The hydrogeochemistry of methane: Evidence from English groundwaters

The presence of methane (CH₄) in groundwater is usually only noticed when it rises to high concentrations; to date rather little is known about its production or natural ‘baseline’ conditions. Evidence from a range of non-polluted groundwater environments in England, including water supply aquifers, aquicludes and thermal waters, reveals that CH₄ is almost always detectable, even in aerobic conditions. Measurements of potable waters from Cretaceous, Jurassic and Triassic carbonate and sandstone aquifers reveal CH₄ concentrations of up to 500 μg/l, but a mean value of < 10 μg/l. However, aquiclude and thermal waters from the Carboniferous and Triassic typically contain in excess of 1500 μg/l. Such high concentrations have so far only been found at redox (Eh) potentials below 0 mV, but in general CH₄ concentration and Eh value are poorly correlated. This suggests a lack of thermodynamic equilibrium, which is confirmed by comparing pe values calculated from the redox couple C(4)/C(− 4) with those derived from Eh. Genesis of CH₄ appears to occur on two timescales: a rapid if low rate of production from labile carbon in anaerobic microsites in the soil, and a much longer, millennium scale of production from more refractory carbon. Methane is rarely measured in groundwater; there is no single ionic determinand which acts universally as a proxy, but a combination of high HCO₃ and low SO₄ concentrations, or the reverse, is an indication that high amounts of CH₄ may be present.     

Na depletion in modern adakites via melt / rock reaction within the sub-arc mantle

Interaction between slab-derived melt and mantle peridotite and the role of slab melt as a metasomatizing agent in the sub-arc mantle is being increasingly recognized. Adakite, the slab melt erupted on the surface, usually exhibits anomalously high MgO, CaO, Cr and Ni contents that indicate interaction with mantle peridotitite. Here we note that Cenozoic adakites have Na₂O contents below 5.8 wt.% with ∼95% samples lower than 5.0 wt.%, and are generally depleted in this component relative to experimental basalt partial melts (mostly beyond 5.0 wt.% and up to 9.0 wt.% Na₂O) produced under 1.5-3.0 GPa conditions that are most relevant to adakite production. We interpret the adakite Na depletion to be also a consequence of the melt / rock reaction that takes place within the hot mantle wedge. During ascent and reaction with mantle peridotite, primary adakite melts gain mantle components MgO, CaO, Cr and Ni but lose Na₂O, SiO₂ and perhaps K₂O to the mantle, leading to Na-rich mantle metasomatism. Selective assimilation of predominately mantle clinopyroxene, some spinel and minor olivine at high T/P has been considered to be an important process in producing high-Mg adakites from primary low-Mg slab melts [Killian, R., Stern, C. R., 2002. Constraints on the interaction between slab melts and the mantle wedge from adakitic glass in peridotite xenoliths. Eur. J. Mineral. 14, 25-36]. In such a process, Na depletion in the assimilated melt is the result of dilution due to the increase in melt mass. Phase relationships in the reaction system siliceous melt + peridotite and quantitative calculation suggest that assimilation of mantle clinopyroxene, olivine and spinel and fractional crystallization of sodic amphibole and orthopyroxene, under conditions of moderate T/P and increasing melt mass, is also an important process that modifies the composition of adakites and causes the Na depletion.     

Mass-dependent fractionation of quadruple stable sulfur isotope system as a new tracer of sulfur biogeochemical cycles

Sulfur isotope studies of post-Archean terrestrial materials have focused on the ratio ³⁴S/³²S because additional isotopes, ³³S and ³⁶S, were thought to carry little information beyond the well-known mass-dependent relationship among multiple-isotope ratios. We report high-precision analyses of Δ³³S and Δ³⁶S values, defined as deviations of ³³S and ³⁶S from ideal mass-dependent relationships, for international reference materials and sedimentary sulfides of Phanerozoic age by using a fluorination technique with a dual-inlet isotope ratio mass spectrometer. Measured variations in Δ³³S and Δ³⁶S are explained as resulting from processes involve branching reactions (two or more reservoirs formed) or mixing. Irreversible processes in closed systems (Rayleigh distillation) amplify the isotope effect. We outline how this new isotope proxy can be used to gain new insights into fundamental aspects of the sulfur biogeochemical cycle, including additional constraints on seawater sulfate budget and processes in sedimentary sulfide formation. The isotope systematics discussed here cannot explain the much larger variation of Δ³³S and Δ³⁶S observed in Archean rock records. Furthermore, Phanerozoic samples we have studied show a characteristic Δ³³S and Δ³⁶S relationship that differs from those measured in Archean rocks and laboratory photolysis experiments. Thus, high precision analysis of Δ³³S and Δ³⁶S can be used to distinguish small non-zero Δ³³S and Δ³⁶S produced by mass-dependent processes from those produced by mass-independent processes in Archean rocks and extraterrestrial materials.     

