High-resolution multivariate analysis of the hydrochemical signature of water corridors in the upper Río de la Plata estuary, Argentina.

Major world river-estuaries integrate the hydrochemical characteristics of the basin with specific signatures which are maintained until complete mixing or discharge to the sea. The chemical signature of distinct water masses and the anthropogenic impact in the Upper Río de la Plata estuary (RLP) were evaluated by high-resolution continuous monitoring (i.e. every 200 m) of conductivity, turbidity, pH, temperature, chlorophyll a and coloured dissolved organic matter (CDOM), discrete analysis of suspended particulate matter (SPM) grain size composition combined with multivariate analysis (K-means clustering, Principal Component Analysis). The characteristic signatures of main RLP tributaries such as the Paraná River, yielding higher conductivity, CDOM, turbidity and coarser SPM, and the Uruguay River, with clearer, more eutrophic waters enriched in very fine SPM, were maintained 60 km seaward from the estuary head. Across the river, three water corridors with distinct signatures and variable widths (3-20 km) were identified reflecting the transition from Paraná to Uruguay River waters. Multivariate techniques also allowed the identification of a polluted coastal corridor (higher conductivity and CDOM and lower turbidity) impacted by wastewater discharges from the metropolitan Buenos Aires and La Plata cities extending 100 km seaward. The combined strategy of high-resolution monitoring, discrete sampling and multivariate techniques was a useful tool to identify water masses, corridors of flow and anthropogenic sources in a heavily urbanized estuary.

Behavior of dioxin like PCBs and PBDEs during early diagenesis of organic matter in settling material and bottom sediments from the sewage impacted Buenos Aires' coastal area, Argentina.

Settling particles (SPs) and sediments collected in the Buenos Aires sewer area were analyzed for dioxin like polychlorinated biphenyls (dlPCBs) and polybrominated diphenyl ethers (PBDEs) to follow early diagenetic changes during transport and deposition of organic matter. SP showed a temporal trend of higher total organic carbon (TOC) and fresher dlPCBs and PBDEs signatures during warm-rainy months related to more efficient washout of residues. TOC-normalized sediment trap concentrations suggest a diagenetic magnification of dlPCBs during cold-dry months due to enhanced decomposition of TOC, whereas most labile PBDEs appear to follow TOC decay. The diagenetic behavior of individual congeners along seasonal changes (cold/warm) and during deposition (bottom sediment/SP) shows the selective preservation of heavier, more persistent congeners with a positive relationship with sediment half-lives. The 3-4 times diagenetic magnification of heavier congeners observed in bottom sediments would be a prevailing long-term pathway for dlPCBs and PBDEs bioaccumulation in detritus feeding organisms.

Trace metals in settling particles from the sewage impacted Buenos Aires coastal area in the Río de la Plata estuary, Argentina.

Sediment traps deployed in Buenos Aires sewage outfall area collected a substantial amount of material (average mass flux 22 ± 12 g cm (2) year(-1)) with very high metal concentrations, mostly in the range of hazardous exposition for organisms (Zn: 138-671, Cu: 41-273, Cr: 44-255 and Pb: 26-260 µg g(-1)). The combination of high mass fluxes and concentrations results in huge metal fluxes (0.005-0.7 to 3.6-31 g m(-2) day(-1) for minor elements and Fe, respectively). Metal concentrations were correlated to the total mass flux and total organic carbon but with different trends for redox-sensitive Fe and Mn (negative) and anthropogenic elements (positive). This reflects the key role of organic discharges promoting anoxia with Fe and Mn evasion, and also contributing toxic metals.

Vertical fluxes and accumulation of trace metals in superficial sediments of the Río de la Plata estuary, Argentina.

