance from the major La Plata-Buenos Aires urban center. A size-related trend overlapped with this spatial gradient : older clams usually showed higher levels and a more degraded PCB signature. CHLPs showed less clear geographical trends due to the presence of multiple sources. CHLP patterns showed a strong dominance of chlordane-related compounds, particularly trans-chlordane which was 2-5 times more abundant than the cis isomer. On a temporal scale, from 1986 to 1993, Asiatic clams presented sustained PCB levels but showed a significant decrease of chlordane and DDT, which suggests reduced inputs in recent years.

Sources, distribution and variability of airborne particles and hydrocarbons in La Plata area, Argentina

Abstract Total suspended particles (TSP), particulate- (ALIp) and semi-volatile aliphatic hydrocarbons (ALIsv) were measured in air sampled during the day and night over 7–8 months in industrial, commercial and residential sectors of La Plata, Argentina. TSP, ALIp and ALIsv ranges were 23–219 μg/m3, 11–447 and 12–719 ng/m3, respectively. Maximum values were recorded at a downtown site whereas the residential station showed lower levels. Concentrations were usually higher during the day and during fall and winter. Two- and three-way ANOVA were performed to evaluate the day-night, inter-station, and inter-month variability. The amount of total variability accounted by these factors was 14, 25 and 23% (p

Massive airborne Endosulfan inputs related to intensive agriculture in Argentina's Pampa

In order to evaluate the impact of intensive agriculture on air quality in the most productive and populated Argentinas Pampas, a comprehensive assessment of airborne Endosulfan (∑Endo) was performed using polyurethane passive samplers deployed from 2010 to 2013 covering the critical period of Endosulfan restrictions at twenty nine sites in the Rural Pampa and Great Buenos Aires Metropolitan Area (GBA: Horticultural and Urban subareas). ∑Endo concentrations were very high and variable (0.01-63 ng m(-3)), exceeding worldwide reported maxima at Horticultural GBA and Rural Pampa with lowest values at Urban GBA (geometric means: 3.1, 1.1 and 0.53 ng m(-3), respectively). The composition was relatively fresh with strong predominance of Endo I (72 ± 18%) over Endo II (23 ± 15%) and Endo SO4 (5 ± 10%). Airborne ∑Endo was significantly correlated to annual soybean crop in Rural Pampa. ∑Endo concentrations showed a temporal pattern defined by consistent peaks enriched in Endo I during summer application periods, cold temperature minima with higher proportions of Endo SO4 and a general exponentially declining trend over time related to incipient control policies.

Airborne PCB patterns and urban scale in the Southern Río de la Plata Basin, Argentina

Atmospheric Polychlorinated Biphenyls (PCBs: ∑ 42 congeners) collected by polyurethane passive samplers (PAS-PUFs) in 29 stations from July 2010 to February 2014 (n=141) in the most productive and populated Southern Rio de la Plata area in Argentina were evaluated to assess concentration gradients, potential sources and compositional profiles related to different land use and urbanization. On a global scale, total airborne PCBs concentrations are low/very low (below detection limit to 937pgm-3) and show a significant potential correlation with urban scale increasing 2.5 times each 10 times increase of population reflecting the primary role of urbanization controlling PCB emissions. Compositional patterns evaluated by principal component analysis (PCA) of individual congeners indicated that highly populated atmospheres are enriched in lighter, more volatile tri, tetra and penta chlorine congeners of lighter Aroclor mixtures (from 1242 to 1254) suggesting actual emission of fresh PCBs signatures from sealants, combustion and/or electrical equipment. Sub urban and rural sites show a gradual transition to heavier Aroclor mixtures (from 1254 to 1260) with predominance of more persistent hexa and hepta PCBs indicating an aged background signal resulting from long range transport and/or re-emission from historic reservoirs such as soils.

