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a b s t r a c tThe Magdalena River is the most important river in Colombia, supplying over 70% of the population of fish and drinking water, and it also is the main river transportation way of the country. It receives effluents from multiple sources along its course such as contaminant agricultural and industrial discharges. To evaluate the toxicity profile of Magdalena River sediments through endpoints such as survival, locomotion, and growth, wild type strains of Caenorhabditis elegans were exposed to aqueous extracts of the sediments. To identify changes in gene expression, GFP transgenic strains were used as reporter genes. Physiological and biochemical data were correlated with metal concentration in the sediments, identifying patterns of toxicity along the course of the river. Levels of some metals such as Cd, Cu, and Ni were above TEC and PEC limits. Effects in survival, growth, and locomotion were observed in most of the samples, and changes in gene expression were evident in the genes mtl-2, sod-4, and gst-1 using fluorescence expression. Cadmium and lead were the metals which were primarily associated with sediment toxicity, and the sampling sites with the highest increased expression of stress response genes were Barrancabermeja and Girardot. However, the diverse nature of toxic profiles observed in C. elegans in the study area showed the pervasiveness of different types of discharges throughout the river system.

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Temporal changes in the amounts of trace elements (As, Co, Cu, Mn, Ni, Pb, and Zn) and their correlations with temporal changes in charcoal abundance in age-dated sediments collected from Lake Thompson in Patagonia, Chile, attest to the substantial pyrogenic remobilization of contaminants that occurred in Patagonia during the mid-1900s. This remobilization was concurrent with the extensive slash and burn period in the region during that period. The changes in concentrations of Co, Cu, and Ni in relation to charcoal abundance in the lacustrine sediments over time were small compared to those of As, Mn, Pb, and Zn. However, the relatively low enrichment factors of all those trace elements, normalized to Fe, indicate that they were predominantly derived from local, natural sources impacted by fires rather than industrial sources. The primarily local source of Pb in the sediments was corroborated by the temporal consistency of its isotopic ratios ( 206 Pb/ 207 Pb: 208 Pb/ 206 Pb), which were similar to previously reported values for natural lead in Central and Southern Chile. However, the pyrogenic remobilization of both natural and industrial trace elements by forest fires in Chile and elsewhere is expected to rise as a consequence of climate change, which is projected to increase both the frequency and intensity of forest fires on a global scale.

The amounts of labile trace metals: [Co] (3 to 11 µg g−1), [Cu] (15 to 69 µg g−1), [Ni] (6 to 15 µg g−1), [Pb] (7 to 42 µg g−1), and [Zn] (65 to 500 µg g−1) in ash collected from the 2012 Williams Fire in Los Angeles, California attest to the role of fires in remobilizing industrial metals deposited in forests. These remobilized trace metals may be dispersed by winds, increasing human exposures, and they may be deposited in water bodies, increasing exposures in aquatic ecosystems. Correlations between the concentrations of these trace metals, normalized to Fe, in ash from the fire suggest that Co, Cu, and Ni in most of those samples were predominantly from natural sources, whereas Pb and Zn were enriched in some ash samples. The predominantly anthropogenic source of excess Pb in the ash was further demonstrated by its isotopic ratios (208Pb/207Pb: 206Pb/207Pb) that fell between those of natural Pb and leaded gasoline sold in California during the previous century. These analyses substantiate current human and environmental health concerns with the pyrogenic remobilization of toxic metals, which are compounded by projections of increases in the intensity and frequency of wildfires associated with climate change.

a b s t r a c tThis study identifies natural and industrial lead remobilized in ash deposits from three bushfires in relatively pristine areas of Australia in 2011 using lead isotopic compositions ( Pb). Lead concentrations in the ash ranged from 1 to 36 mg/kg, bracketing the range of lead (4e23 mg/kg) in surface soils (0e2 cm), subsurface (40e50 cm) soils and rocks. The lead isotopic compositions of ash and surface soil samples were compared to subsurface soils and local bedrock samples. The data show that many of the ash and surface soil lead isotopic compositions were a mixture of natural lead and legacy industrial lead depositions (such as leaded petrol combustion). However, some of the ash samples at each of the sites had lead isotopic compositions that did not fit a simple two end-member mixing model, indicating other, unidentified sources.