Superficial sediments and settling material collected in Buenos Aires coastal area were analyzed to evaluate the accumulation and sources of trace metals. Residual elements showed homogeneous sedimentary concentrations (Fe: 23,846 +/- 4,367; Ni: 10 +/- 2.7; Mn: 706 +/- 314 µg g(-1)) whereas anthropogenic metals presented exponentially decreasing offshore gradients (Zn: 98 +/- 69; Cr: 28 +/- 21; Cu: 19 +/- 15; Pb: 18 +/- 13 µg g(-1)). Anthropogenic impact was evaluated through metal-Fe relationships, Fe-normalized enrichment factors and sediment quality guidelines. The slopes of metal-Fe regressions from background sites were comparable to upper crust metal ratios, excepted Cr which is impoverished, and Mn which is diagenetically enriched. Metal-Fe relationships also hold for most 2.5 km offshore sites but with higher slopes denoting human influence, and are completely lost in 1-2.5 km sediments and trap material which plot over the regressions and exceed sediment quality guidelines.

Sources, vertical fluxes, and equivalent toxicity of aromatic hydrocarbons in coastal sediments of the Río de la Plata Estuary, Argentina.

Settling particles and bottom sediments collected at 1, 2.5, and 4 km off the metropolitan Buenos Aires coast in the Río de la Plata were analyzed to evaluate the sources and toxicity of resolved (PAHs) and unresolved (AROUCM) aromatic hydrocarbons. PAHs (0003-2.1 microg g(-1)) and AROUCM (0.01-78 microg g(-1)) presented the highest concentrations nearthe Buenos Aires port and sewer and decreasing values up- and downstream and along on- and offshore gradients. Sediment traps deployed in the Central area revealed large aromatic fluxes (1.3 +/- 1.5 and 31 +/- 47 mg m(-2) day(-1) for PAHs and AROUCM). The composition of sedimentary PAHs was dominated by uniformly distributed high molecular weight pyrogenic PAHs (53 +/- 11% fluoranthene, pyrene, and heavier PAHs), followed by diagenetically derived perylene more abundant in less polluted sites (29 +/- 15%) and lower molecular weight petrogenic PAHs (18 +/- 7.1% phenanthrene, anthracene, and methylated compounds), which covaried inversely with perylene. PAH diagnostic ratios indicated a stronger influence of petrogenic discharges close to the shore and the prevalence of combustion of fossil fuels and vehicle emissions over wood in offshore sediments. Sediment cores showed sustained hydrocarbon levels with decreasing proportion of petrogenic PAHs and relative enrichment of pyrogenic components and perylene down to 20-cm depth. PAH toxicity assessment by sediment quality guidelines (SQG) and dioxin-equivalent factors (PAH TEQ: 0.08-395 pg g(-1) dw) identified 1-2.5 km sediments close to the port and sewer as the most affected area. According to SQG, dibenz[a,h]anthracene and pyrene were the most critical PAHs, followed by benzo[a]pyrene, benz[a]anthracene, and chrysene. In contrast, PAH TEQs were dominated by indeno[1,2,3-cd]pyrene, benzo[k]fluoranthene, benzo[a]pyrene, perylene, and benz[a]anthracene which accounted for an average 86 +/- 5.7% of total TEQs.

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.

Oil spill in the Rio de la Plata estuary, Argentina: 2-hydrocarbon disappearance rates in sediments and soils.

