Organic matter preservation through complexation with iron minerals in two basins of a dimictic boreal lake with contrasting deep water redox regimes.

The biogeochemical cycles of iron and organic carbon (OC) are closely interconnected in terrestrial and aquatic systems. In ocean waters, the concentration of reactive Fe is tightly controlled by soluble organic ligands. In soils, Fe stabilizes OC by forming aggregates that shield OC from degradation. In lake sediments however, the role of Fe in the preservation of OC has not been explored as extensively yet. We investigated Fe-OC interactions in sediment collected from Lake Tantaré, in which two basins are characterized by contrasting redox conditions. These contrasting redox conditions provide an opportunity to assess their importance in the formation of stable Fe-OC complexes. On average, 30.1 ± 6.4 % of total OC was liberated upon reductively dissolving reactive iron. The Fe-associated and the non-Fe-associated OC pools were characterized at the elemental (OC, TN), isotopic (δ13C, δ15N) and functional group (FTIR) levels. Large differences in OC:Fe and TN:Fe ratios between the two basins were found which were not linked to OM chemical composition but rather to differences in reactive iron concentrations stemming from the higher abundance of iron sulfides in the anoxic basin. Nevertheless, since the affinity of OM for iron sulfides is lower than that for iron hydroxides, using OC:Fe and TN:Fe ratios as a diagnostic tool for the type of OM-Fe interactions should be done with care in anoxic environment. Same caution should be considered for oxic sediments due to the variation of the proportion of iron hydroxides associated with OM from sample to sample.

Isotopic Evidence for Oil Sands Petroleum Coke in the Peace-Athabasca Delta.

The continued growth of mining and upgrading activities in Canada's Athabasca oil sands (AOS) region has led to concerns about emissions of contaminants such as polycyclic aromatic hydrocarbons (PAHs). Whereas a recent increase in PAH emissions has been demonstrated within around 50 km of the main center of surface mining and upgrading operations, the exact nature of the predominant source(s) and the geographical extent of the deposition are still under debate. Here, we report a century-long source apportionment of PAHs using dual (δ(2)H, δ(13)C) compound-specific isotope analysis on phenanthrene deposited in a lake from the Athabasca sector of the Peace-Athabasca Delta situated ∼150 km downstream (north) of the main center of mining operations. The isotopic signatures in the core were compared to those of the main potential sources in this region (i.e., unprocessed AOS bitumen, upgrader residual coke, forest fires, coal, gasoline and diesel soot). A significant concurrent increase (∼55.0‰) in δ(2)H and decrease (∼1.5‰) in δ(13)C of phenanthrene over the last three decades pointed to an increasingly greater component of petcoke-derived PAHs. This study is the first to quantify long-range (i.e., >100 km) transport of a previously under-considered anthropogenic PAH source in the AOS region.

Source Apportionment of Background PAHs in the Peace-Athabasca Delta (Alberta, Canada) Using Molecular Level Radiocarbon Analysis.

The downstream accumulation of polycyclic aromatic hydrocarbons (PAHs) in the Peace-Athabasca Delta (PAD), an ecologically important landscape, is a key issue of concern given the rapid development of the oil sands industry in Northern Alberta, Canada. In addition to PAHs derived from industrial activity (i.e., oil sands mining) within the Athabasca watershed, however, forest fires and erosion of fossil fuel deposits within both the Athabasca and Peace watersheds are two potentially important natural sources of PAHs delivered to the PAD. Consequently, evaluating the environmental impact of mining activities requires a quantitative understanding of natural, background PAHs. Here, we utilize molecular-level natural-abundance radiocarbon measurements on an amalgamated sediment record from a Peace River flood-susceptible oxbow lake in the northern Peace sector of the PAD to quantitatively discriminate sources of naturally occurring alkylated PAHs (fossil and modern biomass). A radiocarbon mass balance quantified a predominantly natural petrogenic source (93% petrogenic, 7% forest fire) for alkylated PAHs during the past ∼50 years. Additionally, a significant petrogenic component determined for retene, a compound usually considered a biomarker for softwood combustion, suggests that its use as a unique forest fire indicator may not be suitable in PAD sediments receiving Peace watershed-derived fluvial inputs.

Century-long source apportionment of PAHs in Athabasca oil sands region lakes using diagnostic ratios and compound-specific carbon isotope signatures.

Evaluating the impact that airborne contamination associated with Athabasca oil sands (AOS) mining operations has on the surrounding boreal forest ecosystem requires a rigorous approach to source discrimination. This study presents a century-long historical record of source apportionment of polycyclic aromatic hydrocarbons (PAHs) in dated sediments from two headwater lakes located approximately 40 and 55 km east from the main area of open pit mining activities. Concentrations of the 16 Environmental Protection Agency (EPA) priority PAHs in addition to retene, dibenzothiophene (DBT), and six alkylated groups were measured, and both PAH molecular diagnostic ratios and carbon isotopic signatures (δ(13)C) of individual PAHs were used to differentiate natural from anthropogenic inputs. Although concentrations of PAHs in these lakes were low and below the Canadian Council of Ministers of the Environment (CCME) guidelines, diagnostic ratios pointed to an increasingly larger input of petroleum-derived (i.e., petrogenic) PAHs over the past 30 years concomitant with δ(13)C values progressively shifting to the value of unprocessed AOS bitumen. This petrogenic source is attributed to the deposition of bitumen in dust particles associated with wind erosion from open pit mines.

