Air concentrations of PCBs and metals at Crab Orchard National Wildlife Refuge /

"May 1995"--Cover.

Dimethylsulphide and halocarbon concentrations taken from 10m integrated samples during the 2012 KOSMOS Finland Mesocosm experiment

The Baltic Sea is a unique environment as the largest body of brackish water in the world. Acidification of the surface oceans due to absorption of anthropogenic CO2 emissions is an additional stressor facing the pelagic community of the already challenging Baltic Sea. To investigate its impact on trace gas biogeochemistry, a large-scale mesocosm experiment was performed off Tvärminne Research Station, Finland in summer 2012. During the second half of the experiment, dimethylsulphide (DMS) concentrations in the highest fCO2 mesocosms (1075-1333 µatm) were 34 % lower than at ambient CO2 (350 µatm). However the net production (as measured by concentration change) of seven halocarbons analysed was not significantly affected by even the highest CO2 levels after 5 weeks exposure. Methyl iodide (CH3I) and diiodomethane (CH2I2) showed 15 % and 57 % increases in mean mesocosm concentration (3.8 ± 0.6 pmol L-1 increasing to 4.3 ± 0.4 pmol L-1 and 87.4 ± 14.9 pmol L-1 increasing to 134.4 ± 24.1 pmol L-1 respectively) during Phase II of the experiment, which were unrelated to CO2 and corresponded to 30 % lower Chl-? concentrations compared to Phase I. No other iodocarbons increased or showed a peak, with mean chloroiodomethane (CH2ClI) concentrations measured at 5.3 (± 0.9) pmol L-1 and iodoethane (C2H5I) at 0.5 (± 0.1) pmol L-1. Of the concentrations of bromoform (CHBr3; mean 88.1 ± 13.2 pmol L-1), dibromomethane (CH2Br2; mean 5.3 ± 0.8 pmol L-1) and dibromochloromethane (CHBr2Cl, mean 3.0 ± 0.5 pmol L-1), only CH2Br2 showed a decrease of 17 % between Phases I and II, with CHBr3 and CHBr2Cl showing similar mean concentrations in both Phases. Outside the mesocosms, an upwelling event was responsible for bringing colder, high CO2, low pH water to the surface starting on day t16 of the experiment; this variable CO2 system with frequent upwelling events implies the community of the Baltic Sea is acclimated to regular significant declines in pH caused by up to 800 µatm fCO2. After this upwelling, DMS concentrations declined, but halocarbon concentrations remained similar or increased compared to measurements prior to the change in conditions. Based on our findings, with future acidification of Baltic Sea waters, biogenic halocarbon emissions are likely to remain at similar values to today, however emissions of biogenic sulphur could significantly decrease from this region.

Geogenic sources and sinks of trace metals in the Larsemann Hills, East Antarctica: Natural processes and human impact

To evaluate the extent of human impact on a pristine Antarctic environment, natural baseline levels of trace metals have been established in the basement rocks of the Larsemann Hills, East Antarctica. From a mineralogical and geochemical point of view the Larsemann Hills basement is relatively homogeneous, and contains high levels of Pb, Th and U. These may become soluble during the relatively mild Antarctic summer and be transported to lake waters by surface and subsurface melt water. Melt waters may also be locally enriched in V, Cr, Co, Ni, Zn and Sri derived from weathering of metabasite pods. With a few notable exceptions, the trace metal concentrations measured in the Larsemann Hills lake waters can be entirely accounted for by natural processes such as sea spray and surface melt water input. Thus, the amount of trace metals released by weathering of basement lithologies and dispersed into the Larsemann Hills environment, and presumably in similar Antarctic environments, is, in general, not negligible, and may locally be substantial. The Larsemann Hills sediments are coarse-grained and contain minute amounts of clay-size particles, although human activities have contributed to the generation of fine-grained material at the most impacted sites. Irrespective of their origin, these small amounts of fine-grained clastic sediments have a relatively small surface area and charge, and are not as effective metal sinks as the abundant, thick cyanobacterial algal mats that cover the lake floors. Thus, the concentration of trace metals in the Larsemann Hills lake waters is regulated by biological activity and thawing-freezing cycles, rather than by the type and amount of clastic sediment supply. (c) 2005 Elsevier Ltd. All rights reserved.