The 6-month assessment of the oil spill impact in the Rio de la Plata described in the preceding paper [Colombo, J.C., Barreda, A., Bilos, C., Cappelletti, N., Demichelis, S., Lombardi, P., Migoya, M.C., Skorupka, C., Suarez, G., 2004. Oil spill in the Rio de la Plata estuary, Argentina: 1 - biogeochemical assessment of waters, sediments, soils and biota. Environmental Pollution] was followed by a 13- and 42-month campaigns to evaluate the progress of hydrocarbon decay. Average sediment hydrocarbon concentrations in each sampling include high variability (85-260%) due to contrasting site conditions, but reflect a significant overall decrease after 3 years of the spill: 17 +/- 27, 18 +/- 39 to 0.54 +/- 1.4 microg g(-1) for aliphatics; 0.44 +/- 0.49, 0.99 +/- 1.6 to 0.04 +/- 0.03 microg g(-1) for aromatics at 6, 13 and 42 months, respectively. Average soil hydrocarbon levels are 100-1000 times higher and less variable (61-169%) than sediment values, but display a clear attenuation: 3678 +/- 2369, 1880 +/- 1141 to 6.0 +/- 10 microg g(-1) for aliphatics and 38 +/- 26, 49 +/- 32 to 0.06 +/- 0.04 microg g(-1) for aromatics. Hydrocarbon concentrations modeled to first-order rate equations yield average rate constants of total loss (biotic+abiotic) twice as higher in soils (k = 0.18-0.19 month(-1)) relative to sediments (0.08-0.10 month(-1)). Individual aliphatic rate constants decrease with increasing molecular weight from 0.21 +/- 0.07 month(-1) for isoprenoids and n-C27, similar to hopanes (0.10 +/- 0.05 month(-1)). Aromatics disappearance rates were more homogeneous with higher values for methylated relative to unsubstituted species (0.17 +/- 0.05 vs. 0.12 +/- 0.05 months(-1)). Continued hydrocarbon inputs, either from biogenic (algal n-C15,17; vascular plant n-C27,29) or combustion related sources (fluoranthene and pyrene), appear to contribute to reduced disappearance rate. According to the different loss rates, hydrocarbons showed clear compositional changes from 6-13 to 42 months. Aliphatics disappearance rates and compositional changes support an essentially microbiologically-mediated recovery of coastal sediments to pre-spill conditions in a 3-4 year period. The lower rates and more subtle compositional changes deduced for aromatic components, suggest a stronger incidence of physical removal processes.

Oil spill in the Rio de la Plata estuary, Argentina: 1. Biogeochemical assessment of waters, sediments, soils and biota.

Aliphatic (ALI) and aromatic (ARO) hydrocarbon concentrations, composition and sources were evaluated in waters, sediments, soils and biota to assess the impact of approximately 1000 tons of oil spilled in Rio de la Plata coastal waters. Total ALI levels ranged from 0.4-262 microg/l in waters, 0.01-87 microg/g in sediments, 5-39 microg/g in bivalves, 12-323 microg/g in macrophytes to 948-5187 microg/g in soils. ARO varied from non-detected 10 microg/l, 0.01-1.3 mug/g, 1.0-16 microg/g, 0.5-6.9 microg/g to 22-67 microg/g, respectively. Offshore (1, 5, 15 km) waters and sediments were little affected and contained low background hydrocarbon levels reflecting an effective wind-driven transport of the slick to the coast. Six months after the spill, coastal waters, sediments, soils and biota still presented very high levels exceeding baseline concentrations by 1-3 orders of magnitude. UCM/resolved aliphatic ratio showed a clear trend of increasing decay: coastal waters (3.3) < macrophytes (6.7) < soils (9.4) < offshore sediments (13) < coastal sediments (17) < clams (52). All environmental compartments consistently indicated that the most impacted area was the central sector close to Magdalena city, specially low-energy stream embouchures and bays which acted as efficient oil traps. The evaluation of hydrocarbon composition by principal component analysis indicated the predominance of biogenic (algae, vascular plant cuticular waxes), background anthropic, pyrogenic and diagenetic hydrocarbons, offshore and in non-impacted coastal sites. In contrast, polluted stations presented petrogenic signatures characterized by the abundance of isoprenoids, low molecular weight n-alkanes and methylated aromatics in different stages of alteration. The petrogenic/biogenic ratio ( n-C23) and petrogenic/pyrogenic relationship (methylated/unsubstitued PAH) discriminated the samples according to the different degree of impact. The following paper present the results of the study of the progress of hydrocarbon disappearance in sediments and soils 13 and 42 months after the spill.

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.