Integrating empirically dissolved organic matter quality for WHAM VI using the DOM optical properties: a case study of Cu-Al-DOM interactions.

Metal speciation is important for understanding the toxicity of metals in aquatic systems, and can be predicted for mixtures of metals in presence of dissolved organic matter (DOM) with thermodynamic models such as WHAM VI. The influence of the DOM source (quality) has been demonstrated, but is presently neglected in predicting Cu activity (WHAM VI). Here we determined the effect of aluminum (Al) competition on copper (Cu) complexation for four different DOMs, from a high-colored DOM (more humic) to a low-colored DOM (less humic). In presence of Al, free Cu activities (defined as free ion activity) increased, consistent with competition between Cu and Al for the same binding sites on all DOM. The apparent competition decreased with increasing DOM color. Equilibrium modeling of Cu speciation with WHAM VI explained 49% of the variance in measured Cu activity. When modified to integrate DOM quality using a new empirical coefficient F related to DOM optical properties, Cu activities predicted from WHAM VI were significantly improved to about 80% of the observed variance explained. The effects of Al on Cu activity were well predicted by WHAM VI. Subsequently, we compared the relative effects of DOM concentration, DOM quality, and Al competition with other determinants of Cu activity represented in legislation and scientific literature (pH and hardness), and qualitatively ranked them by their influence on Cu activity for normal ranges encountered in fresh waters using WHAM VI. Our experimental results indicate that DOM quality is an important variable that should be included in predictive models of ion speciation (WHAM VI) and eco-toxicological models such as the biotic ligand model (BLM).

Isotopic fingerprints of anthropogenic molybdenum in lake sediments.

We measured the molybdenum isotope compositions (δ(98)Mo) of well-dated sediment cores from two lakes in eastern Canada in an effort to distinguish between natural and anthropogenic contributions to these freshwater aquatic systems. Previously, Chappaz et al. (1) ascribed pronounced 20th-century Mo concentration enrichments in these lakes to anthropogenic inputs. δ(98)Mo values in the deeper sediments (reflecting predominantly natural Mo sources) differ dramatically between the two lakes: -0.32 ± 0.17‰ for oxic Lake Tantare and +0.64 ± 0.09‰ for anoxic Lake Vose. Sediment layers previously identified as enriched in anthropogenic Mo, however, reveal significant δ(98)Mo shifts of ± 0.3‰, resulting in isotopically heavier values of +0.05 ± 0.18‰ in Lake Tantare and lighter values of +0.31 ± 0.03‰ in Lake Vose. We argue that anthropogenic Mo modifies the isotopic composition of the recent sediments, and we determine δ(98)Mo(anthropogenic) values of 0.1 ± 0.1‰ (Lake Vose) and 0.2 ± 0.2‰ (Lake Tantare). These calculated inputs are consistent with the δ(98)Mo of molybdenite (MoS(2)) likely delivered to the lakes via smelting of porphyry copper deposits (Lake Vose) or through combustion of coal and oil also containing Mo (Lake Tantare). Our results confirm the utility of Mo isotopes as a promising fingerprint of human impacts and perhaps the specific sources of contamination. Importantly, the magnitudes of the anthropogenic inputs are large enough, relative to the natural Mo cycles in each lake, to have an impact on the microbiological communities.

Evaluation of 1,4-dioxane attenuation processes at the Gelman Site, Michigan, USA.

