The persistence of lead from past gasoline emissions and mining drainage in a large riparian system: Evidence from lead isotopes in the Sacramento River, California

Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of the West Shasta Cu-mining district is derived from past depositions of leaded gasoline emissions. This predominance is the first direct documentation of the geographic extent of gasoline lead persistence throughout a large riparian system (>160,000 km²) and corroborates previous observations based on samples taken at the mouth of the Sacramento River. In addition, new analyses of sediment samples from the hydraulic gold mines of the Sierra Nevada foothills confirm the present-day fluxes into the Sacramento River of contaminant metals derived from historical hydraulic Au-mining that occurred during the latter half of the 19th and early part of the 20th centuries. These fluxes occur predominantly during periods of elevated river discharge associated with heavy winter precipitation in northern California. In the broadest context, the study demonstrates the potential for altered precipitation patterns resulting from climate change to affect the mobility and transport of soil-bound contaminants in the surface environment.     

Calcite precipitation instability under laminar, open-channel flow

We present a 2D numerical model for the growth of calcite from supersaturated aqueous solutions under laminar, open-channel flow conditions. The model couples solution chemistry, precipitation at solution/calcite interfaces, hydrodynamics, diffusion and degassing. The model output is compared with experimental results obtained using an oversaturated calcite solution produced by mixing CaCl₂ and Na₂CO₃. The precipitation rate is observed to increase when the supersaturated solution flows over an obstruction, leading to a growth instability that causes the formation of terraces. At relatively high flow rates, the most important mechanism for this behaviour seems to be hydrodynamic advection of dissolved species either towards or away from the calcite surface, depending on location relative to the obstruction, which deforms the concentration gradients. At lower flow rates, steepening of diffusion gradients around protrusions becomes important. Enhanced degassing over the obstruction due to shallowing and pressure drop is not important on small scales. Diffusion controlled transport close to the calcite surface can lead to a fingering-type growth instability, which generates porous textures. Our results are consistent with existing diffusive boundary layer theory, but for flow over non-smooth surfaces, simple calcite precipitation models that include empirical correlations between fluid flow rate and calcite precipitation rate are inaccurate.     

Exurbia from the bottom-up: Confronting empirical challenges to characterizing a complex system

We describe empirical results from a multi-disciplinary project that support modeling complex processes of land-use and land-cover change in exurban parts of Southeastern Michigan. Based on two different conceptual models, one describing the evolution of urban form as a consequence of residential preferences and the other describing land-cover changes in an exurban township as a consequence of residential preferences, local policies, and a diversity of development types, we describe a variety of empirical data collected to support the mechanisms that we encoded in computational agent-based models. We used multiple methods, including social surveys, remote sensing, and statistical analysis of spatial data, to collect data that could be used to validate the structure of our models, calibrate their specific parameters, and evaluate their output. The data were used to investigate this system in the context of several themes from complexity science, including have (a) macro-level patterns; (b) autonomous decision making entities (i.e., agents); (c) heterogeneity among those entities; (d) social and spatial interactions that operate across multiple scales and (e) nonlinear feedback mechanisms. The results point to the importance of collecting data on agents and their interactions when producing agent-based models, the general validity of our conceptual models, and some changes that we needed to make to these models following data analysis. The calibrated models have been and are being used to evaluate landscape dynamics and the effects of various policy interventions on urban land-cover patterns.     

Church-based social capital, networks and geographical scale: Katrina evacuation, relocation, and recovery in a New Orleans Vietnamese American community

This research examines the role of social capital and networks to explain the evacuation, relocation, and recovery experiences of a Vietnamese American community in New Orleans, Louisiana in the aftermath of Hurricane Katrina. As the single largest community institution, the parish church’s complex bonding and bridging social capital and networks proved particularly critical in part because of its historically based ontological security. The process of evacuation, but especially relocation and recovery, was dependent on deploying co-ethnic social capital and networks at a variety of geographical scales. Beyond the local or community scale, extra-local, regional, and national scales of social capital and networks reproduced a spatially redefined Vietnamese American community. Part of the recovery process included constructing discursive place-based collective-action frames to successfully contest a nearby landfill that in turn engendered social capital and networks crossing ethnic boundaries to include the extra-local African American community. Engaging social capital and networks beyond the local geographical scale cultivated a Vietnamese American community with an emergent post-Katrina cultural and political identity.     