Seasonal and decadal variations in lead sources to eastern North Atlantic mussels.

The concentration of Pb and its stable isotope composition were measured in 216 composite samples of 50 blue mussels (Mytilus edulis (M. edulis)) collected quarterly between 1985 and 2005 at three sites along the French Atlantic coast, one in the La Fresnaye Bay and the others in the Loire and Seine River estuaries. Depending on the sites and time periods, Pb concentrations were 5-66 times higher than the natural background value for the North Atlantic. Even for the samples with the lowest Pb concentrations, the isotopic signature of Pb is very different than that of the regional natural Pb, suggesting that most of the bioaccumulated Pb is anthropogenic in origin. Stable Pb isotope ratios measured in the mussels differ markedly from that of Pb emitted in Western Europe as a result of leaded gasoline combustion, which was still a dominant source of contaminant Pb to the atmosphere during most of our study period. The isotope composition of Pb in the mussels was instead more typical of that of the Pb released to the environment by wastewater treatment plants, municipal waste incinerators, and industries such as metal refineries and smelters. Continental runoff, rather than atmospheric deposition, is therefore identified as the leading transport pathway of Pb along the French Atlantic coast. From the strong seasonal variations in (206)Pb/(208)Pb ratios in the mussels from the Seine Estuary site we also conclude that the resuspension of contaminated sediments, triggered by high river runoff events, is a chief factor affecting the bioaccumulation of Pb in M. edulis . The value of this organism as a biomonitor of coastal contamination is thus further demonstrated.

Non-steady state modeling of arsenic diagenesis in lake sediments.

A one-dimensional reactive transport model describing the coupled biogeochemical cycling of As, C, O, Fe, and S was used to interpret an extensive geochemical sediment (As, Fe, S, (210)Pb, (137)Cs, C(org)) and pore water (As, Fe, SO(4)(2-), SigmaS(-II) and pH) data set collected in the perennially oxygenated basin of an oligotrophic lake. Historical variations in atmospheric deposition of As and SO(4)(2-) were explicitly included as upper boundary conditions in the model calculations. The results show that the depth profile of sediment-bound As reflects both the past changes in As deposition and the diagenetic redistribution of As among the Fe(III) oxyhydroxide and Fe(II) sulfide pools. The model-predicted benthic release of dissolved As to the water column peaks 26 years after the maximum anthropogenic As input to the lake, which occurred around 1950. Two major environmental forcings of the benthic recycling of As are the organic matter degradation in the sediment and the atmospheric sulfate deposition to the lake. More oxidizing conditions associated with lower organic matter degradation rates yield a greater abundance of Fe(III) oxyhydroxides in the topmost sediment, which act as a barrier to pore water As. Variations in sulfate availability have more complex effects on benthic As remobilization, since sulfide produced by sulfate reduction may enhance both the uptake of dissolved As through the precipitation of Fe(II) sulfides and the release of dissolved As through the reductive dissolution of Fe(III) oxyhydroxides.

Chronology of atmospheric deposition of arsenic inferred from reconstructed sedimentary records.

Vertical distributions of As, Fe, and organic C were determined in dated (210Pb and 137Cs) sediment cores obtained from two adjacent basins (one perennially oxic and the other seasonally anoxic) of an oligotrophic headwater lake where atmospheric deposition is the only input of anthropogenic As. Despite similar sources in the two basins, the As profiles in the sediments differed markedly. Differences include the following: (i) As concentrations increased sharply upward close to the sediment surface in the perennially oxic basin due to scavenging of upward diffusing As by Fe oxyhydroxides, whereas they decreased in the seasonally anoxic basin where As scavenging by Fe oxyhydroxides did not occur, and (ii) the magnitude and position of major subsurface As maxima differed between the two basins. We applied a one-dimensional transport-reaction equation to porewater As concentration profiles obtained at the two sites to estimate sedimentary As concentrations at the time of deposition as well as subsequent addition or removal of As at various sediment depths. By multiplying As concentrations at the time of deposition by sediment mass accumulation rates, we were able to estimate variations in As fluxes at the sediment surface over the last two centuries. These fluxes were then transformed into atmospheric As deposition fluxes by applying a correction for basin-specific processes using the ratio of expected from atmospheric deposition to measured unsupported 210Pb inventories at the sampling sites. The resulting chronological profiles of atmospheric fluxes of As deposition are similar in both basins, and are consistent with both the history of specific markers for coal combustion and direct historical measurements of As in dry and wet atmospheric deposition in rural areas of North America. We conclude that the history of As inputs can be reconstructed from As sedimentary records using appropriate corrections for diagenesis and basin-specific processes.