Freshwater resources on low-lying atoll islands are highly vulnerable to climate change and sea-level rise. In addition to rainwater catchment, groundwater in the freshwater lens is a critically important water resource on many atoll islands, especially during drought. Although many atolls have high annual rainfall rates, dense natural vegetation and high evapotranspiration rates can limit recharge to the freshwater lens. Here we evaluate the effects of land-use/land-cover change and managed aquifer recharge on the hydrogeochemistry and supply of groundwater on Roi-Namur Island, Republic of the Marshall Islands. Roi-Namur is an artificially conjoined island that has similar hydrogeology on the Roi and Namur lobes, but has contrasting land-use/land-cover and managed aquifer recharge only on Roi. Vegetation removal and managed aquifer recharge operations have resulted in an estimated 8.6 x 10 5 m 3 of potable groundwater in the freshwater lens on Roi, compared to only 1.6 x 10 4 m 3 on Namur. We use groundwater samples from a suite of 33 vertically nested monitoring wells, statistical testing, and geochemical modeling using PHREEQC to show that the differences in land-use/land-cover and managed aquifer recharge on Roi and Namur have a statistically significant effect on several groundwater-quality parameters and the controlling geochemical processes. Results also indicate a seven-fold reduction in the dissolution of carbonate rock in the freshwater lens and overlying vadose zone of Roi compared to Namur. Mixing of seawater and the freshwater lens is a more dominant hydrogeochemical process on Roi because of the greater recharge and flushing of the aquifer with freshwater as compared to Namur. In contrast, equilibrium processes and dissolution-precipitation non-equilibrium reactions are more dominant on Namur because of the longer residence times relative to the rate of geochemical reactions. Findings from Roi-Namur Island support selective land-use/land-cover change and managed aquifer recharge as a promising management approach for communities on other low-lying 1

Editorial handling by M. Kersten a b s t r a c tLead isotopic and trace element records of two contrasting sediment cores were examined to reconstruct historic, industrial contaminant inputs to Lake Tanganyika, Africa. Observed fluxes of Co, Cu, Mn, Ni, Pb, and Zn in age-dated sediments collected from the lake varied both spatially and temporally over the past two to four centuries. The fluxes of trace elements were lower (up to 10-fold) at a mid-lake site (MC1) than at a nearshore site (LT-98-58), which is directly downstream from the Kahama and Nyasanga River watersheds and adjacent to the relatively pristine Gombe Stream National Park. Trace element fluxes at that nearshore site did not measurably change over the last two centuries (1815-1998), while the distal, mid-lake site exhibited substantial changes in the fluxes of trace elements -likely caused by changes in land use -over that period. For example, the flux of Pb increased by $300% from 1871 to 1991. That apparent accelerated weathering and detrital mobilization of lithogenic trace elements was further evidenced by (i) positive correlations (r = 0.77-0.99, p < 0.05) between the fluxes of Co, Cu, Mn, Ni, Pb, and Zn and those of iron (Fe) at both sites, (ii) positive correlations (r = 0.82-0.98, p < 0.01, n = 9) between the fluxes of elements (Al, Co, Cu, Fe, Mn, Ni, Pb, and Zn) and the mass accumulation rates at the offshore site, (iii) the low enrichment factors (EF < 5) of those trace elements, and (iv) the temporal consistencies of the isotopic composition of Pb in the sediment. These measurements indicate that accelerated weathering, rather than industrialization, accounts for most of the increases in trace element fluxes to Lake Tanganyika in spite of the development of mining and smelting operations within the lake's watershed over the past century. The data also indicate that the mid-lake site is a much more sensitive and useful recorder of environmental changes than the nearshore site. Furthermore, the lead isotopic compositions of sediment at the sites differed spatially, indicating that the Pb (and other trace elements by association) originated from different natural sources at the two locations.