Trends in 1,4-Dioxane Analyses: Implications for Identification and Characterization of Contaminated Groundwater Sites

1,4-Dioxane is a contaminant of emerging concern, and there is significant uncertainty about how its environmental occurrence in groundwater is being assessed given the various analytical methods available. This study compiled public sampling records from 2000 to 2019 that included >106,000 analyses of 1,4-dioxane from 822 different U.S. sites. The 1,4-dioxane detection frequency in the entire dataset (including all methods) was 45%, and the median detected concentration was 10 μg/L, highlighting the dilute nature of 1,4-dioxane in environmental media and the importance of selecting methods with adequate sensitivity. The annual distribution of samples analyzed by each method type confirmed a shift towards methods designed for semi-volatile compounds (Method 8270 and Method 8270 SIM) that exhibited consistently lower reporting limits (median reporting limit for each year typically ≤1 μg/L). In contrast, the method designed for volatile compounds (Method 8260) exhibited less sensitivity for 1,4-dioxane (median reporting limit per year between 40 and 100 μg/L) and its use declined significantly over time with increasing use of the moderately sensitive Method 8260 SIM in later years. This shift contributed to an increase in the 1,4-dioxane detection frequency over time, with a strong correlation between the annual detection frequency and the median reporting limit. Sites where 1,4-dioxane was analyzed but not detected overwhelmingly used less-sensitive methods that may not have been adequate for the expected concentration levels. Given the sub-μg/L groundwater criteria issued for 1,4-dioxane by some regulatory agencies, more sensitive and accurate methods will be increasingly needed to assess compliance.     

Cation substitution in synthetic meridianiite (MgSO<Subscript>4</Subscript>·11H<Subscript>2</Subscript>O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

Meridianiite, MgSO₄·11H₂O, is the most highly hydrated phase in the binary MgSO₄–H₂O system. Lower hydrates in the MgSO₄–H₂O system have end-member analogues containing alternative divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) and exhibit extensive solid solution with MgSO₄ and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO₄ solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO₄ forms an undecahydrate; ZnSO₄ forms an orthorhombic heptahydrate (synthetic goslarite), MnSO₄, FeSO₄, and CoSO₄ form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO₄ crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO₄ forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) ų, is consistent with it being an octahydrate, NiSO₄·8H₂O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co²⁺ or Mn²⁺, 20–30 mol. % Ni²⁺ or Zn²⁺, but less than 10 mol. % of Cu²⁺ or Fe²⁺. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO₄, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg_0.5Cu_0.5)SO₄·7H₂O)]. In the NiSO₄- and ZnSO₄-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO₄- and the FeSO₄-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P2₁/c with Z = 4. The unit-cell volume, V = 1,176.59(5) ų, is consistent with it being an enneahydrate [i.e. (Mg_0.5Ni_0.5)SO₄·9H₂O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) ų, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) ų. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.     

An experimental study of partial melting and fractional crystallization on the HED parent body

We have performed an experimental and modeling study of the partial melting behavior of the HED parent body and of the fractional crystallization of liquids derived from its mantle. We estimated the mantle composition by assuming chondritic ratios of refractory lithophile elements, adjusting the Mg# and core size to match the density and moment of inertia of Vesta, and the compositions of Mg‐rich olivines found in diogenites. The liquidus of a mantle with Mg# (=100*[Mg/(Mg+Fe)]) 80 is ~1625 °C and, under equilibrium conditions, the melt crystallizes olivine alone until it is joined by orthopyroxene at 1350 °C. We synthesized the melt from our 1350 °C experiment and simulated its fractional crystallization path. Orthopyroxene crystallizes until it is replaced by pigeonite at 1200 °C. Liquids become eucritic and crystal assemblages resemble diogenites below 1250 °C. MELTS correctly predicts the olivine liquidus but overestimates the orthopyroxene liquidus by ~70 °C. Predicted melt compositions are in reasonable agreement with those generated experimentally. We used MELTS to determine that the range of mantle compositions that can produce eucritic liquids and diogenitic solids in a magma ocean model is Mg# 75–80 (with chondritic ratios of refractory elements). A mantle with Mg# ~ 70 can produce eucrites and diogenites through sequential partial melting.     

Tsunami exposure estimation with land-cover data: Oregon and the Cascadia subduction zone

A Cascadia subduction-zone earthquake has the potential to generate tsunami waves which would impact more than 1000 km of coastline on the west coast of the United States and Canada. Although the predictable extent of tsunami inundation is similar for low-lying land throughout the region, human use of tsunami-prone land varies, creating variations in community exposure and potential impacts. To better understand such variations, land-cover information derived from midresolution remotely-sensed imagery (e.g., 30-m-resolution Landsat Thematic Mapper imagery) was coupled with tsunami-hazard information to describe tsunami-prone land along the Oregon coast. Land-cover data suggest that 95% of the tsunami-prone land in Oregon is undeveloped and is primarily wetlands and unconsolidated shores. Based on Spearman rank correlation coefficients (r_s), correlative relationships are strong and statistically significant (p < 0.05) between city-level estimates of the amount of land-cover pixels classified as developed (impervious cover greater than 20%) and the amount of various societal assets, including residential and employee populations, homes, businesses, and tax-parcel values. Community exposure to tsunami hazards, described here by the amount and relative percentage of developed land in tsunami-prone areas, varies considerably among the 26 communities of the study area, and these variations relate to city size. Correlative relationships are strong and significant (p < 0.05) for community exposure rankings based on land-cover data and those based on aggregated socioeconomic data. In the absence of socioeconomic data or community-based knowledge, the integration of hazards information and land-cover information derived from midresolution remotely-sensed imagery to estimate community exposure may be a useful first step in understanding variations in community vulnerability to regional hazards.     

High Angular Resolution Studies of Coronal Structures with SOHO

Since January 1996, the Solar and Heliospheric Observatory (SOHO)has been providing unprecedented views of the extended solar coronato heliocentric distances of up to 32 solar radii. During the past threeyears we carried out studies of the morphology and dynamical evolutionof various structures in the solar corona using two instruments on boardSOHO: the Large Angle Spectrometric Coronagraph (LASCO) and the ExtremeUltraviolet Imaging Telescope (EIT). We have applied advanced image resolutionenhancement techniques to explore in detail the characteristics of thesmall-scale structures and/or the low contrast structures in the solarcorona. We describe here the results from these high-angular resolutionstudies, including of the kinematics of several Coronal Mass Ejections andpolar jets.