1,4-Dioxane released at the Gelman Site in Washtenaw County, Michigan, produced a series of contaminant plumes migrating up to 3 km through a heterogenous glacial aquifer system. An analysis of 1,4-dioxane concentrations in the Eastern Area of the Gelman Site between 2011 and 2017 documented a mass balance deficit of 2200 kg in excess of 2100 kg of 1,4-dioxane removed via remediation. Five mechanisms were evaluated to account for the mass deficiency: sorption, matrix diffusion, biodegradation, surface discharge, and bypass of the existing monitoring well network. The mass of 1,4-dioxane sorbed to aquifer and aquitard materials and the mass of 1,4-dioxane diffused into low permeability zones were estimated. However, decreasing aqueous concentrations across most of the contaminated area between 2011 and 2017 are expected to induce desorption and back diffusion during this period. Surface water discharge to a storm drain in the downgradient portion of the site was analyzed using concentration measurements and stream gage data. Results suggest that 1,4-dioxane mass entering the drain during the period between 2011 and 2017 was insufficient to account for the mass deficiency. Although available geochemical measurements indicate predominantly anaerobic aquifer conditions at the Gelman Site, biodegradation of 1,4-dioxane was estimated using first order decay rate constants from other sites where conditions may be more favorable. Results suggest that biodegradation could explain some but not all of the missing mass. Bypass of the downgradient monitoring well network is the most parsimonious explanation for the 1,4-dioxane mass deficit. This conclusion is supported by documented flow path complexity through the aquifer system and the sparse density of monitoring wells in the downgradient Eastern Area. These findings underscore the importance of characterizing aquifer heterogeneity when modeling and remediating persistent groundwater contaminants such as 1,4-dioxane.

Evidence for the onset of mining activities during the 13th century in Poland using lead isotopes from lake sediment cores.

Efforts to study how human activities have influenced the environment since the end of the Roman period to present day are lacking for North Central Europe. Here, we present new lead (Pb) isotope data determined from two sediment cores collected from ancient lakes spanning the last 1500 years, located in the Kuyavian-Pomeranian Voivodeship, Poland. Study sites at Radzyn Chelminski and Rywald were used to differentiate Pb sources. Radzyn Chelminski is located in the vicinity of a late Medieval Teutonic Order castle and town, while Rywald is situated within a relatively pristine area until the 19th century when it became used for agricultural purpose. Core samples were analyzed for Pb concentration and isotopes (206Pb, 207Pb, 208Pb). Bayesian modeling was used to isolate the anthropogenic signal at each site over time. For both sites, Pb enrichment factors relative to titanium (Ti) and upper continental crust values range from 13 to 159. Lead isotopic ratios range from background, pre-anthropogenic local values (206Pb/207Pb = 1.31 ±â€¯0.03‰, 208Pb/206Pb = 1.97 ±â€¯0.04‰) to anthropogenic values (SW Poland coal, ore, slag 206Pb/207Pb = 1.17 ±â€¯0.01‰, 208Pb/206Pb = 2.09 ±â€¯0.01‰). Modeled anthropogenic contribution varies greatly over time, ranging from 14 to 100%. At Radzyn Chelminski, modeled anthropogenic Pb contribution and measured Pb concentration follow similar trends. However, at Rywald, from around A.D.1000 to 1400 CE these profiles diverge significantly. Our new insights highlight different sources of Pb from the 12th century to present day: (1) short range agricultural activities from the town, and (2) long range mining activities. Additionally, prior to the 12th century, our data suggest continental anthropogenic activity possibly favored by a warmer climate.

Biogeochemical controls on the speciation and aquatic toxicity of vanadium and other metals in sediments from a river reservoir.

Effects of hydrologic variability on reservoir biogeochemistry are relatively unknown, particularly for less studied metals like vanadium (V). Further, few studies have investigated the fate and effects of sediment-associated V to aquatic organisms in hydrologically variable systems. Our primary objective was to assess effects of hydrologic manipulation on speciation and toxicity of V (range: 635 to 1620mgkg-1) and other metals to Hyalella azteca and Daphnia magna. Sediments were collected from a reservoir located in a former mining area and microcosm experiments were conducted to emulate 7-day drying and inundation periods. Despite high sediment concentrations, V bioavailability remained low with no significant effects to organism survival, growth, or reproduction. The lack of V toxicity was attributed to reduced speciation (III, IV), non-labile complexation, and sorption to Al/Fe/Mn-oxyhydroxides. Zinc (Zn) increased in surface and porewater with inundation, for some sediments exceeding the U.S. EPA threshold for chronic toxicity. While no effects of Zn to organism survival or growth were observed, Zn body concentrations were negatively correlated with H. azteca growth. Results from this study indicate that V bioavailability and environmental risk is dependent on V-speciation, and V is less influenced by hydrologic variability than more labile metals such as Zn.