Seasonal and inter-annual variability of water quality in the Uruguay River, Argentina

Abstract Water quality of the Uruguay River was evaluated with multi-parametric (temperature, turbidity, conductivity, pH, dissolved oxygen) and sediment trap data (particle flux, total organic carbon and nitrogen contents) and correlated to precipitation, river discharge and El Niño Southern Oscillation (ENSO) indices for the period 2006–2011. Hydro-meteorological parameters averaged 24–85% variability with coincident precipitation (200–400 mm month-1), discharge (7000–28 000 m3 s-1) and turbidity peaks (50–80 NTU) in the austral spring, and absolute maxima during the El Niño 2009 episode. Spectral analysis of discharge and sea-surface temperature anomaly (SSTA) showed consistent variance maxima at approx. 3 and 1.5 years. Deseasonalized discharge was significantly correlated to SSTA. During river floods, pH decreased (from 7.5 to 6.6) and particle dynamics peaked (turbidity: 15–80 NTU; vertical fluxes: 20–200 g m-2 d-1; total solid load: <1000 to 100 000 t d-1),whereas TOC remained stable (3.2 ± 0.8%) and C/N ratios increased (10–12) due to the higher contribution of terrestrial detritus.

Size-related trace metal bioaccumulation in Asiatic clams (Corbicula fluminea) from the Rio de la Plata estuary, Argentina

Asiatic clams from the Rio de la Plata estuary were classified in seven Shell Length (SL) classes (6.0 ≤ SL ≤ 41.0 mm) and analysed for metals to evaluate their bioaccumulation dynamics and characterise the significance of growth-related variability potentially interfering in clam monitoring programmes. Metal concentrations were rather homogeneous (Zn: 223 ± 64; Fe: 222 ± 87; Cu: 29 ± 5.5; Mn: 20 ± 5.5; Cr: 2.9 ± 1.1; Ni: 2.5 ± 0.9; Cd: 0.7 ± 0.3 μg g −1 ). Regression analyses between metal concentrations and clam size, SL, soft tissues dry weight (BW) displayed different patterns: decreasing (Fe-Cd-Cr-Zn), independent (Mn-Ni) and increasing (Cu) concentrations with size, representing accumulation strategies from regulation to net accumulation. Covariance analyses of metal concentrations-SL/BW indicated no significant seasonal differences. Metal particulate phase speciation in the RLP, clam depuration and suspended particulate size-fractionation assays suggest that fine suspended particles are the prevailing clam metal mode of uptake.

Long-Term (1970–2017) Temporal Trends of Polychlorinated Biphenyls in Fish, Settling Material, and Sediments from Populated and Remote Sites in Río de la Plata Estuary, Argentina

Temporal trends of polychlorinated biphenyls (PCBs) were studied for detritivorous fish (1996-2017) and settling material (2002-2017) from polluted Buenos Aires coast and for a dated sediment core (1970-2013) from the outer Río de la Plata estuary. In spite of contrasting concentrations [5.3 ± 6.3 μg·g-1 dry weight (dw) for fish, 48 ± 26 ng·g-1 dw for settling material, and 1.5 ± 0.7 ng·g-1 dw for core], all three revealed exponentially decreasing trends over time (97%, 83%, and 83%, respectively). Time trends showed peak maxima coincident with Argentinas period of maximum PCB usage in 1973-1980 (80 cm depth in the core) and pulse discharges related to PCB banning in 2001-2002 (fish) with a lighter signature enriched in less persistent tri- and tetrachlorobiphenyls. The log-linear PCB time trends compare well with the predicted decrease for a high emission scenario from global emission data; the best fit was observed for the less impacted sediment core (-2%·year-1 versus -3%·year-1 for emission scenario). Steeper slopes are observed for the more polluted settling material (-5%·year-1) and especially for fish, in which the background decline trend tripled after the 2001 PCB pulse (from -7%·year-1 to -21%·year-1). These PCB time trends in related environmental compartments from contrasted sites provide rare evidence for evaluating the effectiveness of control measures in southern South America.