Direct quantification of rare earth element concentrations in natural waters by ICP-MS

A direct quadrupole ICP-MS technique has been developed for the analysis of the rare earth elements and yttrium in natural waters. The method has been validated by comparison of the results obtained for the river water reference material SLRS-4 with literature values. The detection limit of the technique was investigated by analysis of serial dilutions of SLRS-4 and revealed that single elements can be quantified at single-digit fg/g concentrations. A coherent normalised rare earth pattern was retained at concentrations two orders of magnitude below natural concentrations for SLRS-4, demonstrating the excellent inter-element accuracy and precision of the method. The technique was applied to the analysis of a diluted mid-salinity estuarine sample, which also displayed a coherent normalised rare earth element pattern, yielding the expected distinctive marine characteristics. (c) 2006 Published by Elsevier Ltd.

Trace metals in Antarctic ecosystems: Results from the Larsemann Hills, East Antarctica

Sediments, mosses and algae, collected from lake catchments of the Larsemann Hills, East Antarctica, were analysed to establish baseline levels of trace metals (Ag, As, Cd, Co, Cr, Cu, Ni, Sb, Pb, Se, V and Zn), and to quantify the extent of trace metal pollution in the area. Both impacted and non-impacted sites were included in the study. Four different leaching solutions (1 M MgCl2, 1 M CH3COONH4, 1 M NH4NO3, and 0.3 N HCl) were tested on the fine fraction (< 63 mu m) of the sediments to extract the mobile fraction of trace metals derived from human impact and from weathering of basement lithologies. Results of these tests indicate that dilute HCl partly dissolves primary minerals present in the sediment, thus leading to an overestimate of the mobile trace metal fraction. Concentrations of trace metals released using the other 3 procedures indicate negligible levels of anthropogenic contribution to the trace metal budget. Data derived from this study and a thorough characterisation of the site allowed the authors to define natural baseline levels of trace metals in sediments, mosses and algae, and their spatial variability across the area. The results show that, with a few notable exceptions, human activities at the research stations have contributed negligible levels (lower than natural variability) of trace metals to the Larsemann Hills ecosystem. This study further demonstrates that anthropogenic sources of trace metals can be correctly identified and quantified only if natural baselines, their variability, and processes controlling the mobility of trace metals in the ecosystem, have been fully characterised. (c) 2006 Elsevier Ltd. All rights reserved.

Assessment of silicone polymer composites for the trace extraction of herbicides : a tool for environmental forensics

Passive samplers are not only a versatile tool to integrate environmental concentrations of pollutants, but also to avoid the use of live sentinel organisms for environmental monitoring. This study introduced the use of magnetic silicone polymer composites (Fe-PDMS) as passive sampling media to pre-concentrate a wide range of analytes from environmental settings. The composite samplers were assessed for their accumulation properties by performing lab experiments with two model herbicides (Atrazine and Irgarol 1051) and evaluated for their uptake properties from environmental settings (waters and sediments). The Fe-PDMS composites showed good accumulation of herbicides and pesticides from both freshwater and saltwater settings and the accumulation mechanism was positively correlated with the log Kow value of individual analytes. Results from the studies show that these composites could be easily used for a wide number of applications such as monitoring, cleanup, and/or bioaccumulation modeling, and as a non-intrusive and nondestructive monitoring tool for environmental forensic purposes.

Concentrations and d13C compositions of n-alkanes, n-alcohols, n-alkanoic acids in a 34-month time series of suspended sediments from the outflow of the Congo River

The concentrations, distributions, and stable carbon isotopes (d13C) of plant waxes carried by fluvial suspended sediments contain valuable information about terrestrial ecosystem characteristics. To properly interpret past changes recorded in sedimentary archives it is crucial to understand the sources and variability of exported plant waxes in modern systems on seasonal to inter-annual timescales. To determine such variability, we present concentrations and d13C compositions of three compound classes (n-alkanes, n-alcohols, n-alkanoic acids) in a 34-month time series of suspended sediments from the outflow of the Congo River. We show that exported plant-dominated n-alkanes (C25-C35) represent a mixture of C3 and C4 end members, each with distinct molecular distributions, as evidenced by an 8.1 ± 0.7 per mil (±1Sigma standard deviation) spread in d13C values across chain-lengths, and weak correlations between individual homologue concentrations (r = 0.52-0.94). In contrast, plant-dominated n-alcohols (C26-C36) and n-alkanoic acids (C26-C36) exhibit stronger positive correlations (r = 0.70-0.99) between homologue concentrations and depleted d13C values (individual homologues average <= -31.3 per mil and -30.8 per mil, respectively), with lower d13C variability across chain-lengths (2.6 ± 0.6 per mil and 2.0 ± 1.1 per mil, respectively). All individual plant-wax lipids show little temporal d13C variability throughout the time-series (1 Sigma <= 0.9 per mil), indicating that their stable carbon isotopes are not a sensitive tracer for temporal changes in plant-wax source in the Congo basin on seasonal to inter-annual timescales. Carbon-normalized concentrations and relative abundances of n-alcohols (19-58% of total plant-wax lipids) and n-alkanoic acids (26-76%) respond rapidly to seasonal changes in runoff, indicating that they are mostly derived from a recently entrained local source. In contrast, a lack of correlation with discharge and low, stable relative abundances (5-16%) indicate that n-alkanes better represent a catchment-integrated signal with minimal response to discharge seasonality. Comparison to published data on other large watersheds indicates that this phenomenon is not limited to the Congo River, and that analysis of multiple plant-wax lipid classes and chain lengths can be used to better resolve local vs. distal ecosystem structure in river catchments.

