Evaluation of 1,4-dioxane attenuation processes at the Gelman Site, Michigan, USA.

1,4-Dioxane released at the Gelman Site in Washtenaw County, Michigan, produced a series of contaminant plumes migrating up to 3 km through a heterogenous glacial aquifer system. An analysis of 1,4-dioxane concentrations in the Eastern Area of the Gelman Site between 2011 and 2017 documented a mass balance deficit of 2200 kg in excess of 2100 kg of 1,4-dioxane removed via remediation. Five mechanisms were evaluated to account for the mass deficiency: sorption, matrix diffusion, biodegradation, surface discharge, and bypass of the existing monitoring well network. The mass of 1,4-dioxane sorbed to aquifer and aquitard materials and the mass of 1,4-dioxane diffused into low permeability zones were estimated. However, decreasing aqueous concentrations across most of the contaminated area between 2011 and 2017 are expected to induce desorption and back diffusion during this period. Surface water discharge to a storm drain in the downgradient portion of the site was analyzed using concentration measurements and stream gage data. Results suggest that 1,4-dioxane mass entering the drain during the period between 2011 and 2017 was insufficient to account for the mass deficiency. Although available geochemical measurements indicate predominantly anaerobic aquifer conditions at the Gelman Site, biodegradation of 1,4-dioxane was estimated using first order decay rate constants from other sites where conditions may be more favorable. Results suggest that biodegradation could explain some but not all of the missing mass. Bypass of the downgradient monitoring well network is the most parsimonious explanation for the 1,4-dioxane mass deficit. This conclusion is supported by documented flow path complexity through the aquifer system and the sparse density of monitoring wells in the downgradient Eastern Area. These findings underscore the importance of characterizing aquifer heterogeneity when modeling and remediating persistent groundwater contaminants such as 1,4-dioxane.

Determination of 1,4-dioxane in water samples using freeze-assisted liquid-liquid extraction and gas chromatography-mass spectrometry with select reaction monitoring.

In this study, we developed an analytical method for the determination of 1,4-dioxane in aqueous solutions using freeze-assisted liquid-liquid extraction, also known as frozen microextraction, and gas chromatography with triple quadrupole mass spectrometry with select reaction monitoring. The method is capable of quantifying 1,4-dioxane across a broad range of concentrations (1-10 000 µg/L) relevant to contaminated sites, with an instrument detection limit and method detection limit experimentally verified as 2.1 and 2.2 µg/L, respectively. In contrast to methods with similar detection limits that require 50 to 500 mL volume of sample, our method uses only 200 µL of sample. The method presented here facilitates field and laboratory applications where small sample volumes and high precision are required and could be extended to other strongly water-soluble GC-amenable analytes.

Evidence for the onset of mining activities during the 13th century in Poland using lead isotopes from lake sediment cores.

Efforts to study how human activities have influenced the environment since the end of the Roman period to present day are lacking for North Central Europe. Here, we present new lead (Pb) isotope data determined from two sediment cores collected from ancient lakes spanning the last 1500 years, located in the Kuyavian-Pomeranian Voivodeship, Poland. Study sites at Radzyn Chelminski and Rywald were used to differentiate Pb sources. Radzyn Chelminski is located in the vicinity of a late Medieval Teutonic Order castle and town, while Rywald is situated within a relatively pristine area until the 19th century when it became used for agricultural purpose. Core samples were analyzed for Pb concentration and isotopes (206Pb, 207Pb, 208Pb). Bayesian modeling was used to isolate the anthropogenic signal at each site over time. For both sites, Pb enrichment factors relative to titanium (Ti) and upper continental crust values range from 13 to 159. Lead isotopic ratios range from background, pre-anthropogenic local values (206Pb/207Pb = 1.31 ±â€¯0.03‰, 208Pb/206Pb = 1.97 ±â€¯0.04‰) to anthropogenic values (SW Poland coal, ore, slag 206Pb/207Pb = 1.17 ±â€¯0.01‰, 208Pb/206Pb = 2.09 ±â€¯0.01‰). Modeled anthropogenic contribution varies greatly over time, ranging from 14 to 100%. At Radzyn Chelminski, modeled anthropogenic Pb contribution and measured Pb concentration follow similar trends. However, at Rywald, from around A.D.1000 to 1400 CE these profiles diverge significantly. Our new insights highlight different sources of Pb from the 12th century to present day: (1) short range agricultural activities from the town, and (2) long range mining activities. Additionally, prior to the 12th century, our data suggest continental anthropogenic activity possibly favored by a warmer climate.

Absence of biomarker evidence for early eukaryotic life from the Mesoproterozoic Roper Group: Searching across a marine redox gradient in mid-Proterozoic habitability.

