Geochemical and hydrodynamic controls on arsenic and trace metal cycling in a seasonally stratified US sub-tropical reservoir

Abstract The phase distribution of trace metals and oxyanions, including U and As, in 2 surface water bodies was investigated within a South Texas watershed hosting a high density of surface U mine pits and tailings. The objectives of the study were to evaluate the environmental legacy of U mining, with particular emphasis on the spatial and temporal variability of water quality in Lake Corpus Christi, a downstream reservoir that serves as the major water resource to a population of $350,000 people in the region. Lyssy Pond, a livestock pond bordered by U mine tailings, was used as a model casestudy site to evaluate the cycling of U mine-derived oxyanions under changing redox conditions. Although the pond showed seasonal thermal and chemical stratification, geochemical cycling of metals was limited to Co and Pb, which was correlated with redox cycling of Mn mineral phases, and U, which suggested reductive precipitation in the pond's hypolimnion. Uranium levels, however, were too low to support strong inputs from the tailings into the water column of the pond. The strong relationships observed between particulate Cr, Cs, V, and Fe suggest that these metals are associated with a stable particulate phase (probably allochthonous alumino-silicates) enriched in unreactive Fe. This observation is supported by a parallel relationship in sediments collected across a broad range of sediment depositional processes (and histories) in the basin. Arsenic, though selectively enriched in the pond's water column, was dominated by dissolved species throughout the depth of the profile and showed no sign of geochemical cycling or interaction with Fe-rich particles. Arsenic (and other oxyanions) in the water columns of Lake Corpus Christi and Lyssy pond were not affected by the abundant presence of Fe-rich particles but instead behaved conservatively. No evidence was found of anthropogenic impacts of U mines beyond the purely local scale. Arsenic's presence within the Nueces drainage basin is related to interactions between surface and groundwaters with U-and As-rich geological formations rather than largescale transport of contaminants downstream of the U mine pits and tailings. A quantitative mass balance model, constructed using monthly hydrological data for the reservoir, provides quantitative evidence of seasonal evaporative concentration of As in surface waters demonstrating the predominance of hydrodynamic over geochemical constraints, on the cycling of this element

Lignin biomarkers as tracers of mercury sources in lakes water column

This study presents the role of specific terrigenous organic compounds as important vectors of mercury (Hg) transported from watersheds to lakes of the Canadian boreal forest. In order to differentiate the autochthonous from the allochthonous organic matter (OM), lignin derived biomarker signatures [Lambda, S/V, C/V, P/(V ? S), 3,5-Bd/V and (Ad/Al)v] were used. Since lignin is exclusively produced by terrigenous plants, this approach can give a non equivocal picture of the watershed inputs to the lakes. Moreover, it allows a characterization of the source of OM and its state of degradation. The water column of six lakes from the Canadian Shield was sampled monthly between June and September 2005. Lake total dissolved Hg concentrations and Lambda were positively correlated, meaning that Hg and ligneous inputs are linked (dissolved OM r2 = 0.62, p\0.0001; particulate OM r2 = 0.76, p\0.0001). Ratios of P/(V ? S) and 3,5-Bd/V from both dissolved OM and particulate OM of the water column suggest an inverse relationship between the progressive state of pedogenesis and maturation of the OM in soil before entering the lake, and the Hg concentrations in the water column. No relation was found between Hg levels in the lakes and the watershed flora composition—angiosperm versus gymnosperm or woody versus non-woody compounds. This study has significant implications for watershed management of ecosystems since limiting fresh terrestrial OM inputs should reduce Hg inputs to the aquatic systems. This is particularly the case for largescale land-use impacts, such as deforestation, agriculture and urbanization, associated to large quantities of soil OM being transferred to aquatic systems

Dissolved organic matter sources in large Arctic rivers

The biomarker composition of dissolved organic carbon (DOC) of the six largest Arctic rivers was studied between 2003 and 2007 as part of the PARTNERS Project. Samples were collected over seasonal cycles relatively close to the river mouths. Here we report the lignin phenol and p-hydroxybenzene composition of Arctic river DOC in order to identify major sources of carbon. Arctic river DOC represents an important carbon conduit linking the large pools of organic carbon in the Arctic/Subarctic watersheds to the Arctic Ocean. Most of the annual lignin discharge (>75%) occurs during the two month of spring freshet with extremely high lignin concentrations and a lignin phenol composition indicative of fresh vegetation from boreal forests. The three large Siberian rivers, Lena, Yenisei, and Ob, which also have the highest proportion of forests within their watersheds, contribute about 90% of the total lignin discharge to the Arctic Ocean. The composition of river DOC is also characterized by elevated levels of p-hydroxybenzenes, particularly during the low flow season, which indicates a larger contribution from mosses and peat bogs. The lignin composition was strongly related to the average 14C-age of DOC supporting the abundance of young, boreal-vegetation-derived leachates during spring flood, and older, soil-, peat-, and wetland-derived DOC during groundwater dominated low flow conditions, particularly in the Ob and Yukon Rivers. We observed significant differences in DOC concentration and composition between the rivers over the seasonal cycles with the Mackenzie River being the most unique, the Lena River being similar to the Yenisei, and the Yukon being most similar to the Ob. The observed relationship between the lignin phenol composition and watershed characteristics suggests that DOC discharge from these rivers could increase in a warmer climate under otherwise undisturbed conditions

