Pre-Colombian Mercury Pollution Associated with the Smelting of Argentiferous Ores in the Bolivian Andes

The development of the mercury (Hg) amalgamation process in the mid-sixteenth century triggered the onset of large-scale Hg mining in both the Old and New Worlds. However, ancient Hg emissions associated with amalgamation and earlier mining efforts remain poorly constrained. Using a geochemical time-series generated from lake sediments near Cerro Rico de Potosí, once the world’s largest silver deposit, we demonstrate that pre-Colonial smelting of Andean silver ores generated substantial Hg emissions as early as the twelfth century. Peak sediment Hg concentrations and fluxes are associated with smelting and exceed background values by approximately 20-fold and 22-fold, respectively. The sediment inventory of this early Hg pollution more than doubles that associated with extensive amalgamation following Spanish control of the mine (1574–1900 AD). Global measurements of [Hg] from economic ores sampled world-wide indicate that the phenomenon of Hg enrichment in non-ferrous ores is widespread. The results presented here imply that indigenous smelting constitutes a previously unrecognized source of early Hg pollution, given naturally elevated [Hg] in economic silver deposits.     

The Growing Need for Sustainable Ecological Management of Marine Communities of the Persian Gulf

The Persian Gulf is a semi-enclosed marine system surrounded by eight countries, many of which are experiencing substantial development. It is also a major center for the oil industry. The increasing array of anthropogenic disturbances may have substantial negative impacts on marine ecosystems, but this has received little attention until recently. We review the available literature on the Gulfs marine environment and detail our recent experience in the United Arab Emirates (U.A.E.) to evaluate the role of anthropogenic disturbance in this marine ecosystem. Extensive coastal development may now be the single most important anthropogenic stressor. We offer suggestions for how to build awareness of environmental risks of current practices, enhance regional capacity for coastal management, and build cooperative management of this important, shared marine system. An excellent opportunity exists for one or more of the bordering countries to initiate a bold and effective, long-term, international collaboration in environmental management for the Gulf.     

Impact of soil water regime on degradation and plant uptake behaviour of the herbicide isoproturon in different soil types

The environmental fate of the worldwide used herbicide isoproturon was studied in four different, undisturbed lysimeters in the temperate zone of Middle Europe. To exclude climatic effects due to location, soils were collected at different regions in southern Germany and analyzed at a lysimeter station under identical environmental conditions. ¹⁴C-isoproturon mineralization varied between 2.59% and 57.95% in the different soils. Barley plants grown on these lysimeters accumulated ¹⁴C-pesticide residues from soil in partially high amounts and emitted ¹⁴CO₂ in an extent between 2.01% and 13.65% of the applied ¹⁴C-pesticide. Plant uptake and ¹⁴CO₂ emissions from plants were inversely linked to the mineralization of the pesticide in the various soils: High isoproturon mineralization in soil resulted in low plant uptake whereas low isoproturon mineralization in soil resulted in high uptake of isoproturon residues in crop plants and high ¹⁴CO₂ emission from plant surfaces. The soil water regime was identified as an essential factor that regulates degradation and plant uptake of isoproturon whereby the intensity of the impact of this factor is strongly dependent on the soil type.     

Particulate matter in new technology diesel exhaust (NTDE) is quantitatively and qualitatively very different from that found in traditional diesel exhaust (TDE)

Diesel exhaust (DE) characteristic of pre-1988 engines is classified as a "probable" human carcinogen (Group 2A) by the International Agency for Research on Cancer (IARC), and the U.S. Environmental Protection Agency has classified DE as "likely to be carcinogenic to humans." These classifications were based on the large body of health effect studies conducted on DE over the past 30 or so years. However, increasingly stringent U.S. emissions standards (1988-2010) for particulate matter (PM) and nitrogen oxides (NOx) in diesel exhaust have helped stimulate major technological advances in diesel engine technology and diesel fuel/lubricant composition, resulting in the emergence of what has been termed New Technology Diesel Exhaust, or NTDE. NTDE is defined as DE from post-2006 and older retrofit diesel engines that incorporate a variety of technological advancements, including electronic controls, ultra-low-sulfur diesel fuel, oxidation catalysts, and wall-flow diesel particulate filters (DPFs). As discussed in a prior review (T. W. Hesterberg et al.; Environ. Sci. Technol. 2008, 42, 6437-6445), numerous emissions characterization studies have demonstrated marked differences in regulated and unregulated emissions between NTDE and "traditional diesel exhaust" (TDE) from pre-1988 diesel engines. Now there exist even more data demonstrating significant chemical and physical distinctions between the diesel exhaust particulate (DEP) in NTDE versus DEP from pre-2007 diesel technology, and its greater resemblance to particulate emissions from compressed natural gas (CNG) or gasoline engines. Furthermore, preliminary toxicological data suggest that the changes to the physical and chemical composition of NTDE lead to differences in biological responses between NTDE versus TDE exposure. Ongoing studies are expected to address some of the remaining data gaps in the understanding of possible NTDE health effects, but there is now sufficient evidence to conclude that health effects studies of pre-2007 DE likely have little relevance in assessing the potential health risks of NTDE exposures.     