Termination II record, stable isotopes and trace elements of Stagamite MF-3 from Schafsloch Cave

The timing and nature of the penultimate deglaciation, also known as Termination II (T-II), is subject of controversial discussions due to the scarcity of precisely-dated palaeoclimate records. Here we present a new precisely-dated and highly-resolved multi-proxy stalagmite record covering T-II from the high alpine Schafsloch Cave in Switzerland, an area where climate is governed by the North Atlantic. The inception of stalagmite growth at 137.4 ± 1.4 kyr before present (BP) indicates the presence of drip water and cave air temperatures of above 0 °C, and is related to a climate-induced change in the thermal state (from cold-to warm-based) of the glacier above the cave. The cessation of stalagmite growth between 133.1 ± 0.7 and 131.9 ± 0.6 kyr BP is most likely related to distinct drop in temperature associated with Heinrich stadial 11. The resumption of stalagmite growth at 131.9 ± 0.6 kyr BP is accompanied by an abrupt increase in temperature and precipitation as indicated by distinct shifts in the oxygen and carbon isotopic composition as well as in trace element concentrations. The mid-point of T-II is around 131.8 ± 0.6 kyr BP in the Schafsloch Cave record is significantly earlier compared to the age of 129.1 ± 0.1 kyr BP in the Sanbao Cave record from China. The different ages between both records can be best explained by the competing effects of insolation and glacial boundary forcing on seasonality and snow cover extent in Eurasia.

(Table 1, page 754) Estimated concentrations of various elements in nineteen manganese nodules

Using spectrochemical techniques Fe, Si, Mg, Co, Ni, Cu, V, Mo, Ti and Tl have been estimated in nineteen manganese nodules, eight from the Atlantic ocean, seven from the Pacific ocean and four from the Indian ocean. Though data on more samples are required before firm and detailed conclusions can be made about the distribution of elements in manganese nodules, several distinct features appear when the data on the nineteen samples are examined. Certain elements appear to enrich more strongly than others. For example, relative to igneous rocks Mo is much more strongly enriched than V. For several elements (Ni, Cu and particularly Co and Tl) the degree of enrichment in two Fe-low nodules is far smaller than in the other nodules. The magnitude of dispersion of concentration appears to vary considerably for different elements; thus, whereas variation of concentration of V is relatively small, that of Ni, Cu, Co and Tl is far larger. The statistical nature of the distribution of Fe in manganese nodules appears to be characteristic and different from that of the other elements studied so far. Of the possible inter-element relationships examined that of Ni-Cu appears to be the most strongly developed.

Geochemistry, chlorin concentrations and diatom abundance in sediments of lake Rotsee, Switzerland

The effects of eutrophication on short term changes in the microbial community were investigated using high resolution lipid biomarker and trace metal data for sediments from the eutrophic Lake Rotsee (Switzerland). The lake has been strongly influenced by sewage input since the 1850s and is an ideal site for studying an anthropogenically altered ecosystem. Historical remediation measures have had direct implications for productivity and microbial biota, leading to community composition changes and abundance shifts. The higher sewage and nutrient input resulted in a productivity increase, which led predominantly to a radiation in diatoms, primary producers and methanogens between about 1918 and 1921, but also affected all microorganism groups and macrophytes between about 1958 and 1972. Bacterial biomass increased in 1933, which may have been related to the construction of a mechanical sewage treatment plant. Biomarkers also allowed tracing of fossil organic matter/biodegraded oil contamination in the lake. Stephanodiscus parvus, Cyclotella radiosa and Asterionella formosa were the dominant sources of specific diatom biomarkers. Since the 1850s, the cell density of methanogenic Archaea (Methanosaeta spp.) ranged within ca. 0.5-1.8 x 10**9 cells/g dry sediment and the average lipid content of Rotsee Archaea was ca. 2.2 fg iGDGTs/cell. An altered BIT index (BITCH), indicating changes in terrestrial organic matter supply to the lake, is proposed.