A critical look at iron paleoredox proxies: New insights from modern euxinic marine basins

Enrichments in reactive iron occur under euxinic marine conditions, that is, where dissolved sulfide is present in the water column. These enrichments result primarily from the export of remobilized iron from the oxic shelf, which is scavenged from the euxinic water column during syngenetic pyrite formation and deposited in the underlying sediments. Strongly elevated ratios of highly reactive iron to total iron (Fe_HR/Fe_T) and total iron to aluminum (Fe_T/Al) and high degrees of pyritization (DOP) are each products of this enrichment process. These paleoredox proxies are among the most faithful recorders of ancient euxinia.Contrary to previous arguments, iron enrichment is decoupled from biogenic sediment inputs, but it does appear to be a uniquely euxinic phenomenon. In other words, we can rule out a major contribution from preferential physical transport of Fe_HR-rich detrital sediment to the deep basin, which could also operate under oxic conditions. Furthermore, enrichment via the shuttling of iron remobilized from oxic shelves appears to be limited by inefficient transport and trapping processes in deep oxic basins. Elevated Fe_T/Al ratios in the euxinic sediments also cannot be a product of internal enhancement of the reactivity of the detrital iron pool without net Fe_HR addition. These conclusions are supported by observations in the modern Black Sea, Orca Basin, and Effingham Inlet.Fe_T/Al ratios are unambiguous recorders of paleoredox even in sediments that have experienced high degrees of metamorphic alteration. However, this study suggests that high siliciclastic accumulation rates can swamp the enrichment mechanism, resulting in only intermediate DOP values for euxinic sediments and Fe_T/Al ratios that mimic the oxic shelf. Such dilution effects are well expressed in Black Sea basinal turbidites and rapidly accumulating muds on euxinic basin margins. Under conditions of persistent euxinia, varying extents of Fe_HR enrichment can illuminate spatial and temporal gradients in siliciclastic sedimentation. The magnitude of enrichment is a function of the source (shelf) to sink (ocean basin) areal ratio, suggesting that iron proxies can also record ocean-scale paleoenvironmental properties through muted enrichments at times of very widespread euxinia. For the first time, manganese data are interpreted in light of the redox shuttle model. As for the iron data, the Black Sea, Orca Basin, and Effingham Inlet show enrichments in total manganese in the deep euxinic basin, suggesting export from the suboxic porewaters of the oxic shelf and scavenging and burial in the basin. The Black Sea data reveal iron and manganese enrichment across the broad, deep euxinic basin, suggesting efficient lateral transport and deep-water mixing tied to the physical properties of the water column.     

Memories of Fire: Eduardo Galeano and the Geography of Guatemala

In Memory of Fire, a poetic narration of the history of the Americas from pre-Columbian times to the late 20th century, Eduardo Galeano furnishes readers with over 1200 of his trademark vignettes, some 35 of which pertain to Guatemala. Galeano evokes disparate aspects of the geography of Guatemala, past and present, in grounded miniatures of time, place, and episode. His sketches of the experiences of Maya peoples allow us to see them as survivors of three cycles of conquest: (1) conquest by imperial Spain; (2) conquest by local and international capitalism; and (3) conquest by state terror. Composed in the literary mode of creative non-fiction, Memory of Fire serves as an inspirational classroom text, exposing students not only to factual detail but also a powerful artistic imagination.     

Cosmogenic nuclide methods for measuring long-term rates of physical erosion and chemical weathering

Understanding the evolution of geochemical and geomorphic systems requires measurements of long-term rates of physical erosion and chemical weathering. Erosion and weathering rates have traditionally been estimated from measurements of sediment and solute fluxes in streams. However, modern sediment and solute fluxes are often decoupled from long-term rates of erosion and weathering, due to storage or re-mobilization of sediment and solutes upstream from the sampling point. Recently, cosmogenic nuclides such as ¹⁰Be and ²⁶Al have become important new tools for measuring long-term rates of physical erosion and chemical weathering. Cosmogenic nuclides can be used to infer the total denudation flux (the sum of the rates of physical erosion and chemical weathering) in actively eroding terrain. Here we review recent work showing how this total denudation flux can be partitioned into its physical and chemical components, using the enrichment of insoluble tracers (such as Zr) in regolith relative to parent rock. By combining cosmogenic nuclide measurements with the bulk elemental composition of rock and soil, geochemists can measure rates of physical erosion and chemical weathering over 1000- to 10,000-year time scales.     

Responses of resident marsh fishes to stages ofPhragmites australis invasion in three mid Atlantic estuaries

Modification of brackish marshes by nonindigenousPhragmites australis has occurred across a broad geographical area in eastern North America. Among its effects on marsh processes,Phragmites may be increasingly unfavorable to marsh surface fishes as its invasion progresses within an estuary. We assessed the effect of thePhragmites invasion on resident marsh surface fishes by examining the population response ofFundulus heteroclitus (mummichog, 5–48 mm TL) andF. luciae (spotfin killifish, 5–41 mm TL) to four distinct invasion stages in three estuaries of the U.S. mid Atlantic region (New Jersey, Delaware, and Maryland). We documented precipitous declines in mean catch per unit effort ofF. heteroclitus in pit traps from natural marsh (51.6), through initial (33.8), early (12.3), and late invasion stages (2.4) across all sites. A similar pattern was documented forF. luciae, with mean catch per unit effort in pit traps declining from natural marsh (48.9), through initial (39.1), early (9.3), and late invasion stages (2.7). Population structure of both species also changed somewhat across invasion stages such that we collected a narrower size range of individuals of both species from late invasion stages. Patterns suggest that as thePhragmites invasion progresses, there is a decline in habitat function for larval and juvenileF. heteroclitus and an increased risk of extirpation ofF. luciae from brackish marshes along the east coast of the U.S.