Historical perspective of industrial lead emissions to the atmosphere from a Canadian smelter.

Dated sediment cores from four remote Canadian Shield headwater lakes, where atmospheric deposition has been the only input of anthropogenic Pb, situated along a transect extending 300 km from a nonferrous metal smelter, were analyzed for both lead concentrations and isotopic composition; porewater samples collected at the same sites were analyzed for Pb and other geochemical variables. The depth distributions of stable Pb isotope ratios show the presence of several isotopically distinct Pb types since the preindustrial period. Lead from the smelter emissions had an isotopic signature (e.g., 206Pb/207Pb approximately 0.993) that was clearly distinct from those of Pb in aerosols collected at sites remotefrom point sources in Eastern Canada (e.g., 206Pb/207Pb usually approximately 1.15-1.20) and the United States (e.g., 206Pb/207Pb usually approximately 1.15-1.22), allowing the geographical area impacted by the smelter Pb emissions to be traced. On the basis of the sediment Pb isotopic composition, it is estimated that lead from the smelter accounts for 89%, 88%, and 5-34% of the total inventory of anthropogenic Pb deposited in the sediments of lakes located 10, 25, and 150 km from the smelter, respectively; but lead from this point source was not detected in sediments of a fourth lake that is 300 km from the smelter. We also estimate that the amount of smelter-derived Pb deposited within a distance of 150 km is equivalent to 5-10% of the amount released by leaded gasoline combustion in all of Canada. Sharp decreases in the recent Pb fluxes to lake sediments indicate that the measures taken to mitigate metal emissions from the smelter were effective.

Root-induced cycling of lead in salt marsh sediments.

A gold-mercury amalgam microelectrode was used in situ to measure Pb(II) by anodic stripping voltammetry and O2, Fe(II), Mn(II), and HS- by square-wave voltammetry in sediment pore water in a Haliomione portulacoides stand in a Tagus estuary salt marsh. The measurements were made in spring, summer, and fall, and were supplemented with analysis of Pb in solid phases and stable isotope analysis of Pb. In spring, the pore water was anoxic, Fe(II) reached concentrations as high as 1700 micromol/L, and Pb(II) was undetectable (<0.1 micromol/L). However, in summer, the pore water was oxic, Fe(II) was undetectable, and Pb(II) was present throughout the 20 cm deep root zone in concentrations reaching 6 micromol/L. In fall, low levels of O2 and Pb(II) were detected in the upper half of the root zone, and low concentrations of Fe(II) were detected in the lower half. The annual cycle of Pb is controlled by the growth and decay of roots. Roots deliver oxygen, which oxidizes lead-bearing solid phases and releases Pb(II) to the sediment pore water. Iron oxides, which form in the rhizosphere when Fe(II) is oxidized, are apparently not efficient sorbents for Pb(II) under the organic-rich conditions in this sediment. This allows Pb(II) to remain soluble and available for uptake by the roots. In fall and winter,when roots decay and the oxygen flux to the sediment stops, Pb is released from the decaying roots and returned to and precipitated in the anoxic sediment, likely as a sulfide. On an annual basis more than 20% of the total mass of Pb in the root zone cycles between root tissue and inorganic sediment phases. Depending on location, anthropogenic Pb constitutes 30-90% of total Pb in Tagus Estuary salt marshes.

Contribution of municipal effluents to metal fluxes in the St. Lawrence River.

The contribution of urban effluents to the total metal fluxes carried toward the sea by the St. Lawrence, a major world river, is 60% for Ag; 8-13% for Cu, Zn, Mo, Cd, and Bi; and less than 3% for all other measured elements (Al, V, Cr, Mn, Fe Co, Ni, As, Rb, Sr, Zr, Cs, Ba, W, Re, Pb, Th, U). This is inferred from measurements at the Montreal wastewater treatment plant. Except for Ag, municipal effluents do not weigh heavily on the St. Lawrence River metal budget, likely because of the physical-chemical primary treatment applied to most effluents. Compared to direct atmospheric deposition on the surface of the river, effluents would contribute half as much Pb and one-tenth as much Zn. In contrast, effluents deliver twice as much Cd and six times as much Cu as the atmosphere. Stable Pb isotope ratios (206Pb/207Pb, 206Pb/208Pb) in suspended particulate matter from the river indicate that the total Pb content in the river water is three times higher than the pristine level. The ratios of Cr, Ni, Cu, Zn, and Cd to Al in suspended particulate matter are high as compared to pre-industrial sediments, which suggeststhattrace elementfluxes are higher today. To decrease metal levels in the St. Lawrence River further will be a challenge since the sources of metals are not well-known.