Trace Element Partitioning and Accessory Phase Saturation during H2O-Saturated Melting of Basalt with Implications for Subduction Zone Chemical Fluxes

Experimental phase equilibrium and trace element partitioningdata are reported for H₂O-saturated mid-ocean ridge basalt at2·5 GPa, 750–900°C and oxygen fugacities atthe nickel–nickel oxide buffer. Garnet, omphacite andrutile are present at all temperatures. Amphibole and epidotedisappear as residual phases above 800°C; allanite appearsabove 750°C. The Na–Al-rich silicate glass presentin all run products is likely to have quenched from a supercriticalliquid. Trace element analyses of glasses demonstrate the importantcontrol exerted by residual minerals on liquid chemistry. Inaddition to garnet, which controls heavy rare earth elements(HREE) and Sc, and rutile, which controls Ti, Nb and Ta, allanitebuffers the light REE (LREE; La–Sm) contents of liquidsto relatively low levels and preferentially holds back Th relativeto U. In agreement with previous experimental and metamorphicstudies we propose that residual allanite plays a key role inselectively retaining trace elements in the slab during subduction.Experimental data and analyses of allanite-bearing volcanicrocks are used to derive a model for allanite solubility inliquids as a function of pressure, temperature, anhydrous liquidcomposition and LREE content. The large temperature dependenceof allanite solubility is very similar to that previously determinedfor monazite. Our model, fitted to 48 datapoints, retrievesLREE solubility (in ppm) to within a factor of 1· 40over a pressure range of 0–4 GPa, temperature range of700–1200°C and for liquids with anhydrous SiO₂ contentsof 50–84 wt %. This uncertainty in LREE content is equivalentto a temperature uncertainty of only ± 27°C at 1000K, indicating the potential of allanite as a geothermometer.Silicic liquids from either basaltic or sedimentary protolithswill be saturated in allanite except for Ca-poor protolithsor at very high temperatures. For conventional subduction geothermsthe low solubility of LREE (+ Th) in liquids raises questionsabout the mechanism of LREE + Th transport from slab to wedge.It is suggested either that, locally, temperatures experiencedby the slab are high enough to eliminate allanite in the residueor that substantial volumes of H₂O-rich fluids must pass throughthe mantle wedge prior to melting. The solubility of accessoryphases in fluids derived from subducted rocks can provide importantconstraints on subduction zone thermal structure. KEY WORDS: subduction; experimental petrology; allanite; solubility; supercritical liquid; eclogite     