Effects of sulfur dioxide and oxides of nitrogen emission reductions on fine particulate matter mass concentrations: regional comparisons

Two thermodynamic equilibrium models were applied to estimate changes in mean airborne fine particle (PM2.5) mass concentrations that could result from changes in ambient concentrations of sulfate, nitric acid, or ammonia in the southeastern United States, the midwestern United States, and central California. Pronounced regional differences were found. Southeastern sites exhibited the lowest current mean concentrations of nitrate, and the smallest predicted responses of PM2.5 nitrate and mass concentrations to reductions of nitric acid, which is the principal reaction product of the oxidation of nitrogen dioxide (NO2) and the primary gas-phase precursor of fine particulate nitrate. Weak responses of PM2.5 nitrate and mass concentrations to changes in nitric acid levels occurred even if sulfate concentrations were half of current levels. The midwestern sites showed higher levels of fine particulate nitrate, characterized by cold-season maxima, and were projected to show decreases in overall PM levels following decreases of either sulfate or nitric acid. For some midwestern sites, predicted PM2.5 nitrate concentrations increased as modeled sulfate levels declined, but sulfate reductions always reduced the predicted fine PM mass concentrations; PM2.5 nitrate concentrations became more sensitive to reductions of nitric acid as modeled sulfate concentrations were decreased. The California sites currently have the highest mean concentrations of fine PM nitrate and the lowest mean concentrations of fine PM sulfate. Both the estimated PM2.5 nitrate and fine mass concentrations decreased in response to modeled reductions of nitric acid at all California sites. The results indicate important regional differences in expected PM2.5 mass concentration responses to changes in sulfate and nitrate precursors. Analyses of ambient data, such as described here, can be a key part of weight of evidence (WOE) demonstrations for PM2.5 attainment plans. Acquisition of the data may require special sampling efforts, especially for PM2.5 precursor concentration data.     

Modeling dispersion from toxic gas released after a train collision in Graniteville, SC

The Savannah River National Laboratory (SRNL) Weather Information and Display System was used to provide meteorological and atmospheric modeling/consequence assessment support to state and local agencies after the collision of two Norfolk Southern freight trains on the morning of January 6, 2005. This collision resulted in the release of several toxic chemicals to the environment, including chlorine. The dense and highly toxic cloud of chlorine gas that formed in the vicinity of the accident was responsible for 9 fatalities and caused injuries to more than 500 others. Transport model results depicting the forecast path of the ongoing release were made available to emergency managers in the county's Unified Command Center shortly after SRNL received a request for assistance. Support continued over the ensuing 2 days of the active response. The SRNL also provided weather briefings and transport/consequence assessment model results to responders from the South Carolina Department of Health and Environmental Control, the Savannah River Site (SRS) Emergency Operations Center, Department of Energy headquarters, and hazard material teams dispatched from the SRS. Operational model-generated forecast winds used in consequence assessments conducted during the incident were provided at 2-km horizontal grid spacing during the accident response. High-resolution Regional Atmospheric Modeling System (RAMS, version 4.3.0) simulation was later performed to examine potential influences of local topography on plume migration in greater detail. The detailed RAMS simulation was used to determine meteorology using multiple grids with an innermost grid spacing of 125 m. Results from the two simulations are shown to generally agree with meteorological observations at the time; consequently, local topography did not significantly affect wind in the area. Use of a dense gas dispersion model to simulate localized plume behavior using the higher-resolution winds indicated agreement with fatalities in the immediate area and visible damage to vegetation.     

Degradation of explosives-related compounds using nickel catalysts

We report the ability of nickel-based catalysts to degrade explosives compounds in aqueous solution. Several nickel catalysts completely degraded the explosives, although rates varied. Nearly all of the organic explosive compounds tested, including 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), were rapidly degraded to below detection limits by a powdered nickel on an alumina-silicate support (Aldrich nickel catalyst). Perchlorate degradation was minimal (<25%). Degradation of TNT by Aldrich nickel catalyst resulted in apparent first-order kinetics. Significant gaseous 14C was released and collected in an alkaline solution (most likely carbon dioxide) from [14C]RDX and [14C]HMX, indicating heterocyclic ring cleavage. Significant gaseous 14C was not produced from [14C]TNT, but spectrophotometric evidence indicated loss of aromaticity. Degradation occurred in low ionic strength solutions, groundwater, and from pH 3 to pH 9. Degradation of TNT, RDX, and HMX was maintained in flow-through columns of Aldrich nickel catalyst mixed with sand down to a hydraulic retention time of 4h. These data indicate that nickel-based catalysts may be an effective means for remediation of energetics-contaminated groundwater.     

