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.     

Environmental and Biological Assessment of Exposure to Benzene in Petroleum Workers

Occupational exposure to benzene was measured in two gasoline marketing terminals and five major refineries in Singapore. A total of 280 workers were monitored over two years. This assessment was carried out with two primary objectives: (1) To find out the extent of occupational exposure to benzene in the petroleum industry in Singapore, (2) To identify suitable biomarkers for monitoring of low levels of benzene exposure. The exposure was measured in five different categories of petroleum and petrochemical workers, i.e., truck drivers, despatch assistant, process operators, oil movements operators and laboratory technicians. The results revealed wide variations in exposure, from 0.01 to 13.6 ppm for personal time weighted average (TWA) exposure over the whole workshift. The exposure of truck drivers appeared to be the highest, with geometric mean (GM) of 1.98 ppm (ranged from 0.25 to 13.6 ppm). The average benzene exposure for process operators was relative low with a GM of 0.04 ppm. Lowest benzene exposure was found in the laboratory technicians, with a GM of 0.02 ppm. As cigarette smoking is known to affect metabolism of benzene, data analyses on the relationships with environmental exposure were conducted only on the 190 nonsmokers. The results showed that urinary trans, trans-muconic acid (ttMA), unmetabolized benzene in urine (UBZ) and benzene in blood (BBZ) were better biomarkers for low level benzene exposure as compared to urinary phenolic metabolites in urine, such as hydroquinone, phenol and catechol.     

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.     

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: 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.