Origin of the Oceanic Lithosphere

In a global examination of mid-ocean ridge basalt (MORB) glasscompositions, we find that Na₈–Fe₈–depth variationsdo not support modeling of MORBs as aggregates of melt compositionsgenerated over a large range of temperature and pressure. However,the Na₈–Fe₈ variations are consistent with the compositionalsystematics of solidus melts in the plagioclase–spinellherzolite transition in the CaO–MgO–Al₂O₃–SiO₂–Na₂O–FeO(CMASNF) system. For natural compositions, the P–T rangefor melt extraction is estimated to be 1·2–1·5GPa and 1250–1280°C. This P–T range is a closematch with the maximum P–T conditions for explosive pressure-releasevaporization of carbonate-bearing melts. It is proposed thatfracturing of the lithosphere induces explosive formation andescape of CO₂ vapor. This provides the vehicle for extractionof MORBs at a relatively uniform T and P. The upper portionof the CO₂-bearing and slightly melted seismic low-velocityzone flows toward the ridge, rises at the ridge axis to lower-lithospheredepths, melts much more extensively during this rise, and releasesMORB melts to the surface driven by explosively escaping CO₂vapor. The residue and overlying crust produced by this meltingthen migrate away from the ridge axis as new oceanic lithosphere.The entire process of oceanic lithosphere creation involvesonly the upper 140 km. When lithospheric stresses shift fractureformation to other localities, escape of CO₂ ceases, the vehiclefor transporting melt to the surface disappears, and ridgesdie. Inverse correlations of Na₈ vs Fe₈ for MORB glasses areexplained by mantle heterogeneity, and positive variations superimposedon the inverse variations are consistent with progressive extractionof melts from short, ascending melting columns. The uniformlylow temperatures of MORB extraction are not consistent withthe existence of hot plumes on or close to ocean ridges. Inthis modeling, the southern Atlantic mantle from Bouvet to about26°N is relatively homogeneous, whereas the Atlantic mantlenorth of about 26°N shows significant long-range heterogeneity.The mantle between the Charlie Gibbs and Jan Mayen fracturezones is strongly enriched in FeO/MgO, perhaps by a trappedfragment of basaltic crust. Iceland is explained as the productof this enrichment, not a hot plume. The East Pacific Rise,Galapagos Ridge, Gorda Ridge, and Juan de Fuca Ridge samplemantle that is heterogeneous over short distances. The mantlebeneath the Red Sea is enriched in FeO/MgO relative to the mantlebeneath the northern Indian Ocean.     

Phase Relations and Melting of Anhydrous K-bearing Eclogite from 1200 to 1600{degrees}C and 3 to 5 GPa

To investigate eclogite melting under mantle conditions, wehave performed a series of piston-cylinder experiments usinga homogeneous synthetic starting material (GA2) that is representativeof altered mid-ocean ridge basalt. Experiments were conductedat pressures of 3·0, 4·0 and 5·0 GPa andover a temperature range of 1200–1600°C. The subsolidusmineralogy of GA2 consists of garnet and clinopyroxene withminor quartz–coesite, rutile and feldspar. Solidus temperaturesare located at 1230°C at 3·0 GPa and 1300°C at5·0 GPa, giving a steep solidus slope of 30–40°C/GPa.Melting intervals are in excess of 200°C and increase withpressure up to 5·0 GPa. At 3·0 GPa feldspar, rutileand quartz are residual phases up to 40°C above the solidus,whereas at higher pressures feldspar and rutile are rapidlymelted out above the solidus. Garnet and clinopyroxene are theonly residual phases once melt fractions exceed 20% and garnetis the sole liquidus phase over the investigated pressure range.With increasing melt fraction garnet and clinopyroxene becomeprogressively more Mg-rich, whereas coexisting melts vary fromK-rich dacites at low degrees of melting to basaltic andesitesat high melt fractions. Increasing pressure tends to increasethe jadeite and Ca-eskolaite components in clinopyroxene andenhance the modal proportion of garnet at low melt fractions,which effects a marked reduction in the Al₂O₃ and Na₂O contentof the melt with pressure. In contrast, the TiO₂ and K₂O contentsof the low-degree melts increase with increasing pressure; thusNa₂O and K₂O behave in a contrasted manner as a function ofpressure. Altered oceanic basalt is an important component ofcrust returned to the mantle via plate subduction, so GA2 maybe representative of one of many different mafic lithologiespresent in the upper mantle. During upwelling of heterogeneousmantle domains, these mafic rock-types may undergo extensivemelting at great depths, because of their low solidus temperaturescompared with mantle peridotite. Melt batches may be highlyvariable in composition depending on the composition and degreeof melting of the source, the depth of melting, and the degreeof magma mixing. Some of the eclogite-derived melts may alsoreact with and refertilize surrounding peridotite, which itselfmay partially melt with further upwelling. Such complex magma-genesisconditions may partly explain the wide spectrum of primitivemagma compositions found within oceanic basalt suites. KEY WORDS: eclogite; experimental petrology; mafic magmatism; mantle melting; oceanic basalts     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.