Dacthal and chlorophenoxy herbicides and chlorothalonil fungicide in eggs of osprey (Pandion haliaetus) from the Duwamish-Lake Washington-Puget Sound area of Washington state, USA

Current-use chlorophenoxy herbicides including 2,4-dichlorophenoxyacetic acid, dicamba, triclopyr, dicamba, dimethyl tetrachloroterephthalate (DCPA or dacthal), and the metabolite of pyrethroids, 3-phenoxybenzoic acid (3-PBA), and the fungicide, chlorothalonil, were investigated in the eggs of osprey (Pandion haliaetus) that were collected from 15 sites from five study areas Puget Sound/Seattle area of Washington State, USA. DCPA differs from acidic chlorophenoxy herbicides, and is not readily hydrolyzed to free acid or acid metabolites, and thus we developed a new method. Of the 12 chlorophenoxy herbicides and chlorothalonil analyzed only DCPA could be quantified at six of these sites (2.0 to 10.3 pg/g fresh weight). However, higher levels (6.9 to 85.5 pg/g fresh weight) of the unexpected DCPA structural isomer, dimethyl tetrachlorophthalate (diMe-TCP) were quantified in eggs from all sites. diMe-TCP concentrations tended to be higher in eggs from the Everett Harbor area. As diMe-TCP is not an industrial product, and not commercially available, the source of diMe-TCP is unclear. Regardless, these findings indicate that DCPA and diMe-TCP can be accumulated in the food chain of fish-eating osprey, and transferred in ovo to eggs, and thus may be of concern to the health of the developing chick and the general reproductive health of this osprey population.     

DETECTING BASE FLOW IMPACTS IN COASTAL PLAIN STREAMS1

ABSTRACT: An established trend analysis methodology was applied to the problem of identifying and quantifying stream base flow impacts from water withdrawals and water loss through interbasin transfers. Impacts were simulated using base flow values selected from two U.S. Geological Survey (USGS) continuous record streamflow sites located within the Pinelands of southern New Jersey. Study site base flows were regressed against index site base flows with monotonic and step trend tests applied to the residuals from the regression model. The smallest, significantly detectable (α= 0.10) percentage reduction within a given simulation was used as an estimate of the sensitivity of a trend test. Evaluation of the trend analysis methodology led to the following practical considerations regarding trend test sensitivity. The proportion of study site base flow variability explained by index site base flows should be maximized, while at the same time minimizing positive, first-order autocorrelation in the regression residuals. Given the importance of detecting autocorrelation, missing values should be avoided or minimized. The quarterly (three-month) interval reduced the magnitude of autocorrelation relative to a shorter two-month sampling interval. Sensitivity appeared to improve when equalizing the number of values before and after a base flow impact(s) while seasonally biased sampling appeared to reduce sensitivity. Based primarily on past trend detection studies, nonparametric tests were deemed a better choice over their parametric counterparts, due to the lack of stringent data distributional requirements coupled with little or no loss of power even when applied to normally distributed data.     

TRANSPORT OF SEDIMENT-BOUND ORGANOCHLORINE PESTICIDES TO THE SAN JOAQUIN RWER,CALIFORNIA1

ABSTRACT: Suspended sediment samples were collected in west-side tributaries and the main stem of the San Joaquin River, California, in June 1994 during the irrigation season and in January 1995 during a winter storm. These samples were analyzed for 15 organochiorine pesticides to determine their occurrence and their concentrations on suspended sediment and to compare transport during the irrigation season (April to September) to transport during winter storm runoff (October to March). Ten organochiorine pesticides were detected during the winter storm runoff; seven during the irrigation season. The most frequently detected organochlorine pesticides during both sampling periods were p,p'-DDE, p,p'-DDT, p,p'-DDD, dieldrin, toxaphene, and chiordane. Dissolved samples were analyzed for three organochiorine pesticides during the irrigation season and for 15 during the winter storm. Most calculated total concentrations of p,p-DDT, chlordane, dieldrin, and toxaphene exceeded chronic criteria for the protection of freshwater aquatic life. At eight sites in common between sampling periods, suspended sediment concentrations and streamfiow were greater during the winter storm runoff - median concentration of 3,590 mg/L versus 489 mg(L and median streamfiow of 162 ft³/s versus 11 ft³/s. Median concentrations of total DDT (sum of p,p'-DDD, p,p-DDE, and p,p'-DDT), chlordane, dieldrin, and toxaphene on suspended sediment were slightly greater during the irrigation season, but instantaneous loads of organochlorine pesticides at the time of sampling were substantially greater during the winter storm. Estimated loads for the entire irrigation season exceeded estimated loads for the January 1995 storm by about 2 to 4 times for suspended transport and about 3 to 11 times for total transport. However, because the mean annual winter runoff is about 2 to 4 times greater than the runoff during the January 1995 storm, mean winter transport may be similar to irrigation season transport. This conclusion is tentative primarily because of insufficient information on long-term seasonal variations in suspended sediment and organochlorine concentrations. Nevertheless, runoff from infrequent winter storms will continue to deliver a significant load of sediment-bound organochiorine pesticides to the San Joaquin River even if irrigation-induced sediment transport is reduced. As a result, concentrations of organochlorine pesticides in San Joaquin River biota will continue to be relatively high compared to other regions of the United States.