By about 2.0 billion years ago (Ga), there is evidence for a period best known for its extended, apparent geochemical stability expressed famously in the carbonate-carbon isotope data. Despite the first appearance and early innovation among eukaryotic organisms, this period is also known for a rarity of eukaryotic fossils and an absence of organic biomarker fingerprints for those organisms, suggesting low diversity and relatively small populations compared to the Neoproterozoic era. Nevertheless, the search for diagnostic biomarkers has not been performed with guidance from paleoenvironmental redox constrains from inorganic geochemistry that should reveal the facies that were most likely hospitable to these organisms. Siltstones and shales obtained from drill core of the ca. 1.3-1.4 Ga Roper Group from the McArthur Basin of northern Australia provide one of our best windows into the mid-Proterozoic redox landscape. The group is well dated and minimally metamorphosed (of oil window maturity), and previous geochemical data suggest a relatively strong connection to the open ocean compared to other mid-Proterozoic records. Here, we present one of the first integrated investigations of Mesoproterozoic biomarker records performed in parallel with established inorganic redox proxy indicators. Results reveal a temporally variable paleoredox structure through the Velkerri Formation as gauged from iron mineral speciation and trace-metal geochemistry, vacillating between oxic and anoxic. Our combined lipid biomarker and inorganic geochemical records indicate at least episodic euxinic conditions sustained predominantly below the photic zone during the deposition of organic-rich shales found in the middle Velkerri Formation. The most striking result is an absence of eukaryotic steranes (4-desmethylsteranes) and only traces of gammacerane in some samples-despite our search across oxic, as well as anoxic, facies that should favor eukaryotic habitability and in low maturity rocks that allow the preservation of biomarker alkanes. The dearth of Mesoproterozoic eukaryotic sterane biomarkers, even within the more oxic facies, is somewhat surprising but suggests that controls such as the long-term nutrient balance and other environmental factors may have throttled the abundances and diversity of early eukaryotic life relative to bacteria within marine microbial communities. Given that molecular clocks predict that sterol synthesis evolved early in eukaryotic history, and (bacterial) fossil steroids have been found previously in 1.64 Ga rocks, then a very low environmental abundance of eukaryotes relative to bacteria is our preferred explanation for the lack of regular steranes and only traces of gammacerane in a few samples. It is also possible that early eukaryotes adapted to Mesoproterozoic marine environments did not make abundant steroid lipids or tetrahymanol in their cell membranes.

Demosponge steroid biomarker 26-methylstigmastane provides evidence for Neoproterozoic animals.

Sterane biomarkers preserved in ancient sedimentary rocks hold promise for tracking the diversification and ecological expansion of eukaryotes. The earliest proposed animal biomarkers from demosponges (Demospongiae) are recorded in a sequence around 100 Myr long of Neoproterozoic-Cambrian marine sedimentary strata from the Huqf Supergroup, South Oman Salt Basin. This C30 sterane biomarker, informally known as 24-isopropylcholestane (24-ipc), possesses the same carbon skeleton as sterols found in some modern-day demosponges. However, this evidence is controversial because 24-ipc is not exclusive to demosponges since 24-ipc sterols are found in trace amounts in some pelagophyte algae. Here, we report a new fossil sterane biomarker that co-occurs with 24-ipc in a suite of late Neoproterozoic-Cambrian sedimentary rocks and oils, which possesses a rare hydrocarbon skeleton that is uniquely found within extant demosponge taxa. This sterane is informally designated as 26-methylstigmastane (26-mes), reflecting the very unusual methylation at the terminus of the steroid side chain. It is the first animal-specific sterane marker detected in the geological record that can be unambiguously linked to precursor sterols only reported from extant demosponges. These new findings strongly suggest that demosponges, and hence multicellular animals, were prominent in some late Neoproterozoic marine environments at least extending back to the Cryogenian period.

Method for simultaneous oxygen and hydrogen isotope analysis of water of crystallization in hydrated minerals.

The isotopic composition of water in hydrated minerals, such as gypsum and jarosite, has numerous applications in studies of recent climate change, ore formation, and soil development. However, oxygen and hydrogen isotope analysis of water of crystallization is currently a complex procedure. Commonly used techniques involve offline extraction of water from hydrated minerals and subsequent isotope analysis. Such methods are time-consuming, require relatively large sample sizes, and the stepwise procedure has to be carried out with extreme caution to avoid erroneous results. We present a novel online method for the oxygen and hydrogen isotope analysis of water of crystallization in hydrous minerals. Gypsum (CaSO 4.2H 2O) samples, 2 mg in size, are reacted in a simply modified carbon reducing furnace connected to a continuous-flow mass spectrometer system. Analysis time is less than 10 min/sample. The precision (2 std dev mean) of our method for 2-mg gypsum (30 mumol of H 2O) samples is 0.3 per thousand for oxygen and less than 1.4 per thousand for hydrogen isotope measurements. For oxygen isotope analysis alone, samples as small as 0.2 mg of gypsum can be analyzed with a precision of 0.3 per thousand.