Combined dynamics of mercury and terrigenous organic matter following impoundment of Churchill Falls Hydroelectric Reservoir, Labrador

Sediments from two recently (40 years) flooded lakes (Gabbro lake and Sandgirt lake) and an unflooded lake (Atikonak lake) were sampled to investigate the effects of reservoir impoundment on mercury (Hg) and terrigenous organic matter (TOM) loading in the Churchill Falls Hydroelectric complex in Labrador, Canada. Lignin biomarkers in TOM, which exclusively derive from terrestrial vegetation, were used as biomarkers for the presence and source origin of TOM—and for Hg due to their close associations—in sediments. In the two flooded Gabbro and Sandgirt lakes, we observed drastic increases in total mercury concentrations, T-[Hg], in sediments, which temporally coincided with the time of reservoir impoundment as assessed by 210Pb age dating. In the natural Atikonak lake sediments, on the other hand, T-[Hg] showed no such step-increase but gradually and slowly increased until present. T-[Hg] increases in lake sediments after flooding were also associated with a change in the nature of TOM: biomarker signatures changed to typical signatures of TOM from vegetated terrestrial landscape surrounding the lakes, and indicate a change to TOM that was much less degraded and typical of forest soil organic horizons. We conclude that T-[Hg] increase in the sediments of the two flooded reservoirs was the result of flooding of surrounding forests, whereby mainly surface organic horizons and upper soil horizons were prone to erosion and subsequent re-sedimentation in the reservoirs. The fact that T-[Hg] was still enriched 40 years after reservoir impoundment indicates prolonged response time of lake Hg and sediment loadings after reservoir impoundments

Deforestation modifying terrestrial organic transport in the Rio Tapajós, Brazilian Amazon. Organic Geochemistry 32(12

Abstract The concentration and biomarker compositions of sedimentary organic matter (OM) as well as fine and coarse suspended particles were analysed to identify the impact of deforestation on the transport of terrigenous organic matter (OM) in the Rio Tapajo´s, a major tributary to the Amazon. Substantial shifts in the concentration and composition of recently deposited sedimentary OM suggest that intensive deforestation over the last few decades has considerably modified the natural inputs of sedimentary materials to the aquatic ecosystems by disrupting the terrigenous fluxes of humus and soil materials from the drainage basin. The observed compositional changes of bulk OM and land derived biomarkers (e.g. lignin) in recent sediments illustrate a sedimentary enrichment in OM from soil horizons that, under normal forest cover, tend to be retained in the drainage basin. On average, the recently accumulated OM is nitrogenrich ((C/N)a=12-15) and more highly degraded ((Ac/Al)v=0.4-0.6 and DHBA/V=0.15-0.20) than deep materials ((C/N)a=20-30, (Ac/Al)v=0.25-0.4, and DHBA/V=0.05-0.10), showing that this recently accumulated material is more humified than original inputs to the aquatic system, and consistent with increased exportation of fine eroded mineral and organic particles from surface soils along river banks. The present study illustrates the relevance of using OM oxidation products in sediment profiles to evaluate deforestation impacts on aquatic ecosystems and to characterize the nature of eroded soil materials, complementing studies on mineral/metal cycling.

Decomposition dynamics of six salt marsh halophytes as determined by cupric oxide oxidation and direct temperature- resolved mass spectrometry

This paper presents the results of a comparative study on the aerobic decomposition of six salt marsh plant species over a period of 2 yr. In addition to ash-free dry weight (AFDW) determination and elemental analysis (C and N), two analytic methods have been applied to obtain insight into the decomposition dynamics of lignin in the various plant tissues. The analytic methods an (1)cupric oxide (CuO) oxidation followed by gas chromatography-mass spectrometry (GC-MS) and(2) direct temperature-resolved mass spectrometry (DT-MS). AFDW losses could generally be well described by double exponential relations with time. Carbon-to-nitrogen ratios increased during the initial stages of decomposition and decreased again afterward. For five of the six plant species, a correlation between initial lignin content and AFDW loss was observed. Decay dynamics of lignin denoted a rapid relative increase during the first weeks of field exposure, followed by stabilizing contents over the next 2 yr. CuO oxidation data indicate the establishment of a stable "lignin endmember" within 1-2 months. DT-MS data, on the contrary, showed continuous modification of the lignin polymer throughout the duration of the experiment. Evidence was found for the incorporation of (presumably) microbial N-acetylglucosamine in the complex residue produced upon decomposition. Combination of CuO oxidation and DT-MS data suggested that lignin degradation products became attached to the original macromolecular material and could still be identified as lignin-derived material. The data support a humification mechanism via condensation of small degradation products instead of the selective preservation of certain biomacromolecules (like lignin). [KEYWORDS: Grass spartina-alterniflora; dissolved organic-matter; milled wood lignin; white-rot fungi; discriminant-analysis; analytical pyrolysis; early diagenesis; curie-point; chemical characterization; early coalification]