(Table 2, Page 275) Elemental concentrations in manganese nodules used in seawater contact experiments

The gross changes in concentrations of several trace elements in seawater after contact with ferro-manganese particle suspensions has been determined. Cobalt, Fe, and Zn concentrations in the seawater were greatly increased after contact with the par¬ticles. The concentrations of Rb, U, Cs, Sb, and Ag were altered to a lesser degree by this treatment. Similar results were observed where seawater was con¬tacted with suspensions of pelagic sediments. Of the trace elements measured, cobalt and iron appear to be the best elemental indicators of the presence of manganese mining effluents in the ocean. The addi¬tions of the essential elements Co, Fe and Zn toge¬ther with nutrients from the bottom waters may pro¬duce increased biological productivity. However, the toxic trace metals, such as Hg, Cu and Cd which could enter ocean water from the nodules and sedi¬ment and which may be high in effluent-affected areas should be investigated before conclusions as to the likely impact can be reached. Trace element analysis of seawater samples collected at a Pacific Ocean manganese nodule dredging site showed high t race element concentrations, but these are believed to have resulted from contamination during sample collection or storage rather than from the dredging operations.

Strontium and neodymium concentrations and isotopic compositions of Arctic marine sediments

Sr and Nd isotopic compositions of Arctic marine sediments characterize changes of sediment source regions and trace shelf-ocean particle pathways during glacial-interglacial transitions in the eastern Arctic Ocean. In the 140-ka sedimentary record of a marine core from Yermak Plateau, north of Svalbard, 87Sr/86Sr ratios and epsion-Nd values vary between 0.717 and 0.740 and 39.3 and 314.9, respectively. Sr and Nd isotopic composition both change characteristically during glacial-interglacial cycles and are correlated with the extension of the Svalbard/Barents Sea ice sheet (SBIS). The downcore variation in Sr and Nd isotopic composition indicates climatically induced changes in sediment provenance from two isotopically distinct end-members: (1) Eurasian shelf sediments as a distal source; and (2) Svalbard bedrock as a proximal source that coincide with a change in transport mechanism from sea ice to glacial ice. During glacier advance from Svalbard and intensified glacial bedrock erosion, epsion-Nd values decrease gradually to a minimum value of 314.9 due to increased input of crystalline Svalbard bedrock material. During glacial maxima, the SBIS covered the entire Barents Sea shelf and supplied increasing amounts of Eurasian shelf material to the Arctic Ocean as ice rafted detritus (IRD). Epsion-Nd values in glacial sediments reach maximum values that are comparable to the average value of modern Eurasian shelf and sea ice sediments (epsion-Nd = 310.3). This confirms ice rafting as a major sediment transport mechanism for Eurasian shelf sediments into the Arctic Ocean and trace a sediment origin from the Kara Sea/Laptev Sea shelf area. After the decay of the shelf-based SBIS, the glacial shelf sediment spikes during glacial terminations I (epsion-Nd = 310.6) and II (epsion-Nd = 310.1) epsion-Nd values rapidly decrease to values of 312.5 typical for interglacial averages. The downcore Sr isotopic composition is anticorrelated to the Nd isotopic composition, but may be also influenced by grain-size effects. In contrast, the Nd isotopic composition in clay- to silt-size fractions of one bulk sediment sample is similar to within 0.3-0.8 epsion-Nd units and seems to be a grain-size independent provenance tracer.

(Table T1) Trace-element abundances for igneous basement at ODP Site 206-1256

In this report, I present trace element data for basement samples at Ocean Drilling Program (ODP) Site 1256. The samples analyzed represent a subset of the group ("pool") samples from ODP Leg 206, and these trace element data are part of a more comprehensive data suite for the same samples, with analyses of stable and radiogenic isotopes (e.g., Sr, Li, and O) in progress or recently completed that will be presented elsewhere. The trace element analyses were performed in the GeoAnalytical Lab at Washington State University. The following elements were analyzed: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ba, Th, Nb, Y, Hf, Ta, U, Pb, Rb, Cs, Sr, Sc, and Zr. Trace element data indicate that the igneous basement at Site 1256 is geochemically normal mid-ocean-ridge basalt. A massive ponded flow sampled in both Holes 1256C and 1256D is distinguished by higher abundances of rare earth elements (REE) and most of the other trace elements analyzed. One interval of highly altered basalt has significantly higher concentrations of Cs, Rb, and Ba and lower concentrations of Sr, Pb, Zr, Hf, Sc, and most REE than the samples of background alteration or halos. No correlation is obvious between trace element abundance and macroscopic type of alteration within the background alteration or halos.